Chemistry Commons^™

The Infrared Spectrum Of The He-C2d2 Complex, N. Moazzen-Ahmadi, A. R. W. Mckellar, Berta Fernandez, David Farrelly

Chemistry and Biochemistry Faculty Publications

Spectra of the helium-acetylene complex are elusive because this weakly bound system lies close to the free rotor limit. Previously, limited assignments of He–C2D2 transitions in the R(0) region of the ν3 fundamental band (≈2440 cm⁻¹) were published. Here, new He–C2D2 infrared spectra of this band are obtained using a tunable optical parametric oscillator laser source to probe a pulsed supersonic slit jet expansion from a cooled nozzle, and the analysis is extended to the weaker and more difficult P(1) and R(1) regions. A term value approach is used to obtain a consistent set of “experimental” energy levels. …

Thermal Fluctuations Tunneling In Doped Conjugated Polymers, Troy C. Stedman

USF Tampa Graduate Theses and Dissertations

The possibility of using conducting polymers as organic alternatives to widely used inorganic materials for thermoelectric (TE) applications has received much attention in the past few decades. Since conducting polymers are generally inefficient compared to inorganic TE materials, research into their underlying transport mechanisms is required to improve their efficiency. We use a model based on the effects of local thermal fluctuations to characterize the transport in conducting polymer composites. With this model, full linear responses for the current and electronic heat current are obtained. From these responses, the local temperature dependent conductivity, electronic contribution to the thermal conductivity, and …

Au Nanostructured Surfaces For Electrochemical And Localized Surface Plasmon Resonance-Based Monitoring Of Α-Synuclein-Small Molecule Interactions., Xin R Cheng, Gregory Q Wallace, François Lagugné-Labarthet, Kagan Kerman

Chemistry Publications

In this proof-of-concept study, the fabrication of novel Au nanostructured indium tin oxide (Au-ITO) surfaces is described for the development of a dual-detection platform with electrochemical and localized surface plasmon resonance (LSPR)-based biosensing capabilities. Nanosphere lithography (NSL) was applied to fabricate Au-ITO surfaces. Oligomers of α-synuclein (αS) were covalently immobilized to determine the electrochemical and LSPR characteristics of the protein. Cyclic voltammetry (CV) and differential pulse voltammetry (DPV) were performed using the redox probe [Fe(CN)6](3-/4-) to detect the binding of Cu(II) ions and (-)-epigallocatechin-3-gallate (EGCG) to αS on the Au-ITO surface. Electrochemical and LSPR data were complemented by Thioflavin-T (ThT) …

Design, Synthesis And Applications Of Polymer Biomaterials, Frankie Costanza

USF Tampa Graduate Theses and Dissertations

The emergence of antibiotic resistant bacteria has prompted the research into novel kinds of antibacterial small molecules and polymers. Nature has solved this issue with the use of cationic antimicrobial peptides, which act as nonspecific antibiotics against invading species. Herein, we have tried to mimic this general mechanism in a biocompatible and biodegradable polymer micelle based on the polymerization of naturally occurring amino acids lysine and phenylalanine linked to a PEG tether. This amphiphilic structure allows for the spontaneous collapse into stable nanoparticles in solution, which contains a hydrophilic outer layer and a hydrophobic core. Our polymers have shown activity …

Identification And Quantification Of Gaseous Organic Compounds Emitted From Biomass Burning Using Two-Dimensional Gas Chromatography–Time-Of-Flight Mass Spectrometry, L. E. Hatch, W. Luo, J. F. Pankow, Robert Yokelson, C. Stockwell, K. C. Barsanti

