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Thermal Analysis Of Adsorbed Poly(Methyl Methacrylate) On Silica, Frank D. Blum, Erin N. Young, Gregory Smith, Oliver C. Sitton

Chemistry Faculty Research & Creative Works

Modulated differential scanning calorimetry has been used to quantify the glass transitions of small, adsorbed amounts of poly (methyl methacrylate) (PMMA) on silica. While a relatively narrow, single glass transition was found for bulk PMMA, broader two-component transitions were found for the adsorbed polymer. a two-state model based on loosely bound polymer (glass transition similar to bulk) and more tightly bound polymer (glass transition centered around 156°C) was used to interpret the thermograms. on the basis of this model, the amount of tightly bound polymer was found to be approximately 1.3 mg/m 2, corresponding to a 1.1 nm thick layer. …

Functional Replacement Of The Ketosynthase Domain Of Fum1 For The Biosynthesis Of Fumonisins, A Group Of Fungal Reduced Polyketides, Xiangcheng Zhu, Fengan Yu, R. S. Bojja, K. Zaleta-Rivera, Liangcheng Du

Liangcheng Du Publications

The genetic manipulation of the biosynthesis of fungal reduced polyketides has been challenging due to the lack of knowledge on the biosynthetic mechanism, the difficulties in the detection of the acyclic, non-aromatic metabolites, and the complexity in genetically manipulating filamentous fungi. Fumonisins are a group of economically important mycotoxins that contaminate maize-based food and feed products worldwide. Fumonisins contain a linear dimethylated C₁₈ chain that is synthesized by Fum1p, which is a single module polyketide synthase (PKS). Using a genetic system that allows the specific manipulation of PKS domains in filamentous fungus Fusarium verticillioides, we replaced the KS domain …

Closing The Loop: Controlling Type 1 Diabetes Mellitus, Megan Chynoweth

Whittier Scholars Program

Diabetes mellitus is an ever increasing pandemic. Type 1 diabetes mellitus (T1DM), although not the most prevalent form of diabetes mellitus, has had an “average annual increase of 3.09%, meaning the incidence of T1DM would increase 40% from 1998 to 2010”. T1DM leads to many complications: adverse side effects such as retinopathy, neuropathy, and nephropathy. These comorbidities are costing the United States billions of healthcare dollars per year. Delaying complications result in cost savings and improved quality of life, which can be obtained by tightly controlling blood sugars. However, strict control is difficult to attain. Optimal glucose levels may be …

Mechanisms Imposing The Vbeta Bias Of V14a Natural Killer T Cells And Consequences For Microbial Glycolipid Recognition, Paul B. Savage, Dasten G. Wei, Shane A. Curran, Luc Teyton, Albert Bendelac

Faculty Publications

Mouse and human natural killer T (NKT) cells recognize a restricted set of glycosphingolipids presented by CD1d molecules, including self iGb3 and microbial alpha-glycuronosylceramides. The importance of the canonical Valpha 14-Jalpha18 TCR alphachain for antigen recognition by NKT cells is well recognized, but the mechanisms underlying the Vbeta8, Vbeta7, and Vbeta2 bias in mouse have not been explored. To study the influences of thymic selection and the constraints of pairing with Valpha 14-Jalpha 18, we have created a population of mature T cells expressing Valpha 14-Jalpha 18 TCRalpha chain in CD1d-deficient mice and studied its recognition properties in vitro and …

Generating Long-Lasting ¹H And ¹³C Hyperpolarization In Small Molecules With Parahydrogen-Induced Polarization, Thorsten Jonischkeit, Ute Bommerich, Jorg Stadler, Klaus Woelk, Heiko G. Niessen, Joachim Bargon

Chemistry Faculty Research & Creative Works

Recently, Levitt and co-workers demonstrated that conserving the population of long-lasting nuclear singlet states in weak magnetic fields can lead to a preservation of nuclear spin information over times substantially longer than governed by the (high-field) spin-lattice relaxation time T₁. Potential benefits of the prolonged spin information for magnetic resonance imaging and spectroscopy were pointed out, particularly when combined with the parahydrogen induced polarization (PHIP) methodology. In this contribution, we demonstrate that an increase of the effective relaxation time by a factor up to three is achieved experimentally, when molecules hyperpolarized by PHIP are kept in a weak …

Toward Synthesizing A Selective Dopamine Binding Magnetic Resonance Contrast Agent, Judy Lau

