Session 4 - hinze.pdf

Expanding the Utility and Understanding of Room Temperature Ionic Liquids:
Including Micelle Formation and Interactions with Gold Nano-particles
DANIEL W. ARMSTRONG, Department of Chemistry, Iowa State University, Ames,
Iowa 50011, [email protected].

Room temperature ionic liquids (RTILs) cannot be adequately characterized on the basis
of polarity or any single parameter scale. RTILs are complex entities compared to the
relatively simple molecular solve nts used in most chemical processes.[1] They are
capable of a wider range of intermolecular interactions than most other solvents. This
includes: dispersive, n-π, π-π, dipolar, hydrogen bonding, hydrophobic, and ionic
interactions. A multi-parameter scale, that takes into account the many different possible
solvent properties, can be used to properly characterize RTILs as well as other solvents.[1]
Their unique properties appear to induce the formation of solvophobic normal micelles
when surfactants are dissolved in RTILs.[2] Also, gold nano-particles are more easily
formed and dispersed in RTILs than in normal solvents.[3] We can now understand why
RTILs behave differently than single solvents for organic reactions, and which ones are
most promising as MALDI matrixes,[4] for extractions and as chromatographic stationary
phases.[5,6] Chiral ionic liquids and their use will be discussed as well.[7]
Development of a Universal Method for the Determination of Enantiomeric
Compositions of Pharmaceutical Products
CHIEU D. TRAN, Victor I. Grishko and Daniel Oliveira, Department of Chemistry,
Marquette University, P. O. Box 1881, Milwaukee, Wisconsin 53201;
[email protected].
A new method has been developed for the determination of enantiomeric compositions of
a variety of drugs including propranolol, atenolol, and ibuprofen. The method is based
on the use of the near- infrared (NIR) technique to measure diastereomeric interactions
between an added carbohydrate compound with both enantiomeric forms of an analyte
followed by partial least square analysis of the data. The fact that the method works well
with all three macrocyclic carbohydrates with different cavity size (i.e., α-, β- and γ-
cyclodextrin) as well as with sucrose, which is a linear carbohydrate, clearly
demonstrates that it is not necessary to have inclusion complex formation in order to
produce effective diastereomeric interactions. Rather a simple adsorption of the analyte
onto a carbohydrate is sufficient. Since inclusion complex formation is not a requisite,
this method is not limited to the amino acids studies here but is rather universal and
sensitive as it can, in principle, be used to determine enantiomeric compositions for all
types of compounds wit h only microgram concentration and enantiomeric excess as low
as 1.5 %, in water or in a mixture of water and organic solvent. Furthermore, it does not
rely on the use of rather expensive carbohydrates such as cyclodextrins but is equally as
effective even with a simple and inexpensive carbohydrate such as sucrose.
Determination of Environmentally Important Metal Ions by Fluorescence
Quenching in Micellar Solutions
F. Nome, H. D. FIEDLER, E. Sapelli, G. C. Bedendo, R. S. Mello and L. V. Vargas,
Departamento de Quimica, Universidade Federal de Santa Catarina, Caixa Postal 476,
Florianopolis, SC, 88049-970, Brazil, [email protected]
This work describes the determination of environmentally important metal ions by
fluorescence spectroscopy in micellar solutions. Several metal ions have been used as
quenchers of the fluorescence of naphthalene, in aqueous micellar sodium dodecyl sulfate
(SDS). The quenching by the metal ions can be described by the Stern-Volmer equation
and the detection limits are improved with low SDS concentrations. Apparent Stern-
Volmer constants decrease in the order: Fe3+ > Cu 2+ > Cr3+ > Ni2+ > Pb2+ and reflect the
sensitivity of the method. Similarly, using the cationic chelating agent 8-
hydroxyquinoline (8-HQ), allows the simple, rapid and sensitive assay of Zn2+ in aqueous
micellar solutions of cetyl trimethyl ammonium bromide (CTABr). In the absence of
CTABr, the complex formed between 8-HQ and Zn2+ is insoluble. Micelle-enhanced
fluorescence spectroscopy and fluorescence quenching can be used as analytical methods
of general application and is an interesting area of research to improve the detection limit
of several analytical methods.
Solid-Phase Microextraction: a Link between Micellar Extraction and Gas
VERÓNICA PINO, Francisco J. Conde, Juan H. Ayala, Ana M. Afonso and Venerando
González. Department of Analytical Chemistry, Nutrition and Food Sciences, University
of La Laguna, E-38205, Spain, [email protected].
The Micellar Solid-Phase Microextraction (MSPME) is a new technique for sample
treatment. MSPME intends to combine the advantages of the micellar extraction with the
advantages of the gas-chromatography by means of the solid-phase microextraction
(SPME). The present work shows not only the use of MSPME to quantify solutes in solid
matrixes but also its ability to determine partition coefficients of solutes between micellar
media and aqueous phases.
In the first case, the PAHs contained in a reference marine sediment have been extracted
with surfactants. Afterwards, these compounds are removed from the micellar media by
using the adequate SPME fiber, and determined by GC-MS. This step is accomplished
just desorbing the SPME fiber in the injector of the GC, without needing to remove the
surfactant prior to injection. With this new method, the previous treatments in the
analysis of any non-polar compound contained in solid samples could be reduced to a
stage of solubilization of the same ones in a micellar medium followed by a separation
using SPME-GC.
In the second case, the partition coefficients of 16 PAHs and 29 Phenols between ionic
and non- ionic micellar media and aqueous phases have been established using MSPME.
The obtained results show that this technique is especially adequate by its simplicity and
by leaving the binding equilibrium undisturbed.
Development of Functionalized Admicelles in Separation Science
T. SAITOH and M. Hiraide, Graduate School of Engineering, Department of Molecular
Design and Engineering, Nagoya University, Chikusa, Nagoya, Aichi 464-8603, Japan,
[email protected].
Surfactant molecules cooperatively sorb on solid surfaces and form aggregates namely
hemi- micelles or admicelles in the aqueous solution. Through mixing of surfactants,
porous solid materials, and hydrophobic chelating agents or surfactant-conjugated
substrates (affinity ligand) in the aqueous solution led to the formation of media for the
collection of metal ions or proteins. Different from conventional separation media
having chemically bound ligand, the functionalized admicelles have degree of freedom in
the preparation. Furthermore, dynamic property and high water permeability of the
admicelles can facilitate the interaction of ligand with an objective compound. An
admicelle composing of Triton X-100, porous polystyrene-divinylbenzene (Amberlite
XAD-4), and Triton X-100-conjugated Cibabron blue 3GA (affinity ligand) was found to
be useful for purifying lysozyme from egg white, but was ineffective for the collection of
alcohol dehydrogenase (ADH). The uses of octadecylsilyl-silica gel instead of XAD-4
and an affinity ligand having a longer polyoxyethylene moiety were effective for the
separation of ADH from bakers’ yeast.
Powerful Preconcentration Method for Ultra Trace Amounts of Polycyclic Aromatic
Hydrocarbons and its Application to the Environmental Analysis
Shukuro Igarashi, Department of Biomolecular Functional Engineering, Faculty of
Engineering, Ibaraki University, Nakanarusawa 4-12-1, Hitachi, Ibaraki 316-8511, Japan,
[email protected]; and YOSHITAKA TAKAGAI, Laboratory of Physical and
Chemical Science, Cluster of Science and Technology, Fukushima University,
Kanayagawa 1, Fukushima 960-1296, Japan, [email protected].
A preconcentration procedure is one of the most important techniques for the
environmental analysis. In this study, lower ppt levels of polycyclic aromatic
hydrocarbons (PAHs) in environmental water can be determined by the proposed
powerful preconcentration method with high performance liquid chromatography using
fluorescence detection (FL/HPLC). The preconcentration method consists of the
combination of the blue cotton method (solid-phase extraction) and the homogeneous
liquid- liquid extraction. In the case of the homogeneous liquid- liquid extraction, PAHs
in the eluate of solid-phase extraction were extracted into micro volume of sedimented
phase. The proposed method could completely concentrate 1 liter to 20 microliter within
one hour and the 20 microliter of sedimented phase is directly injected into FL/HPLC.
The entire preconcentration factor was 50,000-fold. Six kinds of PAHs were determined
in the range of 3.0 × 10-18 ~ 4.5 × 10-11 mol L-1. These chemicals were also satisfactorily
separated. By changing the combination of various preconcentration methods or
instrumental analysis, the various samples could be analyzed.
Cloud Point Extraction as a Preconcentration Step for the Analysis of Metals in
Environmental and Biological Samples
M. F. Silva, R. A. Olsina and L. FERNÁNDEZ, Área de Química Analítica,
Departamento de Química, Facultad de Química, Bioquímica y Farmacia, Universidad
Nacional de San Luis, 5700 – San Luis, Argentina, [email protected].
Cloud point extraction (CPE) is a powerful separation method with a pronounced
capability to preconcentrate trace and ultra-trace metals in diluted samples of diverse
origin such as environmental, biological and industrial concern. This procedure have
advantages over those currently available including low cost, safety, feasibility for
injection of the surfactant-rich phase into any hydrodynamic analytical system and high
capacity to concentrate a wide variety of analytes of widely varying nature with high
recoveries and very high concentration factors. CPE has been employed for the
preconcentration of metal complexes such as mercury, aluminium and rare-earth
elements prior to inductively coupled plasma atomic optical emission spectrometry (ICP-
OES) and Absorciometry UV-Vis coupled to flow injection (FI). On the other hand, the
possibility to preconcentrate lead and aluminium without added chelating agents has been
demonstrated. Indeed, the coupling of CPE to Capillary Electrophoresis (CE) was
successfully performed to preconcentrate and simultaneously determine lead,
platinum/palladium, and iron/dysprosium. The samples under analysis include different
water samples, human saliva, urine and industrial samples.
Enhanced Organic Photovoltaic Performance from Nanoparticle – Polymer Blends
Marisol Reyes-Reyes, Kyung Kim, DAVID L. CARROLL, The Center for
Nanotechnology and Molecular Materials, Department of Physics, Wake Forest
University, Winston-Salem NC 27109, [email protected], and Seamus Curran,
Department of Physics, New Mexico State University, Las Crucis NM 88001

