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Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
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BOOK OF A3BSTRACTS 2nd INTERNATIONAL MEETING ON DEEP EUTECTIC SYSTEMS
ONLINE 15th-17th JUNE 2021
The Organizing Committee invites you for the 2nd International Meeting
on Deep Eutectic Systems. Due to the pandemic context we are living, the Meeting
will be held exclusively online, from 15th to 17th of June 2021. After the success
of the 1st event, we expect to continue a fruitful series of meetings, where scientists,
students and industry partners can discuss current developments and innovations
in the field of Deep Eutectic Systems. Themes like fundamental properties, scale up
of processes, and development of new products, techniques and approaches will be
addressed. The main objective is to join a group of specialists in this emerging field
and be able, not only to hear the newest developments and discoveries, but also to
discuss and interact with students and other participants. This way, we intend to
provide you a unique opportunity of results dissemination and discussion of new
ideas. This Meeting will have plenary lectures, oral communications, and poster
sessions, which we believe to cover all the most innovative scientific developments.
Hope to see you there!
The Organizing Committee
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Title: The Book of Abstracts of the 2nd International Meeting on Deep Eutectic Systems Publishes abstracts from the following fields: Fundamentals, Pharma, Food, Extraction & Separation, Materials and Biotech. Publishers: Des Solutio - Soluções e Consultoria Científica, Lda ISBN: 978-989-33-1955-0
ORGANIZING COMMITTEE: ▪ Ana Rita C. Duarte, FCT-Universidade Nova de Lisboa, Portugal ▪ Alexandre Paiva, FCT-Universidade Nova de Lisboa, Portugal ▪ Rita Craveiro, FCT-Universidade Nova de Lisboa, Portugal ▪ Luísa Pereira, FCT-Universidade Nova de Lisboa, Portugal
SCIENTIFIC COMMITTEE:
▪ Andrew Abbott – University of Leicester, UK ▪ Francisco Del Monte – CSIC, Madrid, Spain ▪ Gary Baker - Missouri University, EUA ▪ Gregory Warr – University of Sydney, Australia ▪ Jeongmi Lee – Sungkyunkwan University, South Korea ▪ Josué Mota-Morales – CFATA-UNAM, Mexico ▪ Karen Edler – Bath University, UK ▪ Karine Vigier – IC2MP, Poitiers University, France ▪ Maan Hayyan – Sohar University, Sultanate of Oman ▪ Rob Verpoort – Leiden University, Netherlands ▪ Sona Raeissi – Shiraz University, Iran ▪ Zhan-Hui Zhang – Hebei Normal University, Shijiazhuang, China
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Sponsors
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
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Program
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*Western European Summer Time Zone (WEST, UTC±1:00) Detailed program Tuesday, 15th June 2021
* 09:00 Opening session
Plenary lecture
09:15 Understanding the Physicochemical Behavior of Deep Eutectic Solvents Using Computational Modelling: From fundamentals to practical applications Félix Llovell
Oral presentations – FUNDAMENTALS
10:00 Simulation of Equilibrium Phase Diagram and Physicochemical Characterization of Natural Eutectic Solvents
Maha M. Abdallah, Simon Muller, Andres Gonzalez de Castilla, Pavel Gurikov, Maria do Rosário Bronze, Ana A. Matias, Naiara Fernandez
10:15 ATR-IR Spectroscopy for Rapid Quantification of Water Content in Deep Eutectic Solvents
Suha Elderderi, Charlotte Leman-Loubière, Laura Wils, Hugh J. Byrne, Igor Chourpa, Cécile Enguehard-Gueiffier, Emilie Munnier, Abdalla A. Elbashir, Leslie Boudesocque-Delaye, Franck Bonnier
10:30 Is There Depth to Eutectic Systems?
Adriaan van den Bruinhorst, Mark Vis, Gijsbertus de With, Agilio Padua, and Margarida Costa Gomes
10:45 Coffee break and poster sessions
11:45 Micellization of Ionic Surfactants in a Ternary Deep Eutectic System
Ria Atri, Iva Manasi, Adrian Sanchez Fernandez, Oliver Hammond, James Doutch and Karen J. Edler
12:00 DES? Solutions? The Influence of Water on the phase behaviour of Ternary Liquid Mixtures
Ana Roda, Christoph Held, Filipa Santos, Yeong Zen Chua, Aarti Kumar, Hoang Tam Do, Alexandre Paiva and Ana Rita C. Duarte
12:15 Carvone and its eutectic mixtures introduced as tunable, green solvents
Ke Li, Seulgi Kang, Yuli Liu, Inseon Hwang, Jeongmi Lee
12:30 Structure and Interactions in p-Toluene Sulfonic Acid based Deep Eutectic Solvent
Iva Manasi, Elly K Bathke, Stephen M King, Daniel T Bowron and Karen J Edler
12:45
On the Betaine:Urea:xWater NADES system
Maria F. Nava-Ocampo, Lamya Al Fuhaid, Adriano Santana, Szilárd S. Bucs, Robert Verpoorte, Young Choi, Johannes S. Vrouwenvelder, Geert J. Witkamp, Andreia S. F. Farinha
13:00
Biosourced Non-Ionic Low Transition Temperature Mixtures Composed of Fructose and Glycerol: Water and Temperature Impact on the Supramolecular Organization Caprin Benoît, Charton Virginie, Rodier Jean-David, Vogelgesang Boris, Charlot Aurélia, Da Cruz-Boisson Fernande, Fleury Etienne
13:15 Lunch
Oral presentations – PHARM
14:45 Solubility of Mesalazine in Natural Deep Eutectic Solvents
Debora Procopio, Carlo Siciliano, Sonia Trombino, Roberta Cassano, Federica Curcio, Maria Luisa Di Gioia
15:00 Delivery of Deep Eutectic Solvents Comprising Nonsteroidal Anti-inflammatory Drugs using Biopolymer-Based Systems
Sónia N. Pedro, Maria S. M. Mendes, Bruno Miguel Neves, Mara G. Freire, Armando J. D. Silvestre and Carmen S. R. Freire
15:15 Unravelling the target-specific anticancer action of THEDES
Filipe Oliveira, Joana Pereira, Eduardo Silva, Joana M. Silva, Rui L. Reis, Ana Rita C. Duarte
15:30 Eutectic Mixtures as Promising Formulation Strategy for Poorly Water-Soluble Drugs Sarah El Masri, Sophie Fourmentin, Steven Ruellan, Maha Zakhour and Lizette Auezova
15:45 Impact of hydrophilic natural deep eutectic solvents on hydrogels intended for skin application
Iron Mike Ardeza, L. Boudesocque-Delaye. Laura Wils, Xavier Perse, Sybille de La Motte, Emilie Munnier
16:00 Coffee break and poster sessions
Oral presentations – FOOD
17:00 Safety assessment of valorised food by-products using novel analytical procedures based on natural deep eutectic solvents
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Bárbara Socas-Rodríguez, David M. Alonso García, José A. Mendiola, Alejandro Cifuentes and Elena Ibáñez
17:15
A Green Method based on Natural Hydrophobic Deep Eutectic Solvents for Plastic Migrants Determination in Beverages using UHPLC-MS/MS Ruth Rodríguez-Ramos, Álvaro Santana-Mayor, Antonio V. Herrera-Herrera, Bárbara Socas-Rodríguez, Miguel Ángel Rodríguez-Delgado
17:30 NADES in the stabilization of phenolic compounds from sunflower meal
Fernanda de Sousa Bezerra, Danielly C. Ferraz da Costa and Maria Gabriela Bello Koblitz
17:45
Could NaDES assisted one-pot extraction and biotransformation be a relevant strategy to boost activity of natural extracts? Millena Cristina Barros Santos, Nathalie Barouh, Bruno Baréa, Mélina Robert, Pierre Villeneuve, Luiz Cláudio Cameron, Valérie-Lullien, Claire Bourlieu-Lacanal, Mariana Simões Larraz Ferreira and Erwann Durand
Wednesday, 16th June 2021
Plenary lecture
09:00 Design of biobased supramolecular solvents dedicated to plant extraction for cosmetic actives, from research to industrial implementation
Caprin Benoît, Charton Virginie, Vogelgesang Boris
Oral presentations - EXTRACTION & SEPARATION
09:45 Application of Deep Eutectic Solvents for the Extraction of Textile Dyes from Water
L. Villar, J. Páez, A. Domínguez, B. González
10:00 Extraction and Stabilization of Bioactive Compounds From Aromatic Plants Using Sustainable NADES
Sílvia Rebocho, Rita Craveiro, Alexandre Paiva, Ana Rita C. Duarte
10:15 Valorization of vine shoots biomass assisted by acidic deep eutectic solvents
Bruno D. A. Pinheiro, Maria Hijosa-Valsero, André M. da Costa Lopes, Armando J. D. Silvestre
10:30 Using Eutectic Mixtures For The Extraction And Recovery of the Carotenoid Bacterioruberin
Mariam Kholany, Nicolas Schaeffer, Inês P.E. Macário, Telma Veloso, Tânia Caetano, Joana Luísa Pereira, Sónia P.M. Ventura, João A. P. Coutinho
10:45 Coffee break and poster sessions
11:45 Sustainable waste management from wine production
Manuela Panić, Veronika Gunjević, Mia Radović, Kristina Radošević, Marina Cvjetko Bubalo, Natka Ćurko, Karin Kovačević Ganić, Ivana Radojčić Redovniković
12:00
Non-Ionic Hydrophobic Deep Eutectic Solvents as Promising Extraction Agents for the Evaluation of Endocrine Disruptors in Environmental Waters
Álvaro Santana-Mayor, Bárbara Socas-Rodríguez, Ruth Rodríguez-Ramos, Antonio V. Herrera-Herrera, and Miguel Ángel Rodríguez-Delgado
12:15 Insulinotropic effects of apple pomace extracts in Deep Eutectic systems
Heleena Moni Bottu, Lorraine Brennan, Lorrenzo Guazzelli, Angelica Mero, Elena Husanu, Serge Tavernier
12:30 Natural Deep Eutectic Solvents for the Green Extraction of Soy By-Products
Felipe Sanchez Bragagnolo, Bárbara Socas-Rodríguez, Cristiano Soleo Funari, Elena Ibáñez
12:45 Lunch
Oral presentations – MATERIALS
14:15 Deep Eutectic Solvents for wood cellulose purification
Andrea Mezzetta, Greta Colombo Dugoni, Lorenzo Guazzelli, Monica Ferro, Andrea Mele
14:30 A critical study on the influence of DES on the formation of organic biphasic systems
Jean-Baptiste Chagnoleau, Nicolas Papaiconomou, Mona Jamaly, João A. P. Coutinho, Dinis O. Abranches, Xavier Fernandez, Thomas Michel
14:45 Dissolution and Recovery of Lithium-Ion Battery Cathode Materials Using Deep Eutectic Solvents
Dana L. Thompson, Jennifer M. Hartley, Chunhong Lei, Ioanna M. Pateli, Andrew P. Abbott
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15:00 Separation of Lithium from a Simulated Salt-lake Brine using Synergistic Deep Eutectic Solvents
Takafumi Hanada and Masahiro Goto
15:15 Furfural production from xylans through acidic deep eutectic-based systems
Eduarda S. Morais, Mara G. Freire, Carmen S. R. Freire, João A. P. Coutinho, Armando J. D. Silvestre
15:30 Coffee break and poster sessions
16:30 Synthesis of Sugar-Based Polymers From Reactive Natural Low Transition Temperature Mixtures
Gabriel Duaux, Etienne Fleury, Daniel Portinha
16:45 Extraction of Ferulic Acid from Aqueous Systems Using Deep Eutectic Solvents
O. G. Sas, M. López, M. Pita, B. González, A. Domínguez
17:00 Lignin conversion into value-added compounds using an acidic deep eutectic at mild conditions
Filipe H. B. Sosa, Ana Bjelic, João A. P. Coutinho, Mariana C. Costa, Edita J. Grojzdek, Miha Grilc, Andre M. da Costa Lopes
17:15 Indium Mediated Barbier Allylation of Carbonyl Compounds in Deep Eutectic Solvents
Nerea González-Gallardo, Beatriz Saavedra, Gabriela Guillena and Diego J. Ramón
17:30 Make it or Break it: Cu3(BTC)2 Metal-Organic Framework in Reline DES
Renata Avena Maia, Benoît Louis, Stéphane Baudron
Thursday, 17th June 2021
Plenary lecture
09:00 Conversion of Carbohydrates to Value Added Chemicals in the presence of DES
Karine De Oliveira Vigier
Oral presentations – BIOTECH
09:45
Unravelling the in vitro and in vivo toxicity of deep eutectic solvents consisting of safe compounds including choline chloride
Dasom Jung, Jae Back Jung, Seulgi Kang, Ke Li, Inseon Hwang, Ji Hoon Jeong, Hyung Sik Kim and Jeongmi Lee
10:00 Stabilization of Horseradish Peroxidase Using Natural Deep Eutectic Systems
Liane Meneses, Ana Rita C. Duarte, Alexandre Paiva
10:15 Natural deep eutectic solvents as biofilm structural breaker
Maria F. Nava-Ocampo, Lamya Al Fuhaid, Szilárd S. Bucs, Robert Verpoorte, Young Choi, M.C.M. van Loosdrecht, Johannes S. Vrouwenvelder, Geert J. Witkamp, Andreia S. F. Farinha
10:30 Natural deep eutectic solvents for microalgae biorefinery: Spirulina as case of study
Laura Wils, Soukaina Hilali, Suha Elderli, Mervé Yagmur, Charlotte Leman-Loubière, Barbara Clément-Larosière, Franck Bonnier and Leslie Boudesocque-Delaye
10:45 Coffee break and poster sessions
11:30 Poster Award
11:45 NADES for microalgae biorefinery: biomass pre-treatment and comparison with bio-sourced solvents
Laura Wils, Soukaina Hilali, Mervé Yagmur, Barbara Clément-Larosière, and Leslie Boudesocque-Delaye
12:00
Towards Mechanistic Understanding of Naturally Derived Deep Eutectic Solvents Effect on Enzyme Catalyzed Reactions
Attila Kovács, Erik C. Neyts, Iris Cornet and Pieter Billen
12:15 Enhanced Solubilization Of Essential Oils By Combining Deep Eutectic Solvent, Cyclodextrins And Water
Lamia Nakhle, Miriana Kfoury, Isabelle Mallard, Hélène Greige-Gerges, David Landy
12:30 Natural deep eutectic solvents: the future of natural cosmetic formulation?
Iron Mike Ardeza, Leslie Boudesocque-Delaye, Laura Wils, Alexandra Despres, Franck Bonnier, Xavier Perse, Charles Bodet, Igor Chourpa, Emilie Munnier
12:45 Closing session
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
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PLENARY
LECTURES
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
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Design of biobased supramolecular solvents dedicated to
plant extraction for cosmetic actives, from research to
industrial implementation
Caprin Benoît *, Charton Virginie, Vogelgesang Boris,
Gattefossé SAS, 36 chemin de Genas, 69804, Saint-Priest cedex, France
Keywords: NaDES, NaLTTM, Cosmetics, Green chemistry, Eco-friendly plant extraction
process, Sustainable actives, Phytochemical footprint, Biological activity
Natural Deep Eutectic Solvents (NaDES), and more recently Natural Low Transition
Temperature Mixtures (NaLTTM), have emerged as a promising and ecofriendly alternative to
petrochemicals to dissolve plant metabolites. The demand for sustainable and green cosmetics
is in permanent growth and those solvents represent unexplored opportunities to develop
innovative extracts with unique phytochemical footprints and biological activities. However,
despite the number of NADES or NaLTTM described in the literature, only a few can be used
for cosmetic applications because of safety or regulatory issues. This presentation will first
introduce the regulatory framework, the green chemistry and naturalness requirements that a
cosmetic active ingredient has to comply with. In this frame, the research strategy adopted by
Gattefossé to develop and characterize green solvents dedicated to the obtention of fully
biobased plant extracts will be described. A peculiar attention on the value-added of these
systems compared to traditional extraction solvents in terms of phytochemical composition and
biological efficacy on human skin will be then presented. In a second part, this presentation will
introduce some of the technological choices that have been made during scale-up activities to
make the implementation of such extraction processes possible. Finally, the industrial reality
and benefits of biobased actives obtained will be presented through concrete examples.
Figure 1 : Illustration of biological efficacy of an industrialized NaDES plant extract design by Gattefossé.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
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Understanding the Physicochemical Behavior of Deep
Eutectic Solvents Using Computational Modelling: From
fundamentals to practical applications
Fèlix Llovell
Department of Chemical Engineering, Universitat Rovira i Virgili, Avinguda Països Catalans
26, 43007, Tarragona, Spain.
*E-mail: [email protected]
In the last decade, Deep Eutectic Solvents (DESs) have emerged as a new family of compounds
with fascinating properties that can be implemented in a wide variety of industrial processes.
Although there is not full agreement on finding an exact definition for the denomination of
DESs, they are typically understood as the combination of a Hydrogen Bonding Acceptor
(HBA) compound, which is normally a halide salt, and a Hydrogen Bonding Donor (HBD),
which is a neutral complexing agent. The hydrogen-bonding effect causes a substantial decrease
of the melting point compared to that of the individual components, becoming an eutectic
mixture. This fact widens the range of the liquid state, while keeping a negligible volatility.
Compared to Ionic Liquids (ILs), DESs have an easier preparation, which reduces their cost. In
addition, many of them can be formed using natural compounds, originating a subclass known
as Natural Deep Eutectic Solvents (NADES). For this reason, DES are also associated to
greener processes, which can contribute to improve the sustainability of industrial operation
units. [1]. However, as it happened with ILs, the number of possible combinations to form a
DES is enormous, complicating a full characterization of all options to screen the best
compound for a particular application. Nowadays, the mechanisms behind their
physicochemical properties are still not well understood, and this becomes a constraint for the
design of any process involving DESs. In this regard, the use of multiscale simulation provides
a useful path to obtain additional information to guide the experimental work into the right
direction. In this contribution, a general overview of the possibilities that computational
modelling tools can offer to better understand the mechanisms that drive the physicochemical
behavior of DESs is presented [2]. In particular, the use of advanced equations of state or
models explicitly considering hydrogen bonds will be shown, highlighting some practical
examples related to the screening of DESs for greenhouse gases capture applications [3,4].
Acknowledgements
This research is supported by project PID2019-108014RB-C21, funded by the Spanish Ministry of Science and
Innovation, and project KET4F-Gas, SOE2/P1/ P0823, which is co-financed by the European Regional
Development Fund within the framework of the Interreg SUDOE Program.
References
[1] A. Paiva, R. Craveiro, I. Aroso, M. Martins, R. L. Reis, A. R. C. Duarte, ACS Sustainable Chemistry &
Engineering, 2(5) (2014)1063–1071.
[2] I. Alkhatib, D. Bahamon, F. Llovell, M. Abu-Zahra, L.F. Vega, Journal of Molecular Liquids, 298 (2020)
112183.
[3] R.M. Ojeda, F. Llovell, J. Chem. Eng. Data (2018) 63 (2018) 2599−2612.
[4] I.I.I. Alkhatib, M. L. Ferreira, C. G. Alba, D. Bahamon, F. Llovell, A. B. Pereiro, J. M.M. Araújo, M. R.M.
Abu-Zahra, L. F. Vega, Journal of Chemical & Engineering Data 65 (2020) 12, 5844–5861.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
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Conversion of Carbohydrates to Value Added Chemicals
in the presence of DES
Karine De Oliveira Vigier
IC2MP, UMR CNRS 7285, Université de Poitiers
1 rue Marcel Doré, Poitiers, France, [email protected]
The catalytic conversion of carbohydrates to value added chemicals or platform molecules is
the topic of numerous research. One of the challenges is the conversion of a highly concentrated
solution of carbohydrates in an environmentally friendly process. The effect of the solvent
nature will be discussed. An interesting class of solvents is gaining more and more attention:
Deep Eutectic Solvents (DES) or Low Melting Mixtures (LMM). One of the most widespread
components used for the formation of these solvents is choline chloride (ChCl). ChCl is a very
cheap, biodegradable and non toxic quaternary ammonium salts which can be either extracted
from biomass or readily synthesized from fossil reserves (million metric tons) through a very
high atom economy process. In combination with safe hydrogen bond donors such as
carbohydrates, ChCl is capable of rapidly forming a DES/LMM. We have studied several
catalytic systems in the synthesis of furanic derivatives (5-hydroxymethylfurfural and furfural)
showing the benefit effect of these solvents in such reactions. Some examples will be presented
where ChCl can help to control the selectivity of the reaction by providing interactions with the
furanic derivatives avoiding their degradation starting from highly concentrated solutions of
carbohydrates. Some insights of the mechanism will be provided. The hydrogenation of
carbohydrates was also investigated in the presence of DESs and the nature of the solvent was
also studied in order to improve the yield of alditol and the catalyst stability.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
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ORAL PRESENTATIONS
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
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Is There Depth to Eutectic Systems?
Adriaan van den Bruinhorsta,b*, Mark Vis,b,a Gijsbertus de With,b Agilio Padua,a and
Margarida Costa Gomesa a École Normale Supérieure Lyon, Laboratoire de Chimie, 46 allée d’Italie, 69364 Lyon, FR b Eindhoven University of Technology, Chemistry & Chemical Engineering, P.O. Box 513,
5600 MB Eindhoven, NL
Keywords: eutectic depth, S–L equilibria prediction, fusion properties, calorimetry
The key aspect of a deep eutectic system (DES) is the formation of a liquid over a wide
composition range upon mixing its constituents. Easy access to the liquid phase via melting
point depression is at the basis of the broad spectrum of DES applications reported in literature.
We aim to determine the eutectic depth – i.e. the difference between the actual and ideal eutectic
temperature – for a large number of systems to confirm the existence of a distinct group of
mixtures with exceptional melting temperature depressions: the deep eutectic systems. The
depth of a simple eutectic is governed by (i) pure component fusion properties and (ii)
intermolecular interactions between the constituents in the liquid phase. Fusion properties are
available in literature for many pure components. Measuring unknown fusion properties is in
principle straightforward, but can be challenging in practice due to sublimation or thermal
decomposition. Here we present an overview of experimental methods to indirectly obtain the
fusion properties for components that decompose before or upon melting, showcasing the use
of isothermal calorimetry for choline chloride – one of the archetypal DES constituents. The
interaction energies in the liquid phase can be derived from isothermal calorimetry data or from
phase diagrams summarising the solid–liquid equilibria (SLE) of eutectic mixtures. Although
such data is available for common mixtures, it would be unfeasible to experimentally evaluate
all possible (D)ESs owing to the ubiquity of eutectic behaviour. We therefore predicted over
100000 binary phase diagrams from the excess Gibbs energy of mixing using COSMO-SAC1
for components with known fusion properties2 and sigma-profiles1. Comparison of the large
number of predicted and reported SLE phase diagrams showed which fusion properties
typically contribute to deeper eutectics. No discrete groups emerged with respect to eutectic
depth, complicating a strict definition for DESs. However, the presented methodologies to
quantify fusion properties and liquid interactions resulted in a roadmap towards developing
eutectic systems with the desired liquid window, deep or not.
1 F. Ferrarini, G. B. Flôres, A. R. Muniz and R. P. de Soares, AIChE J., 2018, 64, 3443–3455.
2 Fusion properties were extracted from the WolframAlpha database on 04-12-2019.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
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Non-Ionic Hydrophobic Deep Eutectic Solvents as
Promising Extraction Agents for the Evaluation of
Endocrine Disruptors in Environmental Waters
Álvaro Santana-Mayor a,*, Bárbara Socas-Rodríguez b, Ruth Rodríguez-Ramos a,
Antonio V. Herrera-Herrera c, and Miguel Ángel Rodríguez-Delgado a a Departamento de Química, Unidad Departamental de Química Analítica, Facultad de
Ciencias, Universidad de La Laguna (ULL), Avda. Astrofísico Fco. Sánchez, s/n, 38206 San
Cristóbal de La Laguna, España, b Laboratory of Foodomics, Institute of Food Science Research, CIAL, CSIC, Nicolás Cabrera
9, 28049 Madrid, Spain, c Instituto Universitario de Bio-Orgánica Antonio González, Universidad de La Laguna
(ULL), Avda. Astrofísico Fco. Sánchez, 2, 38206 San Cristóbal de La Laguna, España
Keywords: deep eutectic solvent, plastic migrants, microextraction, water samples
Deep eutectic solvents (DESs), labelled as 21st century solvents, have emerged within scientific
community as a promising sustainable alternative to conventional organic solvents. DESs have
remarkable properties that can be tuned depending on the components and their molar ratios.
Since some of their main characteristics are their liquid nature, great stability at room
temperature and high biocompatibility, these neoteric mixtures have been used in analytical
extraction procedures. Furthermore, these eutectic solvents have shown high capacity to extract
a wide variety of compounds with different polarities, as well as metallic species from all types
of matrices, even using low volumes of DESs. In this way, they not only allow the development
of versatile procedures, but also provide a significant degree of pre-concentration and,
therefore, low detection limits. This is especially important in the determination of pollutants,
such as plastic migrants, whose presence even at very low concentrations can result in
significant damage to living beings and the environment. In this work, a terpene-based natural
hydrophobic DES (thymol:menthol, 2:1) has been used as extraction solvent in a simple liquid-
liquid microextraction of 14 phthalates and one adipate from environmental waters (treated
wastewater, runoff and pond waters). The separation and quantification of target analytes were
carried out using an ultra-high performance liquid chromatography-tandem mass spectrometry
system. Good linearity was achieved (R2 higher than 0.9954) and few parameters were
optimised (DES molar ratio and volume) to reach good recovery values (70–120%) and very
low limits of quantification (0.013–0.425 µg/L). Finally, the methodology was applied for the
evaluation of plastic migrants in different waters from Canary Islands destined to agricultural
activities.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
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DES? Solutions? The Influence of Water on the phase
behaviour of Ternary Liquid Mixtures Ana Roda a, Christoph Held b,*, Filipa Santos a, Yeong Zen Chua b, Aarti Kumar c, Hoang
Tam Do c, Alexandre Paiva a and Ana Rita C. Duarte a a LAQV, REQUIMTE, Chemistry Department, FCT-NOVA, 2829-516 Caparica, Portugal
b Institute of Physics, University of Rostock, Albert-Einstein-Str. 23-24, 18051
Rostock, Germany c Laboratory of Thermodynamics, Department of Biochemical and Chemical
Engineering, TU Dortmund, 44227 Dortmund, Germany
Keywords: Solution, water, solid-liquid equilibria, PC-SAFT, spectroscopy, characterization
The influence of water in on the phase behaviour of liquid mixtures like deep eutectic systems
(DES) is a question that has been addressed by different researchers from several perspectives
[1–4]. In the present work, solid liquid equilibria (SLE) studies and spectroscopy analysis were
used to study the impact of water in the liquefaction of ternary mixtures. PC-SAFT predictions
were validated using experimental data of the DES choline chloride:urea (1:2 molar ratio) upon
water addition from ref. [5]. Hence, PC-SAFT was further applied to predict the water influence
on the SLE of the mixture L-arginine:citric acid:H2O using new melting data for L-arginine. A
decrease of about 100K in the melting temperature was predicted when water is added to the L
arginine:citric acid 1:1 (mol) mixture. One possible explanation for this are water-mediated
effects that turned the positive deviations from Raoult’s law (γ>1) into negative deviations
(γ<1), highlighting stronger interactions between the mixture components upon water addition.
Additionally, NMR and FTIR studies were performed to study the hydrogen-bonding
interactions of the system and the possibility of salt formation between L-arginine and citric
acid, which could also explain decreased melting temperatures upon water addition. The
hypothesis of salt formation was refuted by FTIR, while NMR supported an altered hydrogen
bonding network for the ternary systems L-arginine:citric acid:H2O with respect to the
individual aqueous solutions. In sum, both the terms of negative deviation from Raoult’s law
and hydrogen-bonding mediated liquefaction were herein identified for the L-arginine:citric
acid:H2O mixture. Although both terms are compliant with the DES definition, they are also
applicable to strongly non-ideal solutions. Given the complexity of these type of mixtures, this
work aims to emphasize the urge of a more comprehensive definition and the need for additional
tools for fully characterizing these systems.
