Other Chemistry Commons^™

Fluorination Of Aromatic Ring Systems, Stephen G. Dimagno

Department of Chemistry: Faculty Publications

This disclosure relates to reagents and methods useful in the synthesis of aryl fluorides, for example, in the preparation of ¹⁸F labeled radiotracers. The reagents and methods provided herein may be used to access a broad range of compounds, including aromatic compounds, heteroaromatic compounds, amino acids, nucleotides, and synthetic compounds.

Phosphate Esters, Thiophosphate Esters And Metal Thiophosphates As Lubricant Additives, David W. Johnson, John E. Hils

Chemistry Faculty Publications

Phosphate esters, thiophosphate esters and metal thiophosphates have been used as lubricant additives for over 50 years. While their use has been extensive, a detailed knowledge of how they work has been a much more recent development. In this paper, the use of phosphate esters and thiophosphate esters as anti-wear or extreme pressure additives is reviewed with an emphasis on their mechanism of action. The review includes the use of alkyl phosphates, triaryl phosphates and metal containing thiophosphate esters. The mechanisms of these materials interacting with a range of iron and steel based bearing material are examined.

Structure, Theoretical Studies And Coupling Reactions Of Some New Cyclic Boronic Esters, Andrew Kuttler, Sravanthi Durganala, Albert Fratini, Alexander Morgan, Vladimir Benin

Chemistry Faculty Publications

The present report describes the X-ray structural and theoretical studies of some new pinacolboronate esters, and it also outlines the use of the target structures in Suzuki coupling reactions to produce new aromatic or heteroaromatic esters and amides. X-ray structural analysis of the studied compounds revealed that the pinacolborane ring's position with respect to the benzene ring varies, depending on the particular environment. An ortho-positioned carboxylic ester (methyl ester) causes a nearly perpendicular orientation of the pinacolborane unit with respect to the benzene ring, whereas an ortho-positioned amide (N,N-dimethylamide) causes the pinacolborane unit to orient itself nearly coplanar. A plausible …

Characterization By Nmr Of Reactants And Products Of Hydrofluoroether Isomers, Cf3(Cf2)3och3 And (Cf3)2c(F)Cf2och3, Reacting With Isopropyl Alcohol, Howard Knachel, Vladimir Benin, William E. Moddeman, Janine C. Birkbeck, Thomas A. Kestner, Tayna L. Young

Chemistry Faculty Publications

The 3M Company product Novec™ 71IPA DL, a mixture of methoxyperfluorobutane, methoxyperfluoroisobutane and 4.5 wt.% isopropyl alcohol, has been found to be very stable at ambient temperature, producing fluoride at the rate of ~1 ppm/year. Our earlier kinetic and theoretical studies have identified the reaction mechanism. This paper identifies the ¹H and ¹⁹F NMR chemical shifts, multiplicities, and coupling constants of reactants and the major products that result from aging the mixture in sealed Pyrex NMR tubes for periods up to 1.8 years at temperatures from 26 °C to 102 °C. Chemical shifts and coupling constants of fluorine …

Interaction Between Lubricants Containing Phosphate Ester Additives And Stainless Steels, David W. Johnson, Matthew Bachus, John E. Hils

Chemistry Faculty Publications

One way to improve fuel efficiency in today’s jet aircraft engines is to create an environment for higher operating temperatures and speeds. New and improved lubricants and bearing materials must be developed to remain stable in these elevated operating temperatures. Three lubricants, with varying amounts of tricresyl phosphate added as an anti-wear/extreme pressure additive were tested on two different stainless steels at varying temperatures ranging from 300 °C to 350 °C in vacuum. Significant decomposition of the lubricant base-stocks and the phosphate ester additive did occur in most of the trials resulting in the formation of carboxylic acids and phenols. …

Overexpression Of Human Fatty Acid Transport Protein 2/Very Long Chain Acyl-Coa Synthetase 1 (Fatp2/Acsvl1) Reveals Distinct Patterns Of Trafficking Of Exogenous Fatty Acids, Elaina M. Melton, Ronald Cerny, Concetta C. Dirusso, Paul N. Black

