Chemistry Commons^™

Importance Of Aerosol Composition, Mixing State And Morphology For Heterogeneous Ice Nucleation: A Combined Field And Laboratory Approach, Kelly J. Baustian, Daniel J. Cziczo, Matthew E. Wise, Kerri A. Pratt, Gourihar Kulkarni, A. Gannet Hallar, Margaret A. Tolbert

CUP Faculty Research

In this study chemical compositions of background aerosol and ice nuclei were examined through laboratory investigations using Raman spectroscopy and field measurements by single-particle mass spectrometry. Aerosol sampling took place at Storm Peak Laboratory in Steamboat Springs, Colorado (elevation of 3210 m). A cascade impactor was used to collect coarse-mode aerosol particles for laboratory analysis by Raman spectroscopy; the composition, mixing state, and heterogeneous ice nucleation activity of individual particles were examined. For in situ analysis of fine-mode aerosol, ice nucleation on ambient particles was observed using a compact ice nucleation chamber. Ice crystals were separated from unactivated aerosol using …

Remote Sensing Phase Fluorimetry Using Mercury Vapor Lamp, Matthew J. Bohn, Michael A. Lundin

AFIT Patents

An efficient and portable method for remote detection of a target mineral material through frequency domain fluorimetry, a detection technique that measures the time lag between absorption and emission of photons, thereby determining the lifetime of said target mineral material. As claimed and disclosed in the present invention, mercury vapor lamps, a common source of industrial facility lighting, emit radiation that overlaps the UV/blue absorption spectrum of many fluorophores and may be used as an efficient and portable excitation source for remote frequency domain fluorimetry.

Polystyrenesulfonate-Catalyzed Synthesis Of Novel Pyrroles Through Paal-Knorr Reaction, Mandira Banik, Bianca Ramirez, Ashwini Reddy, Debasish Bandyopadhyay, Bimal K. Banik

School of Integrative Biological & Chemical Sciences (Formerly Dept. of Chemistry)

Background: The classical Paal-Knorr reaction is one of the simplest and most economical methods for the synthesis of biologically important and pharmacologically useful pyrrole derivatives.

Results: Polystyrenesulfonate-catalyzed simple synthesis of substituted pyrroles following Paal-Knorr reaction has been accomplished with an excellent yield in aqueous solution. This method also produces pyrroles with multicyclic polyaromatic amines.

Conclusions: The present procedure for the synthesis of N-polyaromatic substituted pyrroles will find application in the synthesis of potent biologically active molecules.

Rational Design And Characterization Of D-Phe-Pro-D-Arg-Derived Direct Thrombin Inhibitors, Ana C. Figueiredo, Christina C. Clement, Sheuli Zakia, Julian Gingold, Manfred Philipp, Pedro J.B. Pereira

Publications and Research

The tremendous social and economic impact of thrombotic disorders, together with the considerable risks associated to the currently available therapies, prompt for the development of more efficient and safer anticoagulants. Novel peptide-based thrombin inhibitors were identified using in silico structure-based design and further validated in vitro. The best candidate compounds contained both l- and d-amino acids, with the general sequence d-Phe(P3)-Pro(P2)-d-Arg(P1)-P1'-CONH2. The P1' position was scanned with l- and d-isomers of natural or unnatural amino acids, covering the major chemical classes. The most potent non-covalent and proteolysis-resistant inhibitors contain small hydrophobic or polar amino acids (Gly, Ala, Ser, Cys, Thr) …

Correction To Fully Enclosed Microfluidic Paper-Based Analytical Devices, Kevin M. Schilling, Anna L. Lepore, Jason A. Kurian, Andres W. Martinez

Chemistry and Biochemistry

There is an error in the units of the concentrations of potassium iodide and trehalose described in the experimental details on page 1581. The correct concentrations are 0.6 M potassium iodide and 0.3 M trehalose.