Chemistry and Biochemistry Faculty Publications

The current understanding of secondary organic aerosol (SOA) formation within biomass burning (BB) plumes is limited by the incomplete identification and quantification of the non-methane organic compounds (NMOCs) emitted from such fires. Gaseous organic compounds were collected on sorbent cartridges during laboratory burns as part of the fourth Fire Lab at Missoula Experiment (FLAME-4) and analyzed by two-dimensional gas chromatography-time-of-flight mass spectrometry (GC x GC-ToFMS). The sensitivity and resolving power of GC x GC-ToFMS allowed the acquisition of the most extensive data set of BB NMOCs to date, with measurements from 708 positively or tentatively identified compounds. Estimated emission factors …

Mechanism Of N -Hydroxylation Catalyzed By Flavin-Dependent Monooxygenases, Somayesadat Badieyan, Robert D. Bach, Pablo Sobrado

Chemistry Faculty Research & Creative Works

Aspergillus fumigatus siderophore (SidA), a member of class B flavin-dependent monooxygenases, was selected as a model system to investigate the hydroxylation mechanism of heteroatom-containing molecules by this group of enzymes. SidA selectively hydroxylates ornithine to produce N5-hydroxyornithine. However, SidA is also able to hydroxylate lysine with lower efficiency. In this study, the hydroxylation mechanism and substrate selectivity of SidA were systematically studied using DFT calculations. The data show that the hydroxylation reaction is initiated by homolytic cleavage of the O-O bond in the C4a-hydroperoxyflavin intermediate, resulting in the formation of an internal hydrogen-bonded hydroxyl radical (HO•). As the HO• moves …

Sulfidic Spring In The Gypsum Karst System Of Monte Conca (Italy): Chemistry And Microbiological Evidences, Marianna Messina, Tiziana Grech, Fiorenzo Fiorenza, Alessandro Marlettta, Pietro Valenti, Salvatore Petralia

International Journal of Speleology

Monte Conca Cave is a karst system placed in Messinian evaporites, consisting of an active cave and a resurgence located on the massif of Monte Conca, Campofranco within the "Riserva Naturale Integrale di Monte Conca". A sulfidic spring is located in the terminal gallery of the cave. To characterize the physical and chemical parameters of the Monte Conca cave and of the sulfidic spring, air temperature, relative humidity, water pH, and concentrations of dissolved sulfides, nitrates and sulfates were monitored. The high sulfide consumption rate in the sulfidic spring, evaluated by a kinetic study, suggests that biotic consumption is dominant. …

The Exchanged Ef-Hands In Calmodulin And Troponin C Chimeras Impair The Ca2+-Induced Hydrophobicity And Alter The Interaction With Orai1: A Spectroscopic, Thermodynamic And Kinetic Study, Drake Jensen, Nicole Reynolds, Ya-Ping Yang, Shubha Shakya, Zhi-Qiang Wang, Dennis J. Stuehr, Chin-Chuan Wei

Chemistry Faculty Research, Scholarship, and Creative Activity

Background

Calmodulin (CaM) plays an important role in Ca²⁺-dependent signal transduction. Ca²⁺ binding to CaM triggers a conformational change, forming a hydrophobic patch that is important for target protein recognition. CaM regulates a Ca²⁺-dependent inactivation process in store-operated Ca²⁺entry, by interacting Orai1. To understand the relationship between Ca²⁺-induced hydrophobicity and CaM/Orai interaction, chimera proteins constructed by exchanging EF-hands of CaM with those of Troponin C (TnC) are used as an informative probe to better understand the functionality of each EF-hand.

Results

ANS was used to assess the context of the induced …

Gamma-Aapeptides As A New Class Of Peptidomimetics: Synthesis, Structures, And Functions, Haifan Wu

USF Tampa Graduate Theses and Dissertations

Peptidomimetics are synthetic oligomers that resemble the activities of peptides. Their advantages over peptides include high stability towards proteolysis and enormous chemical diversity. Over the past two decades, there have been extensive efforts to develop peptide mimics, such as beta-peptides, peptoids, D-peptides, etc. The research on peptidomimetics have led to many important applications in both medicinal and material science. In order to explore new functions, the discovery of peptidomimetics with novel frameworks is essential. We reported the synthesis and evaluation of a new class of peptidomimetics, termed as gamma-AApeptides. Previous studies of gamma-AApeptides have revealed that gamma-AApeptides are highly resistant …