Ronald Cerny Publications

In mammals, the fatty acid transport proteins (FATP1 through FATP6) are members of a highly conserved family of proteins, which function in fatty acid transport proceeding through vectorial acylation and in the activation of very long chain fatty acids, branched chain fatty acids and secondary bile acids. FATP1, 2 and 4, for example directly function in fatty acid transport and very long chain fatty acids activation while FATP5 does not function in fatty acid transport but activates secondary bile acids. In the present work, we have used stable isotopically labeled fatty acids differing in carbon length and saturation in cells …

A Facile, Low-Cost Route For The Preparation Of Calcined Porous Calcite And Dolomite And Their Application As Heterogeneous Catalysts In Biodiesel Production, Rui Wang, Hu Li, Fei Chang, Jiafeng Luo, Milford A. Hanna, Daoyang Tan, Deyu Hu, Yuping Zhang, Baoan Song, Song Yang

Department of Chemistry: Faculty Publications

Despite their potential for biodiesel synthesis, directly calcined minerals rich in magnesium/calcium carbonates are used at the expense of large amounts of the catalyst, high alcohol loading, long processing times, and severe conditions. We report a facile and low-cost route for preparing calcined porous calcite (CPC) and dolomite (CPD) via simple thermal decomposition of the reaction mixtures of natural calcite and dolomite with stearic acid. CPC and CPD, both of which have porous structures, were compared with previously reported catalysts and examined as promising heterogeneous base catalysts under mild conditions. A 40% increase in conversion through CPC and CDC was …

Re2o7-Catalyzed Reaction Of Hemiacetals And Aldehydes With O-, S-, And C-Nucleophiles, Wantanee Sittiwong, Michael W. Richardson, Charles E. Schiaffo, Thomas J. Fisher, Patrick H. Dussault

Department of Chemistry: Faculty Publications

Re(VII) oxides catalyze the acetalization, monoperoxyacetalization, monothioacetalization and allylation of hemiacetals. The reactions, which take place under mild conditions and at low catalyst loadings, can be conducted using hemiacetals, the corresponding O-silyl ethers, and, in some cases, the acetal dimers. Aldehydes react under similar conditions to furnish good yields of dithioacetals. Reactions of hemiacetals with nitrogen nucleophiles are unsuccessful. 1,2-Dioxolan-3-ols (peroxyhemiacetals) undergo Re(VII)-promoted etherification but not allylation. Hydroperoxyacetals (1-alkoxyhydroperoxides) undergo selective exchange of the alkoxide group in the presence of either Re₂O₇ or a Brønsted acid.

Stress Reduction For Pillar Filled Structures, Rebecca J. Nikolic, Adam Conway, Qinghui Shao, Lars Voss, Chin Li Cheung, Mushtaq A. Dar

Department of Chemistry: Faculty Publications

According to one embodiment, an apparatus for detecting neutrons includes an array of pillars, wherein each of the pillars comprises a rounded cross sectional shape where the cross section is taken perpendicular to a longitudinal axis of the respective pillar, a cavity region between each of the pillars, and a neutron sensitive material located in each cavity region.

Preparation Of Phosphonoterephthalic Acids Via Palladium-Catalyzed Coupling Of Aromatic Iodoesters, Nathaniel Ivan, Vladimir Benin, Alexander Morgan

Chemistry Faculty Publications

The current article reports in detail the preparation of two phosphonoterephthalic acids: 2-phosphonoterephthalic acid (1) and 2,5-diphosphonoterephthalic acid (2). Efficient, scalable syntheses have been developed for both compounds based on Pd-catalyzed coupling reactions of iodinated terephthalate esters. Phosphonoterephthalic acids are potentially useful as flame-retardant additives or as monomers for the construction of acid-pendant polymer chains.

