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Separation science,
especially chromatography, is an analytical chemistry discipline
that is used to separate, isolate, and quantify compounds from
complex mixtures. Chemists in pharmaceutical companies use the
separation techniques to isolate a product from a reaction mixture,
to isolate active components from natural products, to identify
possible breakdown products of drugs, and to carry on chiral
separation to isolate the active enantiomeric drug from inactive
one. Environmental chemists use the separation techniques to
quantify the amount of an analyte present in a sample and to assess
the fate and transport of a compound in the environment.
My research
interests are: 1) to synthesize, characterize, and utilize novel
monomeric and polymeric chiral and achiral surfactants and apply
them as pseudostationary phases for enantioseparation of chiral and
achiral molecules using capillary electrophoresis (CE), a separation
science technique; 2) to develop methods for real life experiments,
e.g., quantification of chemicals (drugs and their metabolites) in
body fluids and in environment (PAHs, PCBs, explosive residuals); 3)
to investigate partitioning mechanisms between pseudo-stationary
phases and analytes using linear salvation energy relationships (LSER)
model; 4) to separate carbon nanotubes (CNTs), as a nanoscience
project, using both CE and high performance liquid chromatography (HPLC);
and 5) to use CNTs as pseudostationary phases in CE.
One of my major
goals is to work with undergraduate students on small projects to
make sure our students get involved in research and get enough
experience for graduate school or for a better job. To accomplish
this, I intend to use a variety of analytical tools such as CE, HPLC,
gas chromatography (GC), fluorescence, ultraviolet, infrared
spectrometry, densitometry, and surface tensiometry to make sure
undergraduate students get familiar with a variety of analytical
instruments. Which technique gets more attention will depend on the
availability of the instrument we have in my research laboratory or
in the department. There is a CE and density meter in my research
laboratory. For other technique, I will use the department’s
resources.
CE is a technique
that separates compound mixtures on the basis of electrophoretic
mobility differences. Recently, CE has become widely used in various
fields. CE can offer advantages over other separation techniques
such as HPLC and GC. CE is a powerful and practical tool because of
its high resolution, ability to analyze impure samples, low reagent
consumption, short analysis time and low running cost. Due to these
strengths, CE has been used in the Genome Project as a powerful and
practical separation tool.
By manipulating the
separation media, separation systems can be devised for very
specific purposes. There are several well known CE modes that can be
utilized using the very same instrument. These modes are: capillary
zone electrophoresis (CZE), capillary gel electrophoresis, capillary
isotachophoresis, capillary isoelectric focusing, and micellar
electrokinetic chromatography (MEKC). Due to their lack of
electrical charge, neutral molecules cannot be separated by CZE.
However, in MEKC, the separation media has been manipulated to allow
for the separation of neutral as well as the charged compounds.
MEKC utilizes a
micelle forming compound (called pseudo-stationary phase) to obtain
separation of analytes. Virtually any micelle forming compound can
be added to the buffer system to obtain separation. Sodium dodecyl
sulfate (SDS, the soap found in shampoos), is a commonly used
micelle forming additive. Analytes partition between the mobile
buffer phase (usually aqueous or organic solvent modified) and the
pseudo-stationary phase as they move through the separation
capillary. Conventional surfactant (e.g., SDS) micelles are
successfully used in separations of hydrophilic and slightly
hydrophobic analytes. However, one should add organic modifiers to
the buffer system for separation of highly hydrophobic analytes
(such as polycyclic aromatic hydrocarbons, PAHs). Higher organic
modifier concentrations tend to disrupt the conventional micelles
and eventually affect the separation quality.
Polymeric
surfactants (or molecular micelles) have gained popularity as
potential pseudostationary phases for separations in MEKC in the
recent years. A considerable interest in the use of polymeric
surfactants arises because of their distinct advantages over
conventional micelles. First, they have zero critical micelle
concentration (cmc); thus, they may be used at concentrations well
below the cmc of the unpolymerized surfactants. Second, molecular
micelles are stable in the presence of a high content of organic
solvents due to the covalent bond between surfactant monomers.
Hence, organic additives do not disrupt the primary covalent
structure of the micelle polymer. One should keep in mind that most
biological samples typically comprise polar compounds that may also
contain hydrophobic moieties. Thus, the use of organic solvents in
combination with micelles is often required for the analysis of such
compounds. In addition, the fixed micellar structure prevents
dissociation of surfactant molecules during the electrospray process
in mass spectrometry (MS). Third, due to their high molecular
weight, molecular micelles can be conveniently used in MEKC-MS
applications without background interference from surfactant
monomers of low molecular weights. Fourth, lower surface activity
and low volatility of molecular micelles provide a stable
electrospray and hence less suppression of analyte signal in MEKC-MS.
Carbon nanotube (CNT),
the forth allotrope of carbon, was discovered in 1991. The backbone
of CNT is composed solely of carbon atoms, arranged in benzene rings
forming graphene sheets, rolled up to give seamless cylinders with
several micrometers in length and nanosized diameter. CNTs hold
strong promise for nano- and biotechnological applications. There
are two main types of CNTs, single wall (SWCT) and multi wall carbon
nanotubes (MWCNTs). Depending on their diameter and chirality, CNTs
can be metallic or semiconducting. The semiconducting CNTs offer
possibilities to create semiconductor-semiconductor and
semiconductor-metal junction which may be useful in electronic and
sensor devices. CNTs have been proposed and used in a number of
different applications, including field emission, energy storage,
hydrogen storage, molecular electronics, atomic force microscopy,
and many other areas such as drug delivery systems. Applications of
CNTs in the field of biotechnology are raising great hopes. CNTs
have been proposed as DNA and protein biosensors, ion channel
blockers and as bioseparators. In addition, their use is becoming
relevant in neuroscience research and tissue engineering. CNTs have
also been used for detection of antibodies associated with human
autoimmune diseases with high specificity.
A major drawback of
CNTs is their complete insolubility in all types of solvents. In
addition, CNTs tend to agglomerate in the form of close-packed
arrays termed ‘‘nanoropes’’ owing to their similarity to
conventional ropes. These arrays contain hundreds of nanotubes.
Pure, monodisperse nanotubes will be essential for aforementioned
applications. Dissolution and purification of CNTs are important
steps to fully understand their properties and take a full advantage
of their applications. Several methods have been introduced and
proposed for purification of CNTs. For example, chemical oxidation
removes amorphous carbon and catalyst particles, filtration and
centrifugation are also used to purify CNTs. Size exclusion
chromatography (SEC) and CE effectively purifies carbon nanotubes.
Unfortunately, SEC, and CE do not provide direct, detailed
information on particle size distributions. In addition, a
pre-condition for efficient separation is that the CNT “ropes” are
individualized. This can be achieved by suspending CNTs in aqueous
surfactant solution under sonication, where CNT bundles (or ropes)
split up and the individualized CNTs then being hindered by the
surfactant to rebundle. The excess bundles can be removed by
centrifugation. In this research project, we intended to develop a
method that could be used for separate CNTs based on their chirality
and length. As-prepared CNTs are composed of a variety of nanotubes
with different diameter, length and chiralities. One has to sort
them based on their chirality or length for certain applications.
The separation of CNTs based on length and, especially, chirality
remains a challenge for nanoscientists today. |