Other Chemistry Commons^™

Crystalline Nano Structures, Barry Chin Li Cheung, Joseph Reese Brewer, Nirmalendu Deo

Department of Chemistry: Faculty Publications

The present invention comprises nano obelisks and nanostructures and methods and processes for same. The nano obelisks of the present invention are advantageous structures for use as electron source emitters. For example, the ultra sharp obelisks can be used as an emitter source to generate highly coherent and high energy electrons with high current.

The Tetrafluoroborate Salt Of 4-Methoxybenzyl N-2-(Dimethylamino)Ethyl-N-Nitrosocarbamate: Synthesis, Crystal Structure And Dft Calculations, Helene Hedian, Vladimir Benin

Chemistry Faculty Publications

The tetrafluoroborate salt of 4-methoxybenzyl N-2-(dimethylamino)ethyl-N-nitrosocarbamate was prepared in two steps, via the corresponding carbamate. Its crystal structure is monoclinic, space group P21/c. The unit cell dimensions are: a = 19.499(8) Å, b = 5.877(3) Å, c = 15.757(7) Å, α = 90°, β = 110.019(7)°, γ = 90°, V = 1696.5(12) Å3, Z = 4. The structure exhibits an unexpected, pseudo-gauche conformation with respect to the C2–C3 bond, due to a stabilizing hydrogen bond between the carbonyl oxygen (O1) and the hydrogen atom at the trialkylammonium center (H3n), with a distance between them of …

Application Of Raman Spectroscopy To Lubricants, Lubricated Surfaces And Lubrication Phenomena, David W. Johnson

Chemistry Faculty Publications

Recent advances in lasers and detector technologies and the development of low-cost instruments and fiber-optic probes have brought about an explosion in the lubrication systems being studied by Raman spectroscopy. This article provides examples of the use of Raman spectroscopy in the study of lubrication phenomena, including the characterization of liquid lubricants, lubricant additives, and solid lubricants; the study of vapor-phase lubrication; and the use of coated nanoparticles as lubricants.

A Sodium Salt Of The Dimer Of Boronoterephthalic Acid Anhydride, Scott Simmons, Albert Fratini, Vladimir Benin

Chemistry Faculty Publications

The title compound, sodium bis­(6-carb­oxy-1-hy­droxy-3-oxo-1,3-dihydro-2,1-benzoxaborol-1-yl)oxidanium, Na+·C16H15B2O13-, was prepared in two steps from 2-bromo-p-xylene. Its crystal structure was determined at 140 K and has triclinic (P) symmetry. The compound presents a unique structural motif, including two units of the cyclic anhydride of boronoterephthalic acid, joined by a protonated, and thereby trivalent, oxonium center. Association in the crystal is realized by complementary hydrogen bonding of the carboxyl groups, as well as by coordination of the sodium cations to the oxygen centers on the five-membered rings.

Theoretical Investigation Of A Reported Antibiotic From The 'Miracle Tree' Moringa Oleifera, Michael Horwath, Vladimir Benin

Chemistry Faculty Publications

Moringa oleifera, sometimes called the “Miracle Tree,” has received international attention for its potential to improve health in impoverished tropical areas. In addition to high vitamin content in the leaves and pods, the tree contains compounds with antioxidant and antibacterial properties. This study focused on the theoretical investigation of the suggested structure of one antibacterial compound, “pterygospermin,” whose existence was proposed after some studies of the roots of M. oleifera. The structure of pterygospermin was first proposed by a research group working in the 1950s, but later studies have not found evidence of this compound and have instead …

Structure Function Analysis Of An Adp-Ribosyltransferase Type Iii Effector And Its Rna-Binding Target In Plant Immunity, Byeong-Ryool Jeong, Yan Lin, Anna Joe, Ming Guo, Christin Korneli, Huirong Yang, Ping Wang, Min Yu, Ronald Cerny, Dorothee Staiger, James R. Alfano, Yanhui Xu

Ronald Cerny Publications

Background: HopU1 ADP-ribosylates GRP7, suppressing plant immunity.

