Analytical Chemistry Commons^™

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.

Classification And Cluster Analysis Of Complex Time-Of-Flight Secondary Ion Mass Spectrometry For Biological Samples, Stephen E. Reichenbach, Xue Tian, Qingping Tao, Alex Henderson

School of Computing: Conference and Workshop Papers

Identifying and separating subtly different biological samples is one of the most critical tasks in biological analysis. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) is becoming a popular and important technique in the analysis of biological samples, because it can detect molecular information and characterize chemical composition. ToF-SIMS spectra of biological samples are enormously complex with large mass ranges and many peaks. As a result the classification and cluster analysis are challenging. This study presents a new classification algorithm, the most similar neighbor with a probability-based spectrum similarity measure (MSN- PSSM), which uses all the information in the entire ToF- SIMS …

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 …

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^{- …}

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 …

Phosphorylation Of Muc1 By Met Modulates Interaction With P53 And Mmp1 Expression, Pankaj K. Singh, Michelle E. Behrens, John P. Eggers, Ronald Cerny, Jennifer M. Bailey, Kandavel Shanmugam, Sandra J. Gendler, Eric P. Bennett, Michael A. Hollingsworth

Ronald Cerny Publications

MUC1, a transmembrane mucin, is a key modulator of several signaling pathways that affect oncogenesis, motility, and cell morphology. The interaction of MUC1 cytoplasmic tail (MUC1CT) with signal transducers and its nuclear translocation and subsequent biological responses are believed to be regulated by phosphorylation status, but the precise mechanisms by which this occurs remain poorly defined. We detected a novel association between the Met receptor tyrosine kinase and the MUC1CT. Met catalyzed phosphorylation of tyrosine at YHPM in the MUC1CT. Stimulation of S2-013.MUC1F pancreatic cancer cells with hepatocyte growth factor facilitated nuclear localization of MUC1CT, as determined by real time …

Structure And Biosynthesis Of Heat-Stable Antifungal Factor (Hsaf), A Broad-Spectrum Antimycotic With A Novel Mode Of Action, Fengan Yu, Kathia Zaleta-River, Xiangcheng Zhu, Justin Huffman, Jeffrey C. Millet, Steven D. Harris, Gary Y. Yuen, Xing-Cong Li, Liangcheng Du

Department of Chemistry: Faculty Publications

A screen for antifungal compounds from Lysobacter enzymogenes strain C3, a bacterial biological control agent of fungal diseases, has previously led to the isolation of heat-stable antifungal factor (HSAF). HSAF exhibits inhibitory activities against a wide range of fungal species and shows a novel mode of antifungal action by disrupting the biosynthesis of a distinct group of sphingolipids. We have now determined the chemical structure of HSAF, which is identical to that of dihydromaltophilin, an antifungal metabolite with a unique macrocyclic lactam system containing a tetramic acid moiety and a 5,5,6-tricyclic skeleton. We have also identified the genetic locus responsible …

Corrosion Studies On The Uss Arizona With Application To A Japanese Midget Submarine, Brent M. Wilson, Donald L. Johnson, Hans Vantilburg, Matthew A. Russell, Larry E. Murphy, James D. Carr, Robert J. De Angelis, David L. Conlin

Department of Chemistry: Faculty Publications

The assessment of corrosion on the USS Arizona included the pioneering development of a minimum-impact cost-effective technique to determine the corrosion rate of steel-hulled shipwrecks in seawater. The technique, with potential application worldwide, is illustrated in this paper with the application to a World War II Japanese midget submarine submerged in deep waters off the Oahu, Hawaii, coast.

A Minimum-Impact Method For Measuring Corrosion Rate Of Steel-Hulled Shipwrecks In Seawater, Matthew A. Russell, David L. Conlin, Larry E. Murphy, Donald L. Johnson, Brent M. Wilson, James D. Carr

Department of Chemistry: Faculty Publications

Current research on USS Arizona is focused on a minimum-impact technique for calculating corrosion rate of the battleship’s steel hull by analysing physical and chemical properties of marine encrustation covering the exposed hull. An equation is derived that allows concretion thickness, density, and total iron content to be used to calculate corrosion rate of steel hull plate.

