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
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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
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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