Results: The HopU1 structure has two novel loops required for GRP7 recognition, and HopU1 ribosylates GRP7 at an arginine in position 49 disrupting its function.

Conclusion: HopU1 targets a conserved arginine in GRP7, disabling its ability to bind immunity-related RNA.

Significance: The mechanistic details of how HopU1 recognizes its substrate reveal how HopU1 contributes to pathogenesis.

Human Fatty Acid Transport Protein 2a/Very Long Chain Acyl-Coa Synthetase 1 (Fatp2a/Acsvl1) Has A Preference In Mediating The Channeling Of Exogenous N-3 Fatty Acids Into Phosphatidylinositol, Elaina M. Melton, Ronald Cerny, Paul A. Watkins, Concetta C. Dirusso, Paul N. Black

Ronald Cerny Publications

The trafficking of fatty acids across the membrane and into downstream metabolic pathways requires their activation to CoA thioesters. Members of the fatty acid transport protein/ very long chain acyl-CoA synthetase (FATP/Acsvl) family are emerging as key players in the trafficking of exogenous fatty acids into the cell and in intracellular fatty acid homeostasis.We have expressed two naturally occurring splice variants of human FATP2 (Acsvl1) in yeast and 293T-REx cells and addressed their roles in fatty acid transport, activation, and intracellular trafficking. Although both forms (FATP2a (Mr 70,000) and FATP2b (Mr 65,000 and lacking exon3, which encodes part of the …

Overexpression Of Galnac-Transferase Galnac-T3 Promotes Pancreatic Cancer Cell Growth, Keisuke Taniuchi, Ronald Cerny, Aki Tanouchi, Kimitoshi Kohno, Norihiro Kotani, Koichi Honke, Toshiji Saibara, Michael A. Hollingsworth

Ronald Cerny Publications

O-linked glycans of secreted and membrane bound proteins play an important role in the pathogenesis of pancreatic cancer by modulating immune responses, inflammation, and tumorigenesis. A critical aspect of O-glycosylation, the position at which proteins are glycosylated with N-acetyl-galactosamine on serine and threonine residues, is regulated by the substrate specificity of UDP-GalNAc: polypeptide N-acetylgalactosaminyl-transferases (GalNAc-Ts). Thus, GalNAc-Ts regulate the first committed step in O-glycosylated protein biosynthesis, determine sites of O-glycosylation on proteins, and are important for understanding normal and carcinoma-associated O-glycosylation. We have found that one of these enzymes, GalNAc-T3, is overexpressed in …

Identification And Characterization Of The Anti-Methicillin-Resistant Staphylococcus Aureus Wap-8294a2 Biosynthetic Gene Cluster From Lysobacter Enzymogenes Oh11, Wei Zhang, Yaoyao Li, Guoliang Qian, Yan Wang, Haotong Chen, Yue-Zhong Li, Fengquan Liu, Yuemao Shen, Liangcheng Du

Department of Chemistry: Faculty Publications

Lysobactor enzymogenes strain OH11 is an emerging biological control agent of fungal and bacterial diseases. We recently completed its genome sequence and found it contains a large number of gene clusters putatively responsible for the biosynthesis of nonribosomal peptides and polyketides, including the previously identified antifungal dihydromaltophilin (HSAF). One of the gene clusters contains two huge open reading frames, together encoding 12 modules of nonribosomal peptide synthetases (NRPS). Gene disruption of one of the NRPS led to the disappearance of a metabolite produced in the wild type and the elimination of its antibacterial activity. The metabolite and antibacterial activity were …

Characterizing Rna Dynamics At Atomic Resolution Using Solution-State Nmr Spectroscopy, Jameson R. Bothe, Evgenia N. Nikolova, Catherine D. Eichhorn, Jeetender Chugh, Alexandar L. Hansen, Hashim M. Al-Hashimi

