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Large-Pore Mesoporous Organosilicas And Related Polymer Nanocomposites, Amanpreet Singh Manchanda Sep 2015

Large-Pore Mesoporous Organosilicas And Related Polymer Nanocomposites, Amanpreet Singh Manchanda

Dissertations, Theses, and Capstone Projects

The research work in this dissertation covers the synthesis of mesoporous organosilicas and (organo)silica/polymer nanocomposites. The content can be divided into 4 parts (8 chapters).

The first part of the dissertation is the introduction, which covers the background and progress in the field of mesoporous silicas, periodic mesoporous organosilicas and related inorganic/polymer nanocomposites. The second part of the dissertation (Chapter 2-5) involves the synthesis of mesoporous organosilicas from different organosilane precursors at mild acid concentration (0.1 M HCl) and low temperature (0 or 7 ℃) using Pluronic F127 (EO106PO70EO106) as a surfactant template. Chapter …


Polymer Pen Printing: A Tool For Studying 2d Enzymatic Lithography And Printing 3d Carbon Features, Zhantong Mao Sep 2015

Polymer Pen Printing: A Tool For Studying 2d Enzymatic Lithography And Printing 3d Carbon Features, Zhantong Mao

Dissertations, Theses, and Capstone Projects

Polymer Pen Lithography (PPL) is a promising molecular printing approach which combines the advantages of both microcontact printing (low cost, high-throughput) and the dip pen lithography (DPN) (arbitrary writing, high-resolution) into one cohesive lithography method to create 2 dimensional (2-D) patterns with micro/nano-features on different substrates. The goal of this dissertation is to design and develop a new tool based upon PPL, which is not limited to forming 2D parallel patterns, but can also create 3D complex microstructures, finding applications in both biotechnology and Micro-Electro-Mechanical systems (MEMS) technology. This novel approach is named Polymer Pen Printing. Different from PPL using …


Studies Toward A General Synthesis Of Poly-Substituted Alpha-Hydroxytropolones, Christine Marie Meck Sep 2015

Studies Toward A General Synthesis Of Poly-Substituted Alpha-Hydroxytropolones, Christine Marie Meck

Dissertations, Theses, and Capstone Projects

Chapter 1: This chapter gives a brief history of α-hydroxytropolones, how they were discovered and unique properties of these substrates. Included is a background on the bioactivity of these substrates in cellular targets such as bacteria, fungi, parasites, tumors and toxicity, as well as their ability to inhibit various metallo-based enzymes. Structure activity relationships studies are reviewed on important metalloenzymes HIV-Reverse Transcriptase (RT) and Inositol monophosphatase (IMPase). Finally the chapter finishes with a synthetic overview of α-hydroxytropolones including natural product targets such as puberulic acid, puberulonic acid, β-thujaplicinol, and β-hydroxytropolone.

Chapter 2: A brief review on β-hydroxy-γ-pyrone based oxidopyrylium cycloadditions …


An Analytical Method For Detecting Toxic Metal Cations Using Cyclotriveratrylene Derivative Capped Gold Nanoparticles, Zachary R. Osner, Richard C. Holz, Daniel P. Becker Sep 2015

An Analytical Method For Detecting Toxic Metal Cations Using Cyclotriveratrylene Derivative Capped Gold Nanoparticles, Zachary R. Osner, Richard C. Holz, Daniel P. Becker

Chemistry Faculty Research and Publications

Cyclotriveratrylene-oxime (CTV-oxime) derivatives that terminate with a dithiolate linker were synthesized enabling the supramolecular scaffold to adhere to gold nanoparticles (AuNPs) with the bowl-shaped cavity of the CTV scaffold exposed for utilization in host–guest chemistry. Exposure of these CTV functionalized AuNPs to varying concentrations of di- and trivalent metal cations resulted in the formation of large CTV-AuNP polymeric clusters and an accompanying a shift in the plasmon resonance. These interactions between the CTV-AuNPs and the metal cations in solution provides proof-of-concept that supramolecular functionalized AuNPs can be used as a simple and straightforward, on-site detection system for toxic metal cations …