Investigation And Synthesis Of Novel Graphene-Based Nanocomposites For Hydrogen Storage, Anthony Joseph D'Angelo

USF Tampa Graduate Theses and Dissertations

It is of great interest to develop and utilize a high surface area material with optimized hydrogen sorption properties. The need for a renewable energy source to replace automobile gasoline has become more critical in the past decade. Hydrogen is a viable fuel source for automobile usage; however, the question of how hydrogen will be safely and efficiently stored still remains. Critical factors for optimum hydrogen storage include ambient conditions and low activation temperature for adsorption and desorption phenomena. In order for optimum hydrogen adsorption to be achieved, the properties of (1) high surface area, (2) optimum hydrogen adsorption energy, …

Chemical Mechanism Of Udp-Galactopyranose Mutase From Trypanosoma Cruzi: A Potential Drug Target Against Chagas' Disease, Michelle Oppenheimer, Ana Lisa Valenciano, Karina Kizjakina, Jun Qi, Pablo Sobrado

Chemistry Faculty Research & Creative Works

UDP-galactopyranose mutase (UGM) is a flavoenzyme that catalyzes the conversion of UDP-galactopyranose to UDP-galactofuranose, the precursor of galactofuranose (Galf). Galf is found in several pathogenic organisms, including the parasite Trypanosoma cruzi, the causative agent of Chagas' disease. Galf) is important for virulence and is not present in humans, making its biosynthetic pathway an attractive target for the development of new drugs against T. cruzi. Although UGMs catalyze a non-redox reaction, the flavin must be in the reduced state for activity and the exact role of the flavin in this reaction is controversial. The kinetic and chemical mechanism of TcUGM was …

Design And Construction Of Functional Metal-Metalloporphyrin Frameworks, Le Meng

USF Tampa Graduate Theses and Dissertations

Porous metal-organic frameworks are a new type of functional materials with potential applications for gas storage, gas separation, catalysis, biomedical and chemical sensors. This thesis describes several porous metal-metalloporphyrin frameworks (MMPFs), which were synthesized with a series of transition metals and 5,15-bis(3,5-dicarboxyphenyl)-10,20-bis(2,6-dibromophenyl)porphine. Among these MMPFs, the cobalt MMPF (CoBrPTC) has a fcu structure, which represents the first porphyrin-based MOF with this topology. CoBrPTC was evaluated as heterogeneous catalyst and demonstrated interesting catalytic performances.

Crystal Structures And Small-Angle X-Ray Scattering Analysis Of Udp-Galactopyranose Mutase From The Pathogenic Fungus Aspergillus Fumigatus, Richa Dhatwalia, Harkewal Singh, Michelle Oppenheimer, Dale B. Karr, Jay C. Nix, Pablo Sobrado, John J. Tanner

Chemistry Faculty Research & Creative Works

UDP-galactopyranose mutase (UGM) is a flavoenzyme that catalyzes the conversion of UDP-galactopyranose to UDP-galactofuranose, which is a central reaction in galactofuranose biosynthesis. Galactofuranose has never been found in humans but is an essential building block of the cell wall and extracellular matrix of many bacteria, fungi, and protozoa. The importance of UGM for the viability of many pathogens and its absence in humans make UGMa potential drug target. Here we report the first crystal structures and small-angle x-ray scattering data for UGM from the fungus Aspergillus fumigatus, the causative agent of aspergillosis. The structures reveal that Aspergillus UGM has several …

Structural Basis For Ca 2+-Induced Activation And Dimerization Of Estrogen Receptor Alpha By Calmodulin, Yonghong Zhang, Zhigang Li, David B. Sacks, James B. Ames

School of Integrative Biological & Chemical Sciences (Formerly Dept. of Chemistry)

The estrogen receptor α (ER-α) regulates expression of target genes implicated in development, metabolism, and breast cancer. Calcium-dependent regulation of ER-α is critical for activating gene expression and is controlled by calmodulin (CaM). Here, we present the NMR structures for the two lobes of CaM each bound to a localized region of ER-α (residues 287–305). A model of the complete CaM·ER-α complex was constructed by combining these two structures with additional data. The two lobes of CaM both compete for binding at the same site on ER-α (residues 292, 296, 299, 302, and 303), which explains why full-length CaM binds …

Synthesis, Characterization, And Evaluation Of A Heat Stabilizing Siloxane, Joel D. Kennard

Master's Theses and Doctoral Dissertations

Siloxanes, renowned for their heat resistance and release properties, are prone to oxidize above 200°C. The goal herein is to increase siloxane bath life used in fuser roll applications at temperatures above 200°C, yielding faster production, less waste, and cost savings by keeping the bath viscosity stable through prevention of thermal degradation.