Senior Honors Projects

Magnetic resonance imaging (MRI) is a non-invasive diagnostic methodology used to provide a two-dimensional view of an internal organ or structure, especially the brain and spinal cord. Magnetic resonance contrast agents are usually injected into necessary parts of the body prior to imaging to increase the differences between different tissues or between normal and abnormal tissue, making it easier for a radiologist or doctor to interpret the image that is taken. The development of new and more efficient, effective, and selective contrast agents for various biological processes or chemicals is a growing field of research and study. My project allowed …

Secondary N-Nitrosocarbamate Anions: Structure And Alkylation Reactions. A Dft Study, Vladimir Benin

Chemistry Faculty Publications

The current article reports theoretical studies (DFT: B3LYP/6-31+G(d)) on the structure and alkylation reactions of the anions of some secondary N-nitrosocarbamates, a class of ambident nucleophiles whose chemistry has been little explored. Several anions (1–4), with an increasing size of the carbamate alkyl (aryl) group were investigated, in an attempt to establish the influence of the size of that group on the thermal stability and regioselectivity of alkylation of the title anions. The conclusion is that thermal stability and the mode of reaction are affected significantly only in the presence of very large and branched carbamate groups. The thermal …

Oxidative Damage Caused By Iron Loading Into Ferritin, Talina Christensen Watts

Undergraduate Honors Capstone Projects

Ferritin is the iron storage protein found in humans, animals, plants, fungi and bacteria. We are interested in how iron is loaded and stored in mammalian ferritin. Ferrous iron must be oxidized to ferric iron in order to be stored in ferritin. It is generally believed that ferritin does the loading itself, dependant upon a "ferroxidase activity." Oxidation of iron can result in the production of the hydroxyl radical which can cause oxidative damage to surrounding proteins and other biomolecules. An indicator of oxidative damage to proteins is the formation of carbonyl groups. Using only the H subunit of human …

Faithful Estimation Of Dynamics Parameters From Cpmg Relaxation Dispersion Measurements, Evgenii L. Kovrigin, James G. Kempf, Michael J. Grey, J. Patrick Loria

Chemistry Faculty Research and Publications

This work examines the robustness of fitting of parameters describing conformational exchange (k_ex, p_a/b, and Δω) processes from CPMG relaxation dispersion data. We have analyzed the equations describing conformational exchange processes for the intrinsic inter-dependence of their parameters that leads to the existence of multiple equivalent solutions, which equally satisfy the experimental data. We have used Monte-Carlo simulations and fitting to the synthetic data sets as well as the direct 3-D mapping of the parameter space of k_ex, p_a/b, and Δω to quantitatively assess …

Protein Structure Similarity Clustering: Dynamic Treatment Of Pdb Structures Facilitates Clustering, Bradley D. Charette, Richard G. Macdonald, Stefan Wetzel, David B. Berkowitz, Herbert Waldmann

David Berkowitz Publications

Protein structure similarity clustering (PSSC) [1]– [3] is one of a number of potential guiding principles [4], [5] that have been introduced to focus combinatorial-library design/ protein targeting. PSSC clusters protein targets with similar ligand-binding cores in which little sequence or functional similarity is evident. Lead compounds for one member of the cluster then provide novel starting points in chemical space for ligand development for other members of the PSSC.

We describe herein a new clustering procedure that lends itself to ligand docking, molecular dynamics (MD), and the vector-alignment-search-tool (VAST) [6] algorithm. This MD-assisted approach offers an alternative to the …

Dactinomycin Impairs Cellular Respiration And Reduces Accompanying Atp Formation, Zhimin Tao, Syed S. Ahmad, Harvey S. Penefsky, Jerry Goodisman, Abdul Kader Souid

Chemistry - All Scholarship

The effect of dactinomycin on cellular respiration and accompanying ATP formation was investigated in Jurkat and HL-60 cells. Cellular mitochondrial oxygen consumption (measured by a homemade phosphorescence analyzer) and ATP content (measured by the luciferin-luciferase bioluminescence system) were determined as functions of time t during continuous exposure to the drug. The rate of respiration, k, was the negative of the slope of [O2] versus t. Oxygen consumption and ATP content were diminished by cyanide, confirming that both processes involved oxidations in the mitochondrial respiratory chain. In the presence of dactinomycin, k decreased gradually with t, the decrease being more pronounced …

Identification Of The Binding Region Of The [2fe-2s] Ferredoxin In Stearoyl-Acyl Carrier Protein Desaturase: Insight Into The Catalytic Complex And Mechanism Of Action, Pablo Sobrado, Karen S. Lyle, Steven P. Kaul, Michelle M. Turco, Ida Arabshahi, Ashok Marwah, Brian G. Fox