High-Performance Flexible Solid-State Supercapacitors Based On Mno2-Decorated Nanocarbon Electrodes, Yang Gao, Yun Shen Zhou, Min Qian, Hao Ming Li, Jody G. Redepenning, Li Sha Fan, Xiang Nan He, Wei Xiong, Masoud Majhouri-Samani, Lan Jiang, Yongfeng Lu

Department of Chemistry: Faculty Publications

Flexible energy storage units are highly desired to meet the ever-increasing demands for flexible electronics. In this paper, highly flexible solid-state supercapacitors are fabricated using MnO₂-decorated nanocarbon electrodes and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide–poly(vinylidene fluoride)- hexafluoropropylene ([EMIM][NTf2]–PVdF(HFP)) gel electrolytes. The flexible electrodes are prepared by electrodepositing MnO₂ onto the carbon nanotube/carbon nanoonion (CNT/CNO) films. CNT/CNO films have a large surface area for MnO₂ deposition and work as mechanical supports with high flexibility and light weight. CNOs act as spacers to separate CNTs, introducing mesopores inside the CNT/CNO films for preventing pore blocking during MnO₂ deposition. The supercapacitor exhibits …

Probing The Bifunctional Catalytic Activity Of Ceria Nanorods Towards The Cyanosilylation Reaction, Gonghua Wang, Lu Wang, Xiang Fei, Yunyun Zhou, Renat F. Sabirianov, Wai Ning Mei, Chin Li Cheung

Department of Chemistry: Faculty Publications

Ceria nanorods were demonstrated to be an active, bifunctional catalyst for the cyanosilylation of aldehydes. The catalytic activity of ceria was shown to be positively correlated with a decrease in the coordination numbers of neighbouring oxygen atoms around cerium atoms in the catalyst. Chemisorption and density functional theory studies suggested that the coordinatively unsaturated cerium sites exposed by the surface oxygen vacancy defects functioned as Lewis acid sites and the neighbouring oxygen atoms behaved as Lewis base sites in the catalytic cycle.

An Expanded Genetic Code In Mammalian Cells With A Functional Quadruplet Codon, Wei Niu, Peter G. Schultz, Jiantao Guo

Department of Chemistry: Faculty Publications

We have utilized in vitro evolution to identify tRNA variants with significantly enhanced activity for the incorporation of unnatural amino acids into proteins in response to a quadruplet codon in both bacterial and mammalian cells. This approach will facilitate the creation of an optimized and standardized system for the genetic incorporation of unnatural amino acids using quadruplet codons, which will allow the biosynthesis of biopolymers that contain multiple unnatural building blocks.

Reaction Between Polyol-Esters And Phosphate Esters In The Presence Of Metal Carbides, David W. Johnson, Carolyn Iacullo, John E. Hils

Chemistry Faculty Publications

The reaction of metal carbides with polyol esters found in aerospace lubricants and phosphate esters commonly used as additives was investigated. Carbides were of particular interest since modern materials under consideration at high temperature bearings have surfaces that are primarily metal carbides. Vanadium and chromium carbide were found to react with the ester and phosphate ester by a transesterification reaction, producing an alkyl phosphate which is less stable than the aromatic phosphate esters. In the process, the metal carbide is converted to the metal phosphate and metal polyphosphate, evidenced by the infrared and Raman spectra of the solid residue and …

Probing The Bifunctional Catalytic Activity Of Ceria Nanorods Towards The Cyanosilylation Reaction, Gonghua Wang, Lu Wang, Xiang Fei, Yunyun Zhou, Renat F. Sabirianov, Wai-Ning Mei, Chin Li Cheung

Department of Chemistry: Faculty Publications

Ceria nanorods were demonstrated to be an active, bifunctional catalyst for the cyanosilylation of aldehydes. The catalytic activity of ceria was shown to be positively correlated with a decrease in the coordination numbers of neighbouring oxygen atoms around cerium atoms in the catalyst. Chemisorption and density functional theory studies suggested that the coordinatively unsaturated cerium sites exposed by the surface oxygen vacancy defects functioned as Lewis acid sites and the neighbouring oxygen atoms behaved as Lewis base sites in the catalytic cycle.