Zirconium-89: Radiochemistry And Ligand Development Toward Improved Pet Applications, Melissa Ann Deri Sep 2015

Zirconium-89: Radiochemistry And Ligand Development Toward Improved Pet Applications, Melissa Ann Deri

Dissertations, Theses, and Capstone Projects

Antibodies are attractive targeting vectors for positron emission tomography (PET) based imaging agents due to their high affinity and selectivity to a variety of biological targets. Creating such imaging agents requires a radionuclide with suitable decay characteristics. This role has been filled by zirconium-89 which has a 78.41 h half-life that ideally matches the multi-day biological half-life of IgG antibodies.

However, the use of a radiometal necessitates the use of a bifunctional chelator to bind the metal and conjugate to the antibody. For 89Zr this has been the purview of various derivatives of desferrioxamine B (DFO); however, the observed …


Accessing Medicinally-Relevant Scaffolds Via Organocatalyzed Cascade Reactions, Joshua Hadley Jones Sep 2015

Accessing Medicinally-Relevant Scaffolds Via Organocatalyzed Cascade Reactions, Joshua Hadley Jones

Dissertations, Theses, and Capstone Projects

The field of asymmetric catalysis embodies the efforts of chemists to mimic the stereoselectivity routinely achieved by biological systems. Asymmetric organocatalysis, a sub-field of asymmetric catalysis, is broadly based on the catalytic activity of non-transition metal, small molecules that transmit chirality to substrates. This dissertation describes experimental work towards the construction of versatile, medicinally-relevant molecular scaffolds using chiral, diarylprolinol silyl ether organocatalysts. Specifically, these catalysts were used in 1-pot, iminium-enamine catalyzed cascade reactions to functionalize α,β-unsaturated aldehydes. A comprehensive review of iminium and enamine organocatalysis is provided, including its development towards iminium-enamine cascade reactions. This review provides background for the …


Influence Of Ph And Bulk Density On Carbon Dioxide Efflux In Three Urban Wetland Types, Christopher Chappell, Andra Johnson Sep 2015

Influence Of Ph And Bulk Density On Carbon Dioxide Efflux In Three Urban Wetland Types, Christopher Chappell, Andra Johnson

Professional Agricultural Workers Journal

Abstract

The aim of this study was to understand soil carbon dioxide (CO2) efflux of three different urban wetlands and how pH and bulk density relate to soil CO2 efflux of each wetland. The three wetlands were bottomland, upland, and shrub/scrub. The study was conducted over a twenty week period using the Li-Cor 8100 “closed chamber” method to measure soil CO2 efflux. The findings show that the bottomland wetland efflux was significantly higher than the shrub/scrub and upland wetland. The pH of shrub/scrub was significantly higher than the upland. The bulk density of the bottomland was …


Assessing The Impacts Of Inorganic And Organic Fertilizer On Crop Performance Under A Microirrigation-Plastic Mulch Regime, Niyi S. Omidire, Raymon Shange, Victor Khan, Russell Bean, Jewel Bean Sep 2015

Assessing The Impacts Of Inorganic And Organic Fertilizer On Crop Performance Under A Microirrigation-Plastic Mulch Regime, Niyi S. Omidire, Raymon Shange, Victor Khan, Russell Bean, Jewel Bean

Professional Agricultural Workers Journal

Abstract

This study was conducted at S & B Farm located in Eufaula, AL in 2014. The treatments were Inorganic fertilizer/“Farmer’s Mix” (NPK 13:13:13 + ammonium nitrate mixed in 3:1 ratio); Inorganic fertilizer/“Farmer’s Mix” (NPK 13:13:13 + ammonium nitrate mixed in 3:1 ratio + Bio-grow) plus microbe mix; and Organic Fertilizer – Mighty Grow (4-3-4) with a microbe mix. All fertilizers were applied prior to mulch application after which the following crops squash (Cucurbita pepo L.), cucumber (Cucumis sativus L.), and okra (Abelmoschus esculentus L. Moench) were directly seeded in a complete randomized …


