Pentasectional Regional

Meeting 2016

Book of Abstracts
Technical Sessions

• Advances in energy and fuels

• Analytical chemistry
• Biochemistry and organic chemistry
• Inorganic chemistry and chemical education
• Physical chemistry
• Materials and polymers
• Water and environmental chemistry
• Poster session
• Advances in energy
and fuels
IMPACT OF RESERVOIR WETTABILITY AND PERMEABILITY ON CO2
FLOODING EFFICIENCY; Prem Bikkina1, Jiamin Wan2, Yongman Kim2, Timothy J.
Kneafsey2, Tetsu K. Tokunaga2, 1School of Chemical Engineering, Oklahoma State University,
Stillwater, OK 74078 2Earth Sciences Division, Lawrence Berkeley National Laboratory, 1
Cyclotron Road, Berkeley, CA 94720

Carbon dioxide enhanced oil recovery (CO2 EOR) technique has been applied in the U.S. crude
oil reservoirs for more than four decades and is currently contributing to about 6% of US onshore
oil production. It is anticipated that this portion will significantly increase in the near future due
to the higher volumes of CO2 captured from the natural gas processing and other industrial
sources; recently completed new CO2 pipelines; and the availability of additional natural sources
of CO2. In recent years, CO2 EOR has also been considered as a practical option for sequestering
a significant portion of the CO2 injected to mitigate the greenhouse gas concentration in the
atmosphere. CO2 flooding has been tried in various formats such as miscible, immiscible, water
alternating gas (WAG), and Huff and Puff methods. In general, miscible CO2 flooding (even in
WAG) is more efficient than the immiscible flooding.

Even though the EOR technique has been applied in the field for decades, the effects of reservoir
wettability and permeability heterogeneity on the efficiency of miscible CO2 flooding are not
fully understood. Hence, this work focused on conducting controlled coreflooding experiments
using well characterized twin and split, water-wet and oil-wet Berea core samples to evaluate the
effect of the above parameters on miscible CO2 flooding efficiency. Synthetic brine and n-
hexadecane and were used as aqueous and oil phases, respectively. All the experiments were
conducted with a back pressure of 1400 psig and at 24 ± 1 oC to maintain CO2 miscibility in the
oil. It was revealed that both the wettability and permeability heterogeneity have very strong
influence on the efficiency of miscible CO2 flooding. The experimental results and the
underlying mechanisms will be presented.

Probing the Effect of Water in Catalytic Reactions by In Situ Solid-State NMR

Kuizhi Chen, Maryam Abdolrahmani and Jeffery L. White*
Department of Chemistry, Oklahoma State University
Stillwater, OK 74078

Abstract. Zeolites are solid acid catalysts used extensively in petrochemical processes and also in
methanol-to-hydrocarbon (MTH) chemistry. Industrial quantities of methanol are produced from coal
or biomass. In methanol conversion to hydrocarbons, stoichiometric amounts of water are inevitably
produced, but the role of water is not fully understood. Conventionally, water is considered as a
poison in zeolite-based catalysis. However, both theoretical and experimental works have shown that
water could enhance the MTH conversion rate. Our previous work has shown that water could
enhance the reaction rate for nonpolar molecules in zeolite catalysts (ACS Catalysis 2014, 4, 3039).
Active sites were subsequently characterized in hydrophilic and hydrophobically modified zeolites
(ACS Catalysis 2015, 5, 7480). Aromatic reaction centers are common to almost all hydrocarbon
conversions in zeolites. Specifically, alkylation/dealkylation steps are critical, and have been shown
as key steps in MTH conversion. Ethylbenzene and isopropylbenzene (cumene) are chosen as
representative reagents, and their transformation in zeolites is being investigated by high temperature
in situ solid-state NMR.
* Author to whom all correspondence should be addressed at jeff.white@okstate.ed

NOVEL MATERIALS BEYOND GRAPHENE FOR FLEXIBLE ENERGY STORAGE

DEVICES, Ram K. Gupta, Department of Chemistry, Pittsburg State University 1701 S.
Broadway, Pittsburg, KS 66762, USA

After awarding a Nobel prize in 2009 for the work on graphene, there has been renewed interest
in investigating a variety of layer-structured materials. The layer-structured materials offer
exciting opportunities for the development of advanced energy storage devices. They provide
high transport characteristics, mechanical stability and large surface area, which are essential for
nano-dimensional electronics, catalysis, and energy storage applications. Among various layer-
structured materials, metal chalcogenides are attractive because of their large surface area and
ability to host smaller atoms or ions between the layers. The use of higher-order chalcogenides
provides additional opportunities for redox reactions in addition to the flexibility of tuning the
van der Waals gap between layers. We have systematically studied the effect of thickness on the
electrochemical behavior and specific capacitance of CuSbS2 nanoplates. Electrochemical
studies reveal that nanoplates with thickness of about 55 nm are optimum for obtaining the
highest specific capacitance. In addition, long term cyclic and flexibility measurements were
performed on CuSbS2 nanoplates in different alkaline electrolytes and was observed that LiOH
provides specific capacitance values as high as 120 F/g with exceptionally high electrochemical
cyclic stability. The solid state supercapacitor device fabricated using CuSbS2 nanoplates showed
an aerial capacitance of 40 mF/cm2 with excellent cyclic stability. Our comparative study of
CuSbS2 nanoplates with non-layer structure phases in the Cu–Sb–S system clearly supports the
importance of the layered structure for enhancing energy storage capacity. In conclusion, our
study provides an ultimate facile method to synthesize size and thickness controlled layer-
structured chalcogenide for applications in the next generation of flexible energy storage devices.

* Corresponding author: ramguptamsu@gmail.com (Ram K. Gupta).

A MICROFLUIDIC APPROACH FOR EMULSION FORMATION AND STABILITY
ANALYSIS; Subarna Kole1, Prem Bikkina1 1School of Chemical Engineering, Oklahoma State
University, Stillwater, OK 74078

Emulsions are frequently encountered at various components of the petroleum production system
starting from the reservoir to the refinery. Emulsification and demulsification processes play a
major role in petroleum industry. While the formation of stable emulsions is critical in some
applications such as the enhanced oil recovery using CO2 foams and colloidal nanofluids, many
other applications such as separating the produced water from the crude oil require the separation
of unwanted emulsions into their constituent fluid phases to meet stringent environmental and
production requirements. Hence, it is essential to understand the underlying physicochemical
aspects to effectively control these processes. There are a number of factors that influence
emulsion formation and stability. Droplet size is perhaps one of the most important factors. In
this work, a unique microfluidic setup that has a capability to generate monodispersed water-in-
oil and oil-in-water emulsions is used to determine the effects of type of oil phase, aqueous phase
salinity, salt type, surfactant type and concentration, total flow rate, and water-cut on the droplet
size. Stability analysis of the emulsions is conducted by tracking the temporal evolution of the
sedimenting and coalescing interfaces. The experimental results and the analysis will be
discussed in the presentation.

EFFECT OF STABILIZERS ON HYDRATE FORMATION AND THEIR RHEOLOGICAL

BEHAVIOR Ashwin Kumar Yegya Raman, Deepika Venkataramani, Peter Clark, Clint P.Aichele
School of Chemical Engineering, Oklahoma State University, Stillwater, OK 74078

Flow assurance is one of the major technical problems facing the petroleum industry. Several millions of
dollars have been spent in mitigating pipeline blockages. Despite extensive studies over decades, the
mechanisms by which hydrates are formed are not yet completely understood due to the complex nature
of hydrates. This inadequacy in the fundamental understanding on hydrate formation mechanism has
provided us an impetus to conduct experimental work on cyclopentane hydrate forming emulsions.

Cyclopentane hydrates are studied in model oil systems using surfactant and solid particles, which act as
stabilizing agents. The droplet sizes of the hydrate forming emulsions are quantified before and after the
formation of hydrates. Droplet size distribution and hydrate formation are examined at various water
fractions using different kinds of stabilizing agents. Bench top experiments are performed to explore the
hydrate formation conditions and their morphology. Rheological behavior of hydrate forming emulsions
is studied using different kinds of stabilizing agent. An Olympus BX53 polarized optical microscope with
shear cell and temperature control (-50°C to 450°C) stage is used to quantify droplet size distribution, and
hydrate crystals morphology. A DHR-3 stress controlled rheometer whose temperature can be controlled
between -20°C to 150°C is used to examine the rheological behavior of hydrate forming emulsions.

Characterization of hydrate forming emulsions, understanding the rheological behavior and the
impact of emulsion stabilizers on hydrate formation in oil-dominated systems would provide us a
better understanding of hydrate formation mechanism and their flow properties. An
understanding of the rheological behavior of hydrates would help in enhancing the design of
multiphase flowlines and thereby minimizing the costs involved in transportation of crude oil.

PROMISING ACTIVATED CARBONS DERIVED FROM BIO-WASTE FOR HIGH PERFORMANCE

1 1 1* 1
ENERGY STORAGE DEVICES Charith Ranaweera , Z. Wang , Ram K. Gupta Department of
Chemistry, Pittsburg State University, 1701 S. Broadway, Pittsburg, KS 66762, USA

Batteries, fuel cells and capacitors are the most promising energy storage devices. The energy
storage mechanism and delivery in these devices are quite different, for example in batteries
energy is stored in form of chemical energy and this chemical energy is converted back to
electrical energy during discharging (use) process. On the other hand, in capacitor electrical
energy is stored due to electrostatic principle (or redox process). There has been an increasing
research attention to develop high performance energy storage devices from agriculture waste
and renewable resources. Recycling the agricultural waste not only helps in waste management
but also provides high performance materials for energy applications. In this work, high
performance carbonized jute fibers were synthesized for high temperature energy storage
devices. The structural and electrochemical properties of the carbonized bio-mass were studied.
The X-ray diffraction and Raman spectra of the carbonized jute confirm presence of the graphitic
phase of carbon. The cyclic voltammetry studies suggested that these fibers have high charge
storage capacity (408 F/g) and the fibers showed no degradation in charge storage capacity even
after 5,000 cycles of charge discharge study. In addition to high electrochemical cyclic stability,
they showed excellent flexibility without any degradation to charge storage capacity. The
performance of the supercapacitor device was tested from low temperature to high temperature
to study the effect of temperature on its electrochemical behavior. An improvement of about
60% was observed on increasing the temperature from 5 to 75 oC. Our studies suggest that
carbonized bio-mass could be used for fabrication of stable, high performance and flexible
energy storage devices.

* Corresponding author: ramguptamsu@gmail.com (Ram K. Gupta).

Presenting author: cranaweera@gus.pittstate.edu (Charith Ranaweera)
Controlling Photocatalytic Electron and Energy Transfer Processes: Direct Access to E or Z
Isomers via C–F Alkenylation

Anuradha Singh, Christopher J. Fennell, and Jimmie D. Weaver

Department of Chemistry, Oklahoma State University, Stillwater, Oklahoma 74078,
United States

Many methods developed recently, rely on photoinduced electron transfer from a

photocatalyst. These same photocatalyst can also participate in energy transfer processes.
Understanding the underlying phenomena that control these two processes would, therefore,
be valuable. Herein, we report photocatalytic synthesis of alkenylated perfluoroarenes via the
C–F hydroalkenylation using perfluoroarene and alkyne. Electron transfer enables the C–F
functionalization while selective energy transfer controls the alkene geometry. Importantly, we
observe selectivity of alkene isomers depends on the size and emissive energy of photocatalyst,
but primarily the size. Photocatalyst that have smaller size with high emissive energies provide
the endothermic Z-isomer. Whereas increasing the size of the photocatalyst favors the
formation of kinetic E-isomer (i.e. no isomerization), even with high emissive energy.

HIGHLY EFFICIENT ELECTROCATALYST BASED ON MOS2 FOR HYDROGEN EVOLUTION

1 1 1* 1
REACTION Z. Wang , Charith Ranaweera , Ram K. Gupta Department of Chemistry,
Pittsburg State University, 1701 S. Broadway, Pittsburg, KS 66762, USA

To meet the constantly rising requirement of energy other than traditional fossil fuel and
environment protection, it is a perfect time to development low cost, and efficient
materials for clean energy production. Hydrogen generation by water splitting is one of
the cleanest ways to produce cheaper energy. Hydrogen evolution reaction (HER) is one
of the key steps in water splitting process. Ideally, the thermodynamic potential for HER
should be at 0 V (vs. SHE). However, without an efficient catalyst, this reaction occurred
at higher potential, called overpotential. A good HER catalyst is needed to lower the
overpotential and hence to improve the energy efficiency of this process. Presently,
platinum is the most effective and durable catalyst for HER, but its wide spread use is
precluded due to its cost as well as limited availability. Therefore, it is essential to
develop low-cost and earth-abundant materials to replace precious-platinum based
catalysts. In this work, a facile and scalable one-pot method has been developed to
synthesize carbon coated MoS2. The carbon coated MoS2 is advantageous as this
increases the electrical/ionic conductivity of MoS2. The structural characterization of
MoS2 and carbon coated MoS2 was performed using x-ray diffraction and scanning
electron microscopy. Hydrogen evolution reaction was studied in potential range of 0 to -
0.7 V and observed that carbon coated MoS2 provide lower overpotential compared to
uncoated MoS2.

* Corresponding author: ramguptamsu@gmail.com (Ram K. Gupta)

Presenting author: zwang@gus.pittstate.edu (Z. Wang)

MECHANISTIC ROLE OF SOLVENTS IN HYDROGENATION OF FURANIC

COMPOUNDS: A COMBINED EXPERIMENTAL AND DFT STUDY, Zheng Zhao,a
Reda Bababrik,a,* Bin Wang,a Daniel Resascoa aCenter for Interfacial Reaction Engineering (CIRE),
School of Chemical, Biological and Materials Engineering, The University of Oklahoma, Norman, OK 73019,
USA
*Corresponding author: bababrik@ou.edu

The catalytic upgrading of bio-oil, which is generated through fast pyrolysis of

biomass, to liquid fuel is an attractive, yet challenging, process with significant economic
potential. Liquid-phase heterogeneous catalytic upgrading of bio-oil has its advantage
such as the tunable activity and selectivity that has been observed when using aprotic,
protic or non-polar solvents. Fundamental understanding of the solvent effect will be
valuable for further promoting the liquid-phase heterogeneous catalytic upgrading
strategy. Here, we focus on Furfural (FAL) as the model compound, which is an
important platform chemical in the bio-oil refinery, and discuss the solvent effect on its
reactions through a combined experimental and computational study.
Our recent experimental results show high selectivity towards alcohol products from
aqueous phase catalytic reactions of furfural on a palladium surface. The selectivity can
be switched by the use of polar aprotic solvents such as tetrahydrofuran (THF) where
furanic ring hydrogenation is more favored for the model compound. Density functional
theory (DFT) calculations are performed to investigate adsorption of furanic compounds
on the metal surface as well as study the reaction barriers of hydrogenation of furfural in
different solvents. Moreover, we compare the adsorption and reaction of furanics on
different metal surfaces in different solvents, through which the atomic-scale
understanding of the role of solvent has been achieved. We find that the solvent can
either perturb the molecular adsorption, for example, through formation of hydrogen
bonds with water, or participate directly in the reaction through proton transfer. This
synergistic combination of experiment, theory and computation thus provides detailed
understanding of the reaction mechanism of bio-oil upgrading in a complicated liquid
environment. Finally, I will discuss briefly the effect of water on other reactions of
biomass-derived compounds.
• Analytical chemistry
FUNCTIONALIZED CARBON NANOTUBES AS PSEUDO-STATIONARY PHASES IN
CAPILLARY ELECTROKINETIC CHROMATOGRAPHY - EVALUATION OF RETENTION
ENERGETICS AND ANALYSIS OF A WIDE RANGE OF NEUTRAL AND CHARGED
SPECIES Sarah Alharthi1 and Ziad El Rassi11Department of Chemistry, Oklahoma State University,
Stillwater, OK 74078, USA

Functionalized multiwalled carbon nanotubes (MWCNTs) exhibit unique chemical and physical
properties that significantly enhance separation in capillary electrokinetic Chromatography (EKC). In this
investigation, MWCNTs have been functionalized with hydroxyl, carboxylic and sulfonic groups and
evaluated over a wide range of electrolyte composition with various neutral and charged species, e.g.,
alkylbenzenes, phenylalkyl alcohols, dansyl amino acids, barbiturates, urea herbicides and some
aromatics. Functionalized CNTs have been characterized by spectroscopic methods. In all cases, the
results on the functionalized MWCNTs were compared to those obtained on unmodified MWCNTs in the
presence of SDS in the running electrolyte. The ratio of MWCNTs to SDS affected the electrokinetic
systems under investigation significantly in terms of migration time window and in turn system
resolution. Plots of log k’ of the same solutes on the various MWCNTs were used to evaluate the
retention energetics as well as the hydrophobic phase ratios. While the various MWCNTs showed
homoenergetic retention behaviors, they differed in terms of their hydrophobicity with the sulfonated ones
being the least hydrophobic toward all solutes examined. The migration time window of the
functionalized MWCNTs was quite wide allowing the separation of the various neutral and charged
species investigated with high selectivity and resolution, and yielded a plate count reaching as high as
184,000 plates/m.

BIMETALLIC NANOPARTICLES FOR BIOSENSING APPLICATIONS Asantha C.

Dharmaratne, and Sadagopan Krishnan*1 Department of Chemistry. Oklahoma State University
Stillwater, OK 74078, U.S.A

Nanoparticles in general have gained a lot of attraction due to their unique properties including
optical, electronic, and catalytic. Such properties have been a result of the size and the
composition of nanoparticles. By changing the surface area to volume ratios of nanoparticles as
well as the metallic composition, we can expand the horizons of its applications. Studies have
also shown that the introduction of an additional metal into a nanoparticle system would increase
or improve the overall properties of the nanoparticle compared to its monometallic counterpart.
Such modifications to nanoparticles can play a crucial role in nanodevices for sensing and
catalytic applications. Herein, we present a synthetic protocol to obtain organothiolate protected
gold palladium bimetallic nanoparticles. The main purpose of this gold nanoparticles is to
function as a platform to immobilize biomolecules while palladium nanoparticles enhance the
overall surface plasmon resonance signal. Gold nanoparticles itself has a good surface plasmon
resonance response, but studies have shown that gold palladium bimetallic nanoparticles
combined has a much better response compared to the monometallic counterpart. For biosensing
applications, it is critical to use functionalized water soluble organothiolate ligands such as 4-
mercaptobenzoic acid as a capping agent to ensure the biocompatibility of the nanoparticles.
ANALYSIS OF QUERCETIN AND RESVERATROL IN RED WINES AND GRAPES USING
HPLC Quanxiu Jin, Jianguo Liu, and John Bowen Department of Chemistry, University of Central
Oklahoma

An analytical method for high performance liquid chromatography (HPLC) was developed for the
analysis of the antioxidents resveratrol and quercetin in goji berry. Quantitative results will be presented
for these compounds.

SANDWICH IMMUNOASSAY FOR ULTRASENSITIVE DETECTION OF INSULIN IN

A CLINICAL MATRIX; Jinesh Niroula, Gayan Premaratne, Asantha C. Dharmaratne,
Sadagopan Krishnan, Department of Chemistry, Oklahoma State University, Stillwater, OK
74078

In order to address the lethal complications associated with diabetic condition, it is important to
have timely and continuous detection of insulin levels in blood serum and identify/manage type 1
and type 2 diabetic disorders. With this objective, our focus is to develop a novel, ultra-sensitive
sandwich immunoassay for detecting clinically relevant insulin levels in serum samples. Surface
anti-insulin monoclonal or a polyclonal antibody (Ab1) is covalently attached to a gold
microarray chip. Magnetic particles (MP) conjugated to another primary anti-insulin antibody
(Ab2) are used to capture different concentrations of insulin in human serum and then allowed to
bind the surface antibody, Ab1. Similarly, buffer insulin samples are analyzed for comparison
and to understand the influence of serum matrix in the analytical detection levels. We observed
that magnetic particles minimize the matrix effect and produce amplified signals when Ab1
captures insulin from the bioconjugate samples.

PREPARATION AND CHARACTERIZATION OF SINGLY AND MULTILAYERED

SILICA STATIONARY PHASES FOR HYDROPHILIC INTERACTION LIQUID
CHROMATOGRAPHY
Renuka P. Rathnasekara and Ziad El Rassi, Department of Chemistry, Oklahoma State
University, Stillwater, Ok, 74078
Hydrophilic interaction liquid chromatography (HILIC) which uses a polar (hydrophilic)
stationary phase with an organic-rich hydro-organic mobile phase in order to separate polar
analytes has gained an increasing interest among separation scientists over the past few decades.
Three novel singly and multilayered silica based HILIC stationary phases have been synthesized
by covalent attachment of different polar functionalities to bare silica micro particles. In all
cases, the basic silica support was coated with an epoxy active layer via the reaction of silica
with γ-glycidoxypropyl trimethoxysilane. Thereafter, the activated epoxy silica thus obtained
was covered with a layer of either tris(hydroxymethyl)aminomethane (TRIS) or sorbitol (SOR)
yielding the singly layered silica stationary phase. The TRIS-silica was further coated with a
layer of chondroitin sulfate A (CSA) yielding the multi-layered hydrophilic silica stationary
phase referred to as CSA-TRIS-silica sorbent. An extensive chromatographic characterization
was conducted to assess the extent of each coating step in achieving the singly and multilayered
polar coating of the silica microparticles. This included the effect of mobile phase composition,
e.g., acetonitrile, buffer and pH on retention factor, selectivity, efficiency and peak resolution. As
expected each coating yielded unique retention pattern and selectivity towards the polar and
slightly polar solutes tested.

DETERMINATION OF STRESS IN UNIVERSITY STUDENTS BY MONITORING SALIVA

CORTISOL AND ZINC IN HAIR. Nicolas Shaffer1, Daniel Montalvo1, Jianguo Liu1, S.
Gamagadara1, I Noor-Mohamadi1, J. Olson2, B. Lavine3 and J. Bowen11Department of Chemistry,
University of Central Oklahoma 2Department of Kinesiology, University of Central Oklahoma
3
Department of Chemistry, Oklahoma State University

It is well known that stress will increase concentrations of cortisol in body fluids including saliva, and
will lead to a decrease in zinc in hair. We are developing analytical methods for the analysis of cortisol in
saliva using LCMS, and for zinc in hair using Flame Atomic Absorption. A group of young female
students with long hair will be recruited and tested physically, and then be monitored for cortisol and zinc
to determine the amount of stress brought on by university exams. Preliminary data will be presented.