Chemistry Faculty Research & Creative Works

Stearoyl-acyl carrier protein desaturase (Δ9D) catalyzes the O 2 and 2e- dependent desaturation of stearoyl-acyl carrier protein (18:0-ACP) to yield oleoyl-ACP (18:1-ACP). The 2e- are provided by essential interactions with reduced plant-type [2Fe-2S] ferredoxin (Fd). We have investigated the protein-protein interface involved in the Fd-Δ9D complex by the use of chemical cross-linking, site-directed mutagenesis, steady-state kinetic approaches, and molecular docking studies. The treatment of the different proteins with 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide and N-hydroxy succinimide revealed that carboxylate residues from Fd and lysine residues from Δ9D contribute to cross-linking. The single substitutions of K60A, K56A, and K230A on Δ9D decreased the k …

Erratum: "Hard Sphere Radial Distribution Function Again", Andrij Trokhymchuk, Douglas Henderson, Ivo Nezbeda, Jan Jirsak

Faculty Publications

Some misprints have been found for parameters given by Eqs. 29 and 30 and the relevant equations in the Appendix.

Two New Resorcinarenes: A Pyridine & Acetic Acid Ligand For Metal Coordination And A Deep-Cavity Nitroquinoxaline Resorcinarene, Samantha Sizemore Vernetti

Theses and Dissertations

Functionalizing the upper rim of resorcinarene-based cavitands allows a variety of compounds to be synthesized from a single scaffold. Using the upper-rim moieties as ligands for a variety of transition metal ions further increases the versatility of this class of host compounds. A new resorcinarene-based molecule functionalized with four pyridine and acetic acid ligands has been successfully prepared to explore the properties of metal-assembled complexes. To synthesize this compound, tetra(bromomethyl)cavitand was reacted with N-(2-pyridylmethyl)-N-ethylacetate amine to give ethyl acetate pyridine resorcinarene. Hydrolysis of the ester gave acetic acid pyridine resorcinarene (APRes) in good yield. Complexes with Cu2+, Co2+, and Zn2+ …

2nd Annual Undergraduate Research Conference Abstract Book, University Of Missouri--Rolla

Undergraduate Research Conference at Missouri S&T

No abstract provided.

Chemo-Enzymatic Route To Synthesis Of Biodegradable Polymers And Glycolipid Analogs, Surbhi Bhatt

USF Tampa Graduate Theses and Dissertations

New catalytic synthetic methods in organic chemistry that satisfy increasingly stringent environmental constraints are in great demand by the pharmaceutical and chemical industries. Studies over last 15 years have revealed that activity of enzymes can be increased in organic solvents rather than their natural aqueous environment. Because of their ease of use, high selectivity and environment friendliness, enzymes are enjoying increasing popularity in today's synthesis world.

Chapter 1 describes chemo-enzymatic synthesis of various glycolipid analogs. A highly regioselective macrolactonization was achieved using lipase from Candida antarctica as a catalyst. It also describes evaluation of lipases from different source and their …

Chemistry & Biochemistry Newsletter, Department Of Chemistry & Biochemistry, South Dakota State University

Chemistry & Biochemistry Newsletter: 2002-2015

Inside:

Page 2-4 Campus Mass Spectrometry Facility

Page 4 Alumni News

Page 5 Alum Featured; Scholarships and Awards

Page 6 Two New Departmental Scholarships; Recent Faculty Publications; Funding

Page 7 2006 Chemistry and Biochemistry Graduates

Large Scale Growth And Magnetic Properties Of Fe And Fe₃O₄ Nanowires, Jinbo Yang, H. Xu, Shaoxin You, X.-D. Zhou, C. S. Wang, William B. Yelon, William Joseph James

Materials Science and Engineering Faculty Research & Creative Works

Fe and Fe3O4 nanowires have been synthesized by thermal decomposition of Fe(CO)5, followed by heat treatments. The Fe wires are formed through the aggregation of nanoparticles generated by decomposition of Fe(CO)5. A core-shell structure with an iron oxide shell and Fe core is observed for the as-prepared Fe wires. Annealing in air leads to the formation of Fe2O3/Fe3O4 wires, which after heat treatment in a N2/alcohol atmosphere form Fe3O4 wires with a sharp Verwey [Nature (London) 144, 327 (1939)] transition at 125 K. The Fe3O4 wires have coercivities of 261 and 735 Oe along the wire axis at RT and …

Protein–Protein Interactions Of Tandem Affinity Purification-Tagged Protein Kinases In Rice, Jai S. Rohila, Mei Chen, Shuo Chen, Johann Chen, Ronald Cerny, Chris Dardick, Patrick Canlas, Xia Xu, Michael Gribskov, Siddhartha Kanrar, Jian-Kang Zhu, P C. Ronald, Michael E. Fromm