The methods detailed herein react a hydrosiloxane with an amino functional alcohol (4-(phenylamino)-phenol). The alcoholysis (or dehydrogenative coupling) moves forward with the removal of hydrogen and formation of the desired product (Scheme 1). Reactions were conducted on both NMR scale and lab scale.

The results of the synthesis …

In Situ Synthesis Of Oligonucleotide Arrays On Surfaces Coated With Crosslinked Polymer Multilayers, Adam H. Broderick, Matthew R. Lockett, Maren E. Buck, Yuan Yuan, Lloyd M. Smith, David M. Lynn

Chemistry: Faculty Publications

We report an approach to the in situ synthesis of oligonucleotide arrays on surfaces coated with crosslinked polymer multilayers. Our approach makes use of methods for the "reactive" layer-by-layer assembly of thin, amine-reactive multilayers using branched polyethyleneimine (PEI) and the azlactone-functionalized polymer poly(2-vinyl-4,4′-dimethylazlactone) (PVDMA). Postfabrication treatment of film-coated glass substrates with d-glucamine or 4-amino-1-butanol yielded hydroxyl-functionalized films suitable for the Maskless Array Synthesis (MAS) of oligonucleotide arrays. Glucamine-functionalized films yielded arrays of oligonucleotides with fluorescence intensities and signal-to-noise ratios (after hybridization with fluorescently labeled complementary strands) comparable to those of arrays fabricated on conventional silanized glass substrates. These arrays could …

Drug Delivery Strategies Using Light Sensitive Molecules, Martin Dcona

Theses and Dissertations

Cancer remains one of the most dreaded diseases due to inevitable suffering and possible fatality. Only cardiac disease has caused more deaths than cancer. Present day cancer treatment involves radiation, surgery or chemotherapy. In chemotherapy, an anti-tumoral drug is used to treat the tumor either by killing or stalling the growth of the tumor cells. In certain types of cancer, for e.g. metastatic breast cancer, the first line of therapy is often chemotherapy. But the inability of current clinically approved drugs to selectively target tumor cells, ultimately results in side effects. To reduce these side effects, prodrug therapies have been …

Novel Phosducin-Like Protein Binding Partners: Exploring Chaperone And Tumor Suppressor Protein Interactions, Amy Jetaun Gray

Theses and Dissertations

Many proteins cannot fold into their native state without the assistance of one or more molecular chaperones. Chaperonins are an essential class of chaperones that provide an isolated chamber for proteins to fold. CCT, a group II chaperonin found in eukaryotes assists in the folding of actins, tubulins, and many other cellular proteins. PhLP1 is a member of the phosducin protein family that assists CCT in the folding of Gβ and its subsequent assembly with Gγ. However, previous studies have not addressed the scope of PhLP1 and CCT-mediated Gβγ; assembly. The data presented in Chapter 2 shows that PhLP1 plays …

Follicular Dendritic Cells, Human Immunodeficency Virus Type 1, And Alpha 1 Antitrypsin, Xueyuan Zhou

Theses and Dissertations

HIV/AIDS is raging and causing millions of deaths around the world. The major challenge in treating HIV/AIDS is the establishment of HIV reservoirs where the viruse escapes both drug and immune system attempts at eradication. Throughout the course of HIV/AIDS, productive HIV infection occurs primarily in the lymphoid follicles or germinal centers (GC) surrounding follicular dendritic cells (FDC). In the GCs, FDCs trap and maintain infectious HIV for years and provide these infectious viruses to the host cells. FDCs also attract B and T cells into the GCs and increase the ability of CD4+ T cells to be infected. Additionally, …

Optical And Mass Spectrometric Studies Of A Helium Dielectric-Barrier Atmospheric-Pressure Plasma Jet Used As An Ambient Desorption Ionization Source, Matthew Spencer Heywood

