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Plants As A Source Of Green Corrosion Inhibitors: The Case Of Gum Exudates From Acacia Species (A. Drepanolobium And A. Senegal), J Buchweishaija

Tanzania Journal of Science

The inhibitive performance of gum exudates from Acacia drepanolobium and Acacia senegal from Tanzania, towards the corrosion of mild steel in fresh water has been investigated. The experimental methods include potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) studies. The results indicate that gum exudates (Acacia drepanolobium and Acacia senegal) exhibit good inhibition characteristics to corrosion on mild steel under fresh water medium and the inhibition efficiency of up to 90.7% and 99.7% respectively was attained at 30 oC. Furthermore, the studies have shown that the inhibition performance remained above 90% on both Acacia exudates independent of the raise in temperature. …

Physical And Chemical Composition Of Storage-Ripened Papaya (Carica Papaya L.) Fruits Of Eastern Tanzania, O C Othman

Tanzania Journal of Science

The proximate composition (ash, titratable acidity, crude fat, crude fibre, moisture and sugars), soluble solids, ascorbic acid, polyphenol oxidase activity, macro-nutrients and heavy metal contents of storage-ripened papaya (Carica papaya L.) fruits from Mbezi, Dar es Salaam, Tanzania were determined. The determinations were repeated for early, middle and late-season papaya fruits. The fruits were always harvested at the mature green stage and allowed to ripen during room temperature storage. The results showed that papaya fruits had high moisture content (>85.5%), low acidity (<0.18% c.a.), low crude fat (0.10 g/100 g-edible portion), moderate crude fibre (1.45 g/100 g-edible portion), high ascorbic acid content (>84.5 mg/100 g- fw), moderate total sugars (>13.0%) and soluble solids (>12.9%) content. Early-season …

Physico-Chemical Characteristics Of Storage-Ripened Mango (Mangifera Indica L.) Fruits Varieties Of Eastern Tanzania, O C Othman, G P Mbogo

Tanzania Journal of Science

Two mango (Mangifera indica L.) fruit varieties, Dodo and Viringe, from two localities of Eastern Tanzania, (Muheza in Tanga and Ifakara in Morogoro), were harvested as mature green fruits during early, mid and late season and allowed to ripen while stored at room temperature. The fruits were analyzed for their proximate composition (ash, titratable acidity, crude fat, crude fibre, moisture), reducing and total sugars content, ascorbic acid and total soluble solids content, concentration of four macro elements (Ca, Mg, K, Na) and seven heavy metals (Al, Cd, Cu, Fe, Mn, Pb, Zn). The results showed that the mango fruits had …

A Top-Down Proteomic Approach For The Discovery Of Novel Serum Biomarkers Of Pregnancy-Related Disease, Karen Merrell

Theses and Dissertations

The serum fraction of blood is an ideal material in which to search for novel biomarkers for disease. It is easily obtained through relatively non-invasive means, routinely collected, and a rich treasure-trove of information about the health of an individual. Cells react to signal molecules, take up nutrients, and release waste products, fragments that are the result of proteolysis, and other molecules out into the bloodstream. If these components are unique to the cells in question, that part of the complex mixture that is the blood stream can potentially characterize the health of the tissue or organ those cells are …

Simultaneous, Noninvasive Observation Of Elastic Scattering, Fluorescence And Inelastic Scattering As A Monitor Of Blood Flow And Hematocrit In Human Fingertip Capillary Beds, Joseph Chaiken, Jerry Goodisman, Bin Deng, Rebecca J. Bussjager, George Shaheen

Chemistry - All Scholarship

We report simultaneous observation of elastic scattering, fluorescence, and inelastic scattering from in vivo near-infrared probing of human skin. Careful control of the mechanical force needed to obtain reliable registration of in vivo tissue with an appropriate optical system allows reproducible observation of blood flow in capillary beds of human volar side fingertips. The time dependence of the elastically scattered light is highly correlated with that of the combined fluorescence and Raman scattered light. We interpret this in terms of turbidity (the impeding effect of red blood cells on optical propagation to and from the scattering centers) and the changes …