A PROTOTYPE MICROFLUIDIC IMMUNOLOGICAL BIOSENSOR FOR POINT-OF-CARE

DIAGNOSTICS Mary M. Tappert 1, Jane Jarshaw 1, Dana Horne2, Robert E. Brennan 1, William
Wilson3, and John Bowen 2,*1 Department of Biology, University of Central Oklahoma, 100 N.
University Drive, Edmond, Oklahoma 73034; E-Mails: mtappert@uco.edu; jjarshaw@uco.edu;
rbrennan1@uco.edu, 2 Department of Chemistry, University of Central Oklahoma, 100 N. University
Drive, Edmond, Oklahoma 73034; E-Mails: dhorne1@uco.edu; jbowen@uco.edu, 3 Microbiology,
USDA-ARS-NPA, Manhattan, KS 66502

Abstract: Modern technology has generated a large number of techniques for identifying pathogenic
organisms and diagnosing diseases, but many commonly used diagnostic procedures—including ELISA
and PCR—are expensive and must be performed by trained laboratory personnel, which limits their
usefulness in rural, developing-world, and home-user applications. Cheaper diagnostic techniques, such
as the lateral flow assay and the microfluidic paper-based analytical device, are much more useful in these
settings but have other limitations; the lateral-flow assay, for example, generally requires high sample
concentrations, while the microfluidic paper-based analytical device depends on the presence of enzymes
in the analyte. By leveraging the affinity of proteins for nitrocellulose (as in Western blotting) and the
sensitivity of fluorescent labeling, we have developed a prototype biosensor that combines the strengths
of lateral-flow and microfluidic paper-based devices into a “microfluidic immunoassay biosensor” that
reliably detects the presence of antibodies in a sample of only 30 µL volume. This type of device can be
produced cheaply and operated by an untrained user even when only small amounts of analyte are
available.
Label-Free Real-Time Imaging of Cancer Protein-Protein Interactions and Small Molecule
Inhibitions by a Surface Plasmon Resonance Microarray Charuksha Walgama1, Zainab H. Al
Mubarak1, Bing Zhang2, Mayowa Akinwale1, Anuruddha Pathiranage1, Junpeng Deng2, Darrell
K. Berlin1, Doris M. Benbrook3, and Sadagopan Krishnan11 Department of Chemistry, Oklahoma
State University, Stillwater, OK, USA, 74078.2Department of Biochemistry and Molecular
Biology, Oklahoma State University, Stillwater, OK, USA, 74078. 3Department of Obstetrics
and Gynecology, University of Oklahoma HSC, Oklahoma City, USA, 73104.

We present a surface plasmon resonance imaging (SPRi) microarray - platform to study cancer
protein-protein interactions and their inhibition by small molecules. In vitro interaction between
tumor suppressor p53 and its negative regulator murine double minute 2 (MDM2) protein was
successfully imaged on a 16 spot (gold) SPRi multi-array chip with a 3.5-fold greater specificity
over the mutant p53 controls. This imaging array involves a rapid microfluidic system attached
to the SPR imager and a single step immobilization of p53 transactivational domain (TAD)
peptides on the gold surface as self-assembled monolayers (SAMs). Then different nanomolar to
micromolar concentrations of MDM2 oncoprotein in a buffer solution was allowed to bind the
surface p53 TAD. Real time percentage reflectivity changes of the array spots upon the
interaction of MDM2 to surface p53 TAD were monitored and used for calculating apparent
binding kinetics. We additionally measured the inhibition of MDM2-p53 interaction by Nutlin-
3a (a potential drug in preclinical stages), and obtained an apparent IC50 value of 90 nM that
was in agreement with the values reported based on other in vitro studies. Additionally,
molecular level mass changes were obtained by using a quartz crystal microbalance (QCM).

Acknowledgements – Financial support by Oklahoma State University is gratefully

acknowledged.
• Biochemistry and
organic chemistry
PHOTOREDOX MEDIATED C-H ARYLATION OF 2-BROMOAZOLES Amandeep
Arora and Jimmie D. Weaver, Department of Chemistry, Oklahoma State University,
Stillwater OK 74078
Direct functionalization of azole compounds with Arene-H is rare and challenging. Herein we
report a photoredox catalyst, fac-Ir(ppy)3, catalyzed coupling reaction of an unfunctionalized
arene-H and 2-bromoazoles mediated by visible light which provides access to several medicinal
and biological active motifs. This simple novel method has broad substrate scope, excellent
functional group compatibility, and high yields products. This method has been found to work
effectively for the functionalization of a number of derivatives of the 2-bromoazoles including
thiazoles, imidazoles, and oxazoles. In addition to simple hydrocarbon arene-H’s, the method
also works for a variety of N-and S-heterocycles as the C–H partner. Furthermore, the reaction
demonstrates anti-Minisci product selectivity upon addition to basic heterocycles again in good
to excellent yields.

NUCLEOPHILIC ADDITIONS TO POLARIZED VINYLARENES, Richard A. Bunce,

Krishna Kumar Gnanasekaran and Junghak Yoon, Department of Chemistry, Oklahoma State
University, Stillwater, OK 74078 USA

The addition of nucleophiles to the terminal double bond carbon of a styrene incorporating an
electron-withdrawing group at the ortho or para position has been studied. The conditions for
this transformation have been optimized and structural modifications to the substrate have been
explored. The structural modifications included variation of the activating group on the aromatic
ring and the substituents on the side chain double bond. The study revealed that nitro
substitution gave the best results for addition of carbon and nitrogen nucleophiles. Other
substituted systems had problems with polymerization or degradation under the robust reaction
conditions. The reaction generally proceeded well with methyl on the carbon of the double
bond, but was slowed by substitution at the position.
SYNTHESIS AND BIOLOGICAL EVALUATION OF ALKYL-SUBSTITUTED 2,4-
DIAMINOPYRIMIDINES AS ANTIBACTERIAL AGENTS Richard A. Bunce, Baskar
Nammalwar, N. Prasad Muddala and K. Darrell Berlin, Department of Chemistry, Oklahoma
State University, Stillwater, OK 74078

A series of substituted 2,4-diaminopyrimidine derivatives (1) has been prepared and evaluated
for potency against several bacterial agents including Bacillus anthracis and Staphylococcus
aureus. MIC and IC50 values were determined for these diaminopyrimidine derivatives and
revealed that structures bearing small alkyl and/or planar substituents at R1 of the phthalazine
ring showed the highest levels of activity. Other substitutions yielded compounds that were still
potent, but the activity was slightly lower. Co-crystallization of the derivative with R1 = propyl
with B. anthracis DHFR and X-ray studies showed a clear preference for the S enantiomer. This
talk will discuss the synthesis of these drug candidates and summarize the various activities.

Synthesis of 4,8-bis(2-dodecyloxy)benzo-[1,2-b:4,5-b]dithiophene-1,1,5,5-tetraoxide
(BDT[SO2]2) based organic semiconductors via Copper catalyzed C-H activation;Devang P.
Khambhati1, Dr.Toby Nelson1,1Department of Chemistry, Oklahoma State University, Stillwater,
OK 74078

Organic semiconductors have gained tremendous interest in recent decades due to their use in
organic solar cells, organic thin film transistors and organic light emitting diodes. Generally,
these materials have been synthesized using conventional C-C coupling reactions such as
Suzuki, Stille, Kumada couplings, which employ use of hazardous organometallic reagent. In
contrast, C-H activated direct arylation offers many advantages like elimination of
organometallic reagent and higher atom efficiency. Here, we have utilized copper catalyzed C-H
activation to synthesize 4,8-bis(2-dodecyloxy)benzo-[1,2-b:4,5-b]dithiophene-1,1,5,5-tetraoxide
(BDT[SO2]2)-based small molecules as organic semiconductors. Reaction conditions were
optimized for various parameters like catalysts, ligands and base. Further research for the scope
of reaction and properties of these molecules are in progress.
ACCESS TO MULTIFLUORINATED BIARYLS VIA PHOTOCATALYTIC DUAL C-F,
C-H FUNCTIONALIZATION; Sameera M. Senaweera and Jimmie D. Weaver
Department of Chemistry, Oklahoma State University, Stillwater, Oklahoma 74078, United
States

Multi-fluorinated biaryls are an important class of molecules with a range of applications in

pharmaceutical, agrochemical and material science fields. Even though, the biaryls are
accessible via well-established cross-coupling methods, fluorinated biaryls are synthetically
challenging due to the difficulty associated with the selective fluorination. An alternative
approach is to couple an arene with a fluoroarene possessing C-F bonds in the anticipated
locations. These strategies heavily rely on traditional cross-coupling methods which utilize
organometallics and halides (or pseudohalides) on either one or both coupling partners. We have
developed a single step photocatalytic method to access multifluorinated biaryls with no
derivatization of either of the coupling partners. The mild conditions allow the reaction to
proceed with good functional group tolerance and facilitate a broad scope of fluorinated biaryls
to be formed. The reaction takes place by addition of an electron to the perfluoroaryl system,
C–F fragmentation to give a polyfluoroaryl radical which adds to the π-system of a range of
arenes, finally it is followed by oxidation and rearomatization to give a multifluorinated biaryl.
Furthermore, the reaction conditions permit the access to anti-Minisci products of some basic
heterocycles. Finally, we demonstrate the utility of this method by synthesizing complex
multifluorinated biaryls which contain between two and five Caryl-F bonds via synergistic use of
SNAr chemistry along with the photocatlytic hydrodefluorination.

Preference: Presentation
Novel Magnetic Relaxation Nanosensors: An Unparalleled “Spin” on Influenza Diagnosis;

Tyler Shelby,‡ Tuhina Banerjee,‡Jyothi Kallu, Irene Zegar, Lisa A. Clough± and Santimukul
Santra*, *Department of Chemistry, Pittsburg State University, 1701 S. Broadway Street, Pittsburg, KS
66762, USA.

Influenza is well known for its ability to rapidly mutate, leading to the frequent emergence of
pathogenic strains. Rapid detection and diagnosis of pathogenic strains would allow for
expedited treatment, and quicker resolutions to the ever-arising flu pandemics. Vital to the rise of
pathogenic strains is the mutation of viral genes coding for hemagglutinin, the influenza-
associated glycoprotein responsible for viral binding and entry. Slight mutations allow the
protein to adopt new binding affinities, granting it access to new cell receptors. Considering this,
we propose the development of novel functional magnetic relaxation nanosensors (MRnS) for
the rapid detection of influenza through targeted binding with hemagglutinin. A group of small
molecule ligands and entry blocker (EB) peptides with known binding affinities for
hemagglutinin variants were conjugated to iron oxide nanoparticles (IONPs) to develop
functional MRnS. Positive detection of various hemagglutinin (H1N1 and H5N1) HA1 subunits
was easily possible with protein concentrations as little as 1.0 nM using sialic acid (2,6- and 2,3-
sialic acid, respectively) and entry blocker peptides (EB Peptide, ALRPL and Ste)-conjugated
MRnS. Most importantly, detection using functional MRnS was achieved within minutes, and
was able to differentiate between various influenza subtypes. Current methods used to diagnose
influenza, such as RT-PCR, ELISA, and viral culturing, while largely effective, are complex,
time-consuming and costly. As well, they are not as sensitive or specific, and have been known
to produce false-positive results. In contrast to these methods, targeted MRnS is a robust, point-
of-care diagnostic tool featuring simple, rapid and low-cost procedures. These qualities, as well
as high sensitivity and specificity, and low turnaround times, make a strong case for the
diagnostic application of MRnS in clinical settings.

References

1. Kumar, S.; Henrickson, Kelly; Clinical Microbiology Reviews 2012, 25(2), 344-361.
2. Sin, M.; Mach, K.; Wong, P.; Liao, J. Expert Rev. Mol. Diagn. 2014, 14(2), 225-244.
3. Qasim, M. Journal of Nanoscience and Nanotechnology 2014, 14(10), 7374-7387.
4. Mahony, J. Clinical Microbiology Reviews 2008, 21(4), 716-747.
5. WHO 2007
6. Chen, W.; He B.; Li C.; Zhang X.; Wu W.; Yin X.; Fan B.; Fan X.; Waang J. Journal of
Medical Microbiology 2007, 56(Pt 5), 603-607.
7. Liong, M.; Hoang, A.; Chung, J.; Gural, N.; Ford, C.; Min, C.; Shah, R.; Shmad, R.;
Fernandez-Suarez, M.; Fortune, S.; Toner, M.; Lee, H.; Weissleder, R. Nature
Communications 2013, 4(1752)
8. Kaittanis, C.; Santra, S.; Perez, J. JACS 2009, 131(35), 12780-91
9. Perez, J.; Simeone, F.; Saeki, Y.; Josephson, L.; Weissleder, R. J. Am. Chem. Soc. 2003,
125(34), 10192-10193
10. El-Boubbou, K.; Gruden, C.; Huang, X. J. Am. Chem. Soc. 2007, 129(44) 13392-13393
11. Kaittanis, C.; Naser, S.; Perez, J. Nano Letters 2007, 7(2), 380-383
12. Lin, L.; Cong, Z.; Cao, J.; Ke, K.; Peng, Q.; Gao, J.; Yang, H.; Liu, G.; Chen, X. ACS Nano
2014, 8(4) 3876-3883
13. Kaittanis, C.; Santra, S.; Santiestebal, O.; Henderson Ii, T.; Perez, J. JACS 2011, 133(10),
3668-3676
14. Liu, J.; Liu, Y.; Bu, W.; Bu, J.; Sun, Y.; Du, J.; Shi, J. JACS 2014, 136(27), 9701-9709
15. Haun, J.; Devaraj, N.; Marinelli, B.; Lee, H.; Weissleder, R. ACS Nano 2011, 5(4), 3204-
3213
16. Kaittanis, C.; Boukhriss, H.; Santra, S.; Naser, S.; Perez, J. PLoS One 2012, 7(4), e35326
17. Wu, W.; Air GM. Virology 2004, 329(1), 213-214
18. Sieben, C.; Kappel, C.; Zhu, R.; Wozniak, A.; Rankl, C.; Hinterdorfer, P.; Helmut, G.;
Herrmann, A. Proc. Natl. Acad. Sci. USA 2012, 109(34), 13626-13631
19. Sauter, N.; Bednarski, M.; Wurzburg, B.; Hanson, J.; Whitesides, g.; Skehel, J.; Wiley, D.
Biochemistry 1989, 28(21), 8388-8396
20. McCullough, C.; Wang, M.; Rong, L.; Caffrey, M. PLos One 2012, 7(7), e33958
21. Santiesteban, O.; Kaittanis, C.; Perez, J. Angew. Chem. Int. Ed. Engl. 2012, 51(27), 6728-
6732
22. Santiesteban O.; Kaittanis, C.; Perez, J. Small 2014, 10(6), 1202-1211
23. Matsubara, T.; Onishi, A.; Saito, T.; Shimada, A.; Inoue, H.; Taki, T.; Nagata, K.; Okahata,
Y.; Sata, T. J Med. Chem. 2010, 53(11), 4441-4449
24. Jones, JC.; Turpin, EA.; Bultmann, H.; Brandt, CR.; Schultz-Cherry, S. Journal of Virology
2006, 80(24), 11960-11967
25. Liu, Q.; Liu, DY.; Yang, ZQ. Acta. Pharmacol. Sin. 2013, 34(10) 1257-1269
26. Yang, J.; Li, M.; Shen, X.; Liu, S. Viruses 2013, 5(1), 352-373
27. Shen, x.; Zhang, X.; Liu, S. Journ. Thor. Dis. 2013, 5(2), S149-159.

STRAIN INDUCED COUPLINGS MEDIATED BY VISIBLE LIGHT Kamaljeet Singh and

Jimmie D. Weaver, Oklahoma State University, Stillwater OK 74078
Bioconjugation strategy has emerged as a powerful tool in labeling of biomolecules such as
proteins, lipids, glycans and various other biomolecules. The Cu-catalyzed click reaction
emerged as a benchmark in this field. However, due to cytotoxicity of Cu towards live cells, the
practicality of click reaction has been limited. Since then, various strategies have been developed
which utilized strain energy associated with the geometries of specific organic molecules which
are distorted from ideal geometries. Owing to the fast kinetics and selectivity, various
methodologies, such as strain promoted azide alkyne cycloaddition (SPAAC), strain promoted
alkyne nitrone cycloaddition (SPANC), strained alkene-azide reactions, photoclick
cycloadditions, inverse-electron-demand Diels-Alder (IED-DA) reactions, were developed. But
these methodologies are limited to the synthesis of starting strained molecules cyclooctynes or
trans-cyclooctenes, which have very poor stability (particularly cyclooctynes). Herein a new
approach towards this limitation is developed. Strained benzofused trans-cycloheptene was
generated in situ and coupled with azides using Ir-based photocatalyst mediated by visible light.
The reaction follows a pseudo first order kinetics with rate constant 0.0025 ± 0.0009 s-1 and a
half-life of 4.6 min. Various azides are compatible under the reaction conditions yielding 58-
90% of the 1,2 dihydrotriazole products. The reaction is accelerated by the presence of water
which can be advantageous during labeling of proteins. This strategy eliminates the need for
synthesis of strained molecules. This methodology can be applied for labeling other
biomolecules as the reaction proceeded smoothly in presence of bovine serum albumin (BSA)

Selective Perfluoro- and Polyfluoroarylation of Oxazolones; Synthesis of Polyfluorinated α-

Amino Acids, Kip A. Teegardin and Dr. Jimmie Weaver, The Department of Chemistry,
Oklahoma State University, Stillwater, OK 74074
In this presentation we describe the monoselective per- and poly-fluoroarylation of oxazolones,
an acidic α-amino acid surrogate, which can be easily deprotonated and undergo nucleophilic
addition leading to fluoroarylated α-amino acids. The reaction takes place quickly and upon
opening of the lactone the α-N-benzoyl polyfluoroarylated amino acid products can be isolated
without chromatography. Finally, we describe the deprotection and isolation as well as discuss
some versatile applications of these unnatural amino acids in modern biology.

Benzo[ghi]perylene triimides: Synthesis, Characterization and

Comparison of Electrochemical and Spectroscopic Properties, Lakshmi C.
Kasi Viswanath , The Department of Chemistry, Oklahoma Baptist University, Stillwater, OK
74075
Benzo[ghi]perylene imides constitute a unique class of fluorescent perylene dyes which
possesses great synthetic diversity due to the presence of large number of reactive active sites
(availability of third imide region). Taking advantage of this additional active site we
synthesized a new series of benzo[ghi]perylene triimides comprising of alkyl- and aryl-
substituents in the third imide region. The core extension of perylene diimides performed using a
diels alder reaction to afford diimido anhydride (3) which provided access to the various
triimides with an yield ranging from 58% – 69%. The combined spectroscopic and
electrochemical studies revealed strong electron accepting propeties of the triimides which finds
application in various optoelectronic devices and as non-fullerene electron acceptors in
photovoltaics.

References

1. Kasi Viswanath, L. C.; Shirtcliff, L. D.; Krishnan, S.; Handa, N. V.; Darrell Berlin, K.
Tetrahedron Lett. 2014, 55 (30), 4199–4202.
2. Rybtchinski, B.; Sinks, L. E.; Wasielewski, M. R. J. Am. Chem. Soc 2004, 126 (39),
12268–12269.
3. Kasi Viswanath, L. C.; Shirtcliff, L. D.; Krishnan, S.; Darrell Berlin, K. Dyes Pigm.
2015, 112, 283–289.
• Inorganic chemistry
and chemical
education
SYNTHESIS AND HETEROBIMETALLIC ANCHORING OF THE FIRST P-LINKER
FEATURING MERCAPTO AND ISOCYANO JUNCTION GROUPS WITHIN THE
SAME MOLECULE; Jason C. Applegate1, Monisola K. Okeowo1, Nathan R. Erickson1, Cindy
L. Berrie1, Nikolay N. Gerasimchuk2, and Mikhail V. Barybin1
1
Department of Chemistry, University of Kansas, Lawrence, Kansas 66045 2Department of
Chemistry, Missouri State University, Springfield, Missouri 65897

Mercapto and isocyano groups are frequently employed junction u nits in designing materials for
molecular electronics applications. While the organic linkers in such materials feature
symmetrical anchoring, a recent theoretical quest for asymmetrical anchoring unveiled a novel
paradigm in the design of molecular rectifiers.1 This presentation will introduce the chemistry of
a linear azulenic -bridge terminated with one mercapto and one isocyano junctions that was
developed through a combined synthetic, spectroscopic, and theoretical study. Specifically, the
synthesis, monometallic and heterobimetallic complexation, as well as the molecular and
electronic structures of a 2-isocyano-6-mercaptoazulene linker will be discussed.2

References

1. Dyck, C. V.; Ratner, M. A. Nano Lett. 2015, 15, 1577.

2. Applegate, J. C.; Okeowo, M. K.; Erickson, N. R.; Neal, B. M.; Berrie, C. L.;
Gerasimchuk, N. N.; Barybin, M. V. Chemical Science 2016, 7, 1422.

A NEW PARADIGM FOR SELF-ASSEMBLY OF HIGHLY ORDERED

ORGANOMETALLIC CHARGE-TRANSFER MATERIALS; Mikhail V. Barybin

Department of Chemistry, The University of Kansas, Lawrence, KS 66045

Organometallic crystal engineering often capitalizes on the use of noncovalent phenomena, such
as π-stacking, hydrogen bonding and charge transfer interactions, to assemble functional
supramolecular materials. In this project, we sought to incorporate metallocene and metal
carbonyl complexes, arguably the two most ubiquitous motifs in organometallic chemistry, into
new charge-transfer coordination platforms featuring conjugated linear diisocyanoarene linkers.
Three different synthetic routes to ([Cp2Co]2[{(OC)5V}2( -1,4-CNC6Me4NC)])∞ held together
via synergistic -stacking and CoIII/VI- contact ion interactions will be presented. The dianion
[{(OC)5V}2( -1,4-CNC6Me4NC)]2- constitutes the first subvalent organometallics containing a
diisocyanoarene bridge. X-ray crystallographic, 51V NMR, infrared, electronic absorption, and
electrochemical data pertaining to the above supramolecular ensemble and related species will be
discussed.
Simple, Selective Methods for Chiral Metallocene Preparation; Richard Buck1, Qing Yang1
1
Chevron Phillips Chemical Company LP, Bartlesville, OK 74003

Metallocene compounds serve as precatalysts in a variety of important commercial applications.

The chiral structure possessed by many of these is often key to their catalytic function.
Traditional preparation methods often lack selectivity and can result in poor isolated yields or
purity in the final product. While new selective methods continue to be developed, these often
rely on either complicated metal precursors or highly specific conditions that do not lend
themselves to generality. Herein, we report examples of simple group 4 bis(amide) complexes
that provide enhanced chemo- and stereoselective control over the critical bond formation steps
versus traditional methods. The bis(amide) complexes are readily prepared and react under mild
conditions. This method has allowed for the stepwise addition of Cp-type ligands to prepare
chiral unbridged metallocenes, as well as the preparation of bridged metallocenes with high
diastereoselectivity.

A New, Study-Based Approach to Improving General Chemistry Performance; Jordan,

M.R. The Department of Chemistry, Oklahoma Baptist Univesity, Shawnee OK 74804

A new approach to enhancing student performance in General Chemistry courses was developed.
This method is based on the idea teaching study skills and encouraging studying. This method
has resulted in noticeable improvement in student achievement in both General Chemistry I and
II courses.