Theses and Dissertations

Recently there has been a surge in the field of mass spectrometry centered around the concept of rapid analysis of target analytes with minimal or no sample preparation. The target analyte undergoes desorption from its surface of origin and is subsequently ionized under ambient conditions. The technique is termed ambient desorption/ionization mass spectrometry (ADI-MS). Since the introduction of ADI-MS in 2004, there has been an explosion of research based around the development of novel ambient desorption/ionization (ADI) sources with the capability of desorbing and ionizing a variety of target analytes from various sampling surfaces. One type of ADI source uses …

Removal Of Bisphenol A Model Compounds And Related Substances Using Octolig®, Rachael Josephine Alessio

USF Tampa Graduate Theses and Dissertations

Bisphenol A used in the production of polycarbonate plastics and epoxy resins is ubiquitous in the environment. The raw material is released to the environment during the manufacturing process and by leaching from consumer products. Recent studies are suggesting that low-dose amounts of Bisphenol A may have adverse health effects on humans. The possibility of removing Bisphenol A from natural water sources or from solvents used to extract the material from consumer products before they enter the market has been studied. The use of model compounds and related substances (4-isopropylphenol, 4-(t-butyl) phenol, and nitrophenols) have been used to study their …

Towards One Key To One Lock: Catalyst Modified Indium Oxide Nanoparticle Thin Film Sensor Array For Selective Gas Detection, Kun Yao, Daniela Caruntu, Sarah Wozny, Rong Huang, Yumi H. Ikuhara, Baobao Cao, Charles J. O'Connor, Weilie Zhou

Advanced Materials Research Institute (AMRI)

Homogeneous In2O3 nanoparticles (NPs) were self-assembled into thin film sensor arrays on a single chip, with further surface modification by noble metal catalysts. The NP film sensor arrays show clear current responses when exposed to different target gases, and both sensitivity and selectivity were greatly improved. Particularly, the sensors modified with Au, Pd, and Pt nanocatalysts demonstrated higher sensitivity to H2S, H-2 and CO, respectively, making the gas discrimination direct and simple, like "one key to one lock". The particle size dependence of the noble metal modifiers to the sensitivity was further investigated by tuning the sputtering parameters. Three different …

A Microwave-Assisted Bismuth Nitrate-Catalyzed Unique Route Toward 1,4-Dihydropyridines, Debasish Bandyopadhyay, Stephanie Maldonado, Bimal K. Banik

School of Integrative Biological & Chemical Sciences (Formerly Dept. of Chemistry)

The classical Hantzsch reaction is one of the simplest and most economical methods for the synthesis of biologically important and pharmacologically useful 1,4-dihydropyridine derivatives. Bismuth nitrate pentahydrate under microwave irradiation is proven to act as a very efficient catalyst for a one-pot, three-component synthesis of 1,4-dihydropyridines in excellent yields from diverse amines/ammonium acetate, aldehydes and 1,3-dicarbonyl compounds within 1-3 min under solvent-free conditions. The present environmentally benign procedure for the synthesis of 1,4-dihydropyridines is suitable for library synthesis and it will find application in the synthesis of potent biologically active molecules. The excellent yield and extreme rapidity of the method …

Compound-Specific Stable Isotopic Analysis Of Protein Amino Acids: Ecological Applications In Modern And Ancient Systems, Greg Ellis

USF Tampa Graduate Theses and Dissertations

Stable isotopic analysis of the major biochemically important elements is an increasingly utilized tool in the study of ecology. Patterns of isotopic fractionation in carbon and nitrogen are used to determine trophic linkages, nutrient pathways, and sources of primary production in numerous contexts. Traditional techniques rely on measurements made of bulk samples such as tissue, but emerging methods using individual chemical compounds provide a means of achieving deeper understanding in a variety of inquiries.

Amino acids, as the building blocks of proteins, are the dominant nitrogen-bearing biomolecules and are a major constituent of all life. Patterns of isotopic fractionation during …

Session A-1: Environmental Chemistry – Chemistry In Context, Branson Lawrence

Professional Learning Day

The use of the ACS curriculum combined with group and individual projects to teach entry level chemistry through the context of environmental chemistry.