[1] Y. Dai, et al. Food Chem. 187 (2015) 14–19. doi:10.1016/j.foodchem.2015.03.123.
[2] O.S. Hammond et al. Angew. Chemie - Int. Ed. 56 (2017) 9782–9785. doi:10.1002/anie.201702486.
[3] H. Passos, et al. ACS Sustain. Chem. Eng. 4 (2016) 2881–2886. doi:10.1021/acssuschemeng.6b00485.
[4] J. Baz, et al. Phys. Chem. Chem. Phys. 21 (2019) 6467–6476. doi:10.1039/c9cp00036d.
[5] X. Meng, et al. New J. Chem. 40 (2016) 4492–4499. doi:10.1039/c5nj02677f.
Acknowledgements This project has received funding from the ERC-2016-CoG 725034 and was supported by the Associate Laboratory for Green Chemistry-LAQV, financed by national funds from FCT/MCTES (UID/QUI/50006/2019. C.H. and Y.Z.C. thank German Science Foundation (DFG) for funding (HE 7165/6-1 and CH 1922/1-1).
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
17
Lignin conversion into value-added compounds using an
acidic deep eutectic at mild conditions
Filipe H. B. Sosaa,b, Ana Bjelicc, João A. P. Coutinhoa, Mariana C. Costab, Edita J. Grojzdekc,
Miha Grilcc, Andre M. da Costa Lopesc,d* aCICECO, Department of Chemistry, University of Aveiro, Campus Universitário de
Santiago, Aveiro, Portugal. bSchool of Chemical Engineering (FEQ), University of Campinas (UNICAMP), Campinas,
Brazil. cDepartment of Catalysis and Chemical Reaction Engineering, National Institute of
Chemistry, Hajdrihova 19, 1000 Ljubljana, Slovenia dCECOLAB - Collaborative Laboratory Towards Circular Economy, R. Nossa Senhora da
Conceição, 3405-155 Oliveira do Hospital
Keywords: lignin, deep eutectic solvents, depolymerisation, value-added compounds.
The heterogeneous and complex structure of lignin and its low reactivity undermines the
valorisation of this macromolecule, thus the development of novel lignin conversion processes
is demanding. In this study, an acidic DES ([Ch]Cl:Oxa) in presence or absence of co-catalysts
(H2SO4 and H2O2) was used as benign solvent to valorise Kraft lignin (KL) and Organosolv
(OL) by breaking down their structure into value-added aromatic compounds. The obtained
data showed maximum yields between 25.3 wt% and 27.7 wt% of lignin depolymerisation
products after OL and KL breakdown. Moreover, the profile of depolymerisation products was
distinct between examined lignins as well as between acidic ([Ch]Cl:Oxa and
[Ch]Cl:Oxa/H2SO4) and acidic oxidative treatments ([Ch]Cl:Oxa/H2O2). The acidic treatments
of KL favoured the formation of syringol and acetosyringone, while vanillic and syringic acids
were the main products in the acidic treatments of OL. On the other hand, the presence of H2O2
in DES promoted electrophilic substitutions of chloride from [Ch]Cl in the aromatic ring of
lignin monomers. In both cases, lignin oligomers were detected in depolymerization extracts.
Moreover, the regenerated lignin samples after depolymerisation disclosed different
characteristics in contrast to their precedent technical lignins, including esterification with
oxalic acid, lower molecular weight and increase of phenolic group content. These
physicochemical modifications are expected to give functionalization to regenerated lignins.
Therefore, the integration of lignin depolymerisation into valued added monomers and
oligomers with functionalization of remaining lignin towards new bio-based materials seems
promising with this DES technology.
Acknowledgments: This work was financed in part by the CAPES, FAPESP, CNPq, and partially developed
within the scope of the project CICECO, FCT Ref. UIDB/50011/2020 & UIDP/50011/2020. Authors would like
to thank COST Action CA17128 for financing the STSM of Filipe H. Sosa enabling collaboration with National
Institute of Chemistry in Ljubljana.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
18
Deep Eutectic Solvents for wood cellulose purification
Andrea Mezzetta*, a Greta Colombo Dugoni,b Lorenzo Guazzelli,a Monica Ferro,b Andrea
Meleb
a Department of Pharmacy, University of Pisa, Via Bonanno 33, 56126 Pisa, Italy, b Department of Chemistry, Materials and Chemical Engineering “G. Natta”, Politecnico di
Milano, Piazza L. da Vinci, 32, 20133 Milano, Italy
Keywords: lignin, hemicellulose, Kraft cellulose purification, choline acetate based DESs
In the last decade the urgency to find alternative renewable sources brought to global attention
the possibility to convert lignocellulosic biomass into energy, value-added products and biofuel.
Lignocellulosic biomass is the most abundant biomass on earth with an annual production of
170-200 billion tons and it is mainly composed by lignin (10-30%), cellulose (38-50%) and
hemicellulose (23-32%). In consideration of the biorefinery processes, the robust structure of
biomass represents an obstacle for the fractionation of the components in order to produce
substrates to be converted in platform chemicals or biofuel.1
Deep eutectic solvents (DESs) hold great promises in the area of biomass processing. Indeed,
a few DESs displayed remarkable efficiency in the solubilization of lignocellulosic
biopolymers.2,3 However, more investigations are needed to fully unveil DESs potential in this
area of research.
Herein, we present three novel DESs composed of choline acetate (ChOAc) as hydrogen bond
acceptor (HBA) and three different hydrogen bond donors (HBD): glycolic acid (GlyA),
levulinic acid (LevA) and imidazole (Im). DESs were tested neat and in presence of water for
their ability to solubilize a reference hemicellulose as well as for the treatment of wood cellulose
containing 16% of hemicellulose. High values of hemicellulose dissolution (40-45% wt)
demonstrated the potential of the proposed DESs as solvents for this biopolymer. DESs also
exhibited a selective solubility towards hemicellulose, leading to cellulose purification.
References
1. Loow, Y.-L., New, E. K., Yang, G. H., Ang, L. Y., Foo, L. Y. W., Wu, T. Y. Cellulose 2017, 24, 3591–3618.
2. Zdanowicz, M., Wilpiszewska, K., Spychaj, T. Carbohydr. Polym. 2018, 200, 361–380
3. Sheldon, R. A. Chem. – A Eur. J. 2016, 22, 12984–12999
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
19
On the Betaine:Urea:xWater NADES system
Maria F. Nava-Ocampoa, Lamya Al Fuhaida, Adriano Santanaa, Szilárd S. Bucsa, Robert
Verpoorteb, Young Choib, Johannes S. Vrouwenveldera, Geert J. Witkampa, Andreia S. F.
Farinhaa* a Water Desalination and Reuse Center, King Abdullah University of Science and
Technology, Thuwal, Saudi Arabia. b Institute Biology Leiden, Leiden University, Leiden, The Netherlands.
Keywords: betaine, urea, NADES, NMR, Modelling
This study focuses on the structures within the betaine-urea-water (B:U:W) NADES system.
Solutions spanning a range of molar ratios of betaine, urea, and water were prepared, varying
the temperature and preparation times. On the clear transparent liquids, attenuated total
reflection Fourier-transform infrared spectroscopy (ATR-FTIR) and liquid Nuclear Magnetic
Resonance (1H and 13C NMR) were done. In addition, Density Functional Theory (DFT) and
the Natural Bond Orbital (NBO) analyses were performed using Gaussian software. Our
experimental results show that, in non-anhydrous conditions, for one mole of betaine mixed
with one mole of urea, a minimum of three moles of water are needed to obtain a stable NADES.
However, a metastable transparent liquid can be formed with less water molecules. In such
liquids, betaine crystals easily grew when seeded. Comparison of the 13C NMR spectra of
B:U:W 1:1:2 and 1:1:3 showed for the latter that the carbonyl groups from betaine and urea
formed stronger hydrogen bonds, and the CH3 group of betaine becomes more deprotected (less
electron rich) by the addition of the extra water molecule. After simulating the less energetic
conformation from different supramolecular structures of B:U:W (1:1:2 and 1:1:3), we
compared the experimental with simulated 13C NMR spectra. The compared spectra resulted
in similar chemical shifts tendencies which makes us confident that this is the most probable
supramolecular structure on the ternary B:U:W 1:1:2 and 1:1:3 NADES system (Figure 1).
Figure 1. Structural conformations of B:U:W 1:1:2 (A) and 1:1:3 (B) based on the minimum
energy obtained by computational modelling.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
20
Towards Mechanistic Understanding of Naturally Derived
Deep Eutectic Solvents Effect on Enzyme Catalyzed
Reactions
Attila Kovács a,*, Erik C. Neyts b, Iris Cornet c and Pieter Billen a
a iPRACS research group, University of Antwerp, Groenenborgerlaan 171, 2020 Antwerp,
Belgium, b PLASMANT research group, University of Antwerp, Universiteitsplein 1, 2610 Antwerp,
Belgium, c BioWAVE research group, University of Antwerp, Groenenborgerlaan 171, 2020 Antwerp,
Belgium
Keywords: Biocatalysis, Molecular dynamics, Reaction modeling
Natural deep eutectic solvents (NADES) are a novel class of solvents, offering more benign
properties compared to common organic solvents. NADES are mixtures of naturally derived
compounds (usually a quaternary ammonium salt and a hydrogen bond donating component,
like organic acids or polyols) forming a strong intermolecular hydrogen bonding system. This
network stabilizes the liquid mixture, which results in a significantly decreased melting point
compared to the initial compounds. This property allows the use of NADES as reaction
media/solvents for various chemical reactions. This is typically in the food, feed, cosmetic and
pharmaceutical industries, where biocompatibility is required. However, to efficiently design
NADES for biocatalysis, a better understanding of their effect on these reactions is needed.
Fundamentally, this comes down to the description of the exact hydrogen bonding network and
its interaction with the reaction actors. Modeling methods, allowing for such fundamental
descriptions (like density functional theory or molecular dynamics), suffer from limitations of
accessible time and length scales, which makes their application impractical for bulk media.
We hypothesize that describing the effect that the NADES have on enzymatic reactions is
feasible solely through solvation energies of the substrates, medium viscosities and enzyme
stability in NADES. If these effects describe indeed their behavior sufficiently, this simpler
model could be developed to design neoteric solvents.
As a case study, we monitored the initial enzyme activity and the final conversion rate of lipase
catalyzed vinyl laurate transesterification in n-hexane together with various choline chloride
based NADES with different compositions and molar ratios. We determined the solubility of
substrates and the viscosity of solvents by experimental methods and we used MD based
simulation to investigate enzyme stability and to calculate solvation free energies of substrates
in NADES. Also, we determined the relationship of these properties to the enzyme activity and
conversion rate to evaluate their utility in predicting the reaction parameters.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
21
Safety assessment of valorised food by-products using
novel analytical procedures based on natural deep eutectic
solvents
Bárbara Socas-Rodríguez *, David M. Alonso García, José A. Mendiola, Alejandro Cifuentes
and Elena Ibáñez
Laboratory of Foodomics, Institute of Food Science Research, CIAL, CSIC, Nicolás Cabrera
9, Madrid, 28049, Spain
Keywords: natural deep eutectic solvent; food assessment; by-product; green extraction
In recent years, the application of deep eutectic solvents (DESs) as alternative materials has
sharply increased in different fields. Their low toxicity and great versatility make them excellent
candidates to replace conventional organic solvents. Besides, the broad spectrum of raw
materials and their high availability provide great versatility to DES-based approaches.
Particular attention has been paid to the so-called natural-DESs (NaDESs). These materials are
exclusively constituted by natural components that enhance the low toxicity nature and
biocompatibility of DESs and favour their use in biological and food applications [1].
Globalisation of food industry has led to important economic benefits, but it has also brought
about the increase of food waste with negative effects on the environment. This concern
requires the establishment of effective strategies to reduce the impact of the organic residues
generated. In this sense, the valorisation of food by-products has been suggested as a suitable
approach to tackle this issue. However, as occur with the rest of food products, the
commercialization of valorised by-products also requires a strict control to ensure consumers’
safety. In this sense, the development of sustainable methodologies allowing the reliable
assessment of food by-products’ safety while complying with the principles of sustainability
constitute an issue of great importance [2].
In this work a novel and sustainable approach based on the application of betaine-based
hydrophilic NaDESs as extraction solvents has been proposed for the evaluation of food safety
in combination with chromatographic separation and mass spectrometry detection. The
methodology has resulted suitable for the efficient and reliable determination of pesticides in
fruit by-products.
References:
[1] Liu et al. Natural Deep Eutectic Solvents: Properties, Applications, and Perspectives. J. Nat. Prod., 2018, 81,
679–690.
[2] A. Nayaka, Brij Bhushan, An overview of the recent trends on the waste valorization techniques for food
wastes. J. Environ. Manage., 233 (2019) 352–370
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
22
Biosourced Non-Ionic Low Transition Temperature
Mixtures Composed of Fructose and Glycerol: Water and
Temperature Impact on the Supramolecular Organization
Caprin Benoît a,b,*, Charton Virginie b, Rodier Jean-David b, Vogelgesang Boris b,
Charlot Aurélia a, Da Cruz-Boisson Fernande a, Fleury Etienne a a Laboratoire Ingénierie des Matériaux Polymères, UMR CNRS 5223, INSA Lyon, bâtiment
Jules Verne, 17 avenue Jean Capelle, 69621 Villeurbanne, France b Gattefossé SAS, 36 chemin de Genas, 69804, Saint-Priest cedex, France
Keywords: LTTM, H-bonds, DOSY & NOESY NMR, green chemistry
Deep Eutectic Solvents (DES), Natural Deep Eutectic Solvents (NaDES) or Low Transition
Temperature Mixtures (LTTM) constitute an appealing class of neoteric solvents generally
meeting some criteria of green chemistry. Most of the time, their high viscosity compromises
their industrial implementation, and water addition is an effective means to valuably increase
their fluidity. Therefore, the effect of water on the internal organisation and the physical and
chemical properties of these solvents is an emerging issue in scientific literature.1,2 In this frame,
the present contribution deals with the preparation and the thorough characterization of entirely
biobased ternary mixtures composed of glycerol (G), fructose (F) and water (W). We previously
shown that combination of glycerol and fructose with water allows for engineering efficient
eco-friendly solvents in the field of vegetal extraction and understanding interactions at the
molecular level is a fundamental starting point that must be studied.3 In order to meet this
objective, this work focuses on i) the elucidation of a ternary diagram from a homemade library
of F/G/W mixtures ii) the examination of molecular interactions between the three components
from NOESY and pulsed field gradient NMR experiments with an accent on the effect of the
molar composition and temperature variation iii) the analysis of thermal and rheological
properties in order to establish relationships between the structure at the molecular level and
the resulting properties. This comprehensive study is expected to be helpful for further
applications of F/G/W mixtures in green and sustainable chemical technologies.
1. Delso, I.; Lafuente, C.; Muñ
oz-Embid, J.; Artal, M. NMR study of choline chloride-based deep eutectic solvents. Journal of Molecular Liquids,
2019, 290, 111236.
2. López, N.; Delso, I.; Matute, D.; Lafuente, C.; Artal, M. Characterization of xylitol or citric acid: Choline
chloride:water mixtures: Structure, thermophysical properties, and quercetin solubility. Food Chemistry, 2020, 306,
125610.
3. Caprin, B.; Charton, V.; Demarne, F.; Extraits végétaux destinés à la cosmétique, solvants et procédés pour les obtenir.
Brevet FR 3 036 618 B1. 2 novembre 2018
4. Caprin, B.; Charton, V.; Rodier, J.D.; Boisson-Da Cruz, F.; Charlot, A.; Fleury, E.; Elucidation of the Supramolecular
Structure of Non-Ionic Biobased Low Transition Temperature Mixtures. Submitted, 2020.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
23
Valorization of vine shoots biomass assisted by acidic deep
eutectic solvents
Bruno D. A. Pinheiroa, Maria Hijosa-Valserob, André M. da Costa Lopesa,c, Armando J. D.
Silvestrea aCICECO – Aveiro Institute of Materials, Department of Chemistry, University of Aveiro,
3810-193, Aveiro, Portugal bCentro de Biocombustibles e Bioproductos, Instituo Agrario de Castilla y Léon (ITACyl),
Villarejo de Órbigo, 24358, Léon, Spain cCECOLAB – Collaborative Laboratory Towards Cicrcular Economy, R. Nossa Senhora da
Conceição, 3405-155, Oliveira do Bairro, Portugal
Keywords: deep eutectic solvents, vine shoots, phenolic compounds, anthocyanins.
Wine production is an essential economic engine in most regions across the Iberian Peninsula.
However, this activity generates a high amount of by-products, such as vine shoots, which need
to be handled and valorized within a circular economy perspective. Therefore, sustainable and
cheap processes capable of extracting value from these raw materials are required. In this work,
acidic deep eutectic solvents (DES) were tentatively used as green solvents in the extraction of
value-added compounds from vine shoots prior to its fractionation. DES combining cholinium
chloride ([Ch]Cl) as hydrogen bond acceptor (HBA) with different hydrogen bond donors
(HBD), such as p-toluenesulfonic acid (pTSA), malic acid (MA), glycolic acid (GLY), tartaric
acid (TART), citric acid (CIT), were studied. These acidic DES showed capacity to extract
phenolic compounds, including anthocyanins, where [Ch]Cl:pTSA demonstrated the best
performance among them. The extraction of these compounds with [Ch]Cl:pTSA was further
examined by studying HBA:HBD molar ratio, time, temperature and water content in DES (25
wt% and 50 wt%). A higher molar ratio of [Ch]Cl enabled a better selectivity towards the
extraction of anthocyanins, possibly due to the stabilization of the anthocyanin flavylium cation
by the Cl- as counterion. In addition, the presence of water (25 wt%) improved anthocyanin
extraction, although decreasing its selectivity. Moreover, prolonged extraction (> 1 h)
negatively affected the extraction performance due to anthocyanins degrading. The optimal
conditions towards selective extraction of anthocyanins was obtained with [Ch]Cl:pTSA (3:1)
at 80 °C for 1 h reaching a maximum yield of 6.46 (± 0.02) mg.gbiomass-1. These anthocyanin-
rich extracts not only may provide antioxidant activity, but also disclose potential to be used in
natural dyeing applications, due to its deep red color.
Acknowledgements: This work was performed in the frame of BIOVINO (0688_Biovino_6_E) and financed by
the research program INTERREG V-A España-Portugal (POCTEP) 2014-2020. The authors also acknowledge
FCT/MCTES for the financial support to CICECO (UIDB/50011/2020 & UIDP/50011/2020).
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
24
Dissolution and Recovery of Lithium-Ion Battery Cathode
Materials Using Deep Eutectic Solvents
Dana L. Thompson a, Jennifer M. Hartley a*, Chunhong Lei a, Ioanna M. Pateli a,b, Andrew P.
Abbott a a School of Chemistry, University of Leicester, Leicester, LE1 7RH, UK
b Stephenson Institute for Renewable Energy, University of Liverpool, Liverpool, L69 7ZF,
UK
Keywords: lithium ion batteries, recycling, circular economy, dissolution, recovery
The decarbonisation of transport necessitates the proliferation of electric vehicles, resulting in
a significant increase in demand for lithium-ion batteries (LIBs). To prevent a build-up of
hazardous waste when electric vehicles reach end-of-life, a circular economy model is required
whereby the LIB is recycled and used in new electric vehicles. The majority of value within the
LIB lies with metals such as Co and Ni. The metal ratios vary across different battery
chemistries. In this work, a deep eutectic solvent consisting of oxalic acid and choline chloride
is utilised to develop a recycling procedure for the selective dissolution and recovery of
Ni/Mn/Co (NMC) elements. Through the addition of water or oxalic acid (OxA) to the leachate,
the solubility of Mn and Co decreases and results in the precipitation of metal oxalate species
(Figure 1). This allows for the recovery of the metals as precursors suitable for use in LIBs,
with 97-99 % efficiency.
Figure 1: Images of the mixed element solutions (left to right) before any additions, and after
the addition of water or the anti-solvents 0.5, 1.0 and 1.8 M OxA solution at t=0 min.
I. M. Pateli, D. Thompson, S. S. M. Alabdullah, A. P. Abbott, G. R. T. Jenkin and J. M. Hartley, Green Chem.,
2020.
D. L. Thompson, J. M. Hartley, S. M. Lambert, M. Shiref, G. D. J. Harper, E. Kendrick, P. Anderson, K. S. Ryder,
L. Gaines and A. P. Abbott, Green Chem., 2020.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
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Synthesis of Sugar-Based Polymers From Reactive Natural
Low Transition Temperature Mixtures
Gabriel Duaux, Etienne Fleury, Daniel Portinha,*
Université de Lyon CNRS, UMR 5223, INSA Lyon, IMP@INSA Villeurbanne F-69621,
France
Keywords: Natural Low transition temperature mixture ; Polymerization ; crosslinking.
Deep Eutectic Solvents (DES) [1] or Low Transition Temperature Mixtures (LTTM) [2], have
appeared as a new class of solvents obtained by mixing two or more substances, which form
mixtures with melting point or glass transition temperature much lower than that of their
individual components. Like ionic liquids, many of such solvents have numerous attractive
physicochemical properties (chemical and thermal stability, non-flammability, low volatility
high electrical conductivity etc..) and in the field of polymers, present the potential of replacing
conventional organic compounds as solvents, plasticizers, additives etc. Moreover, similarly to
functional ionic liquids, some DES/LTTM have been designed such as one over their
components act as a monomer (DEMs : Deep Eutetic Monomers) [3], opening the scope for a
large variety of novel possible uses of these renamed Deep Eutectic Systems. More recently,
combinations of agro-based, natural, metabolites or renewable components have appeared and
been named Natural DES (NaDES) [4] or LTTM (NaLTTM) [2], which undoubtedly represent
a very interesting family of raw materials to be developed in the framework of green chemistry.
So far, the academic and industrial uses of NaDES have mainly concerned the extraction of
molecules of interest for food, pharmaceuticals, and cosmetics or as solvent for organic
synthesis. In this communication, the synthesis of carbohydrate polymers from Natural Low
Transition Temperature Monomer Mixtures (NaLTTMM) made of functional natural polyols
and organic acids will be presented [5]. The preparation process and physicochemical properties
(viscosity, transition temperature, pH etc) of the mixtures will first be presented. Then their
polymerization will be discussed, in particular as a function of the reaction temperature that is
always lower than the melting points of monomers taken separately. Structural parameters of
the polymer (chemical bonds type, molecular weight, topology etc) can be adjusted by operation
conditions and careful selection of the starting raw materials, which will be discussed during
this communication.
[1] E. L. Smith et al., Chem. Rev., vol. 114, no. 21, pp. 11060–11082, 2014.
[2] E. Durand et al., Biochimie, vol. 120, pp. 119–123, 2016.
[3] M. Isik et al., Macromol. Rapid Commun., vol. 37, no. 14, pp. 1135–1142, 2016.
[4] Y. H. Choi et al., Plant Physiol., vol. 156, no. 4, pp. 1701–1705, 2011.
[6] G. Duaux et al., submitted.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
26
Solubility of Mesalazine in Natural Deep Eutectic Solvents
Debora Procopio, Carlo Siciliano, Sonia Trombino, Roberta Cassano, Federica Curcio,
Maria Luisa Di Gioia*
Department of Pharmacy, Health and Nutritional Sciences, University of Calabria,
87036, Arcavacata of Rende (CS), Italy
Keywords: Natural deep eutectic solvents, drug solubility, choline chloride
Natural deep eutectic solvents (NADESs) are recognised as the third liquid state in the living
organisms, beside water and lipid. As such, they have recently gained great attention in many
fields of science and technology. They show a potential as solvents for pharmaceutical
applications thanks to their biodegradability, low toxicity and ability to dissolve several water-
insoluble compounds and macromolecules. Choline chloride represents the most commonly
used hydrogen bond acceptors (HBA) in the formation of DESs. Due to it being a complex B
vitamin, commonly used as food additive, the choline-based NADESs can be considered
harmless and non-toxic. In the present work, we report the solubility of low water-insoluble
mesalazine in several choline chloride-based NADESs. These were prepared combining the
ChCl with several natural HBDs at different molar ratio. The solubility profile of mesalazine
were measured employing the shake flask method at different temperatures. Moreover, the
molecular interactions between the DESs and drug have been investigated using dynamic light
scattering (DLS) and polarized optical microscope (POM) measurements, as well as nuclear
molecular resonance (NMR) techniques. The results showed that the DES formed by choline
chloride and lactic acid exerted the strongest ability to promote the solubility of mesalazine
among all DESs. The increase in solubility is justified by the establishment of hydrogen bonds
between mesalazine and the DES components. These early observations laid the foundation for
the development of a new DES-based mesalazine delivery system.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
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Furfural production from xylans through acidic deep
eutectic-based systems
Eduarda S. Morais a,*, Mara G. Freire a, Carmen S. R. Freirea, João A. P. Coutinhoa, Armando
J. D. Silvestrea a CICECO—Aveiro Institute of Materials, Department of Chemistry, University of Aveiro,
3810-193, Aveiro, Portugal
Keywords: deep eutectic solvents, furfural, acid catalysis, xylans
Furfural has been identified as a key platform chemical derived from biomass. This chemical
can be obtained from hemicelluloses through acid hydrolysis and subsequent dehydration,
followed by separation from the reaction media using organic solvents [1]. However, nowadays
it is imperative to find more sustainable ways of producing furfural. Deep eutectic solvents
(DES) emerged as a greener alternative to conventional solvents used in chemical processes
due to their simple preparation and unique physicochemical properties. Moreover, they may be
of natural origin, and may be designed to be biodegradable and recyclable [2]. Therefore, DES
are good candidates to be used in biotechnological processes, such as in the extraction and
conversion of polysaccharides into added-value chemicals.
In this work, we report the use of acidic based deep eutectic solvents for the hydrolysis of xylans
into xylose and further dehydration into furfural. The effects of the DES molar ratio,
temperature, solid/liquid ratio and amount of water were investigated, and the process was
optimized for maximum furfural production. The DES [Ch]Cl:Malic acid was used in
microwave-assisted reactions as both solvent and catalyst for furfural production [3]. The
process developed allowed an outstanding 75.0% of furfural yield in 2.5 minutes of reaction
time with microwave heating. The recovery and recyclability of the solvents was evaluated,
being possible to reuse the DES in at least three cycles. The obtained results highlight the
potential of greener and recyclable solvents based on deep eutectic mixtures for the creation of
integrated platforms for the valorization of hemicellulose fractions in biomass.
[1] Mika L., et al. Chemical Reviews, 2018, 118, 505–613
[2] Khandelwal S., et al. Journal of Molecular Liquids. 2016, 215, 345–86.
[3] Morais E. S., et al. ChemSusChem. 2020, 13, 784-790.
This work was developed within the scope of the project CICECO-Aveiro Institute of Materials, 640
UIDB/50011/2020 & UIDP/50011/2020, financed by national funds through the FCT/MCTES. The work was
funded by FCT/MCTES through the project MultiBiorefinery (POCI-01-0145- 654 FEDER-016403) and
DeepBiorefinery [PTDC/AGR-TEC/1191/2014], E. S. Morais acknowledges FCT/MCTES for the PhD grant
[SFRH/BD/129341/2017].
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
28
Natural deep eutectic solvents: the future of natural
cosmetic formulation?
Iron Mike Ardeza a,b, Leslie Boudesocque-Delaye a, Laura Wils a, Alexandra Despres c,
Franck Bonnier b, Xavier Perse b, Charles Bodet d, Igor Chourpa b, Emilie Munnier b,*
a SIMBA EA 7502 Synthèse et isolement de molecules bioactives, Université de Tours,
Faculté de Pharmacie, 31 avenue Monge 37200 Tours, France
b NMNS EA 6295 Nanomédicaments et Nanosondes, Université de Tours,
Faculté de Pharmacie, 31 avenue Monge 37200 Tours, France. c RCP design Global- CERTESENS,
56 avenue Marcel Dassault, 37200 Tours, France d EA 4331 LITEC Laboratoire Inflammation, Tissus épithéliaux et Cytokines, Université de Poitiers,
1 rue Georges Bonnet 86073 Poitiers, France
Keywords: NaDES, extraction, stability, toxicity, formulation, sensoriality
Natural Deep Eutectic Solvents (NaDES) constitute a new generation of green ionic liquids,
first introduced as solvents with unique properties in chemistry by Abbott et al. in 20031
Recently, NaDES have focused the interest of cosmetic industry due to their unique properties.