Heterogeneous Oxidation Of Catechol, Elizabeth A. Pillar, Ruixin Zhou, Marcelo I. Guzman Sep 2015

Heterogeneous Oxidation Of Catechol, Elizabeth A. Pillar, Ruixin Zhou, Marcelo I. Guzman

Chemistry Faculty Publications

Natural and anthropogenic emissions of aromatic hydrocarbons from biomass burning, agro-industrial settings, and fossil fuel combustion contribute precursors to secondary aerosol formation (SOA). How these compounds are processed under humid tropospheric conditions is the focus of current attention to understand their environmental fate. This work shows how catechol thin films, a model for oxygenated aromatic hydrocarbons present in biomass burning and combustion aerosols, undergo heterogeneous oxidation at the air–solid interface under variable relative humidity (RH = 0–90%). The maximum reactive uptake coefficient of O3(g) by catechol γO3 = (7.49 ± 0.35) × 10–6 occurs for …


Antimalarial Drug Discovery Using Triazoles To Overcome Chloroquine Resistance, Elias Sibhatu Tesfaselassie Sep 2015

Antimalarial Drug Discovery Using Triazoles To Overcome Chloroquine Resistance, Elias Sibhatu Tesfaselassie

Dissertations and Theses

Malaria is considered as one of the most prevalent and debilitating diseases affecting humans. Plasmodium falciparum is the most virulent form of the parasite which developed resistance to several antimalarial drugs. Chloroquine is one of the most successful antimalarials developed that is safe, effective, and cheap. However, its use has been limited due to the emergence of drug resistance. Click chemistry, particularly, the copper(I)-catalyzed reaction between azides and alkynes has shown to have a cutting-edge advantage in medicinal chemistry by its reliability, selectivity and biocompatibility.

Triazole-based antimalarials were synthesized via copper(I)-catalyzed alkyne-azide cycloaddition reaction by modifying the aliphatic chains terminal …


Effects Of Interferons And Double-Stranded Rna On Human Prostate Cancer Cell Apoptosis, Haiyan Tan, Chun Zeng, Junbo Xie, Norah J. Alghamdi, Ya Song, Hongbing Zhang, Aimin Zhou, Di Jin Sep 2015

Effects Of Interferons And Double-Stranded Rna On Human Prostate Cancer Cell Apoptosis, Haiyan Tan, Chun Zeng, Junbo Xie, Norah J. Alghamdi, Ya Song, Hongbing Zhang, Aimin Zhou, Di Jin

Chemistry Faculty Publications

Prostate cancer is the second most commonly diagnosed cancer among men in the United States. Prostate cancer therapy is severely hampered by lack of response and development of resistance to conventional chemotherapeutic drugs in patients. Therefore, the development and discovery of new drugs have become an urgent clinical need. Interferons (IFNs), a family of pleiotropic cytokines, exert antitumor activities due to their anti-proliferative, immunomodulatory and proapoptotic functions. Here, we report that pretreatment of prostate cancer PC-3 cells with IFNs sensitized these cells to double-stranded RNAs (dsRNAs)-induced apoptosis. The enhancement effect of IFN treatment was dependent on IFN subtypes, in particular, …


Molecular Helices As Electron Acceptors In High-Performance Bulk Heterojunction Solar Cells, Yu Zhong, M. Tuan Trinh, Rongsheng Chen, Geoffrey E. Purdum, Petr P. Khlyabich, Melda Sezen, Seokjoon Oh, Haiming Zhu, Brandon Fowler, Boyuan Zhang, Wei Wang, Chang-Yong Nam, Matthew Y. Sfeir, Charles T. Black, Michael L. Steigerwald, Yueh-Lin Loo, Fay Ng, X.-Y. Zhu, Colin Nuckolls Sep 2015

Molecular Helices As Electron Acceptors In High-Performance Bulk Heterojunction Solar Cells, Yu Zhong, M. Tuan Trinh, Rongsheng Chen, Geoffrey E. Purdum, Petr P. Khlyabich, Melda Sezen, Seokjoon Oh, Haiming Zhu, Brandon Fowler, Boyuan Zhang, Wei Wang, Chang-Yong Nam, Matthew Y. Sfeir, Charles T. Black, Michael L. Steigerwald, Yueh-Lin Loo, Fay Ng, X.-Y. Zhu, Colin Nuckolls