Porous Polymer Coatings As Substrates For The Formation Of High-Fidelity Micropatterns By Quill-Like Pens, Michael Hirtz, Marcus Lyon, Wenqian Feng, Andrea E. Holmes, Harald Fuchs, Pavel A. Levkin

Department of Chemistry: Faculty Publications

We explored the potentials of microarray printing using quill-like microcantilevers onto solid supports that are typically used in microspot printing, including paper, polymeric nitrocellulose and nylon membranes. We compared these membranes with a novel porous poly(2-hydroxyethyl methacrylate-co-ethylene dimethacrylate) support (HEMA) with narrow pore size distribution in the 150 nm range, which demonstrated advantages in pattern definition, spot homogeneity, and consistent spot delivery of different dyes (phloxine B and bromophenol blue) with diameters of several micrometres. The bromophenol blue arrays on HEMA support were used to detect the presence of bovine serum albumin (BSA). In the presence of BSA, …

Single Transcriptional And Translational Preq1 Riboswitches Adopt Similar Pre-Folded Ensembles That Follow Distinct Folding Pathways Into The Same Ligand-Bound Structure, Krishna C. Suddala, Arlie J. Rinaldi, Jun Feng, Anthony M. Mustoe, Catherine D. Eichhorn, Joseph A. Liberman, Joseph E. Wedekind, Hashim M. Al-Hashimi, Charles L. Brooks Iii, Nils G. Walter

Department of Chemistry: Faculty Publications

Riboswitches are structural elements in the 50 untranslated regions of many bacterial messenger RNAs that regulate gene expression in response to changing metabolite concentrations by inhibition of either transcription or translation initiation. The preQ₁ (7-aminomethyl-7-deazaguanine) riboswitch family comprises some of the smallest metabolite sensing RNAs found in nature. Once ligand-bound, the transcriptional Bacillus subtilis and translational Thermoanaerobacter tengcongensis preQ₁ riboswitch aptamers are structurally similar RNA pseudoknots; yet, prior structural studies have characterized their ligand-free conformations as largely unfolded and folded, respectively. In contrast, through single molecule observation, we now show that, at nearphysiological Mg²⁺ concentration and pH, …

Iodonium Cyclophanes For Secure Arene Functionalization, Stephen Dimagno

Department of Chemistry: Faculty Publications

This disclosure relates to compounds, reagents, and methods useful in the synthesis of aryl fluorides, for example, in the preparation of 18F labeled radiotracers. For example, this disclosure provides universal “locked” aryl substituents that result in StereoElectronic Control of Unidirectional Reductive Elimination (SECURE) from diaryliodonium salts. The reagents and methods provided herein may be used to access a broad range of compounds, including aromatic compounds, heteroaromatic compounds, amino acids, nucleotides, and synthetic compounds.

Application Of Pyrolysis-Gc/Ms To The Study Of Biomass And Biomass Constituents, Anne E. Ware

Theses and Dissertations--Chemistry

Fast pyrolysis, the rapid thermal decomposition of organic material in the absence of oxygen, is a process that can be used to convert biomass into liquid fuels and chemicals. When performed at the micro-scale, pyrolysis is useful for characterizing biomass structure, as well as determining the pyrolysis products that can be generated from specific biomass feedstocks. Indeed, microscale pyrolysis coupled with on-line analysis of the pyrolysis vapors by GC/MS, so-called pyrolysis-GC/MS (Py-GC/MS), is a technique that can be used to characterize the structure and composition of the various components of lignocellulosic and microalgal biomass based on their pyrolysate distributions. Pyrolysates …

Reactions Of Methyl Perfluoroalkyl Ethers With Isopropyl Alcohol: Experimental And Theoretical Studies, Howard Knachel, Vladimir Benin, Chadwick Barklay, Janine C. Birkbeck, Billy D. Faubion, William E. Moddeman

Chemistry Faculty Publications

The reaction of an isomeric mixture of the methyl perfluoroalkyl ether, C4F9OCH3 (Novec-7100), in the presence of isopropyl alcohol (IPA) and/or water has been studied by measuring the rate of product formation using an ion-selective electrode (ISE) for fluoride ion, Karl Fisher coulometric titrations for water, and 1H and 19F NMR spectroscopy for product identification and rate studies. The results showed the methyl perfluoroalkyl ether to be very stable with products forming at the rate of ∼1 ppm per year at a laboratory temperature of 20 °C. Measurements over the temperature range of 6° to 100 °C were made on …