Their high solvent power, combined with their stabilizing ability, make NaDES suitable as a
sustainable alternative to prepare greener active ingredient from vegetal or biotechnological
biomasses. Unlike organic solvent ordinary used to extract active molecules from plants or
algae, NaDES are not volatile and will persist in the final cosmetic formulation. The present
talk will expose the principal points that must be particularly taken into account at every step
of the development of a NaDES- based cosmetic product, from the NaDES composition to the
sensory impact on final product and their harmlessness towards skin. Concrete examples will
illustrate each key points to give a global overview of the benefice/risk balance of NaDES in
cosmetics.
1 Abbott, A.P., Boothby, D., Capper, G., Davies, D.L., Rasheed, R.K., 2004. Deep Eutectic Solvents Formed
between Choline Chloride and Carboxylic Acids: Versatile Alternatives to Ionic Liquids. J. Am. Chem. Soc. 126,
9142–9147.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
29
Natural Deep Eutectic Solvents for the Green Extraction
of Soy By-Products
Felipe Sanchez Bragagnolo a,b, Bárbara Socas-Rodríguez a, Cristiano Soleo Funari b, Elena
Ibáñez a* a Laboratory of Foodomics, Institute of Food Science Research, CIAL, CSIC, Nicolás Cabrera
9, 28049 Madrid, Spain b Faculty of Agricultural Sciences, São Paulo State University, Av. Universitária 3780,
18610-034, Botucatu, São Paulo, Brazil
* E-mail: [email protected]
Keywords: Soy By-Products, Natural Deep Eutectic Solvents, Hansen Solubility, Green
Chemistry
Soybean is the major oilseed crop worldwide, with 336.47 million tons produced in 2019/2020.
However, this vast production has been leaving by-products (roots, branches, leaf, and pods)
behind that could be valorised considering their composition in high-added compounds such as
fatty acids, saponins, tannins, organic acids, isoflavones, etc. This approach can be of interest
to reduce the environmental impact of leaving the wastes in the landfield. For this purpose, a
green approach combining Natural Deep Eutectic Solvents (NaDES) and Pressurized Liquid
Extraction (PLE) has been employed for generating extracts with potential bioactivity
properties. Besides, Hansen Solubility Parameters (HSP) have been used for guiding the
selection of the best NaDES composition targeting the most valuable compounds. Two
sequential processes have been tested; a) firstly, a defatting process, in which n-heptane as a
benchmark solvent in PLE (at three temperatures (40, 80, 120 °C)), has been compared to
natural hydrophobic DES (NaHDES composed of the secondary metabolites identified in n-
heptane soy by-products extracts by GC-Q-TOF-HRMS). Moreover, NaHDES with more HSP
similarity with n-heptane have also been selected. b) Secondly, EtOH:H2O (7:3) (v/v), as the
reference solvent in PLE, and hydrophilic NaDES were considered. Different bioactivities,
depending on extracts’ composition, can be expected, such as antioxidant, anti-inflammatory,
and anti-neurodegenerative activities.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
30
NADES in the Stabilization of Phenolic Compounds from
Sunflower Meal
Fernanda de Sousa Bezerra a,*, Danielly C. Ferraz da Costa b and Maria Gabriela Bello
Koblitz a a Federal University of the State of Rio de Janeiro - UNIRIO, Food and Nutrition Graduate
Program – PPGAN. 296 Pasteur Av. 2nd floor. Urca, Rio de Janeiro - RJ. Brasil. 22290-240. b State University of Rio de Janeiro – UERJ, Nutrition Institute. 524 São Francisco Xavier St.,
12th floor F. Maracanã, Rio de Janeiro - RJ. Brasil. 20550-900.
Keywords: natural deep eutectic solvents, chlorogenic acid, ultrasound, storage
Sunflower meal is the main by-product generated from the extraction of the oil from this seed
and is normally destined for animal feeding. However, it is a bioactive rich material with up to
4% of phenolic compounds, in which 70% are represented by the chlorogenic acid family.
Traditionally, organic solvents are used to extract polyphenols, but there is a search for more
sustainable solvents to avoid the purification steps necessary for the application of these extracts
by the food, cosmetics, and pharmaceutical industries. Natural deep eutectic solvents (NADES)
have already demonstrated to be a more biodegradable and efficient alternative. Moreover,
NADES may also improve the stability of phenolic compounds in the extracts. The objective
of this work was to obtain phenolic extracts from sunflower meal applying two different
formulations of NADES and to evaluate the stability of the phenolic compounds in these
extracts under different storage conditions, using a hydroethanolic extract (40%) as the control.
All extracts were obtained by ultrasound assisted extraction (UAE) and stored at -18ºC, 8ºC
other 25ºC. Samples were analysed immediately after extraction and after 1, 7, 15, 30 and 60
days of storage. Extraction with lactic acid:glucose (5:1), choline chloride:glycerol (1:1) and
hydroethanolic solution resulted in 95.54 mg of chlorogenic acid/L, 60.39 mg of chlorogenic
acid/L and 33,72 mg of chlorogenic acid/L, respectively. The lactic acid:glucose NADES was
the most efficient in stabilizing phenolic compounds over storage time, regardless of
temperature. However, all extracts showed significant phenolic loss after 7 days and the choline
chloride:glycerol NADES showed a decrease of 71% in chlorogenic acid on the 30th day of
storage. These assays are under reiteration to confirm the results.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
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Unravelling the target-specific anticancer action of THEDES Filipe Oliveira a*, Joana Pereira a, Eduardo Silva b, Joana M. Silva b, Rui L. Reis b, Ana Rita
C. Duarte a a LAQV-REQUIMTE, Departamento de Química, Faculdade de Ciências e Tecnologia,
Universidade Nova de Lisboa, Caparica, Portugal b 3B’s Research Group, University of Minho, Avepark 4805-017 Barco, Guimaraes, Portugal
c ICVS/3B’s PT Government Associated Laboratory, Braga/Guimaraes
Keywords: Green chemistry, THEDES, Terpenes, NSAIDs, Solubility, Cancer therapy
The remarkable bioactive properties of DES have now been widely described. Eutecticity has
proven to be a promising tool in the development of new and effective therapeutic agents,
contributing to modern medicine most challenging battles, such as antibacterial and antibiofilm,
antifungal, and anticancer. Additionally, the tailor-made versatility and compliance with the
green chemistry metrics, have pushed forward the possible therapeutic applications of eutectic
formulations. In this work, we aim to unravel what we consider to be the next step in the
comprehension and consolidation of such therapeutic systems – target-specificity. By allying
the anticancer and anti-inflammatory properties of terpenes with nonsteroidal anti-
inflammatory drugs (NSAID), we have already observed and described THEDES selective
action towards cancer cells (Colorectal cancer cells), without compromising normal intestinal
cells viability. So, what are the specific cellular targets and consequent responses from the
eutectic exposure? Using a multidisciplinary approach, from the design, preparation and
characterization of THEDES, to the study of their bioavailability and bioactivity; to the
evaluation of THEDES specific cell target, we expect to untangle THEDES cytotoxic
mechanisms and establish this technology as an innovative approach in the cancer challenge.
Acknowledgments: This project has received funding from the European Union’s Horizon 2020 (European
Research Council) under grant agreement No ERC-2016-CoG 725034. This work was also supported by the
Associate Laboratory for Green Chemistry (LAQV) financed by national funds from FCT/MCTES
(UIDB/50006/2020).
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
32
Separation of Lithium from a Simulated Salt-lake Brine
using Synergistic Deep Eutectic Solvents
Takafumi Hanadaa and Masahiro Goto a,* a Department of Applied Chemistry, Graduate School of Engineering, Kyushu University, 744
Motooka, Nishi-ku, Fukuoka, Japan.
Keywords: Liquid-Liquid extraction, Lithium, Salt-lake brine
Lithium (Li) recovery from salt-lake brines have attracted much attention owing to the
abundance of the resources much greater than that of ores. However, current situation in Li
production from salt-lake brines is facing challenges such as long-term process of the solar
evaporation. To meet the increasing demand of Li, the liquid-liquid extraction which is the
developed metal refining technique is expected to be applied for the Li recovery from salt-lake
brines. To date, various Li extraction system such as ion-recognition using crown ethers or
synergistic extraction using two or more mixed extractants have been investigated. On the other
hand, due to the environmental impacts of volatile and toxic organic diluents used in the liquid-
liquid extraction procedure, benign alternatives such as ionic liquids and deep eutectic solvents
(DESs) are desired.
Here, we show a novel concept “synergistic DESs” for the selective recovery of Li from salt-
lake brines. We found that the mixture of the synergistic extractants for Li, beta-diketones and
phosphine oxides, shows the melting point depression deeper than that of their ideal mixture.
The extraction performance of Li using the DES was compared with the traditional solvent
extraction system using toluene as diluent, as shown in Fig. 1. Interestingly, the DES performed
the synergy in Li extraction, which both beta-diketones and phosphine oxides could coordinate
to Li to form stable extracted complexes. Finally, we successfully applied the DES for the
selective recovery of Li from the simulated salt-lake brine.
Fig. 1. Comparison of Li extraction performance between the traditional solvent extraction
using toluene as diluent, and DES without dilution
0
20
40
60
80
100
1M-HTTA 0.5M-TOPO HTTA/TOPO intoluene
HTTA/TOPO-DES
%E
HTTA/TOPO-DESP
O
O
FF
F
S
O
Thenoyltrifluoroacetone
(HTTA, m.p. 317 K)
Trioctylphosphine oxide
(TOPO, m.p. 325 K)
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
33
Insulinotropic effects of apple pomace extracts in Deep
Eutectic systems
Heleena Moni Bottua, Lorraine Brennana*, Lorrenzo Guazzellib, Angelica Merob, Elena
Husanub, Serge Tavernierc a Institute of Food and Health, University College Dublin, Dublin 4, Ireland
b Department of Pharmacy, University of Pisa, Italy
c iPRACS, University of Antwerp, Belgium
* [email protected], [email protected]
There is growing interest in the potential of new environment friendly solvent systems for
extracting bioactive compounds from foods. Our objective is to investigate the ability of
different extraction systems to extract bioactives from apple pomace a food waste. The
bioactivity was focused on antioxidant potential and ability to secrete insulin from pancreatic
beta cells (BRIN BD11). We assessed 20 wet and dry apple pomace extracts. Their antioxidant
effects were examined using DPPH antioxidant capacity as % of scavenging activity and by
FRAP antioxidant capacity expressed as µM TE/mg d.w sample. The effects of the extracts on
cell viability and cell proliferation were assessed and at lowest concentration where the cell
viability was not affected, we examined the ability to stimulate insulin secretion. Statistical
analysis was performed with graph pad prism using Analysis of Variance (ANOVA) and
Benferroni post hoc comparisons. The results demonstrate that the dry apple pomace extracts
from classical extraction system exhibit potential insulinotropic effects and in vitro antioxidant
effects. Among extracts from various DES systems lyophilized dry extracts of apple pomace in
DES ChCl:EG (1:4) demonstrated an ability to promote insulin secretion. Research is on-going
to examine these effects further.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
34
Impact of hydrophilic natural deep eutectic solvents on
hydrogels intended for skin application
Iron Mike Ardeza a,b,*, L. Boudesocque-Delayea, Laura Wils a, Xavier Perse a, Sybille de La
Motte b, Emilie Munnier b a SIMBA EA 7502 Synthèse et isolement de molecules bioactives, Université de Tours,
Faculté de Pharmacie, 31 avenue Monge 37200 Tours, France b NMNS EA 6295 Nanomédicaments et Nanosondes, Université de Tours,
Faculté de Pharmacie, 31 avenue Monge 37200 Tours, France
Keywords: Natural deep eutectic solvents, cosmetics, hydrogels, physicochemical
charcteristics
NaDES as a novel green solvent has gained, in recent years, a positive momentum for cosmetic
ingredients preparation from vegetal biomasses. Many combinations particularly
betaine/glycerol and glucose/glycerol has displayed a great potential for both extraction and
stabilization of several phenolic compounds and epigallocatechin-3-gallate respectively 1,2.
This study aims to evaluate the impact of the incorporation of these well-known NaDES in a
cosmetic gel intended for skin application. Betaine/glycerol (BG) and glucose/glycerol (GG)
were incorporated at 3 different concentrations (1%, 5% and 10%) in two different hydrogels
one based on a hemisynthetic cellulose derivative and the other on vegetable gum. The
organoleptic and physico-chemical characteristics of the NaDES-enriched gels were observed
before and after 30 days at room temperature (25°C) and in accelerated aging conditions (40°C,
75°C humidity). Obtained results showed that the incorporation of NaDES in gels does not
change significantly the pH of the formulations, but has a variable impact on the viscosity of
the gels depending on the composition of the NaDES, their concentration and the incorporation
method. These results highlight how important it is to understand the NaDES interaction with
the formula ingredients for an efficient predictive approach of their compatibility as ingredients
in cosmetic formulations.
1Fanali, C.; Della Posta, S.; Vilmercati, A.; Dugo, L.; Russo, M.; Petitti, T.; Mondello, L.; De Gara, L. Extraction,
Analysis, and Antioxidant Activity Evaluation of Phenolic Compounds in Different Italian Extra-Virgin Olive
Oils. Molecules 2018, 23, 3249. 2Jeong, K.M.; Ko, J.; Zhao, J.; Jin, Y.; Yoo, D.E.; Han, S.Y.; Lee, J. Multi-functioning deep eutectic solvents
asextraction and storage media for bioactive natural products that are readily applicable to cosmetic products.J.
Clean. Prod.2017,151, 87–95.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
35
Structure and Interactions in p-Toluene Sulfonic Acid
based Deep Eutectic Solvent
Iva Manasia*, Elly K Bathkea,, Stephen M Kingb, Daniel T Bowronb and Karen J Edler a a Department of Chemistry, University of Bath, Claverton Down, Bath, BA2 7AX, UK.,
b ISIS Neutron and Muon Source, Rutherford Appleton laboratory, Oxford, OX11 0QX, UK
Keywords: Deep-eutectic solvent; p-toluene sulfonic acid; choline chloride; DES structure;
surfactants assembly.
Changing the H-bonding components and their ratios can alter the physicochemical properties
of deep eutectic solvents (DES). Recent studies have shown p-toluene sulfonic acid (pTSA)
forms room temperature liquids with choline chloride (ChCl) at different molar ratios: 1:1, 1:2
and 2:1 (Rodriguez Rodriguez et al., 2019). They also showed that the composition affects the
physical properties of these liquids and their ability to dissolve metal oxides. In this work we
look at the structure of pTSA/ChCl based liquid mixtures at two molar ratio, 1:1 (eutectic point)
& 1:2, using total neutron scattering experiments and Empirical Potential Structure Refinement
(EPSR) modelling to understand how composition impacts structure which in turn influences
properties and interactions in these mixtures.
Additionally, we also evaluate the solubility of cationic surfactants; alkyltrimethyl ammonium
bromides (CnTAB), in these pTSA/ChCl based liquids. CnTABs are insoluble in
1pTSA:2ChCl, whereas in 1pTSA:1ChCl and 2pTSA;1ChCl they form micelles. We
characterise CnTAB (n=12, 14, 16) micelles at these two compositions using Small Angle
Neutron Scattering and also look at interaction of water with the micelles. These studies help
determine the interaction of DES components with the surfactant and the influence of varying
pTSA and water ratios on these interactions. This provides potential for controlled surfactant
templating and allowing rheology modification in such systems.
References:
Rodriguez Rodriguez, N., MacHiels, L., & Binnemans, K. (2019). P-Toluenesulfonic Acid-Based Deep-
EutecticSolvents for Solubilizing Metal Oxides. ACS Sustainable Chemistry and Engineering, 7(4), 3940–3948.
https://doi.org/10.1021/acssuschemeng.8b05072
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
36
Sustainable waste management from wine production
Manuela Panića, Veronika Gunjević a, Mia Radović a, Kristina Radošević a, Marina Cvjetko
Bubalo a, Natka Ćurko a, Karin Kovačević Ganić a, Ivana Radojčić Redovnikovića a Faculty of Food Technology and Biotechnology, University of Zagreb, Pieroti street 6,
10000 Zagreb, Croatia
Keywords: COSMO-RS, green extraction, natural deep eutectic solvents, polyphenols
Food processing generates a substantial volume of solid organic by-products. Only small
amounts of these by-products are up-graded or recycled and used usually for composting or
even discarded in open areas potentially causing environmental problems. Wine production by-
products, such as grape pomace, are the most abundant worldwide and have been lately often
evaluated as a source of biological active compounds due to high content of polyphenolics. In
the last few years, the extraction and identification of phenolic compounds from natural sources
has become a major area of scientific research. Due to their complex structure, there is no
universal extraction method suitable for extraction of all plant phenolic, whereby conventional
extraction techniques are usually associated with high organic solvent consumption and long
extraction times. One of the organic solvents replacement could be natural deep eutectic
solvents (NADES) since NADES can dissolve both polar and non-polar compounds. They may
be used for very efficient extraction of natural products from plants, such as polyphenols. Since
NADES has high safety profile it is expected that extract obtained by NADES may be directly
used in food, pharmaceutical, cosmetical and agrochemical products without the need for
expensive downstream purification steps.
NADES is designed solvents, so to save time and money, it should be designed rationally for
polyphenolics extraction. Currently, COSMO-RS can design new solvent structures with
tailored properties and thus the trial-and-error method of NADES preparation can be avoided
Therefore, the aim of this stufy is to design efficient NADES for extraction of polyphenols from
wine production by-products.
Acknowledgements: The work was supported by the European Union through the European regional development
fund, Competitiveness and Cohesion 2014-2020 (KK.01.1.1.07.0007.)
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
37
Unravelling the in vitro and in vivo toxicity of
deep eutectic solvents consisting of safe compounds
including choline chloride
Dasom Jung a, Jae Back Jung a, Seulgi Kang a, Ke Li a, Inseon Hwang a, Ji Hoon Jeong a,
Hyung Sik Kim a and Jeongmi Lee a,* a School of Pharmacy, Sungkyunkwan University, Suwon, Gyeonggi 16419, Republic of
Korea
Keywords: deep eutectic solvents; toxicity; toxico-metabolomics; oxidative stress
Safety of deep eutectic solvents (DESs) has been taken for granted because their constituents
generally have low toxicity. Herein, we prepared eight different DESs using edible components,
including choline chloride (ChCl), organic acids (lactic acid and malic acid), polyols (glycerol,
xylitol, and sorbitol), sugars (glucose and fructose), and urea. In in vitro cytotoxicity assessment
on HepG2 and HEK293T cell lines, both DESs and the simple aqueous mixtures of the DES
components were generally more cytotoxic than the individual components. Moreover, some
DESs presented lower IC50 than the aqueous mixtures. Next, a toxico-metabolomics study was
performed on CU (1:2) that consists of ChCl and urea (1:2 molar ratio) because its popular
usage in many applications. The animal study was based on five groups of mice that were orally
administered saline, ChCl, urea, aqueous mixture of ChCl and urea, and CU (1:2). After 24 h,
serum, kidney, and liver samples were collected and analysed for metabolic profiling using gas
chromatography-mass spectrometry and liquid chromatography-mass spectrometry. Metabolic
profiles of the DES-treated mice were generally distinct from the others, as evidenced in the
principal component analysis and orthogonal projection to latent structure discriminant
analysis. The identified differential marker metabolites suggest that the DES toxicity may be
associated with oxidative stress and ammonia stress. The DES-induced oxidative stress was
confirmed by several biochemical assays including superoxide dismutase activity, catalase
activity, and malondialdehyde assays. The ammonia assay showed that blood of the DES-
treated mice had significantly increased ammonia levels compared with the control mice.
Ammonia could be produced during DES preparation from ChCl and urea with and without
heating and also could be produced from ChCl and organic acids with heating. Collectively,
our study suggests that ChCl-based DESs may not be simply considered as pure and safe
mixtures. The current presentation is based on our recent publication in Green Chemistry (2021,
in press).
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
38
Micellization of Ionic Surfactants in a Ternary Deep
Eutectic System
Ria Atri,a,b Iva Manasi,b Adrian Sanchez Fernandez,b Oliver Hammond,a,b James Doutchc and
Karen J. Edlerb,*
a EPSRC Centre for Doctoral Training in Sustainable Chemical Technologies, University of
Bath, Bath, BA2 7AY, UK b Department of Chemistry, University of Bath, Bath, BA2 7AY, UK
c ISIS Pulsed Neutron and Muon Source, Science & Technology Facilities Council,
Rutherford Appleton Laboratory, Didcot, OX11 0QX, UK
Keywords: surfactant self-assembly, ternary systems, small angle scattering, micelles
Deep eutectic systems (DES), have shown the ability to support the self-assembly of both
anionic and cationic surfactant molecules. In order to use this in applications such as templated
materials synthesis, it is of interest to study a system which simultaneously facilitates the
synthesis of metal oxides and is capable of solubilising suitable surfactant molecules.
We have previously developed solvothermal syntheses of metal oxides using the choline
chloride:urea DES [1, 2] and aim to extend our method to include the surfactant templated
synthesis of porous materials. The urea component in the DES is essential to the reaction
pathway, however we have not been able solubilise both cationic and anionic surfactants in
choline chloride:urea. To overcome this, we have turned to a three component DES comprising
choline chloride, urea and glycerol which is capable of supporting the self-assembly of both
cationic (CnTAB) and anionic (sodium dodecyl sulfate) surfactants. The micellization of these
surfactants in the ternary DES at various urea:glycerol ratios has been investigated using small
angle neutron scattering (SANS) techniques. [3]
Fitting of the SANS data has revealed that elongated micelles are obtained in both cases. We
have demonstrated that the micelle morphology displays composition dependence, with a
higher glycerol content in the DES giving rise to more spherical micelles. This could be due to
a higher counterion solubility with increased glycerol, whereas at higher urea content the
counterions may preferentially pack at the micelle corona.
References:
[1] O.S. Hammond, K.J. Edler, D.T. Bowron, L. Torrente-Murciano, Nature Commun. 8 (2017) 14150.
[2] O.S. Hammond, S. Eslava, A.J. Smith, J. Zhang, K.J. Edler, J. Mater. Chem. A 5 (2017) 16189
[3] R.S. Atri, A. Sanchez-Fernandez, O.S. Hammond, I. Manasi, J. Doutch, J.P. Tellam, K.J. Edler, J. Phys.
Chem. B 124 (2020) 6004.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
39
Carvone and its eutectic mixtures introduced as tunable,
green solvents
Ke Li, Seulgi Kang, Yuli Liu, Inseon Hwang, Jeongmi Lee*
School of Pharmacy, Sungkyunkwan University, Suwon, 16419 Republic of Korea.
* Corresponding author. E-mail: [email protected]; tel.: +82-31-290-7784; fax: +82-31-
292-8800.
Keywords: carvone; eutectic solvents; tunable green solvent; liquid-liquid extraction.
Development of tunable and renewable solvents has been the Achilles's heel in green extraction
processes. In this study, R-(-)-carvone and its eutectic mixtures were investigated as green and
tunable solvents with low viscosity. A series of carboxylic acids, terpenes and a benzoate ester
could apparently form stable eutectic mixtures with carvone at various mole fractions of
carvone. The solid-liquid equilibrium diagrams of the mixtures unveiled that most of the
mixtures remained liquid at room temperature within a wide range of mole fractions and that
some combinations could be classified as deep eutectic solvents. The examined eutectic
mixtures at certain mole fractions showed varying properties in terms of density and polarity,
but they had low viscosity and reasonable biodegradability. Finally, taking advantage of these
favourable solvent properties, we applied these mixtures to liquid-liquid extraction system
using model dyes and high-value natural pigments from red algae. The results suggest that the
carvone-based eutectic mixtures could extract hydrophobic dye and pigments with varying
efficiencies and selectivity depending on the type of eutectic mixtures. Thus, this study
proposes carvone and its eutectic mixtures as promising green solvents.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
40
Enhanced Solubilization Of Essential Oils By Combining
Deep Eutectic Solvent, Cyclodextrins And Water
Lamia Nakhlea,b, Miriana Kfourya, Isabelle Mallardb, Hélène Greige-Gergesa, David Landy*b
a Bioactive Molecules Research Laboratory, Faculty of Sciences, Lebanese University, 90656
Jdaidet el-Metn, Lebanon
b Unité de Chimie Environnementale et Interactions sur le Vivant (UCEIV, EA 4492), SFR
Condorcet FR CNRS 3417, Université du Littoral Côte d’Opale (ULCO), 145 Av. M.
Schumann, F-59140 Dunkerque, France
⁎ Email of the corresponding author: [email protected]
Keywords: cyclodextrin, deep eutectic solvents, essential oil, solubility.
There is a strong demand to overcome the poor solubility of active natural molecules in
pharmaceutics and food technology. Many efforts are therefore devoted to develop
formulations based on delivery systems and/or biodegradable and sustainable green solvents
[1] [2]. This study focuses on developing formulations combining native, modified or
polymerized cyclodextrins (CD) with choline chloride/ urea deep eutectic solvent (DES) and
water. The formulations were characterized for their density and viscosity, before being
investigated for their ability to reduce the volatility of essential oils (EO) using Headspace Gas
Chromatography (HSGC). A solubility increase was observed for various EO with all the tested
systems (water/CD, DES/water¸ DES/water/CD), when compared to water alone. Besides being
able to reduce the viscosity of the solvent, the presence of a certain amount of water (20-30
wt%) favor the retention of EO in the formulation when using CD, since water molecules
improve the complexation phenomena and therefore the solubilizing efficiency of the DES/CD
mixture. For a better understanding of the solubilization mechanisms, the affinity of DES and
of EO components for CD was assessed by isothermal titration calorimetry.
[1] M. Kfoury, L. Auezova, H. Greige-Gerges, and S. Fourmentin, “Promising applications of cyclodextrins in
food: Improvement of essential oils retention, controlled release and antiradical activity,” Carbohydrate Polymers,
vol. 131, pp. 264–272, Oct. 2015, doi: 10.1016/j.carbpol.2015.06.014.
[2] T. El Achkar et al., “New generation of supramolecular mixtures: characterization and solubilization studies,”
International Journal of Pharmaceutics, p. 119443, May 2020, doi: 10.1016/j.ijpharm.2020.119443.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
41
NADES for microalgae biorefinery: biomass pre-treatment
and comparison with bio-sourced solvents
Laura Wils a,*, Soukaina Hilali a, Mervé Yagmur a, Barbara Clément-Larosière b,
and Leslie Boudesocque-Delaye a
a SIMBA EA 7502 Synthèse et isolement de molécules bioactives, Université de Tours,
Faculté de Pharmacie, 31 avenue Monge 37200 Tours, France
b Aqua Eco Culture,
7 rue d’Armor Maroué, 22403 Lamballe, France
Keywords: microalgae, biorefinery, pre-treatment, bio-sourced solvent, NADES
Microalgae are a unique sustainable resource of biomolecules for cosmetic, pharmaceutical,
food and feed industries. In this markets, microalgae are usually used as powder or global
extract, targeting one class of metabolite for one defined species. For example, Spirulina
(Arthrospira platensis) is extracted for its high content of a phycobiliprotein, the phycocyanin.
Phycocyanin is a highly promising metabolite exhibiting antioxidant, anti-cancer and anti-
inflammatory activity. The high demand for phycocyanin concentrated product in food and
cosmetic market had led to an exponential increase amount of microalgal biomass by-product.
This by-product can be further valorized since most of the lipophilic pigments were not
recovered as well as other high value metabolites like free fatty acids (FFA).