Publications and Research

Despite numerous organic semiconducting materials synthesized for organic photovoltaics in the past decade, fullerenes are widely used as electron acceptors in highly efficient bulk-heterojunction solar cells. None of the non-fullerene bulk heterojunction solar cells have achieved efficiencies as high as fullerene-based solar cells. Design principles for fullerene-free acceptors remain unclear in the field. Here we report examples of helical molecular semiconductors as electron acceptors that are on par with fullerene derivatives in efficient solar cells. We achieved an 8.3% power conversion efficiency in a solar cell, which is a record high for non-fullerene bulk heterojunctions. Femtosecond transient absorption spectroscopy revealed …


Photoacoustic Calorimetry Studies Of The Earliest Events In Horse Heart Cytochrome-C Folding, Tarah A. Word Sep 2015

Photoacoustic Calorimetry Studies Of The Earliest Events In Horse Heart Cytochrome-C Folding, Tarah A. Word

USF Tampa Graduate Theses and Dissertations

The protein folding problem involves understanding how the tertiary structure of a protein is related to its primary structure. Hence, understanding the thermodynamics associated with the rate-limiting steps for the formation of the earliest events in folding is most crucial to understanding how proteins adopt native secondary and tertiary structures. In order to elucidate the mechanism and pattern of protein folding, an extensively studied protein, Cytochrome-c (Cc), was chosen as a folding system to obtain detailed time-resolved thermodynamic profiles for the earliest events in the protein folding process. Cytochrome-c is an ideal system for understanding the folding process for several …


Investigаtiоn Оf 3d Structures Оf Γ-Aaрeрtide Bаsed Peрtidоmimetics, Qiao Qiao Sep 2015

Investigаtiоn Оf 3d Structures Оf Γ-Aaрeрtide Bаsed Peрtidоmimetics, Qiao Qiao

USF Tampa Graduate Theses and Dissertations

Oligomers which have a tendency to form well-defined secondary structures are called foldamers. They offer an attractive opportunity for the design of novel molecules that mimic the structures and functions of proteins and enzymes including biocatalysis and biomolecular recognition. Herein a new class of non-natural γ-AApeptides and their derivatives are synthesized and studied in our lab. Previous studies of γ-AApeptides have revealed that they are highly resistant to proteolysis, and have virtually limitless potential in functional group diversity. However, to improve the bio-activity and explore new bio-applications, the understanding of the folding conformation of γ-AApeptides are necessary. Thus, NMR spectroscopy …


Identifying The Tautomeric Form Of A Deoxyguanosine-Estrogen Quinone Intermediate, Douglas E. Stack Sep 2015

Identifying The Tautomeric Form Of A Deoxyguanosine-Estrogen Quinone Intermediate, Douglas E. Stack

Chemistry Faculty Publications

Mechanistic insights into the reaction of an estrogen o-quinone with deoxyguanosine has been further investigated using high level density functional calculations in addition to the use of 4-hyroxycatecholestrone (4-OHE1) regioselectivity labeled with deuterium at the C1-position. Calculations using the M06-2X functional with large basis sets indicate the tautomeric form of an estrogen-DNA adduct present when glycosidic bonds cleavage occurs is comprised of an aromatic A ring structure. This tautomeric form was further verified by use of deuterium labelling of the catechol precursor use to form the estrogen o-quinone. Regioselective deuterium labelling at the C1-position of the estrogen A ring allows …


Utilization Of Antibody-Conjugated Gold Nanoparticles, Dynamic Light Scattering And Sers In Influenza Virus Detection, Yen Hoang Lai Sep 2015

Utilization Of Antibody-Conjugated Gold Nanoparticles, Dynamic Light Scattering And Sers In Influenza Virus Detection, Yen Hoang Lai