Planar-To-Tubular Structural Transition In Boron Clusters: B20 As The Embryo Of Single-Walled Boron Nanotubes, Boggavarapu Kiran, Satya S. Bulusu, Hua-Jin Zhai, Soohaeng Yoo, Xiao Cheng Zeng, Lai-Sheng Wang

Xiao Cheng Zeng Publications

Experimental and computational simulations revealed that boron clusters, which favor planar (2D) structures up to 18 atoms, prefer 3D structures beginning at 20 atoms. Using global optimization methods, we found that the B₂₀ neutral cluster has a double-ring tubular structure with a diameter of 5.2 Å. For the B₂₀^- anion, the tubular structure is shown to be isoenergetic to 2D structures, which were observed and confirmed by photoelectron spectroscopy. The 2D-to-3D structural transition observed at B₂₀, reminiscent of the ring-to-fullerene transition at C₂₀ in carbon clusters, suggests it may be considered as the embryo …

Modifications Of Human Βa1/Βa3-Crystallins Include S-Methylation, Glutathiolation, And Truncation, Veniamin N. Lapko, Ronald Cerny, David L. Smith, Jean B. Smith

Ronald Cerny Publications

Disulfide bonding of lens crystallins contributes to the aggregation and insolubilization of these proteins that leads to cataract. A high concentration of reduced glutathione is believed to be key in preventing oxidation of crystallin sulfhydryls to form disulfide bonds. This protective role is decreased in aged lenses because of lower glutathione levels, especially in the nucleus. We recently found that human [1]-crystallins undergo S-methylation at exposed cysteine residues, a reaction that may prevent disulfide bonding. We report here that βA1/A3-crystallins are also methylated at specific cysteine residues and are the most heavily methylated of the human lens crystallins. Among the …

Analysis Of Free Analyte Fractions By Rapid Affinity Chromatography, David S. Hage, William A. Clarke

Department of Chemistry: Faculty Publications

The invention is generally directed toward an analytical method to determine the concentration of the free analyte fraction in a sample. More particularly, the method encompasses applying a sample comprising a free and bound analyte fraction to an affinity column capable of selectively extracting the free fraction in the millisecond time domain. The signal generated by the free fraction is then quantified by standard analytical detection techniques. The concentration of the free fraction may then be determined by comparison of its signal with that of a calibration curve depicting the signal of known concentration of the same analyte.

Oligothiophenes And Synthesis Thereof, Andrzej Rajca

Department of Chemistry: Faculty Publications

Novel oligothiophenes and intermediates therefor are disclosed together with a process for synthesizing them. The oligothiophenes are in the form of a helix which contains five-membered rings unsaturated heterocycles that are cross-conjugated and annelated into a helix.

Creating Nanocavities Of Tunable Sizes: Hollow Helices, Bing Gong, Huaqiang Zeng, Jin Zhu, Lihua Yuan, Yaohua Han, Shizhi Cheng, Mako Furukawa, Ruben D. Parra, Audrey Y. Kovalevsky, Jeffrey L. Mills, Ewa Skrzypczak-Jankun, Suzana Martinovic, Richard D. Smith, Chong Zheng, Thomas Szyperski, Xiao Cheng Zeng

Xiao Cheng Zeng Publications

A general strategy for creating nanocavities with tunable sizes based on the folding of unnatural oligomers is presented. The backbones of these oligomers are rigidified by localized, threecenter intramolecular hydrogen bonds, which lead to well-defined hollow helical conformations. Changing the curvature of the oligomer backbone leads to the adjustment of the interior cavity size. Helices with interior cavities of 10 Å to >30 Å across, the largest thus far formed by the folding of unnatural foldamers, are generated. Cavities of these sizes are usually seen at the tertiary and quaternary structural levels of proteins. The ability to tune molecular dimensions …