Bioinspired Molybdenum(VI)-oxo, Vanadium(V)-oxo 2D and 3D Clusters with Redox

Inactive Divalent Cations; Ahmed M. Moneeb, Allen W. Apblett Department of Chemistry,
Oklahoma State University, Stillwater, Oklahoma 74078

The redox active metal-oxo functional group plays an essential role in tuning the catalytic
activity of the active site complexes in various biologically important metalloenzymes. Although
several biomimetic synthetic metal-oxo based complexes have been synthesized successfully
using advanced synthetic strategies, the main drawback preventing the efficient utilization of
these materials as catalysts under aerobic catalytic conditions is the lack of stability in non-
biological environment settings. One promising synthetic approach to overcome the weak
stability of the synthetic active site models is to integrate these moieties into higher coordination
systems such as coordination polymers and metal-organic frameworks. Based on this concept
and inspired by the unique structure of the active site of the oxygen evolving center (OEC) in the
metalloprotein of photosystem II, we successfully synthesized and structurally characterized a
variety of polymeric coordination systems containing a redox active M-oxo [M= Mo(VI) or
V(V)] center connected to redox inactive cation [Ca(II), Sr(II), Ba(II), Zn(II)] via α–hydroxy
acids ligands (α-hydroxyisobutyric acid or benzilic acid). The synthetic approach and the solid
state crystal structure of the prepared materials will be reported. The effect of the coordination
number preference of the divalent cation and the influence of the structural features of the
organic ligand on the adopted covalent Mo(VI) – O – M(II) bonding and the non-covalent
intermolecular interactions of the prepared coordination systems will be discussed .

Reactions of 2-mercapto nicotinic acid, 4-mercapto salicylic acid and pyrimidine

thiols with Platinum, Copper and Silver A. K. Fazlur Rahman, frahman@ossm.edu, Pedro-
lozano-DeAos, Department of Chemistry, Oklahoma School of Science and Mathematics, 1141 N
Lincoln Blvd, Oklahomacity, OK 73104, Fax: 405-521-6442

This presentation will illustrate our effort to coordinate metal ions such as copper, silver and platinum
with thiols nicotinic acids, thionicotinic acids. For example, Copper II nitrate reacts with 2-mercapto-
nicotinic acid (H2Mna, C6H5NO2S) in water at 800C to form a binuclear, water soluble compound of
formulae [(C12H8CuN2O8S2). (H2O)2].( 1) . Crystal structure analysis of the complex (1) shows that during
the course of the reaction the mercapto(RSH) group has converted to RSO3H by the reduction of the
nitrate to NO. Reaction of copper ion and silver ion with tetrahydropyrimidine thiol gives corresponding
coordinated complexes which have been characterized by X-ray crystallography.
• Physical chemistry
TIME BASE CORRECTION OF STM IMAGES AND POST-PROCESSING REMOVAL OF 60
HZ NOISE AND ITS HARMONICS Lloyd A. Bumm, Mitchell P. Yothers, Homer L. Dodge
Department of Physics & Astronomy, The University of Oklahoma, Norman, OK 73019.

Nearly every electronic measurement contains unwanted components from the 60 Hz power and its
harmonics. Although the components at 60 Hz are imperceptible by eye in our images, they are distinct
narrow band peaks in the signal spectrum (~5 fA/√Hz in current above a 300 aA/√Hz noise floor and ~3
pm/√Hz in topography above a 200 fm/√Hz noise floor). We are interested to remove this unwanted
signal because it could interfere with advanced measurements we are performing on our STM images.
Because our typical high resolution STM image is acquired in 221 data points over 500 seconds, we in
principle have a transform limited bandwidth of 2 mHz, so it should be possible to surgically perform
phase-sensitive removal of the 60 Hz components without degrading the DC to 1 kHz STM image data.
This should be possible because the 60 Hz noise is time correlated while the STM data is space
correlated. This task is complicated by fact that the 221 points are not acquired at regular intervals. In
addition the frequency of the 60 Hz power grid fluctuates ±30 mHz over a time scale of minutes to hours.
To address this problem we have implemented time base correction so that the time of each data point is
known to better than 1 µs. A 60 Hz signal from the power grid is also recorded and serves as a reference
from which the noise signals can be reconstructed and subtracted. We will discuss the issues in
performing post processing removal and report on our results.

KINETICS OF H-ABSTRACTION FROM THIOPHENOLS BY TERT-BUTOXY AND N-

BUTYL THIYL RADICAL, Paritosh Das, Retired from Department of Chemistry, Physics, and
Engineering, Cameron University, Lawton, OK 73505

Results from a time-resolved study based on nanosecond laser flash photolysis will be presented
for kinetics of hydrogen abstraction from a series of p-substituted thiophenols by tert-butoxy and
n-butyl thiyl radical. These two radicals were photogenerated by 337-nm laser pulse excitation of
mixtures (1:1, v/v) of di-tert-butyl peroxide and n-butyl disulfide, respectively, with benzene or
methanol. The measured bimolecular rate constants are in the ranges: (4-17)×108 and (3-8)×108
M-1s-1 for tert-butoxy radical in benzene and methanol, respectively. The corresponding data for
n-butyl thiyl radical are smaller by an order of magnitude. The presentation will include a
comparison of the kinetic data with those for H-abstraction by tert-butoxy radical from phenols
and aliphatic thiols.
AN ORGANOCHROMIUM MOLECULAR WIRE FEATURING A LINEAR
TERAZULENIC π-LINKER: A SYNTHETIC, SPECTROSCOPIC, AND
COMPUTATIONAL STUDY, Nathan R. Erickson1, Mikhail V. Barybin1
1
Department of Chemistry, University of Kansas, Lawrence, KS 66045

The azulenic scaffold, a polar 10 π-electron nonbenzenoid aromatic unit composed of fused 5-
and 7-membered sp2-carbon rings, is an attractive motif for designing new materials supporting
charge delocalization and transport at the nanoscale.1 In this work a linear, π-conjugated
organometallic platform containing Cr0 termini bridged by a terazulenic linker was synthesized.
Its molecular and electronic structures were addressed by a variety of spectroscopic and
electrochemical methods, as well as computationally using Density Functional Theory.
Specifically, this presentation will highlight the chemistry of the first terazulenic molecular
linker (n=3, X=NC in Figure 1) and discuss its redox and spectroscopic signatures.

Figure 1

References
1
Applegate, J. C., Okeowo, M. K., Erickson, N. R., Neal, B. M., Berrie, C. L., Gerasimchuk N.
N., Barybin, M. V. Chem. Sci., 2016, 7, 1422-1429.

ACCURATE PREDICTION OF CYCLOHEXANE-TO-WATER DISTRIBUTION

COEFFICIENTS WITH MOLECULAR DYNAMICS SIMULATION; Shanaka
Paranahewage1, Christopher J. Fennell1
1
The Department of Chemistry, Oklahoma State University, Stillwater, Oklahoma 74075

Accurate prediction of distribution coefficients of small molecules between different chemical

environments is critical for the development and efficacy assessment of new drug candidates.
Unfortunately, inaccurate atom type parameters can result systematic biases in estimations of
distribution coefficients from molecular dynamic simulations. We have tested different scaling
methods of force field parameters to determine the distribution coefficients between cyclohexane
and water for a set of 30 small molecules, spanning a broad swath of chemical interest, using
detailed molecular simulations. We found that the solvent dielectric quality and condensed phase
polarization of the ligand plays a critical role inaccurate estimation of these values and the
removal of systematic biases in simulation parameters. Based on the study set results and
procedure developed, we have estimated cyclohexane-to-water distribution coefficients for 53
ligands as part of the SAMPL5 prediction.

ELECTROCHEMICAL INVESTIGATION OF THE STABILITY OF A SILVER

BROMIDE MONOLAYER ON AU(111) USING EC-STM, Jesse A. Phillips, Heather
Morgan, Lauren Jackson, Greg Jones, Dr. Sanwu Wang, Dr. Erin V. Iski, The Department of
Chemistry and Biochemistry, The Univeristy of Tulsa, Tulsa, OK 74104,

In previous research completed by Iski et al., it was found that through specific electrochemical
methods, a silver (Ag) monolayer could be formed on a Au(111) surface in an electrochemical
environment in both a chloride-free and chloride-rich solution. The previous study showed that,
in a chloride-free environment, the Ag monolayer could be formed and atomically resolved;
however, once removed from the cell, it could be completely removed via hydrogen flame
annealing. Interestingly, in the presence of chloride, the same Ag monolayer was formed and
was found to be extremely thermally stable after removal from the cell and was resistive to
temperatures as high as 1,000 K. The atomic structure of these films can be studied with
electrochemical scanning tunneling microscopy (EC-STM), which not only allows for atomic
scale imaging of the surface layer within an electrochemical environment, but also facilitates the
taking of cyclic voltammograms (CVs), which can be used to examine the redox behavior of the
systems. Despite many studies on these types of surface layers, very few publications have
directly studied their extreme thermal stability. Since it is known that the stability of bulk metal
halide structures decreases as the halogen ion increases in size, an investigative study was
performed following the same procedure, substituting chloride with bromide. As with the AgCl
system, once AgBr was used to form the Ag monolayer, a new surface structure formed which
was also thermally resistive to a hydrogen flame. CVs taken in the same region as those in the
previous work show a definite surface modification by AgBr with different peak data than those
taken with AgCl. Further electrochemical studies into this new Ag monolayer formed in a
bromide environment are being conducted in an attempt to better understand the properties of
this surface and the type of redox chemistry occurring at these potentials in comparison to the
chloride layer formed previously. Furthermore, density functional theory (DFT) will also be used
to look at the equilibrium coverage and the diffusion barrier of the bromide on the Ag
monolayer. Using EC-STM and DFT, we plan to study the ways in which this remarkable
stability is imparted to the single crystal surface under ambient conditions.
AN OXIDATION STUDY OF DECANETHIOL UNDER SELF-ASSEMBLED MONOLAYER
GROWTH CONDITIONS, Cody J. Ray, Lloyd A. Bumm, Homer L. Dodge Department of Physics &
Astronomy, The University of Oklahoma, Norman, OK 73019.

The Bumm group has been studying the growth of decanethiol self-assembled monolayers (SAMs) on Au(111)
from decanethiol vapor at elevated temperatures. Under these conditions, thiols can be oxidized by O2 to produce
disulfides. We will discuss nuclear magnetic resonance (NMR) spectroscopy studies of growth conditions. These
conditions include the extent of oxidation, the efficacy of purging the growth vessel with N 2, and the permeation
of Viton O-rings by decanethiol, didodecyl disulfide, and O2. We perform quantitative NMR measurements to
measure both the relative extent of oxidation and the amount of decanethiol remaining at the conclusion of the
growth. Measurements using Viton-O-ring-sealed stainless-steel growth vessels show that oxidation can be
greatly reduced by both purging the vessel with N2 and passivating the surface of the stainless steel. However,
there was significant loss of decanethiol due to permeation into the Viton O-rings. We designed a copper-gasket-
sealed growth vessel to eliminate the permeation as well as an auxiliary purge vessel to allow the growth vessel
to be sealed while being purged by N2. Preliminary results from NMR studies show no measurable oxidation or
loss of decanethiol at temperatures as high as 200°C.

On the Existence of Trans-Cyclohexene, Winston Trinh, Kamaljeet Singh, And Jimmie Weaver
Department of Chemistry, Oklahoma State University, Norman, OK

For nearly forty years, the existence of trans-cyclohexene has been postulated; which is believed to be
accessible via UV-irradiation of cis-cyclohexene. In the undergraduate textbook, the smallest possible
cycle in which double bond can exist in a trans-cycle form is cyclooctenene. Herein, the first
stereochemical evidence of the existence of trans-cyclohexene is reported. We are using the convenient
method utilizing a photocatalyst and blue LEDs, which helps to access oxabicyclic structures, possibly
via trans phenyl cyclohexene. In a rare example of uphill catalysis, we are to synthesize endergonic
products and reverse back to the starting material when light is turned off, suggesting a new possible
class of chemical switch.
PROPERTIES AND DYNAMICS OF INDIVIDUAL SCANNING TUNNELING MICROSCOPE IMAGE FEATURES

Mitchell P. Yothers, Lloyd A. Bumm

Homer L. Dodge Department of Physics & Astronomy, The University of Oklahoma, Norman, OK 73019.

Scanning tunneling microscope (STM) images of ordered surfaces can cover hundreds of unit cells with
good resolution of each atomic or molecular feature. We index these image features and study their
positon compared to the other symmetry equivalent features and the best-fit lattice. Using software we
have developed in Matlab, we have analyzed STM images of graphite(0001) and alkanethiol self-
assembled monolayers (SAMs) on Au(111). The features are identified and located by a cross-correlation
of the image with a 2D Gaussian kernel. We then modify the locations of these molecules according to
models of piezoelectric hysteresis, piezoelectric creep and sample drift by using the known symmetry of
the crystalline surface (from e.g. x-ray diffraction) as an internal standard. By using the locations of
these indexed features on alkanethiol SAMs, we have made measurements of chain tilt direction and
angle by measuring longer-chain thiols mixed within the SAM; deviations of each basis feature location
from the best-fit lattice as a measure of conformational flexibility; and the lattice offset across domain
boundaries and gold atomic steps. Similar measurements on graphite have very little noise, giving some
insight on the fundamental resolution of the STM. In the future, we plan to analyze other measurements
that could be attached to individual surface features using this technique, including defect probability
measurements and structure variation around defects and boundaries.

Preference: 20-minute talk

 • Materials and
polymers


ENZYME ELECTROCATLYSIS USING CARBON NANOTUBE BASED BUCKPAPER
ELECTRODES Mayowa Akinwale1, Roberto Montealegre1, Charuksha Walgama1 and
Sadagopan Krishnan1 1The Department of Chemistry, Oklahoma State University, Stillwater,
Oklahoma 74078

Today there are many materials available to choose from with conductive properties for
experiments, but conductive nanomaterials have continued to emerge as one of the most useful
for various electrocatalytic applications. Nanomaterials have attracted more attention due their
superior electronic properties and large surface area, resulting in easier development of enzyme
electrocatalytic and biosensing systems. This particular study, examines enzyme electrocatalysis
using multiwalled carbon nanotube based bucky papers. Bucky papers were prepared with
different thicknesses ranging from 80 to 400 μM via the vacuum filtration method. Bucky paper
morphology and electrochemical properties were characterized using microscopy and
conductivity/capacitance, respectively. Direct oxygen reduction was also measured using cyclic
voltammetry for bucky papers immobilized with metalloproteins.

FERROCENE CONTAINING POLYURETHANES FOR IMPROVED FLAME-

RETARDANT PROPERTIES Michael Giffin, Tim Dawsey and Charles J. Neef, Department
of Chemistry, Pittsburg State University, Pittsburg, KS, 66762

Flame retardant polyurethanes are needed for various commercial and industrial applications;
toward that end ferrocene derivatives with multiple hydroxyl groups were synthesized for
incorporation into polyurethane thin films for testing. The derivatives synthesized were di-(2,3-
dihydroxypropyl) ferrocene 1-1’-dicarboxylate and 2,3-dihydroxypropyl ferrocene carboxylate.
These compounds were characterized using FT-IR spectroscopy, 1H-NMR and 13
C-NMR
spectroscopy. These derivatives were incorporated into a commercially available polyol mixture
at various weight percentages, mixed with toluene di-isocyanate, and cast as thin films on glass
plates. Each film was tested for flame retardance using a standard burn test chamber and thermal
stability in both nitrogen and air. Volatile organic compounds testing were also performed on
selected films. In addition, potential synergistic effects of the ferrocenyl polyols with triphenyl
phosphine was studied.
SECONDARY CRYSTALLIZATION AND AGING IN ETHYLENE-BASED
CARBOXYLIC ACID IONOMERS, Brian Grady, School of Chemical, Biological and
Materials Engineering, 100 East Boyd, EC Room T-223, Norman, OK 73069

Ionomers are polymers with a small fraction of ionic functional groups attached to the polymer
backbone. It is widely known that neutralization of these ionic groups with metal ions changes
the crystallization kinetics of the ionomer. For zinc-neutralized ethylene carboxylic acid
ionomers, a classic relationship of Flory did not hold true, namely that the fractional crystallinity
of a random copolymer depended on the identity of the comonomer. This result did not
invalidate the theory, rather Flory did not consider the case of a second phase, namely the ionic
aggregate phase, which did not disappear upon melting. Further, the rates of formation of
secondary crystals relative to the crystallization amount at infinite time was independent of
neutralization level for the phase-separated ionomers; in other words the Avrami constants n and
K were independent of neutralization level for the secondary crystals. Very careful absolute heat
capacity measurements were also used to examine the existence of immobilized amorphous
phases and it was shown calorimetrically that an immobilized amorphous phase exists above the
melting point of the polyethylene segments in the neutralized materials and that the amount of
this phase increases with increasing neutralization level. In this presentation, preliminary results
from other neutralizing cations will also be shown and compared to the results of the zinc-
neutralized materials.

HIGH FUNCTIONALITY POLYOLS FROM CASTOR OIL BY THIOL–ENE

REACTIONS, Mihail Ionescu*, Dragana Radojčić*, Xianmei Wan*, Maha Laxmi Shrestha*,

Zoran S. Petrović*, and Thomas Upshaw** * Pittsburg State University, Kansas Polymer
Research Center, Pittsburg, Kansas 66762.
** Chevron Phillips Chemical Company LP, Bartlesville Technology Center, Bartlesville, OK
74003.

Castor oil is a natural polyol with a triglyceride structure, where the main fatty acid (~90%) is
ricinoleic acid, containing 18 carbon atoms, a double bond between C9-C10 and hydroxyl group
at C12. Unfortunately, castor oil has too low of functionality (around 2.7 OH groups/mol) and too
low of hydroxyl number (around 160-168 mg KOH/g) to be used as sole polyol for rigid
polyurethane foams of acceptable physical-mechanical properties. New polyols with higher
functionality and higher hydroxyl number, derived from castor oil, were synthesized by using
photochemical thiol-ene and nucleophilic Michael thiol-ene reactions. From the newly
synthesized high functionality castor oil polyols, as sole polyols, cast polyurethanes and rigid
polyurethane foams were prepared with good physical-mechanical properties. The rigid
polyurethane foams from new synthesized castor oil polyols are suitable for all of the following
applications: thermal insulation of freezers, refrigerated rooms, storage tanks, and pipes used in
the food and chemical industry, for thermal insulation of buildings, as wood substitutes, and for
packaging

SYNTHEIS OF THIOL BASED CYCLIC CARBONATES, I. Javni1, O. Bilic1, V. Jaso1, D.

Radojcic1, M. Wan1, M. Ionescu1 and T. A. Upshaw2,
1
Kansas Polymer Research Center, Pittsburg State University, Pittsburg, KS 66762
2
Chevron Phillips Chemical Company LP, Bartlesville Technology Center, Bartlesville, OK
74003-6670

The synthesis of thiols and their further use is an important part of utilization of hydrogen sulfide, which
is a significant by product of hydrodesulfurization of fuel in petroleum refineries. Thiols react easily with
double bonds by thiol-ene reactions. These reactions are example of “click” chemistry because they
advance very rapidly. They proceed almost quantitatively, and are not inhibited either by oxygen or
humidity. Thiol-ene reactions are the method of choice for synthesis of thioether-epoxides, which can be
used as precursors for synthesis of five members cyclic carbonates. The carbonate synthesis proceeds by
reaction of epoxy group with carbon dioxide at moderate temperature and pressure and in the presence of
specific catalysts. Cyclic carbonates are excellent starting materials for new organic compounds,
plasticizers, solvents, fuel additives, lubricants, etc. They react relatively easily with most of hydrogen
donors. Alcohols produce esters and reaction with carboxylic acids gives mixtures of hydroxyalkyl esters
and diesters. Reaction of cyclic carbonates and amines is utilized for the synthesis of urethanes by a non-
isocyanate route. Cyclic carbonates are made from variable precursors, but utilization of thiols
(mercaptans) were not significantly examined. We used bio-based thiols made from soybean oil and
castor oil, and a cycloaliphatic polymercaptan, all produced by Chevron Phillips. The thioether-epoxy
compounds were made in the first step by thiol-ene reaction, and epoxy groups were converted to cyclic
carbonate in the second step. The cyclic carbonates were yellow to dark brown transparent liquids of
viscosity from 4 to 57 Pa.s. The chemical analysis proved that the conversion of thiols to cyclic
carbonates was successful and the products had the expected chemical structure. The reaction with
amines confirmed that the synthesized thioether-cyclocarbonates can be used as monomers for
preparation of polyurethanes by non-isocyanate route.
SURFACE BONDING AND THERMAL PROPERTIES OF POLYMERS ARE INFLUENCED

BY INTERMOLECULAR INTERACTIONS AT INTERFACES, Hamid Mortazavian,

Christopher J. Fennell, and Frank D. Blum, Department of Chemistry, Oklahoma State University,

Stillwater, OK 74078, United States

We performed direct comparisons of the thermal properties and intermolecular interactions of

adsorbed poly(vinyl acetate) (PVAc) and poly(methyl methacrylate) (PMMA) with similar
molecular masses and adsorbed amounts on silica, using temperature-modulated differential
scanning calorimetry (TMDSC) and molecular modeling. Compared to their bulk counterparts,
adsorbed PMMA showed a larger amount of tightly-bound polymer and a larger change in glass
transition compared to adsorbed PVAc. These observations suggested that the interactions
between PMMA and silica were stronger than those between PVAc and silica. Molecular
modeling of these surface-adsorbed polymers showed that PMMA associates more strongly with
silica than does PVAc through additional hydrogen-bonding interactions. Additionally,
simulations showed that the polymer-polymer interactions are stronger in PMMA than PVAc,
helping explain why a PMMA mobile-component is not observed in TMDSC thermograms.