Blends of single walled carbon nanotubes (SWNTs), semiconducting nanostructures,
nano- metals (Ag, Au), and/or fullerene derivatives with conjugated polymers (MEH-
PPV, PFO, PEDOT, P3OT, P3HT), have been of great interest recently as a mechanism
to raise the overall performance efficiency of organically-based, flexible, devices such as
photovoltaics, organic light emitting diodes, and more. We have recently developed
novel methods for controlling both the electronic properties of the nano-phase and the
long range “meso-structure” of the blend. Through the use of selective doping (boron
and nitrogen dopants) in carbon nano-structures we have demonstrated control over the
donor-acceptor role of the nano-phase in the host, allowing for tailoring of the specific
trapping levels introduced. Thus, as we show with time-of-flight, we are able to
introduce donor or acceptor states within the HOMO-LUMO gap of the host, and control
the relative positions of these states. Secondly, we have demonstrated that an order can
be created within the nano-phase, with controlled placement and orientation of the nano-
particles. These ordered nano-blends of conjugated systems exhibit a number of exciting
properties including: modified carrier mobilities, optical absorption, and exciton
separation dynamics. In this work we integrate this meta- functional nano-phase blend
into a standard flexible organic photovoltaic device. Using commodity polymers,
surprisingly high efficiencies can be obtained.
Morphological Control and Spectrometric Applications of Gold Nanorods
S. YAMADA, Department of Applied Chemistry, Graduate School of Engineering,
Kyushu University, 6-10-1 Hakozaki, Higashi-ku, Fukuoka 812-8581, Japan
[email protected].
Gold nanorods (NRs), rod- like nanoparticles, show characteristic two plasmon bands
based on a longitudinal oscillation mode along the long axis (far-red/near- infrared region)
and a transverse mode perpendicular to the long axis (visible region). Thus, the NR
shows a distinct dichroic property. Quite recently, we developed a novel and simple
method for the preparation of gold NRs, by the combination of chemical reduction and
subsequent photoirradiation. We have first succeeded in well-dispersed fixing of the gold
NRs onto a glass substrate by the layer-by- layer approach. When the NR-modified plate
was immersed into the solvent, the longitudinal plasmon band showed substantial red shift,
while the transverse SP band showed no substantial shift. The degree of peak shift was
roughly correlated with the order of refractive index (dielectric constant) of the solvent.
The monoparticle layer film of gold NRs was also prepared at the liquid- liquid interface.
The NR film showed distinctly larger Raman scattering signals than the corresponding
nanospheres film. We also prepared the aggregate of phosphatidylcholine-modified NRs
and DNA. Controlled release of DNA from the aggregates was possible by pulsed
irradiation of near-infrared laser light.