Preliminary X-Ray Diffraction Studies Of The Transcriptional Inhibitory Antibody Fab41.4, Johanna Mazlo, Robyn L. Stanfield, Ian A. Wilson, Steven H. Hinrichs, John J. Stezowski

Department of Chemistry: Faculty Publications

The binding of transcription factor ATF-1 to DNA contributes to gene expression and regulation of cell growth. Antibody Mab41.4, raised against ATF-1, and its derivatives Fab41.4 and scFv41.4 inhibit specific DNA binding in vitro and induce apoptotic death of tumor cells in vivo. Structural studies of Fab41.4 were performed to gain insight into the mechanism of action of this potentially therapeutic antibody. The optimal conditions for crystallization of Fab41.4 were determined. Crystals were needle-like in appearance, displayed C2 space-group symmetry and diffracted to a resolution of 1.6 Å. The unit-cell parameters were determined to be a = 186.64, b = …

Octafluoro-Meso Tetraarylporphyrins And Methods For Making These Compounds, Stephen G. Dimagno

Department of Chemistry: Faculty Publications

The novel compounds of the present invention are f-octafluoro-meso-tetraarylporphyrins of formula (I) and their metallic complexes of formula (II):

B-octafluoro-meso-tetraaryl porphyrins are Synthesized by reacting 3,4-difluoropyrrole with an aromatic aldehyde in the presence of boron trifluoride etherate, followed by oxidation. The difluoropyrrole used in this reaction is pro duced by reacting 3,3,4,4-tetrafluoropyrroline or its corre sponding Salt, 3,3,4,4-tetrafluoropyrrolidinium Salt, with a base Such as potassium tert-butoxide. The metalloporphyrins of the present invention are Synthesized by deprontonating B-octafluoro-meso-tetraarylporphyrin ligands and treating Said ligands with metal ions.

Heavily Fluorinated Sugar Analogs, Stephen G. Dimagno

Department of Chemistry: Faculty Publications

Heavily fluorinated Sugar analogs of formula

wherein R₁ is selected from alkyl, alkenyl, aryl, CH₂OH, -CH₂-O-alkyl, -CH₂-O-aryl, -CH₂OPO₃H, -CH₂-O-carbohydrate, -CH₂-NH-peptide, or -CH₂-O-peptide; wherein R₂ is selected from hydroxy, -O-carbohydrate, -NH-peptide,

wherein R₃ is selected from H, halogen, lower alkyl, lower alkenyl, lower haloalkyl, lower haloalkenyl, amino, mono- or di-lower alkylamino; wherein R₄ is Selected from amino, hydroxy, alkoxy, or halogen; and wherein R₅ is H or amino. The compounds of formula (I) are useful as antiviral and antineoplastic agents …

Method Of Storing Active Zero Valent Zinc Metal, Reuben D. Rieke

Department of Chemistry: Faculty Publications

A novel Zerovalent Zinc species and an organozinc reagent are disclosed. The Zerovalent Zinc species is directly pro duced by reaction of a reducing agent on a Zinc Salt, preferably Zn(CN). The organozinc regent results from the reaction of the Zerovalent Zinc species and an organic compound having one or more stable anionic leaving groups. These organozinc reagents include a wide spectrum of functional groups in the organic radical, and are useful in a variety of reactions Schemes.

Method For The Synthesis Of Α-Oxranyl Amino Acids, David B. Berkowitz, Michelle L. Pedersen

Department of Chemistry: Faculty Publications

The present invention is related to a novel class of decar-boxylase enzyme inhibitors consisting of α-oxiranyl amino acids and derivatives thereof and a method of synthesizing Such compounds.

Pyrrolic Compounds, Michael J. Therien, Stephen Dimagno

Department of Chemistry: Faculty Publications

Novel methylpyrroles are provided, as well as processes for their preparation.