Synthesis And Coordination Chemistry Of New Oxazoline And Benzoxazole Based Ligands With Lanthanides, Edicome Cornel Shirima

Chemistry and Chemical Biology ETDs

In Chapter 1, a brief literature review on the chemistry of lanthanides (Ln) and actinides (An) is described. In addition, the coordination chemistry of lanthanides/actinides with various ligands comprised of organic backbones has also been described. In Chapters 2 and 3 the syntheses of oxazoline and benzoxazole ligands is described. Both ligands contain a hard donor group (P=O) and the nitrogen (N) atom from the heterocycle as a relatively softer donor atom. In Chapter 2 the oxazoline ligand was synthesized in two steps reaction that involves substitution with Ph₂P group and oxidation of the phosphine into P=O by …

Ion Transport Behaviors Upstream And Downstream From The Sampling Cone Of An Inductively Coupled Plasma Mass Spectrometer, Haibin Ma

Theses and Dissertations

Inductively coupled plasma - mass spectrometry (ICP-MS) is the technique of choice worldwide for trace elemental determinations because of its excellent ionization ability, low detection limits and fast analysis speeds. However, the ICP-MS still suffers from some disadvantages, such as spectral overlap and severe matrix effects. Matrix effects or interferences, partly arise from changes in the analyte transmission through the interfacial region between the ICP and mass spectrometer with changes in sample matrix. Better understanding of the transmission behaviors of analyte through the sampling and skimmer cones will provide the insights needed to alleviate matrix interferences and to improve the …

Relaxation Of Vibrationally Excited Trifluorobenzene And Tetrafluorobenzene By Collisions With Carbon Dioxide, Alan M. Johnson

Theses and Dissertations

An investigation into the relaxation of highly vibrationally excited trifluorobenzene and tetrafluorobenzene following collisions with carbon dioxide was performed using diode laser transient absorption spectroscopy. A 248 nm excimer laser prepared the vibrationally hot (E'~41,000 cm-1) fluorobenzene molecules. Large amounts of translational and rotational energy are transferred through collisions between the hot donor molecule and CO2. Rate constants and collisional probabilities were calculated by probing the high J states (J=58~80) of CO2 in the vibrational ground state, 0000, with measurements taken 1 µsec, ¼ the mean gas collision time, following each excimer laser pulse. The energy transfer probability distribution function, …

Single-Molecule Protein Unfolding In Solid State Nanopores, David Talaga, Jiali Li

Department of Chemistry and Biochemistry Faculty Scholarship and Creative Works

We use single silicon nitride nanopores to study folded, partially folded, and unfolded single proteins by measuring their excluded volumes. The DNA-calibrated translocation signals of β-lactoglobulin and histidine-containing phosphocarrier protein match quantitatively with that predicted by a simple sum of the partial volumes of the amino acids in the polypeptide segment inside the pore when translocation stalls due to the primary charge sequence. Our analysis suggests that the majority of the protein molecules were linear or looped during translocation and that the electrical forces present under physiologically relevant potentials can unfold proteins. Our results show that the nanopore translocation signals …

Reactivity-Dependent Pcr: Direct, Solution-Phase In Vitro Selection For Bond Formation, David J. Gorin, Adam S. Kamlet, David R. Liu

Chemistry: Faculty Publications

(Figure Presented) In vitro selection is a key component of efforts to discover functional nucleic acids and small molecules from libraries of DNA, RNA, and DNA-encoded small molecules. Such selections have been widely used to evolve RNA and DNA catalysts and, more recently, to discover new reactions from DNA-encoded libraries of potential substrates. While effective, current strategies for selections of bond-forming and bond-cleaving reactivity are generally indirect, require the synthesis of biotin-linked substrates, and involve multiple solution-phase and solid-phase manipulations. In this work we report the successful development and validation of reactivity-dependent PCR (RDPCR), a new method that more directly …