One crucial aspect to investigate to develop microalgae biorefinery is the biomass pre-
treatment. In fact, microalgae cell-wall are well-known to be robust and to limit dramatically
the access of intracellular metabolites, like FFA. Here we report the investigation of the impact
of biomass pre-treatment of A. platensis on FFA biorefinery using NADES and bio-sourced
solvents. Three pre-treatments were compared: cell disruption by freezing, air-drying and by-
product from phycobiliprotein extraction with water. The impact on biomass integrity, FFA
recovery and profile were investigated and NADES extraction performance were compared to
bio-sourced solvents. In our work, fatty acid based NADES were highlighted as the most
promising to recover FFA from Spirulina, after and before phycocyanin extraction. These data
open the way to the design of a multi-step Spirulina biorefinery scheme using NADES.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
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Natural deep eutectic solvents for microalgae biorefinery:
Spirulina as case of study Laura Wils a, Soukaina Hilali a, Suha Elderli b, Mervé Yagmur a, Charlotte Leman-Loubière a,b
Barbara Clément-Larosière c, Franck Bonnier b and Leslie Boudesocque-Delaye a,*
a SIMBA EA 7502 Synthèse et isolement de molecules bioactives, Université de Tours,
Faculté de Pharmacie, 31 avenue Monge 37200 Tours, France
b NMNS EA 6295 Nanomédicaments et Nanosondes, Université de Tours,
Faculté de Pharmacie, 31 avenue Monge 37200 Tours, France
c Aqua Eco Culture,
7 rue d’Armor Maroué, 22403 Lamballe, France
Keywords: NADES, microalgae, biorefinery, fatty acids, phycobiliprotein
Microalgae are promising renewable resources of various biomolecules of interest like protein,
pigments (phybiliprotein, carotenoids, chlorophylls), polysaccharides and lipids especially
polyunsaturated (PUFA), for various markets (food, feed, pharmaceutics, cosmetic).1,2
Microalgae were usually used as powder or global extract, targeting one class of metabolite for
one defined species. For example, Spirulina (Arthrospira platensis) is extracted for it high
content of phycocyanin.1 The increasing demand of phycobiliprotein concentrated product in
food marked led to the extraction of increasing amount of microalgal biomass, using water as
the main solvent.3 By-product generated were usually used as is, even if other high value
metabolites like free fatty acids (FFA), especially polyunsaturated one, or carotenoids could be
still valorised. A sustainable biorefinery approach would be a good opportunity for microalgae
industry. In this context, Natural Deep Eutectic Solvents (NADES) represent an exciting
opportunity. In the DERMIC project, the use of NADES for the extraction of both
phycobilliproteins and apolar metabolites (FFA and carotenoids) were investigated. Biomass’
pre-treatment, NADES library screening and intensification of unitary operation were
investigated highlighting the high potential of NADES to generate concentrated extracts. The
sequential used of NADES for the valorization of all metabolites was conducted and
demonstrated the feasibility of the integration of NADES in all steps of biorefinery scheme.
1 Dolganyuk, V.; Belova, D.; Babich, O.; Prosekov, A.; Ivanova, S.; Katserov, D.; Patyukov, N.; Sukhikh, S.
Microalgae: A Promising Source of Valuable Bioproducts. Biomolecules 2020, 10, 1153.
https://doi.org/10.3390/biom10081153 2 Guillerme, J.-B.; Couteau, C.; Coiffard, L. Applications for Marine Resources in Cosmetics. Cosmetics. 2017, 4
(3), 35. https://doi.org/10.3390/cosmetics4030035. 3 Fernando Pagels, A. Catarina Guedes, Helena M. Amaro, Anake Kijjoa, Vitor Vasconcelos, Phycobiliproteins
from cyanobacteria: Chemistry and biotechnological applications, Biotechnology Advances, Volume 37, Issue 3,
2019, Pages 422-443, https://doi.org/10.1016/j.biotechadv.2019.02.010.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
43
Stabilization of Horseradish Peroxidase Using Natural
Deep Eutectic Systems
Liane Meneses a, Ana Rita C. Duarte a,b, Alexandre Paiva a,b*
a LAQV/REQUIMTE, Departamento de Química, Faculdade de Ciências e Tecnologia,
Universidade Nova de Lisboa, 2829-516 Caparica, Portugal b Des Solutio, Avenida Tenente Valadim nº17 2ºF, 2560-275 Torres Vedras, Portugal
Keywords: Natural Deep Eutectic Solvents, Enzymes, Horseradish Peroxidase, Enzymatic
Activity, Stabilization
The applications of deep eutectic systems (DES) have grown over the past few years and they
have become a viable alternative as media for preservation of different compounds, such as
antioxidants, phenolics or even proteins. Some choline-based systems had already been
reported effective for the stabilization of the enzyme Horseradish Peroxidase (HRP). However,
they face restrictions in which concerns their utilisation on some industries making it of the
utmost importance to replace such compounds in their formulations. Hence, in this work, the
application of natural deep eutectic systems (NADES) for the stabilization of HRP was
assessed. Betaine and sugar-based systems were used in different combinations and molar
ratios. Phosphate buffer saline (PBS) was used for control experiments. The enzyme’s stability
was tested at 37, 60 and 80 ⁰C for different incubation times. The effect on HRP’s stability was
evaluated through enzymatic activity assays. Preliminary results shown that, upon 6h
incubation in Betaine:Sorbitol:Water (1:1.3), HRP’s enzymatic activity has a 2-fold increase,
when compared to the control experiments performed in PBS. The possibility to extrapolate
these findings to more relevant and sensitive molecules could open new possibilities for the
pharmaceutical or cosmetic industries.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
44
Application of Deep Eutectic Solvents for the Extraction of
Textile Dyes from Water
L. Villar, J. Páez, A. Domínguez, B. González*
Advanced Separation Processes Group, Isaac Newton Building, Department of Chemical
Engineering, Universidade de Vigo, Lagoas-Marcosende, 36310, Vigo, Spain
Keywords: Deep Eutectic Solvents, Liquid-Liquid Extraction, Malachite Green, Industrial
Wastewater.
Currently, textile industry is continuously growing due to the fast-fashion trend, which involves
the consumption of huge number of garments in a short period. The dyeing process is a critical
step in this industrial activity that generates the discharged of high amount of coloured
wastewater due to the presence of textile dyes. These dyes are responsible of water
contamination due to their high toxicity and their contribution to water opacity, which caused
the kill of aquatic life. Among these dyes is Malachite Green which is an artificial dye
traditionally used for leather, cotton and silk fabrics dyeing.
With the aim of removing Malachite Green from water, Liquid-Liquid Extraction (LLE)
technique was useful applied for the extraction of pollutants from water, due to its efficiency
and versatility. However, the main drawback is the use of Volatile Organic Compounds (VOCs)
that have a high toxicity. In this line, Deep Eutectic Solvents (DESs) are presented as replacing
agents for VOCs.
In this work, three hydrophobic DES based on Thymol and Decanoic acid in different molar
proportions were applied for the extraction of Malachite Green from water. Samples were
prepared by mixing aqueous solutions of Malachite Green in different concentrations with a
known amount of DES as extraction agent. Then both phases were separated and the extraction
efficiency of the process was studied measuring Malachite Green absorbance in aqueous phase
using an UV-Vis spectrophotometer.
As a result, all DESs presented extraction efficiencies higher than 95% for all studied
concentrations, proving that can be suitable to remove Malachite Green from water that
contributes to the recycle of water promoting the decrease of its consumption.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
45
Simulation of Equilibrium Phase Diagram and
Physicochemical Characterization of Natural Eutectic
Solvents
Maha M. Abdallaha, b *, Simon Muller c, Andrés Gonzalez de Castilla c, Pavel Gurikov d,
Maria do Rosário Bronze a, b, e, Ana A. Matias a, Naiara Fernandez a a Institute of Experimental Biology and Technology, Portugal
b Institute of Chemical and Biological Technology, New University of Lisbon, Portugal c Institute for Thermal Separation Processes, Hamburg University of Technology, Germany
d Laboratory for Development and Modelling of Novel Nanoporous Materials, Hamburg
University of Technology, Germany e FFULisboa, Faculty of Pharmacy, University of Lisbon, Portugal
* E-mail address of corresponding author: [email protected]
Keywords: Deep eutectic solvents, physicochemical characterization, equilibrium phase
diagram
Eutectic solvent systems are prepared from natural terpene-based components, including
menthol, thymol, camphor and borneol. The solid-liquid equilibrium (SLE) phase diagrams are
predicted using the models UNIFAC and COSMO-RS with two different parametrization
levels. The ideal, experimental and predicted eutectic points are obtained for each system. The
deviation from ideality is studied to assess if the system could be considered as deep eutectic
solvents (DES). For instance, Thymol:Borneol system has shown a clear negative deviation
from ideality in the SLE curves using the models and experimentally and may be considered as
DES (Figure 1). The thermodynamic parameters, including the degradation, glass transition and
crystallization temperatures, are measured using DSC and TGA. Furthermore, the chemical
structure and interactions are analyzed on the basis of FTIR and 1H NMR to confirm the
presence of intermolecular hydrogen bonding in the eutectic systems. The difference in the
chemical interactions between the pure compounds and the eutectic systems, observed
experimentally and analyzed by simulation, proves that in fact the systems do not act as an ideal
mixture, which confirms their behavior as possible DES.
Figure 1: Ideal, experimental and predicted SLE
phase diagrams of the terpene-based solvent
systems. (Thy: Thymol, Bor: Borneol)
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
46
Natural deep eutectic solvents as biofilm structural
breaker
Maria F. Nava-Ocampoa, Lamya Al Fuhaida, Szilárd S. Bucsa, Robert Verpoorteb, Young
Choib, M.C.M. van Loosdrechtc, Johannes S. Vrouwenveldera, Geert J. Witkampa, Andreia S.
F. Farinhaa*
a Water Desalination and Reuse Center, King Abdullah University of Science and
Technology, Thuwal, Saudi Arabia. b Institute Biology Leiden, Leiden University, Leiden, The Netherlands.
c Department of Biotechnology, Faculty of Applied Sciences, Delft University of Technology,
Delft, The Netherlands.
Keywords: green solvent, aerobic granular sludge, EPS, biofilm
Natural Deep Eutectic Solvents (NADES) are composed of supramolecular interactions of two
or more natural compounds, such as organic acids, sugars, and amino acids. In this study, using
NADES is presented as a possible technology for biofilm structural breaker in complex systems.
The NADESs were analyzed before and after the biofilm treatment by attenuated total reflection
Fourier-transform infrared spectroscopy and fluorescence excitation-emission matrix
spectroscopy. Our results indicate that the green solvents could extract up to ≈70 percent of the
main components of the biofilms extracellular matrix. The weakening of the biofilm structure
enhanced its solubilization and removal. NADES have the potential to be an environment
friendly, green biofilm solvent to extract valuable compounds from the extracellular polymeric
substance (EPS) and to control biofouling in membranes system used for water treatment and
cooling towers.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
47
Using Eutectic Mixtures For The Extraction And Recovery
Of The Carotenoid Bacterioruberin
Mariam Kholany a, Nicolas Schaeffer a, Inês P.E. Macário a,b, Telma Veloso a,b, Tânia Caetano
b, Joana Luísa Pereira b, Sónia P.M. Ventura a,*, João A. P. Coutinho a a CICECO - Aveiro Institute of Materials, Department of Chemistry, University of Aveiro,
3810-193 Aveiro, Portugal b CESAM – Centre for Environmental and Marine Studies, Department of Biology,
University of Aveiro, 3810-193, Aveiro, Portugal
Keywords: Bacterioruberin, carotenoid, eutectic mixture, extraction
In the biorefinery context, both bulk and specialty chemicals can be produced and extracted
from biomass, resulting in a potentially more sustainable alternative to petroleum-derived
products. An example of this is Haloarchaea, an interesting class of extremophile
microorganisms, also present in the Aveiro salt pans. Amongst these, Haloferax mediterranei
is a highly promising candidate for the production of bacterioruberin owing to its rapid growth
and ability to consume a variety of carbon sources. Bacterioruberin is an uncommon C50
carotenoid with great biotechnological interest. This type of carotenoid exhibits a higher
antioxidant capacity than the C40 carotenoids such as β-carotene, which can be explained due
to the higher number of pairs of conjugated double bonds. This makes this carotenoid
remarkably interesting for the food, pharmaceutical and biomedical industries. In this work, the
valorization of Haloferax mediterranei ATCC 33500 was pursued through the recovery of
bacterioruberin and its separation and purification from the remaining cell components. In an
effort to formulate food and cosmetic grade compatible extracts, pigment recovery was
accomplished through the use of bio-derived eutectic solvents. Operational conditions such as
the solid-liquid ratio, concentration of eutectic mixture, hydrogen bond-donor and hydrogen-
bond acceptor ratio and the time of extraction were accessed. These eutectic mixtures arise as
more sustainable and appropriate solvents compared to the typical solvents used in chemical
processes because of their simple preparation, extraction efficiency and integration of the
extraction and separation in a “one-pot” method by using water as counter-solvent.
Acknowledgments: This work was developed within the scope of the project CICECO-Aveiro Institute of
Materials, UIDB/50011/2020 & UIDP/50011/2020 and CESAM, UIDB/50017/2020 & UIDP/50017/2020,
financed by national funds through the FCT/MCTES. The authors are also grateful to the FCT for the doctoral
grants of M. Kholany (SFRH/BD/138413/2018), I.P.E. Macário (SFRH/BD/123850/2016) and T. Veloso
(SFRH/BD/147346/2019).
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
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Could NaDES assisted one-pot extraction and
biotransformation be a relevant strategy to boost activity
of natural extracts? Millena Cristina Barros Santos1,2; Nathalie Barouh3,4; Bruno Baréa3,4, Mélina Robert4, Pierre
Villeneuve3,4, Luiz CláudioCameron2; Valérie-Lullien5, Claire Bourlieu-Lacanal5, Mariana
Simões Larraz Ferreira1,2* and Erwann Durand3,4*
¹LabBio - Laboratory of Bioactives, Food and Nutrition Graduate Program - PPGAN, Federal
University of State of Rio de Janeiro – UNIRIO, Rio de Janeiro, Brazil. 2IMasS-LBP - Center of Innovation in MS-Laboratory of Protein Biochemistry, UNIRIO, Rio
de Janeiro, Brazil. 3CIRAD, UMR QualiSud, F-34398 Montpellier, France
4QualiSud, Univ Montpellier, CIRAD, Institut Agro, IRD, Univ Réunion, Montpellier,France. 5IATE, Univ Montpellier, INRAE, Institut Agro, Montpellier, France.
* [email protected] and [email protected]
Keywords: NaDES, extraction, biotransformation, natural extracts, rice bran.
NaDES have been already proposed as a promising strategy to improve extraction efficiency of bioactive
compounds from plant biomass. What makes NaDES interesting is their unpredictable and strong
solubilization capacity, providing enriched extracts with higher phytochemical concentration. In
addition, NaDES have been reported to be excellent liquids to stabilize and protect molecules from
degradation, mostly due to the supramolecular network of tightly interconnected molecules. Last but not
the least, NaDES may offer all characteristics to design atom economy, efficient, low cost and
sustainable development for ready-to-use formulation, while being fully compatible with food and feed
applications. Concomitantly, the structural modification of molecules has been recognized as an
effective approach to strengthen the chemical efficiency of bioactive compounds. For example,
modification of antioxidant molecules could further result in a better capacity to retard oxidation of
lipid-based formulations. Although more challenging, such a strategy is even more interesting when the
modification takes place enzymatically; for safety and potential health benefits reasons, but also for
many others that align with the green chemistry principles. Here, metabolomics approaches focusing on
phenolic compounds (PC) was applied to characterize the complexity of pigmented rice bran NaDES
extracts. Compared to a binary mixture of water and ethanol (60:40 v/v), NaDES showed a specificity
to extract PC and demonstrated an interesting radical scavenging activity. In parallel, a characterization
of the lipid extraction profile showed the presence of different classes of lipids, which confirmed the
richness and abundance of diverse classes of bioactive compounds (PC/lipids). Our scientific
challenging aimed at investigating whether, and how, NaDES could sublimate activity of natural
occurring molecules in plant biomass. Thus, our strategy was to use these media properties to develop
a sustainable one-pot extraction and biotransformation environment to (i) promote antioxidant
enrichment (including PC and lipids) of a natural extract, and to (ii) enzymatically modify the structure
of compounds. Lipase was used to modify structures of enriched NaDES extract, and the samples were
tested for their ability to prevent lipid oxidation in an oil-in-water emulsion system. PV and TBARS,
determined during an incubation period, demonstrated an efficient antioxidant activity of our
biotransformed extracts. Thus, NaDES could favor the extraction and the biotransformation of natural
extracts, resulting in new functionalized compounds with improved antioxidant activities in emulsions.
These extracts can be used as natural additives at doses higher than the levels naturally found in cereals.
Omics tools will be applied to elucidate the structural rearrangement between the extracted compounds
from rice bran that justify the protection against lipid oxidation.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
49
Indium Mediated Barbier Allylation of Carbonyl
Compounds in Deep Eutectic Solvents
Nerea González-Gallardo, Beatriz Saavedra, Gabriela Guillena* and Diego J. Ramón*
Departamento de Química Orgánica and Instituto de Síntesis Orgánica (ISO), Facultad de
Ciencias Universidad de Alicante, Apdo. 99, 03080 Alicante, Spain.
* E-mail: [email protected], [email protected]
Keywords: Indium, Barbier Allylation, Deep Eutectic Solvent, Green Chemistry
This study describes, for the first time, the in-situ generation of indium organometallic reagents
in environmentally-friendly Deep Eutectic Solvents (DESs). The allylation process of different
carbonyl compounds was achieved mediated by indium metal, and using cheap allyl chloride
derivatives. The unique DESs properties allowed the reaction to be performed at room
temperature and under air obtaining yields from 52 to 99%. It was possible to recycle the
reaction medium at least 4 consecutive cycles without any decrease on the results. Also, a linear
correlation between the yield of the reaction and the densities of the DESs was observed. Thus,
this methodology could represent a practical and sustainable alternative to traditional protocols.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
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A critical study on the influence of DES on the formation
of organic biphasic systems
Jean-Baptiste Chagnoleau1, Nicolas Papaiconomou1*, Mona Jamaly1, João A. P. Coutinho2,
Dinis O. Abranches and Xavier Fernandez1, Thomas Michel1,
1Université Côte d'Azur, CNRS, Institut de Chimie de Nice, UMR 7272, Nice, France. 2CICECO – Aveiro Institute of Materials, Department of Chemistry, University of Aveiro,
3810-193 Aveiro, Portugal.
*Corresponding author: [email protected]
Keywords: DES, organic biphasic systems, phase diagrams, natural compounds, partition
coefficients, COSMO-RS.
In the current context of sustainable development and circular economy, new sustainable
processes and techniques for obtaining pure natural compounds is subject of intense studies.
Recent works1,2 have reported that Deep Eutectic Solvents (DES) added to two miscible organic
solvents (e.g., ethanol and heptane) trigger a phase demixion and the formation of a biphasic
system, that can be further applied to the partitioning of natural compounds. A critical study on
the relevance of using DES was however lacking.3
In this talk, in order to get a better understanding at the mechanisms in play for the formation
of biphasic systems and on the partitioning of natural compounds, we studied six systems based
on heptane and ethanol and a third compound being either glycerol, ethylene glycol, levulinic
acid, or the corresponding DES formed with choline chloride. Phase diagrams for these six
systems are reported and compared together. Measurements of the partition constants of five
natural compounds (quercetin, apigenin, coumarin, b-ionone and a-tocopherol) within these
systems was also measured. Finally, all phase diagrams and partition coefficients measured in
this work were compared to calculations carried out with the help of COSMO-RS model.
Figure 1. Comparison
between experimental
and calculated values
for log(KD) of several
natural compounds.
Yellow: H/E/LevA.
Blue: H/E/Ch:EG.
Grey: H/E/Glyc. Light
blue: H/E/Ch:LevA.
Orange: H/E/Ch:EG.
Green: H/E/Ch:Glyc.
Full colour:
Experimental. Dashed
colour: Calculated.
1: Bezold F.; Weinberger M. E.; Minceva M. Fluid Phase Equilibria 2017, 437, 23–33.
2: Bezold F.; Minceva M. A J. Chrom. A 2019, 1587, 166–171.
3: Chagnoleau J.-B.; Papaiconomou N.; Jamali M.; Abranches D.O.; Coutinho J.A.P; Fernandez X.; Michel T.
ACS Sus. Chem. Eng. 2021, submitted.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
51
Extraction of Ferulic Acid from Aqueous Systems Using
Deep Eutectic Solvents
O. G. Sas, M. López, M. Pita, B. González, A. Domínguez*
Advanced Separation Processes Group, Isaac Newton Building, Department of Chemical
Engineering, Universidade de Vigo, Lagoas-Marcosende, 36310, Vigo, Spain
Keywords: Deep Eutectic Solvents, Liquid-Liquid Extraction, Ferulic acid, UV-Vis
spectrophotometry.
Ferulic acid is one of the most common bioactive compounds that belongs to cinnamic acid
derivatives of phenol, it is presented on cell walls of many vegetables. This compound is
suitable for more and more applications, such as cosmetic, medical or food field. Consequently,
this high demand make necessary the recovery of ferulic acid from wastewater of some
industrial processes, as palm oil or beer production.
Among different used extraction techniques is Liquid-Liquid Extraction (LLE), which main
advantage is the possibility of recovering the target compound, as well as, the extraction agent.
In the last years, Deep Eutectic Solvents (DESs) have emerged as versatile solvents replacing
volatile organic compounds (VOCs) used conventionally in LLE.
In this work, one hydrophobic DES, Thymol:Menthol (1:1), was used in order to remove ferulic
acid from water samples of different initial concentrations. Ternary system formed by {DES +
Acid + Water} were mixed at controlled conditions, immediately DES-rich phase and water-
rich phase were separated using a centrifuge. The concentration of acid that remains in water-
rich phase was measured by UV-Vis spectrophotometry and the extraction capability of DES
was assessed.
The obtained results showed that the extraction percentage was higher than 90% for all studied
initial concentrations.
To conclude, Thymol:Menthol (1:1) is an appropriated solvent for the extraction of ferulic acid
from water, allowing the posterior reuse of both DES and extracted compound contributing to
a circular economy.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
52
Make it or Break it: Cu3(BTC)2 Metal-Organic
Framework in Reline DES
Renata Avena Maia a, Benoît Louis b,*, Stéphane Baudron a,* a CNRS, CMC UMR 7140, Université de Strasbourg, 4 rue Blaise Pascal, F-67000
Strasbourg, France. b CNRS, ICPEES UMR 7515, Université de Strasbourg, 25 rue Becquerel, F-67087
Strasbourg, France.
* [email protected], [email protected]
Keywords: Metal-Organic Frameworks • reline • structure transformation • CuBTC
The fate of the Metal-Organic Framework (MOF) Cu3(BTC)2 (BTC = 1,3,5-
benzenetricarboxylate) in reline DES (choline chloride/urea 1:2) was investigated,
demonstrating that not only reline can be used to make this MOF but also to transform it into
another crystalline material. Cu3(BTC)2 synthesized in reline showed good textural properties
and a particular rose morphology. Upon optimizing the reaction conditions such as
concentration, temperature, and metal/ligand ratio, it was found that another structure
Cu2(BTC)Cl, also forms. Furthermore, it was unequivocally demonstrated that, upon heating in
reline, Cu3(BTC)2 behaves as a metastable architecture, converting to the non-porous chloride-
incorporating material. Thus, a novel feature of DES in MOF synthesis is uncovered: its role as
a structure-directing agent, triggering the transformation between two different MOF
structures.1
1 R. A. Maia, B. Louis, S. Baudron, Dalton Trans. 2021, doi: 10.1039/D1DT00377A.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
53
A Green Method based on Natural Hydrophobic Deep
Eutectic Solvents for Plastic Migrants Determination in
Beverages using UHPLC-MS/MS
Ruth Rodríguez-Ramos a,*, Álvaro Santana-Mayor a, Antonio V. Herrera-Herrera b, Bárbara
Socas-Rodríguez c, Miguel Ángel Rodríguez-Delgado a a Departamento de Química, Unidad Departamental de Química Analítica, Facultad de
Ciencias, Universidad de La Laguna (ULL). Avda. Astrofísico Fco. Sánchez, s/n. 38206 San
Cristóbal de La Laguna, España, b Instituto Universitario de Bio-Orgánica Antonio González, Universidad de La Laguna
(ULL), Avda. Astrofísico Fco. Sánchez, 2, 38206 San Cristóbal de La Laguna, España, c Laboratory of Foodomics, Institute of Food Science Research, CIAL, CSIC, Nicolás Cabrera
9, Madrid, 28049, Spain
Keywords: phthalate ester, green solvent, microextraction, soft drink
Among the plastic additives applied in the manufacture of polymers, phthalic acid esters (PAEs)
constitute the most widely used to improve the properties of final products such as flexibility.
Due to the ease of PAEs to migrate from plastic materials in contact with food to the immediate
environment, the development of analytical protocols capable of quantitatively determining
these organic contaminants at low concentration levels, at which detrimental effects for human
health have been demonstrated, is extremely necessary. In this context, natural hydrophobic
deep eutectic solvents (NaHDESs) have emerged as a green alternative to reduce the use of
conventional extraction solvents, due to their inherent advantages such as high biocompatibility
and biodegradability, easy synthesis, high availability of raw materials and low cost. Moreover,
the application of small volume of NaHDES is compatible with the development of
microextraction techniques which resulted in a lower environmental impact. In this work, a
sustainable analytical method based on NaHDES as extraction solvent in vortex-assisted-
dispersive liquid-liquid microextraction has been developed for the extraction of 15 plastic
migrants from soft drinks. With this aim, different eutectic mixtures formed by the monoterpene
thymol and medium-chain fatty acids (octanoic acid and decanoic acid) in different molar ratios
have been firstly evaluated. Once the molar ratio that led to the highest absolute recovery of
PAEs was determined, other parameters that also showed a remarkable influence on extraction
efficiency were optimised by univariate protocol. The validation of the analytical methodology
was carried out for cold infusions and tonic waters, obtaining recovery values in the range 71–
124% and limits of quantification of the method of 0.025–1.25 μg/L. Analyses of real samples
were carried out using ultra-high performance liquid chromatography coupled to tandem mass
spectrometry for a reliable identification and quantification.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
54
Eutectic Mixtures as Promising Formulation Strategy for
Poorly Water-Soluble Drugs
Sarah El Masria,b, Sophie Fourmentina,*, Steven Ruellana, Maha Zakhourb and Lizette
Auezovab a Unité de Chimie Environnementale et Interactions sur le Vivant (UCEIV), EA 4492 SFR
Condorcet FR CNRS 3417, Université du Littoral-Côte d'Opale, Dunkerque, France
b Bioactive Molecules Research Laboratory, Doctoral School of Sciences and Technologies,
Faculty of Sciences, Lebanese University, Fanar, Lebanon.
*Corresponding author: [email protected]
Keywords: deep eutectic solvents, cyclodextrins, solubility.
According to the Biopharmaceutics Classification System (BCS), up to 70% of the new
chemical entities suffer from poor water solubility1. This represents a serious challenge to the
successful development of new therapeutics in the pharmaceutical industry2. Many approaches
have been employed to address the formulation challenges of poorly water-soluble drugs,
including drug delivery systems such as liposomes, cyclodextrins, solid lipid nanoparticles, …3.
In this context, deep eutectic solvents (DES), particularly those consisting of components from
natural origin, have emerged as solvents of great promise for pharmaceutical applications
because of their biodegradability, low toxicity and ability to dissolve chemically diverse
compounds, including water-insoluble ones4. In this study we have investigated, along with
classical DES, a new generation of DES called supramolecular deep eutectic solvents
(SUPRADES)5 based on cyclodextrins (CD), cage molecules able to encapsulate various guests
in their hydrophobic cavity and known for their use as functional pharmaceutical excipients to
enhance drug solubility3. We were interested in comparing the solubilizing potential of these
two classes and highlighting the benefit of combining the solubilization properties of a solvent
and a drug carrier. Our results showed a significant increase in solubility for the different active
pharmaceutical ingredients (API) studied, with factors ranging from 574 to 22440. For most of
the studied API, the solubility was either equally enhanced in both DES, or more enhanced with
the SUPRADES. Even upon water addition, the DES based on CD were more efficient in
retaining their solubilizing potential. We assumed that this is due to the formation of inclusion
complexes in the SUPRADES and their aqueous solutions; this hypothesis was validated by
NMR studies. We were also interested in eutectic mixtures based on API. Different mixtures
were prepared and investigated for their ability to maintain supersaturation in aqueous media.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
55
Extraction and Stabilization of Bioactive Compounds
From Aromatic Plants Using Sustainable NADES
Sílvia Rebocho a,*, Rita Craveiro a, Alexandre Paiva a,b, Ana Rita C. Duarte a,b
a LAQV-REQUIMTE, Departamento de Química, Faculdade Ciências e Tecnologia,
Universidade Nova de Lisboa, 2829-516 Caparica, Portugal b Des Solutio, Avenida Tenente Valadim nº 17 2º F, 2560-265 Torres Vedras, Portugal
Keywords: Natural deep eutectic systems, antioxidants, extraction, Salvia officinalis.