DENSITY FUNCTIONAL THEORY STUDY OF CHEMICAL FUNCTIONALIZATION

OF TWO-DIMENSIONAL MATERIALS, Tong Mou1, Bin Wang1
1
School of Chemical, Biological and Materials Engineering, University of Oklahoma, Norman,
Oklahoma 73019

Graphene, as the first exfoliated two-dimensional (2D) material, has gained significant attention
regarding its appealing electronic properties and potential applications in electronic devices,
sensors and catalysis. Many of these properties rely on functionalization of the basal plane
through surface modification. The interest has recently been extended to other two-dimensional
materials that also show unique electronic and optical properties. In this study, we performed
first-principles density functional theory (DFT) calculations to investigate chemical
functionalization of monolayer graphene along with phosphorene, hexagonal boron nitride (h-
BN) and molybdenum disulfide (MoS2) with phenyl and phenolate species. We examined their
adsorption properties and relative stability through calculation of binding energies. Their
electronic structures (density of states) were calculated in comparison with the pristine structures
to reveal how these different functional groups modify their electronic properties. Our results
indicated that chemical functionalization of all the materials with phenyl groups could be an
effective influence on their electronic properties by introducing defect levels around the Fermi
level and between the band gaps. Instead, only phosphorene is sensitive to the presence of
phenolate, which could not be adsorbed on any other materials that we have tried. The results
would help shed some light on the promising electronic properties of 2D materials for future
device and sensor applications.
CHARACTERIZATION AND ASSEMBLY OF POLYMER ELECTROLYTE FOR
NANOBATTERY ARRAY USING ION BEAM DEPOSITION
John W. Ostrander, Dale Teeters
University of Tulsa Department of Chemistry and Biochemistry

Deveolpment and progress in nanotechnology and nano-devices create an ever increasing

demand for new components. An important component in nano-device control is a crossbar system
where bars perpendicular to each other run below and above a membrane holding the item of
interest. The space where the bars cross above and below can now be accessed by an external
sensor/controller. Employing the Focused ion beam deposition feature of a scanning electron
microscope (SEM/FIB) we are able to fabricate prototype components for such a crossbar system that
accesses nanobatteries on an alumina substrate. These conductive channels used in crossbars systems we
formed by controlled platinum deposition accessing nanobattery array components housed in an AAO
membranes.
The fabricated system will be tested by employing Atomic Force microscope (AFM) tip in
contact t with the deposited metal bars allowing Electro Impedence Spectroscopy (EIS) to be conducted
for investigation of the individual micro circuit and determination of nanobattery performance

STRUCTURE OF HEXADECYLTRIMETHOXYSILANE ON SILICA; Helanka J. Perera1

and Frank D. Blum1 Department of Chemistry, Oklahoma State University, Stillwater, OK
74078, USA
The structural assemblies of hexadecyltrimethoxysilane (HDTMS) on silica particles were
studied by temperature–modulated differential scanning calorimetry (TMDSC),
thermogravimetric analysis (TGA), and Fourier transform infrared spectroscopy (FTIR).
HDTMS molecules adsorbed at very small adsorbed amounts (< 0.8 mg/m2) molecules were
directly bound to the silica surface as isolated molecules and their aggregates were more likely to
be amorphous. These molecules were found to have very small enthalpies for both melting and
crystallization of HDTMS hydrocarbon chains. The enthalpies were found to increase linearly
with adsorbed amounts. With increasing adsorbed amount of HDTMS (> 0.8 mg/m2) melting and
crystallization enthalpies increased exponentially and reached the bulk HDTMS enthalpy for
samples with more than 15 mg/m2. The increased enthalpies for samples with more than 0.8
mg/m2 during transitions indicate that HDTMS molecules underwent structural changes, from
surface to bulk.
SYNTHESIS AND CHARACTERIZATION OF EUMELANIN-INSPIRED
POLYARYLENES
K. A. Niradha Sachinthani , Toby L. Nelson*
The department of Chemistry, Oklahoma State University, Stillwater, Oklahoma.74075

Melanin is a natural pigment found in most of the organisms including human and it is the
primary determinant of the skin tone in humans. It is also found in hair, eye, inner ear and brain
of human. Melanin acts as UV protective agent against harmful UV radiation. There are three
basic types of melanin where eumelanin (black-brown variety) is the most common. Scientists
have already isolated natural eumelanin, black-brown insoluble biomacromolecule, from the ink
sac of cuttlefish Sepia. It has been determined that eumelanin is composed of two building
blocks 5,6-dihydroxyindole and 5,6-dihydroxyindole carboxylic acid but the exact structure of
eumelanin remains unsolved. Both natural and synthetic eumelanin exhibit remarkable light
absorbing and electrical properties. For forty years, the accepted paradigm to explain
eumelanin’s unique properties have been identified that it was a disorder natural semiconductor,
a compound that requires an external stimulus in order to be electrically conductive. In the last
few years, Meredith and coworkers groundbreaking work has established eumelanin as an
electronic-ionic conductor which open the door to many bioelectronics applications like
biocompatible implantable devices. However, the current eumelanin materials have poor
solubility, produce thin, brittle films with poor morphologies and are mostly poly-dispersed
nanoparticles. Thus such properties are not well-suited for analysis and fabrication of printable
electronic devices. In order to develop well-defined, soluble eumelanin-inspired materials, a
eumelanin inspired core, methyl 4,7-dibromo-5,6-dimethoxy-1-methyl-1H-indole-2-carboxylate
(DBI) was synthesized as a new building block for organic semiconductors. In this study
eumelanin-inspired polyarylenes were synthesized by copolymerizing DBI with different aryl
groups such as fluorene, carbazole and phenylene. The effect of arylene group on optoelectronic
properties was explored. These polymers exhibit blue light emitting properties which may be
potentially applicable in organic light emitting diode (OLED)s. The synthesis and
characterization of eumelanin- inspired polyarylenes will be presented.

A NEW SOLID-STATE NMR METHOD REVEALS THE INFLUENCE OF CHAIN

STRUCTURE AND THERMAL HISTORY ON THE CRYSTAL-AMORPHOUS
INTERFACE IN POLYETHYLENES; Arifuzzaman Tapash1, Paul J. DesLauriers2, Jeffery L.
White1
1
The Department of Chemistry, Oklahoma State University, Stillwater, OK 74078 2Chevron
Phillips Chemical Company, Bartlesville, OK 74004

A simple solid-state NMR method is presented here to quantitatively determine the distribution
of solid polyethylene (PE) chain segments in different morphological regions. The rigid chains in
the crystalline phase with all-trans chain conformations, the non-crystalline trans-gauche mobile
chains, mobile all-trans chains, and rigid trans-gauche chains fractions were reliably quantified
using the developed method. A wide range of well-characterized polyethylene samples were
studied, which reveals that the amount of crystal-amorphous interface region increases with the
chain length of linear metallocene-PEs. Topologically different polyethylene that have certain
amounts of short-chain branches (SCB), long chain branches (LCB), and LCB’s that contain
SCB’s exhibit unique morphological behavior relative to the linear PE’s of similar M w (1). The
method also reveals the variations in the morphology due to different thermal histories.
Thermally quenched polyethylenes were found to have higher interface content than that of the
annealed or as-synthesized PEs. Phase composition results obtained by this simple experiment
are quantitative, reliable and reproducible. The results suggest a route to large-scale design and
control of interfacial morphology in polyethylenes and related properties.

References
1. Tapash, A.; DesLauriers, P. J.; White, J. L. Macromolecules 2015, 48, 3040-3048.

ION CONDITION OF A POLYMER IN A NANOSTRUCTURED CERAMIC

COMPOSITE ELECTROLTYE; Dale Teeters1, Indumini Jayasekara1
1
The Department of Chemistry and Biochemistry, The University of Tulsa, Tulsa, OK 74104

Highly conducting polymer electrolytes are necessary for commercial use in all solid state
batteries. A novel composite electrolyte having increased ion conduction consisting of a
polymer electrolyte in a ceramic nanostructure is described and characterized. The
nanostructured composite consists of 200 nm thick rods of poly(ethylene oxide) polymer in
channels of nanoporous alumina membranes. The confinement of the electrolyte in this
nanostructure increased the ion conduction of the polymer by three orders of magnitude.
Thermal analysis data exhibited a broad endotherm for confined PEO while non-confined PEO
polymer electrolyte had a melt endotherm that was sharper. In addition, the melting temperature
for the confined PEO was lower compared to the melting temperature for the non-confined PEO.
Analysis of these melting temperature shows that the crystallite thickness for the confined PEO
is much smaller than non-confined PEO. It is postulated that smaller crystallites could result in a
more amorphous phase being present in the polymer matrix contributing to the enhanced ion
conduction. In addition, the confinement of polyethers in pores is known to result in stretching
and ordering of the backbone, which has been proposed to increase ion conduction. The ordering
of the polymer chains will be investigated by IR spectroscopy. The presence of more amorphous
polymer and ordering of the backbone would seem to be the major factor involved in the
enhancement of ion conduction observed.
ELECTRICAL PROPERTIES AND DFT STUDIES OF COPOLYMERS FROM 3-
PEHENYL[5]FERROCENOPHANE-1,5-DIMETHYLENE AND VARIOUS PARA
SUBSTITUTED PHENYLMALEIMIDES, Henry M. Thomas, Benjamin O. Tayo, and
Charles J. Neef, Department of Chemistry, Pittsburg State University, Pittsburg, KS, 66762

Ferrocene containing polymers are of considerable attention due to their well understood
chemistry and stable redox responses. Our research has focused on understanding the spatial
arrangement and electrical properties of alternating copolymers from 3-
phenyl[5]ferrocenophane-1,5-dimethylene with various para substituted phenylmaleimides.
Cyclic voltammetry using these chemically modified electrodes with aqueous sodium perchlorate
showed two redox waves indicating electronic interaction between the ferrocenyl and maleimide
moieties. To better understand the electronic interactions, UV spectra were obtained and first-
principle studies using density functional study (DFT) was used to obtain the optimized
geometries. DFT studies clearly showed the ferrocenyl moiety in close proximity to the
maleimide moiety, suggesting that electronic interactions could result between these two
moieties.
• Water and
environmental
chemistry
COORDINATION POLYMERS FOR SORPTION OF ARSENIC AND PHOSPHATE
FROM CONTAMINATED WATERS. Allen Apblett1, David Corter, Alan Piquette1, and
Travis Reed1
1
Department of Chemistry, Oklahoma State University, Stillwater, OK, 74078

Novel materials and processes have been developed that can be used to remove arsenic from
drinking water and semiconductor manufacturing waste and can also remove phosphate from
aquaria with high efficiency. These materials are metal organic coordination polymers that have
startlingly high capacities for arsenic and phosphate that exceed 15% by weight. The sorption of
the target ions is effective over a wide range of pH and varied water chemistry. Phosphate
removal from aquarium waters exceeds that of commercial products for the same purpose and is
effective even in saltwater tanks. These materials are also amenable to developing processes for a
one-step treatment of aqueous waste streams from gallium arsenide production. Removal of
arsenic from juice and rice syrup is also possible.

GETTING NON-ESSENTIAL ELEMENTS OUT OF WATER WITH

NANOMETRIC INORGANIC ION-EXCHANGERS; Allen Apblett1, Cory Perkins1,
and Travis Reed1
1
Department of Chemistry, Oklahoma State University, Stillwater, OK, 74078

Recently the Apblett research group has discovered the unprecedented ability of certain
nanometric oxide materials to adsorb toxic heavy metals from water via an ion exchange
process. For example, nanometric calcium tungstate efficiently removes lead, cadmium,
and uranyl ions via a process that releases calcium ions into solution. As ion exchange
proceeds, the CaWO4 is transformed to the tungstate of the heavy metal: for example
PbWO4 (stolzite) is produced by adsorption of Pb2+ ions. A slightly different ion-
exchange process occurs when zinc oxide nanonoparticles are exposed to other transition
metal ions as those of copper and cobalt. In this instance zinc is released and bright blue
or pink solids containing copper and cobalt ions, respectively, are formed. The capacities
and selectivities for the toxic metals are quite high. Examples of treating industrial
wastewaters, juice, and milk will be presented.

ANALYSIS OF THE LEACHING OF DIBUTYL PHTHALATE FROM A

COMMERCIAL FAUCET HOSE USING SOLID PHASE MICROEXTRACTION
(SPME) AND GAS CHROMATOGRAPHY-MASS SPECTROSCOPY (GC-MS), Megan
Brown1, and John Bowen1

1 Department of Chemistry, University of Central Oklahoma, 100 N. University Drive,

Edmond, Oklahoma 73034; E-Mails: mbrown73@uco.edu; jbowen@uco.edu
Abstract: Dibutyl Phthalate, a plasticizer and suspected endocrine disruptor has been found to
leach from plastic hoses and pipes used in tap water systems. For this study, an analytical method
using Solid Phase Micro Extraction (SPME) and Gas Chromatography Mass Spectroscopy
(GCMS) was designed using Benzyl Benzoate as an internal standard. The method will be used
to determine the leaching of dibutyl phthalate with time from a commercial polyvinyl chloride
replacement hose used for a home sink.

SYNTHESIS OF REDUCED GRAPHENE OXIDE AND THE EFFECTS OF

ADSORPTION OF ORGANIC COMPOUNDS BY STRUCTURE, Author(s): Tye Chapman,
John Bowen, Barry Lavine, Affiliation: University of Central Oklahoma, Oklahoma State
University, Contact Information: jbowen@uco.edu

A low-cost synthesis of reduced graphene oxide (RGO), derived from the Hummers and Offeman
method was developed. A commercial grade graphite lubricant was exfoliated with concentrated
acid, oxidized by permanganate to produce graphene oxide (GO) This was then reduced using
hydrazine hydrate to produce a form of graphene on the surface of the particles. The RGO was
analyzed using Raman Spectroscopy and scanning electron microscopy (SEM). The RGO was
then used to compare the adsorption of dibutyl phthalate from water onto RGO versus activated
charcoal. The adsorption was analyzed by difference using solid phase micro extraction (SPME)
and gas chromatography mass spectrometry.

DETERMINATION OF DIBUTYL PHTHALATE IN INFANT FORMULA, Dalton

Lewis1, and John Bowen2 1Edmond North High School, Edmond, OK, 2University of Central
Oklahoma, Edmond, OK

Phthalate ester plasticizers, including dibutyl phthalate have been implicated as endrocrine
disruptors. These compounds leach from plastics into liquids and many were banned from toys
and baby products in 1996, but is commonly found in water in contact with PVC piping. For this
study, an analytical method was adapted to detect and quantitate phthalate esters in infant
formulas and baby food sold in plastic containers for the head space analysis using gas
chromatograph mass spectroscopy with concentration by solid phase microextraction (HS SPME
GC-MS). Results from various products will be discussed.
PARPALD REAGENT TO ENHANCE SURFACE PLASMON MICROARRAY
IMAGING TOWARD DETECTION OF ALDEHYDES, Zainab H Al Mubarak, Lucy
Lehoczky, Cassandra Rodenbaugh, and Sadagopan Krishnan, Department of Chemistry,
Oklahoma State University, OK-74078.

Formaldehyde (FA) is regarded as the most indoor pollutant among volatile organic compounds.
It is also a carcinogenic substance that causes considerable damages in human body tissues such
as causing central nervous system damage and pulmonary diseases. Additionally, elevated levels
of FA in human body fluids such as in urine, serum, and saliva reflect some critical health
conditions such as lung cancer and renal failure. Considering the enormous interests for
environmental monitoring and clinical diagnosis of FA, it is essential to have a sensitive imager
to sense FA at lowest concentration levels, ~ ppb. Surface plasmon Resonance imaging (SPRi) is
highly sensitive to the refractive index (RI) changes on or above the gold surface ~ (1 pixel = 3.7
X 10-5 RI difference). Additionally, microarray imaging-based approaches are advantageous with
respect to simplicity, multi-analyte detection features, and throughput. Moreover, real time
monitoring of bioassay is rapid and provide binding kinetics. Herein, we present a room-
temperature formaldehyde microarray sensor with enhanced sensitivity for detection of FA
assisted by the purpald reagent.

Acknowledgements – Financial support by Oklahoma State University is gratefully

acknowledged.

METHOD DEVELOPMENT FOR INDIRECT ANALYSIS OF GLYPHOSATE ON

GCMS, Jon Pope2, Devon Colby1, and John Bowen2 1Edmond North High School, Edmond, OK
2
University of Central Oklahoma, Edmond, OK

Abstract: An analytical method for the analysis of glyphosate in soil or water has been
developed using Gas Chromatography Mass Spectroscopy (GCMS). Glyphosate is extracted
from the sample substrate and derivatized. The derivatized sample is extracted and evaporated to
dryness and then solvated using ethyl acetate with benzyl benzoate as an internal standard.
• Poster session
UTILIZING VOLATILE ORGANIC COMPOUNDS TO DIFFERENTIATE BETWEEN
METHICILLIN RESISTANT AND SENSITIVE STRAINS OF STAPHYLOCOCCUS AUREUS USING
SOLID PHASE MICRO EXTRACTION (SPME) AND GAS CHROMATOGRAPHY-MASS
SPECTROMETRY (GC-MS) Garrett Dressler1, Robert Brennan2, David von Minden1 and John Bowen1
1
Department of Chemistry, University of Central Oklahoma, Edmond, OK
2
Department of Biology, University of Central Oklahoma, Edmond, OK

It is well known that microorganisms can and do give off distinct odors such as body odor or the characteristic
odor of yeast. In light of that knowledge, pure strains of Staphylococcus Aureus, both methicillin resistant and
methicillin sensitive, were sampled during this study. The motivation behind this was to attempt to identify the
different volatile organic compounds (VOC) given off by both the resistant and sensitive strains. The end goal of
the study was to be able to establish that the resistant strains give off unique VOC’s apart from the sensitive
strains. Solid Phase Micro Extraction (SPME) is a very useful technique for the analysis of VOC’s. Therefore,
for this study, headspace samples were collected using SPME with subsequent analysis using Gas
Chromatography/Mass Spectrometry (GC-MS). Data and results to be presented.

Development of an Enzyme Based Sensor for Formaldehyde Detection Using a Screen Printed Electrode,
Sabrina Farias, Gayan Premaratne, and Sadagopan Krishnan, Department of Chemistry. Oklahoma State
University Stillwater, OK 74078, U.S.A

Lung, breast, prostate and bladder cancers are some of the most common cancers among the cancer patient
population. Identifying these cancers using specific biomarkers at an early stage of disease would allow better
treatment outcomes and thus reduce the fatality rate. Formaldehyde has recently been recognized as one of the
key volatile organic biomarkers elevated in body fluids. Our goal is to develop an electrochemical biosensor for
detection of low levels of formaldehyde in clinical samples. Our biosensor design involves the pi-pi stacking of
carbon nanotubes (CNTs) with pyrene compounds to covalently attach formaldehyde dehydrogenase (FDH) by a
carbodiimide chemistry. Screen-printed electrodes (SPEs) with gold working electrode, silver reference
electrode and carbon paste auxiliary electrode were used for this experiment. The FDH catalyzed oxidation
reaction converts formaldehyde to formic acid using NAD+ as the electron acceptor to yield NADH. The
electrons from NADH is mediated to the electrode surface by 1, 2-napthaquinone sulfonic acid. The main
advantage of using NAD-dependent dehydrogenase-based biosensors is that O2 does not interfere in the
electrochemical formaldehyde detection. We are able to detect formaldehyde levels of 0.05, 0.1, 1, 10, and 50
ppm in urine matrices with further research direction aimed at achieving much lower levels.

Acknowledgements. We are grateful for the financial support by the National Institute of Diabetes and
Digestive and Kidney Diseases of the National Institutes of Health under Award Number R15DK103386. We
also thank partial support for this project by Oklahoma State University.
MATRIX ISOLATION OF BALENINE IN ARGON AT 18 K USING FTIR SPECTROSCOPY,
Hannah J. White1, Ashley L. Rand, Gary Ritzhaupt, William B. Collier*, Department of Biology and
Chemistry, Oral Roberts University, Tulsa, Oklahoma, 74171

Balenine is an analog compound of carnosine, is pharmaceutically interesting, and has a partially

known biological function in mammalian biochemistry. But how it functions is still unknown. This
presentation presents the 18 K frozen argon matrix isolated FTIR spectrum of balenine. The molecule
contains multiple functional groups causing hydrogen bonding that cause strong polymerization. This
makes it difficult to study using normal infrared spectroscopy. This experiment presents the matrix
isolated monomer, dimer spectrum of balenine. Theoretical studies are underway to understand the
structure and hydrogen bonding of this unique molecule. Because of the extensive perturbing
hydrogen bonding in the solid phase, such a study would have been impossible to achieve with
normally collected solid phase FTIR spectra.

*Correspondence author - William B. Collier, Ph.D., Professor of Chemistry, Department of Biology

and Chemistry, Oral Roberts University, Tulsa, Oklahoma, 74171, wcollier@oru.edu, (918-495-6927)

A Study of Iodine Gas Scrubber Efficiency and Iodine Distribution in Northwestern Oklahoma Brine
Waters, Jason R. Wickham1, Austin Anderson1, Cori Hoffman1, Rebecca Fenton2, and David Edlin2

1) Department of Natural Science, Northwestern Oklahoma State University, 709 Oklahoma BLVD, Alva, OK
73717

2) Iofina, 19940 CR 480, Alva, OK 73717

In the late 1970's, it was discovered that the brine waters of NW OK contain significant amounts of Iodine
(above 60 ppm). However, the exact amounts and distributions of Iodine throughout this region were unknown.
Currently, the majority of the world's supply of Iodine comes from mining Iodate minerals in Chile (≈ 65%),
brine water aquifers in NW Oklahoma (≈ 5%) and Japan (≈ 25%), and seaweed extraction. With the growing
need for Iodine compounds in the various fields the demand for Iodine is higher than ever. Thus, Iofina has
recruited the aid of NWOSU to quantify the Iodine concentrations and distribution throughout the brine aquifer,
as well as, determine the longevity of these iodine concentrations. Currently, this study has to the discovery of
new sites within the aquifer that may be of commercial interest and has taken an in-depth look at three of these
possible sites, as well as, measuring iodine fluctuations up to 100 ppm which is a much larger fluctuation than
the expected 10 ppm. Currently, we are investigating rather these fluctuations are due to the changed from
vertical to horizontal wells or inhomogeneity within the brine aquifer. We also studied iodine gas scrubber
efficiencies, which captures Iodine gas during the crystallization process. A balance between fluid recirculation
rate, air flow, internal surface area, and a chemical balance without disrupting other plant operations is needed,
which will result in improved overall iodine recovery capture.
Development of an Iodine Plant Efficiency Program and Iodine Distribution in Northwestern Oklahoma
Brine Waters, Jason R. Wickham1, Cori Hoffman1, Austin Anderson1, and David Edlin2

1) Department of Natural Science, Northwestern Oklahoma State University, 709 Oklahoma BLVD, Alva, OK
73717, 2) Iofina, 19940 CR 480, Alva, OK 73717

OVEREXPRESSION AND PURIFICATION OF LYSOSTAPHIN FROM STAPHYLOCOCCUS SIMULANS,

Taylor McClure and Sung-Kun Kim, The Department of Natural Sciences, Northeastern State University,
Tehlaquah, OK 74464

Lysostaphin is an enzyme that has the ability to cleave the pentaglycin in the cell wall of Staphylococci.
Although the enzyme was discovered decades ago, the enzyme mechanism has not been known. In order to
obtain the enzyme, we used an expression vector for cloning and overexpressed the enzyme in E. coli. Owing to
the presence of six histidines as a tag in the enzyme, we used a nickel affinity column to purify the enzyme.
SDS-PAGE displayed one band with an molecular weight of approximately 27 kDa, which is consistent with the
calculated value. The enzyme activity was tested with Staphylococcus aureus at the optical density at 600 nm,
and the disappearance of turbidity stemming from the presence of the bacteria was shown, indicating that the
purified enzyme is sufficiently active to cleave the bacterial cell wall.