Luminescent Nanoparticles as Labels for Biological Molecules
THOMAS NANN, Freiburg Materials Research Center (FMF), University of Freiburg,
Stefan-Meier-Strasse 21, D-79104 Freiburg, Germany, Luminescent nanoparticles such as semiconductor nanocrystals (so called Quantum Dots [QDs]) or rare earth doped nanoparticles gained increasing interest over the past several years. Compared with organic fluorophores, such particles possess substantial optical advantages: For example they don’t bleach under excitation, possess a narrow – often tuneable – spectral linewidth and make new detection techniques possible e.g. upconversion luminescence or lifetime multiplexing. The application of these particles in bioanalytics is promising, but a pre-requisite is, that they are colloidally stable in biological buffers and can be coupled to appropriate biomolecules. Since high-quality (monodisperse) nanoparticles are usually synthesised in non-polar media as for example trioctylphosphinoxide (TOPO) or high-boiling alkanes, the particle surface must be derivatised in such a way that on the one hand the phase-transfer is possible and on the other hand biomolecules such as proteins or nucleotides can be coupled selectively.
First an overview of luminescent nanoparticles, which are used in bioanalytic
applications, is given. Preparation methods regarding those applications are discussed.
Furthermore, different possibilities for non-polar/polar phase-transfers are presented.
Thereby the encapsulation of single nanoparticles with silica layers will be a special
emphasis (cf. figure 1). Moreover, possibilities for the coupling of nanoparticles to
biomolecules are discussed. Finally, some examples for the imaging of biological
systems with luminescent nanoparticles are presented.
Nanostructure -Assisted Laser Desorption Ionization Mass Spectrometry in
Nancy H. Finkel, Zhong Guo, Amel Ganawi, and LIN HE, Department of Chemistry,
The North Carolina State University, Raleigh, NC 27695, [email protected].
Surface-assisted laser desorption ionization mass spectrometry (SALDI-MS) has drawn
considerable attention for its efficiency in detection of species in the low- mass region.
Nevertheless, the correlation of the surface property of roughened inorganic substrate
with its desorption ionization efficiency remains unclear. We report herein a new
nanofabrication method to generate well-controlled surface features and systematically
vary the surface geometry with the aim of seeking a fundamental understanding of the
SALDI mechanism. Specifically, convective self-assembly is used to generate close-
packed 2-D nanoparticle arrays on a flat Si surface. This hexagonal-packed nanoparticle
array is then used as a mask in nanosphere lithography to selectively remove portions of
Si surfaces in reactive ion etching (RIE) and generates triangle-shaped nanocavities in
periodic patterns with pre-defined feature parameters. Mass spectrometry detection of
small molecules and peptides on such substrates shows good sensitivity with little
fragmentation and minimal background interference. Ordered feature size, shape, and
surface density are tailored by varying fabrication conditions. The impacts of surface
geometries on MS performance are correlated. The thermal properties of the substrates
are investigated. The use of the substrates in metabolite profiling and quantitation of
Arabidopsis thaliana extracts is also presented.
Gold Nanoparticle Matrices for Bioanalysis using Matrix-Assisted Laser Desorption
KATHERINE A. STUMPO, John A. McLean and David H. Russell, Laboratory for
Biological Mass Spectrometry, Department of Chemistry, Texas A&M University,
College Station, TX, 77843, [email protected].
Nanoparticles, esp. gold nanoparticles (AuNPs), have found wide application in chemical
biology and biochemical applications. Importantly, the optical and electronic properties
of NPs depend on size, shape, composition, and derivatization. Thus, NPs can be tailored
to specific applications, e.g. using functionalized AuNPs for selective isolation of target
analytes. We present here the utility of AuNPs and surface derivatized AuNPs as
potential matrices for matrix-assisted laser desorption ionization (MALDI) mass
spectrometry (MS). These alternative substrates offer a number of advantages over
conventional MALDI matrices (e.g. small organic acids): (i) greater flexibility in sample
deposition conditions (e.g. pH, solvents, etc.), (ii) relatively uncomplicated spectra in the
matrix region (low mass range), (iii) Au-cluster species as internal standards for mass
calibration, and (iv) AuNPs afford a very high shot-to-shot and spot-to-spot
reproducibility (<10 % RSD). Furthermore, the surface chemistry of AuNPs also plays an
important role in the ionization process, and has been investigated. Surface association of
ions and the solvent structure around these species in solution have an effect on analyte
interactions with the AuNPs, thus leading to changes in ionization efficiency. These
studies present many interesting avenues that can be pur sed in various chemical biology
Chemical Separations Using Nanoparticles
LUIS A. COLON, Jason A. Anspach, Hector Colón, Glorimar Vicente, and Melissa N.
Dunkle, Department of Chemistry, University at Buffalo, The State University of New
York, Buffalo, NY 14260-3000, [email protected].
The use of chromatographic columns packed with small particle diameters allows the
exploration of the theoretical limits in liquid chromatography, as theory predicts that a
reduction in particle diameter would provide an increase in separation efficiency with a
concomitant reduction in analysis time. Our research group has been exploring such
predictions by first synthesizing organosilica particles with diameters in the nanometer
range and using them for capillary electrochromatography (CEC) and ultrahigh pressure
liquid chromatography (UHPLC). Although a gain is noticeable when using particle
diameters below 1 µm, the actual gain combined with practical considerations are factors
to consider in the separation formats studied. Using another nanoparticle technology and
the nanoscale separation technique of capillary electrophoresis, we also explore the use of
fluorescent nanoparticles as “labeling” tags to enhance detection of biomolecules. We
will discuss our recent findings as we implement these new technologies in chemical
Gold Nanoparticles in Open-Tubular Capillary Electrochromatography and
Supercritical Fluid Extraction
JEREMY D. GLENNON, Elizabeth Guihen, Li Yang, Norma M. Scully, Anne M.
O'Keeffe, Niamh M. J. Curran, Jean-Marie Prat, and Gerard P. O'Sullivan, Department of
Chemistry, Analytical & Biological Research Facility (ABCRF), and Supercritical
Fluid Center, University College Cork, Cork, Ireland, [email protected].
Nanoparticles exhibit unique size-dependent optical, catalytic, magnetic, and electronic
properties compared to their bulk counterparts and can enhance a variety of technologies
including chemical processing, medical, electronic, environmental, separation and
sensing applications. Gold nanoparticles in particular, are among the most stable metal
nanoparticles, and are viewed as key materials and building blocks, with emerging
applications in biology, catalysis and nanotechnology.