Metathesis-Based Synthesis Of Jasmonate And Homojasmonate Lactones, Candidates For Extracellular Quorum Sensing Molecules In Candida Albicans, Su C. Cho, Patrick Dussault, Amber D. Lisec, Ellen C. Jensen, Kenneth W. Nickerson

Department of Chemistry: Faculty Publications

Ring-closing metathesis of jasmonate esters is shown to provide a rapid entry to jasmonate lactones. The lactones were investigated as possible quorum sensing molecules for the fungi Candida albicans. Assays demonstrated no effect on fungal morphology at concentrations up to 96 mM.

Substituted Polythiophenes From Highly Reactive Zinc Reagents, Reuben D. Rieke

Department of Chemistry: Faculty Publications

A novel Zerovalent zinc species and an organozinc reagent are disclosed. The zerovalent zinc species is directly pro duced by reaction of a reducing agent on a zinc salt, preferably Zn(CN)₂. The organozinc reagent results from the reaction of the zerovalent zinc species and an organic compound having one or more stable anionic leaving groups. These organozinc reagents include a wide spectrum of functional groups in the organic radical, and are useful in a variety of reactions schemes.

Cross-Coupling Of Organic Compounds Using Cuprous Odide, Reuben D. Rieke

Department of Chemistry: Faculty Publications

Cross-coupling or addition reactions of organic compounds, including acid halides, allylic halides, and C.B-unsaturated carbonyl containing compounds, with organozinc com pounds may be readily and Safely carried out in the presence of cuprous iodide. The use of this catalyst in the coupling reaction provides for the preparation of commercially useful products in the pharmaceutical, agrochemical and other industries.

Α-Vinyllysine And Α-Vinylarginine Are Time-Dependent Inhibitors Of Their Cognate Decarboxylases, David B. Berkowitz, Wan Jin Jahng, Michelle L. Pedersen

Department of Chemistry: Faculty Publications

(±)-α-Vinyllysine and (±)-α-vinylarginine display time-dependent inhibition of L-lysine decarboxylase from B. cadaveris, and L-arginine decarboxylase from E. coli, respectively. A complete Kitz-Wilson analysis has been performed using a modification of the Palcic continuous UV assay for decarboxylase activity.

Synthesis Of Higher Α-Chlorovinyl And Α-Bromovinyl Amino Acids: The Amino Protecting Group Determines The Reaction Course, David B. Berkowitz, Michelle L. Pedersen, Wan Jin Jahng

Department of Chemistry: Faculty Publications

N-Trifluoroacetyl α-vinyl amino esters are smoothly converted to the corresponding α-chlorovinyl or α-bromovinyl amino esters through the agency of phenyselenyl chloride or phenylselenyl bromide, respectively, followed by oxidation and pyrolysis. Exclusively the (E)-extemal halovinyl isomer and the internal halovinyl isomer are observed. The amino protecting group is a critical determinant of the reaction course (alkene addition vs. 5-exo-trig-like cyclization).

Highly Reactive Form Of Copper And Reagents Thereof, Reuben D. Rieke

Department of Chemistry: Faculty Publications

A novel Zerovalent copper species and an organocopper reagent are disclosed. The Zerovalent copper species is directly produced by reaction of a reducing agent with a combination of copper(I) cyanide or halide and an alkali metal halide salt. The organocopper reagent resulting from the reaction of the zerovalent copper species and an organic compound having one or more stable anionic leaving groups is a stable reagent that will not significantly homocouple and under controlled conditions tolerates the presence of nitrile, epoxide, imine, enone, ketone, ester, allyl and benzyl groups within the organo radical. The reagent can be controlled so that …

Highly Reactive Zerovalent Metals From Metal Cyanides, Reuben D. Rieke

Department of Chemistry: Faculty Publications

Novel zerovalent metal species and organometallic reagents are disclosed. The zerovalent metal species are directly produced by reaction of a reducing agent on a metal cyanide salt. Preferably, the zerovalent metal species are directly produced by reaction of an alkali metal reducing agent with a metal cyanide salt. The organometallic reagent results from the reaction of the zerovalent metal species and an organic compound having one or more stable anionic leaving groups.