Digital Commons Network^™

Growth Of Nanotubes For Probe Microscopy Tips, Jason H. Hafner, Chin Li Cheung, Charles M. Lieber

Barry Chin Li Cheung Publications

Carbon nanotubes, which have intrinsically small diameters and high aspect ratios and which buckle reversibly, make potentially ideal structures for use as tips in scanning probe microscopies, such as atomic force microscopy (AFM)^{1, 2, 3, 4}. However, the present method of mechanically attaching nanotube bundles for tip fabrication is time consuming and selects against the smallest nanotubes, limiting the quality of tips. We have developed a technique for growing individual carbon nanotube probe tips directly, with control over the orientation, by chemical vapor deposition (CVD) from the ends of silicon tips. Tips grown in this way may become …

Defective Interleukin (Il)-18-Mediated Natural Killer And T Helper Cell Type 1 Responses In Il-1 Receptor-Associated Kinase (Irak)-Deficient Mice, Palanisamy Kanakaraj, Karen Ngo, Ying Wu, Ana Angulo, Peter Ghazal, Crafford A. Harris, John Siekierka, Per A. Peterson, Wai Ping Fung-Leung

Department of Chemistry and Biochemistry Faculty Scholarship and Creative Works

Interleukin (IL)-18 is functionally similar to IL-12 in mediating T helper cell type 1 (Th1) response and natural killer (NK) cell activity but is related to IL-1 in protein structure and signaling, including recruitment of IL-1 receptor-associated kinase (IRAK) to the receptor and activation of c-Jun NH2-terminal kinase (JNK) and nuclear factor (NF)-κB. The role of IRAK in IL-18-induced responses was studied in IRAK-deficient mice. Significant defects in JNK induction and partial impairment in NF-κB activation were found in IRAK-deficient Th1 cells, resulting in a dramatic decrease in interferon (IFN)-γ mRNA expression. In vivo Th1 response to Propionibacterium aches and …

Gas Sparging And Humic Acid Sorption/Desorption, Masaki Sakakibara

Masters Theses

Partition coefficients (K_DOC) for sorption of PAHs and chlorinated benzenes to dissolved humic acids (HA) were measured using gas-sparging methodology. The resulting K_DOC values were significantly lower than the K_OW-based K_DOC values, which generally appear to provide reliable estimates for K_DOC values. The K_DOC values measured by gas sparging were also strongly influenced by the concentration of HA in solution, as measured by dissolved organic carbon content (DOC). Increasing DOC concentration consistently resulted in decreased K_DOC values for all compounds investigated. Previous studies have claimed that K_DOC values measured using …

Structural And Kinetic Studies Of A Cisplatin-Modified Dna Icosamer Binding To Hmg1 Domain B*, Elizabeth R. Jamieson, Matthew P. Jacobson, Carmen M. Barnes, Christine S. Chow, Stephen J. Lippard

Chemistry: Faculty Publications

The high mobility group (HMG) domain is a DNA-binding motif found in the non-histone chromosomal proteins, HMG1 and HMG2, and some transcription factors. Experimental evidence has demonstrated that HMG-domain proteins can play a role in sensitizing cells to the anticancer drug cisplatin. Fluorescence resonance energy transfer (FRET) experiments were performed in the present study to investigate structural changes that accompany complex formation between the HMG domain B of HMG1 and a cisplatin-modified, 20-base pair double-stranded DNA probe containing fluorescein and rhodamine tethered at its two ends. The binding affinity of HMG1 domain B for the cisplatin-modified DNA probe was investigated …

Synthesis And Crystal Structure Of Tetrachloro (1,10-Phenanthroline) Platinum (Iv), Robert M. Granger Ii, Jill N. Granger, Kelly Del Campo, Molly B. Becherer, Phillip E. Fanwick

Virginia Journal of Science

We report the crystal structure determination of tetrachloro( l,10-phenan­throline)platinum(IV). X-ray data indicate there is little steric repulsion between the cx.-hydrogens on the phenanthroline ligand and the chloride ligands in the equatorial plane.

Hydrogen Bonding And Cooperative Effects In Mixed Dimers And Trimers Of Methanol And Trifluoromethanol: An Ab Initio Study, Ruben D. Parra, Xiao Cheng Zeng

Xiao Cheng Zeng Publications

Ab initio calculations are used to provide information on the mixed dimers and cyclic trimers of the methanol-trifluoromethanol system. In order to better understand the systems, the monomers and their corresponding dimers and trimers are also investigated. Molecular structures and harmonic frequencies are obtained at the B3LYP/6-311++G(d,p) level. Interaction energies are calculated with the MP2 and B3LYP methods using the 6-311++G(d,p), 6-311++G(2d,2p), and 6-311++G(3d,2p) basis sets for the dimers and heterodimers. The 6-311++G(d,p) basis set was used to calculate the …

Monte Carlo Study Of The Capacitance Of The Double Layer In A Model Molten Salt, Douglas Henderson, Dezso Boda, Kwong-Yu Chan

