IN THE NAME OF IN THE NAME OF GODGOD

Nanoparticles in modern Nanoparticles in modern

separation scienceseparation science

Nano scienceNanotechnology is science, engineering, and technology conducted at the

nanoscale , which is about 1 to 100 nanometers.

nanotechnology are the study and application of extremely small things

and can be used across all the other science fields

, such as chemistry, biology,

physics ,materials science

, and engineering.

E.Guihen,TrendsAnal.Chem.46(2013)1-14 2

Nanoparticle applications in modern

separation scienceUse of NPs in:

•Capillary electrophoresis

•Open tubular capillary electro chromatography

•Liquid chromatography

•Gas chromatography

•Ion chromatography

•Microchip electrophoresisE.Guihen,TrendsAnal.Chem.46(2013)1-14

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The Potential of NPs in separation science

1. NPs are relatively easy to synthesize.

2. NP size is carefully controlled during chemical using the reaction

conditions (e.g. , temperature ,pressure , and solution pH).

3. NPs differ in their chemical and physical properties from the parent

bulk-chemical material

4. NPs can be functionalized by a wide range of different chemistries , with

amino(NH2), thiol(SH)and carboxyl(COOH).

E.Guihen,TrendsAnal.Chem.46(2013)1-14

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The Potential of NPs in separation science

5.Several Kinds of NP and nanostructure have been applied to separation

science , including fullerenes, nanotubes ,silica, polymers,

zeolite ,lipids ,latex , metal oxides , and Silver NPs(Ag NPs)and Au NPs

6.AuNPs are the most popular in separation science,due to their inert

nature ,ease of functionality with thiol groups

7.NPs display a large surface area-to-volume ratio,which is ideal for low

mass transfere in chromatography .This feature is also invaluable in

miniaturized electro-migration techniques (e.g.,MCE)

E.Guihen,TrendsAnal.Chem.46(2013)1-14 5

The Potential of NPs in separation science1. These applications are mainly reported in academic research

Laboratories ,where separation success has been greater than or

equivalent to current state-of-the-art chromatographic and

electrophoretic methods .

2. In spite of this Success ,this technology has not penetrated industrial

chemistry laboratories (e.g., pharmaceuticals and forensics).

3. In some cases ,these small particles have offered extraordinary benefits

in terms of separation efficiency , selectivity and resolution

E.Guihen,TrendsAnal.Chem.46(2013)1-14 6

Features of Nano particles in analytical chemistry

NPs have been used in analytical chemistry

•Mono functional NPs : have been the selected choice and have

primarily been used in analytical chemistry to provide a single function

•Multi functional NPs : can achieve a multi or mixed effect using one

system and applications to in medical imaging and drug delivery , could hold great

potential in the separation of complex biological sample ,as many analytes may

be monitored simultaneously

E.Guihen,TrendsAnal.Chem.46(2013)1-147

Some of the characteristic chemical features of a

monolayer-protected gold NP(AuNP)colloidal solution

The characteristic strong wine-red

color is apparent

E.Guihen,TrendsAnal.Chem.46(2013)1-14 8

Some of the characteristic chemical features of a monolayer-protected gold NP (Au NP) colloidal solution

E.Guihen,TrendsAnal.Chem.46(2013)1-149

(TEM)Shows the solution consists of spherical particles with an average size of 5nm

Visible spectrum shows Weak plasmon -resonance absorption maxima in therange )490–510nm(with λmax of 501nm,which further confirms the nanometer)nm(range of the Au NPs

A multifunctional NP

E.Guihen,TrendsAnal.Chem.46(2013)1-1410

A multifunctional NP, which can be doped with a different NP and/or a dye.

Liquid chromatographyLiquid chromatography

E.Guihen,TrendsAnal.Chem.46(2013)1-14 11

• In LC,NPs have been used less extensively due the high back pressure

that would be generated coupled with frictional heating effects.

LC instrumentation is not designed to with stand the ultra high pressures

that a nano -sized packed bed would generate.