Ronald Cerny Publications

Forty-one rice cDNAs encoding protein kinases were fused to the tandem affinity purification (TAP) tag and expressed in transgenic rice plants. The TAP-tagged kinases and interacting proteins were purified from the T1 progeny of the transgenic rice plants and identified by mass spectrometry. Ninety-five percent of the TAP-tagged kinases were recovered. Fifty-six percent of the TAP-tagged kinases were found to interact with other rice proteins. A number of these interactions were consistent with known protein complexes found in other species, validating the TAP-tag method in rice plants. Phosphorylation sites were identified on four of the kinases that interacted with either …

Spectral Shape As An Indicator Of Molecular Weight In Chromophoric Dissolved Organic Matter, John Robert Helms

Chemistry & Biochemistry Theses & Dissertations

Spectral slope is a term used to parameterize featureless absorbance spectra according to their shape. Spectral slope is obtained by calculating the slope of the log-linearized absorption spectrum over a given range of wavelengths. Past studies have shown that spectral slope is related to molecular size in fulvic acids. A simple method of spectral analysis that compares spectral slopes obtained from two distinct regions of the UV spectra of aquatic dissolved organic matter is demonstrated. The ratio of these slopes (R_S) shows considerable change during photo-oxidation, variation within estuaries, and substantial shifts with depth in the upper 1000 …

Synthesis Of Aspernigrin A, Erica Joerger

Undergraduate Theses and Capstone Projects

Aspernigrin A is a compound correlated with inhibiting the growth of cancer cells in the colon. A five-step synthesis was designed for aspernigrin A, projected to yield four intermediates and the final product. The intermediates were analyzed by high field 1HNMR and FT-IR spectroscopy before proceeding to the next step. A model pyridone ring system was successfully prepared from a commercially available pyrone precursor in two steps. These results provide a proof of concept that the synthetic scheme should successfully yield the natural product.

The High-Resolution Structures Of The Neutral And The Low Ph Crystals Of Aminopeptidase From Aeromonas Proteolytica, William Desmarais, David L. Bienvenue, Krzysztof P. Bzymek, Gregory A. Petsko, Dagmar Ringe, Richard C. Holz

Chemistry Faculty Research and Publications

The aminopeptidase from Aeromonas proteolytica (AAP) contains two zinc ions in the active site and catalyzes the degradation of peptides. Herein we report the crystal structures of AAP at 0.95-Å resolution at neutral pH and at 1.24-Å resolution at low pH. The combination of these structures allowed the precise modeling of atomic positions, the identification of the metal bridging oxygen species, and insight into the physical properties of the metal ions. On the basis of these structures, a new putative catalytic mechanism is proposed for AAP that is likely relevant to all binuclear metalloproteases.

Synthetic Studies Of 1,10-Phenanthroline Derivatives As Novel Catalysis Ligands And Their Application In Transition Metals Catalyzed Reactions, Son Duc Tran

Dissertations

The preparation of 1,10-phenanthroline derivatives entailed ring opening reactions of 1,10-phenanthroline epoxide as a key transformation, affording novelbidentate nitrogen ligands with new stereogenic centers in the 5- and 6-position. This research was concerned with (i) the epoxidation of 1,10-phen, (ii) epoxide ring opening reactions, (iii) the formation of trans -5,6-disubstituted-1,10-phenanthroline metal complexes, and (iv) application of 1,10-phenanthroline derivatives in metal-catalyze reactions such as palladium-catalyzed allylic substitution and aminohalogenation reactions; Zinc-catalyzed direct aldolreaction, and acetophenone reduction; Nickel-catalyzed Michael addition reaction.

A Comparative Genomic Analysis Of Chlorella Nc64a Virus Ny-2a And Chlorella Pbi Virus Mt325 From The Family Phycodnaviridae, Lisa A. Fitzgerald

Department of Chemistry: Dissertations, Theses, and Student Research

The family Phycodnaviridae consists of a morphologically similar but genetically diverse group of large dsDNA viruses which infect both fresh and marine water eukaryotic algae. Two viruses, the 370 kb Chlorella NC64A virus NY-2A and the 313 kb Chlorella Pbi virus MT325, from the family Phycodnaviridae, genus Chlorovirus, were sequenced, analyzed, and compared to the prototype chlorella virus PBCV-1. The NY-2A genome, the largest chlorella viral genome sequenced to date, contains 886 open reading frames (ORFs) of 65 codons or larger and encodes 404 putative proteins and 7 tRNAs. The MT325 genome, the smallest chlorella viral genome sequenced to date, …

Gas Chromatography: Mass Spectrometry Of Chemical Agents And Related Interferents, Lailiang Zhai