Department of Chemistry: Faculty Publications

Many recently discovered non-coding RNAs do not fold into a single native conformation, but rather, sample many different conformations along their free energy landscape to carry out their biological function. Unprecedented insights into the RNA dynamic structure landscape are provided by solution-state NMR techniques that measure the structural, kinetic, and thermodynamic characteristics of motions spanning picosecond to second timescales at atomic resolution. From these studies a basic description of the RNA dynamic structure landscape is emerging, bringing new insights into how RNA structures change to carry out their function as well as applications in RNA-targeted drug discovery and RNA bioengineering.

Corrosion Rate Trajectories Of Concreted Iron And Steel Shipwrecks And Structures In Seawater— The Weins Number, Donald L. Johnson, D. J. Medlin, L. E. Murphy, J. D. Carr, D. L. Conlin

Department of Chemistry: Faculty Publications

The Weins number (Wn) concept is proposed to predict the long-term corrosion rate of wrought iron and steel in seawater for variable marine environments. Plotted as a function of reciprocal absolute temperature, Weins numbers generate a linear plot from which the corrosion rates are calculated when temperature, oxygen concentration, and concretion thickness are known. Application of the theory of absolute reaction rates is described.

Transition States In Ei Reactions, Charles A. Kingsbury

Department of Chemistry: Faculty Publications

The pyrolysis of amine oxides, sulfoxides, selenoxides, and esters to form alkenes is believed to be a concerted reaction with a cyclic transition state. Phosphine oxides, sulfones, and nitro compounds are unreactive. This study seeks to identify reasons for the lack of reactivity of the latter. Transition states were located for all substrates progressing from RHF/3-21G* to the MP2/6-31+G(d,p) level (in certain cases). For sulfones and nitro compounds, two possible reasons for lack of reactivity were considered: (1) Atoms approaching one another in the transition state may be considered to participate in a local n_O→σ*_{CH …}

Process For Preparation Of Conducting Polymers, Reuben D. Rieke

Department of Chemistry: Faculty Publications

Methods of preparing conducting polymers and the conductive polymers prepared therefrom are provided. The method includes a) combining a monomer-metal complex together with a manganese (II) halide to provide a monomer-manga nese complex, and b) combining the monomer-manganese complex together with a metal catalyst to provide the conductive polymer. Electronic devices can be made using the polymers prepared as described herein.

Self-Assembled Heteroleptic Chiral Ligands, Asymmetric Catalyst Systems And Methods, James M. Takacs

Department of Chemistry: Faculty Publications

A method of synthesizing a heteroleptic, multiple metal containing metallocyclic catalyst, particularly Suited for asymmetric catalysis, comprising combining a plurality of plural functional group-containing, monodentate ligands of complementary chirality, said plural functional groups being tethered to each other by tethers in the presence of a scaffold structural metal Ms or derivative thereof, wherein at least one functional group on each ligand combines to ligate M to form a bidentate, M_s centered ligand scaffold containing the remaining functional groups and combining said bidentate ligand scaffold with a catalytic metal M_c or derivative thereof whereby the remaining functional groups combine …

Corrosion Of Steel Shipwreck In The Marine Environment: Uss Arizona—Part 1, Donald L. Johnson, Brent M. Wilson, James D. Carr, Matthew A. Russell, Larry E. Murphy, David L. Conlin

Department of Chemistry: Faculty Publications

The USS Arizona has remained submerged in Pearl Harbor, Hawaii, since the Japanese attack on December 7, 1941. The ship presents a potential hazard from fuel oil still present in the ship’s hull. As an important factor in management decisions, the effect of corrosion after nearly 65 years is being studied to determine the integrity of the ship’s structure. Coupon samples from the hull revealed decreasing corrosion rates from ~1 to 3 mpy (0.03 to 0.08 mm/y) from just below the water surface to the mudline. This is about one-third of that expected in the absence of biofouling or concretion. …