Functional Expression And Characterization Of A Truncated Candida Antarctica Lipase B In Yeast, Samantha Robinson

Theses and Dissertations

Candida antarctica lipase B is an enzyme capable of hydrolyzing ester bonds in a lipid-water interface with potential to become a useful biocatalyst for production of biodiesel fuel. Enzymatically catalyzing the transesterification of triacylglycerides to produce fatty acid alkyl esters (biodiesel) is an environmentally cleaner alternative to the current process which utilizes chemical reagents as catalysts. Optimization and development of strains to express highly active, stable, large quantities of these biocatalysts is essential for inexpensive production of biodiesel. Additionally, lipase enzymes can be immobilized onto a resin, eliminating the need to recover the catalyst from the product and allowing multiple …

Analysis Of The Surface Density And Reactivity Of Perfluorophenylazide And The Impact On Ligand Immobilization, Gilad Zorn, David G. Castner, Anuradha Tyagi, Xin Wang, Hui Wang, Mingdi Yan

Chemistry Faculty Publications and Presentations

Perfluorophenylazide (PFPA) chemistry is a novel method for tailoring the surface properties of solid surfaces and nanoparticles. It is general and versatile, and has proven to be an efficient way to immobilize graphene, proteins, carbohydrates, and synthetic polymers. The main thrust of this work is to provide a detailed investigation on the chemical composition and surface density of the PFPA tailored surface. Specifically, gold surfaces were treated with PFPA-derivatized (11-mercaptoundecyl) tetra(ethylene glycol) (PFPA-MUTEG) mixed with 2-[2-(2-mercaptoethoxy)ethoxy]ethanol (MDEG) at varying solution mole ratios. Complementary analytical techniques were employed to characterize the resulting films including Fourier transform infrared spectroscopy to detect fingerprints …

Working With High School Students, The Pros And Cons", Luciana Aronne

Cleveland State University Regional Chemistry Teaching Symposium: March 12 & 13, 2015

No abstract provided.

A Simple Method For Tuning The Glass Transition Process In Inorganic Phosphate Glasses, René Fulchiron, Imane Belyamani, Joshua U. Otaigbe, Véronique Bounor-Legaré

Faculty Publications

The physical modification of glass transition temperature (T_g) and properties of materials via blending is a common practice in industry and academia and has a large economic advantage. In this context, simple production of hitherto unattainable new inorganic glass blends from already existing glass compositions via blending raises much hope with the potential to provide new glasses with new and improved properties, that cannot be achieved with classical glass synthesis, for a plethora of applications such as computers screens, glass-to-metal seals, and storage materials for nuclear wastes. Here, we demonstrate that blends of the specific glass compositions …

Csu 4th Annual Regional Chemistry Symposium: March 12 & 13, 2015, Zhihai Li Dr.

Cleveland State University Regional Chemistry Teaching Symposium: March 12 & 13, 2015

CSU 4th Annual Regional Chemistry Symposium: March 12 & 13, 2015

Register here for the 4th Annual Regional Chemistry Symposium March 12 & 13, 2015 Fee: $100 for two days $50 for one day Limited Time special registration fee! The registration fee for the two-day symposium is $100 and includes breakfast, lunch, an outstanding wine and cheese social hour, and discount rates on lodging. A schedule of events will also include a list of Cleveland's best sights, sounds and tastes.