Theses and Dissertations

Influenza A H3N2, H1N1, and influenza B viruses primarily cause winter illness in humans, leading to significant morbidity and mortality in the population of the very young, the elderly, and people with chronic disease. In addition to the regular seasonal epidemics of influenza, influenza pandemics associated with the emergence of new influenza A strains are threatening due to high levels of mortality, social disruption, and economic losses. These novel strains are not affected by the human immunity developed to older strains of influenza, therefore can spread readily and infect a vast number of people. The most recent flu pandemic outbreak …


Synthesis, Crystal Structures, And Dft Calculations Of Three New Cyano(Phenylsulfonyl)Indoles And A Key Synthetic Precursor Compound, William Montgomery, Justin Lopchuk, Gordon Gribble, Jerry Jasinski Sep 2015

Synthesis, Crystal Structures, And Dft Calculations Of Three New Cyano(Phenylsulfonyl)Indoles And A Key Synthetic Precursor Compound, William Montgomery, Justin Lopchuk, Gordon Gribble, Jerry Jasinski

Dartmouth Scholarship

Three cyano-1-(phenylsulfonyl)indole derivatives, 3-cyano-1-(phenylsulfonyl) indole, (I), 2-cyano-1-(phenylsulfonyl)indole, (II), and 2,3-dicyano-1-(phenylsulfonyl) indole, (III), and a key synthetic precursor 1-(phenylsulfonyl)-1-(1,1-dimethylethyl) indole-3-carboxamide, (IV), have been synthesized and their structures determined by single crystal X-ray crystallography. (I), C15H10N2O2S, is orthorhombic with space group P 212121 and cell constants: a = 4.9459(3) Å, b = 10.5401(7) Å, c = 25.0813(14) Å, V = 1307.50(14) Å3 and Z = 4. (II), C15H10N2O2S, …


Effect Of Quercetin, Genistein And Kaempferol On Glutathione And Glutathione-Redox Cycle Enzymes In 3t3-L1 Preadipocytes, William Y. Boadi, Paul K. Amartey, Andrew Lo Sep 2015

Effect Of Quercetin, Genistein And Kaempferol On Glutathione And Glutathione-Redox Cycle Enzymes In 3t3-L1 Preadipocytes, William Y. Boadi, Paul K. Amartey, Andrew Lo

Chemistry Faculty Research

Context and objective: Many studies have shown that cellular redox potential is largely determined by glutathione (GSH), which accounts for more than 90% of cellular nonprotein thiols. The aim of this study was to delineate the effect of three flavonoids – namely, quercetin, kaempferol and genistein – and exogenous GSH on oxidative damage by the Fenton’s pathway through the GSH and GSH-redox cycle enzymes in 3T3-L1 cells. Materials and methods: 3T3-L1 preadipocytes were exposed to each flavonoid and GSH at concentrations of 0, 5, 10, 15, 20 and 25 µM and then GSH levels and activities of glutathione peroxidase (GSH-Px), …


Efficient Photochemical Synthesis Of Peptide-Α-Phenylthioesters, Andrew Pardo, Tyrone J. Hogenauer, Zhefeng Cai, Julian A. Vellucci, Efrain M. Castillo, Carl W. Dirk, Andreas H. Franz, Katja Michael Sep 2015

Efficient Photochemical Synthesis Of Peptide-Α-Phenylthioesters, Andrew Pardo, Tyrone J. Hogenauer, Zhefeng Cai, Julian A. Vellucci, Efrain M. Castillo, Carl W. Dirk, Andreas H. Franz, Katja Michael

College of the Pacific Faculty Articles

Low yields and substantial epimerization of peptide-α-thioesters often compromise the overall efficiency of native chemical ligation (NCL). Peptide arylthioesters are more reactive than peptide alkylthioesters in NCL, but are also more difficult to handle due to their propensity to hydrolyze, and are therefore often generated in situ. However, pre-prepared peptide arylthioesters are required for some NCL applications. Here we present a 7-nitroindoline-based photochemical method that generates protected peptide phenylthioesters under neutral reaction conditions via their activated esters from photoreactive peptide precursors in high isolated yields, and with low levels of epimerization. This method is fully compatible with Fmoc-strategy solid-phase peptide …