To-date, very little research has been devoted to the application of nanoparticles in
separation science. The significant advances, which have been made in electrophoresis
and microchip separations, show the promise to enhance separation performance by using
nanoparticles. For example, latex nanoparticles have been used to coat a micromachined
channel on-chip, and on-chip ion chromatography of inorganic anions, nitrate, nitrite, and
iodide, has been achieved.
In this paper, important new roles for gold nanoparticles in open-tubular
electrochromatography (OTCEC), and in the extraction of this precious metal using
supercritical carbon dioxide will be highlighted. Specifically, the use of alkylthiolgold
nanoparticles in OTCEC to improve the efficiency of separation and the selectivity
between selected solutes will be demonstrated, in particular, for hydrophobic test solutes
and for selected polycyclic aromatic hydrocarbons (PAHs).
Development, Evaluation and Application of Nanoparticles as Stationary Phases for
Gas Chromatography

ROBERT E. SYNOVEC,a Gwen M. Gross,a and Jay W. Grate,b (a) Center for Process
Analytical Chemistry, Department of Chemistry, Box 351700, University of Washington,
Seattle, WA 98195. (b) Pacific Northwest National Laboratory, Richland, WA 99352
[email protected]
We are exploring using a thin film of gold-centered monolayer protected nanoparticles
(MPNs) as a stationary phase for open-tubular gas chromatography (GC). The MPN
films have thermodynamic and mass transfer properties that serve them well, providing
good chemical selectivity and high separation efficiencies (high N). High surface area-
to-volume ratios of MPNs provide ample sample loading capacity. A majority of our
work has been with dodecanethiol MPNs, with a dodecanethiol monolayer linked to a
gold nanoparticle. Films of dodecanthiol MPNs ranging from 10 to 60 nm provided
efficient separations with various capillary dimensions. The MPNs have a nominal
diameter of about 3 nm, so film depths are only a few nanoparticle diameters. High-
speed separations with dodecanethiol MPNs in a film depth of ~ 15 nm in a square
channeled capillary have been achieved and these results hold considerable promise for
the development of “high performance” microfabricated GC. We are also investigating
MPN columns for ultra high-speed GC, where separations of several analytes in a
fraction of a second are achieved, engendering the notion that GC can function like a
chemical sensor. Current development of polar stationary phases utilizing 4-
chlorobenzenethiol MPNs and 4-(trifluoromethyl)benzenethiol MPNs will also be
Non-Cross-Linking Aggregation of DNA-Carrying Nanoparticles for Single-Base
Substitution Assay
MIZUO MAEDA, Kazuo Hosokawa, and Kae Sato, Bioengineering Laboratory, RIKEN,
2-1, Hirosawa, Wako 351-0198, Japan, [email protected].