Faculty Publications

Monte Carlo simulations are reported for charged hard spheres at high density near a charged wall. This system is a simple model for a molten salt double layer. Unfortunately, the reduced temperatures that correspond to experiment are very small. This results in a large Boltzmann factor. As a result, we are unable to obtain meaningful results for such low values and report results only for moderately low values of the reduced temperature. Even so, our results should be a useful benchmark. Further, we are able to give a qualitative answer to an interesting question. We find that at low temperatures …

Infrared Cavity Ringdown Spectroscopy Of Methanol Clusters: Single Donor Hydrogen Bonding, R. A. Provencal, J. B. Paul, K. Roth, C. Chapo, R. N. Casaes, R. J. Saykally, G. S. Tschumper, H. F. Schaefer

Chemistry Faculty Research & Creative Works

Infrared cavity ringdown laser absorption spectroscopy has been used to study the O-H stretching vibrations of jet-cooled methanol clusters in direct absorption. Rovibrational bands for (CH₃OH)₂, (CH₃OH)₃, and (CH₃OH)₄ have been measured. Both bonded and free O-H stretches were measured for the dimer, indicating that its structure is linear. Five bands were assigned to the methanol trimer, indicating the presence of a second cyclic isomer in the molecular beam. A detailed study of the free O-H stretching region shows that methanol clusters larger than dimer must exist in cyclic …

Study On Steel Corrosion In Simulated Biofilm Environment In Seawater, Qing-Fei Wang, Jing Sui, Run-Xi Su, De-Ying Kong, Shi-Zhe Song

Journal of Electrochemistry

Biofilm is one of the main factors that influence metal corrosion in seawater environment. According to the structure and property of biofilm, a natural biopolymeric gel, calcium alginate(an extracellular biopolymer containing carboxylate functional groups) can deposite on metal surfaces to form films. Corrosion behavior of alloyed steel E2, 10CrMoAl and 18-8 stainless steel were studied in simulated biofilm environment by various electrochemical methods ,including measurements of the corrosion potential, polarization curves,galvanic current and electrochemical impedance. The results show that such an approach is informative to reveal “how” and “to what extent” biofilm can influence the metal corrosion process.

Electrohydrodimerization Of Fumarodinitrile On Liquid Gallium Electrode, He Wei, Huang Ying, Sheng-Tao Zhang

Journal of Electrochemistry

Electrohydrodimerization (EHD) of fumarodinitrile on liquid gallium electrode can take place not only in hydrotropic solution of tetraethylammonium p-toluenesulphonate (TEA-PTS), but also in aqueous solution containing low concentration of strong surfactants, such as TritonX-100. In solution without organic surfactant, FDN yields a single two-electron reduction wave corresponding to the formation of a saturated monomer called as butanedinitrile. If some TEA-PTS or TritonX-100 is added into the solution, the original two-electron wave is splitted into two continuous single-electron reduction wave and corresponding EHD of fumarodinitrile is obtained.

Macrocyclic Antibiotics As Separation Agents, Daniel W. Amstrong

Chemistry Faculty Research & Creative Works

Macrocyclic antibiotics having ring structures with at least 10 members act as separation agents in crystallization, precipitation, filtration, electrophoresis and chromatography. The macrocyclic antibiotics include ansamacrolides, macrolides, marocyclic peptides, polyenes and derivatives thereof. The process has been found to be especially advantageous for separation of optical isomers by electrophoresis and chromatography.

[2,3:5,6]Dibenzo[2.2.2]Octa-2,5,7-Triene (C2/C) And [2,3:5,6]Dibenzo[2.2.2]Octa-2,5-Diene, Lary Burrows, John M. Masnovi, Ronald J. Baker

Chemistry Faculty Publications

Two barrelene homologs are reported. Strain in the bicyclic framework of [2,3:5,6]dibenzo[2.2.2]octa-2,5,7- triene, (I) (C16H12), which is manifest in the deviations from ideality of the bond angles in the central bicyclic ringoSyStem and compression of the double bond [1.312 (3)A], is reduced in the more saturated derivative, [2,3:5,6]dibenzo[2.2.2]octa-2,5-diene, (II) (CI6H14), with the corresponding single bond being 1.5380 (19)A. The formation of isomorphs of (I) in both chiral (C2) and achiral (C2/c) space groups has implications for asymmetric syntheses involving solid (I) which rely on a non-centrosymmetric space group.