Nabr Poisoning Of Au/Tio2 Catalysts: Effects On Kinetics, Poisoning Mechanism, And Estimation Of The Number Of Catalytic Active Sites, Bert D. Chandler, Shane Kendell, H. Doan, Rachel Korkosz, L. C. Grabow, Christopher J. Pursell

Chemistry Faculty Research

Sodium bromide was used to intentionally poison a commercial Au/TiO2 catalyst with the goals of understanding the nature of halide poisoning and evaluating the number and nature of the catalytic active sites. A series of eight poisoned catalysts were prepared by impregnating the parent catalyst with methanolic solutions of NaBr. Each catalyst was tested with CO oxidation catalysis under differential reactor conditions; O2 reaction orders and Arrhenius activation energies were determined for each material. All of the kinetic data, including a Michaelis−Menten analysis, indicated that the primary effect of adding NaBr was to reduce the number of catalytically active sites. …

Probe Functionalization With A Rhop-3 Antibody: Toward A Rhop-3 Antigen Immunosensor For Detection Of Malaria, Salaam Saleh, Susan Moreno Molek, Perera N. Indika, Alan Riga, Tobili Sam Yellowe, Mekki Bayachou

Chemistry Faculty Publications

The antibody specific for the malaria protein, Rhop-3, and FL-Rhop-3, were immobilized on the surface of a gold electrode modified with cysteamine. Colloidal gold was used to enhance the detection signal for Rhop-3 antigens. The Rhop-3 antibody was also immobilized on gold electrodes preactivated with dithiobis(succinimidyl proprionate) (DSP). Immobilization was performed at room temperature and at 37 °C. Cyclic voltammetry (CV) was used to monitor the interaction between the immobilized antibody and its cognate antigen in solution, using ferricyanide, K3Fe(CN)6, as reporting electroactive probe. Tests indicate recognition of Rhop-3 protein by the immobilized antibody. Antigen recognition was enhanced by incubation …

Tris(3-Nitropentane-2,4-Dionato-Κ O,O′)-Cobalt(Iii), Dean Johnston

Chemistry Faculty Scholarship

The structure of the title compound, [Co(C5H6NO4)3], consists of a CoIII ion octahedrally coordinated by three bidentate 3-nitro­pentane-2,4-dionate ligands. The complex was prepared via the nitration of tris­(2,4-penta­nedionato-κ2 O,O′)cobalt(III) with a solution of copper(II) nitrate in glacial acetic acid. The central C atom and the nitro group of one 3-nitro­pentane-2, 4-dionate ligand are disordered over two positions with an occupancy ratio of 0.848 (4):0.152 (4). A second nitro group is also disordered over two orientations with an occupancy ratio of 0.892 (7):0.108 (7). Two of the ligand methyl groups form C—H⋯O inter­actions with two different nitro groups to form chains …

Room Temperature Syntheses Of Entirely Diverse Substituted Β-Fluorofurans, Li Yan, Kraig A. Wheeler, Roman Dembinski

Faculty Research and Creative Activity

Synthesis of highly substituted 3-fluorofurans is reported. The sequence began with preparation of tertbutyldimethylsilyl alk-1-en-3-yn-1-yl ethers from 1,4-disubstituted alk-3-yn-1-ones. Subsequent fluorination of alkenynyl silyl ethers with Selectfluor gave 2-fluoroalk-3-yn-1-ones in almost quantitative yield. Subsequent 5-endo-dig cyclizations using chlorotriphenylphosphine gold(I)/silver trifluoromethanesulfonate (5/5 mol%), N-bromo- or N-iodosuccinimide and gold(I) chloride/zinc bromide (5/20 mol%), all at room temperature, provided a facile method for the generation of substituted 3-fluoro-, 3-bromo-4-fluoro-, and 3-fluoro-4-iodofurans in good yields. Also, 2,2-difluoroalk-3-yn-1-ones were prepared by fluorination of alk-3-yn-1-ones under organocatalytic conditions. The structures of (Z)-tertbutyldimethylsilyl but-1-en-3-yn-1-yl ether, 3-bromo-4-fluorofuran, and 3-fluoro-4-(phenylethynyl)furan were confirmed by X-ray crystallography.