The graft copolymer consisting of poly(N-isopropylacrylamide) (PNIPAAm) and single-
stranded DNA was prepared as a DNA-conjugated material. Interestingly, the DNA-
conjugate was found to form nanoparticles above physiological temperature (Langmuir,
20, 313-319 (2004)). We found that non-cross linking aggregation of the nanoparticles
was induced by the hybridization of the surface-bound DNA with the full- match
complementary DNA, but not with one-base mismatch. The results demonstrated that the
non-cross linking aggregation of DNA-carrying nanoparticles is useful for analyzing
various SNPs. The core material is not restricted to PNIPAAm; DNA- functionalized
gold nanoparticle (15 nm diameter) was found to show a similar aggregation
phenomenon induced only by the fully-complementary DNA, resulting in rapid color
change within 3 min at ambient temperature (J. Am. Chem. Soc., 125, 8102-8103 (2003)).
This methodology is general in principle and applicable for wide variety of clinical
Enzymatic Amplification of Che mical Signals Inspired by Biological Signal
J. KIKUCHI and Y. Sasaki, Graduate School of Materials Science, Nara Institute of
Science and Technology, Ikoma, Nara 630-0192, Japan, [email protected].
Intermolecular communication between a receptor and an effector on the biomembrane
surface plays a pivotal role of the information processing in biological system. We have
recently developed an artificial intermolecular communication system on colloidal lipid
vesicles, as a molecular device, inspired by the biological signal transduction. The system
is constituted in combinations of an artificial ditopic receptor, an enzyme as an effector,
and a bilayer-forming synthetic lipid. The cationic bilayer membrane formed with the
synthetic peptide lipids or the Cerasome- forming lipids was an effective platform for self-
assembling of such functional molecules. On the membrane surface, the enzymatic
activity was effectively synchronized with ditopic recognition of the receptor toward an
external signal and a mediator species between the receptor and the effector. Marked
signal selectivity which is characteristic to the aqueous colloidal interface was observed.
The signal transduction efficiency was sensitively tuned with gel to liquid-crystalline
phase transition of the matrix membrane. The present molecular device acts as a unique
sensing system, in which the information on the molecular recognition of various
biologically important species by the receptor is transmitted to the enzyme and amplified
chemically as the catalytic reaction.
Triggered Drug Release from Membrane Coated Silica Nanoparticles
Li Chen and ZEEV ROSENZWEIG, Department of Chemistry, University of New
Orleans, New Orleans, LA 70148, [email protected].
The presentation will focus on the recent development of a new and improved
nanoparticle formulation for drug delivery applications. It is based on the idea that it is
possible to increase the density of drug molecules in nanometer-sized particles compared
to micrometer-sized particles because of the increased surface area. The increasing
loading efficiency may prove useful in applications require high dose of drugs.
Furthermore, because of their small dimensions the particles could permeate through cells
and tissues and even through the blood brain barrier. Recent studies in our laboratory
focused on the synthesis of drug containing phospholipids-coated silica nanoparticles and
their utility as drug carriers. Drug release from these particles is triggered by exposing
them to anti microbial peptides at micromolar levels. When combined with selective
targeting capabilities the drug containing nanoparticles could target cells and then release
their drug content in response to a trigger signal. The chemical and physical features of
the particles and their interaction with cells in cell culture will be discussed.
Analytical Measurements Using Polymeric Surfactants
ISIAH MANUEL WARNER, Department of Chemistry, Louisiana State University,
Baton Rouge, LA 70903, [email protected].
Over the past several years, we have employed polymeric surfactants as analytical
reagents, particularly as mobile phase additives for separations in capillary
electrophoresis. We have shown that our polymeric surfactants are broadly applicable to
the separation of a variety of analytes, including the separation of chiral compounds by
use of chiral polymeric surfactants. More recently, applications for the development of
novel nanomaterials in the presence of polymeric surfactants have been explored. Our
studies have shown that these polymers are more suitable than conventional micelles for
both separations and spectroscopic applications. In this talk, I will focus on the use of
polymeric surfactants as separation reagents and for the development of spectroscopic
probes. The advantages of these reagents in comparison to regular micelles will also be
discussed, particularly with regard to the wide variety of applications. A comparison of
the use of polymeric surfactants for separations and spectroscopy will also be made
directly to separations and spectroscopy by use of conventional (unpolymerized)
Liposome Enhanced Firefly Bioluminescent Assay of ATP in the Presence of