Enzyme Localization, Crowding, And Buffers Collectively Modulate Diffusion-Influenced Signal Transduction: Insights From Continuum Diffusion Modeling, Peter M. Kekenes-Huskey, Changsun Eun, J. A. Mccammon Sep 2015

Enzyme Localization, Crowding, And Buffers Collectively Modulate Diffusion-Influenced Signal Transduction: Insights From Continuum Diffusion Modeling, Peter M. Kekenes-Huskey, Changsun Eun, J. A. Mccammon

Chemistry Faculty Publications

Biochemical reaction networks consisting of coupled enzymes connect substrate signaling events with biological function. Substrates involved in these reactions can be strongly influenced by diffusion “barriers” arising from impenetrable cellular structures and macromolecules, as well as interactions with biomolecules, especially within crowded environments. For diffusion-influenced reactions, the spatial organization of diffusion barriers arising from intracellular structures, non-specific crowders, and specific-binders (buffers) strongly controls the temporal and spatial reaction kinetics. In this study, we use two prototypical biochemical reactions, a Goodwin oscillator, and a reaction with a periodic source/sink term to examine how a diffusion barrier that partitions substrates controls reaction …


Characterization Of Folic Acid And Poly(Amidoamine) Dendrimer Interactions With Folate Binding Protein: A Force-Pulling Study, Pascale R. Leroueil, Stassi Dimaggio, Abigail N. Leistra, Craig D. Blanchette Sep 2015

Characterization Of Folic Acid And Poly(Amidoamine) Dendrimer Interactions With Folate Binding Protein: A Force-Pulling Study, Pascale R. Leroueil, Stassi Dimaggio, Abigail N. Leistra, Craig D. Blanchette

University Faculty Publications and Creative Works

Atomic force microscopy force-pulling experiments have been used to measure the binding forces between folic acid (FA) conjugated poly(amidoamine) (PAMAM) dendrimers and folate binding protein (FBP). The generation 5 (G5) PAMAM conjugates contained an average of 2.7, 4.7, and 7.2 FA per dendrimer. The most probable rupture force was measured to be 83, 201, and 189 pN for G5-FA2.7, G5-FA4.7, and G5-FA7.2, respectively. Folic acid blocking experiments for G5-FA7.2reduced the frequency of successful binding events and increased the magnitude of the average rupture force to 274 pN. The force data are interpreted as arising from a network of van der …


Design, Synthesis And Evaluation Of Bivalent Inhibitors Of Trehalose-6-Phosphate Phosphatase, Chunliang Liu Sep 2015

Design, Synthesis And Evaluation Of Bivalent Inhibitors Of Trehalose-6-Phosphate Phosphatase, Chunliang Liu

Chemistry and Chemical Biology ETDs

The D-glucose disaccharide α, α-D-trehalose is synthesized by a variety of bacteria, fungi, plants and invertebrates to support cell survival by functioning as a fuel, a metabolic regulator or a protectant against environmental stress. Five different trehalose biosynthetic pathways are known to exist, one of which, the OtsA/OtsB pathway is common among pathogenic bacteria and fungi and is also found in parasitic nematodes. Previously reported otsA and otsB gene knockout (or knockdown) experiments have shown that both pathway enzymes are essential for M. tuberculosis cell growth and host colonization. RNAi gene silencing carried out in the nematode model system Caenohabditis …


Mining Public Databases For Discovery Of Structure And Function Within The Hotdog-Fold Thioesterase And Had Phosphatase Enzyme Families, Sarah Toews Keating Sep 2015

Mining Public Databases For Discovery Of Structure And Function Within The Hotdog-Fold Thioesterase And Had Phosphatase Enzyme Families, Sarah Toews Keating

Chemistry and Chemical Biology ETDs

For my doctoral work, I have developed strategies to mine public databases for data that can be used to infer structural and functional information for the hotdog-fold and HADSF superfamilies. For the hotdog-fold superfamily, I used curated and automatically applied annotations of structure, taxonomic lineage, function, and subfamily membership from the UniProtKB, gene context and taxonomic information from the NCBI, and the results of several in-depth explorations of subfamily/function and structural class membership. Based on the distribution of the aforementioned annotations mapped onto a sequence similarity network (SSN), I applied structural assignments to sequences and/or specific function/subfamily assignments to ~143,000 …