INTRODUCTORY BIOORGANIC STUDY OF FIREFLY LUCIFERASE – AN ENZYME TO

DRIVE BIOLUMINESCENCE; Cornelia Mihai, Dalton Pannell, Brady Fields, Yeboah Gyening,
Department of Natural Sciences, Northwestern Oklahoma State University, Alva, OK 73717
The objective of the proposed research project is to initiate a comprehensive bioorganic study of Firefly
luciferase which will consist of: extraction of luciferase from dry firefly lanterns, purification and
analysis of luciferase. This introductory study will be used to develop new laboratory experiments
which will be incorporated in the Biochemistry laboratory course currently taught in the Department of
Natural Sciences at NWOSU.
 SYNTHESIS OF NOVEL 1, 2, 3-TRIAZOLES USING CLICK CHEMISTRY
Mary Tohidi, Ph.D. Mark Bannon
Department of Chemistry, Physics and Engineering, Cameron University, Lawton OK
2880 W. Gore Blvd. Lawton OK

Abstract:
Since the proposal by Barry Sharpless in 2001, The copper(I) –catalyzed reaction leading to the
formation of 1,2,3-triazoles from the reaction between azides and terminal alkynes has become
known as Click Chemistry with wide array of papers reported their synthesis and applications.
These reactions acquired the name because of the modular nature of the reagents and the fast
facile reaction between the reagents which click into each other almost like a seat belt.
The reactions are specifically having the benefit for undergraduate research because of the mild
conditions, benign solvents and limited by product which therefor does not need exhaustive
purification process and generally lead to a high yield of a pure regioselectivity in the formation
of the 1, 4-disubstituted Triazoles.

+
Here we are reporting synthesis of few 1,4-disubstitued -1-H-1,2,3-Triazoles

References:
1.John E. Moses and Adam D. Moorhouse, The Growing application of click chemistry.
Chem.Soc.Rev., 2007,36,1249-1262
1.Kolb, H.C.; Finn, M.G.; Sharpless, K.B., Click Chemistry: Diverse chemical function from a
new good reactions. Angew.Chem.,Int. Ed.Engl.2001, 40, 2004-2021
2.Prakasam Thirumurgan, Darius Matosiuk and Krzysztof Jozwiak, Click Chemistry for Drug
Development and Diverse Chemical-Biology Applications. Chem. Rev., 2013,113(7), 4905-4979
3.W. D. Sharpless, Peng Wu and James G. Lindberg, Just Click it: Undergraduate Procedures for
the Copper (I) Catalyzed Formation of 1,2,3-Triazoles from Azides and Terminal Acetylenes.
Journal of Chemical Education ,2005, Volume,82, No. 12 1833- 1835

SYNTHESIS OF ETHYL 4-(3-HYDROXYPHENYL)-6-METHYL-2-OXO-1,2,3,4-

TETRAHYDROPYRIMIDINE-5-CARBOXYLATE AND ITS EFFECT ON THE
PROLIFERATION RATES OF HEK 293T FIBROBLAST CELLS, Benjamine A. Welch1,
William P. Ranahan1, Lois A Ablin1
1
Department of Biology and Chemistry, Oral Roberts University, Tulsa, OK 74171

In a three-component Biginelli reaction, 3-hydroxybenzaldehyde was used as a precursor for ethyl 4-(3-
hydroxyphenyl)-6-methyl-2-oxo-1,2,3,4-tetrahydropyrimidine-5-carboxylate. This 3-hydroxyphenyl Biginelli
product was then tested as an anti-cancer agent against fibroblastic cancer cells using BioVision’s Quick Cell
Proliferation Assay Kit II. Three concentrations of the Biginelli product in DMSO (50µg/1µL, 100µg/2µL, and
150µg/3µL) were tested against lines of cells in a 96-well plate. All concentrations tested showed significant
decreases in proliferation of cancer cells compared to controls.

NSF IMPROVING UNDERGRADUATE STEM EDUCATION (IUSE): DETERMINING

PROTEIN FUNCTION FOR 4DIU AND 3DS8 USING IN SILICO COMPUTATIONAL
MODELING, AND IN VITRO RECOMBINANT DNA CLONING, AND ENZYME KINETICS;
Jordan Maddox1, Elijah Bell1, and Robert Stewart1
1
The Department of Biology and Chemistry, Oral Roberts University, Tulsa,, OK 74171

NSF IUSE Project 1503811 seeks to improve training of undergraduate biochemistry students to be
more effective scientists by testing the hypothesis that undergraduate students can characterize proteins
of unknown function as the central theme of their biochemistry teaching laboratory. This project is a
collaborative effort between students and faculty at six different campuses (California Polytechnic San
Luis Obispo, Hope College, Oral Roberts University, Rochester Institute of Technology, St. Mary’s
University, and Ursinus College). There are approximately 3,000 proteins in the Protein Data Bank for
which the 3D structures are known but their cellular functions are not known. In the present study, the
known structures of two proteins, 4DIU and 3DS8, were subjected to computational analysis to predict
their functions using well-established in silico methods such as, ProMOL, DALI, Pfam, the Catalytic
Site Atlas, and BLAST. This analysis strongly suggests both proteins are members of the family of
alpha/beta hydrolases, and more specifically, carboxylesterases of enzyme class 3. Z-scores, RMSDs,
and Levenshtein distances were calculated for both proteins against a data bank of protein motifs. In
order to conduct kinetic measurements against potential substrates, milligrams quantities of the two
proteins were sought. Since neither protein is available commercially, they were expressed from
bacterial plasmids readily available from the Materials Repository at the Biodesign Institute of Arizona
State University. The pET vectors were extracted and purified from phage resistant DH5-α bacterial
cells. The vectors were transfected into BL21(DE3) competent E. coli and grown with ampicillin
selection. Single colonies were overexpressed in LB/ampicillin media with IPTG as the protein
promoter. Expressed proteins were purified using IMAC protocols and assayed using SDS-PAGE.
Preliminary kinetics using 4-nitrophenylphosphate was positive for both proteins but larger quantities
of protein are needed to determine kinetics parameters, such as, turnover numbers and Michaelis-
Menten constants.
CATALYTIC REDUCTIVE COUPLING AND DEOXYGENATION OF ALCOHOLS; Gabrielle
R. Kasner, Camille Boucher-Jacobs, J. Michael McClain II, Kenneth M. Nicholas

The Department of Chemistry and Biochemistry, University of Oklahoma, Norman, OK 73019

The transformation of abundant alcohols to more valuable products such as fuels and chemicals has
created the need for development of novel reactions. We have found that several activated alcohols are
able to undergo either deoxygenation or reductive coupling depending on the alcohol, with yields
ranging from 75-90% in some cases. The reaction involves triphenylphosphine as a reducing agent and
an oxo-rhenium catalyst, (PPh3)2ReIO2. Our progress with determining the scope and mechanism of
these reactions thus far will be presented.

UTILIZATION OF THE GREENHOUSE GASES, REGULATED EMISSIONS AND ENERGY

IN TRANSPORTATION (GREET) MODEL TO ANALYZE A REPRESENTATIVE BIOMASS
TO LIQUID PROCESS; Cora Skjaerlund1, and Robert Stewart1
1
The Department of Biology and Chemistry, Oral Roberts University, Tulsa,, OK 74171

The purpose of this poster is to apply the Greenhouse gases, Regulated Emissions, and Energy in
Transportation (GREET) model to evaluate the energy efficiency and emissions associated with the
conversion of biomass to diesel and naphtha products along with the corresponding export of heat
energy in the form of steam and hot water. The GREET model is the standard in performing life cycle
analyses for transportation fuels. The energy efficiencies, carbon balance, water balance, steam
products, and exports are all analyzed for this calculation. The conversion process incorporates all of
the major process steps associated with gasifying biomass into a synthesis gas, converting the synthesis
gas into hydrocarbons using the Fischer Tropsch process and subsequently hydrocracking the linear
paraffin products into diesel fuel. The heat and material balance for the plant includes all of the major
process steps, as well, as the power requirements required for oxygen generation and the other
electrical equipment. The summary breakdown for the energy and mass inputs and outputs can be
used as a guide for comparing the energy efficiency and emissions associated with other conversion
processes. This poster presents the results of applying the GREET model to a model case.
 13
A REMARKABLY SENSITIVE C NMR APPROACH TO QUANTIFYING
DONOR/ACCEPTOR CHARACTERISTICS OF ISOCYANIDE LIGANDS; Zachary Wood,
Jason C. Applegate, Nathan R. Erickson, Mason D. Hart, and Mikhail V. Barybin*

Department of Chemistry, University of Kansas, Lawrence, KS 66045

Azulene is a nonbenzenoid aromatic hydrocarbon featuring fused 5- and 7-membered carbon rings. Analysis of
the 13C NMR signatures exhibited by the octahedral [(-NC)Cr(CO)5] core in a series of related complexes
[(OC)5Cr(2-isocyano-6-X-1,3-diethoxycarbonylazulene)] (X = -N C, Br, H, SH, SCH2CH2CO2CH2CH3,
SAuPPh3, etc.) unveiled remarkably consistent inverse-linear correlations (13COtrans) vs. (13CN) and (13COcis)
vs. (13CN).1 This concept allowed remote tuning of the electron richness of the Cr(0) center through mediation
by the 2,6-azulenic framework. Similar 13C NMR trends were also discovered for several families of benzenoid
isocyanoarene complexes (ArNC)Cr(CO)5 (Ar = aryl). The above (13CO)/ (13CN) NMR analysis serves as a
convenient tool for discerning even subtle electronic differences in the -donor/ -acceptor ratios of organic
isocyanide ligands CNR. It relies on the spectroscopic feedback from the entire [(-NC)Cr(CO)5] moiety and
offers a simple and quantitatively more accurate alternative to the method involving correlation of the carbonyl
13
C chemical shifts with the corresponding CO force constants (kCO) for complexes (RNC)Cr(CO)5.

1. Applegate, J. C.; Okeowo, M. K.; Erickson, N. R.; Neal, B. M.; Berrie, C. L.; Gerasimchuk, N.
N.; Barybin, M. V. Chemical Science 2016, 7, 1422.

BIOSENSORS FROM COPOLYMERS OF VINYLFERROCENE AND 4-

VINYLIMIDAZOLIUM, Ashlyn Conner and Charles J. Neef, Department of Chemistry, Pittsburg

State University, Pittsburg, KS, 66762

Ferrocene containing polymers have stable redox properties which make them attractive for various
applications such as biosensors, energy storage, and as catalyst. Previous work within our lab with
copolymers of vinylferrocene with vinylpyridine has shown that these materials are promising as
biosensors for the selective detection of dopamine and serotonin. In this research, we have focused on
replacing the pyridine moiety with an imidazole moeity followed by alkylation to the imidazolium.
Chemically modified electrodes were prepared by solution casting these materials onto a platinum
electrode for subsequent cyclic voltammetry or chronoamperometry studies using sodium chloride as
the supporting electrolyte. In this study, we examined the ratio of ferrocene to imidazolium within the
polymer and the resulting effects on the detection of dopamine.
FT-IR STUDIES ALDOL NONDENSATION OVER TiO2-BASED
NANOMATERIALS, Dilip K Paul, Salehin Mahbub, Juan Gaucin

Department of Chemistry, Pittsburg State University, Pittsburg, KS 66762

The role of acid-base sites on Ga-In doped TiO2-nanomaterials was determined using various probe
molecules adsorbed on the surface at different temperatures using a specially designed ultra-high
vacuum (UHV) infrared cell. The UHV cell is attached to a vacuum manifold which is continually
pumped by a 60 L turbo-molecular pump and a diaphragm roughing pump to obtain a routine pressure
of 1x10-8 Torr. It was found that at 233 K, acetaldehyde adsorbed through hydrogen bonding to surface
hydroxyl groups as well as through Lewis acid sites over pretreated TiO2-based surfaces. The
formation of 2-butenal was observed as the product of aldol condensation reaction. This C-C bond
formation is found to be due to the presence of Brᴓnsted and Lewis acid sites. Upon blocking these
acid sites with NH3 adsorption, the C-C bond formation can be substantially suppressed, which in turn
indicates that acid sites indeed are responsible for C-C bond formation. Various TiO2-based
nanomaterials were compared in order to elucidate the contribution of local surface structures.

ELECTRONIC PROPERTIES OF COPOLYMERS CONTAINING HEXYLTHIOPHENE

AND DIBENZO[a,c]PHENAZINE, Jacob Wylie and Charles J. Neef

Department of Chemistry, Pittsburg State University, Pittsburg, KS, 66762

Thiophene containing polymers continue to receive considerable attention within Donor-Acceptor-

Donor (D-A-D) conjugated systems for their potential use in photovoltaic cells, energy storage devices,
and sensors. A potential useful electron acceptor for D-A-D systems is dibenzo[a,c]phenazine. Our lab
has focused on the synthesis and electronic properties of copolymers of 2,5-dibromo-3-hexylthiophene
with 2,7-dibromodibenzo[a,c]phenazine. Copolymers were synthesized at various ratios of thiophene to
phenazine to evaluate the effect of varying monomer ratio on the electronic properties of the materials.
Synthesis, electrochemistry, and UV spectra will be presented.
A COMPARISON OF TWO CHROMATOGRAPHIC METHODS TO QUANTITATE CAFFEINE AND ITS
METABOLITES IN HUMAN URINE, Wayne A. Adams and Norman E. Schmidt, Department of Chemistry,
Tabor College, Hillsboro, Kansas 67063

Both gas chromatography mass spectroscopy (GCMS) and high performance liquid chromatography (HPLC)
gave relatively similar results for caffeine and caffeine metabolites in human urine. In this research test subjects
consumed 6.5 ounces of Coca-Cola® and 45 minutes later contributed a urine sample for analysis.

In the GCMS analysis samples were extracted twice with methylene chloride containing the internal standard
anthracene. Samples were then concentrated by blowing nitrogen over the solvent to a volume of ~1 milliliter.
1.0 microliter was then injected into the GCMS. The internal standard, caffeine, and four metabolites were
identified through this method. Analysis on the GCMS took ~ 5 minutes and the overall process took about 30
minutes.

In the HPLC analysis samples were extracted twice with 85% chloroform and 15% isopropanol. The internal
standard 8-chlorotheophylline was then added. The extract was then centrifuged and the non-aqueous layer
blown to dryness with nitrogen. The sample was reconstituted with water, filtered and 20 microliters were
injected into the HPLC running at 1.0 mL per minute with 70% water and 30% methanol. The internal standard,
caffeine, and four metabolites were identified through this method. Analysis on the HPLC took ~ 7 minutes and
the overall process took about 45 minutes.

The GCMS method was easier to perform and slightly faster. However, the caffeine and metabolites had a
tendency to decompose at temperatures necessary for GC separation. The HPLC method had more difficulties
separating the peaks and took longer to perform. However, decomposition of caffeine and metabolites was not a
problem.

CONCENTRATION OF HEAVY METALS IN THE TISSUES OF THE HOUSE MOUSE (Mus musculus),
Nathaniel J. Burnham and Norman E. Schmidt, Department of Chemistry, Tabor College, Hillsboro, Kansas
67063

Of the four different types of tissues from the House Mouse (Mus musculus), the liver was found to contain the
highest concentrations of heavy metals. Mice were subjected to three different levels of cadmium concentrations
in their drinking water for two months: 0 cadmium added, 10 ppb cadmium added, and 100 ppb cadmium added.
After two months the mice were euthanized and dissected. Four different body tissues were analyzed for heavy
metal concentrations: small intestines, skin, heart, and liver. Samples were analyzed by digesting the tissues in
boiling concentrated nitric acid, then diluting to 25 mL with distilled water. Diluted samples were next analyzed
using anodic stripping voltammetry and standard addition. In all samples the liver contained the most heavy
metals and skin the least. As expected the higher the concentration of cadmium in the drinking water the higher
the concentration of cadmium in the tissue. The highest concentration of cadmium found was 53 ppm in the
liver of mice having 100 ppb cadmium in their drinking water.
MICROWAVE SYNTHESIS OF TETRAPHEYNLPORPHYRINS AND
TETRAPHENYLPORPHYRIN DERIVATIVES, Pasang Hyolmo and Elizabeth Ann
Nalley, Department of Chemistry, Physics and Engineering, Cameron University, Lawton,
Oklahoma 73505

Allowing many chemical reactions to be completed within minutes, microwave heating has
revolutionized preparative chemistry. As a result, this technology has been widely adopted in both
academic and industrial laboratories. Integrating microwave-assisted chemistry into undergraduate
laboratory courses enables students to perform a broader range of reactions in the allotted lab period. As a
result, they can be introduced to chemistry that would otherwise have been inaccessible due to time
constraints (for example, the need for an overnight reflux). A number of the chemical transformations use
water as a solvent in lieu of classical organic solvents. This contributes to greener, more sustainable
teaching strategies for faculty and students, while maintaining high reaction yields.
Tetraphenylporphyrins can be synthesized from pyrrole and benzaldehyde using a conventional
microwave oven. This synthesis and other synthesis of other derivatives of tetraphenylporphyrins will be
described

SYNTHESIS OF AZO DYES PREPARED FROM DIAZONIUM SALTS AND THEIR

APPLICATIONS IN SOLAR CELLSs, Emmanuel Ilondior and E. Ann Nalley, Department of
Chemistry, Physics and Engineering, Cameron University, Lawton, OK 73505

Arenediazonium salts are generated by the reaction of a primary amine with nitrous acid
(produced from sodium nitrite) as shown below. The aromatic amines (anilines) are generated by
the reduction of the corresponding nitro compound, which is easily prepared via electrophilic
nitration of the ring (see nitration of methyl benzoate). The diazonium salts are unstable at
temperatures above 5 - 10°C and some explode if allowed to dry. The aliphatic counterpart can
be prepared in the same way; however, even at low temperature it is more unstable and can
spontaneously decompose by loss of nitrogen to produce carbocation. A useful reaction of
diazonium ions is their use as electrophiles in electrophilic aromatic substitution reactions. They
will react with highly activated aromatic systems (phenols, arylamines) to yield azo compounds
(diazo coupling reaction). Due to the extended system of delocalized pi electrons, azo
compounds are usually colored and therefore have found use as dyes. In this presentation, the
synthesis of several dyes will be described. These dyes were tested as possible photoreceptors
in dye sensitized solar cells. The results of these tests will be discussed.
SYNTHESIS OF MALACHITE GREEN AND ITS APPLICATION IN SOLAR CELLS, James
Lutz and E. Ann Nalley, Department of Chemistry, Physics and Engineering, Cameron University,
Lawton, OK 73505

In this research a new synthesis of Malachite Green has been developed using microwave
technology to prepare the dye. The procedure for synthesizing the dye and its application in dye-
sensitized solar cells will be discussed. These cells consist of titanium dioxide nanocrystals that
are coated with light-absorbing dye molecules and immersed in an electrolyte solution, which is
sandwiched between two glass plate Light striking the dye frees electrons and creates "holes"--
the areas of positive charge that result when electrons are lost. The semiconducting titanium
dioxide particles collect the electrons and transfer them to an external circuit, producing an
electric current. The cells can be connected in series to produce cells with voltages as high as
five volts which can be used to power a small motor.

THE EFFECTS OF PCBP2 ON IRON HOMEOSTASIS AND IRON RELATED

PROTEINS IN LIVERS OF PCBP2 KNOCKDOWN MICE, Alexander Rivas1
,
Department of Chemistry, Physics & Engineering, Cameron University, Lawton, OKa
73505, 2Dr. Fengmin Li and Dr. Caroline Philpott, Liver Disease Branch, NIDDK,
Bethesda, MD

Iron is an essential co-factor for many proteins involved in central cellular processes and is toxic
at high concentrations. Therefore, iron storage, uptake and utilization are tightly regulated. Four
major iron related genes have been studied in this project: Ferritin, the ubiquitous iron storage
protein, Hepcidin, a liver hormone that controls cellular iron release, Iron Regulatory Protein 2
(IRP2) and the Transferrin receptor, a transmembrane iron importer. These proteins respond to
fluctuations in iron concentration and function to bring iron to stable levels. Poly (rC)–binding
proteins 2 (PCBP2) is one of the members of the PCBP family, a multifunctional adaptor protein
family that bind cytosolic iron for delivery to target apoproteins. In this poster, we will discuss
how an iron over-load phenotype is observed in heterozygous PCBP2 Knockdown mice.
Endogenous expression of Hepcidin and the transferrin receptor reveal that heterozygous mice
may be experiencing a phenotypic iron overload caused by a partial absence of PCBP2.

USING MICROWAVES FOR ORGANIC SYNTHESIS IN UNDERGRADUATE

ORGANIC LABS,Alexander Rivas and Elizabeth Nalley, , Department of Chemistry,
Physics and Engineering, Cameron University, Lawton, OK 73505

Allowing many chemical reactions to be completed within minutes, microwave heating has
revolutionized preparative chemistry. As a result, this technology has been widely adopted in
both academic and industrial laboratories. Integrating microwave-assisted chemistry into
undergraduate laboratory courses enables students to perform a broader range of reactions in the
allotted lab period. As a result, they can be introduced to chemistry that would otherwise have
been inaccessible due to time constraints (for example, the need for an overnight reflux). A
number of the chemical transformations use water as a solvent in lieu of classical organic
solvents. This contributes to greener, more sustainable teaching strategies for faculty and
students, while maintaining high reaction yields. The advantages inherent in microwave use
make it ideal for the undergraduate laboratory. Although students are exposed to many different
reactions in the classroom, many important organic reactions described in undergraduate
textbooks are presently not included in the laboratory course owing to long reaction times, high
temperatures, or sensitive reagents that present a potential danger to the students. In this poster,
five syntheses using microwave heating will be described

MICROWAVE SYNTHESIS OF PHENYL SALICYLATE AND PHENYL SALICYLATE

DERIVATIVES, Sujana Rupakheti and Elizabeth Ann Nalley, Department of Chemistry,
Physics and Engineering, Cameron University, Lawton, Oklahoma 73505
Allowing many chemical reactions to be completed within minutes, microwave heating has
revolutionized preparative chemistry. As a result, this technology has been widely adopted in
both academic and industrial laboratories. Integrating microwave-assisted chemistry into
undergraduate laboratory courses enables students to perform a broader range of reactions in the
allotted lab period. As a result, they can be introduced to chemistry that would otherwise have
been inaccessible due to time constraints (for example, the need for an overnight reflux). A
number of the chemical transformations use water as a solvent in lieu of classical organic
solvents. This contributes to greener, more sustainable teaching strategies for faculty and
students, while maintaining high reaction yields. Phenyl Salicylate can be synthesized from
Salicylic Acid and Phenol using a conventional microwave oven. This synthesis and other
synthesis of other derivatives phenyl salicylate will be discussed and the use of these products as
starting materials for other reaction including Xanthone will also be described.