HIROFUMI TANI and Tamio Kamidate, Division of Biotechnology and Macromolecular
Chemistry, Graduate School of Engineering, Hokkaido University, Sapporo 060-8628,
JAPAN. [email protected].
The firefly bioluminescence (BL) assay has been widely used for the determination of
ATP in living cells. In this assay, the ATP extractants such as surfactants are required for
the release of ATP from cells, but they often inhibit the BL enzyme, luciferase. On the
other hand, surfactants are known to incorporate into liposomes composed of vesicular
lipid bilayers. In addition, cationic liposomes were found to enhance the BL intensity.
Thus, a cationic surfactant being used as an extractant, liposomes can eliminate the
inhibitory extractant and can transform into the BL-enhancer, cationic liposomes, by
incorporating cationic surfactants. In this study, we exploited such a double advantage of
liposomes for the BL assay of ATP in the presence of cationic surfactants. Liposomes
consist of phosphatidylcholine and cholesterol were prepared by the extrusion method
using a polycarbonate filter. Benzalkonium chloride (BAC) was used as an ATP
extractant. The detection limit for ATP in the mixtures containing 0.06% BAC was
25pM in the absence of liposomes. On the other hand, the BL intensity was remarkably
increased by the addition of liposomes into the assay mixture, resulting in the
enhancement of the sensitivity for ATP. The detection limit was improved to be 400fM.
Structure and Dynamics of Cationic and Nonionic Micelles: Neutron Scattering
L. J. Magid and W.-R. CHEN, Department of Chemistry, University of Tennessee,
Knoxville, TN 37996-1600; P. D. Butler, NIST Center for Neutron Research, National
Institute of Standards and Technology, Gaithersburg, MD 20899-8562; and D. Bossev,
Physics Dept., Indiana University, Bloomington, IN 47405, [email protected] and
[email protected].
Micellar morphology in aqueous micellar solutions of cationic surfactants such as CTAX
and CPyX can be manipulated by changing the counterion. Organic counterions that
penetrate the micellar interface, such as salicylate and tosylate, produce very large, semi-
flexible wormlike micelles. Flexibility depends on the surfactant’s head group, the
counterion, and the concentration of added salts. Increasing concentrations of NaSal or
NaTos cause the micelles to undergo size reversion back to globules; the salt
concentration at which this occurs is counterion-dependent. SANS data that allow
micellar contour lengths, persistence lengths and cross-sectional radii to be determined
will be presented, and size reversion will be found to correlate with the unfavorable
energetics of decreasing radii. Our fitting protocol incorporates changes to the widely-
used Pedersen-Schurtenberger scattering functions.
Neutron spin-echo studies on the local dynamics of linear and branched wormlike
cationic and nonionic micelles will also be presented, as well as of saturated micellar
Studies of Reversible Guanosine Gels
LINDA B. MCGOWN1, Victoria A. Dowling2 andLawrence W. Dick2, (1) Department
of Chemistry and Chemical Biology, Rensselaer Polytechnic Institute, 118 Cogswell,
Troy, NY 12180; (2) Department of Chemistry, Duke University, Gross Chemical
Laboratory, Durham, NC 27708, [email protected].
Guanosine gels (G-gels) are self-assembled networks of hydrogen-bonded guanine
tetrads formed by guanosine nucleosides and nucleotides. G- gels combine desirable
properties, such as reversibility, tunability, aqueous solubility, and biocompatibility, with
the unique ability to non-covalently and reversibly introduce functionality directly into
the G-tetrad network of the gel via hydrogen bonding. Their degree of organization and
viscosity are dependent upon monomer concentration, temperature, pH and cation
content, providing a variety of parameters that can be used to control their
formation/disassembly and to reversibly modulate their properties. This talk will present
results of experiments in which G-gels are used for chiral separations in capillary gel
chromatography and molecular probe studies of these gel phases related to their
performance in chiral separations. Results will also be presented for gels that are under
investigation for bioencapsulation.

Hydrogen Bonded Molecular Macrocluster Formation at the Solid - Liquid
KAZUE KURIHARA, Institute of Multidisciplinary Research for Advanced Materials,
Tohoku University, Katahira, Aoba-ku, Sendai 980-8577, Japan,
[email protected].
Liquid molecules at the solid- liquid interfaces often exhibit different properties from
those in the bulk, which is attributed to the surface- induced structuring of liquids.
Elucidation of these properties is important in nanoscience and nanotechnology. We
recently have found that liquid molecules with the hydrogen bonding functionalities
(alcohol, carboxylic acid, and amide) form a hydrogen bonded organized structure, which
we call “molecular macrocluster”, on the silica (glass and oxidized silicon) surface when
they are adsorbed from their mixtures with non-polar solvents. The surface silanol
groups are essential for this structure formation. FTIR-ATR spectroscopy demonstrates
the hydrogen bonding interactions between the sur face silanol groups and adsorbed
molecules in addition to those between adsorbed molecules. Surface forces measurement
reveals the long ranged attraction (e.g. extending to 30 ~ 40 nm for normal monohydric
alcohol in cyclohexane) due to the contact of the opposed adsorption layers. Half the
attraction range is close to the adsorbed layer thickness, which is extraordinarily long
range. Interesting differences are observed in the mode of adsorption depending on the
chemical groups. Dynamic properties of adsorbed molecules, ethanol on glass in
cyclohexane, are studied by NMR spectroscopy. We utilize this molecular macrocluster
for preparing polymer thin- films on solid surface.