Cloning And Characterization Of Sas0754, A Hypothetical Protein From Community Associated Staphylococcus Aureus, Unknown Unknown

Symposium 2012

Community associated Staphylococcus aureus (strain MSSA476) is a gram positive cocci capable of infecting many different parts of the body and known to cause serious infections that can be fatal, such as bacterial arthritis and acute endocarditis. To find effective ways of fighting against CA-MRSA strains we must learn more about their ability to infect. The focus of this study was cloning and characterization of a protein referred to as SAS0754. The size of SAS0754 is 340 amino acids and the gene sequence is 1023 nucleotides. The hypothetical function of this protein is that it is an extracellular matrix binding …

A Convenient Synthesis Of 2,6-Dichlorohomonicotinic Acid, Chase Buchanan, Richard W. Fitch

Symposium 2012

In our synthetic efforts toward the alkaloid phantasmidine, we required a convenient source of the title compound. Herein, we describe a short synthesis of 2,6-dichlorohomonicotinic acid by direct allylation of 2,6-dichloropyridine with LDA/allyl chloride, followed by permanganate oxidation of the side chain [figure1]. Yields for the allylation are high, while permanganate oxidation required more adjustment. Successful conditions require the modest acidification of the mixture with acetic acid and cleanup by acid base workup. No chromatography is needed.

Convenient Parallel Synthesis Of Alkyl- And Aryl-S-Tert-Butyl Thiothers, Rebecca Norcross, Jessica Stanfield, Richard W. Fitch

Symposium 2012

While preparing novel cysteine derivatives as oxidation catalysts, we needed S-tert-butylcysteine. We also examined acid-promoted tert-butylation of thiols using tert-butanol as reagent and solvent. While cysteine and aminoethanethiol work well using tBuOH in 4M HCl, other thiols fail in the aqueous environment and aerobic conditions. We examined a variety of aliphatic and aromatic thiols in tBuOH with H2SO4 catalysis and found that argon sparging and the use of 1 eq of acid led to good yields in a parallel format.

Identification And Analysis Of Stereoselective Drug Interactions With Low Density Lipoprotein By High-Performance Affinity Chromatography, Matt Sobansky, David S. Hage

Department of Chemistry: Faculty Publications

Columns containing immobilized low density lipoprotein (LDL) were prepared for the analysis of drug interactions with this agent by high-performance affinity chromatography (HPAC). R/SPropranolol was used as a model drug for this study. The LDL columns gave reproducible binding to propranolol over 60 h of continuous use in the presence of pH 7.4, 0.067 M potassium phosphate buffer. Experiments conducted with this type of column through frontal analysis indicated that two types of interactions were occurring between R-propranolol and LDL, while only a single type of interaction was observed between S-propranolol and LDL. The first type …

Unusual Activities Of The Thioesterase Domain For The Biosynthesis Of The Polycyclic Tetramate Macrolactam Hsaf In Lysobacter Enzymogenes C3, Lili Lou, Haotong Chen, Ronald Cerny, Yaoyao Li, Yuemao Shen, Liangcheng Du

Ronald Cerny Publications

HSAF is an antifungal natural product with a new mode of action. A rare bacterial iterative PKSNRPS assembles the HSAF skeleton. The biochemical characterization of the NRPS revealed that the thioesterase (TE) domain possesses the activities of both a protease and a peptide ligase. Active site mutagenesis, circular dichroism spectra and homology modeling of the TE structure suggested that the TE may possess uncommon features that may lead to the unusual activities. The iterative PKS-NRPS is found in all polycyclic tetramate macrolactam gene clusters, and the unusual activities of the TE may be common to this type of hybrid PKS-NRPS.

