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Pentasectional Regional Meeting 2016

Book of Abstracts

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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

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• Advances in energy and fuels

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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

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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 [email protected]

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: [email protected] (Ram K. Gupta).

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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

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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 ENERGY STORAGE DEVICES Charith Ranaweera1, Z. Wang1, Ram K. Gupta1* 1Department 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: [email protected] (Ram K. Gupta). Presenting author: [email protected] (Charith Ranaweera)

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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 REACTION Z. Wang1, Charith Ranaweera1, 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

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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: [email protected] (Ram K. Gupta) Presenting author: [email protected] (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 a

Center for Interfacial Reaction Engineering (CIRE),

School of Chemical, Biological and Materials Engineering, The University of Oklahoma, Norman, OK 73019,

USA

*Corresponding author: [email protected]

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

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environment. Finally, I will discuss briefly the effect of water on other reactions of biomass-derived compounds.

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• Analytical chemistry

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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.

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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

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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 3Department 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: [email protected]; [email protected]; [email protected], 2 Department of Chemistry, University of Central Oklahoma, 100 N. University Drive, Edmond, Oklahoma 73034; E-Mails: [email protected]; [email protected], 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.

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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.

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• Biochemistry and organic chemistry

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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 D carbon of the double bond, but was slowed by substitution at the E position.

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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.

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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

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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

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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

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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.

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• Inorganic chemistry and chemical education

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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 1Department 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 S-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(P-1,4-CNC6Me4NC)])∞ held together via synergistic S-stacking and CoIII/VI- contact ion interactions will be presented. The dianion [{(OC)5V}2(P-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.

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Simple, Selective Methods for Chiral Metallocene Preparation; Richard Buck1, Qing Yang1

1Chevron 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

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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, [email protected], 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.

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• Physical chemistry

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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.

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AN ORGANOCHROMIUM MOLECULAR WIRE FEATURING A LINEAR TERAZULENIC π-LINKER: A SYNTHETIC, SPECTROSCOPIC, AND COMPUTATIONAL STUDY, Nathan R. Erickson1, Mikhail V. Barybin1

1Department 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

1Applegate, 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 1The 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

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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.

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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 N2, 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.

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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

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• Materials and polymers

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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 13C-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.

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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

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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, 1Kansas Polymer Research Center, Pittsburg State University, Pittsburg, KS 66762 2Chevron 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.

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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

1School 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.

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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.

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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 1The 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

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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 Mw (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

1The 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.

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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.

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• Water and environmental chemistry

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COORDINATION POLYMERS FOR SORPTION OF ARSENIC AND PHOSPHATE FROM CONTAMINATED WATERS. Allen Apblett1, David Corter, Alan Piquette1, and Travis Reed1

1Department 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

1Department 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: [email protected]; [email protected]

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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: [email protected]

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.

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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

2University 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.

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• Poster session

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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.

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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, [email protected], (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.

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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.

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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

1Department 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

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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 1The 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.

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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 1The 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.

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A REMARKABLY SENSITIVE 13C 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 G(13COtrans) vs. G(13CN) and G(13COcis) vs. G(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 G(13CO)/G(13CN) NMR analysis serves as a convenient tool for discerning even subtle electronic differences in the V-donor/S-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 13C 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.

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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.

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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.

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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.

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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

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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

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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.

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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.

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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

1The 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.

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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.

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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

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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

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

2Department 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.

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Development of a Networked Sensor Array for Gas Microseepage Detection near Injection Well Sites; Wesley Honeycutt1, Nicholas F. Materer1, M. Tyler Ley2, Taehwan Kim2

1The Department of Chemistry, Oklahoma State University, Stillwater, OK 74078 2 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

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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.

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HYDROGEN BONDING DIRECTED PHOTOCATALYTIC HYDRODEFLUORINATION; ASELECTIVELY ACCESS TO PARTIALLY POLYFLUORINATED AROMATICS, Mohammad BaniKhaled1, Jimmie Weaver 1

1The 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.

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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 15N, 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.

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SNARFING FOR THE FUTURE: POLYFLUORINATED BUILDING BLOCKS;

Jon I. Day1, Jimmie Weaver*,1

1The 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

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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.

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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*

1Department of Chemistry, Pittsburg State University, 1701 S. Broadway, Pittsburg, KS 66762, USA

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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: [email protected] (Ram K. Gupta).

Presenting author: [email protected] (Sara Alkhalaf)

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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.

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PROMISING ACTIVATED CARBONS DERIVED FROM BIO-WASTE FOR HIGH PERFORMANCE ENERGY STORAGE DEVICES, Charith Ranaweera1, Z. Wang1, Ram K. Gupta1* , 1Department 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: [email protected] (Ram K. Gupta). Presenting author: [email protected] (Charith Ranaweera)

HIGHLY EFFICIENT ELECTROCATALYST BASED ON MOS2 FOR HYDROGEN EVOLUTION REACTION, Z. Wang1, Charith Ranaweera1, 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).

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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: [email protected] (Ram K. Gupta) Presenting author: [email protected] (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.

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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

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DFT Study of the Dissociative Adsorption of Chloro- and Dichlorobenzene on the Si(100) Surface; Eric Butson1, Qing Zhu2, Nicholas Materer1

1The 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 [email protected]

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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 Najera, C. Chem. Soc. Rev. 2011, 40, 5084−5112.

4. Sonogashira, K.; Tohda, Y.; Hagihara, N. Tetrahedron Lett. 1975, 16, 467−4470.

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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.

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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: [email protected] (Ram K. Gupta).

Presenting author: [email protected] (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

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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

1Bhishma R. Sedai, and 1Frank D. Blum 1Department 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.

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ISOCYANATE-FREE URETHANES BY THIOL-ENE REACTION

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

1Kansas Polymer Research Center, Pittsburg State University, Pittsburg, KS 66762 2Chevron 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

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(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

1Chemical, 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.

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VEGETABLE OIL BASED POLYMERCAPTANS AS CURING AGENTS FOR EPOXY RESINS, Dragana Radojcic1, Ivan Javni1, Tom Upshaw2 1Kansas Polymer Research Center, Pittsburg State University, Pittsburg, KS 66762 2Chevron 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

1The 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.

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EFFECT OF PROCESSING ON GENERAL PURPOSE AND ENGINEERING THERMOPLASTIC POLYMER PROPERTIES; Kyle Schwenker1, Vlad Jaso2, Jeanne H. Norton3

1Department 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

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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.

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14. Liu, J.; Liu, Y.; Bu, W.; Bu, J.; Sun, Y.; Du, J.; Shi, J. JACS 2014, 136(27), 9701-9709

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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

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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 1The 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 Mw (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.

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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.

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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

1Kansas Polymer Research Center, Pittsburg State University, Pittsburg, KS 66762 2Department of Chemistry, Pittsburg State University, Pittsburg, KS 66762 3Honeywell 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.