Distribution of tert-Butylhydroquinone in Food-Like Emulsions Stabilized by C12E6
K. GUNASEELAN and Laurence S. Romsted, Rutgers, The State University of New
Jersey, Department of Chemistry and Chemical Biology, Wright-Rieman Laboratories,
New Brunswick, New Jersey 08903, [email protected].
We have developed a new approach for estimating the distributions of antioxidants in
opaque, surfactant based, macroemulsions based on the pseudophase model for
homogenous microemulsions. The distribution of t-butylhydroquinone, TBHQ, in
emulsions composed of tributyrin, C12E6, and acidic water is described by two partition
constants between the oil and interfacial, P I
O , and the water and interfacial, PW , regions. O and PW requires fitting two independent data sets with two independent mathematical relations and solving two equations simultaneously. One data set was obtained by electrochemical determination of the observed rate constant, kobs, for reaction of TBHQ with an arenediazonium ion probe as a function of C12E6 volume fraction. The second data set was obtained by determining the partition constant, P W TBHQ between tributyrin and water in the absence of surfactant by UV-Visible spectrometry, P W = 0.015. The values of the partition constants in the emulsion are: PO W = 7.11 x 102. Application of this approach to a variety of antioxidants in emulsions containing different food oils and emulsifiers should provide new insight into
the factors controlling antioxidant distributions and may lead to a development of a new
scale of antioxidant efficiency.

Partitioning of Polar Aromatic Compounds to Organogels and Application for their
Extractive Removal from Organic Solvents
Melissa M. Stouffer, Julianne M. Braun, Dai Fang, and WILLIE L. HINZE, Department
of Chemistry, Wake Forest University, PO Box 7486, Winston-Salem, North Carolina
27109, [email protected].
Organogels are formed by the addition of gelatin to Aerosol OT [bis(2-ethylhexyl)
sodium sulfosuccinate] reverse micelle solutions at elevated temperatures followed by
cooling. The “solid” organogels have been shown to retain many of the general
properties exhibited by traditional reverse micelle solutions. Some of the general features
and characteristics of these materials will be described. Results regarding the stability of
organogels in a variety of organic solvents and aqueous mixtures will be presented.
Partitioning data for the interaction of polar aromatic compounds (such as substituted
anilines, phenols, naphthols) with the AOT organogels will be presented and compared to
the partitioning observed for the same interaction with solution AOT inverted micelles.
The use of organogels to remove (extract) and/or concentrate organic solutes from
organic solvents will be discussed and the relevant extraction parameters summarized.
In addition, the use of such an approach as a preconcentration technique prior to
spectroscopic chemiluminescent determinations will be illustrated. Preliminary data
obtained using CTAB [hexadecyltrimethylammonium bromide] based organogels will
also be presented.
Analytical Applications of Metal Nanoparticles
O. A. SADIK, M. Omole, D. Andreescu, and A. Wanekaya, State University of New
York at Bingha mton, Chemistry Department, Binghamton, NY 13902-6000,
[email protected].
Palladium nanoparticles are of particular interest as catalyst for the synthesis of specialty
chemicals, nuclear waste and environmental applications. The objective of this work was
to develop a reliable experimental procedure for the synthesis and analytical applications
of Pd-based nanoparticle. In designing advanced materials for nanosensors and
environmental remediation, nanomaterial synthesis procedures are increasingly required
to control the shape and size. Consequently, we have synthesized palladium nanoparticles
through the reduction of Pd (II) acetate using polyamic acid (PAA) as a reducing agent in
an organic medium at room temperature. The approach is based on subsequent capping
and stabilization of the resulting palladium nanoparticles by the PAA. The Pd-based
nanostructured materials were characterized using UV/Vis spectroscopy, scanning
electron microscopy and transmission electron microscopy (TEM). TEM image analysis
showed the synthesized PAA- metal hybrid as well dispersed particle of different shapes
(Spherical, pyramidal and octahedral). The particle sizes were in the range of 8.3-13.0
nm. In this presentation, we will show that palladium nanoparticles of variable shape may
be synthesized using a simple one step procedure involving the reduction of a palladium
salt by polyamic acid at room temperature. The possibility of fabricating a PAA- metal
hybrid material for environmental remediation and biosensing would be presented.

Colloidal CdSe Quantum Dots as Novel Luminescent Probes for Selective and
Sensitive Analytical Determination of Trace Amounts of Ions in Water Samples
J. M. COSTA-FERNANDEZ, M. T. Fernández-Argüelles, W. J. Jin, R. Pereiro, and A.
Sanz-Medel, Department of Physical and Analytical Chemistry, University of Oviedo,
33006 Oviedo, Spain, [email protected].
Recent developments are stressing the importance of adequate surface chemistry in the
development of highly luminescent, water-soluble and biocompatible quantum dots
(QDs) for applications in bioanalysis and diagnostics [1, 2]. Moreover, analytical
chemists have also started to explore these nanomaterials for the development of a new
generation of luminescence optical probes.
Luminescence of QDs is very sensitive to their surface states; therefore, it is reasonable
to expect that eventual chemical or physical interactions between a target chemical
species with the surface of the nanoparticles would result in changes on their surface
charge affecting the efficiency of the core electron-hole recombination.
Following this approach, water-soluble surface- modified CdSe QDs have been
synthesized and evaluated as optical probes for selective and sensitive determination of
trace amounts of small ions (free cyanide and copper (II)) in aqueous solutions based on
fluorescence quenching measurements.
After QDs synthesis, a photostimulation was necessary in order to obtain a stabilized
emission profile resulting in reliable responses to the presence of the analytes. Moreover,
the addition of surfactant agents to the measured aqueous solution was found to greatly
stabilize the colloidal QDs and the fluorescent signals, resulting in a very high sensitivity
for analyte detection (detection limits in the low ng ml-1 range are obtained) [3].