Supramolecular Self-Assembly Strategies Involving Water Soluble Calixarenes., Irene Ling

Student Works (2010-2019)

Fundamental investigations of host-guest interactions on the supramolecular self-assembly involving water-soluble p-sulfonatocalix[4]arene, with a series of imidazolium-based cations and pyrrolidinium cation with variable alkyl chain lengths, which featured extensively in ionic liquids have been established. Combinatorial studies incorporating multiple components concerning p-sulfonatocalix[4]arene, imidazolium cations or pyrrolidinium cation, phosphonium cations and lanthanide ions have been developed, which yielded diverse solid state motifs with a common structural characteristic that the imidazolium or pyrrolidinium cation resides in the cavity of the calixarene. Shorter terminal alkyl chain of mono-imidazolium molecules, i.e. n-ethyl and n-butyl imidazoliums are confined in the „molecular capsule‟, being encapsulated by …

Improved Arene Fluorination Methodology For I(Iii) Salts, Bijia Wang, Linlin Qin, Kiel D. Neumann, Shriharsha Uppaluri, Ronald Cerny, Stephen G. Dimagno

Ronald Cerny Publications

The use of low polarity aromatic solvents (benzene or toluene) and/or the removal of inorganic salts results in dramatically improved yields of fluorinated arenes from diaryliodonium salts. This methodology is shown to “scale down” to the conditions used typically for radiotracer synthesis.

Corrosion Of Steel Shipwrecks In The Marine Environment: Uss Arizona—Part 2, Donald L. Johnson, Brent M. Wilson, James D. Carr, Matthew A. Russell, Larry E. Murphy, David L. Conlin

Department of Chemistry: Faculty Publications

This article is a continuation of Part 1 (October 2006 MP) on the USS Arizona hull. It discusses additional methods being investigated for use in determining corrosion rates with a minimal impact on the existing structure. Marine biofouling (concretion) has accumulated on the hull. Concretion samples have been studied using x-ray diffraction, environmental electron microscopy, and corrosion potential (E_corr) to characterize the relationship between concretion and the steel substrate. The data presented in this study confirm the viability of concretion analysis as a minimum-impact procedure to estimate the corrosion rate of mild steel in seawater.

Corrosion Of Civil War Era Sub Marine Explorer—Part 2, Donald L. Johnson, James D. Carr, Brent M. Wilson, Larry E. Murphy, James P. Delgado

Department of Chemistry: Faculty Publications

The Sub Marine Explorer was designed and built by Julius H. Kroehl, who was born in Prussia in 1820. After migrating to the United States in 1838 and becoming a citizen, he served in the Union Navy (United States Navy during the Civil War) as an underwater demolitions expert. He left the Navy in 1863 and began designing a “sub-marine” that would facilitate Union forces’ mine removal and obstruction clearance. At the end of the Civil War, he became an engineer for the Pacific Pearl Co., an organization interested in using the craft to recover pearls from deep sea oyster …

Corrosion Of Civil War Era Sub Marine Explorer—Part 1, Donald L. Johnson, James D. Carr, Brent M. Wilson, Larry E. Murphy, James P. Delgado

Department of Chemistry: Faculty Publications

The Sub Marine Explorer is one of five submersibles (submarines) constructed prior to 1870 that have survived either in museums or as in situ archaeological sites around the world. Since 1869, the wreck of Explorer has emerged at low tide on the beach of Isla San Telmo, Archipiélago de las Perlas, Panama, located ~75 km southwest of Panama City in the Bay of Panama. In 2001, James Delgado visited the site. Locals described the wreck as a World War II-era Japanese midget submarine. Delgado consulted with Richard Wills, an expert on American Civil War submarines, and confirmed that the well-preserved …

Method For Monitoring The Stereoselectivity And Relative Rate Of Organic Chemical Reactions, David R. Berkowitz, Sangeeta Dey, Kannan R. Karukurichi, Weijun Shen

Department of Chemistry: Faculty Publications

A method for monitoring the stereoselectivity of at least one organic chemical reaction and the relative rate of at least one organic chemical reaction, wherein the reaction produces a product that can exist as at least two stereoisomers, is provided herein. Also disclosed are methods for identifying and preparing catalysts for the above reactions.