Applications of Gold in Cancer treatment, Albert Cai, Nadia Sirajuddin

A.K.Fazlur Rahman

Department of Chemistry, Oklahoma School of Science and Mathematics, Oklahoma City,

OK 73104

Chemotherapy, also known as chemo, or CTx, is a cancer treatment program that uses chemical
drugs to either reduce or eliminate cancer. Chemotherapy works by stopping the growth of
cancer cells, but damage to healthy cells also occur as a side-effect. Chemotherapy can cure
cancer, reduce symptoms, or contain the cancer from spreading. Chemotherapy uses different
chemicals to treat different types of cancer. One of the more commonly used elements to treat
cancer is gold. Gold is a very chemically inactive or inert metal, making it useful for human
medicinal applications because it will not degrade or react with other cells when traveling in the
human system. Gold can be used to diagnose diseases such as malaria, HIV/AIDS, and cancer as
well as treat diseases like arthritis and cancer. Newer drugs being developed, many of which
contain gold, are designed to specifically target cancer cells in an effort to reduce the harmful
side-effects from killing healthy cells. The most significant property of gold is the ability of
sulfur to bond to gold nanoparticles. This property is a major factor in curing cancer diseases
because of the concept of attaching cancer drugs to gold through thiol groups. While cancer
drugs like Taxol have successfully been able to attach to gold nanoparticles, improvements upon
these gold-containing cancer drugs is a major area of research for modern medicine. This
presentation will give a brief overview of the types of gold-containing compounds available for
chemotherapeutic purposes.

Taxol : Update of a Cancer Drug, Shandel Change, Akshaya

Santhanaraj, Faculty Advisor : A.K.Fazlur Rahman, Ph.D.

Department of Chemistry, Oklahoma School of Science and Mathematics,

Oklahoma City, OK 73104

Taxol, chemically known as paclitaxel, is a chemotherapy drug that slows or stops the growth of
cancerous cells. It can treat a variety of cancers, such as breast, ovarian, lung, bladder, prostate,
melanoma, and other types of solid tumor cancers. It is administered intravenously, which
causes the inflammation of the vein through which it is given. This drug is a cytoskeletal drug
that targets tubulin. One of the key characteristics of taxol is its ability to behave as an
antimicrotubule agent. After being affected, the taxol-treated cells have defects in mitotic spindle
assembly, chromosome segregation, and cell division. What makes Taxol different is that it
stabilizes the microtubule polymer and prevents it from disassembly, where as other tubulin-
trageting drugs inhibit microtubule assembly. When these microtubules are protected from
disassembly, chromosomes cannot achieve a metaphase spindle configuration, blocking the
progression of mitosis. The unique capacity of this drug places it as the most important
medication needed in any basic health system pertaining to cancer.
ASSESSMENT OF THE LEAD CONTAMINATION CRISIS IN FLINT, MICHIGAN

Keirah Jefferson

The Department of Chemistry, Oklahoma School of Science and Mathematics, 1141 N Lincoln
Blvd, Oklahoma City, OK 73104

Lead is toxic for consumption because it debilitates the human nervous system and causes
significant neurological damage. Residents in the city of Flint, Michigan have been supplied with
lead contaminated water for over a year, lowering the quality of life for many, harming children,
and even causing deaths. Many other regions have experienced high lead concentrations in the
environment as well, making this more than simply a regional issue. After compiling information
from news sources, medicinal websites, and chemical archives, I learned that the ease of which
the crisis could have been avoided speaks to the corruption present in municipal authorities.
Flint, Michigan is the illustration of the need for municipalities to more highly prioritize public
health and speak openly about environmental concerns.

Nonsteroidal Anti-Inflammatory Drugs (NSAIDs) : How Do They Work

Michael Lee and Shreya Nuguri, Oklahoma School of Science and Mathematics,

1141 N Lincoln Blvd, OKC, OK 73104

Faculty Advisor: A. K. Fazlur Rahman Ph.D

Non-Steroidal anti-inflammatory agents, such as aspirin and celecoxib, act by inhibiting the
biosynthesis of prostaglandins (PGs from arachidonic acid (AA). There are two human enzymes
that catalyze the first step in the biosynthesis of PG’s cyclooxygenase 1- and 2 (COX-1 and
COX-2). NSAIDS are usually used for the treatment of acute or chronic conditions where pain
and inflammation are present. Since most NSAIDS inhibit the activity of COX-1 and COX-2, It
is believed that inflammatory function is a part of the human healing process as it resolves in
pain and fever. In this presentation we discuss an overview of inflammation and how the anti-
inflammatory drugs work.
Anesthetics and Drug Design, Austin Rhoadarmer, Pedro Lozano-DeAos
Oklahoma School of Science and Mathematics
Oklahoma City, OK 73104

Faculty Advisor : A.K.Fazlur Rahman, Ph.D.

An anesthetic is simply a drug that induces the effect of anesthesia which is defined as an

induced, temporary state with the characteristics of one or more of the following: pain relief,

paralysis, amnesia, and unconsciousness. Anesthetics generally fall into the three categories of

general anesthesia, dissociative anesthesia, and conduction anesthesia. Anesthetics are valued

due to their importance in medicine and surgical techniques. Drugs such as Midazolam and

Propofol are among the most commonly used anesthetics. The way these drugs are designed is

linked to what exactly the drug is needed for in the categories of anesthetics. The actual

mechanism behind how anesthesia works is a topic of debate among the scientific community as

of now, but is still a large consideration on how these drugs are developed. This paper sets out to

examine the exact mechanisms behind how anesthetic drugs are synthesized and used.

ARTEMISININ: FROM FOLKLORE TO MODERN MEDICINE; Maggie Zhang1,

Amanda Pan1, Mansi Gattani1
1
The Department of Chemistry, Oklahoma School of Science and Mathematics, Oklahoma City,
OK 73104

An estimated 2 billion people are infected with at least one parasite. Parasitic diseases have
ravaged mankind. In particular, malaria causes about 2.5 million deaths annually, presenting a
health crisis throughout the world. The 2015 Nobel Prize in Medicine provided a possible
solution to combat this debilitating disease in the compound Artemisinin, which was discovered
by Chinese scientist Dr. Youyou Tu. This compound and its drug derivatives have fundamentally
changed treatment of malaria. This presentation aims to provide an overview of the cause and
cure of the parasitic disease, malaria. The authors will examine the source, extraction, structure
and the application of Artemisinin.
Capsaicin and dihydro-Capsaicin, Angela Zhu, Jackie Oh, Howie Chen

Department of Chemistry, Oklahoma School of Science and Mathematics,

Oklahoma City, OK 73104.

Hot red chili peppers, which are one of the most frequently and heavily consumed spices in the world. Its
principal ingredient capsaicin has analgesic and anti-inflammatory properties, relieving pain from various
diseases and medical conditions, including nervous system problems such as diabetic neuropathy, joint
problems such as osteoarthritis, and skin conditions such as psoriasis.

Capsaicin has also been researched for its capability to cause cancer cells to commit suicide. The
molecule binds to the surface of the cancer cells and affects the membrane surrounding and protecting
them. It specifically targets the mitochondrial redox-system in SCC derived cells as well as induces
apoptosis in transformed cells. It is also associated with the suppression of plasma membrane NADH-
oxidoreductase (PMOR), an enzyme that transfers electrons from the cytoplasm to external electron
acceptors such as oxygen. Capsaicin is hot-hot-hot.

GRAPHENE BASED SOLID PHASE EXTRACTION COMBINED WITH GC/MS FOR THE
REMOVAL OF ORGANIC COMPUNDS IN ENVIRONMENTAL WATER SAMPLES

KELSEY ANDERSON, DYLAN DAVIDSON, ERANDI MAYADUNNE

Science Department, Murray State College, One Murray Campus, Tishomingo, OK 73460

Haloacetic acids and halomethanes are reported as contaminants in tap water system in Southern
Oklahoma [1]. These chemicals exhibit carcinogenic properties, neuropathy, and weight loss, so
their occurrence in drinking water makes them hazardous to human health [2, 3]. Graphenes are
emerging class of nanomaterials whose adsorption properties have not been well understood [4].
The aim of the research project is to identify adsorbent properties of graphene oxide and
characterizing graphene in terms of its ability to purify water by removing organic contaminants.
Graphene has synthesized using Hummers methods [5]. A known volume of water (30 mL)
containing a fixed amount of an organic contaminant will be in contact with varying amounts of
graphene oxide (1g-5g). The amount of organic contaminants that absorbs on the graphene can
be determined by measuring the amount of organic contaminant in the water before and after
contact with graphene. The organic compounds in the water samples are subjected to the solid
phase micro extraction (SPME) and then analyzed using Gas chromatograph equipped with a
flame ionization detector. Preliminary data is showing that Southern Oklahoma water bodies has
contaminates with organic compounds. Graphene oxide has the ability to absorb organic
compounds from water samples. Increasing amount of graphene in contact with water samples
from 3 g to 5 g has increased the absorption of organic contaminant in water.
1. Monthly analysis of tap water, Environmentally resources technologies, LLC, Ada, OK
2. B. A. Lyon, M. J. Farré, G. A. De Vera, J. Keller, A. Roux, H. S. Weinberg and W.
Gernjak Organic matter removal and disinfection byproduct management in South East
Queensland’s drinking water , ., Water Science & Technology: Water Supply, 14-4 ,
2014
3. Susan D. Richardson*† and Thomas A. Ternes., Water Analysis: Emerging Contaminants
and Current Issues, Analytical Chemistry., 2014, 86 (6), pp 2813–2848
4. George Z. Kyzas, Eleni A. Deliyanni* andKostas A. Matis., Graphene oxide and its
application as an adsorbent for wastewater treatment., Journal of Chemical Technology
and Biotechnology, Volume 89, Issue 2, pages 196–205, February 2014
5. William S. HummersJr., Richard E. Offeman., Preparation of Graphitic Oxide., J. Am.
Chem. Soc., 1958, 80 (6), pp 1339–1339
SWELLABLE pH SENSITIVE POLYMER PARTICLE FOR PHYSIOLOGICAL pH
SENSING, Kaushalya Sharma Dahal 1, Sandhya Rani Pampati 1 and Barry K. lavine1
1 Department of Chemistry, Oklahoma State University, OK, 74078

Swellable polymers functionalized to respond to pH have been prepared from microgels of poly
(N-propylacrylamide) copolymerized with methacrylic acid, ethacrylic acid and propacrylic acid.
When these N-propylacrylamide polymer particles are dispersed in a hydrogel, large changes
occur in the turbidity of the membrane (measured by an absorbance spectrometer) as the pH of
the solution in contact with the membrane is varied. Changes of approximately 0.5 absorbance
units were observed in the swelling and shrinking of these pH sensitive copolymers of N-
propylacrylamide. Swelling was nonionic as the ionic strength of the solution in contact with the
copolymers was increased from 0.1M and 1.0M without a concomitant decrease in swelling. For
many of the copolymers, swelling was also reversible in both low and high ionic strength pH
buffered media at both ambient and physiological temperatures. Changes in the composition of
the formulation used to prepare these copolymers could be correlated to their response to
changes in the pH of the buffer solution in contact with them.

PATTERN RECOGNITION ANALYSIS OF MALDI-IMS-MS N-LINKED GLYCAN

PROFILES PERFORMS FOR DETECTION OF ESOPHAGEAL ADENOCARCINOMA
T. Ding1, M. M. Gaye2, B. K. Lavine1

1
Department of Chemistry, Oklahoma State University, Stillwater, OK 74078
2
Department of Chemistry, Indiana University, Bloomington, IN 47405

This study describes the identification of N-linked glycan circulating biomarkers collected from
MALDI-IMS-MS and analyzed by pattern recognition techniques for in-vitro diagnoses to screen
a population at risk for esophageal adenocarcinoma (EAC). 58 serum samples from patients
diagnosed with Barrett’s esophagus (BE), high-degrade dysplasia (HGD), EAC and from normal
controls (NC) were analyzed by MALDI-IMS-MS. The training set consisted of 90 spectra from
known phenotypes and the validation set consisted of 26 blinds. Nine N-linked glycans generated
by MALDI-IMS-MS were investigated as potential cancer biomarkers. A classifier developed
using principle component analysis allowed for the correct phenotype prediction of 20 of the 26
blinds. To improve prediction accuracy, preprocessing of the mass spectral data using the Symlet
6 wavelet was undertaken and wavelet coefficients selected by a genetic algorithm for pattern
recognition analysis were able to correctly classify 25 of the 26 blinds. The pattern recognition
experiments described here as well as others confirm that this set of mass spectral data contain a
wealth of information relevant to differentiating the disease states associated with esophageal
cancer.
Development of a Networked Sensor Array for Gas Microseepage Detection near Injection
Well Sites; Wesley Honeycutt1, Nicholas F. Materer1, M. Tyler Ley2, Taehwan Kim2
1 2
The Department of Chemistry, Oklahoma State University, Stillwater, OK 74078 The
Department of Civil Engineering, Oklahoma State University, Stillwater, OK 74078

As part of the current drive to reduce carbon emissions to mitigate global climate change, many
are considering the possibility of subterranean sequestration as a means of storing excess CO2.
This undertaking will require new technology to ensure its safe implementation. An array of
sensors was developed using commercially available technologies to detect CO2, CH4, and
atmospheric conditions near ground level. These solar-powered sensors are wirelessly networked
to coordinate data retrieval, giving a reliable analysis of gas concentration over a broad area.
Current results from this networked array on the environmental background show expected
concentration changes based on daily variation, weather conditions, and animal presence.

SURFACE PLASMON RESONANCE IMAGING OF ONSET OF TYPE-1 DIABETES

BASED ON BIOMARKERS OTHER THAN GLUCOSE

Presenter: Manoj K. Patel,

Authors and Affiliation: Manoj K. Patel and Sadagopan Krishnan
Department of Chemistry, Oklahoma State University, Stillwater 74078, Oklahoma, USA

Diagnosis of diabetes type 1 (T1D) at an early stage of development is essential for effective
treatment to control its progression and reduce the cases. T1D Biomarkers such as glutamic acid
decarboxylase autoantibodies (GADA) and insulinoma-associated-2 autoantibodies (IA-2A) are
very specific and useful candidates for T1D diagnosis, monitoring of disease progression.
Millions of people worldwide are affected by diabetes that creates serious health problems if not
managed at an earlier stage. Over recent years, the prevalence of diabetes, in particular T1D, has
significantly increased from 5% to 10%, and this has in turn impacted the incidence of associated
lethal complications in children and adults. There is a great need for the development of efficient
and accurate methods for diagnosis of diabetes at earlier stages. Over the past two decades, many
groups have demonstrated that the usual platform including lateral flow assays, radio immune
assay (RIA), and the enzyme-linked immunosorbent assay (ELISA) for clinical diagnosis of
T1D. Currently, there is no specific test and techniques being available for onset detection of
T1D. In this context, we focus on developing a novel surface plasmon resonance microarray
imager (SPRi)-immunosensors for the detection of T1D biomarkers before its progression. SPRi
is a unique and powerful optical detection technique and with an appropriate surface chemistry
design, one can achieve highly sensitive detection of biological analytes based on refractive
index changes occurring on a gold surface interfaced with a glass prism.

Keywords: Type1 Diabetes, SPRi, Biomarkers, Immunosensors

AN ULTRASENSITIVE MICROARRAY IMAGING TECHNOLOGY TO

SELECTIVELY DETECT LUNG CANCER MICRORNA MARKERS
Gayan Premaratne, Zainab Al Mubarak, and Sadagopan Krishnan

Department of Chemistry, Oklahoma State University, Stillwater, OK 74078

Amongst all cancer types lung cancer is the leading cause of cancer deaths in the world. The
objective of this research is to develop a novel microarray platform for one step detection of
microRNAs (miRs) as a diagnostic indicator of lung cancer. Such microarray platform offers a
highly sensitive and minimally invasive prognostic method. miRs are a group of small RNAs
with approximately 22 nucleotides in length, that function mainly by binding to the 3ʹ-
untranslated regions of specific target messenger RNAs (mRNAs) to repress protein translation
or cleave mRNAs. miRs have received immense attention due to their important roles in
diseases. Elevated miR levels can be used as biomarkers for the onset of various cancers. In this
study, our objective is to achieve detection of clinically relevant levels of miRs useful for early
lung cancer detection by a microarray imaging methodology. As an initial method development,
this study involved the detection of target oligonucleotide containing the nucleotide sequence of
miR-21 via hybridization with complementary single stranded DNA that acts as a capture probe
on the array surface. A control oligonucleotide that has no complementary sequence for the
target sequence or capturing probe was used to test the accuracy. We used a glass chip with 17
gold spots (each of 1 mm diameter) in developing the surface plasmon resonance microarray
imager (SPRi). 50 nm gold nanoparticles were used to conjugate with the target oligonucleotide
in order to enhance the SPRi signals upon hybridization. Sub-picomolar detection level was
achieved in our preliminary studies. The future goal is to detect a pool of miR markers directly
in a clinical matrix by designing a multiplexed array platform.
Acknowledgements – Financial support by Oklahoma State University is gratefully
acknowledged.
HYDROGEN BONDING DIRECTED PHOTOCATALYTIC
HYDRODEFLUORINATION; ASELECTIVELY ACCESS TO PARTIALLY
POLYFLUORINATED AROMATICS, Mohammad BaniKhaled , Jimmie Weaver 1
1

1
The Department of Chemistry, Oklahoma State University, Stillwater, OK 74074

The formation new bonds via C–F bond cleavage of polyfluorinated aromatics is proving to be

important strategy in synthetic chemistry due to the significant biological impact fluorine has on

many pharmaceuticals, agrochemicals, and materials. Previously our group described strategy to

selectively reduce the C–F bonds in perfluoroarenes by photocatalytic hydrodefluorination

(HDF). In this case, the regioselectivity of the C–F fragmentation was primarily dictated by the

electronics of the arene ring. Herein, we present a hydrogen bond directed photocatalytic HDF

reaction which utilizes the presence of a hydrogen bond moiety to circumvent the electronic bias.

Through this strategy, many of new partially fluorinated arenes can be selectively accessed with

high regioselectivity.
MECHANISM OF YEAST N-GLYCOSYLATION: STRUCTURAL
CHARACTERIZATION OF OST4P AND ITS MUTANT

Bharat Chaudhary, Suman Mazumder and Smita Mohanty

Department of Chemistry, Oklahoma State University, Stillwater, OK 74078

N-linked glycosylation of proteins is an essential and highly conserved co-translational protein

modification reaction that occurs in all eukaryotes. The enzyme that carries out this reaction is
called oligosaccharyltransferase (OST). In this reaction, OST modifies the side chain of a
specific Asparagine residue with a carbohydrate group in nascent proteins. Genetic defects cause
a series of disorders that includes but not limited to mental retardation, developmental delay,
hypoglycemia etc. Complete loss of N-glycosylation is lethal in all organisms. In yeast, OST
consists of nine subunits. OST4p is the smallest subunit. Mutation of Valine (V) at position 23 to
Aspartate (D) causes defects in N-glycosylation of proteins. To understand the structure, function
and role of Ost4p in this reaction, we are characterizing Ost4p and its mutant by high-resolution
solution NMR and circular dichroism (CD) studies. To this end, we have overexpressed, purified
15
N, 13C-labeled Ost4p and the mutant OST4p (V23D), and reconstituted in membrane mimetic.
The assignments of Ost4p using 3-dimensional NMR, and the preliminary structure calculated
will be presented. The 2D {1H, 15N} HSQC spectrum of mutant OST4p (V23D) is significantly
different from that of the wild-type suggesting that the mutant has a completely different
conformation than the wild-type protein.

References

1. Zubkov S, Lennarz WJ, Mohanty S. Structural basis for the function of a minimembrane
protein subunit of yeast oligosaccharyltransferase. Proceedings of the National Academy
of Sciences of the United States of America. 2004;101(11):3821-3826.
2. Kim H, Park H, Montalvo L, Lennarz WJ. Studies on the role of the hydrophobic domain
of Ost4p in interactions with other subunits of yeast oligosaccharyl transferase.
Proceedings of the National Academy of Sciences of the United States of America.
2000; 97(4):1516-1520.
SNARFING FOR THE FUTURE: POLYFLUORINATED BUILDING BLOCKS;

Jon I. Day1, Jimmie Weaver*,1

1
The Department of Chemistry, Oklahoma State University, Stillwater, Oklahoma 74078

Although fluoro-organics are rare in nature, or perhaps because of it, the importance of fluorine
in pharmaceuticals and agrochemicals has grown substantially in recent years, despite the
multistep processes required to fluorinate desired positions in molecules, especially in
polyfluoro-organics.

In light of this, we are developing syntheses

that help alleviate this problem by beginning with
inexpensive, commercially available perfluorinated
reagents and performing C-F functionalization
reactions on them. This will aid the synthetic
community in a twofold manner by not only adding new reactions to the body of scientific
knowledge, but also providing highly fluorinated, small molecule building blocks that can be
further elaborated into complex partially fluorinated molecules.

In order to accomplish this, we sought to provide facile access to highly fluorinated

benzylic amines. It was envisioned the amine would come from reduction of nitro group, which
itself would come from a SnAr reaction with nitromethane (Scheme 1). Given our intention to
provide useful building blocks, special attention was given to the development of reaction
conditions, workup, and isolation such that the methods should be amenable to scaling.
Additionally, we have investigated substituted nitroalkanes as well. The results of our going
progress will be presented.

Preference: Poster
BENZO[4,5]IMIDAZO[2,1-b]QUINAZOLIN-12-ONES AND BENZO[4,5]IMIDAZO[1,2-
a]PYRIDO[2,3-d]-PYRIMIDINE-5-ONES BY A SEQUENTIAL N-ACYLATION-SNAr
REACTION Krishna Kumar Gnanasekaran, N. Prasad Muddala and Richard A. Bunce,
Department of Chemistry, Oklahoma State University, Stillwater, OK 74078-3071, USA

An efficient synthesis of benzo[4.5]imidazo[2,1-b]quinazolin-12-ones and benzo[4,5]imidazo-

[1,2-a]pyrido-[2,3-d]pyrimidin-5-ones is reported from the reaction of 2-aminobenzimidazole
with 2-haloaroyl chlorides. The reaction takes advantage of the 1,3-disposition of nucleophilic
centers in the 2-aminoimidazole and the similar arrangement of electrophilic sites in the acid
chloride to assemble the central six-membered ring. The reaction sequence involves a sequential
N-acylation-SNAr reaction carried out in one flask to prepare these fused-ring heterocyclic
structures. The reaction has relatively broad scope, and gives 76-98% yields for the two-step
sequence. The final products exist in a tautomeric equilibrium, which can be blocked by
acylation at N6.