To pay with credit card, visit CSU's ShopNet page at https://campusnet.csuohio.edu/ShopNet/index.jsp

You may also pay the fee in person on …

A Novel Chemosynthetic Peptide With Β-Sheet Motif Efficiently Kills Klebsiella Pnuemoniae In A Mouse Model, Shirui Tan, Changpei Gan, Rongpeng Li, Yan Ye, Shuang Zhang, Xu Wu, Yi Yan Yang, Weimin Fan, Min Wu

Chemistry Faculty Publications

Klebsiella pneumoniae (Kp) is one of the most common pathogens in nosocomial infections and is increasingly becoming multiple drug resistant. However, the molecular pathogenesis of Kp in causing tissue injury and dysregulated host defense remains elusive, further dampening the development of novel therapeutic measures. We have previously screened a series of synthetic antimicrobial beta-sheet forming peptides and identified a peptide (IRIKIRIK; ie, IK8L) with a broad range of bactericidal activity and low cytotoxicity in vitro. Here, employing an animal model, we investigated the antibacterial effects of IK8L in acute infection and demonstrated that peritoneal injection of IK8L to mice down-regulated …

Coordination Geometry Of Lead Carboxylates - Spectroscopic And Crystallographic Evidence, Jaclyn Catalano, Anna Murphy, Yao Yao, Glenn P A Yap, Nicholas Zumbulyadis, Silvia A. Centeno, Cecil Dybowski

Department of Chemistry and Biochemistry Faculty Scholarship and Creative Works

Despite their versatility, only a few single-crystal X-ray structures of lead carboxylates exist, due to difficulties with solubility. In particular, the structures of long-chain metal carboxylates have not been reported. The lone electron pair in Pb(ii) can be stereochemically active or inactive, leading to two types of coordination geometries commonly referred to as hemidirected and holodirected structures, respectively. We report 13C and 207Pb solid-state NMR and infrared spectra for a series of lead carboxylates, ranging from lead hexanoate (C6) to lead hexadecanoate (C18). The lead carboxylates based on consistent NMR parameters can be divided in two groups, shorter-chain (C6, C7, …

The Stoichiometry Of Metal Assisted Etching (Mae) Of Si In V2o5 + Hf And Hooh + Hf Solutions, Kurt W. Kolasinski, William B. Barclay, Yu Sun, Mark Aindow

Chemistry Faculty Publications

No abstract provided.

Design And Synthesis Of Bioactive Peptidomimetics, Yaogang Hu

USF Tampa Graduate Theses and Dissertations

Protein-Protein Interactions (PPIs) play a very important role in biological functions and therefore the inhibition of specific Protein-Protein Interactions has a huge therapeutic value. The most successful small molecular PPIs inhibitors do not fit with the prevalent `Rule of Five' drug profile. To overcome the disadvantages of small molecular PPIs inhibitors, peptide based PPIs inhibitors were developed. Herein we describe the development of a new class of peptidomimetics AA-peptides. The AApeptides were designed based on chiral PNA backbone. Substitution of nucleobases yields AApeptides that are resistant to proteolysis and capable of mimicking peptides. Two types of AApeptides were discussed in …

Optimization Of Aggregating Agents And Sers Substrates For Sers Detection Of Cotinine And Trans 3'-Hydroxycotinine, Sungyub Han

USF Tampa Graduate Theses and Dissertations

This dissertation mainly focuses on applications of Surface Enhance Raman Scattering (SERS) to detect tobacco-related biomarkers with optimized experimental conditions (pH and aggregating agents) and SERS substrates (silica core and silver shell nanoparticles). Cotinine (COT) and trans 3-hydroxycotinine (3HC), metabolized from nicotine as one of main chemicals of tobacco, have been used as tobacco biomarkers because their half-life are longer than that of nicotine, which enable to monitor the tobacco exposure. The effects of aggregating agents and pH on SERS detection of COT and 3HC were investigated. Aggregating agents play an important role in SERS detection of target molecules since …

Operators In Quantum Machanics, Ronald Lovett

Topics in Quantum Mechanics

No abstract provided.