The Role Of Smpb In The Early Stages Of Trans-Translation, Deanna June Cazier

Theses and Dissertations

Ribosomes stall on defective messenger RNA transcripts in eubacteria. Without a mechanism to release stalled ribosomes, these cells would die. Transfer-messenger RNA (tmRNA) and small protein B (SmpB) reactivate stalled ribosomes in a process known as trans-translation. Together, tmRNA and SmpB mimic alanyl-tRNA, entering the A site of stalled ribosomes and accepting transfer of the stalled polypeptide. A portion of tmRNA is then positioned as a template for the ribosome to resume translating. The tmRNA open reading frame encodes a proteolysis tag to mark the aberrant polypeptide for degradation and a stop codon to release the ribosome. How are tmRNA …

Structural Evidence For Consecutive Hel308-Like Modules In The Spliceosomal Atpase Brr2, L. Zhang, T. Xu, Corina Maeder, L.-O. Bud, J. Shanks, J. Nix, C. Guthrie, J. A. Pleiss, R. Zhao

Chemistry Faculty Research

Brr2 is a DExD/H-box helicase responsible for U4/U6 unwinding during spliceosomal activation. Brr2 contains two helicase-like domains, each of which is followed by a Sec63 domain with unknown function. We determined the crystal structure of the second Sec63 domain, which unexpectedly resembles domains 4 and 5 of DNA helicase Hel308. This, together with sequence similarities between Brr2's helicase-like domains and domains 1-3 of Hel308, led us to hypothesize that Brr2 contains two consecutive Hel308-like modules (Hel308-I and Hel308-II). Our structural model and mutagenesis data suggest that Brr2 shares a similar helicase mechanism with Hel308. We demonstrate that Hel308-II interacts with …

The Use Of Fourier Transform (Ft) Surface-Enhanced Raman Scattering For Biochemical Analysis, Robert Butler Jeffers

Chemistry & Biochemistry Theses & Dissertations

Surface-enhanced Raman scattering (SERS) is a powerful spectroscopic technique that has created exciting opportunities in the field of bioanalytical chemistry, where it combines ultrasensitive detection of biologically relevant molecules with vibrational spectroscopy. Due to the difficulties in preparing reproducible SERS active substrates, SERS has been mainly used as a qualitative tool. In order for SERS to be utilized as a viable tool for quantitative analysis, simple, facile SERS substrates which generate clean, highly reproducible signals must be developed. This dissertation deals with the evaluation of three different methods of SERS that led to the development of a novel substrate for …

Probing Single-Molecule Interfacial Geminate Electron−Cation Recombination Dynamics, Yuanmin Wang, Xuefei Wang, H. Peter Lu

Chemistry Faculty Publications

Interfacial electron-cation recombination in zinc-tetra (4-carboxyphenyl) porphyrin (ZnTCPP)/TiO(2) nanoparticle system has been probed at the single-molecule level by recording and analyzing photon-to-photon pair times of the ZnTCPP fluorescence. We have. developed a novel approach to reveal the hidden single-molecule interfacial electron-cation recombination dynamics by analyzing the autocorrelation function and a proposed convoluted single-molecule interfacial electron-cation recombination model. Our results suggest that the fluctuations of the interfacial electron transfer (ET) reactivity modulate the ET cycles as well as the interfacial electron-cation recombination dynamics. On the basis of this model, the single-molecule electron-cation recombination time of ZnTCPP/-TiO(2) system is deduced to be …

Fluorenylidene−Pyrroline Biomimetic Light-Driven Molecular Switches, Laura Rivado-Casas, Diego Sampedro, Pedro J. Campos, Stefania Fusi, Vinicio Zanirato, Massimo Olivucci

Chemistry Faculty Publications

A new family of biomimetic photoactivated molecular switches based in the retinal chromophore is described. Expedient synthesis allows a library of compounds with a different substitution pattern, including chiral substituents, to be obtained. The effect of substitution, solvent, and light source on the photoisomerization step has been assessed. The absorption maximum has been red-shifted ca. 50 nm with respect to related systems and rotation is now easily achieved by using visible light.

Section Abstracts: Chemistry

Virginia Journal of Science

Abstracts of the Chemistry Section for the 87th Annual Meeting of the Virginia Academy of Science, May 27-29, 2009, Virginia Commonwealth University, Richmond Virginia.