Immobilization Method For Producing Active Α1-Acid Glycoprotein, David S. Hage, Hai Xuan

Department of Chemistry: Faculty Publications

A method and kit for immobilization of a glycoprotein. The method may include activating an affinity Support. The affinity Support may be activated by reacting the affinity Support with a compound that is reactive with one or more functional groups included within the glycoprotein. The method may also include oxidizing the glycoprotein in which oxidation conditions are selected to yield an oxidized glycoprotein that is biologically active and contains a Sufficient number of reactive aldehyde groups for coupling to a Support. For example, the oxidized glycoprotein may include five reactive aldehyde groups. In addition, the method may include reacting the …

Preparation And Characterization Of Some Substituted Benzyl N-Nitrosocarbamates Containing An N-2-(Methylthio)Ethyl Or A Bis(2-Aminoethyl)Sulfide Functionality, Satya Venkata, Eric Shamo, Vladimir Benin

Chemistry Faculty Publications

The synthesis and characterization of some substituted benzyl N-nitrosocarbamates with an N-2-(methylthio)ethyl or a bis(2-aminoethyl)sulfide functionality is reported, as a part of a long-term goal to design and prepare novel photolabile structures that could be used as substances for controlled release of alkylating and/or crosslinking agents. The synthesis was accomplished by reaction of benzyl chloroformates with the corresponding amines, resulting in the preparation of carbamates. The latter were subsequently nitrosated, utilizing two different N-nitrosation methods, to yield the target structures.

Androgen-Stimulated Udp-Glucose Dehydrogenase Expression Limits Prostate Androgen Availability Without Impacting Hyaluronan Levels, Qin Wei, Robert Galbenus, Ashraf Raza, Ronald Cerny, Melanie A. Simpson

Ronald Cerny Publications

UDP-glucose dehydrogenase (UGDH) oxidizes UDP-glucose to UDP-glucuronate, an essential precursor for production of hyaluronan (HA), proteoglycans, and xenobiotic glucuronides. High levels of HA turnover in prostate cancer are correlated with aggressive progression. UGDH expression is high in the normal prostate even though HA accumulation is virtually undetectable. Thus, its normal role in the prostate may be to provide precursors for glucuronosyltransferase enzymes, which inactivate and solubilize androgens by glucuronidation. In this report, we quantified androgen dependence of UGDH, glucuronosyltransferase, and HA synthase expression. Androgen dependent and independent human prostate cancer cell lines were used to test the effects of UGDH …

A Multi-Step Nmr Screen For The Identification And Evaluation Of Chemical Leads For Drug Discovery, Kelly A. Mercier, Matthew D. Shortridge, Robert Powers

Department of Chemistry: Faculty Publications

A multi-step NMR based screening assay is described for identifying and evaluating chemical leads for their ability to bind a target protein. The multi-step NMR assay provides structure-related information while being an integral part of a structure based drug discovery and design program. The fundamental principle of the multi-step NMR assay is to combine distinct 1D and 2D NMR techniques, in such a manner, that the inherent strengths and weakness associated with each technique is complementary to each other in the screen. By taking advantage of the combined strengths of 1D and 2D NMR experiments, it is possible to minimize …

Anhydrous Fluoride Salts And Reagents And Methods For Their Production, Stephen G. Dimagno, Haoran Sun