Case Studies Of The Hot Dog-Fold And Acyl-Adenylate-Forming Superfamilies: Characterizing The Importance Of Functional Divergence In Cellular Metabolism, Lucas R. Zimney Sep 2015

Case Studies Of The Hot Dog-Fold And Acyl-Adenylate-Forming Superfamilies: Characterizing The Importance Of Functional Divergence In Cellular Metabolism, Lucas R. Zimney

Chemistry and Chemical Biology ETDs

Some of the biggest contributors to cellular respiration (and cellular metabolism in general) are acyl-CoA derivatives, a subclass of biological thioesters. Known to function in a variety of pathways, the regulation of their formation and breakdown are critical, carried about by acyl-CoA synthetases and thioesterases, respectively. The work reported within this dissertation will focus on functional divergence within two enzyme superfamilies -- the hot dog-fold and acyl-adenylate-forming superfamilies — and can be broken down into two main parts. Part one will look at tracking the functional divergence within the hot dog-fold superfamily thioesterases. A highly evolved thioesterase, flK, has been …


Determination Of Triapine, A Ribonucleotide Reductase Inhibitor, In Human Plasma By Liquid Chromatography Tandem Mass Spectrometry, Ye Feng, Charles A. Kunos, Yan Xu Sep 2015

Determination Of Triapine, A Ribonucleotide Reductase Inhibitor, In Human Plasma By Liquid Chromatography Tandem Mass Spectrometry, Ye Feng, Charles A. Kunos, Yan Xu

Chemistry Faculty Publications

Triapine is an inhibitor of ribonucleotide reductase (RNR). Studies have shown that triapine significantly decreases the activity of RNR and enhanced the radiation-mediated cytotoxicity in cervical and colon cancer. In this work, we have developed and validated a selective and sensitive LC-MS/MS method for the determination of triapine in human plasma. In this method, 2-[(3-fluoro-2-pyridinyl)methylene] hydrazinecarbothioamide (NSC 266749) was used as the internal standard (IS); plasma samples were prepared by deproteinization with acetonitrile; tripaine and the IS were separated on a Waters Xbridge Shield RP18 column (3.5 µm; 2.1 × 50 mm) using a mobile phase containing 25.0% methanol and …


A Mechanism For Biologically Induced Iodine Emissions From Sea Ice, A. Saiz-Lopez, Christopher S. Blaszczak-Boxe, L. J. Carpenter Sep 2015

A Mechanism For Biologically Induced Iodine Emissions From Sea Ice, A. Saiz-Lopez, Christopher S. Blaszczak-Boxe, L. J. Carpenter

Publications and Research

Ground- and satellite-based measurements have reported high concentrations of iodine monoxide (IO) in coastal Antarctica. The sources of such a large iodine burden in the coastal Antarctic atmosphere remain unknown.We propose a mechanism for iodine release from sea ice based on the premise that micro-algae are the primary source of iodine emissions in this environment. The emissions are triggered by the biological production of iodide (I�) and hypoiodous acid (HOI) from micro-algae (contained within and underneath sea ice) and their diffusion through sea-ice brine channels, ultimately accumulating in a thin brine layer (BL) on the surface of sea ice. Prior …


The Ras G Domain Lacks The Intrinsic Propensity To Form Dimers, Elizaveta A. Kovrigina, Azamat R. Galiakhmetov, Evgenii L. Kovrigin Sep 2015

The Ras G Domain Lacks The Intrinsic Propensity To Form Dimers, Elizaveta A. Kovrigina, Azamat R. Galiakhmetov, Evgenii L. Kovrigin