Dynamic Light Scattering And Microelectrophoresis: Main Prospects And Limitations, Vuk Uskoković

Pharmacy Faculty Articles and Research

Microelectrophoresis based on the dynamic light scattering (DLS) effect has been a major tool for assessing and controlling the conditions for stability of colloidal systems. However, both the DLS methods for characterization of the hydrodynamic size of dispersed submicron particles and the theory behind the electrokinetic phenomena are associated with fundamental and practical approximations that limit their sensitivity and information output. Some of these fundamental limitations, including the spherical approximation of DLS measurements and an inability of microelectrophoretic analyses of colloidal systems to detect discrete charges and differ between differently charged particle surfaces due to rotational diffusion and particle orientation …

Synthesis And Flame Retardant Testing Of New Boronated And Phosphonated Aromatic Compounds, Vladimir Benin, Sravanthi Durganala, Alexander Morgan

Chemistry Faculty Publications

The present report describes the preparation and use of some dimethyl terephthalate derivatives in transition metal-catalyzed coupling reactions to produce new reactive flame retardants. Dimethyl iodoterephthalate and dimethyl 2,5-diiodoterephthalate were successfully employed in the preparation of phosphonic and boronic esters and acids. The latter were tested for heat release with a microcombustion calorimeter (ASTM D7309) to determine the potential for heat release reduction of these flame retardant molecules. The results showed that the addition of boronic or phosphonic acids greatly lowered the heat release, due to a condensed phase (char formation) mechanism. Adding ester groups to the boronic acids or …

Quantitative Analysis Of Some Important Metals And Metalloids In Tobacco Products By Inductively Coupled Plasma-Mass Spectrometry (Icp-Ms), Syed Ghulam Musharraf, Muhammad Shoaib, Amna Jabbar Siddiqui, Muhammad Najam-Ul-Haq, Aftab Ahmed

Pharmacy Faculty Articles and Research

Background: Large scale usage of tobacco causes a lot of health troubles in human. Various formulations of tobacco are extensively used by the people particularly in developing world. Besides several toxic tobacco constituents some metals and metalloids are also believed to pose health risks. This paper describes inductively coupled plasma-mass spectrometric (ICP-MS) quantification of some important metals and metalloids in various brands of smoked, sniffed, dipped and chewed tobacco products.

Results: A microwave-assisted digestion method was used for sample preparation. The method was validated by analyzing a certified reference material. Percentage relative standard deviation (% R.S.D.) between recovered …

Ccpa Regulates Arginine Biosynthesis In Staphylococcus Aureus Through Repression Of Proline Catabolism, Austin S. Nuxoll, Steven M. Halouska, Marat R. Sadykov, Mark L. Hanke, Kenneth W. Bayles, Tammy Kielian, Robert Powers, Paul D. Fey

Department of Chemistry: Faculty Publications

Staphylococcus aureus is a leading cause of community-associated and nosocomial infections. Imperative to the success of S. aureus is the ability to adapt and utilize nutrients that are readily available. Genomic sequencing suggests that S. aureus has the genes required for synthesis of all twenty amino acids. However, in vitro experimentation demonstrates that staphylococci have multiple amino acid auxotrophies, including arginine. Although S. aureus possesses the highly conserved anabolic pathway that synthesizes arginine via glutamate, we demonstrate here that inactivation of ccpA facilitates the synthesis of arginine via the urea cycle utilizing proline as a substrate. Mutations within putA, rocD, …

Unraveling The Structural Complexity In A Single-Stranded Rna Tail: Implications For Efficient Ligand Binding In The Prequeuosine Riboswitch, Catherine D. Eichhorn, Jun Feng, Krishna C. Suddala, Nils G. Walter, Charles L. Brooks Iii, Hashim M. Al-Hashimi

Department of Chemistry: Faculty Publications

Single-stranded RNAs (ssRNAs) are ubiquitous RNA elements that serve diverse functional roles. Much of our understanding of ssRNA conformational behavior is limited to structures in which ssRNA directly engages in tertiary interactions or is recognized by proteins. Little is known about the structural and dynamic behavior of free ssRNAs at atomic resolution. Here, we report the collaborative application of nuclear magnetic resonance (NMR) and replica exchange molecular dynamics (REMD) simulations to characterize the 12 nt ssRNA tail derived from the prequeuosine riboswitch. NMR carbon spin relaxation data and residual dipolar coupling measurements reveal a flexible yet stacked core adopting an …