New chelating glucose-based surfactants
Transcript of New chelating glucose-based surfactants
New chelatingglucose-based surfactants
Nadège FERLIN
Laboratoire des Glucides – UMR 6219
Université de Picardie Jules VERNE
AMIENS
A Greener Chemistry for Industry – 2 au 5 octobre 2007 – Villeneuve d’Ascq
I. GENERAL : Heavy metals pollution
In France, more than 3800 sites are polluted by heavy metalsPollution due to human activitiesCause environmental and health problems
To treat :
Biological treatements : phytoremediationPermeabilisationPhysical and chemical treatments : oxido-reduction, precipitation, extractions, flotation
I. GENERAL : FlotationEvacuate metallic pollutants of an aqueous phase with surfactants and an air bubbling
Surfactant :Amphiphilic molecule
Hydrophilic moiety:Polar head ionic or non-ionic
Hydrophobic moietyCarbon chain
Adsorption at the interfaces then formation of micelles :decrease superficial and interfacial tensions, detergency, emulsion, foaming,…
What about flotation ?
Pollutedwater
Adding ofsurfactants
Adsorption
Air bubbling Evacuation of pollutantswith the foam
S
S-
RO
S
S-
N
R
R
I. GENERAL : Chelating Surfactant
Koide et al.
NO2
R
H2N
R N N
SO3 -
-O3S
X
X
X = COOH, SO3-
R N N X
Uranium’s flotation Bull. Chem. Soc. Jpn., 56, 3364-69, (1983) Bull. Chem. Soc. Jpn., 59, 715-720, (1986)
Woller et al. : Quinoline and oxime derivatesfor liquid-liquid extraction
N
OH
R
N
OH
R
Colloid surface A, 117, 189-200, (1996)
Sawada et al. : hydrophobicallymodified EDTA for cosmetic use
N
N
COOR
COO-
-OOC
-OOC
US Patent Application 0030032573, (2003)
II. SYNTHESIS : Our molecules
Chelating functionY = OH, aminoacids skeleton
Hydrophilichead
(glucose)
Hydrophobic tailGlycosidation of fatty alcohol
O
OH
OH
OH
OR
HN
O
Y
In 3 steps :Oxidation of theprimary alcohol
Target :Best efficiency as possible for metalextraction combined with easy, fastand non-expensive reactions
Sugar :Good solubility in water, non-toxicNatural and cheap ressources
Sugar-based surfactants are known as biogradable and good foaming agents
II. SYNTHESIS : Glycosidation
O
OAc
OAc
OAc
OAc
OR
O
OAc
OAc
OAc
OAc
OAc
a) ROH (2eq), ZnCl2, µ-waves
b) Ac2O, Py
ρ = 70-80 %
O
OH
OH
OH
OR
OH
MeONa, MeOH
ρ > 90 %
Use of microwaves irradiation : often use in green chemistryNo solvent, economy of energiesVery fast reactions with good yieldUseful with different fatty alcohols R = CnH(2n+1) avec n=6, 8, 10, 12, 16Control of the anomers ratio
II. SYNTHESIS : Glycosidation
% alpha
0
0.2
0.4
0.6
0.8
1
0.5 1 2 3 4 5 7 9 10 11
reaction time (min)
Hexanol
Octanol
Decanol
Dodecanol
Hexadecanol
Control of the anomers ratio
Difficulties to separate the anomers
II. SYNTHESIS : Oxidation
Oxidation on protected glucosides
Direct oxidation
O
OH
OH
OH
OC8H17
COOH
O
OH
OH
OH
OH
OC8H17
TEMPO : ρ = 89 %Very long reaction, purification problems
O2/Pt in basic medium : ρ = 36 %Long reaction and expensive
O
OH
OH
OH
OH
OC8H17
O
OAc
OAc
OAc
OTr
OC8H17
O
OH
OH
OH
OC 8H17
COOH
O
OAc
OAc
OAc
OC 8H17
COOH
a) TrCl, Pyb) Ac2O
ρ = 84 %
CrO3 cat., H5IO6CH3CN/H2O
ρ = 85 %
MeONa, MeOH
ρ > 90 %
II. SYNTHESIS : Coupling – Hydroxamic acid
Unprotected coumpond
Protected compound
O
OH
OH
OH
OC8H17
COOH
O
OH
OH
OH
OC8H17
COOMe
O
OH
OH
OH
OC8H17
CONHOH
Anh MeOH, H2SO4
ρ = 90%
NH2OH 50% aqueous, MeOH
ρ = 73%
O
OAc
OAc
OAc
OC8H17
COOH
O
OAc
OAc
OAc
OC8H17
COOMe
O
OH
OH
OH
OC8H17
CONHOH
MeI, Bu4NIKHCO3,anh. DMF
ρ = 75%
NH2OH 50% aqueous, MeOH
ρ = 67%
III. INTERFACIAL PROPERTIES
γ
Log (C)
CMC critical micellar concentration
Measure the superficial tension depending on the log of the concentration
water
air
micelle
HLB calculated by modelisation
Other properties are also determined
III. INTERFACIAL PROPERTIES
20,6 ± 2,6 C8 β CONHOH
20,7 ± 1,3C8 α CONHOH
15,6 ± 1,5C8β COOH
13,1 ± 1,8C8α COOH
CMC (mM)Compounds
The « capillar » method (Castro et al, J. Chem. Educ., 78, 347, (2001))
Method reposing on Laplace law
Capillar in a solution of surfactants Difference of pression is proportional to the tension
γ = (r/2)*d*g*∆h
Octyl-α-D-glucopyranoside : 10.0
IV. METAL EXTRACTIONFlotation test
Tested metals : Fe(III), Cu(II), Cd(II), Cr(III), Ni(II), Zn(II)
3 times reapeted
Mixing of surfactant and metal introduced in a column reliated to a pump air
Quantification by ICPUse the « adding method » because of the matrix effect of the surfactants
III. METAL EXTRACTION
Visual good resultswith iron and C8bCONHOH
Initial Residual liquid Foam
0
0.5
1
1.5
2
2.5
3
3.5
Ef
C8aCOOH C8bCOOH C8aCONHOH C8bCONHOH
Fe
Cd
Cu
Extraction factor
Ef =liquidmetal
foammetal
C
C
ACKNOWLEGMENTS
Laboratoire des GlucidesUPJV-AMIENS (France)
Pr. José KOVENSKY and Dr. Eric GRANDGaétane SERVANT, Thomas MEYER, Sébastien DAUPHIN and Danavathani KANTHASANY
Centro de Estudios Transdiciplinarios
del Agua (CETA)Facultad veterinarias
de BUENOS AIRES (Argentina)
Pr. Alicia FERNÀNDEZ-CIRELLIDr. Mariano CASTRO, Carlos OJEDA and Diego GRASSI
Financial supports: Délegation Générale pour l’Armement CNRS - CONICET
Thanks for your attention
Any questions ?