• In 2002 , Cintron and Colon slurry-packed organo -silica NPs into

fused silica capillaries )50-µm internal diameter(,which were then

tested in ultra high pressure LC )UHPLC(.

Liquid chromatographyLiquid chromatography

E.Guihen,TrendsAnal.Chem.46(2013)1-14 12

Chromatograms of a test mixture obtained at pressures of (left) 5000 psi and (right)50,000psi1)ascorbic acid;(2)hydroquinone;(3)resorcinol;(4)catechol(5) 4-methylcatechol. dp = 670nm.UVdetectionat215nm. Fused silica packed column . Column included stability under extreme acidic (pH<1)and basic (pH>11) conditions

Short analysis times and High separation efficiencies)500,000plates/m( for LC

Pressure LC(UHPLC).

Liquid Liquid chromatographychromatography

• In 2006 Kobayashi et al reported three kinds of thiol-modified AuNP-coated

polystyrene packing for LC . Compared to the octadecyl silica(ODS)column ,

different selectivities for aromatic compounds were observed using this column ,

indicating that this kind of novel column could be used to achieve unique

separation for different samples.

• Wu et al.reported a novel core-shell composite[ SiO2-nLPD (liquid-phase

deposition)], consisting of µm-sized silica spheres as a core and nm-sized titania

particles as a surface coating, were prepared by LPD.

• The benefit of last method:The benefit of last method:

E.Guihen,TrendsAnal.Chem.46(2013)1-1413

Liquid chromatographyLiquid chromatography(1) pyridine;(2)o-methylaniline;(3)N-methylaniline;and,(4)N,N-dimethylaniline

• the work showed that the core-shell composite can efficiently separate phosphate

compounds due to the Lewis acid-base interaction between titania and phosphate

group ,when used as LC packing

E.Guihen,TrendsAnal.Chem.46(2013)1-14 14

Liquid chromatographyLiquid chromatography

• Dun et al. Developed a zirconia-based LC packing material,ZrO2/SiO2, which

consisted of µm-sized silica spheres as core and nm-sized zirconia particles as a

surface coating , formed by layer-by-layer self assembly . The support

,ZrO2/SiO2, and the stationary-phase,C18 bonded ZrO2/SiO2 , exhibited

excellent chemical stability . In addition ,good permeability was observed for

both . The large specific surface area and good permeability of ZrO2/SiO2

permitted a high loading of chiral polymer Onto it , and greatly improved the

enantioselectivity and the resolution for chiral separations

E.Guihen,TrendsAnal.Chem.46(2013)1-14 15

Gas chromatographyGas chromatography

• GC has seen even less activity in relation to the use of NP stationary phases.

Perhaps this may be because GC has enjoyed very high efficiency due to the long

capillary Lengths and fast diffusion rates compared to LC. Also , the stationary

phases in GC need to be very inert and withstand very high temperatures , so

they may not be suitable for NPs

E.Guihen,TrendsAnal.Chem.46(2013)1-14 16

Gas chromatographyGas chromatography• Na et al developed a ionic liquid-dispersed silica NPs(IL-SN)capillary column,

Combining properties of silica NPs and IL for GC . By Dispersing silica NPs in a

conventional ILof1-butyl-3-Methyl imidazolium hexafluoro phosphate([Bu-

MIm][BF6]) This coating integrated the advantages of silica NPs (i.e. large surface

area ,and highly dispersed behavior)and the IL(i.e. extended liquid State

temperature range ,and chemical stability),hence increasing interactions

between the stationary phase and target analytes .

Mixtures of a wide range of organic compounds ,Including alcohols , esters ,

alkanes , aromatic compounds,

as well as isomers and non-polar compounds ,were Separated using the IL-SN

capillary column .