Intramolecular S···O Chalcogen Bond As Stabilizing Factor In Geometry Of Substituted Phenyl-Sf3 Molecules, Vincent De Paul Nziko, Steve Scheiner

Chemistry and Biochemistry Faculty Publications

Density functional methods are used to examine the geometries and energetics of molecules containing a phenyl ring joined to the trigonal bipyramidal SF3 framework. The phenyl ring has a strong preference for an equatorial position. This preference remains when one or two ether -CH2OCH3 groups are added to the phenyl ring, ortho to SF3, wherein an apical structure lies nearly 30 kcal/mol higher in energy. Whether equatorial or apical, the molecule is stabilized by a S···O chalcogen bond, sometimes augmented by CH···F or CH···O H-bonds. The strength of the intramolecular S···O bond is estimated to lie in the range between …

Simultaneous Analysis Of The Ballik-Ramsay And Phillips Systems Of C2 And Observation Of Forbidden Transitions Between Singlet And Triplet States, Wang Chen, Kentarou Kawaguchi, Peter F. Bernath, Jian Tang

Chemistry & Biochemistry Faculty Publications

6229 lines of the Ballik-Ramsay system (b₃Σ_g^--a₃Π_u) and the Phillips system (A¹Π_u-X¹Σ_g⁺) of C₂ up to v = 8 and J = 76, which were taken from the literature or assigned in the present work, were analyzed simultaneously by least-squares fitting with 82 Dunham-like molecular parameters and spin-orbit interaction constants between the b₃Σ_g^- and X¹Σ_g⁺ states with a standard deviation of 0.0037 cm^-1 for the whole data set. As a …

State-To-State Reaction Dynamics Of ¹⁸O+³²O₂ Studied By A Time-Dependent Quantum Wavepacket Method, Wenbo Xie, Lan Liu, Zhigang Sun, Hua Guo, Richard Dawes

Chemistry Faculty Research & Creative Works

The title isotope exchange reaction was studied by converged time-dependent wave packet calculations, where an efficient 4th order split operator was applied to propagate the initial wave packet. State-to-state differential and integral cross sections up to the collision energy of 0.35 eV were obtained with ³²O₂ in the hypothetical j₀ = 0 state. It is discovered that the differential cross sections are largely forward biased in the studied collision energy range, due to the fact that there is a considerable part of the reaction occurring with large impact parameter and short lifetime relative to the rotational period …

Wigner High-Electron-Correlation Regime Of Non-Uniform Density Systems: A Quantal-Density-Functional-Theory Study, Douglas Mortimer Achan

Dissertations, Theses, and Capstone Projects

The Wigner regime of a system of electrons in an external field is characterized by a low electron density and a high electron-interaction energy relative to the kinetic energy. The low correlation regime is in turn described by a high electron density and an electron-interaction energy smaller than the kinetic energy. The Wigner regime of a nonuniform electron density system is investigated via quantal density functional theory (QDFT). Within QDFT, the contributions of electron correlations due to the Pauli exclusion principle, Coulomb repulsion, and correlation-kinetic effects are separately delineated and explicitly defined. The nonuniform electron density system studied is that …

Highly-Selective Chemiresistive Sensing And Analysis Of Vapors Using Functionalized Nanotubes, Deon Hines

Dissertations, Theses, and Capstone Projects

Specifically, the project involves the development of a diversified array of nanostructured gas-sensors comprised of selectively, novel surface-functionalized carbon nanotubes (for analyte selectivity by virtue of functionality). Harnessing carbon nanotubes with various electron withdrawing and donating groups help in determining their affinity toward certain prognostic gaseous markers thus increasing specificity of such created sensors. We have devised synthetic routes that have led to the facile production of covalently polyfunctionalized nanotubes in high yield. Seven carbon nanotube analogues were systematically considered and then chemically synthesized, from pristine single-walled nanotubes (SWNT's), for use as the main component of sensory units that was …

Cationic Amphiphilic Synthetic Macromolecules With Superior Antibacterial Activity, Ashish Punia