This work describes an innovative sustainable approach for the extraction of individual
bioactive constituents from aromatic plants, particularly from sage (Salvia officinalis). This
plant is rich in unique and highly concentrated essential oils, with extremely attractive
properties. The most prevalent compounds in this plant are the phenolic compounds, as caffeic
acid and its derivatives as rosmarinic acid, and the diterpenes such as carnosic acid and
carnosol, and the triterpene ursolic acid. Properties such as antioxidant, anti-inflammatory,
antimicrobial, anti-cancer, antitumor and applications with health benefits are very interesting
to investigate, especially towards new oncology and neurodegenerative treatments, as
Alzheimer’s disease.
In this work, we use natural deep eutectic systems (NADES) to design more sustainable
extraction processes. Combinations of compounds such as glucose, trehalose, lactic acid,
glycerol, menthol or betaine, are used in adequate molar ratio to form our systems. The
screening of the most promising systems for extraction was carried out with two methods: heat
and stirring (HS) and ultrasound assisted extraction (UAE), under the same conditions of
temperature (40°C), time (1h) and solid/liquid ratio (1:20). In general, the most promising
results were reach using UAE. The results revealed that in the extracts of menthol based DES,
carnosic acid and carnosol are the predominant compounds, with the values of 14.27±0.81 mg
of carnosic acid/g sage and 1.73 ± 0.09 mg of carnosol/g sage for the system menthol: myristic
acid (8:1). On the other hand, rosmarinic acid was not detect in this extract, which revealed, for
this system, a selectivity for more nonpolar compounds. Lactic acid based systems revealed
more promising results for the extraction of rosmarinic acid, namely for lactic acid:glucose
(5:1) and lactic acid:proline (3:1), with concentrations of 1.76±0.21 and 2.91±0.13 mg of
rosmarinic acid/g sage, respectively. Thus, a simultaneous extraction of the compounds, with
different polarities is being explored, taking advantage of the selectivity of the systems.
Acknowledgements: This project has received funding from the European Union’s Horizon 2020 (European
Research Council) under the grant agreement No ERC-2016-CoG 725034. This work was also supported by the
Associate Laboratory for Green Chemistry - LAQV which is financed by national funds from FCT/MCTES
(UIDB/50006/2020 and UIDP/50006/2020).
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
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Delivery of Deep Eutectic Solvents Comprising
Nonsteroidal Anti-inflammatory Drugs using Biopolymer-
Based Systems
Sónia N. Pedro a, *, Maria S. M. Mendes a, Bruno Miguel Neves b, Mara G. Freire a, Armando
J. D. Silvestre a and Carmen S. R. Freire a a CICECO - Aveiro Institute of Materials, Department of Chemistry, University of Aveiro,
Aveiro, Portugal b Department of Medical Sciences and Institute of Biomedicine – iBiMED, University of
Aveiro, 3810-193 Aveiro, Portugal
Keywords: Active pharmaceutical ingredients, nonsteroidal anti-inflammatory drugs, deep
eutectic solvents, drug delivery, controlled release.
Nonsteroidal anti-inflammatory drugs (NSAIDs) are widely prescribed in the treatment of pain
conditions, including arthritic ones. However, their usefulness is mainly limited by dose-
dependent adverse effects, such as gastrointestinal damage, cardiovascular risks and renal
toxicity. These effects can be minimized by appropriate topical delivery systems, which deliver
the active pharmaceutical ingredients (APIs) locally, further reducing the systemic
concentration. However, a main disadvantage of topical drug delivery systems comprising
NSAIDs, such as patches, is their difficulty to convey the API through the stratum corneum.
With this in mind, we have considered the use of deep eutectic solvents (DES) as alternative
solvents to increase the solubility, therapeutic efficacy and delivery of NSAIDs, such as
ibuprofen and ketoprofen. Aiming to unveil the DES influence on the NSAIDs efficacy, we
have studied the anti-inflammatory properties of these formulations in vivo in Raw 264.7
macrophages cell lines. Finally, we have successfully encapsulated these formulations in
alginate-based systems, obtaining good encapsulation efficiencies (>66%) for the NSAIDs
studied and controlled release profiles over a 2-hour period at body’s temperature. The DES-
based systems here developed sustain the promising ability of DES to improve not only the
APIs characteristics but also the biopolymer systems’ properties, enabling more effective drugs
delivery.
Acknowledgments: This work was developed within the scope of the project CICECO-Aveiro Institute of
Materials, UIDB/50011/2020 & UIDP/50011/2020, financed by national funds through the FCT/MEC and when
appropriate co-financed by FEDER under the PT2020 Partnership Agreement. S. N. Pedro acknowledges the PhD
grant SFRH/BD/132584/2017.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
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ATR-IR Spectroscopy for Rapid Quantification of Water
Content in Deep Eutectic Solvents Suha Elderderi a, b, Charlotte Leman-Loubière c, Laura Wils c, Hugh J. Byrne e, Igor Chourpa a,
Cécile Enguehard-Gueiffier c, Emilie Munnier a, Abdalla A. Elbashir f, Leslie Boudesocque-
Delaye c, Franck Bonnier a,*
a Université de Tours, Faculté de pharmacie, EA 6295 NMNS, Tours, France b University of Gezira, Faculty of Pharmacy, Gezira, Sudan.
c Université de Tours, EA 7502 SIMBA, Tours, France e FOCAS Research Institute, TUDublin, Dublin 8, Ireland
f University of Khartoum, Faculty of Science, Khartoum, Sudan
Keywords: Infrared spectroscopy, Attenuated Total Reflectance, multivariate analysis, water
quantification, deep eutectic solvent
NADES have a wide range of applications, mainly as solvents for plant extractions,
biocatalysis, and nanoparticle synthesis. Water content is very critical, impacting significantly
on NADES properties and can lead to NADES disruption. NADES are hygroscopic; therefore
controlling H2O concentration appears essential for their optimal use after storage. In the
present study, Attenuated Total Reflectance–infrared spectroscopy (ATR-IR) coupled to
multivariate analysis, namely Partial Least Squares Regression (PLSR), was investigated as a
rapid, label free and cost-effective tool for measuring the water concentration of NADES. ATR-
IR enables direct molecular characterisation of samples without pre-analytical protocols. A
drop can be deposited on the ATR crystal to collect a spectral signature specific to NADES
chemical composition. Betaine_Glycerol, Choline Chloride_Glycerol and Glucose_Glycerol
were selected as NADES model systems. For the purpose of the study, a range of water
concentrations between 0% (w/w) and 40% (w/w) was prepared for each model. PLSR results
demonstrate the robustness of the analysis, yielding R2 values of 0.99 and Root Mean Square
Error of Cross Validation (RMSECV) of respectively 0.2602% w/w, 0.6883% w/w and
0.7034% w/w. Moreover, the percentage relative error achieved is below a 5% threshold. This
preliminary work shows the potential of ATR-IR spectroscopy as a tool for water quantification
in the 3 NADES systems studied. Such analytical protocols can support the development of
green chemistry, which currently represents a major focus of interest in both research and
industrial environments.
Reference: S. Elderderi et al. ATR-IR spectroscopy for rapid quantification of water content in deep eutectic
solvents, Journal of Molecular liquids. 311 (2020) 113361. https://doi.org/10.1016/j.molliq.2020.113361.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
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POSTER PRESENTATIONS
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
59
Determination of the Enthalpy of Fusion of Choline
Chloride Using Dissolution and Titration Calorimetry
Adriaan van den Bruinhorst*, Margarida Costa Gomes
École Normale Supérieure Lyon, Laboratoire de Chimie, 46 allée d’Italie, 69364 Lyon, FR
Keywords: fusion properties, choline chloride, isothermal calorimetry, excess enthalpy
Deep eutectic systems (DESs) are mixtures with a eutectic temperature significantly below the
ideal eutectic point that can be used as alternative liquid media. The liquid window of a DES is
determined by the fusion properties of its pure constituents and by the intermolecular
interactions in the liquid phase. Choline chloride (ChCl) is one of the most commonly studied
DES constituents, but it decomposes before melting thus rendering the fusion properties
inaccessible by direct experimental measurement1. We therefore aim to determine the enthalpy
of fusion indirectly using isothermal dissolution and titration calorimetry.
To date, two enthalpies of fusion were reported for ChCl: 4.3 kJ mol−1 from solid–liquid
equilibria1 and 29.8 kJ mol−1 from the enthalpy of dissolution2. They differ significantly owing
to various factors. Non-idealities in the free energy of mixing were omitted1 or assumed to be
composition and solvent independent2, and solid–solid transition of ChCl was not considered2.
A re-evaluation of the ChCl mixing behaviour and the derived fusion properties is pertinent.
Using the thermodynamic cycle above, we explored the mixing behaviour of ChCl in a series
of diols via isothermal dissolution calorimetry and isothermal titration calorimetry. The
thermodynamic consistency was validated using solid–liquid equilibrium data, considering the
solid–solid transition of ChCl. Via this route, we could quantify the contributions of the
intermolecular interactions and the fusion properties to the (non-)ideality of the eutectic phase
behaviour for mixtures containing ChCl.
References:
1 L. Fernandez, L. P. Silva, M. A. R. Martins, O. Ferreira, J. Ortega, S. P. Pinho and J. A. P. Coutinho,
Fluid Phase Equilib., 2017, 448, 9–14.
2 P. López-Porfiri, J. F. Brennecke and M. Gonzalez-Miquel, J. Chem. Eng. Data, 2016, 61, 4245–4251.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
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Development of high barrier electrospun poly(3-
hydroxybutyrate-co-3-hydroxyvalerate) films using deep
eutectic solvents technology for food packaging
applications
Ahmet Ozan Basar, Cristina Prieto, Jose M. Lagaron*
Novel Materials and Nanotechnology Group, IATA-CSIC, Valencia, Spain
Keywords: DES, PHBV, electrospinning, food packaging, barrier properties, active
properties
In the present study, high barrier electrospun poly(3-hydroxybutyrate-co-3-hydroxyvalerate)
(PHBV) films will be developed with the use of novel deep eutectic solvents (DES) technology
for food packaging applications. PHBV is a biodegradable aliphatic polyester produced by
microorganisms. However, its application in food packaging sector has been also limited due
to several drawbacks, such as weak mechanical properties, poor thermal stability, and narrow
processing windows [1]. DES, on the other hand, are the new generation of solvents with several
unique properties, such as negligible volatility, broad range of polarity, high solubilization and
stabilization capacity for a wide range of compounds, and as well as biodegradability,
sustainability, plasticization ability, low cost, and simple preparation [2]. Hence, this study aims
to improve PHBV film properties with the addition of DES via electrospinning technique. For
this, different formulations of DES will be selected to plasticize PHBV in order to achieve films
that can withstand thermoforming. Furthermore, thermoformable active electrospun PHBV
films containing natural antioxidant, antimicrobial, and as well as nano-oxygen scavenger
particles will also be developed for novel use in the food packaging applications using DES as
solvents. After the production, the characterizations of the electrospun structures will be carried
out in terms of morphological by scanning electron microscopy (SEM); size and distribution of
the particles by transmission electron microscopy (TEM); composition and interactions by
attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR); thermal
properties by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC);
mechanical properties; water vapour permeability and water sorption by gravimetric methods;
oxygen scavenging properties by oxygen absorption assay based on fluorescence; antioxidant
capacity by DPPH and ABTS methods; and lastly the antimicrobial performance by the
bactericidal inhibitory method.
References:
[1] Yu, H. et al., RSC Advances, 2014, 4, 59792.
[2] Y. Dai et al., Food Chemistry, 2015, 1870 14–19.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
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Innovative Material for the Extraction of Alkylphenols
from Animal-based Milk Samples
Álvaro Santana-Mayor a,*, Ruth Rodríguez-Ramos a,
Bárbara Socas-Rodríguez b, and Miguel Ángel Rodríguez-Delgado a
a Departamento de Química, Unidad Departamental de Química Analítica, Facultad de
Ciencias, Universidad de La Laguna (ULL), Avda. Astrofísico Fco. Sánchez, s/n, 38206 San
Cristóbal de La Laguna, España b Laboratory of Foodomics, Institute of Food Science Research, CIAL, CSIC, Nicolás Cabrera
9, 28049 Madrid, Spain
Keywords: alkylphenols, deep eutectic solvent, milk, liquid chromatography
Alkylphenols (APs) are commonly used as additives in the plastic industry as well as the
production of textiles, paper or utilised as surfactants in industrial or agricultural applications,
among others. The widespread use of these compounds, their persistence and their possible
effects on human health and the environment have alerted the scientific community and popular
society. APs represent an important group of endocrine disruptors that can mimic or induce
similar responses to the natural hormones of organisms and not only alter their reproductive
system, but also cause other serious damages at low concentration levels. Thus, the evaluation
of those matrices susceptible to suffer APs migration from the packaging that contains them is
of vital importance to guarantee public and environmental health. Milk is a product highly
consumed by the population due to it is an important source of proteins and sugars, as well as
other important nutrients. Therefore, guaranteeing its quality and safe consumption is crucial.
Migration of APs from plastic materials can occur throughout the entire food chain including
processing and storage, and even transportation. In this sense, and added to the complexity of
milk samples, the analysis of these compounds can be a real challenge. In this regard, deep
eutectic solvents (DESs) have emerged as promising solvents and replacement of toxic organic
solvents and have been applied in many fields including industry and medicine, but also have
demonstrated their potential as extraction agents in analytical chemistry procedures. With the
aim of improving extraction methods for the extraction of APs in milk matrices towards greener
and sustainable protocols, in this work a new method based on a DES-lab-made material has
been developed for the analysis of APs in animal-based milk samples. The separation and
quantification of the target analytes were carried out by ultra-high performance liquid
chromatography coupled to a tandem mass spectrometry system. The whole methodology was
thoroughly optimised and validated for the determination of APs in animal-based milk matrices.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
62
NADES, a new class of cryoprotectant agents inspired by
nature
Ana Rita Jesus a, Alexandre Paiva a,*, and Ana Rita C. Duarte a
a LAQV@REQUIMTE, Departamento de Química, Faculdade de Ciências e Tecnologia,
Universidade Nova de Lisboa, 2829-516, Caparica, Portugal
Keywords: cryopreservation, natural products, eutectic systems
Cell cryopreservation with high rates of post-thawing survival remains a major challenge and
many environmental factors can seriously affect cellular function during the freezing process
such as the cryoprotectant agents (CPAs). [1] Natural Deep Eutectic Solvents (NADES have
emerged in the last decade as alternative solvents for many applications. [2] Some components
are found in animals living in extreme cold environments and are involved in the hibernation
process allowing them to survive during winter time,[3] which inspired us to develop NADES
as a new class of CPAs [4]. Herein, we present the successful cryopreservation of mammalian
cells. Cytotoxicity evaluation has showed that these NADES are non-toxic with IC50 values
ranging from 1.0-2.2 M. Differential Calorimetry Scanning (DSC) was used to evaluate the
thermal behavior of these eutectic systems, showing the strong effect on the water
crystallization/freezing and melting processes. Thus, NADES are able to reduce the formation
of ice crystals, and therefore reducing the cell damage during the freezing/thawing processes.
Post-thawing studies showed that some of these systems are in fact able to efficaciously
cryoprotect cells, resulting in high-rates of post-thawing cell survival.
References
[1] B. Stokich, Q. Osgood, D. Grimm, S. Moorthy, N. Chakraborty, M. A. Menze, Cryobiology 69 (2014) 281–
290
[2] A. Paiva, R. Craveiro, I. Aroso, M. Martins, R. L. Reis, A. R. C. Duarte, ACS Sustainable Chemical
Engineering. 2 (2014) 5, 1063–1071
[3] A. Gertrudes, R. Craveiro, Z. Eltayari, R. L. Reis, A. Paiva, A. R. C. Duarte, ACS Sustainable Chemistry
Engineering, 5 (2017) 9542−9553
[4] V. I.B. Castro, R. Craveiro, J. M. Silva, R. L. Reis, A. Paiva, A. R. C. Duarte, Cryobiology, 83 (2018) 15-26
Acknowledgements
This project has received funding from the European Research Council (ERC) under the European Union’s
Horizon 2020 Research and Innovation Programme, under grant agreement No ERC-2016-CoG 725034. This
work was also supported by the Associate Laboratory for Green Chemistry – LAQV, financed by national funds
from FCT/MCTES (UID/QUI/50006/2019) and by FCT/MCTES through the project CryoDES (PTDC/EQU-
EQU/29851/2017).
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
63
Kraft lignin solubility in aqueous solutions of deep eutectic
solvents
Filipe H. B. Sosaa,b, Andre M. da Costa Lopes a,c*, João A. P. Coutinhoa, Mariana C. Costab. aCICECO, Department of Chemistry, University of Aveiro, Campus Universitário de
Santiago, Aveiro, Portugal. bSchool of Chemical Engineering (FEQ), University of Campinas (UNICAMP), Campinas,
Brazil. cCECOLAB - Collaborative Laboratory Towards Circular Economy, R. Nossa Senhora da
Conceição, 3405-155 Oliveira do Hospital
Keywords: deep eutectic solvents, Kraft lignin, solubility, hydrotropy, depolymerization, non-
derivatization
Pulp and paper companies have shown increasing interest in Kraft lignin valorization rather
than its combustion to enhance carbon source (wood) efficiency and process sustainability.
However, the low solubility of Kraft lignin and the lack of efficient and environmentally safe
solvents for its dissolution is hindering successful developments of new applications. A
promising approach for the dissolution of this macromolecule may rely on the use green
solvents, such as deep eutectic solvents (DES). In this study, the ability of eleven DES based
on cholinium chloride ([Ch]Cl) as hydrogen bond acceptor (HBA) combined with alcohols or
carboxylic acids as hydrogen bond donors (HBDs) to dissolve Kraft lignin and their potential
to chemically modify it was examined. The influence of the chemical structure of HBDs,
HBD:HBA molar ratio, and water content on Kraft lignin solubility were investigated (313.15
K). The obtained results showed that HBDs play an important role in Kraft lignin dissolution,
and the efficiency is governed by its chemical nature (alcohol or carboxylic), chain length, and
molar ratio to HBA. The Kraft lignin solubility was enhanced by increasing both the HBD’s
carbon chain length and the molar ratio. Among studied solvents, [Ch]Cl:HEXA (1,6-
hexanediol) and [Ch]Cl:MaleA (maleic acid) were the best solvents for kraft lignin dissolution,
allowing 32.99 and 34.97 wt % solubility at 313.15 K, respectively. Moreover, the addition of
water negatively affected the lignin solvation power of DES. Thermal treatments of Kraft lignin
at 393.15 K showed that carboxylic acid-based DESs promote chemical modifications to lignin,
especially the disruption of several C−O bonds (e.g. β-O-4), while alcohol-based DESs were
found to be non-derivatizing solvents by maintaining the lignin chemical structure. These
results show the versatility of DES, which, depending on the HBA and HBD combination, and
their chemical nature, may offer distinct scenarios for lignin valorization.
Acknowledgments: This work was financed in part by the CAPES, FAPESP, CNPq, and partially developed
within the scope of the project CICECO, FCT Ref. UIDB/50011/2020 & UIDP/50011/2020.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
64
Deep Eutectic Systems as Potential Solubilization Vehicles
for Mometasone Furoate and Dexamethasone
Â. Rochaa, A. Paivaa,*, T. Alvesb, L. Godinhoc, F. Oliveiraa, I. Sá-Nogueirac, J. Martob, H.
Ribeirob, A. Duartea a LAQV-REQUIMTE, Department of Chemistry, NOVA School of Science and Technology,
NOVA University of Lisbon, Campus de Caparica, 2829-516 Caparica, Portugal b Research Institute for Medicines (iMed.ULisboa), Faculty of Pharmacy, University of
Lisbon, Av. Prof. Gama Pinto,1649-003 Lisboa, Portugal c UCIBIO, Department of Life Sciences, NOVA School of Science and Technology, NOVA
University of Lisbon, Campus de Caparica 2829-516 Caparica, Portugal
Keywords: Deep eutectic systems, Active pharmaceutical ingredients, Solubility, Emulsions
Mometasone furoate (MF) and dexamethasone (DEX) are corticosteroids commonly used in
the treatment of allergies, skin diseases and autoimmune diseases due to their anti-inflammatory
properties. Despite their widespread use these corticosteroids are hindered by their very low
water solubilities.
Deep eutectic systems (DES) are defined as a mixture of two or more compounds, which at a
specific molar ratio present a strong depression of the melting point when compared with those
of its individual components. DES which are liquid at room temperature can be used as solvents.
These systems are advantageous because they can be easily prepared in high purity at low cost,
and, when composed by natural compounds, are inherently biodegradable and have low
toxicity. DES have been successfully employed in the solubilization of several active
pharmaceutical ingredients (APIs) due to their high stabilization and solubilization power. In
addition, by changing the components of the eutectic system, the solubility, permeation and
absorption of APIs can be increased by several folds, when compared with water, or tuned to
suit the specific needs of each application.
Herein, we report the use of DES based on natural organic acids and terpenes for the
solubilization of MF and DEX. In some cases, DES are able to dissolve up to 2.3 times the
amount of drug observed for Transcutol® P, one of the most commonly used co-solvents in
pharmaceutical formulations. These systems also exhibit interesting antimicrobial activities and
can potentially be used as preservatives. As proof of concept, MF solubilized in DES was used
to prepare o/w emulsions for skin delivery. The study included optimization of the emulsions
and subsequent characterization, namely pH, droplet size, rheology and in vitro permeation
studies.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
65
NADES as emerging sustainable systems for the
extraction and stabilization of bioactive compounds from
Rosemary
Vieira C.a,*, Craveiro R.a, Paiva, A.a,b, Duarte, A.R. a,b, Rebocho S.a a LAQV-REQUIMTE, Departamento de Química, Faculdade Ciências e Tecnologia,
Universidade Nova de Lisboa, 2829-516 Caparica, Portugal b Des Solutio, Avenida Tenente Valadim nº 17 2ºF, 2560-265 Torres Vedras
Keywords: Natural deep eutectic systems, extraction, Rosmarinus officinalis, antioxidant
activity.
Rosemary (Rosmarinus officinalis) is a natural source of bioactive compounds and essential oil
with high antioxidant activity. It has been used since ancient times as a medicinal herb and
currently is widely used due to its inherent pharmacological and therapeutic potential.
Regarding this, the demand for these compounds in pharmaceutical, food, and cosmetic
industries increased the value of this plant. The development of new promising and sustainable
techniques of extraction has received a lot of attention. Recently, a new class of green solvents,
known as natural deep eutectic systems (NADES) came to offer suitable systems, with high
solvent power, low toxicity, biodegradability and lower environmental impact. The present
work aims to extract the principal bio compounds from rosemary, such as rosmarinic acid,
carnosol, and carnosic acid using these alternative solvents. For that, a NADES screening was
made, using the same conditions of temperature, S/L molar ratio and time, under two different
methods, heat and stirring (HSE) and ultrasound-assisted extraction (UAE), to test the solvent
efficiency. In terms of total phenolic content, best results were achived with lactic acid:glucose
(5:1), reaching up to 2% mg GAE/mg rosemary. The quantification of the compounds was also
made, with the most promising results for rosmarinic acid 0.833 mg/g rosemary and carnosol
1.751 mg/g rosemary using menthol:myristic acid (8:1), and carnosic acid 6.722 mg/g rosemary
with menthol:lauric acid (2:1). It was demonstrated that the polarity of the systems interferes
with the selectivity of the extracted compounds, so a fractional extraction with opposite
character systems was performed. Preliminary results demonstrate that, in some cases, the
combined systems showed better capability of extraction, comparative to the individual
systems.
Acknowledgements: This project has received funding from the European Union’s Horizon 2020 (European
Research Council) under grant agreement No ERC-2016-CoG 725034; This work was also supported by the
Associate Laboratory for Green Chemistry - LAQV which is financed by national funds from FCT/MCTES
(UIDB/50006/2020 and UIDP/50006/2020).
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
66
Evaluation of deep eutectic systems as alternative solvents
in conservation and restoration
Cláudio Fernandesa, Ana Rita C. Duarte a,* a LAQV, REQUIMTE, Departamento de Química da Faculdade de Ciência e Tecnologia,
Universidade Nova de Lisboa, 2829-516 Caparica, Portugal
Keywords: varnishes; Dammar; Mastic; NADES; Polarity; Solubility; Nile red; physical
properties; thermodynamic properties
Natural deep eutectic solvents (NADES) are considered as green solvents and due their
promising sustainability, they have been applied in many research fields. In this study the main
goal is to use some NADES systems to replace the traditional solvents commonly used
conservation and restoration in the removal of unwanted varnishes layers of a paint. The toxicity
potential of these traditional solvents, such as toluene or acetone is well known in chemistry
fields. For the replacement is hence important to have the knowledge about the intrinsic
physicochemical properties of a solvent that may act as substitute. Polarity and solubility are
then proposed as the best tools required for this study. Using Nile red as a dye, it may confirm
some similarity between the polarity of deep eutectic and traditional solvents. On another hand,
according to the polarity, it is possible to determine the best solvent to solubilize the natural
resin varnishes. Besides that, the use of some arithmetic models can also be applied to estimate
the critical or thermodynamic properties, as they are useful tools to predict the behaviour of
solvents, which can establish certain conditions for their application. We have further proven
that it is indeed possible to dissolve natural varnishes such as Dammar or Mastic in hydrophobic
DES, such as Menthol : Lauric acid, Menthol : Decanoic acid or Menthol : Thymol.
Acknowledgements:
This project has received funding from the European Union’s Horizon 2020 (European Research Council) under
grant agreement No ERC-2016-CoG 725034 and was supported by the Associate Laboratory for Green Chemistry-
LAQV which is financed by national funds from FCT/MCTES (UIDB/50006/2020).
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
67
Strategies for the implementation of extractions using
Natural Deep Eutectic Systems at an industrial scale
Rente D.1, Paiva A.1,2 Duarte A.1,2,* 1LAQV, REQUIMTE, Departamento de Química da Faculdade de Ciências e Tecnologia,
Universidade Nova de Lisboa, 2829-516 Caparica, Portugal 2Des Solutio, Avenida Tenente Valadim, nº 17, 2ºF, 2560-275 Torres Vedras, Portugal
Keywords: Extraction, NaDES, Residues, Scale-up
The potential of Natural Deep Eutectic Solvents (NaDES) for the extraction of a wide array of
phytochemicals has been thoroughly explored in literature. Nevertheless, their application at an
industrial scale is still far from being widespread. While problems associated with different
extraction methods exist, such as reactor geometry, type of mixing (ultrasounds, mechanical,
microwave) inside the reactor, energetic costs, during scale up, a large part has to do with the
choice of NaDES to be used. These problems arise mainly from the physicochemical properties
of NaDES such as its characteristic higher viscosity that may cause problems in handling or
mass transfer phenomena as well as production costs. Potential solutions to these problems
could be modulating the properties of the NaDES by controlling the ratio of the hydrogen bond
donor to the hydrogen bond acceptor or controlling properties inside the reactor by optimizing
extraction times, temperatures, solid to liquid ratios, or the amount of water added to enhance
the extraction yields. The aim of this work is to identify barriers to the scale up of extraction
using NaDES and offer potential solutions.