IN VITRO GLYCOSYLATION OF MEMBRANE PROTEINS

Leshani A. Liyanage, Gabriel A. Cook
The Department of Chemistry, Oklahoma State University, Stillwater, Oklahoma 74078
Glycoproteins are incredibly important proteins, making up a large percentage of the proteome
and taking part in nearly every biological process. Oligosaccharides are covalently attached to
the polypeptide through a highly specific enzymatic process. N-linked glycosylation is the most
abundant type of glycan attachment in proteins. One of the enzymes that catalyzes this process is
N-glycosyltransferase (NGT), which recognizes the consensus sequence, –Asn-X-Ser/Thr–,
within the protein and catalyzes the glycosidic bond formation between sugar donors containing
nucleoside phosphate and the sidechain amide nitrogen of the asparagine residue. The attachment
of the sugar moiety can influence the physiochemical and biological properties of proteins by
affecting their folding, modulating interactions with other biomolecules and modifying their
functions in cellular level. Therefore, we are using in vitro protein glycosylation to evaluate the
effects of this modification on protein structure, dynamics and interactions. We are specifically
interested in determining the effects of glycosylation on membrane glycoproteins. For the in
vitro studies of N-glycosylation, WALP peptides with an engineered glycosylation site will be
used, as these simple peptides have been shown to be effective models for characterizing
membrane proteins. The most important components of our strategy for in vitro studies of
glycosylation of membrane proteins is the incorporation of the protein into lipid environments
that ensure that the protein remains folded in a native confirmation while providing conditions
that allow the glycosylating enzyme to retain its activity. Therefore, a wide range of detergents
and lipid assemblies such as micelles, isotropic bicelles and nanodiscs are used as membrane
mimics. Glycosylation of these samples will be performed using Escherichia coli expressed
NGT from the Actinobacillus pleuropneumoniae genome. Mass spectrometry, Quartz Crystal
Microbalance (QCM), gel electrophoresis and NMR will be used for detection of
glycosyltransferase activity and to characterize the reaction adducts.
Studies of the Structure, Function and Dynamics of Cancer Protein Syndecan-1 Paul Morgan and
Gabriel A. Cook
Department of Chemistry, Oklahoma State University

Syndecan-1 belongs to a family of four transmembrane heparin sulfate proteoglycans. The

syndecan family is involved in the regulation of angiogenesis and cell proliferation, cell-to-cell
interaction and cell adhesion through the activation of growth factors1. Studies have also
demonstrated that the shedding of the syndecan-1 soluble ectodomain inhibits FGF2-induced cell
proliferation and is also a potent stimulator for melanoma tumor growth and metastasis2. Each
syndecan has a short cytoplasmic domain, a highly conserved single spanning transmembrane
domain, and a large extracellular domain with attachment sites for three to five heparin sulfates or
chondroitin sulfates. To date, only the structure of the cytoplasmic domain of syndecan-4 has
been solved. Our initial computational studies predict that the large ectodomain of syndecan-1 is
intrinsically disordered but may adopt a more defined secondary structure upon ligand binding.
Despite the significance of these proteins, very little is known about their structure and dynamics.
We have cloned and expressed syndecan-1 in E. coli and have purified milligram quantitates from
growths in LB and M9 minimal media. This is the first time that full-length syndecan-1 has been
expressed and purified in E. coli cultures. Nuclear Magnetic Resonance Spectroscopy will be
employed to characterize this important protein and look at the effect that glycosylation has on its
properties.

References:
1. Echtermeyer F, Streit M, Wilcox-Adelman S, Saoncella S, Denhez F, Detmar M, Goetinck P.
Delayed wound repair and impaired angiogenesis in mice lacking syndecan- 4. J Clin Invest.
2001;107:R9–R14

2. Mali M, Elenius K, Miettinen HM, Jalkanen M. Inhibition of basic fibroblast growth factor-
induced growth

promotion by overexpression of syndecan-1. J Biol Chem. 1993;268:24215–24222.

FABRICATION AND CHARACTERIZATIONS OF METAL OXIDE

NANOFIBERS FOR ENERGY APPLICATIONS , Sara Alkhalaf, Ram K. Gupta1*

1
Department of Chemistry, Pittsburg State University, 1701 S. Broadway, Pittsburg, KS
66762, USA
 Nanostructured materials have attracted considerable research interest for their
applications as catalyst, energy storage, fuel cells, etc. The main objective of this work is
to synthesize and characterize nanofibers of metal oxides using electrospun technique and
use them for energy storage applications. Various metal oxides such as NiMn2O4,
CoMn2O4 and ZnMn2O4 were prepared as 1 dimensional (1-D) architecture using
processable polymers and metal salts. The synthesized nanofibers were structurally and
electrochemically characterized. The supercapacitive performance of these nanofibers
was examined using cyclic voltammetry (CV) and galvanostatic charge-discharge
techniques. The CoMn2O4 nanofibers showed a promising value of ~ 120 F/g in 3M
NaOH. The effect of different electrolytes such as LiOH, NaOH and KOH on the
electrochemical properties of these metal oxide nanofibers was also investigated. It was
observed that the charge storage capacity depends on the electrolyte used. The
supercapacitor device fabricated using these nanofibers showed that charge storage
capacity increases with increase in temperature. Our results suggest that electrospun
nanofibers could be used for energy storage applications.

* Corresponding author: ramguptamsu@gmail.com (Ram K. Gupta).

Presenting author: s.a.k.2027@gmail.com (Sara Alkhalaf)

EFFECT OF STABILIZERS ON HYDRATE FORMATION AND THEIR
RHEOLOGICAL BEHAVIOR, Ashwin Kumar Yegya Raman, Deepika Venkataramani, Peter
Clark, Clint P.Aichele, School of Chemical Engineering, Oklahoma State University,
Stillwater, OK 74078

Flow assurance is one of the major technical problems facing the petroleum industry. Several
millions of dollars have been spent in mitigating pipeline blockages. Despite extensive studies
over decades, the mechanisms by which hydrates are formed are not yet completely understood
due to the complex nature of hydrates. This inadequacy in the fundamental understanding on
hydrate formation mechanism has provided us an impetus to conduct experimental work on
cyclopentane hydrate forming emulsions.

Cyclopentane hydrates are studied in model oil systems using surfactant and solid particles,
which act as stabilizing agents. The droplet sizes of the hydrate forming emulsions are quantified
before and after the formation of hydrates. Droplet size distribution and hydrate formation are
examined at various water fractions using different kinds of stabilizing agents. Bench top
experiments are performed to explore the hydrate formation conditions and their morphology.
Rheological behavior of hydrate forming emulsions is studied using different kinds of stabilizing
agent. An Olympus BX53 polarized optical microscope with shear cell and temperature control (-
50°C to 450°C) stage is used to quantify droplet size distribution, and hydrate crystals
morphology. A DHR-3 stress controlled rheometer whose temperature can be controlled between
-20°C to 150°C is used to examine the rheological behavior of hydrate forming emulsions.

Characterization of hydrate forming emulsions, understanding the rheological behavior

and the impact of emulsion stabilizers on hydrate formation in oil-dominated systems
would provide us a better understanding of hydrate formation mechanism and their flow
properties. An understanding of the rheological behavior of hydrates would help in
enhancing the design of multiphase flowlines and thereby minimizing the costs involved
in transportation of crude oil.
PROMISING ACTIVATED CARBONS DERIVED FROM BIO-WASTE FOR HIGH PERFORMANCE
1 1 1* ,
ENERGY STORAGE DEVICES, Charith Ranaweera , Z. Wang , Ram K. Gupta
1
Department of Chemistry, Pittsburg State University, 1701 S. Broadway, Pittsburg, KS 66762,
USA

Batteries, fuel cells and capacitors are the most promising energy storage devices. The energy
storage mechanism and delivery in these devices are quite different, for example in batteries
energy is stored in form of chemical energy and this chemical energy is converted back to
electrical energy during discharging (use) process. On the other hand, in capacitor electrical
energy is stored due to electrostatic principle (or redox process). There has been an increasing
research attention to develop high performance energy storage devices from agriculture waste
and renewable resources. Recycling the agricultural waste not only helps in waste management
but also provides high performance materials for energy applications. In this work, high
performance carbonized jute fibers were synthesized for high temperature energy storage
devices. The structural and electrochemical properties of the carbonized bio-mass were studied.
The X-ray diffraction and Raman spectra of the carbonized jute confirm presence of the graphitic
phase of carbon. The cyclic voltammetry studies suggested that these fibers have high charge
storage capacity (408 F/g) and the fibers showed no degradation in charge storage capacity even
after 5,000 cycles of charge discharge study. In addition to high electrochemical cyclic stability,
they showed excellent flexibility without any degradation to charge storage capacity. The
performance of the supercapacitor device was tested from low temperature to high temperature
to study the effect of temperature on its electrochemical behavior. An improvement of about
60% was observed on increasing the temperature from 5 to 75 oC. Our studies suggest that
carbonized bio-mass could be used for fabrication of stable, high performance and flexible
energy storage devices.

* Corresponding author: ramguptamsu@gmail.com (Ram K. Gupta).

Presenting author: cranaweera@gus.pittstate.edu (Charith Ranaweera)

HIGHLY EFFICIENT ELECTROCATALYST BASED ON MOS2 FOR HYDROGEN EVOLUTION

1 1
REACTION, Z. Wang , Charith Ranaweera , Ram K. Gupta1* 1Department of Chemistry,
Pittsburg State University, 1701 S. Broadway, Pittsburg, KS 66762, USA

To meet the constantly rising requirement of energy other than traditional fossil fuel and
environment protection, it is a perfect time to development low cost, and efficient materials for
clean energy production. Hydrogen generation by water splitting is one of the cleanest ways to
produce cheaper energy. Hydrogen evolution reaction (HER) is one of the key steps in water
splitting process. Ideally, the thermodynamic potential for HER should be at 0 V (vs. SHE).
However, without an efficient catalyst, this reaction occurred at higher potential, called
overpotential. A good HER catalyst is needed to lower the overpotential and hence to improve
the energy efficiency of this process. Presently, platinum is the most effective and durable
catalyst for HER, but its wide spread use is precluded due to its cost as well as limited
availability. Therefore, it is essential to develop low-cost and earth-abundant materials to replace
precious-platinum based catalysts. In this work, a facile and scalable one-pot method has been
developed to synthesize carbon coated MoS2. The carbon coated MoS2 is advantageous as this
increases the electrical/ionic conductivity of MoS2. The structural characterization of MoS2 and
carbon coated MoS2 was performed using x-ray diffraction and scanning electron microscopy.
Hydrogen evolution reaction was studied in potential range of 0 to -0.7 V and observed that
carbon coated MoS2 provide lower overpotential compared to uncoated MoS2.

* Corresponding author: ramguptamsu@gmail.com (Ram K. Gupta)

Presenting author: zwang@gus.pittstate.edu (Z. Wang)

REACTION OF HYDEROGEN PEROXIDE WITH NANOMETRIC VANADIUM

BRONZE; Asma Alothman, Nicholas Materer, Zeid Alothman, Allen Apblett
Department of Chemistry, Oklahoma State University, Stillwater, Oklahoma 74078

It is crucial to develop new sensors or improve the existing one for the detection of peroxide
based explosives to insure and grant the safety of both civilians and military personnel from any
terrorist threats. Among many sensor-based materials, molybdenum bronze reagents were proven
to be one of the best solutions to successfully neutralize and detect explosive compounds in a
rapid and safe one step onsite method under ambient conditions. Vanadium bronzes are more
electrochemically-stable analogs of the molybdenum bronzes that can be used to prepare sensors
with enhanced selectivity and air stability. The preparation and characterization of vanadium
reagent will be described. Developing and optimizing the sensitivity of vanadium based sensors
for a hydrogen peroxide based explosives will be investigated.
Bimetallic Single-Source Precursor Approach for the Synthesis of Mo Ternary Oxides
Alqahtani Fahad, Apblett Allen, Department of Chemistry, Oklahoma State University, Stillwater, OK
74078.

Metal molybdates receive considerable attention due to their unique chemical and physical
properties. Bimetallic molybdates can be synthesized hydrothermally or by using several other
methods. However, the low temperature single source precursor approach will result in obtaining the
targeting molecule with high surface area by avoiding sintering. Previously, bimetallic molybdates and
vandates have been successfully synthesized using bimetallic salts of alpha carboxylic acid precursors.
In this investigation, the synthesis of nickel and cobalt molybdates using alpha amino acids will be
reported. The characterization of these precursors and the obtained bimetallic oxides by spectroscopic,
thermogravimetric analysis, and X-ray powder diffraction technics will be discussed.

Solid State Reaction of Titanium with Silicon Dioxide, Chundira Brown and Dwight L. Myers
Department of Chemistry, East Central University, Ada, OK 74820

There are questions concerning the reaction of titanium dioxide (rutile) with silica. It is uncertain
whether they combine to form a titanium silicate or not, and at what temperatures. Both are important
as potential materials or reaction products in thermal barrier coatings or environmental barrier coatings
in combustion environments, as for example in gas turbine technologies. The extent of reaction and
temperature range are important questions to answer for this chemical system. Solid state reactions of
titanium dioxide with silicon dioxide are being attempted. Mixtures of the two oxides have been
subjected to heatings at various temperatures from ca. 1200-1500ᵒ C. Samples are being
characterized before and after heating by means of X-ray diffraction and diffuse reflectance infrared
spectroscopy, transmission infrared spectroscopy, and/or diffuse reflectance UV/Vis spectroscopy as
appropriate. Results to date will be presented
DFT Study of the Dissociative Adsorption of Chloro- and Dichlorobenzene on the Si(100)
Surface; Eric Butson1, Qing Zhu2, Nicholas Materer1
1
The Department of Chemistry, Oklahoma State University, Stillwater, OK 74074 2 University of
Pittsburgh, Department of Chemical and Petroleum Engineering, Pittsburgh, Pennsylvania, 15261

The dissociative adsorption of chlorobenzene and dichlorobenzene on Si(100) surface was modeled
using density functional theory. A double and triple dimer cluster was used to represent the (100) face
of silicon. Initial adsorption occurs by breaking one double bond on the phenyl ring and forming two
new carbon- silicon bonds with the silicon dimer. For further dissociation to occur, the system must
undergo a spin crossing process from the singlet electronic configuration to a higher energy triplet
state. After this spin crossing event, the chlorine can then bond to the silicon surface. The possible
mechanisms of dissociation are explored for both chlorobenzene and dichlorobenzene. The proposed
mechanism suggest that chlorobenzene adsorbs on a dimer row, while dichlorbenzene adsorbs in
between dimer rows. The minimum energy crossing point for the spin crossing is found by minimizing
the energy gradients between the two electronic states. The probability of spin crossing at the minimum
energy crossing point is calculated, and the activation energy for the process is determined. It is found
that the activation energies for the spin crossings are small in comparison to the other steps in the
proposed mechanisms.

Probing the Effect of Water in Catalytic Reactions by In Situ Solid-State NMR

Kuizhi Chen, Maryam Abdolrahmani and Jeffery L. White* Department of Chemistry, Oklahoma State
University Stillwater, OK 74078
Abstract. Zeolites are solid acid catalysts used extensively in petrochemical processes and also in
methanol-to-hydrocarbon (MTH) chemistry. Industrial quantities of methanol are produced from coal
or biomass. In methanol conversion to hydrocarbons, stoichiometric amounts of water are inevitably
produced, but the role of water is not fully understood. Conventionally, water is considered as a poison
in zeolite-based catalysis. However, both theoretical and experimental works have shown that water
could enhance the MTH conversion rate. Our previous work has shown that water could enhance the
reaction rate for nonpolar molecules in zeolite catalysts (ACS Catalysis 2014, 4, 3039). Active sites
were subsequently characterized in hydrophilic and hydrophobically modified zeolites (ACS Catalysis
2015, 5, 7480). Aromatic reaction centers are common to almost all hydrocarbon conversions in
zeolites. Specifically, alkylation/dealkylation steps are critical, and have been shown as key steps in
MTH conversion. Ethylbenzene and isopropylbenzene (cumene) are chosen as representative reagents,
and their transformation in zeolites is being investigated by high temperature in situ solid-state NMR.
* Author to whom all correspondence should be addressed at jeff.white@okstate.edu
DEVELOPMENT OF N-HETEROCYCLIC CARBENE COPPER COMPLEXES WITH
APPLICATIONS IN MULTIPLE CROSS-COUPLING CONDITIONS.
Doaa Domyati1 and Laleh Tahsini1
1Department of Chemistry, Oklahoma State University, Stillwater, 74074
N-heterocyclic carbenes (NHCs) have become a focal point in many catalytic systems including cross-
coupling reactions owing to their strong bonding to metals and stability of their complexes.
Sonogashira coupling involving the reaction of an aryl halide and a terminal alkyne has been a useful
one-step approach in the synthesize of natural products and biologically active molecules.1 The
traditional Sonogashira reaction is performed in the presence of a Pd catalyst and a copper co-catalyst2
which is a disadvantage to industrial application due to the significantly higher cost of Pd. Herein we
report the syntheses of some novel copper–NHC complexes for the potential catalytic applications in
Sonogashira coupling reactions. The cationic and neutral Cu(I) complexes of electronically and
sterically divergent NHC ligands, ItBu, IiPr, IPr, and SIPr were prepared with good to excellent yields
via the reaction of a copper precursor and an in-situ generated carbene (Figure 1). The “all at once”
mixing of copper precursor, imidazolium salt and the base was confirmed to lead to no clean product.
The prepared complexes were all fully characterized by 1H NMR, 13C NMR, and elemental analysis
and will be used in the cross- coupling reaction of phenylacetylene and phenyl iodide.

Figure 1. NHC carbine ligands

References
3. Chinchilla, R. and Nájera, C. Chem. Soc. Rev. 2011, 40, 5084−5112.
4. Sonogashira, K.; Tohda, Y.; Hagihara, N. Tetrahedron Lett. 1975, 16, 467−4470.
ZINC OXIDE/ZINC SULFIDE NANOSTRUCTURES AS FLAME RETARDANT
COATINGS

Yi-Wei Wang,1 Thushara J. Athauda,1 Qingsheng Wang2 and Yolanda Vasquez1

1
Department of Chemistry, Oklahoma State University, Stillwater, OK 74078.
2
Department of Chemical Engineering, Oklahoma State University, Stillwater, OK 74078.

According to the most recent data available, fires cause approximately 1.3 million accidents
annually that result in 3,257 deaths, 15,775 injuries and an estimated $11.6 billion in direct
property losses. Flame-retardant materials play an increasingly important role in reducing or
preventing damages caused by fires. Organo-halogen compounds, phosphorus compounds,
nitrogen-based compounds and nanocomposites are among the different classes of fire retardants
developed in the past several decades. In this study, we report that ZnO nanorods and ZnO/ZnS
core/shell nanorods show promising behavior as flame-retardant materials when coated onto
cotton fabrics. ZnO and ZnO/ZnS nanorods were nucleated and grown onto cotton materials
using a multi-step hydrothermal synthesis. The properties of the ZnO and ZnO/ZnS such as heat
release rate, total smoke release and mass loss rate of the materials were tested using a cone
calorimeter. During the combustion test, ZnO and ZnO/ZnS nanorods were able to reduce the
heat release rate and total smoke release from 117.77 kW/m2 and 18.3 m2/m2 to about 70 kW/m2
and 6 m2/m2, respectively. At the end of the test, instead of burning into ash, ZnO and ZnO/ZnS
nanorods coated cotton samples were able to maintain the shape and protect the aluminum
holders from being burned through. The flame-retardant properties were confirmed by the test
results.
 ELECTROCHEMICAL PROPERTIES OF NANOSTRUCTURED NICKEL OXIDE FOR

SUPERCAPACITORS, Muidh Albalawi, Ram K. Gupta* Department of Chemistry, Pittsburg

State University, 1701 S. Broadway, Pittsburg, KS 66762, USA

The increasing demand for energy in the world led to focus on more efficient energy storage

devices. Energy can be stored in various kind of devices such as batteries, capacitors and fuel

cells. Among them, supercapacitors are very attractive due to their high power densities, fast

charge-discharge behavior and long life cycles. They can be used in hybrid cars and devices

where high-power delivery is required. The objective of this work is to study the effect of

morphology of nickel oxide on their electrochemical properties. The morphology of nickel oxide

was modified using various surfactants. Structural characterization performed using scanning

electron microscopy reveals the nanostructure of nickel oxides. The electrochemical properties of

nickel oxide were studied using cyclic voltammetry and galvanostatic charge –discharge

measurements. A very high specific capacitance of about 315 F/g was observed at 5 mV/s in

alkaline electrolyte. It was observed that charge storage capacity depends on morphology of

nickel oxide.

* Corresponding author: ramguptamsu@gmail.com (Ram K. Gupta).

Presenting author: alothmani2008@hotmail.com (Muidh Albalawi)

NOVEL NON-HALOGENATED FLAME RETARDANT COMPOUNDS

Austin Bailey, Tim Dawsey and Charles J. Neef

Department of Chemistry, Pittsburg State University, Pittsburg, KS, 66762

Two different boron compounds, bis(tetramethylammonium) decaborate, TMAD, and

bis(tetrabutylammonium) decaborate, TBAD were studied as potential replacements for
halogenated flame retardants. Current commercially available, halogenated flame retardants are
not environmentally friendly and release strong acids upon burning. TMAD and TBAD were
combined with triphenylphosphine oxide and cast in polyurethane films at varying levels. These
samples were then cut into strips and burned in a UL-94 flame chamber. These samples were
also tested via TGA for degradation temperature. These varying levels were tested via several
Design of Experiments constructed within Minitab software. Results thus far have shown the
potential for these compound combinations to be used as flame retardants. Studies to determine
the optimal ratio of additives for flame retardancy will be presented.