Dissertations, Theses, and Capstone Projects

The increasing prevalence of antibiotic resistant bacteria (superbugs) has created a pressing need for new systems of antimicrobial agents. In this dissertation, I report on my extensive research on the design, synthesis, and development of synthetic amphiphilic macromolecules with antimicrobial activity and very low hemolytic impact. Synthetic amphiphilic polymers attack bacteria directly to rupture the cell membrane through electrostatic and hydrophobic interactions. However, the toxicity of such synthetic amphiphilic polymers against mammalian cells have impeded their therapeutic applications. We investigated the systematic structure/activities relationships for antibacterial and hemolytic activities of amphiphilic polyacrylates and poly(vinyl esters). Acrylate homopolymers with various lengths …

Label-Free Detection Of Cancer Cells With Polysilicon Sensor Chips And Biomolecule-Assisted Synthesis Of Shape-Controlled Nanoparticles, Menglu Shi

Dissertations, Theses, and Capstone Projects

Constant effort has been made for the detection of cancer cells. Recently, ovarian and kidney cancer cell lines have been shown to have higher cellular elasticity as compared to normal cells assessed by monitoring the degree of deformation under hyposmotic pressure. This method has been modified and applied to various cases. In cancer cells, the oncogenic mutant p53 (mtp53) protein is present at high levels and contributes to tumor growth and metastasis. Herein the influence of mtp53 on the mechanical property of breast cancer cells was assessed by monitoring the swelling ratio of cells with time using the impedance measurements. …

Synthesis And Characterization Of A Novel Polyacetal & Design And Preparation Of Superhydrophobic Photocatalytic Surfaces, Yuanyuan Zhao

Dissertations, Theses, and Capstone Projects

Polyacetal polymers are thermoplastic resins that play an important role in industry because of numerous industrial applications including automobile; household appliance; etc. The first part of this thesis (Chapter 2) is about the synthesis of a new acetal copolymer that exhibits superior thermal stability. The second part of this thesis (Chapter 3) is about the preparation and applications of TiO₂-based polymer nanocomposite films, where the reactive oxygen species (ROS) are generated on the solid surface. Catalytic nanocomposite films are an active area of research because of their potential uses for environmental remediation and chemical synthesis. Furthermore, to …

Coordination Of Metronidazole To Cu(Ii): Structural Characterization Of A Mononuclear Square-Planar Compound Joshua H., Joshua H. Palmer, Ja-Shin Wu, Rita K. Upmacis

Faculty Papers and Publications

The reaction between metronidazole [1-(2-hydroxyethyl)-2-methyl-5-nitroimidazole, MET] and CuCl₂•2H₂O in methanol solution has allowed isolation of blue crystals of composition Cu(MET)₂Cl₂•MeOH. These crystals have been shown by X-ray diffraction to consist of mononuclear square-planar trans-Cu(MET)₂Cl₂ molecules in which the metronidazole ligands are trans to each other, as are the Cl ligands. The structure of this compound is very different from other compounds that have been obtained from the reaction between CuCl₂•2H₂O and metronidazole, namely [Cu(MET)₂(μ-Cl)Cl]2 and [Cu(MET)₂(μ-Cl)(OH₂)]₂[Cl]_{2 …}

Biomolecule Mediating Synthesis Of Inorganic Nanoparticles And Their Applications, Zengyan Wei

Dissertations, Theses, and Capstone Projects

Project 1.

The conventional phage display technique focuses on screening peptide sequences that can bind on target substrates, however the selected peptides are not necessary to nucleate and mediate the growth of the target inorganic crystals, and in many cases they only show moderate affinity to the targets. Here we report a novel phage display approach that can directly screen peptides catalytically growing inorganic nanoparticles in aqueous solution at room temperature. In this study, the phage library is incubated with zinc precursor at room temperature. Among random peptide sequences displayed on phages, those phages that can grow zinc oxide (ZnO) …