Acknowledgements:
This project has received funding from the European Union’s Horizon 2020 (European Research Council) under
grant agreement No ERC-2016-CoG 725034. This work was supported by the Associate Laboratory for Green
Chemistry- LAQV which is financed by national funds from FCT/MCTES (UID/QUI/50006/2019). Alexandre
Paiva would like to thank the financial support of FCT/MCTES under the project IF/01146/2015
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
68
The Liquid Structure Of Deep Eutectic Solvents Based On
Different Tartaric Acid Enantiomers From Neutron
Diffraction And Atomistic Modelling
Elly K. Bathke a*, Daniel T. Bowronb and Karen J. Edlerc
a* [email protected], Department of Chemistry, University of Bath, Claverton Down, Bath
BA2 7AY, UK, b [email protected] ISIS Neutron and Muon Source, Science and Technology
Facilities Council, Rutherford Appleton Laboratory, Didcot OX11 0QX, UK, c [email protected] Department of Chemistry, University of Bath, Claverton Down, Bath
BA2 7AY, UK
The structure of Deep Eutectic Solvents (DES) is dominated by H-bonds formed between the
component molecules. In this the structure of the components play an important role through
effects such as access to hydrogen bonding sites and steric hindrance, leading to changes in
physicochemical properties such as melting point and viscosity between DES consisting of
similar but slightly different precursors. Water has also been found to influence their properties
and has to be considered due to the hygroscopic nature of most DES, but which can
also be used to modify the DES properties for specific applications.
Here we present the structure of L-Tartaric Acid:Choline Chloride (molar ratio 1:2), DL-
Tartaric Acid:Choline Chloride (molar ratio 1:2) and L-Tartaric Acid:Choline Chloride:Water
(molar ratio 1:2:2) DES through total neutron scattering and EPSR modelling. We investigate
the influence of using either a single enantiomer of Tartaric Acid or the racemic mixture, both
of which are widely available, as well as the influence of the addition of 2 moles of water on
the structure.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
69
Solid-liquid equilibrium of eutectic solvents composed by
choline chloride under high pressures.
Fernanda P Pelaquim a, Mariana C. Costa a,*, Irede A. L. Dalmolin b a University of Campinas, School of Chemical Engineering, Campinas, São Paulo, Brazil
b Universidade Tecnológica Federal do Paraná, UTFPR, Francisco Beltrão, Paraná, Brazil
Keywords: Eutectic solvents, Solid-liquid equilibrium (SLE), high pressure, phase diagrams,
variable-volume view cell.
Greener technology is one of the most important topics to be developed by chemistry, since it
aims to reduce the negative influence of human being in the world, which acts to decrease the
environmental pollution mainly caused by our lifestyle. Deep eutectic solvents (DESs) have
appeared as an alternative to some current aggressive organic solvents [1] and they are receiving
great attention. According to Abbott et al. (2004) [2] DESs are mixtures of amides with
quaternary ammonium salts that had melting point much lower than their pure compounds. This
melting point lowering happens due to formation of a hydrogen bonding complex between a
hydrogen bonding donor (HBD) and a hydrogen bonding acceptor (HBA) at a well-defined
stoichiometric ratio close or equal to the eutectic composition of the mixture. In 2018, Martins
et al. [3] defined that DESs are not new compounds or pseudo-pure compounds, but just
mixtures. So, DES should be a mixture of pure compounds for which the temperature of the
eutectic point is many degrees below the temperature of the eutectic point of ideal liquid
mixture. Otherwise, they should be called just eutectic solvent (ESs). Considering this new
definition and ES uses, it is important to comprehend their phase equilibria at ambient pressure
[4] and also under high pressure. So, this work aimed to determine the solid-liquid equilibrium
of the eutectic solvent composed by choline chloride (1) + ethylene glycol (2) and choline
chloride (1) + 1,3 propanediol (2) at pressures between 60 and 250 bar, 1:2 molar ratio and 4%
water content. The pressure versus temperature diagrams were constructed from experimental
data determined using a high-pressure variable-volume view cell. It was possible to observe a
linearity behavior in both phase diagrams. The increase of pressure implied in a slight
temperature increase, getting around 22 °C, as expected for choline chloride (1) + ethylene
glycol (2).
References:
1. Dai, Y.; van Spronsen, J.; Witkamp, G.J.; Verpoorte, R.; Choi, Y.H. Natural deep
eutectic solvents as new potential media for green technology. Anal. Chim. Acta 2013.
2. Abbott, A.P.; Capper, G.; Davies, D.L.; Rasheed, R.K.; Tambyrajah, V. Novel solvent
properties of choline chloride / urea mixtures. R. Soc. Chem. 2003, 70–71.
3. Martins, M.A.R.; Pinho, S.P.; Coutinho, J.A.P. Insights into the Nature of Eutectic and
Deep Eutectic Mixtures. J. Solution Chem. 2018, 1–21.
4. Crespo, E.A.; Silva, L.P.; Martins, M.A.R.; Bülow, M.; Ferreira, O.; Sadowski, G.;
Held, C.; Pinho, S.P.; Coutinho, J.A.P. The Role of Polyfunctionality in the Formation of
[Ch]Cl-Carboxylic Acid-Based Deep Eutectic Solvents. Ind. Eng. Chem. Res. 2018, 57, 11195–
11209.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
70
Solubility, stability and cytotoxic evaluation of different
anti-tuberculosis drugs combined in therapeutic liquid
mixtures
Filipa Santos a, Ana Rita C. Duarte a,*
a LAQV, REQUIMTE, Departamento de Química da Faculdade de Ciências e Tecnologia,
Universidade Nova de Lisboa, 2829-516 Caparica, Portugal
Keywords: therapeutic liquid mixtures, tuberculosis
Tuberculosis continues to be one of the deathliest infectious diseases worldwide and, in 2019,
the average of deaths was 1.2 million. In spite, of this disease being considerable treatable the
treatment involves a prolonged regimen of various antibiotics, which may cause serious
adverse effects and leading to a low compliance of the treatment by the patient, contributing
for the ineffectiveness of the treatment and emergence of drug resistance. The approaches
used for preventing and treating tuberculosis infection and disease are the same, since their
development at around 50 years ago. Due to that and to the emergence of drug resistance to
the various antibiotics used it is surely needed a breakthrough investigation to find
alternatives able to rapidly reduce the incidence to tuberculosis, mainly in low-burden
countries.
In this work, we use green chemistry approaches such as preparation of therapeutic liquid
mixtures with anti-tuberculosis drugs currently used in therapy for the improvement of their
performance and therefore to reduce the dose administered and incidence of severe adverse
effects. Previously reported therapeutic liquid mixtures (with ethambutol and arginine) were
used, and combined with first-line drugs anti-tuberculosis to evaluate its solubility in
phosphate buffered saline, stability (by NMR and UV-vis), in vitro cytotoxicity and
permeability in human alveolar epithelial cells (A549).
Acknowledgements:
This project has received funding from the European Union’s Horizon 2020 (European
Research Council) under grant agreement No ERC-2016-CoG 725034 and was supported by
the Associate Laboratory for Green Chemistry-LAQV which is financed by national funds from FCT/MCTES
(UIDB/50006/2020).
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
71
Deep eutectic systems: new methodologies for toxicity
assessment
Filipe Oliveira a, Inês João Ferreira a, Sara Valente a, Alexandre Paiva a, Mario Diniz a, Ana
Rita C. Duarte a* a LAQV@REQUIMTE, Departamento de Química, Faculdade de Ciências e Tecnologia,
Universidade Nova de Lisboa, 2829-516 Caparica, Portugal, *[email protected]
Deep eutectic solvents (DES) are a mixture of two or more components, combining a hydrogen
bond acceptor (HBA) and a hydrogen bond donor (HBD), resulting in a mixture with a melting
point lower than those of its individual components. The deep melting point decrease lead to
the opportunity of having a mixture of solid compounds in the liquid form at room temperature
[1,2]. These systems have been emerging as a sustainable alternative to conventional organic
solvents in a wide range of applications [3].
The toxicology assessment of a system/compound is essential for the protection of human
health and the environment, however, currently there is a lack of studies concerning eutectics
biodegradability and biocompatibility. DES toxicity profile is depended on their concentration,
individual components, and interaction with living organisms. Therefore, the intuit of this work
is to establish innovative methodologies for the toxicity assessment of DES in two different
contexts: i) a pharmacological context where the system’s cytotoxic effect is tested at
concentrations that can be used in the pharmaceutical industry; ii) and also in an environmental
context where the system’s ecotoxicity is tested considering measured environmental
concentrations (MEC). The eutectic-promoted cytotoxic effect was quantitatively assessed via
cell viability assays in a mouse fibroblast continuous cell line (L929) and human keratinocytes
cell line (HaCat), here working as a preliminary safety indicator [4]. The ecotoxicity studies
were performed in two animal models: zebrafish and mussels, simple models recurrently used
in environmental toxicology assessment [5][6]. Furthermore, the activity of different key
enzymes involved in cell protection against toxic compounds, namely in antioxidant pathways,
oxidative stress, and against changes in cell membrane structure, were also considered. The
promising results herein reported revealed DES as systems with tailor-made toxic effect, were
the choice and fine-tuning of its individual components should be carefully considered in a
situation manner. Therefore, the main goal of this work was to establish methodologies for DES
toxicity assessment. Acknowledgments
The research leading to these results has received funding granted through the project Des.solve (ERC
consolidator), ERC-2016-COG 725034. This work was supported by the Associate Laboratory for Green
Chemistry- LAQV which is financed by national funds from FCT/MCTES (UIDB/50006/2020)
References
1. Abbott AP, Capper G, Davies DL, Rasheed RK, Tambyrajah V. Novel solvent properties of choline
chloride/urea mixtures. Chem Commun. 2003;9(1):70–1.
2. Abbott AP, Boothby D, Capper G, Davies DL, Rasheed RK. Deep Eutectic Solvents formed between
choline chloride and carboxylic acids: Versatile alternatives to ionic liquids. J Am Chem Soc. 2004;126(29):9142–
7.
3. Paiva A, Craveiro R, Aroso I, Martins M, Reis RL, Duarte ARC. Natural deep eutectic solvents - Solvents
for the 21st century. ACS Sustain Chem Eng. 2014;2(5):1063–71.
4. ISO/EN10993-5. Biological Evaluation of Medical Devices - Part 5: Tests for in vitro cytotoxicity. Vol.
5. 2009. p. 1–34.
5. Valavanidis A, Vlachogianni T. Ecotoxicity Test Methods and Ecological Risk Assessment. Aquatic and
Terrestrial Ecotoxicology Tests under the Guidelines of International Organizations. www.chem-tox-ecotox.org.
2015;1:1–29.
6. Rubinstein AL. Zebrafish assays for drug toxicity screening. Vol. 2, Expert Opinion on Drug Metabolism
and Toxicology. Taylor & Francis; 2006. p. 231–40.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
72
Understanding the molecular level behaviour of eutectic
systems
Hugo Monteiro1, Alexandre Paiva1 and Ana Rita C. Duarte1 1LAQV-REQUIMTE, Chemistry Department, NOVA SCHOOL OF SCIENCE AND
TECHNOLOGY, 2829-516 Caparica, Portugal
Keywords: DES, MD simulations, Green Chemistry, Force fields
With the needs of modern times, the world seeks new solutions to environmental problems and
science pursues to respond to these needs. Solvents play a very important role in multiple
industries such as the pharmaceutical industry. This industry, in order to decrease the
environmental impact, is replacing traditional solvents (e.g. organic solvents) for more
sustainable green solvents, such as ionic liquids or deep eutectic systems (DES) [1]. DES are
mixtures of compounds with very interesting characteristics. While the raw materials possess
high melting points in their pure state, they however, become liquid at room temperature, after
preparation at a particular composition. They also present low toxicity, low vapor pressure,
good solvation power and the process to obtain them is cheaper when compared to ionic liquids
as no chemical synthesis is required for their production [2,3,4]. DES have been used as a
greener alternative for many applications, such as alternative solvents, polymers production,
biodiesel treatment [2] Nonetheless, the full potential of DES will only be unravelled after the
understanding of the thermodynamic properties of DES. In this sense, molecular dynamics
(MD) have been applied to study DES systems in order to comprehend the behaviour at
molecular level. MD applications allied to experimental data can lead us to a better
understanding of this green system and avoid the application of harsh solvents. In this work
Force field calculations were done density and viscosity studies were applied in order to
compare with experimental data.
References:
1.Gutiérrez. A; Atilhan. M; Apricio. S ; A theoretical study on lidocaine solubility in deep eutectic solvents :
Phys.Chem.Chem.Phys., 2018, 20, 27464
2.García. G; Atilhan. M; Aparicio. S; The impact of charges in force field parameterization for molecular
Dynamics simulations of deep eutectic solvents : Journal of molecular liquids 211 (2015) 506-514
3.Paiva, A; Craveiro, R; Aroso, I. ; Martins. M; Reis, R. Duarte, R ; Natural Deep Eutectic Solvents –Solvents
for the 21st Century : ACS Sustainable Chem. Eng. 2014, 2, 5, 1063-1071
4.Kaur, S. ; Gupta, A. ; Kashyap, K.; Nanoscale Spatial Heterogeneity in Deep Eutectic Solvents : ACS J.Phys.
Chem. B 2016, 120, 6712-6720
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
73
Citrus-Processing Waste Valorisation: Extraction of Rutin
and Naringin from Orange Peels Using Deep Eutectic
Solvents
Inês S. Cardosoa,*, Armando J. D. Silvestrea, Mara G. Freirea aCICECO – Aveiro Institute of Materials, Department of Chemistry, University of Aveiro,
Campus Universitário de Santiago, 3810-193 Aveiro, Portugal
Keywords: citrus-processing by-products, citrus peels, extraction, phenolic compounds,
naringin, rutin, deep eutectic solvents
Citrus-processing industries produce large amounts of by-products, among which citrus peels
represent a significant fraction. Given that citrus peel contains phenolic bioactive compounds
of high value (e.g., rutin and naringin) with economic relevance, the development of sustainable
extraction processes to isolate these fractions is a priority to valorise these by-products. Within
the circular economy context, this work intends to valorise orange peels through the isolation
of added-value phenolic compounds using sustainable extraction processes. For this purpose,
aqueous solutions of deep eutectic solvents (DES) have been studied. The results obtained show
that designed DES aqueous solutions are able to increase the solubility of rutin and naringin by
several orders of magnitude. Experimental design of experiments was then applied to optimize
extraction conditions using selected DES. Under the identified optimal conditions, the proposed
process resulted in the efficient extraction of rutin and naringin from orange peels, with
maximum extraction yields of 6.72 and 18.20 mg/g of biomass. This process is a competitive
and more sustainable alternative to replace conventional processes using volatile organic
solvents.
Acknowledgments: This work was developed within the scope of the project CICECO-Aveiro Institute of
Materials, UIDB/50011/2020 & UIDP/50011/2020, financed by national funds through the FCT/MEC and when
appropriate co-financed by FEDER under the PT2020 Partnership Agreement. Inês S. Cardoso acknowledges FCT
for the PhD grant SFRH/BD/139801/2018.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
74
Deep Eutectic Solvent with Betaine: toxicological studies
towards applications in products for human consumption
Ferreira I.J. a, Paiva A. a, Diniz M.a and Duarte A.R. a* a LAQV@REQUIMTE, Departamento de Química, Faculdade de Ciências e Tecnologia,
Universidade Nova de Lisboa, 2829-516 Caparica, Portugal,
Keywords: Toxicity, Deep Eutectic Solvents, Green Solvents
Deep Eutectic Solvents (DES) are a mixture of two or more components where at least one is a
hydrogen bond acceptor (HBA) and other a hydrogen bond donor (HBD). These combinations
result in a decrease in the melting point of mixture in comparison with the melting point of any
of the individual components. DES appear as a “green alternative” to organic solvents, and
cheaper than ionic liquids. But, at the moment, the number of studies concerning the real
biodegradability and biocompatibility is reduced. It is within this context that this work was
carried out. With the intuit to study the toxicity of a DES and its individual components by
intraperitoneal injection, different concentrations that can be relevant were tested. These studies
were performed with zebrafish, a simple animal model recurrently used in pharmacological and
environmental tests. The preliminary results demonstrated very low toxicity in the
concentrations tested. For instance, up to 1000 µM when the system betaine: glycerol (1:2) and
their individual components were tested in an toxicity context by intraperitoneal injection. The
activity of different enzymes involved in antioxidant pathways, protection towards toxic
compounds, oxidative stress and changes in barrier structure, namely glutathione S-transferase
activity, catalase activity, total antioxidant capacity, lipoperoxidation and glutathione
peroxidase activity were tested and demonstrate the low toxicity of the system tested. The
promising results herein presented show that in fact DES can be in the future the new class of
green solvents, not only used in pharmaceutical industry but also in cosmetic and chemical
engineering processes.
Acknowledgements:
The research leading to these results has received funding granted through the project Des.solve (ERC
consolidator), ERC-2016-COG 725034. This work was supported by the Associate Laboratory for Green
Chemistry- LAQV which is financed by national funds from FCT/MCTES (UIDB/50006/2020)
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
75
Fatty acid based eutectic systems to improve solubility and
sustained release of simvastatin
Isabel Teixeira*, João Baixinhob, Alexandre Paivaa, ARC. Duartea, Naiara Fernándezb, Rita
Craveiroa, a LAQV@REQUIMTE, Departamento de Química, Faculdade de Ciências e Tecnologia,
Universidade Nova de Lisboa, 2829-516 Caparica, Portugal, b iBET-Instituto de Biologia Experimental e Tecnológica, Food & Health Division, 2781-901
Oeiras, Portugal,
Keywords: Simvastatin, Fatty acids, Deep eutectic systems, PGSS
Simvastatin is a well-known lipid lowering drug, commonly used to treat hypercholesterolemia,
but that can also have effects in osteogenesis promoting bone regeneration. Although it is
effective, it has very limited water-solubility and is classified as a type II drug according to the
Biopharmaceuticals Classification System (BCS). It is then necessary to find methods to
improve simvastatin solubility and consequent bioavailability, allowing the reduction of drug
dosage, improving drug-patient compliance, and making the process more sustainable. Lipid-
base solvents and drug delivery systems have been reported to increase the solubility of poorly
water-soluble drugs, such as simvastatin, and a recent class of solvents, named deep eutectic
systems (DES), are reported to increase the solubility and bioavailability of several drugs. Fatty
acid-based DES can be obtained and have already been reported for biomedical applications.
In this work, DES based on fatty acids such as capric, lauric, myristic and stearic acids, are
prepared and characterized. Simvastatin solubility in these DES was studied and an increase of
90% was obtained, compared with solubility in water. Additionally, micronization techniques
are proposed to improve simvastatin solubility and bioavailability. A supercritical CO2 (scCO2)
assisted technique was carried out, Particles from Gas Saturated Solutions (PGSS). Operating
conditions such as temperature, pressure, among others, were studied and particle size and
shape, as well as simvastatin loading were optimized. The use of DES and scCO2 technologies
is proved valid for enhancement of simvastatin solubility and for the production of efficient
drug delivery systems.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
76
Composition of Hydrophobic Deep Eutectic Solvents
controlling rate of polymerisation in the ATRP of styrene
Jake Hooton a,*, Dr. Antoine Buchard a, Prof. Gareth Price b and Prof. Karen Edler a a Department of Chemistry, University of Bath, Claverton Down, Bath, BA2 7AY,
UK b Khalifa University, Al Saada St, Zone 1, Abu Dhabi, United Arab Emirates
Keywords: Hydrophobic Deep Eutectic Solvents, Polymerisation, Atom Transfer
Radical Polymerisation, Styrene, Rate Constant, Component Variation, Composition
Variation
The kinetics of Atom Transfer Radical Polymerisation (ATRP) have been examined for the
monomer styrene within a series of “Type V” hydrophobic deep eutectic solvents, composed
of L-menthol and members of the natural aliphatic carboxylic acid family, from chain length
C8 (caprylic acid) to chain length C18 (stearic acid). Each solvent was prepared at its eutectic
composition. The initiation system was based on the Activators Regenerated by Electron
Transfer (ARGET)-ATRP method, using copper(I) bromide, Me6TREN ligand, and tin(II)
ethyl hexanoate reducing agent. The apparent rate constant of propagation was found to be
higher, in a consistent trend, for eutectic mixtures composed of aliphatic carboxylic acids of
longer chain length (Figure 1). Concomitantly, these eutectic mixtures are also composed of
a higher composition of L-menthol. Further experimentation also revealed that the rate
constants increase with L-menthol composition in the mixture, in mixtures prepared from
consistent chemical species (lauric acid and L-menthol). These trends are rationalised through
comparison with a number of different physicochemical properties of the eutectic mixtures,
such as viscosity, surface tension, and solvent polarity, and a discussion of relative molecular
volume and localised concentration of the monomer, and eutectic mixture components.
Figure 1: Variation of the apparent rate
constant of the ATRP of styrene in eutectic
mixtures composed of an aliphatic carboxylic
acid and L-menthol (denoted CX:Menthol
where X is the number of carbon atoms in the
carboxylic acid). Polymerisation conditions
[Styrene] : [EBiB] : [CuBr] : [Me6TREN] :
[Sn(EH)2] = 96 : 1 : 0.096 : 0.48 : 0.96.
Styrene concentration 1.65 mol dm-3.
Reaction temperature 110°C.
10
8
6
4
2
0
6 8 10 12 14 16 18 20
X (Chain Length) in CX:Menthol
k ap
p (3
h)
/ 1
0-5
s-1
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
77
Sustainable valorisation of a by-product: Recovery of
polyphenols from out of caliber kiwifruits using deep
eutectic solvents
Jean-Baptiste Chagnoleau1, Nicolas Papaiconomou1*, João A. P. Coutinho2, and Xavier
Fernandez1 1Université Côte d'Azur, CNRS, Institut de Chimie de Nice, UMR 7272, Nice, France.
2CICECO – Aveiro Institute of Materials, Department of Chemistry, University of Aveiro,
3810-193 Aveiro, Portugal.
*Corresponding author:
Keywords: Actinidia deliciosa Hayward, hydrophilic deep eutectic solvents, antioxidant
activity, solid−liquid extraction.
Kiwis are fruits with excellent bioactive properties1, but their production generates tons of
wastes every year. In particular, several tons of kiwis are discarded because out of caliber.2 In
this work, a sustainable valorisation of this by-product is proposed by extracting bioactive
compounds using sustainable solvents. Deep eutectic solvents (DES) have recently attracted
considerable attention due to the fact that they are eco-friendly, non-toxic and exhibit low
volatility3. In order to study the influence of DES on the extraction of polyphenols, a screening
of different DES and several conventional solvents was carried out. To that end, solid-liquid
extractions of kiwi peels were performed, and the performance of the extraction solvent was
assessed using a DPPH test. The latter is used worldwide and based on a simple and fast method
which was used to analyse the antioxidant activities of the kiwi peel extracts dissolved in DES4.
Using this strategy, several DES were found to yield extracts with high antioxidant activities
compared to reference systems. Finally, in cases where an extract separated from DES would
be required, a stripping step using liquid-liquid extraction with ethyl acetate was studied.
Acknowledgements:
This work was partly developed within the scope of the project CICECO-Aveiro Institute of Materials,
UIDB/50011/2020 & UIDP/50011/2020, financed by national funds through the FCT/MEC and when
appropriate co-financed by FEDER under the PT2020 Partnership Agreement.
(1) Richardson, D. P.; Ansell, J.; Drummond, L. N. The Nutritional and Health Attributes of Kiwifruit: A
Review. Eur. J. Nutr. 2018, 57 (8), 2659–2676.
(2) Nunley, M. From Farm to Fork to Landfill: Food Waste and Consumption in America, 2013.
(3) Llorente, D. R.; Barcala, A. C.; Torrellas, S. Á.; Águeda, V. I.; García, J.; Larriba, M. A Review of the
Use of Eutectic Solvents , Terpenes and Terpenoids in Liquid – Liquid Extraction Processes. Processes 2020, 1–
54.
(4) Foti, M. C. Use and Abuse of the DPPH• Radical. J. Agric. Food Chem. 2015, 63 (40), 8765–8776.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
78
Stabilisation of Aromas: Supercritical Carbon Dioxide
Extraction Coupled with Deep Eutectic Solvents
Jelena Vladić a*, Alexandre Paiva a, Ana Rita C. Duarte a a Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, Caparica, Portugal
* [email protected]; [email protected]
Keywords: aroma, supercritical carbon dioxide, deep eutectic solvent
Due to their numerous pharmacological and sensory properties, the significance of natural
aromas has long been recognised. Moreover, their application in different industries is
constantly increasing including the pharmaceutical, cosmetics, beverage, and food industry.
Conventional methods of isolation of these mixtures of volatile compounds are time-consuming
and non-selective. Therefore, these shortcomings have been overcome with the development of
superior extraction approaches. Supercritical carbon dioxide extraction (ScCO2) is an
established green and highly efficient technology for isolation of aromas present in different
natural matrixes. Despite the efficiency of this process, the instability of aromas limits their
application. For these reasons and in addition to defining optimal extraction procedures for the
recovery of aromas, it is necessary to define an optimal procedure that will provide the stability
of aromatic volatile compounds and secure their properties in the long term. Deep eutectic
solvents (DES) are solvents of high absorption capacity in which various natural compounds
have high solubility. Additionally, these alternative solvents are affordable, biodegradable, and
easy for manipulation.
Therefore, the main goal of this study is to develop and optimize a procedure for isolation and
stabilisation of aromas. The extraction of aromas from different natural materials will be
performed using ScCO2. By varying process parameters and analyzing their impact on the
extraction efficacy and chemical composition of the extracts, the most optimal extraction
parameters will be established. The following step will be to stabilise aromas with DES by
dispersing the recovered aromas in DES. To achieve optimal stabilisation, characterization and
optimization of DES systems will be conducted. In addition, the chemical profile of stabilised
aromas will be monitored during storage under different conditions.
Acknowledgements: This project has received funding from the European Union’s Horizon 2020 research and
innovation programme under the Marie Sklodowska-Curie grant agreement No 101003396.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
79
Simple and ecofriendly preparation of chin-glucan
complexes from white button mushroom using deep
eutectic solvents
Hireem Kim a, Seulgi Kang a, Ke Li a, Dasom Jung a, Keunbae Park a and Jeongmi Lee a,*
aSchool of Pharmacy, Sungkyunkwan University, Suwon, Gyeonggi 16419, Republic of Korea
Keywords: Chitin-glucan complex; mushroom; deep eutectic solvent; Agaricus bisporus
Deep eutectic solvents (DESs) have been used in various applications as ecofriendly and safe
solvents. In the present study, we applied DESs to prepare various kinds of chitin-glucan
complexes (CGCs) from Agaricus bisporus, commonly known as white button mushroom. A
conventional chemical method involving the treatment of mushroom with NaOH solution and
ultrasonic irradiation yielded one type of CGC, a residue that is NaOH-insoluble and thus,
called alkali-insoluble matter (AIM). In contrast, each DES yielded two types of CGCs, one
from the DES-insoluble residue (DES_P) and another from the DES-soluble extract (DES_S).
As a result, ten CGCs could be prepared from five different DESs, and they contained varying
chitin-to-glucan ratios that were also different from that of AIM. BU composed of betaine and
urea produced BU_S and BU_P at the highest yields among the ten CGCs, and their protein
and mineral contents were reasonably low. BU_S and BU_P had different acetylation degrees
(77.3% versus 57.3%), however, both degraded at 318 °C and had remarkably low
crystallinity (32.0−37.0%) compared to AIM, commercial chitin, and the reported CGCs.
Different from AIM, the surface of BU_S and BU_P was very porous and rough, and this is
probably because of reduced H-bonds and lowered crystallinity. This study is the first
presentation of a simple and ecofriendly method to prepare CGCs from mushroom, having no
concerns of allergenic proteins included in the chitinous materials.
The current presentation is based on our recent publication in International Journal of
Biological Macromolecules (2021,Vol. 169:122-129).