E.Guihen,TrendsAnal.Chem.46(2013)1-14 17

Gas chromatographyGas chromatography

E.Guihen,TrendsAnal.Chem.46(2013)1-14 18

GC chromatograms of mixtures of volatile)A(and non-volatile )B(aromatic compounds by

three capillary columns .)a(Ionic liquid-dispersed silica nanoparticles )NPs(capillary

column;)b(silver NPs capillary column ;and,)c(ionic liquid capillary column .Column

temperature Was 50 C for)A(,and 50 C )5min(–100 C )20min(for)B(

MicrochipMicrochip electrophoresis electrophoresis

E.Guihen,TrendsAnal.Chem.46(2013)1-14 19

For protein, DNA, RNA and other important bio molecular analysisFor protein, DNA, RNA and other important bio molecular analysis

Where by pre concentration ,derivatization ,separation and detection of complex biological samples are carried out on-chip based plat forms

Separation Separation mechanismmechanism of the electrophoretic of the electrophoretic microchipmicrochip system system

E.Guihen,TrendsAnal.Chem.46(2013)1-14 20

Microchip electrophoresisMicrochip electrophoresis

Liang et al developed for the modification of a poly (dimethylsiloxane) (PDMS)

microchip channel with polydopamine/AuNPs(PDA/AuNPs)

•The AuNPs were highly and uniformly dispersed in/on the polydopamine matrix

with an arrow size distribution . A high-speed , efficient separation of five amino

Acid was obtained on the poly dopamine / AuNP-functionalized PDMS microchips.

E.Guihen,TrendsAnal.Chem.46(2013)1-14 21

Types of Columns

E.Guihen,TrendsAnal.Chem.46(2013)1-1422

Capillary Electrophoresis And Open Tubular capillary electro chromatography

• NPs use in OTCEC as inner wall coatings or powerful additives to the background

electrolyte(or used as pseudo stationary phase(PSP)-CEC where by NPs are

added to the buffer)

• highly efficient electro chromatographic separations by using alkylthiol Au NPs

• Nilsson et al. High lighted that NP-based CEC gives high speed and

resolution , greater peak capacity ,requires small amounts of sample and

can be coupled with MS

• Zhu et al coated the inner walls of a capillary for OTCEC with magnetic NPs

E.Guihen,TrendsAnal.Chem.46(2013)1-1423

Capillary Electrophoresis And Open Tubular capillary electro chromatography

• Yang et al used cyclodextrin-modified AuNPs for enantiomeric separation of drugs and amino acids

E.Guihen,TrendsAnal.Chem.46(2013)1-14 24

Capillary Electrophoresis And Open Tubular capillary electro chromatography

• Qu et al investigated the use of an octadecyl-amine capped AuNP

capillary column for bio analysis

• Wang et al Added silica NPs to the buffer in CE

• Li et al demonstrated the use of amphiphilic silica NPs as PSP in CE for

separation of basic and aromatic compounds

E.Guihen,TrendsAnal.Chem.46(2013)1-1425

Ion chromatographyIon chromatography

Monolithic columns are frequently used in separation science

Cao and co-workers developed a porous polymer monolithic capillary column

modified with Au NPs coated with exchange able functionalities that allowed easy

switching of separation modes by a simple ligand-exchange process

E.Guihen,TrendsAnal.Chem.46(2013)1-14 26

Ion chromatographyIon chromatographySurface modifications of a single poly (glycidyl methacrylate-co-ethylene dimethacrylate) Surface modifications of a single poly (glycidyl methacrylate-co-ethylene dimethacrylate) monolith reacted with cystamine and containing gold nanoparticles (AuNPs)monolith reacted with cystamine and containing gold nanoparticles (AuNPs)The dashed arrow indicates that the same functionality can also be prepared via direct reaction of the AuNPs containing the monolith with the respective thiol group containing compound

E.Guihen,TrendsAnal.Chem.46(2013)1-14 27

First, the column is treated with3-thio propionic acid ,then with mercaptoethanol ,and finally with cystamine .

Ion chromatographyIon chromatography

E.Guihen,TrendsAnal.Chem.46(2013)1-14 28

Separation of proteins in ion exchange mode using a poly)glycidyl

methacrylate-co-ethylene dimethacrylate( monolithic column with attached gold

nanoparticles )Au NPs( and modified with sodium 2-mercapto ethane sulfonate .

)1(myoglobin;)2(ribonuclease 3( cytochrome

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