Synthesis of Semiconductor Nanoparticles as Probe to Detect Supersaturated
Dissolved Oxygen
YONGXIA ZHANG, Duane T. Johnson, Che mical & Biological Engineering
Department, University of Alabama, Tuscaloosa, AL 35487-0203,
[email protected].
High-quality ZnS nanocrystrals are synthesized with a coordinating solvent (i.e. high
boiling-point long chain amine) using zinc stearate and elemental sulfur as the precursors.
Spherical ZnS nanoparticles (~2nm) were obtained and characterized using several
different techniques (XRD, SEM, TEM and UV-Vis). Fluorescence intensity and decay
rate of ZnS were acquired using a fluorometer. The ZnS nanoparticles have a good
fluorescence at 400 nm and a long decay time (~2.5ms). The fluorescence intensity and
decay time are inversely proportional to the dissolved oxygen concentration. Calibrating
this relationship allows one to determine the concentration of dissolved oxygen by
measuring the fluorescence intensity and/or the fluorescence decay rate. The slow decay
rates and bright fluorescence make ZnS nanoparticles potential probes for measuring
supersaturated dissolved oxygen, which is difficult to obtain using other techniques.

Hybridization of DNA Functionalized Silver and Gold Nanoparticles in Aqueous
Dispersions and on Gold Films
Iryna Tokareva and ELIZA HUTTER, Department of Chemistry, Clarkson University,
Box 5814, Potsdam, NY 13699, [email protected].
Silver and gold nanoparticles were successfully functionalized by 12mer oligonucleotides
and hybridized onto gold nanoparticles in dispersions. The optical and hybridization
properties of DNA linked gold-silver ,silver-silver and gold-gold colloidal nanoparticles
are described. In addition, the self-assembly of homo-oligonucleotides on gold films and
their hybridization with their complementary pairs, unlabeled or labeled by gold and
silver nanoparticles, were detected by Polarization Modulated Fourier Transform Infrared
Reflection Absorption Spectroscopy (PM-FTIRRAS). PM-FTIRRAS was found to be
capable to detect the base pairing between DNA strands and distinguish between the
types of oligonucleotides (adenine or thymine) attached to the nanoparticles.
Novel Evaluation Method of Nanoparticle Dispersibility in Nanocomposites
by TEM-Computerized Tomography and 3D Image Analysis
H. SASAKURA1, H. Yoden2, S. Noda3 and Y. Yamaguchi3, (1) Japan Chemical
Innovation Institute, The University of Tokyo, 7-3-1 Hongo, Bunkyo-Ku, Tokyo 113-
8656, JAPAN; (2) Japan Chemical Innovation Institute, Hiroshima University, 1-4-1
Kagamiyama, Higashihiroshima, 739-8527, JAPAN; (3) Department of Chemical System
Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-Ku, Tokyo 113-8656,
JAPAN, [email protected].

We propose a novel evaluation method to characterize three-dimensional (3D) structures
of nanoparticles in nanocomposites by using 3D images obtained from a transmission
electron microscopy assisted by computerized tomography (TEM-CT). Since physical
properties such as transparency, dimensional stability and thermal durability depend on
the dispersibility of nanoparticles in a nanocomposite, it is crucial to reveal the 3D
structures of nanocomposites.
The silica nanoparticle/epoxy nanocomposite evaluated is a model material to figure out
our proposed method. First, the nanocomposite 3D images are reconstructed by TEM-CT.
Second, the nanoparticle images are separated from the nanocomposite by binarization.
Third, the summation of the shortest distances between each separated particle is
normalized by an ideal distance between two particles under fcc structure, which is
defined as Universal Factor (UF) as an index of the particle dispersibility to
quantitatively evaluate the 3D structure of nanoparticles. It is found that silica
nanoparticles in the nanocomposite are well dispersed because the UF of the
nanocomposite is 0.85.
We also show the simple analytical validation in order to estimate the error of the length
subject to the novel evaluation method.

Systems Based on Polymeric Surfactant – Polyvinylpyrrolidone and Organic
Reagents: Properties and Utilization in Analysis
O.V. MIKULENKO and F.A. Chmilenko, Department of Analytical Chemistry,
Dnepropetrovsk National University, Dnepropetrovsk, Ukraine, 49050,
[email protected].
The influence of polymeric surfactant - polyvinylpyrrolidone (PVP) for various
molecular masses (8⋅103 - 360⋅103) on spectroscopic, protolytical and complex formation
properties of organic reagents (dyes of different classes) is established with the methods
of UV-, visual and IR-spectroscopy. It is shown that addition PVP in solution of azo-,
triphenylmethane and trioxyfluorone dyes leads to shift of absorption strips maximum of
reagents, displacement of reagent dissociation. One can use PVP to modify complex
formation of organic reagents with ions of metals: it is shown in increase of contrast and
sensitivity of analytical reactions. On the basis of PVP adducts with organic reagents we
propose manufacturing of electrochemical sensors for direct determination of polymer
content in solution. The conditions of sensors work are established in model and real
solutions of medicine. The complex techniques of spectroscopy and electrochemical
determination of PVP concentration in medicine, bioobjects, waste water,
spectrophotometry techniques of determination of average molecular mass of PVP in
substation and metal ion content in different objects are developed.


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GUIDE POUR LA RÉDACTION ET LA PRÉSENTATION DES THÈSES A L’USAGE DES DOCTORANTS * * Le présent guide concerne les thèses de doctorat au sens propre du terme, à l’exclusion des thèses d’exercice en médecine ou odontologie. Valoriser les thèses en privilégiant l’internet …. 3 Valoriser dans le respect de la réglementation …. 4 Comment structurer sa thèse po

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