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
80
Overcoming the Colorectal Cancer Challenge With
Therapeutic Deep Eutectic Systems Pereira J. a,*, Castro M. a, Oliveira F. a, Duarte A. a
a LAQV-REQUIMTE, Departamento de Química, Faculdade de Ciências e
Tecnologia,Universidade Nova de Lisboa, Caparica, Portugal
Keywords: Colorectal cancer, THEDES, NSAID, Natural compounds, Terpenes
Cancer remains a major health problem worldwide, with colorectal cancer (CRC) being the
third most incident.1 Inflammation has been highly associated with cancer development and
maintenance,2 therefore, the reduction of the inflammatory microenvironment represents a
promising therapeutic strategy. The use of nonsteroidal anti-inflammatory drugs (NSAIDs) to
reduce CRC risk has already been described.2
Deep eutectic systems (DES) are based on the combination of different components which
together present a deep decrease in their melting point. These systems are most widely in
compliance with the green chemistry metrics and have low production costs, thus presenting
an alternative to conventional solvents.3 When an active pharmaceutical ingredient is part of a
DES it is designated by therapeutic deep eutectic system (THEDES).3 To evaluate THEDES
potential therapeutic activity, seven new THEDES based on natural occurring molecules with
anticancer properties combined with NSAIDs were prepared: Safranal:Ibuprofen (3:1),
Safranal:Iburofen (4:1), Menthol:Ibuprofen (3:1), Menthol:Ketoprofen (4:1),
Menthol:Flurbirpofen (4:1), Linalool:Ketoprofen (4:1) and Linalool:Flurbiprofen (4:1). The
evaluation of these THEDES physico-chemical properties alongside with the assessment of its
bioavailability and bioactivity, were explored in this work as an integrative approach to
determine their anti-CRC activity. Our first results show that Safranal:Ibuprofen (3:1),
Safranal:Ibuprofen (4:1) and Menthol:Ibuprofen (3:1) present promising therapeutic activity
towards CRC cells due to a selective cytotoxic action towards cancer cells.
Refernces: (1) Bray, F.; Ferlay, J.; Soerjomataram, I.; Siegel, R. L.; Torre, L. A.; Jemal, A. Global Cancer Statistics 2018:
GLOBOCAN Estimates of Incidence and Mortality Worldwide for 36Cancers in 185 Countries. CA. Cancer J.
Clin. 2018, 68 (6), 394–424.
(2) Terzić, J.; Grivennikov, S.; Karin, E.; Karin, M. Inflammation and Colon Cancer. Gastroenterology 2010, 138
(6), 2101–2114.
(3) Zainal-Abidin, M. H.; Hayyan, M.; Ngoh, G. C.; Wong, W. F.; Looi, C. Y. Emerging Frontiers of Deep Eutectic
Solvents in Drug Discovery and Drug Delivery Systems. J. Control. Release 2019, 316, 168–195.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
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Choline Chloride – based Deep Eutectic Solvents to obtain
phenolics from Rosmarinus officinalis L.
José Pedro Wojeicchowskia,b*, Ana M. Ferreiraa, Caroline Marquesb, Luciana Igarashi-Mafrab,
João A.P.Coutinhoa, Marcos R. Mafrab a CICECO – Aveiro Institute of Materials, Department of Chemistry, University of Aveiro
(UA), 3810-193, Aveiro, Portugal. b Department of Chemical Engineering, Federal University of Paraná (UFPR), 81531-990,
Curitiba, Parana, Brazil.
Keywords: COSMO-RS, rosemary, carnosic acid, and rosmarinic acid
In the last years, deep eutectic solvents (DES) have emerged as an alternative to the hazardous
organic solvents to extract natural bioactive compounds from natural matrices. In this study,
the most common hydrogen bond acceptor, choline chloride ([Ch]Cl), was combined with
different hydrogen bond donors (HBD). Solid-liquid extractions were carried out with these
solvents, at 30°C, 2.5h and 1:20 (solid-liquid ratio), in order to extract antioxidants compounds,
carnosic acid (CA) and rosmarinic acid (RA), from Rosmarinus officinalis L. An in silico
solubility study using the quantum thermodynamic model, Conductor-like Screening Model for
Real Solvents (COSMO-RS), was made. Results indicated good correspondence between
computational and experimental data, as observed by the high correlation (> 0.73) between total
phenolic contents and predicted solubility (log xsolute) of CA and RA, Fig.1. These results reveal
that the higher the solubility of a compound in a solvent, the greater the achieved extraction
efficiency. Chromatographic analyses supported it, once the lowest content of CA and RA, 4.12
and 6.21 mg/g respectively, was found by DES with zinc chloride as HBD. Thus, besides
showing the successful rosemary bioactive compounds extraction using DES, this work also
demonstrated that COSMO-RS is a useful tool for selecting solvents instead of the trial-and-
error methodology.
Fig.1. Relative solubility of carnosic acid ()
and rosmarinic acid () into different hydrated
DES (30 % of water, 30 ºC), and their
phenolic content in mg GAE/g (bars) obtained
by these solvents.
Acknowledgments: This work was developed within the scope of the project CICECO-Aveiro Institute
of Materials, UIDB/50011/2020 & UIDP/50011/2020, financed by national funds through the
FCT/MCTES. J.P. Wojeicchowski acknowledges Coordenação de Aperfeiçoamento de Pessoal de Nível
Superior (CAPES, Brazil) for the scholarship, Finance Code 001.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
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Stability and Crystal Formation in Betaine-Urea-Water
NADES System
Lamya Al Fuhaida, Maria F. Nava-Ocampoa, Szilárd S. Bucsa, Robert Verpoorteb, Young Choib,
Geert J. Witkampa, Andreia S. F. Farinhaa*
a Water Desalination and Reuse Center, King Abdullah University of Science and
Technology, Thuwal, Saudi Arabia. b Institute Biology Leiden, Leiden University, Leiden, The Netherlands.
Predicting compound combinations yielding a (NA)DES and its resulting properties is not yet
possible. Similarly, the stability of the obtained liquid cannot be predicted from molecular
considerations. After their preparation at elevated temperatures, we have observed that some
NADES exhibited crystal formation when transferred to room temperature or below. This study
addresses the effect of curing temperature and time on the stability and crystallization of
different molar ratios of betaine-urea-water (BUW) NADES. The samples were characterized
by Fourier-transform infrared spectroscopy and 1D and 2D nuclear magnetic resonance to
unravel the bonding and supramolecular organization, and the crystal structure was resolved by
single-crystal X-ray diffraction. Proton NMR analysis of the crystals’ mother liquor allowed
the extrapolation of the maximum ratios that can form stable BUW NADES. Moreover, to
investigate the role of water and the minimum moisture content that has to be present in the
system, thermogravimetric analysis was performed, and the enthalpies of vaporization were
calculated from isothermal microcalorimetry measurements. Our results revealed that more
extended curing periods at higher temperatures increased the (meta)stability of NADES.
Despite the variation in the crystals’ macro-morphology, all unstable BUW NADES created
hydrogen-bonded orthorhombic betaine hydrate crystals. Additionally, water loss upon drying
showed two different kinetics, an initial phase characterized by a fast decline of mass, followed
by a longer, slower one. This pattern indicates that part of the water molecules is trapped within
the supramolecular network through hydrogen bonding, whereas the rest is less tightly bound.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
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NADES-based formulations of Spirulina enriched in free
fatty acids: preparation, characterization and skin-impact
Laura Wils a,*, Charlotte Leman-Loubière a, b , Nicolas Bellin c, Barbara Clément-Larosière b,
Charles Bodet c and Leslie Boudesocque-Delaye a
a EA 7502 SIMBA, Faculté de Pharmacie, Université de Tours, 31 avenue Monge,
37200 Tours, France b Aqua Eco Culture, 7 rue d’Armor Maroué,
22403 Lamballe, France c EA 4331 LITEC, Pole Biologie Santé - Bât. B38 1 rue Georges Bonnet BP 633
86022 Poitiers Cedex
Keywords: NADES, Spirulina, cytotoxicity, cutaneous microbiota, keratinocyte, free fatty
acids
Cosmetic industry was intensively involved in the green transition, especially by the
development of sustainable biocosmetic ingredient (renewable raw materials, sustainable
process). In this context, the use of microalgae as a source of ingredients has focused the interest
of cosmetic industry for some years now, as they represent a huge potential for innovation in
the field. In fact microalgae is a renewable resource of various biomolecules of cosmetic
interest: phycobiliproteins, polyunsaturated fatty acids (PUFA), and carotenoids.
Free fatty acids (FFA) as anti-inflammatory, microbiota regulator and moisturizing agents are
new cosmetic targets. FFA are commonly extracted by organic solvent (chloroform, hexane)
incompatible with a topical use and required purification and evaporation additional steps. In
this context, Natural Deep Eutectic Solvents (NADES) represent an exciting opportunity to
overcome current processes by developing a new green approach compatible with a topical use.
The first part of the work was focused on NADES development for FFA microalgal extraction,
using Arthrospira platensis (Spirulina) as a model. Resulting NADES formulations were
characterized by LC-MS, HPLC and spectrophotometric assays. A first screening of the
NADES was carried out on their selectivity for pigment (chlorophyll, carotenoid,
phycobiliprotein) and FFA. Six of them were intensified before biological evaluation. Then,
selected NADES and the resulting extracts were evaluated towards skin inflammation and
microbiota. The cytotoxicity of the solvents and associated extracts was evaluated on human
keratinocytes and on four bacterial strains (pathogens or commensals): Staphylococcus aureus,
Staphylococcus epidermidis, Cutibacterium acnes and Corynebacterium xerosis individually.
Our data demonstrated the good harmlessness of NADES and formulation on human
keratinocytes and highlighted the huge potential of some of them towards microbiota
regulation.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
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Use of COSMO-RS for design of THEDES
as improved formulation of chiral drug
Kristina Radoševića, Ivana Radojčić Redovnikovića,*, Manuela Panića, Mia Radovića, Marina
Cvjetko Bubaloa, Jasmina Lapića, Senka Djakovića, Marko Rogošićb a Faculty of food technology and biotechnology, Pierottijeva 6, 10 000 Zagreb, Croatia
b Faculty of Chemical Engineering and Technology, Marulićev trg 19, 10 000 Zagreb, Croatia
Keywords: COSMO-RS, natural deep eutectic solvents, bioavailability, permeability,
therapeutic deep eutectic solvents
Designing new, environmentally-friendly, and tuneable solvents have been dramatically
expanding in popularity in order to overcome the flaws of organic solvents from technological,
environmental and economic aspects. Though it is sometimes relatively easy to find an
appropriate natural deep eutectic solvent (NADES) for certain process and application, this is
occasionally ungrateful procedure, meaning that sometimes is difficult to predict which
mixtures and in which molar ratios will originate as a NADES and also which solvent properties
will be exerted. Therefore, the composition of NADES and their physical, thermal, chemical or
biological properties should be characterized on case-by-case scenario. Abundance of possible
NADES formulations, especially when possible addition of certain amount of water is taken
into account, makes it impossible to prepare and characterize all of them, pointing out the need
for development of predictive NADES structure-activity mathematical models. Approaches
used so far for screening appropriate/ideal NADES (out of enormous pool of structural
possibilities) have been governed by time consuming empirical methods, while systematic
investigation in NADES structure-activity relationship, as a backbone for rational design of
these solvents, is still lacking. Current literature suggests COSMO-RS, software that can predict
thermodynamic properties and phase equilibrium which would help in designing the best
possible solvent for a certain application. COSMO-RS can design new solvent structures with
tailored properties and thus the trial-and-error method of NADES preparation can be avoided.
The aim of this work is to rationally design NADES for solubilisation of poorly-water soluble
active pharmaceutical ingredients (APIs) as well as the preparation of therapeutic deep eutectic
solvents (THEDES). It is expected that such approach will enable better solubility, permeability
and bioavailability of the APIs, with probably better stability of active compound with
preserved or maybe even enhanced activity.
Acknowledgements: The work was supported by the Croatian Science Foundation (Grant No. 7712)
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
85
Design and application of novel dihydrogen
phosphate cholinium-based DES
M.S. Álvareza,*, F.J. Deivea,, M.A. Longoa,, A. Rodrígueza a Department of Chemical Engineering, Campus Lagoas-Marcosende 36310, Vigo
Pontevedra, Spain
*E-mail: [email protected]
Keywords: Dihydrogen phosphate cholinium-based DES, synthesis, lipases, stability.
Deep eutectic solvents (DES) are presented as promising green and sustainable solvents with
numerous applications in biotechnology, environmental remediation, drug bioavailability or
chemical processes [1, 2]. Since the eutectic mixture named reline was reported by Abbot [3]
as a new class of solvent, choline chloride salt has been selected as a model hydrogen
bond acceptor (HBA) and combined with several hydrogen bond donor (HBD) promoting an
extensive library of tunable solvents. Among other fields, biocatalysis is one of the
prominent niches where these new solvents have arisen interest, especially in those catalytic
reactions where partial or total absence of water is essential [4].
In this study, we propose the quaternary ammonium salt, choline dihydrogen phosphate as HBA
combined with ethylene glycol (ChDHP:E (1:2)) and glycerol (ChDHP:G (1:2) or both
(ChDHP:E:G (1:1:1)) as HBD for evaluating the stability of the commercial lipase B
from Candida antarctica. After all DES were prepared following the literature methods,
density, viscosity, refractive index, NMR and DSC measurements were performed in order to
carry out a comprehensive physicochemical and structural characterization. Further, the effect
of DES in lipase stability was evaluated in terms of residual lipase activity after
thermal incubation for 1 hour at 40ºC in pure DES and in 2 M solutions. The results have shown
that the residual activity after incubation in pure DES and 2 M solutions was over 60% and
90%, respectively, observing a clear trend in the order (ChDHP:E> ChDHP:G> ChDHP:E:G).
In conclusion, these new DES could be an alternative as co-solvents in biocatalytic
reactions like biodiesel production.
References:
[1] A. Fernández, F.J. Deive, A. Rodríguez, M.S. Álvarez. J. Mol. Liq. 2020, 305, 112824- 112831.
[2] C.J. Clarke, W.C. Ti, O. Levers, A. Brohl, et al. Chem. Rev. 2018, 118, 747–800. [3] A.P. Abbott, G.
Capper, D.L. Davies, R. Rasheed, et al. Chem. Commun. 2003, 1, 70-71. [4] M. Pätzold, S. Siebenhaller, S.
Kara, A. Liese, et al. Trends Biotechnol 2019, 37, 943-959.
Acknowledgements: The authors thank Xunta de Galicia and Spanish Ministry of Science, Innovation and
Universities for funding through a postdoctoral grant (ED481D-2019/017) and the project RTI2018-094702-B-
I00.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
86
Picolinium-based Deep Eutectic Systems (DESs) in the
Lubrication of Silicon Surfaces
Mariana Donatoa,b, Mónica Antunesa,c, Rogério Colaçoc, Luís C. Branco*b, Benilde Saramago*a a Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av.
Rovisco Pais, 1049-001 Lisboa, Portugal b LAQV-REQUIMTE, Departamento de Química, Faculdade de Ciências e Tecnologia,
Universidade Nova de Lisboa, Campus da Caparica, 2829-516 Caparica, Portugal c IDMEC-Instituto de Engenharia Mecânica, Departamento de Engenharia Mecânica, Instituto
Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal
* Corresponding authors: [email protected]; [email protected]
Keywords: deep eutectic systems, lubricants, silicon, friction coefficient.
Deep eutectic systems (DESs) have recently been proposed as “green” alternatives to mineral
oils and ionic liquids (ILs) in the lubrication of several surfaces.[1,2] DESs have similar physical
properties to ILs but have the advantage of being cheaper and easier to prepare. In a previous
work, we have synthesized sulphur-containing DESs that showed very interesting lubrication
properties.[3] Herein, new picolinium salts-based DESs were prepared and tested in the
lubrication of silicon surfaces which are relevant for nano/microelectromechanical systems
(NEMS/MEMS). All prepared DESs were characterized in terms of their water content,
viscosity, wettability and tribological properties. The friction coefficients were measured using
steel spheres against Si surfaces. The most promissory DESs showed a good tribological
performance, both in terms of friction and wear reduction comparing to commercial lubricants.
Figure 1. Schematic representation of the (nano)tribometer system and the interactions between
the DESs and the Si surface.
Acknowledgements
The authors thank the financial support by FCT – MCTES (UID/QUI/00100/2013, UID/QUI/50006/2013 and
IF/0041/2013/CP1161/CT00, SFRH/BD/140079/2018) and Solchemar company.
References
[1] M. T. Donato, R. Colaço, L. C. Branco, B. Saramago, J. Mol. Liq. 2021.
[2] A. Somers, P. Howlett, D. MacFarlane, M. Forsyth, Lubricants 2013, 1, 3–21.
[3] M. Antunes, M. T. Donato, V. Paz, F. Caetano, L. Santos, R. Colaço, L. C. Branco, B. Saramago,
Tribol. Lett. 2020, 68, 1–14.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
87
NADES-assisted valorisation of orange peel waste by the
integrated biorefinery approach
Manuela Panića, Martina Andlara, Marina Tišmab, Tonči Rezića, Darijo Šibalicb, Marina
Cvjetko Bubaloa*, Ivana Radojčić Redovnikovića
aFaculty of Food Technology and Biotechnology, University of Zagreb, Pierotijeva 2, 10000
Zagreb, Croatia bJosip Juraj Strossmayer University of Osijek, Faculty of Food Technology Osijek, Franje
Kuhača 18, Osijek HR-31000, Croatia
Keywords: Biorefinery, D-limonene, Natural deep eutectic solvents, Orange peel waste,
Pectin methylestrase, Polyphenols, (R)-1-phenylethanol, SWOT analysis
Orange peel waste obtained from orange juice and canned food production present one of the
most abounded wastes from the food industry. Yearly 70 Mt of the oranges is produced
worldwide among which the peel comprises about 40-50% of the total orange weight as a
leftover which needs to be disposed of as waste. Valorisation of orange peel waste by following
the biorefinery concept is usually carried out via several platforms: (1) direct application as
animal feed and fertilizer; (2) the use as a substrate for the production of biofuels, proteins,
industrially valuable enzymes, and other biotechnological products (e.g. citric and succinic
acid); (3) extraction of bioactive compounds (e.g. essential oils, and organic acids), pectin, and
enzymes (e.g. pectin methylesterase). Natural deep eutectic solvents (NADESs) – assisted
valorisation of orange peel waste fully fits the green biorefinery concept since these solvents
are of low cost and are prepared from natural raw materials with 100% atom economy.
This research investigates the use of seven NADESs for valorisation of orange peel waste, with
the final goal to propose a unique NADES for integrated biorefinery. Initial screening of
NADESs revealed the excellent ability of cholinium-based NADES with ethylene glycol as
hydrogen bond donor (ChEg50) to serve as a medium for orange peel-catalysed kinetic
resolution (hydrolysis) of (R,S)-1-phenylethyl acetate with high enantioselectivity, as well as
it’s stabilizing effect on the hydrolytic enzymes. The ChEg50 also showed a satisfactory
capacity to extract D-limonene, and excellent capacity to extract polyphenols, and proteins from
the peel. Based on the obtained results, the integrated biorefinery of orange peel waste using
ChEg50 in a multistep process was performed. Firstly, enantioselective kinetic resolution was
performed (step I; ee = 83.2%, X = 35%), followed by isolation of the product 1-phenylethanol
(step II; h = 82.2%) and extraction of polyphenols (step III; h = 86.8%) from impoverished
medium. Finally, the residual orange peel was analysed for sugar and lignin content, and results
revealed the potential of waste peel for the anaerobic co-digestion process. The main
bottlenecks and futures perspective of NADES-assisted integrated biorefinery of orange peel
waste were outlined through SWOT analysis
Acknowledgements: The work was supported by the Croatian Science Foundation (Grant No. 7712 and 9550)
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
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Synthesis of PLLA/PCL Blends with Tunable Properties
Obtained Via Ring Opening Polymerization of Eutectic
Mixtures Composed of LLA y ε-CL
Castillo-Santillan M.a, Perez-Garcia M. G.b, Martinez-Richa A.b, Torres-Lubian J.R.b, Mota-
Morales J.D.a,*.
[email protected], [email protected], [email protected],
[email protected], [email protected],*.
Keywords: Blend PLLA/PCL, DES monomers, Biodegradable polyesters.
PCL and PLLA are among the most common biocompatible and biodegradable polyesters used
in areas such as packaging and 3D printing. Replacing the great quantities of volatile organic
solvents (VOCs) and organometallic compounds normally used in the process of ROP of ε-
caprolactone (CL) and L-lactide (L-LA) has been challenging.
It has been reported that the ROP of DESs composed of L-LA and CL (3:7 molar ratio,
respectively) proceed at low temperature (37ºC) with the use of organocatalysts and in
solventless conditions with full conversions, along with an unusual composition consisting of
a blend of homopolymers. (1,2)
Together with the absence of volatile organic solvents and metallic catalysts, controlling the
final polyesters' properties, such as mechanical properties and their profile degradation will
open the path for their use in biomedical and related areas. These properties depend upon
various parameters such as molecular weight, polymer architecture, and polymers’ crystallinity.
In this work, the ROP of DESs composed of L-LA and CL was studied at various temperatures
below and above the melting point of PCL. A blend of homopolymers were obtained composed
of PLLA and PCL. It is noteworthy that practically PCL's molecular weight was increased in
ca 35% of the final blend, and even open the possibility to modify the crystallinity in these final
polyesters.
References:
1. Perez-García M., et al., ACS Appl. Mater. Interfaces, 2016, 8, 16939-16949.
2. Coulembier O., et al., Chem. Sci., 2012, 3, 723.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
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Application of low-temperature eutectic solvents in the
extraction of ellagitannins and phenolic acids from
Alchemilla vulgaris
Martina Jakovljević and Maja Molnar,
Faculty of Food Technology Osijek, Josip Juraj Strossmayer University of Osijek, Franje
Kuhača 20, 31000 Osijek, Croatia,
Keywords: deep eutectic solvents, extraction, ellagitannins, optimization, RSM
Due to the growing use of bioactive components in the food and in the pharmaceutical industry,
rapid development of various methods for their extraction and separation is required. In the last
few years, deep eutectic solvents (DESs), composed of a hydrogen bond acceptor (HBA) and
hydrogen bond donor (HBD) components, stand out as an appropriate substitution to
conventional solvents due to their properties, with emphasis on non-toxicity, thermal stability
and biodegradability, with easy preparation and low price of components. Alchemilla vulgaris L. is a plant that is often used in folk medicine as it possesses numerous
health-promoting benefits due to its specific chemical composition with emphasis on phenolic
acids and elagitannins. The most important components with antioxidant activity in sage are
phenolic acids, such as gallic and ellagic acid as well as elagitannins which can be extracted by
various extraction techniques, most commonly solid-liquid extraction.
The aim of this paper was to select the most suitable choline chloride based deep eutectic
solvent for the extraction of gallic and ellagic acid as well as elagitannins from lady's mantle
(Alchemilla vulgaris L.) and then optimize extraction conditions for extraction with stirring and
heating, ultrasound-assisted extraction and mechanoextraction. Seventeen different choline
chloride-based DESs with different volumes of water (10%, 30%, and 50% (v/v)) were used for
the extraction at different temperatures (30, 50, and 70 °C) to investigate the influence on this
extraction parameters on yield of desired components. The results obtained were compared with
the results obtained by extraction with conventional solvents. Gallic and ellagic acid content
was obtained by high-performance liquid chromatography with diode-array detector (HPLC-
DAD) and total ellagitannins were determined spectrophotometrically in the obtained extracts.
Screening revealed that among 17 different DESs, the most suitable solvent is choline chloride:
urea (1:2) and the most suitable extraction technique is extraction with stirring and heating.
According to the results, the prepared solvents prove to be a good substitute for organic solvents
in the extraction of bioactive components from lady's mantle plant.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
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A comprehensive study of CO2 absorption and desorption
by choline chloride levulinic acid-based deep eutectic
solvents
Mohaned Aboshatta ,Vitor Magueijo
Department of Chemical and Process Engineering, University of Strathclyde, Glasgow,
UK
Keywords: Deep eutectic solvents, Choline Chloride, Levulinic Acid, CO2 Absorption, DESs
Regeneration, Carbon Capture, Green Sorbent
Over the last six decades, the concentration of
CO2 in the atmosphere has increased
dramatically, reaching a value of 414 ppm in
January 2021. Amine absorption is currently
the most used and established method for CO2
capture; however, it has environmental
shortcomings and is energy intensive. Deep
eutectic solvents (DESs) are among the most
favourable alternatives to overcome
conventional amines for CO2 capture. DESs are
greener and more benign solvents for CO2
capture than ionic liquids due to their
biodegradability, nontoxicity, and low prices.
In this work, the solubility of CO2 in choline
chloride/levulinic acid-based deep eutectic
solvents (ChCl: LvAc DESs) was measured at
different temperatures, pressures and stirring speeds using a vapour liquid equilibrium rig.
DESs regeneration (CO2 desorption) was performed using a heat treatment method. FTIR
was used to verify the absorption and desorption of CO2 by ChCl: LvAc DESs at different
temperatures. The molar ratios of ChCl: LvAc were selected as (1:2) and (1:3) with different
water contents of 0%, 2.5% and 5%. Henry’s constants for CO2−DESs have been calculated
with values ranging between 4.6 to 14.2 MPa under these conditions. Thermodynamic
properties such as enthalpy, entropy and standard Gibbs free energy changes of CO2
dissolution were calculated from the solubility data correlations. Results showed that the
solubility of CO2 increases with increasing water content, pressure, stirring speed and molar
ratio of the HBD and decreases with increasing temperature. Statistical analysis of results
revealed significant second and third orders interactions among input variables along with
the optimal operating conditions these give the highest CO2 absorption by ChCl: LvAc
DESs. DESs regeneration was performed at different temperatures, the optimal regeneration
temperature of these compositions is estimated to be 353 K. In this work, DESs exhibited
good recyclability as samples have lost only 0.48% of their initial weight after five
consecutive cycles of CO2 absorption at 25 °C and desorption at 80 °C. Finally, ChCl: LvAc
DESs showed high selectivity towards CO2 over N2 with up to 5.63 at 50% mole CO2 and 25 °C which makes ChCl: LvAc DESs more viable for CO2 absorption processes.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
91
Extraction of ellagic acid from defatted raspberry seeds
using NADES
Nemanja Teslića,*, Boško Marića, Branimir Pavlićb, Filipa Santosc, Filipe Oliveirac, Nadiia
Khakimovaa, Alena Stupara, Milica Pojića, Anamarija Mandića, Aleksandra Cvetanovićb, Ana
Rita C. Duartec, Aleksandra Mišana a Institute of Food Technology, University of Novi Sad, Blvd. cara Lazara 1, 21000 Novi Sad,
Serbia b Faculty of Technology, University of Novi Sad, Blvd. cara Lazara 1, 21000 Novi Sad, Serbia
c LAQV, REQUIMTE, Departamento de Química Nova School of Science and Technology,
2829-516 Caparica, Portugal
Keywords: NADES, raspberry seed, ellagic acid, hydrolysis, extraction
Ellagic acid and its metabolites have several health beneficial effects due to their antioxidative,
hepatoprotective, antimicrobial, antiproliferative activities etc. Most of the ellagic acid in
raspberry seeds is present in form of ellagitannins which have low bioavailability. Therefore,
ellagic acid has to be hydrolysed from ellagitannins. Acid hydrolysis often requires use of
strong mineral acids which are hazardous for human health. Natural Deep Eutectic Systems
(NADES) composed of organic acids (citric, malic, lactic and tartaric acid) as hydrogen-bond
donors and betaine or sugars (fructose and glucose) as hydrogen-bond acceptors could serve as
alternative hydrolysis media which are edible and nontoxic for human health. Ten different
combinations of NADES where made and used for hydrolyzation and extraction of ellagic acid
from defatted raspberry seeds. In order to compare efficiency of the process, ellagic acid was
also recovered from raspberry seeds with aqueous ethanol (80% w/w) and 2M HCl in methanol.
Obtained extracts were analysed in terms of total polyphenol content (TPC), antioxidant activity
(AOA) measured with DPPH assay and ellagic acid content (EAC) determined by HPLC. All
NADES exhibited higher TPC, AOA and EAC comparing to aqueous ethanol extract. NADES
had significantly lower EAC comparing to 2M HCl in methanol extract, however, usage of
NADES allows us to produce non-hazardous and ready-to-use-extracts which could further be
used in food and cosmetic industry.