Excess Of Glucocorticoid Induces Cardiac Dysfunction Via Activating Angiotensin Ii Pathway, Sreerupa Ghose Roy, Priyanka De, Debasri Mukherjee, Vivek Chander, Aditya Konar, Debasish Bandyopadhyay, Arun Bandyopadhyay

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

Background: Glucocorticoid is widely used as an anti-inflammatory drug in various diseases however excess of it often causes cardiovascular complications. The present study was undertaken to understand the molecular mechanism of glucocorticoid-induced cardiac dysfunction.

Methods: Rats were treated daily with synthetic glucocorticoid, dexamethasone with or without mifepristone or losartan up to 15 days. Hemodynamic parameters were measured by PV-loop method using Millar's instrument. Cardiac remodelling, fibrosis and oxidative stress were monitored after 15 days.

Results: The systolic blood pressure was increased whereas the heart beat and cardiac output (n=6) were decreased by dexamethasone. Dexamethasone caused increase in the heart …

Novel Cinchona Alkoloid Derived Ammonium Salts As Phase-Transfer Catalysts For The Asymmetric Synthesis Of Beta-Hydroxy Alpha-Amino Acids Via Aldol Reactions And Total Synthesis Of Celogentin C., Bing Ma

Theses and Dissertations

Project I. Cinchona alkaloid-derived quaternary ammonium salts have been successfully used as phase-transfer catalysts, particularly in asymmetric alkylations. Our group applied this type of catalyst in the synthesis of β-hydroxy α-amino acids via aldol reactions and discovered that the Park-Jew catalyst afforded good yields and good enantiomeric excess of the syn diasteromers, but negligible diastereoselectivity. This project was therefore focused on the synthesis of novel cinchonidine-derived catalysts with the Park-Jew catalyst as the lead structure. The C3 position of cinchonidine nucleus was modified to achieve dimers and catalysts possessing electron-deficient alkyne and alkene moieties. Synthesized catalysts were tested in the …

A Cox-2 Inhibitor Nimesulide Analog Selectively Induces Apoptosis In Her2 Overexpressing Breast Cancer Cells Via Cytochrome C Dependent Mechanisms, Bin Chen, Bin Su, Shiuan Chen

Chemistry Faculty Publications

Epidemiological and animal model studies have suggested that non-steroidal anti-inflammatory drugs (NSAIDs) can act as chemopreventive agents. The cyclooxygenase-2 (COX-2) inhibitor nimesulide shows anti-cancer effect in different type of cancers. In the current study, five breast carcinoma cell lines were used to explore the anti-cancer mechanisms of a nimesulide derivative compound 76. The compound dose dependently suppressed SKBR-3, BT474 and MDA-MB-453 breast cancer cell proliferation with IC50 of 0.9 μM, 2.2 μM and 4.0 μM, respectively. However, it needs much higher concentrations to inhibit MCF-7 and MDA-MB-231 breast cancer cell growth with IC50 at 22.1 μM and 19.6 μM, respectively. …

Hydrazinecarbothioamide Group In The Synthesis Of Heterocycles, Ashraf A. Aly, Alan B. Brown, Talaatt Ibrahim El-Emary, Ashraf M. Mohamed Ewas, Mohamed Ramadan

Chemistry and Chemical Engineering Faculty Publications

The review summarizes recent literatures dealing with hydrazinecarbothioamide group in thiocarbohydrazides and other derivatives including their physical and chemical properties along with their applications in the synthesis of heterocycles.