Bond Resonance In Superconducting Rapid Cooled Alloys: (Bi1.7pb0.3sr2can‐1cuno2n+4+Δ)2, N=1 To 9 Detected By Novel Local Atomic Enhanced Xrd, K Tyson, J Kmiec, Juana Acrivos, D. Gulamova, J Chigvinadze

Faculty Publications, Chemistry

We discuss bond resonance in high temperature layer superconducting cuprates, HTLSC alloys: (Bi1.7Pb0.3Sr2Can‐1CunO2n+4+δ)2,n=1‐9 called (2s:2:n‐1:n) prepared in Uzbekistan from melts in concentrated sun flux, followed by rapid cooling, SFQA technology that preserves melt tiling, Tc,n measured in Tiblisi, and local atomic enhanced synchrotron X‐ray diffraction, XRD near the Cu K‐edge at DOE National Laboratory SLAC‐SSRL. The SFQA alloys structure indexed in the ideal D17 4h Space Group indicates (n‐1) units: (CuO2)1/2/Ca/(CuO2)1/2 are intercalated at each end of the n=1 phase [(CuO2)1/2/SrO/Bi1.7Pb0.3O/Bi1.7Pb0.3O/SrO/(CuO2)1/2]2. Surface effects lead to different n‐phase mixing, and periodic lattice distortions, PLD, through bond resonance in crystal axes: 2(rCu+2+rO‐2)=4.2Å …

Microarray Analysis As A Strategy To Identify And Characterize Glycome Regulatory, John F. Rakus

Chemistry Faculty Research

Glycosylation involves the post-translational addition of carbohydrates to protein molecules and is an intricate and indispensable biochemical process. Study of this complicated network of interactions is hindered by the lack of a coding template analogous to the genetic code, and by the vast structural complexity inherent to carbohydrate polymers. We use lectins (non-enzymatic carbohydrate-binding proteins of non-immunological origin) as microarray probes to identify carbohydrate features expressed on cellular surfaces. Specifically, we utilized lectin microarray technology to investigate the differences in carbohydrates expressed by the cell lines of the Nation Cancer Institute’s NCI-60 panel. Our investigation identified tissue-specific expression differences in …

Photochemistry Of Monochloro Complexes Of Copper(Ii) In Methanol Probed By Ultrafast Transient Absorption Spectroscopy, Andrey S. Mereshchenko, Suman K. Pal, Kanykey E. Karabaeva, Patrick Z. El-Khoury, Alexander N. Tarnovsky

Chemistry Faculty Publications

Ultrafast transient absorption spectra in the deep to near UV range (212-384 nm) were measured for the [Cu-II(MeOH)(5)Cl](+) complexes in methanol following 255-nm excitation of the complex into the ligand-to-metal charge-transfer excited state. The electronically excited complex undergoes sub-200 fs radiationless decay, predominantly via back electron transfer, to the hot electronic ground state followed by fast vibrational relaxation on a 0.4-4 Ps time scale. A minor photochemical channel is Cu-Cl bond dissociation, leading to the reduction of copper(H) to copper(I) and the formation of MeOH center dot Cl charge-transfer complexes. The depletion of ground-state [Cu-II(MeOH)(5)Cl](+) perturbs the equilibrium between several …

Synthesis And Analysis Of Novel Copolymers Of Ring-Substituted 2-Phenyl-1, 1-Dicyanoethylenes And Styrene, Subha Ramnarayan

College of Science and Health Theses and Dissertations

Trisubstituted Ethylene (TSE) monomers, ring substituted 2-phenyl-1, 1-dicyanoethylenes are synthesized by knoevenagel condensation of ring substituted benzaldehyde with malononitrite, catalyzed by piperidine. TSE monomers are copolymerized with system by radical chain polymerization.

K-Shell X-Ray Spectroscopy Of Atomic Nitrogen, M. M. Sant'anna, Gunnar Ohrwall, Wayne C. Stolte, Alfred S. Schlachter, Dennis W. Lindle, B. M. Mclaughlin

Chemistry and Biochemistry Faculty Research

Absolute K-shell photoionization cross sections for atomic nitrogen have been obtained from both experiment and state-of-the-art theoretical techniques. Because of the difficulty of creating a target of neutral atomic nitrogen, no high-resolution K-edge spectroscopy measurements have been reported for this important atom. Interplay between theory and experiment enabled identification and characterization of the strong 1s → np resonance features throughout the threshold region. An experimental value of 409.64 ± 0.02 eV was determined for the K-shell binding energy.