Acknowledgment/Funding
Authors would like to thank the Ministry of education, science and technological development
of the Republic of Serbia, Grant No. 451-03-9/2021-14/ 200222; the Science Fund of the
Republic of Serbia, PROMIS, Grant No. 6060592, DEStiny; and the European Union, Horizon
2020 (European Research Council), Grant no ERC-2016-CoG 72503 for the funding.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
92
Phloroglucinol Solubility in Aqueous Mixtures Of Deep
Eutectic Solvents and water: Measurements And PC-
SAFT Modeling
Nicolás Gajardo-Parra a, Bruno Sepulveda-Orellanab, Hoang T. Do a, José Matías Garrido,c José
R. Pérez-Correa,b Gabriele Sadowski a, Roberto I. Canalesb and Christoph Held a,* a Laboratory of Thermodynamics, Department of Biochemical and Chemical
Engineering,Technische Universität Dortmund, Emil-Figge-Str. 70, 44227 Dortmund,
Germany, b Departamento de Ingeniería Química y Bioprocesos, Pontificia Universidad Católica de
Chile, Avenida Vicuña Mackenna 4860, Macul, Santiago 7820244, Chile c Departamento de Ingeniería Química, Universidad de Concepción, Concepción 4070386,
Chile
* E-mail: [email protected]
Keywords: Deep eutectic solvents, Phloroglucinol, PC-SAFT, Solubility.
Phlorotannins are phenolic compounds recognized as an essential source of antioxidants in
brown algae. They are mainly present in the seaweed cell-walls and represent between 5 and
30% of the algae dry weight. Phloroglucinol is the basic unit from which the phlorotannins
polymerize; thus, its thermodynamic behavior is essential for designing the extraction of this
solute. Deep eutectic solvents (DES) are emerging as extracting solvents in operations that
involve the recovery of natural compounds. DES are advantageous due to their
biodegradability, easy preparation, and adaptability. Several authors have studied the DES
capacity to enhance the extraction yields; however, aqueous mixtures of DES are usually
needed to reduce the viscosity of the extracting solution. In this work, the solubility of
phloroglucinol is measured in pure water; aqueous solutions of different hydrogen bond donors
as ethylene glycol, 1,3-propanediol, and glycerol; and aqueous mixtures of deep eutectic
solvents using choline chloride as the hydrogen bond acceptor, and ethylene glycol, 1,3-
propanediol, and glycerol as the hydrogen bond donors. All the measurements were performed
from 293.15 K to 313.15 K at different water concentrations at 101.3 kPa. As expected,
solubility increases with temperature and decreases with the increasing amount of water in the
mixture. The results show that the aqueous mixtures of DES perform better than the aqueous
solutions of pure hydrogen bond donors for all the temperatures and water concentrations. On
the other hand, the highest solubility was obtained in the ethylene glycol-based DES, followed
by 1,3 propanediol and glycerol, which suggests the importance of the molecular structure and
interactions on the solubility of phloroglucinol. Powder X-ray diffraction was measured for the
non-dissolved phloroglucinol after the equilibrium showing that the compound is dihydrated,
changing the structure from the pure crystal. All the solid-liquid equilibrium results were
accurately modeled with PC-SAFT using the solubility product approach for dihydrates.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
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The Influence of Urea Derivatives on Nonideal
Mixing Behavior of Choline-based Deep Eutectic
Solvents
Omid Shayestehpour a, Stefan Zahn a,* a Leibniz Institute of Surface Engineering, Permoserstraße 15, 04318 Leipzig,
Germany * [email protected]
Omid Shayestehpour, Stefan Zahn
Keywords: molecular dynamics simulations, physicochemical
properties,activity coefficients, computational studies
Recently, experimental activity coefficients for homologous DESs based on choline chloride
and urea were reported by Silva et al. [1] It was highlighted that urea is mainly responsible
for negative deviations from ideality while choline chloride shows overall small deviations
from ideal mixing behavior. Motivated by this seminal study, we have carried out
molecular dynamics simulations to identify the molecular impact of the urea derivative on the
liquid structure of these mixtures.
We observed a strong correlation between the experimentally obtained activity coefficients and
coordination numbers of the HBD sites around chloride anion (Fig. 1) [2]. Furthermore, the
interaction of the oxygen atom of urea with the cationic core facilitates displacement of the
chloride anion from the cationic center toward its hydroxyl group. The substitution of hydrogen
atoms by methyl groups forces the nonpolar alkyl chains to interact with the cationic center.
Additionally, indications for formation of nonpolar domains within the liquid and, thus,
nanoscale segregation is visible as soon as one hydrogen atom of urea is replaced by an alkyl
group.
Fig. 1 Plot of the activity coefficients of choline chloride in mixture with a series of urea derivatives, versus the number
of hydrogen bond donor sites close to the chloride anion. urea (U), thiourea (TU), 1-methylurea (MU), 1,3-
dimethylurea (13MU), 1,1-dimethylurea (11MU).
[1] Silva, L. P. et al., Phys. Chem. Chem. Phys. 2019, 21, 18278. [2]
Shayestehpour, O. and Zahn, S., J. Phys. Chem. B 2020, 124, 35, 7586.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
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Natural Deep Eutectic Solvents as sustainable solvent for
Suzuki-Miyaura cross-coupling reactions applied to
imidazo-fused heterocycles
Pierre-Olivier Delayea*, Mélanie Pénichon, Leslie Boudesocque-Delaye, Cécile Enguehard-
Gueiffier a University of Tours, EA 7502 SIMBA, Faculty of Pharmacy, 31
Avenue Monge, Tours, France. * [email protected]
Keywords: deep eutectic solvent, imidazopyridine, Suzuki–Miyaura coupling, sustainable
chemistry
Herein, we present the first Suzuki–Miyaura cross-coupling in a sustainable natural deep
eutectic solvent (NaDES) applied to biologically relevant imidazo-fused scaffolds imidazo[1,2-
a]pyridine and imidazo[1,2-b]pyridazine. The choline chloride/glycerol (1:2, mol/mol) NaDES
allowed the functionalisation of diverse positions on the heterocycles with various boronic
acids, by using 2.5 mol% of readily available Pd(OAc)2. Notably, the catalytic system proceeds
without any ligands or additives, without protection from the atmosphere. System recycling has
been carried out up to five times.
P.-O. Delaye et al, SynOpen 2018, 2, 306–311.
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Density predictions of DESs by proposing novel group
contribution and atomic contribution models
Reza Haghbakhsh a,b, Sona Raeissi b, Ana Rita C. Duarte a,*
a LAQV, REQUIMTE, Departamento de Química da Faculdade de Ciências e
Tecnologia,Universidade Nova de Lisboa, 2829-516 Caparica, Portugal. b School of Chemical and Petroleum Engineering, Shiraz University, Mollasadra Ave., Shiraz
71348-51154, Iran.
Keywords: DES; green solvent; physical property; modelling; density.
The necessity of taking green chemistry from the labs and computers into the industries is
urgent. The Deep Eutectic Solvents (DESs) are a promising family of green solvents that
possess the desired characteristics of liquids and solids simultaneously. In addition, they have
the potential to be designed or engineered to have the most adequate characteristics for the
application in mind. However, because they are novel, global density estimation models are
not available without requiring other DES properties as their input. This is limiting when one
requires screening for feasibility studies in DESs, especially since a large number of DESs will
be proposed in the future. This study presents, for the first time, a group contribution (GC)
model for densities of DESs. For even greater simplicity, an atomic contribution (AC) model
is also proposed. Both of these models are developed using the most up-to-date databank,
consisting of different types of DESs. The approach is to decompose the molecular structure
into a number of simple predefined groups or atoms. The resulting errors in densities were less
than 3% for both the GC and AC models. Since for a designer solvent, the predictive capability
is of significant importance, the errors of predictions were also checked and shown to be of
high reliability. In this manner, very simple, global, and highly accurate models are proposed
for DESs that do not require any physical property information. This will allow them to be used
as useful predictive models for novel types of green solvents with high potentials in green
technology.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
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Experimental investigation of viscosities for the
mixtures of Ethaline + methanol and Ethaline + ethanol
Reza Haghbakhsh a,b, Ana Rita C. Duarte a, Sona Raeissi b,* a LAQV, REQUIMTE, Departamento de Química da Faculdade de Ciências e
Tecnologia, Universidade Nova de Lisboa, 2829-516 Caparica, Portugal. b School of Chemical and Petroleum Engineering, Shiraz University, Mollasadra Ave.,
Shiraz 71348-51154, Iran.
Keywords: DES, Ethaline, Methanol, Ethanol, Viscosity, Experiment
Scientists and researchers are continually working on proposing green solvents as
alternatives to conventional solvents in order to minimize environmental pollution of the
chemical industries. This will also minimize health concerns for those whose work
environments involve toxic organic solvents. A new category of solvents, the Deep Eutectic
Solvents (DESs), have recently attracted researchers due to their unique physical and chemical
properties, including low volatility, nontoxicity, inflammability, ease of synthesis, and
biodegradability. However, since DESs are still rather new, their properties are mostly not yet
investigated. Viscosity is among the most important properties for a solvent, as it is required
for transport calculations (including mass, heat, or momentum transfer), as well as in
thermodynamic modelling. Industrial simulations also require information on viscosities. In
addition to pure DESs, the viscosities of DES mixtures with different substances must also be
known. Only a limited number of studies on the viscosities of DES mixtures are available in
literature, which themselves are mostly devoted to only aqueous mixture of DESs.
In this work, the dynamic viscosities of mixtures of Ethaline (1 choline chloride + 2
ethylene glycol) with methanol and ethanol are investigated experimentally. This deep eutectic
solvent is one the most commonly researched DESs in the literature. The novel experimental
viscosity data for Ethaline + methanol or ethanol cover the full composition range within a
temperature range of 283.15 to 333.15 K at atmospheric pressure.
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Esterification of rac-menthol in Deep Eutectic
Systems Using Immobilized CRL.
Rita Craveiro a,*, Tânia Neto a, Ana Rita C. Duarte a, Alexandre Paiva a a
LAQV@REQUIMTE, Departamento de Química, Faculdade de Ciências e Tecnologia,
Universidade Nova de Lisboa, 2829-516 Caparica, Portugal,
Secondary alcohols, such as rac-menthol have an undeniable importance in pharmaceutical
or food industries, given its therapeutic properties, characteristic flavor and aroma. Considering
rac-menthol, only the (-)-menthol presents the desired and valuable properties, so a
separation strategy is need for its resolution. Enzymatic kinetic resolution has proved as an
efficient strategy, as for example carrying out an esterification of rac-menthol, catalyzed by an
enzyme such as a lipase. This type of reactions is usually carried out in organic solvents, but
the use of deep eutectic systems (DES) as reaction medium has only recently began to be
explored, presenting several advantages. The use of DES, which are composed by the reaction
substrates, rac-menthol and a fatty acid (lauric acid) has been proposed and allows the
production of the menthyl ester of interest, allowing its posterior separation. In this work, rac-
menthol (M) and lauric acid (LA) DES was used simultaneously as reaction substrates and
reaction solvent. The esterification reaction was catalyzed by Candida Rugosa lipase producing
menthyl laurate (ML), and it was explored the effect of immobilizing the enzyme onto solid
supports to allow its reutilization. Three supports were used, porous acrylic resins XAD16N
and XAD7HP, as well as siliceous porous material Celite 577 fine, yielding an immobilization
efficiency >98%. Different amounts of CRL (13 and 25 mg/mL) were immobilized in the
supports. Celite 577 fine, loaded with 25 mg/mL of CRL, is the support that results in higher
specific activity of CRL, as well as higher ML yield. The effect of water activity was also
evaluated, and when the supported enzyme and DES were incubated in aw between 0.3-0.5.
reaction efficiency was higher. Enzyme reutilization was also evaluated and proved possible.
These results show that enzymatic immobilization is useful for rac-menthol esterification in
DES, and it envisages it is useful for the design of enzymatic packed-bed reactors, allowing this
reaction to occur continuously.
Acknowledgements: The research leading to these results has received funding from the European Union
Horizon 2020 Program under the agreement number ERC-2016-CoG 725034 (ERC Consolidator Grant
Des.solve). This work was supported also by the Associate Laboratory for Green Chemistry-LAQV which is
financed by the ERDF under the PT2020 Partnership Agreement (POCI-01-0145-FEDER-007265). A. Paiva
acknowledges the financial support from project IF/01146/2015 and CryoDES, PTDC/EQU-EQU/29851/2017.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
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Exploring the use of eutectic solvents in the extraction of
proanthocyanidins from by-products
Rodrigo T. Neto a,*, Sónia A. O. Santos a, Joana Oliveira b and Armando J. D. Silvestre a a CICECO - Aveiro Institute of Materials, Chemistry Department, University of Aveiro,
Campus de Santiago, 3810-193 Aveiro, Portugal, b REQUIMTE - Laboratório Associado para a Química Verde, Departamento de Química e
Bioquímica, Faculdade de Ciências, Universidade do Porto, Rua do Campo Alegre, 687,
4169-007 Porto, Portugal
Keywords: Eutectic solvent, proanthocyanidin, microwave, degree of polymerization,
galloylation percentage
Proanthocyanidins, or condensed tannins, are natural polymers composed of catechin units and
its derivatives. These components have been increasingly used in the production of leather,
wood agglomerates and wine, and therefore, their global demand has also increased.
Proanthocyanidins rich extracts are generally obtained with pressurized hot aqueous sulfite
solution using as raw material dedicated crops such as quebracho or mimosa. This method has
low specificity and yield, yet with high cost, which limits their industrial application.
Consequently, the development of novel extraction methodologies and the use of more
sustainable biomass sources such as agroforestry by-products is of great importance. In this
vein, Eutectic Solvents (ESs) have been proposed has good alternatives for conventional
solvents due to their low price, easiness of preparation, biocompatibility, and ability of being
custom made to a specific application.
Herein, we report the use of ESs in the extraction of proanthocyanidins from white grape
pomace. Several hydrogen bond acceptor and donor combinations were tested from which
choline chloride and glycerol can be highlighted due to their high extraction yield. Furthermore,
these compounds synergize very well with the addition of water and ethanol further contributing
to the development of a cheap and sustainable extraction process. In addition, with this
quaternary solvent system it is possible to control the mean degree of polymerization and
galloylation percentage of the final extract, allowing for a customization of the extracts’
characteristics that no other extraction process offers.
Auxiliary extraction techniques such as microwave radiation was also explored from which a
similar yield was obtained by using a combination of choline chloride, lactic acid and water,
with the advantage of achieving it in a shorter period of time and with a higher mean degree of
polymerization reinforcing the potential that ESs have in the improvement of proanthocyanidin
extraction.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
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A Natural Hydrophobic Deep Eutectic Solvent-based
Analytical Method for the Extraction of Plastic migrants
from Edible Matrices
Ruth Rodríguez-Ramos a,*, Álvaro Santana-Mayor a, Bárbara Socas-Rodríguez b, Miguel
Ángel Rodríguez-Delgado a a Departamento de Química, Unidad Departamental de Química Analítica, Facultad de
Ciencias, Universidad de La Laguna (ULL). Avda. Astrofísico Fco. Sánchez, s/n. 38206 San
Cristóbal de La Laguna, España, b Laboratory of Foodomics, Institute of Food Science Research, CIAL, CSIC, Nicolás Cabrera
9, Madrid, 28049, Spain
Keywords: alkylphenol, phthalate, deep eutectic solvent, food, microextraction
Endocrine disrupting compounds have raised great concern in recent years since they can affect
the normal functioning of the hormonal system of humans and biota through different
mechanisms (mimicking or blocking the natural hormone, etc.), even at low concentrations.
Among them, alkylphenols and phthalates are important groups of this kind of contaminants
due to their wide use as additives in plastic industry, what makes them omnipresent in
environment and consumer goods, including foodstuff. This is why analytical methodologies
to determine these organic pollutants at trace levels in edible matrices are needed. In this way,
sustainable research trends have led to the development of a new generation of green solvents,
the so-called deep eutectic solvents (DESs). These neoteric materials have demonstrated several
advantages compared to volatile organic solvents, traditionally used in the extraction step of
sample preparation, such as low cost and easy synthesis, biodegradability, biocompatibility and
non- or low toxicity. Among them, hydrophobic deep eutectic solvents (HDESs) have emerged
as an ideal group of DESs to be applied for extraction in aqueous samples. Within HDESs,
mainly formed by poorly water-soluble compounds, ionic- and non-ionic solvents can be
distinguished, the latter being generally more hydrophobic. The aim of this work was to develop
a dispersive liquid-liquid microextraction based on HDESs formed by combinations of camphor
with menthol and thymol, for the extraction of a group of alkylphenols and phthalates from
vegetable-based milk samples. After the evaluation of HDESs extraction performance, the
methodology was optimised and validated obtaining results that showed its suitability for the
established analytical purpose with recovery values in the range 70-120%, for most analytes.
Separation and quantification were carried out by using ultra-high performance liquid
chromatography coupled to tandem mass spectrometry with low limits of quantification in the
range of µg/kg.
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
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Enhanced Antibiofouling Paints Using Deep Eutectic
Solvents Based on Natural Compounds
Valente S.1, Oliveira F.1, Paiva A.1 Gaudêncio S.1,2, Duarte A. R.1
1LAQV-REQUIMTE, Chemistry Department, Faculty for Sciences and Technology,
NOVA University of Lisbon, 2829-516 Caparica, Portugal 2UCIBIO, Chemistry Department, Blue Biotechnology and Biomedicine Lab, Faculty
for Sciences and Technology, NOVA University of Lisbon, 2829-516 Caparica,
Portugal
Corresponding author email: [email protected]
Keywords: Marine biofouling, Napyradiomycines, Deep eutectic system, Antifouling
paints
Marine biofouling is one of the most challenging problems currently faced by marine
technology. This phenomenon is defined as the undesirable colonization of submerged
man-made surfaces by fouling organisms. Presently, this represents a great material and
economic loss in marine operations, while rising a series of environmental concerns. It is
estimated that antifouling coatings provide the shipping industry with annual fuel savings
of $60 billion, and reduced emissions of 384 million and 3.6 million tonnes per annum,
for carbon dioxide and sulphur dioxide, respectively. However, there is still absent a
universal and green antifouling system. Natural marine products are a potential source
for the discovery of antifouling compounds, representing a promising sustainable
alternative. In this study, the ability of napiradiomycins to inhibit micro and macrofouling
species was explored, with particular emphasis on developing sustainable antifouling
products, namely paints and coatings. Deep eutectic systems (DES) are a promising
alternative to organic solvents commonly used in conventional antifouling products and
they have emerged in the literature as an excellent option for this purpose. In this work,
the DES were based on natural occurring molecules with antifouling activity, such as fatty
acids (oleic acid and 3-hydroxybutyric acid) and terpenes (menthol), which prove to be
good candidates for preparing sustainable, effective and cheap antifouling painting
supplements. For this purpose, firstly DES was characterized by differential scanning
calorimetry (DSC) and nuclear magnetic resonance (NMR), followed by the evaluation
of DES antimicrobial potential towards microorganisms, namely, Staphylococcus aureus
(ATCC 25922), and the results demonstrate that these systems have antimicrobial activity.
The ecotoxicity assessment is currently ongoing in a marine representative animal model
– mussels - a simple model recurrently used in environmental toxicology evaluation. I
hope that my work will be an asset to improve the sustainability of the marine industry.
Acknowledgements: This project has received funding from the European Union’s Horizon
2020 (European Research Council) under grant agreement No ERC-2016-CoG 725034. This work
was also supported by the Associate Laboratory for Green Chemistry – LAQV – which is financed
by national funds from FCT/MCTES (UID/QUI/50006/2019)
Book of Abstracts - 2nd International Meeting on Deep Eutectic Systems
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Glycerol based NADES as green solvents for ultrasound-
assisted extraction of phycocyanin from Arthrospira
platensis-RSM optimization and ANN modeling
Soukaina Hilali a,*, Laura Wils a, Mervé Yagmur a, Barbara Clément-Larosière b, Franck Bonnier c and Leslie Boudesocque-Delaye a
a SIMBA EA 7502 Synthèse et isolement de molecules bioactives, Université de Tours,
Faculté de Pharmacie, 31 avenue Monge 37200 Tours, France b Aqua Eco Culture, 7 rue d'Armor Maroué, 22400 Lamballe, France
c NMNS EA 6295 Nanomédicaments et Nanosondes, Université de Tours,
Faculté de Pharmacie, 31 avenue Monge 37200 Tours, France
Keywords: Natural Deep Eutectic Solvent, Spirulina, Phycoprotein, Reponse surface
methodology, artificial neural network
The aim of this study was to investigate the eco-extraction of Arthrospira platensis
phycocyanin’s via ultrasound-assisted process using different naturel deep eutectic solvents
(NADES). Response surface methodology (RSM) and artificial neural network (ANN) were
adapted in this study for the generation of predictive models to simulate and optimize
phycocyanin extraction for each given NADES. Input parameters were extraction time (15–60
min), temperature (25–50°C), and water addition ratio (20–60%). Those variables were
investigated in order to study their influence on phycocyanin extraction efficiency using Box-
Behnken design. Additionally, correlation coefficients (R2) as well as errors analysis such as
the root mean square error (RMSE), standard error of prediction (SEP), relative percent
deviation (RPD) were calculated and further used to compare the prediction abilities of RSM
and ANN using the validation data set. The stability of phycocyanin in the extract was also
investigated and included in RSM and ANN setting leading to an innovative relevant approach
to design extraction process.
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Biomass-derived itaconic acid-based polyelectrolytes
for synthesis of self-assembled nanocomposite hydrogels
Kacper Mielczareka, Sonia Bujokb, Samuel Wierzbicki, Hynek Benešb,*, Szczepan Bednarza,*
a Faculty of Chemical Engineering and Technology, Cracow University of Technology
Warszawska 24, 31-155 Cracow, Poland, b Institute of Macromolecular Chemistry CAS
Heyrovsky Sq. 2, 162 06 Prague 6, Czech Republic
* [email protected] (HB), [email protected] (SB)
Keywords: Deep Eutectic Solvents, photopolymerization, physical hydrogels, biomonomers
Itaconic acid (IA) is an important renewable monomer, considered as bio-based alternative to
petrochemical acrylic or methacrylic acid. Here, we summarise our very recent findings that
daylight-induced and initiator-free polymerization of Deep Eutectic Monomers (DEMs)
enables synthesis of IA-based polyelectrolytes with unexpected high-molecular weight, which
are suitable for fabrication of self-assembled nanocomposite hydrogels [1]. Relations between
kinetics of initiation and termination processes in DEMs and structure – properties of polymers
obtained will be discussed. The self-assembling behaviour of the polyelectrolytes in the
nanoparticle/dispersant aqueous systems will be also outlined.
References:
[1] K. Mielczarek, M. Łabanowska, M. Kurdziel, R. Konefał, H. Beneš, S. Bujok, G. Kowalski, S. Bednarz. High-
molecular-weight polyampholytes synthesized via daylight-induced, initiator-free radical polymerization of
renewable itaconic acid. Macromolecular Rapid Communications 41 (2020) 190061. DOI:
10.1002/marc.201900611
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Thermal and rheological analysis of different natural deep
eutectic solvents (NADES). Application to the eco-
extraction of bioactive compounds from quinoa leaves
(Chenopodium quinoa Willd.)
Verónica Taco a.c*, Dennys Almachi b, Pablo Bonilla b, Samira Benali b, Jean-Marie Raquezb,
Pierre Duez c, Amandine Nachtergael c a Facultad de Ciencias Químicas, Universidad Central del Ecuador, Quito-Ecuador,
b Center of Innovation and Research in Materials, University of Mons, Mons-Belgium, c Unit of Therapeutic Chemistry and Pharmacognosy, Faculty of Medicine and Pharmacy,
University of Mons, Mons-Belgium
Keywords: NADES, thermal and rheological behaviours, quinoa leaves, eco-extraction
Introduction: Natural deep eutectic solvents (NADES) have emerged as a recent generation of
green solvents. They can dissolve efficiently natural compounds with the major advantages of
biodegradability and biocompatibility; their physico-chemical properties can be fine-tuned by
modulating their composition and water content. Quinoa is one of the most important
pseudocereals of Andean origin, rich in bioactive compounds. The thermal and rheological
behaviours of different NADES were investigated and their suitability to extract bioactive
compounds from quinoa leaves was assessed.
Methods: Quinoa leaves, variety INIAP Tunkahuan, were collected in the Instituto Nacional
de Investigaciones Agropecuarias (INIAP), Quito-Ecuador. NADES were prepared by heating
method in the following molar ratios: malic acid-choline chloride (chcl)-water (w) (1:1:2, A),
chcl-glucose-w (5:2:5, B), proline-malic acid-w (1:1:3, C), glucose-fructose-sucrose-w
(1:1:1:11, D), 1,2-propanediol- chcl-w (1:1:1, E), lactic acid-glucose-w (5:1:3, F), glycerol-
chcl-w (2:1:1, G) and xylitol-chcl-w (1:2:3, H). Different amounts of water were added to
NADES A to D to decrease their viscosities; the effects of water addition on NADES thermal
stabilities and viscosities were studied by calorimetry (DSC) and rheometry (evaluation of shear
stress using a rheometer cone /plane), respectively. The flavonoids profiles of NADES-quinoa
leaves extracts were evaluated using HPTLC.
Results: The NADES viscosity significantly decreased after water addition; 17.5%, 20%, 10%
and 10% were the maximum amounts of water that could be added to NADES A, B, C and D,
respectively, to avoid the disruption of eutectic environment. The viscosities of all NADES
were highly dependent on time and shear stress. NADES E and G gave the best results in terms
of stability and extraction efficiency of flavonoids from quinoa leaves.
Conclusions and perspectives: Eco-extraction of quinoa leaves bioactive compounds is
possible using NADES; given their low toxicity, these solvents allow direct addition of extracts
to food formulations and pharmaceutical products thanks to a good understanding of thermal
and rheological behavior of NADES. The stability of NADES-quinoa leaves extracts is now
being investigated by chromatography and calorimetry.
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Preparation of Thermo-responsive Hydrogels via
Polymerizable Deep Eutectic Monomer Solvents
Yeasmin Nahara,*, Stuart C. Thicketta, Alex C. Bissembera , James Horneb and Vinh Truongc a School of Natural Sciences (Chemistry), University of Tasmania, Hobart, TAS 7001,
Australia b Central Science Laboratory, University of Tasmania, Hobart, TAS 7001, Australia
cSchool of Chemistry and Physics, Queensland University of Technology, Brisbane, QLD
4000, Australia
We report the preparation of thermoresponsive poly(N-isopropylacrylamide) (polyNIPAM)
hydrogels via the free radical polymerization of deep eutectic monomer solvents (DEMs) for
the first time, where NIPAM serves as a polymerizable hydrogen bond donor. DEMs were
prepared by a simple heating and stirring protocol using NIPAM and either choline chloride
(ChCl) or acetylcholine chloride (AcChCl) (as hydrogen bond acceptor) in various ratios to
yield low-melting point liquids (as low as 15 °C). 1D and 2D NMR spectroscopy supported the
association of the NIPAM and choline salts present within the DEM structure, in addition to
the low self-diffusion coefficients of the species present compared to when dissolved in water.
Thermogravimetric analysis demonstrated an enhanced thermal stability of the DEMs
compared to NIPAM. Hydrogels prepared by free-radical polymerization of the prepared DEMs
in the presence of N,N′-methylenebisacrylamide (BIS) as crosslinker showed a significant
increase in reaction rate compared to the equivalent reaction in water, which was attributed in
part to the high viscosity of the DEMs. These gels exhibited thermoresponsive swelling
behaviour when immersed in water. Specifically, gels prepared via DEMs featured reduced
swelling capacity and increased mechanical strength relative to those prepared by aqueous
polymerization, attributed to a significant increase in cross-linking density.
Figure 1. The formation of deep eutectic monomer solvents and Schematic diagram of thermo-responsive hydrogels
formation.
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https://eventos.fct.unl.pt/desmeeting2021