Antibiotic Resistance In Mycobacterium Tuberculosis. Peroxidase Intermediate Bypass Causes Poor Isoniazid Activation By The S315g Mutant Of M. Tuberculosis Catalase-Peroxidase (Katg), Javier Suarez, Kalina Ranguelova, Johannes Schelvis, Richard S. Magliozzo

Department of Chemistry and Biochemistry Faculty Scholarship and Creative Works

KatG (catalase-peroxidase) in Mycobacterium tuberculosis is responsible for activation of isoniazid (INH), a pro-drug used to treat tuberculosis infections. Resistance to INH is a global health problem most often associated with mutations in the katG gene. The origin of INH resistance caused by the KatG[S315G] mutant enzyme is examined here. Overexpressed KatG[S315G] was characterized by optical, EPR, and resonance Raman spectroscopy and by studies of the INH activation mechanism in vitro. Catalase activity and peroxidase activity with artificial substrates were moderately reduced (50 and 35%, respectively), whereas the rates of formation of oxyferryl heme:porphyrin π-cation radical and the decay of …

Chemical Modification Of Reactive Multilayered Films Fabricated From Poly(2-Alkenyl Azlactone)S: Design Of Surfaces That Prevent Or Promote Mammalian Cell Adhesion And Bacterial Biofilm Growth, Maren E. Buck, Anthony S. Breitbach, Sonja K. Belgrade, Helen E. Blackwell, David M. Lynn

Chemistry: Faculty Publications

We report an approach to the design of reactive polymer films that can be functionalized post-fabrication to either prevent or promote the attachment and growth of cells. Our approach is based on the reactive layer-bylayer assembly of covalently crosslinked thin films using a synthetic polyamine and a polymer containing reactive azlactone functionality. Our results demonstrate (i) that the residual azlactone functionality in these films can be exploited to immobilize amine-functionalized chemical motifs similar to those that promote or prevent cell and protein adhesion when assembled as self-assembled monolayers on gold-coated surfaces and (ii) that the immobilization of these motifs changes …

X-Ray Structural Characterization Of Charge Delocalization Onto The Three Equivalent Benzenoid Rings In Hexamethoxytriptycene Cation Radical, Vincent J. Chebny, Tushar S. Navale, Ruchi Shukla, Sergey V. Lindeman, Rajendra Rathore

Chemistry Faculty Research and Publications

Definitive X-ray crystallographic evidence is obtained for a single hole (or a polaron) to be uniformly distributed on the three equivalent 1,2-dimethoxybenzenoid (or veratrole) rings in the hexamethoxytriptycene cation radical. This conclusion is further supported by electrochemical analysis and by the observation of an intense near-IR transition in its electronic spectrum, as well as by comparison of the spectral and electrochemical characteristics with the model compounds containing one and two dimethoxybenzene rings.

Web Based Classes For Enhancement Of Prelaboratory Lectures, Tiffany Hesser, Michael Collura

Chemistry and Chemical Engineering Faculty Publications

The use of web classes, such as Tegrity Campus1, as a supplement to pre laboratory reading or a replacement for pre laboratory lectures could become a standard tool in laboratory education protocol. In classes with multiple lab sections and instructors, pre laboratory lectures can lack consistency and it can be difficult to gauge the students’ level of preparation. With the ever increasing exposure to technology, students generally prefer information in a digital and multimedia form, rather than textbook readings. Therefore, this method can prove to better prepare students prior to laboratory experiments, increasing the overall understanding of the chemical reactions …

Louisiana: A Model For Advancing Regional E-Research Through Cyberinfrastructure, Daniel S. Katz, Gabrielle Allen, Ricardo Cortez, Carolina Cruz-Neira, Raju Gottumukkala, Zeno D. Greenwood, Les Guice, Shantenu Jha, Ramsesh Kolluru, Tevfik Kosar, Lonnie Leger, Honggao Liu, Charlie Mcmahon, Jarek Nabrzyski, Bety Rodriguez-Milla, Ed Seidel, Greg Speyrer, Michael Stubblefield, Brian Voss, Scott L. Whittenburg

Chemistry and Biochemistry Faculty Publications

Louisiana researchers and universities are leading a concentrated, collaborative effort to advance statewide e-Research through a new cyberinfrastructure: computing systems, data storage systems, advanced instruments and data repositories, visualization environments and people, all linked together by software programs and high-performance networks. This effort has led to a set of interlinked projects that have started making a significant difference in the state, and has created an environment that encourages increased collaboration, leading to new e-Research. This paper describes the overall effort, the new projects and environment and the results to date.