Department of Chemistry: Faculty Publications

Anhydrous organic fluoride salts and reagents prepared by a method comprising the nucleophilic Substitution of a fluorinated aromatic or fluorinated unsaturated organic compound with a salt having the formula: [Q_nM]^x+A_x^- in an inert polar, aprotic solvent; wherein M is an atom capable of supporting a formal positive charge, the n groups Q are independently varied organic moieties, n is an integer such that the [Q_nM] carries at least one formal positive charge, x is an integer defining the number of formal positive charge(s), +, carried by the [Q_nM], A^{- …}

Preparation Of Halogenated Derivatives Of Thiazolo[5,4-D]Thiazole Via Direct Electrophilic Aromatic Substitution, Vladimir Benin, Alan T. Yeates, Douglas Dudis

Chemistry Faculty Publications

Chlorination and bromination reactions of thiazolo[5,4-d]thiazole led to the generation of its mono- and dihalogenated derivatives. These are the first instances of successful direct electrophilic aromatic substitution in the thiazolo[5,4-d]thiazole ring system. X-ray analysis demonstrates that both 2-bromothiazolo[5,4-d]-thiazole and 2,5-dibromothiazolo[5,4-d]thiazole are planar structures, with strongly manifested π-stacking in the solid state. Theoretical analysis of the pyridine-catalyzed halogenation (MP2/6-31+G(d) and B3LYP/6-31+G(d)calculations) reveals that introduction of one halogen actually leads to a slightly enhanced reactivity towards further halogenation. Several halogenation mechanisms have been investigated: 1) The direct C-halogenation with N-halopyridine as electrophile; …

C–N Bond Rotation And E–Z Isomerism In Some N-Benzyl-N-Methylcarbamoyl Chlorides: A Dft Study, Michael Horwath, Vladimir Benin

Chemistry Faculty Publications

The current report presents the first theoretical study of the restricted CN bond rotation in carbamoyl chlorides. Several N-benzyl-N-methylcarbamoyl chlorides were investigated, with varying pattern of substitution in the aromatic ring. Optimizations and frequency calculations were conducted employing DFT at the B3LYP/6-31+G(d) level of theory. Each of the studied structures exhibits a pair of rotamers (s-Z and s-E), generated upon rotation around the C(O)N bond. The s-E isomer is the global minimum in every case, but the preference for it is usually less than 1 kcal/mol. Two possible transition state structures were identified …

Phosphorylation Of Claudin-5 And Occludin By Rho Kinase In Brain Endothelial Cells, Masaru Yamamoto, Servio H. Ramirez, Shinji Sato, Tomomi Kiyota, Ronald Cerny, Kozo Kaibuchi, Yuri Persidsky, Tsuneya Ikezu

Ronald Cerny Publications

Critical to the proper maintenance of blood-brainbarrier (BBB) integrity are the endothelial tight junctions (TJs). Posttranslational modifications of essential endothelial TJ proteins, occludin and claudin-5, contribute and possibly disrupt BBB integrity. Our previous work has shown that Rho kinase (RhoK) activation mediates occludin and claudin-5 phosphorylation resulting in diminished barrier tightness and enhanced monocyte migration across BBB in the setting of human immunodeficiency virus-1 encephalitis (HIVE). To determine whether RhoK can directly phosphorylate TJ proteins, we examined phosphorylation of cytoplasmic domains of recombinant claudin- 5 and occludin by RhoK. We found that RhoK predominately phosphorylated two sites on occludin (T382 …

Methods In Industrial Biotechnology For Chemical Engineers, Florentin Smarandache, W.B. Vasantha Kandasamy

Branch Mathematics and Statistics Faculty and Staff Publications

Industrial Biotechnology is an interdisciplinary topic to which tools of modern biotechnology are applied for finding proper proportion of raw mix of chemicals, determination of set points, finding the flow rates etc., This study is significant as it results in better economy, quality product and control of pollution. The authors in this book have given only methods of industrial biotechnology mainly to help researchers, students and chemical engineers. Since biotechnology concerns practical and diverse applications including production of new drugs, clearing up pollution etc. we have in this book given methods to control pollution in chemical industries as it has …