EFFECT OF VISCOSITY, SOLVENTS, AND ULTRA-SONICATION ON THE

FLUOROSILANE TREATED DIATOMACEOUS EARTH/POLYSTYRENE SURFACES

1
Bhishma R. Sedai, and 1Frank D. Blum
1
Department of Chemistry, Oklahoma State University, Stillwater, Oklahoma, 74078
USA

The effect of viscosity of binder, different solvents and ultra-sonication on surfaces prepared
from treated diatomaceous earth (DE) particles and polystyrenes has been studied.
Superhydrophobic DE particles were prepared by treating DE with 3-
(heptafluoroisopropoxy)propyltrimethoxysilane (HFIP-TMS). The amount of grafted silane
coupling agent in treated DE was calculated using thermogravimetric analysis (TGA). The
presence of HFIP-TMS on the surface of DE was confirmed by Fourier Transform Infrared
Spectroscopy (FTIR). The effect of viscosity was observed in coatings prepared with polystyrene
of two different number average molecular masses (Mn = 20,000 g/mol. and Mn =280,000
g/mol.) in tetrahydrofuran. In the same coating compositions, the coatings mixture with less
viscous binder developed superhydrophobicity with fewer treated DE particles. The treated DE
particles and polystyrene dispersions in different solvents; tetrahydrofuran, ethylacetate,
dichloromethane and toluene, were used to make coating mixtures. Treated DE/PS surfaces
prepared in all four solvent systems exhibited similar topography required for
superhydrophobicity. The coating mixtures prepared in different solvent systems were subjected
to ultra-sonication and the sonicated samples were used to make coatings. The ultra-sonicated
samples also retained the topography required for superhydrophobicity. The coatings were
characterized by contact angle measurements and scanning electron microscopy.
ISOCYANATE-FREE URETHANES BY THIOL-ENE REACTION

O. Bilic1, I. Javni1, M. Ionescu1, M. Wan1 and T. A. Upshaw2

1
Kansas Polymer Research Center, Pittsburg State University, Pittsburg, KS 66762
2
Chevron Phillips Chemical Company LP, Bartlesville Technology Center, Bartlesville, OK
74003-6670

Polyurethanes, commonly prepared by the reaction of isocyanates with polyols are among the
most broadly used class of polymers, due to their excellent physical and mechanical properties.
However, the depletion of petrochemical resources, negative effect of carbon dioxide on the
environment, and reduced use of the highly toxic and hazardous isocyanate starting materials
continues to be a major force for strong demand for their replacement with renewable
components. An alternative approach that continues to receive attention from the research
community is the use of polyfunctional thioether-cyclic carbonates reacted with diamines to
produce polyurethanes without the need for toxic and hazardous isocyanates. However, most
cyclic carbonates of vegetable oils are produced by reacting epoxidized oils with carbon dioxide
resulting in a cyclic carbonate structure directly anchored on the long chain fatty acid.
Alternatively, a highly reactive thiol group, instead of the naturally occurring hydroxyl groups,
can be leveraged in a thiol-ene reaction to facilitate placement of a terminal cyclic carbonate
which will allow enhanced reactivity. Our work investigates the production of isocyanate-free
polyurethanes via the thiol-ene reaction of thiol functional polyols with allyl glycidyl ethers as a
procedure to separate the cyclic carbonate from the chain and thus enhance access for reaction
with diamines producing isocyanate-free polyurethanes. Mechanical and thermal properties are
reported on work to date, and plans for continued improvement to the process are discussed.

DEVELOPMENT AND CHARACTERISTICS OF NON-ISOCYANATE SPRAY

INSULATION FOAMS, Nikola Bilic, Kansas Polymer Research Center, Pittsburg State
University, Pittsburg, KS 66762

Although polyurethane spray foams continue as the construction industry’s insulation of choice,
at approximately 2lb/ft3 (32kg/m3) and with R-values of approximately 6.3 (h·ft2·°F/Btu) per
inch of thickness, pressure continues to mount for a “greener” option, based on less toxic raw
materials. As such, the aim of this work, conducted at the Kansas Polymer Research Center
(KPRC), was to develop an approach to non-isocyanate foams with insulation values, installation
procedures, and performance criteria comparable to those of PUR foams presently on the market,
while reducing health risk to installation workers. The KPRC approach was to develop an epoxy-
based foam offering that would allow application of a spray foam using a familiar two-
component procedure. Five years of efforts have led to two non-isocyanate spray insulation foam
formulations producing densities of ~30 kg/m3 and ~33 kg/m3, with R values above 7
(h·ft2·°F/Btu). In addition, these foams exhibit acceptable mechanical (compression strength
~160-180kPa) and outstanding fire retardant (flammability weight loss ~ 8-9%) properties.

THE EFFECTS OF CONTROLLED LATERAL CONFINEMENT WIDTH AND

SURFACE CHEMISTRY ON CTAB ADSORPTION ONTO SILICA;

Joshua Hamon1, Dr. Brian Grady1

1
Chemical, Biological and Materials Engineering, University of Oklahoma, OK 73019

The effects of lateral confinement on an adsorbed surfactant layer are the subject of these
works. The pattern used to induce confinement were nano-trenches with silica at the bottom and
walls of either pure polymethyl methacylate (PMMA) or a copolymer of PMMA and methacrylic
acid (MAA) to vary hydrophobicity. An atomic force microscope was used to measure the
thickness of the adsorbed aggregates within the trench structures and compared to the images and
thicknesses of aggregates with no confinement. Pillar type structures are currently being
fabricated which will allow for confinement induced through a lack of surface area. The ultimate
goal of this research is to compare the results found using these nano-structures with simulations
performed using similar geometric confinement.

MODEL REACTION OF AMINES WITH INTERNAL EPOXIDES; Jian Hong, Dragana

Radojčić, Mihail Ionescu, Xianmei Wan, Ivan Javni and Zoran S. Petrović

Kansas Polymer Research Center, Pittsburg State University, Pittsburg, Kanas 66762

The model reaction of an amine with 9,10-epoxyoctadecane is helpful to understand the reaction
of amines with epoxidized vegetable oils. The reactivity of internal epoxides, as in epoxidized
fatty acids, with primary amines was investigated using primary amines and a model epoxide
compound, 9,10-epoxyoctadecane, which was a mixture of cis- and trans- isomers. The reactions
were carried out at 100 °C, 170 °C and 200 °C for 24 hours. It was observed that the reaction of a
primary amine with the internal epoxide does not proceed to any significant extent, even at 200
°C, in the absence of catalysts. It also revealed that the key step in the reaction of amine with
epoxidized vegetable oils, in the absence if a catalyst, is amidation.
VEGETABLE OIL BASED POLYMERCAPTANS AS CURING AGENTS FOR EPOXY
RESINS, Dragana Radojcic1, Ivan Javni1, Tom Upshaw2
1
Kansas Polymer Research Center, Pittsburg State University, Pittsburg, KS 66762
2
Chevron Phillips Chemical Company LP, Bartlesville Technology Center, Bartlesville, OK
74003-6670

Three vegetable oil (VO) based polymercaptans (PM) were investigated as curing agents for a
commercial bisphenol A diglycidyl ether (BADGE) type epoxy resin: mercaptanized soybean oil
(PM-358), mercaptohydroxy or mercaptanized epoxidized soybean oil (PM-407), and
mercaptanized castor oil (PM-805C). Various tertiary amines were used as accelerators. Curing
kinetics were studied by isothermal rheological measurement using a dynamic time swipe test at
a frequency of 10 Hz and 15 Pa shear stress. The measurements were done at 25 °C, 40 °C, 60
°C and 80 °C. Time to the gel-point (gel time) was taken to be the one corresponding to the
intersection of storage (G`) and loss (G``) modulus. Gel time at different temperatures was used
to calculate activation energies of these curing systems. For the purpose of comparison, BADGE
was also cured with diethylenetriamine (DETA), a common curing agent for epoxy-resins. The
epoxy resin gelled significantly faster when cured with polymercaptans than with DETA. It was
found that reactivity of the mercapto group (-SH) toward an epoxy group depended strongly on
the presence of non-reactive hydroxyl groups in the molecule structure. A hydroxyl group in the
vicinal position (PM-407), and in β or γ position (PM-805C), increased the reactivity of the thiol
group when compared to a thiol with no hydroxyls in close proximity (PM-358).

LOW TEMPERATURE SYNTHESIS OF COBALT DOPED ZINC OXIDE FOR THE

USE IN SEMICONDUCTOR MATERIALS; Travis Reed, Allen Apblett
1
The Department of Chemistry, Oklahoma State University, Stillwater, Oklahoma 74074

The interest in semiconductor materials for the use in electrical and optical applications is of
large importance. The properties of these materials vary quite drastically and are still in need of
improvement. Zinc oxide is a widely used material due to the availability and low cost. Zinc
oxide shows high electron mobility and high thermal conductivity which is of great interest.
Doping zinc oxide with cobalt allows for tailoring of the electronic properties by altering the
width of its bandgap. Cobalt doped zinc oxide is easily synthesized from the decomposition of
the corresponding pyruvic acid oxime precursor. This precursor decomposes at a relatively low
temperature, which leaves the metal oxide and releases small organic fragments. In this study we
will discuss the synthesis of cobalt/zinc pyruvic acid oxime and the decomposition into the oxide
species.
EFFECT OF PROCESSING ON GENERAL PURPOSE AND ENGINEERING
THERMOPLASTIC POLYMER PROPERTIES; Kyle Schwenker1, Vlad Jaso2, Jeanne H.
Norton3
1
Department of Chemistry, 2Kansas Polymer Research Center, 3Department of Plastics
Engineering Technology; Pittsburg State University, 1701 South Broadway, Pittsburg, KS 66762

Injection molding is the fastest growing process in the plastics industry with high production
rates and low cycle times. This process allows production of complex and intricate shapes and
allows multiple parts to be created in the same cycle. Previously processed material known as
“regrind” is often used in injection molding. Successive rounds of processing can reduce
molecular weight. Lower molecular weight can negatively affect properties of the final injection
molded plastic part. In this study, we demonstrate that any plastic formulation we process via
lab-scale extrusion is appropriate for injection molding. Two semi-crystalline polymers
(polypropylene and nylon-6) and two amorphous polymers (polystyrene and polycarbonate) were
processed by extrusion and subsequent injection molding. Thermal properties and mechanical
properties were compared to virgin polymer properties and properties of samples processed by
two rounds of injection molding. Polystyrene and Nylon-6 did not demonstrate any significant
loss of thermal or mechanical properties. Polypropylene demonstrated a reduction in onset of
degradation with successive rounds of processing, but no significant loss of mechanical
properties. Polycarbonate did not exhibit any changes in thermal properties, but reductions in
break stress and break elongation were observed with successive rounds of processing.

Novel Magnetic Relaxation Nanosensors: An Unparalleled “Spin” on Influenza Diagnosis;

Tyler Shelby,‡ Tuhina Banerjee,‡Jyothi Kallu, Irene Zegar, Lisa A. Clough± and Santimukul
Santra*

*Department of Chemistry, Pittsburg State University, 1701 S. Broadway Street, Pittsburg, KS

66762, USA.

Influenza is well known for its ability to rapidly mutate, leading to the frequent emergence of
pathogenic strains. Rapid detection and diagnosis of pathogenic strains would allow for
expedited treatment, and quicker resolutions to the ever-arising flu pandemics. Vital to the rise of
pathogenic strains is the mutation of viral genes coding for hemagglutinin, the influenza-
associated glycoprotein responsible for viral binding and entry. Slight mutations allow the
protein to adopt new binding affinities, granting it access to new cell receptors. Considering this,
we propose the development of novel functional magnetic relaxation nanosensors (MRnS) for
the rapid detection of influenza through targeted binding with hemagglutinin. A group of small
molecule ligands and entry blocker (EB) peptides with known binding affinities for
hemagglutinin variants were conjugated to iron oxide nanoparticles (IONPs) to develop
functional MRnS. Positive detection of various hemagglutinin (H1N1 and H5N1) HA1 subunits
was easily possible with protein concentrations as little as 1.0 nM using sialic acid (2,6- and 2,3-
sialic acid, respectively) and entry blocker peptides (EB Peptide, ALRPL and Ste)-conjugated
MRnS. Most importantly, detection using functional MRnS was achieved within minutes, and
was able to differentiate between various influenza subtypes. Current methods used to diagnose
influenza, such as RT-PCR, ELISA, and viral culturing, while largely effective, are complex,
time-consuming and costly. As well, they are not as sensitive or specific, and have been known
to produce false-positive results. In contrast to these methods, targeted MRnS is a robust, point-
of-care diagnostic tool featuring simple, rapid and low-cost procedures. These qualities, as well
as high sensitivity and specificity, and low turnaround times, make a strong case for the
diagnostic application of MRnS in clinical settings.

References

1. Kumar, S.; Henrickson, Kelly; Clinical Microbiology Reviews 2012, 25(2), 344-361.
2. Sin, M.; Mach, K.; Wong, P.; Liao, J. Expert Rev. Mol. Diagn. 2014, 14(2), 225-244.
3. Qasim, M. Journal of Nanoscience and Nanotechnology 2014, 14(10), 7374-7387.
4. Mahony, J. Clinical Microbiology Reviews 2008, 21(4), 716-747.
5. WHO 2007
6. Chen, W.; He B.; Li C.; Zhang X.; Wu W.; Yin X.; Fan B.; Fan X.; Waang J. Journal of
Medical Microbiology 2007, 56(Pt 5), 603-607.
7. Liong, M.; Hoang, A.; Chung, J.; Gural, N.; Ford, C.; Min, C.; Shah, R.; Shmad, R.;
Fernandez-Suarez, M.; Fortune, S.; Toner, M.; Lee, H.; Weissleder, R. Nature
Communications 2013, 4(1752)
8. Kaittanis, C.; Santra, S.; Perez, J. JACS 2009, 131(35), 12780-91
9. Perez, J.; Simeone, F.; Saeki, Y.; Josephson, L.; Weissleder, R. J. Am. Chem. Soc. 2003,
125(34), 10192-10193
10. El-Boubbou, K.; Gruden, C.; Huang, X. J. Am. Chem. Soc. 2007, 129(44) 13392-13393
11. Kaittanis, C.; Naser, S.; Perez, J. Nano Letters 2007, 7(2), 380-383
12. Lin, L.; Cong, Z.; Cao, J.; Ke, K.; Peng, Q.; Gao, J.; Yang, H.; Liu, G.; Chen, X. ACS Nano
2014, 8(4) 3876-3883
13. Kaittanis, C.; Santra, S.; Santiestebal, O.; Henderson Ii, T.; Perez, J. JACS 2011, 133(10),
3668-3676
14. Liu, J.; Liu, Y.; Bu, W.; Bu, J.; Sun, Y.; Du, J.; Shi, J. JACS 2014, 136(27), 9701-9709
15. Haun, J.; Devaraj, N.; Marinelli, B.; Lee, H.; Weissleder, R. ACS Nano 2011, 5(4), 3204-
3213
16. Kaittanis, C.; Boukhriss, H.; Santra, S.; Naser, S.; Perez, J. PLoS One 2012, 7(4), e35326
17. Wu, W.; Air GM. Virology 2004, 329(1), 213-214
18. Sieben, C.; Kappel, C.; Zhu, R.; Wozniak, A.; Rankl, C.; Hinterdorfer, P.; Helmut, G.;
Herrmann, A. Proc. Natl. Acad. Sci. USA 2012, 109(34), 13626-13631
19. Sauter, N.; Bednarski, M.; Wurzburg, B.; Hanson, J.; Whitesides, g.; Skehel, J.; Wiley, D.
Biochemistry 1989, 28(21), 8388-8396
20. McCullough, C.; Wang, M.; Rong, L.; Caffrey, M. PLos One 2012, 7(7), e33958
21. Santiesteban, O.; Kaittanis, C.; Perez, J. Angew. Chem. Int. Ed. Engl. 2012, 51(27), 6728-
6732
22. Santiesteban O.; Kaittanis, C.; Perez, J. Small 2014, 10(6), 1202-1211
23. Matsubara, T.; Onishi, A.; Saito, T.; Shimada, A.; Inoue, H.; Taki, T.; Nagata, K.; Okahata,
Y.; Sata, T. J Med. Chem. 2010, 53(11), 4441-4449
24. Jones, JC.; Turpin, EA.; Bultmann, H.; Brandt, CR.; Schultz-Cherry, S. Journal of Virology
2006, 80(24), 11960-11967
25. Liu, Q.; Liu, DY.; Yang, ZQ. Acta. Pharmacol. Sin. 2013, 34(10) 1257-1269
26. Yang, J.; Li, M.; Shen, X.; Liu, S. Viruses 2013, 5(1), 352-373
27. Shen, x.; Zhang, X.; Liu, S. Journ. Thor. Dis. 2013, 5(2), S149-159.
PREPARATION OF NEW SILICON-FUNCTIONALIZED POLYMERCAPTANS BY
THIOL-ENE REACTION, Maha L. Shrestha, Thomas A. Upshaw and Mihail Ionescu*

Kansas Polymer Research Center, Pittsburg State University, Pittsburg, Kansas 66762

Various Silicon functionalized compounds were prepared from thiol-ene reaction between
thiol group of polymercaptans (obtained from Chevron-Phillips) to the double bonds of
vinylsilanes or allyl silanes.

a) Reactions with vinyl silanes:

b) Reactions with allyl silanes:

Where R’=alkyl or alkoxy groups

Thiol-ene reaction was initiated photochemically under UV light or thermally by using radical
initiators. Thus, synthesized polythioether with alkoxy groups would be useful for preparation of
new cross-linked compounds via Sol-Gel reaction.

HIGH REFRACTIVE INDEX CROSS-LINKED MATERIALS FROM MERCAPTANS

AND VINYL MONOMERS VIA SIMPLE THIOL-ENE CLICK CHEMISTRY

Madhusudhan Srinivasan1, Tom Upshaw2, Timothy Dawsey1, Ivan Javni1

1
– Kansas Polymer Research Center, Pittsburg State University, Pittsburg, KS-66762, USA
2
– Chevron Phillips Chemical Company LLC. Bartlesville, OK-74003, USA

Cross-linked materials with high refractive indices 1.57 -1.59 were synthesized via a simple
thiol-ene coupling of commercially available mercaptans and vinyl monomers. The materials
exhibit very good clarity and high transparency in the 400 – 1100 nm window which makes them
attractive for optical applications. The materials exhibit glass transition temperatures of 50 – 60o
C and very high thermal stability with degradation temperatures as high as 360o C. Additionally
condensable siloxane type monomers were also synthesized via thiol-ene addition, which can be
sol-gel condensed to organic – inorganic hybrid materials for optical applications. The reaction is
flexible and occurs under ambient conditions or under UV light with or without photoinitiator,
making this attractive for synthesis of wide variety of high refractive index materials.

A NEW SOLID-STATE NMR METHOD REVEALS THE INFLUENCE OF CHAIN

STRUCTURE AND THERMAL HISTORY ON THE CRYSTAL-AMORPHOUS
INTERFACE IN POLYETHYLENES; Arifuzzaman Tapash1, Paul J. DesLauriers2, Jeffery L.
White1
1
The Department of Chemistry, Oklahoma State University, Stillwater, OK 74078 2Chevron
Phillips Chemical Company, Bartlesville, OK 74004

A simple solid-state NMR method is presented here to quantitatively determine the distribution
of solid polyethylene (PE) chain segments in different morphological regions. The rigid chains in
the crystalline phase with all-trans chain conformations, the non-crystalline trans-gauche mobile
chains, mobile all-trans chains, and rigid trans-gauche chains fractions were reliably quantified
using the developed method. A wide range of well-characterized polyethylene samples were
studied, which reveals that the amount of crystal-amorphous interface region increases with the
chain length of linear metallocene-PEs. Topologically different polyethylene that have certain
amounts of short-chain branches (SCB), long chain branches (LCB), and LCB’s that contain
SCB’s exhibit unique morphological behavior relative to the linear PE’s of similar M w (1). The
method also reveals the variations in the morphology due to different thermal histories.
Thermally quenched polyethylenes were found to have higher interface content than that of the
annealed or as-synthesized PEs. Phase composition results obtained by this simple experiment
are quantitative, reliable and reproducible. The results suggest a route to large-scale design and
control of interfacial morphology in polyethylenes and related properties.

References
1. Tapash, A.; DesLauriers, P. J.; White, J. L. Macromolecules 2015, 48, 3040-3048.
NOVEL DRUG COCKTAIL-CARRYING ANTI-OXIDANT NANOCERIA FOR THE TREATMENT
OF CANCER, ShugufthaNaz, Tuhina Banerjee, JyothiKallu, ShoukathSulthana, Filbert Totsingan,± Richard
Gross± and Santimukul Santra*

*Department of Chemistry, Pittsburg State University, Pittsburg, KS 66762. ±Department of Chemistry and
Chemical Biology, Rensselaer Polytechnic Institute, Troy, NY 12180

Oncogenic K-RAS, one of the major histologic subtypes of Non-Small-Cell Lung Cancer (NSCLC) accounts
for 25% of the lung cancer related deaths. Hsp90, a ubiquitously expressed molecular chaperone is considered
to be a promising target for therapeutic intervention. It is known to interact with several client proteins that are
important in the pathogenesis of the cancer. Ganetespib, an Hsp90 inhibitor has been shown to have superior
anti-tumor activity in several K-RAS mutant NSCLC cell lines. In addition, lactonic sophorolipids (LSL), a
class of chemo-enzymatically modified glycolipids, are known to be promising immunomodulators and have
shown to decrease the mortality rate in rat model of sepsis by down-regulating pro-inflammatory cytokines.
Recent studies have also demonstrated the anticancer activity of LSL on several cell lines including esophageal,
lung and pancreatic cancer cells.
Herein, unique drug cocktail comprising of ganetespib and LSL targeting Hsp90 signaling and inflammatory
pathways will be used for NSCLC therapy. Owing to its redox active properties, nanoceria (NC) will be
specifically used as the drug delivery platform to supplement the therapeutic potency of the drugs. In this study,
LSL and ganetespib carrying nanoceria will be formulated for the targeted treatment of NSCLC. Detail
experimental results including, targeted drug delivery, cytotoxicity, drug release and fluorescence microscopy
will be discussed.
CHARACTERIZATION OF MOLECULAR WEIGHT AND STRUCTURE OF
POLYSILOXANES BY GPC/SEC WITH TRIPLE DETECTION CAPABILITY

Xianmei Wan1, Alisa Zlatanic1, Jamie M. Messman,3 and Petar R. Dvornic1,2

1
Kansas Polymer Research Center, Pittsburg State University, Pittsburg, KS
66762
2
Department of Chemistry, Pittsburg State University, Pittsburg, KS 66762
3
Honeywell Federal Manufacturing & Technologies LLC, Kansas City, MO
64147

ABSTRACT

Polysiloxanes are the most common and arguably still the most important
organosilicon polymers used in polymer chemistry. Their properties, such as average
molar weight, molecular weight distribution and branching predetermine many of their
possible applications. Size-exclusion chromatography (SEC) with triple detection
capabilities: multi-angle light scattering (MALS), differential refractive index (dRI)
and viscometry provides the perfect tool for the determination of these properties
without the need for external standards or column calibration. In such triple detection
systems, dRI is used to calculate concentration, refractive index increment (dn/dc), and
injection recovery, whereas MALS provides the measure of absolute molecular weights
and radius of gyration while viscometry contributes intrinsic viscosity, hydrodynamic
radii, and structural parameters, including those specific for polymer branching. In this
work, five polysiloxane samples with similar chemical composition but different
molecular weights were analyzed by SEC with triple detectors using toluene as the
eluent. The concentrations of samples used were nominally 5% (w/vol) and 200 µL
solutions were injected in each run. The RI signal was negative because the refractive
index increment (dn/dc) of these polysiloxanes in toluene was negative. The molecular
weight averages, Mn and Mw, were calculated using the dn/dc data generated from
sample concentrations while assuming 100% mass recovery. The measured weight
average molecular weights ranged from 8,600 to 69,200. The intrinsic viscosity and
hydrodynamic radii increased with the increase in molecular weight. The values of
dn/dc for five polymers were relatively constant since these polymers had similar
chemical compositions. Mark-Houwink-Sakurada parameters, K and α, were calculated
from intrinsic viscosity data. The exponent α ranged from 0.65 to 0.70 indicating linear
polymer configuration in a thermodynamically good solvent.