Mnte-2-Pyp And Radiation In A Prostate Cancer Model: Implications For Radiotherapy, Adeola Y. Makinde

Loma Linda University Electronic Theses, Dissertations & Projects

A major limitation of successful radiation therapy in cancer treatment is the increase in normal tissue damage as higher doses are used to achieve greater tumor destruction. Radiation dose optimization in cancer therapy requires achieving maximum tumor destruction with minimal damage to normal tissue Antioxidants have been shown to protect normal tissues against radiation damage, as radiation-induced tissue damage results predominantly from reactive oxygen species that directly damage cellular components. However, for effective use as normal tissue radioprotectants in radiotherapy, these antioxidants must not protect the tumors. Mn (III) tetrakis (N-ethylpyridinium-2-yl) porphyrin (MnTE-2-PyP) is a metalloporphyrin antioxidant that has been …

Linking Conformation Change To Hemoglobin Activation Via Chain-Selective Time-Resolved Resonance Raman Spectroscopy On Protoheme/Mesoheme Hybrids, Gurusamy Balakrishnan, Mohammed Ibrahim, Piotr J. Mak, Jessica Hata, James R. Kincaid, Thomas G. Spiro

Chemistry Faculty Research and Publications

Time-resolved Resonance Raman spectra are reported for Hb tetramers, in which the αand β chains are selectively substituted with mesoheme. The Soret absorption band shift in meso- relative to protoheme permits chain-selective excitation of heme RR spectra. The evolution of these spectra following HbCO photolysis show that geminate recombination rates and yields are the same for the two chains, consistent with recent results on 15N-heme isotopomer hybrids. The spectra also reveal systematic shifts in the deoxy-heme ν4 and νFe-His) RR bands, which are anti-correlated. These shifts are resolved for the successive intermediates in the protein structure, which have previously been …

Genetic Analysis Of Ribosome Stalling And Rescue, Douglas Ray Tanner

Theses and Dissertations

In eubacteria, ribosome stalling on broken messenger RNA transcripts can lead to cell death. The trans-translation quality control mechanism rescues many of these stalled ribosomes. In this process, tmRNA enters stalled ribosomes by mimicking a transfer RNA, accepting the stalled nascent peptide. The ribosome then releases the broken mRNA and resumes translation on a coding region within tmRNA itself. Translation of tmRNA marks the nascent peptide for destruction by the addition of a short proteolysis tag and the ribosome is released at a stop codon within the tmRNA open reading frame. An intriguing aspect of trans-translation is that …

Reductive Decomposition Of A Diazonium Intermediate By Dithiothreitol Affects The Determination Of Nos Turnover Rates, Perera N. Indika, Talal Sabbagh, Jean A. Boutros, Mekki Bayachou

Chemistry Faculty Publications

Accurate determination of nitrite either as such or as the breakdown product of nitric oxide (NO) is critical in a host of enzymatic reactions in various settings addressing structure–function relationships, as well as mechanisms and kinetics of molecular operation of enzymes. The most common way to quantify nitrite, for instance in nitric oxide synthase (NOS) mechanistic investigations, is the spectrophotometric assay based on the Griess reaction through external standard calibration. This assay is based on a two-step diazotization reaction, in which a cationic diazonium derivative of sulfanilamide is formed as intermediate before the final absorbing azo-product. We show that this …

The Use Of Soil Enzyme Activities And Active Carbon As Indicators Of Soil Quality In Response To Management Practices, Tracy Marie Woodruff

Student Theses and Dissertations

In order to meet the increasing needs of food, fiber, and fuel, management practices that enhance the soil health must be sought out. The two studies conducted examined the effects of management practices on soil enzyme activities and active carbon concentration. A forested ecosystem in Oregon was examined following nutrient treatments on forest plots. The effects of tillage, residue management and time on soil enzyme activities and active C were measured in a greenhouse study from the University of Arkansas in Fayetteville, AR, USA. In both studies, β-glucosidase, arylsulfatase, acid phosphatase, and active carbon were analyzed in soil samples. Results …