Chemistry Faculty Research and Publications

Ras GTPase is a molecular switch controlling a number of cellular pathways including growth, proliferation, differentiation, and apoptosis. Recent reports indicated that Ras undergoes dimerization at the membrane surface through protein-protein interactions. If firmly established this property of Ras would require profound reassessment of a large amount of published data and modification of the Ras signaling paradigm. One proposed mechanism of dimerization involves formation of salt bridges between the two GTPase domains (G domains) leading to formation of a compact dimer as observed in Ras crystal structures. In this work, we interrogated the intrinsic ability of Ras to self-associate in …


Globally Profiling Sialylation Status Of Macrophages Upon Statin Treatment, Dan Wang, Huan Nie, Evgeny Ozhegov, Lin Wang, Aimin Zhou, Yu Li, Xue Long Sun Sep 2015

Globally Profiling Sialylation Status Of Macrophages Upon Statin Treatment, Dan Wang, Huan Nie, Evgeny Ozhegov, Lin Wang, Aimin Zhou, Yu Li, Xue Long Sun

Chemistry Faculty Publications

Sialic acids (SAs) are widely expressed on immune cells and their levels and linkages named as sialylation status vary upon cellular environment changes related to both physiological and pathological processes. In this study, we performed a global profiling of the sialylation status of macrophages and their release of SAs in the cell culture medium by using flow cytometry, confocal microscopy and liquid chromatography tandem mass spectrometry (LC-MS/MS). Both flow cytometry and confocal microscopy results showed that cell surface α-2,3-linked SAs were predominant in the normal culture condition and changed slightly upon treatment with atorvastatin for 24 h, whereas α-2,6-linked SAs …


An Allosteric Interaction Links Usp7 To Deubiquitination And Chromatin Targeting Of Uhrf1, Zhi-Min Zhang, Scott B. Rothbart, David F. Allison, Qian Cai, Joseph S. Harrison, Lin Li, Yinsheng Wang, Brian D. Strahl, Gang Greg Wang, Jikui Song Sep 2015

An Allosteric Interaction Links Usp7 To Deubiquitination And Chromatin Targeting Of Uhrf1, Zhi-Min Zhang, Scott B. Rothbart, David F. Allison, Qian Cai, Joseph S. Harrison, Lin Li, Yinsheng Wang, Brian D. Strahl, Gang Greg Wang, Jikui Song

College of the Pacific Faculty Articles

The protein stability and chromatin functions of UHRF1 (ubiquitin-like, containing PHD and RING finger domains, 1) are regulated in a cell-cycle-dependent manner. We report a structural characterization of the complex between UHRF1 and the deubiquitinase USP7. The first two UBL domains of USP7 bind to the polybasic region (PBR) of UHRF1, and this interaction is required for the USP7-mediated deubiquitination of UHRF1. Importantly, we find that the USP7-binding site of the UHRF1 PBR overlaps with the region engaging in an intramolecular interaction with the N-terminal tandem Tudor domain (TTD). We show that the USP7-UHRF1 interaction perturbs the TTD-PBR interaction of …


An Analytical Method For Detecting Toxic Metal Cations Using Cyclotriveratrylene Derivative Capped Gold Nanoparticles, Zachary R. Osner, Richard C. Holz, Daniel P. Becker Ph.D. Sep 2015

An Analytical Method For Detecting Toxic Metal Cations Using Cyclotriveratrylene Derivative Capped Gold Nanoparticles, Zachary R. Osner, Richard C. Holz, Daniel P. Becker Ph.D.

Chemistry: Faculty Publications and Other Works

Cyclotriveratrylene-oxime (CTV-oxime) derivatives that terminate with a dithiolate linker were synthesized enabling the supramolecular scaffold to adhere to gold nanoparticles (AuNPs) with the bowl-shaped cavity of the CTV scaffold exposed for utilization in host–guest chemistry. Exposure of these CTV functionalized AuNPs to varying concentrations of di- and trivalent metal cations resulted in the formation of large CTV-AuNP polymeric clusters and an accompanying a shift in the plasmon resonance. These interactions between the CTV-AuNPs and the metal cations in solution provides proof-of-concept that supramolecular functionalized AuNPs can be used as a simple and straightforward, on-site detection system for toxic metal cations …