Theses and Dissertations

One of the main problems encountered in chemical analysis operations in the field is collecting sufficient sample from the source and transferring that sample to the measurement instrument for fast separation and identification. I have been involved in developing a field-portable gas chromatography-mass spectrometry (GC-MS) system with solid phase microextraction (SPME) sampling for point detection of chemical agents. The objective is to minimize the analysis time between sampling and detection of a potential chemical threat. SPME offers a convenient means for sampling gaseous and liquid samples, concentrating the analytes, and transferring the analytes to the injection port of a GC …

The Structure Of Β-Carbonic Anhydrase From The Carboxysomal Shell Reveals A Distinct Subclass With One Active Site For The Price Of Two, Michael R. Sawaya, Gordon C. Cannon, Sabine Heinhorst, Shiho Tanaka, Eric B. Williams, Todd O. Yeates, Cheryl A. Kerfeld

Faculty Publications

CsoSCA (formerly CsoS3) is a bacterial carbonic anhydrase localized in the shell of a cellular microcompartment called the carboxysome, where it converts HCO^-₃ to CO₂ for use in carbon fixation by ribulose-bisphosphate carboxylase/oxygenase (RuBisCO). CsoSCA lacks significant sequence similarity to any of the four known classes of carbonic anhydrase (α, β, γ, or δ), and so it was initially classified as belonging to a new class, ϵ. The crystal structure of CsoSCA from Halothiobacillus neapolitanus reveals that it is actually a representative member of a new subclass of β-carbonic anhydrases, distinguished by a lack of active site …

Membrane-Based Protein Preconcentration Microfluidic Devices, Yi Li

Theses and Dissertations

Interest in microchip capillary electrophoresis (CE) is growing due to the rapid analysis times provided and small sample input requirements. However, higher-concentration samples are typically needed because of the small (~pL) detection volumes in these devices. I have made membrane-based protein preconcentration systems in capillary and microchip designs to increase the detectability of low-concentration biological samples. A photopolymerized ion-permeable membrane interfaced with a microchannel in poly(methyl methacrylate) (PMMA) formed the preconcentrator. When a voltage was applied between the sample reservoir and the ionically conductive membrane in a capillary-based system, R-phycoerythrin was concentrated more than 1,000 fold, as determined by laser-induced …

Rapid, Sequence-Specific Detection Of Unpurified Pcr Amplicons Via A Reusable, Electrochemical Sensor, Rebecca Lai, Eric T. Hagally, Sang-Ho Lee, H. T. Soh, Kevin W. Plaxco, Alan J. Heeger

Rebecca Lai Publications

We report an electrochemical method for the sequence-specific detection of unpurified amplification products of the gyrB gene of Salmonella typhimurium. Using an asymmetric PCR and the electrochemical E-DNA detection scheme, single-stranded amplicons were produced from as few as 90 gene copies and, without subsequent purification, rapidly identified. The detection is specific; the sensor does not respond when challenged with control oligonucleotides based on the gyrB genes of either Escherichia coli or various Shigella species. In contrast to existing sequence-specific optical- and capillary electrophoresis- based detection methods, the E-DNA sensor is fully electronic and requires neither cumbersome, expensive optics nor …

Distinct Ceramide Synthases Regulate Polarized Growth In The Filamentous Fungus Aspergillus NidulansD, Shaojie Li, Liangcheng Du, Gary Yuen, Steven D. Harris

Liangcheng Du Publications

In filamentous fungi, the stabilization of a polarity axis is likely to be a pivotal event underlying the emergence of a germ tube from a germinating spore. Recent results implicate the polarisome in this process and also suggest that it requires localized membrane organization. Here, we employ a chemical genetic approach to demonstrate that ceramide synthesis is necessary for the formation of a stable polarity axis in the model fungus Aspergillus nidulans. We demonstrate that a novel compound (HSAF) produced by a bacterial biocontrol agent disrupts polarized growth and leads to loss of membrane organization and formin localization at …

Supplemental Materials For "Distinct Ceramide Synthases Regulate Polarized Growth In The Filamentous Fungus Aspergillus NidulansD", Shaojie Li, Liangcheng Du, Gary Yuen, Steven D. Harris

Liangcheng Du Publications

Four figures not included in the print edition of the above-referenced article, that was published in Molecular Biology of the Cell, Vol. 17, 1218–1227 (March 2006). :

Figure 1 - barA mutants are resistant to the effects of HPLC-purified HSAF.

Figure 2 - Alignment of Lag1 homologues.

Figure 3 - Alignments of BasA homologues.

Figure 4 - Growth defects of lagA mutants.