Role Of Reactive Oxygen Species In Mercapto-Methylimidazole-Induced Gastric Acid Secretion And Stress-Induced Gastric Ulceration, Uday Bandyopadhyay, Dipak Das, Debasish Bandyopadhyay, Mrinalini Bhattacharjee, Ranajit K. Banerjee

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

The objective of the present study is to delineate the role of reactive oxygen species in drug-induced gastric hyperacidity and stress-induced gastric ulceration. We reported earlier that mercaptomethylimidazole (MMI), an antithyroid drug, induces gastric acid (HCl) secretion partially through H2receptor activation of the parietal cell by histamine release and partially through an intracellular mechanism. While studying the latter, MMI-induced acid secretion was found to correlate well with the inactivation of the peroxidase, an important H2O2metabolizing enzyme of the mucosa. MMI activates the isolated parietal cell for acid secretion, which is sensitive to omeprazole. Peroxidase and catalase activity of the isolated …

Relationship Between Udp-Glucose 4-Epimerase Activity And Oligoglucose Glycoforms In Two Strains Of Neisseria Meningitidis, F K. Lee, B W. Gibson, William Melaugh, A Zaleski, M A. Apicella

Chemistry Faculty Publications

Sodium dodecyl sulfate-polyacrylamide gel analysis of lipooligosaccharide (LOS) from Neisseria meningitidis has demonstrated considerable microheterogeneity in the variable region of LOS due to the presence of novel glycoforms. As a step toward understanding the basis for the expression of these novel glycoforms, we have examined the LOS structures and UDP-glucose 4-epimerase (epimerase) activity levels in two strains (NMB and MA-1) and their respective galE mutants. Strain NMB was found to have low epimerase activity and to contain multiple glycoforms, some of which appear to contain only glucose sugars. The galE mutant had only the oligoglucose glycoforms. Strain MA-1 had higher …

Iron-Induced Oxidative Stress In Erythrocyte Membranes Of Non-Insulin-Dependent Diabetic Nigerians, Gbolahan W. Okunade, Odutayo O. Odunuge, Olufunso O. Olorunsogo

Faculty Publications

The presence of higher level of endogenous free radical reaction products in the erythrocyte ghost membrane (EGM) of Non-insulin-dependent diabetes mellitus (NIDDM) subjects compared with that of normal healthy controls has been demonstrated. The EGMs of NIDDM subjects were also shown to be more susceptible to exogenously generated oxidative stress than those of normal healthy individuals. The decreased level of reactive thiol groups in the EGM of NIDDM individuals supported this observation. We propose that the presence of significant levels of non-heme iron in the EGM of NIDDM subjects is an indication of the potential for iron-catalysed production of hydroxy …

Reversal Of Sodium Arsenite Inhibition Of Rat Liver Microsomal Ca2+ Pumping Atpase By Vitamin C, Odutayo O. Odunuge, Gbolahan W. Okunade, Olufunso O. Olorunsogo

Faculty Publications

Sodium arsenite (NaAsO2), at 10% of its median lethal dose, was administered to rats with and without vitamin C pretreatment. Liver microsomal fraction was isolated and the activity of Ca2+-ATPase was assayed. Sodium arsenite was found to inhibit the activity of the liver microsomal Ca2+-ATPase to 50% to that of control rats. The specific activity of the enzyme in rats administered sodium arsenite with vitamin C pretreatment was not significantly different from that of control rats.

Classification Of Explosives Transformation Products In Plant Tissue, Steven L. Larson, Robert P. Jones, Lynn Escalon, Don Parker

United States Army Corps of Engineers, Omaha District

Explosives contamination in surface or groundwater used for the irrigation of food crops and phytoremediation of explosives-contaminated soil or water using plant-assisted biodegradation have brought about concerns as to the fate of explosives in plants. Liquid scintillation counting, high-performance liquid chromatography, and gel permeation chromatography were utilized to characterize explosives (hexahydro-1,3,5-trinitro-1,3,5-triazine and trinitrotoluene) and their metabolites in plant tissues obtained from three separate studies. Analyzing tissues of yellow nutsedge (Cyperus esculentus), corn (Zea mays), lettuce (Lacuta sativa), tomato (Lyopersicum esculentum), radish (Raphanus sativus), and parrot feather (Myriophyllum aquaticum) …

Investigation Of Iron-Removing Agents, Melanie Wolfe

Theses, Dissertations and Capstones

Benign chemical agents for removing iron from people with iron-overload diseases are lacking; thus the purpose of this investigation is to evaluate the toxicity of acetaminophen in iron-overloaded mice compared to normal mice and to evaluate the iron-mobilizing ability of this agent in an iron-overloaded mouse model. Female Hilltop (ICR) CVF mice, ranging between six months to one year of age, were used in these experiments. Mice were given intraperionteal(ip) injections of 300 mg/kg ferric hydroxide-dextran complex for a total of five, eight, or thirteen injections to achieve an iron-overloaded state. Iron-overloaded mice were given ip injections of either 350,200, …

Cyclopropane Fatty Acid Expression In Plants, Katherine M. Schmid

Scholarship and Professional Work - LAS

Pants [sic] are transformed with a bacterial cyclopropane fatty acid synthase gene to produce lipids containing cyclopropane fatty acids. Using this technology dihydrosterculate is produced in oilseed crops such as rape.

Molecular Composition Of The Louse Sheath, Craig N. Burkhart, B Artur Stankiewicz, Irene Pchalek, Michael A. Kruge, Craig G. Burkhart

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

Flash pyrolysis-gas chromatography/mass spectrometry was used to assess the chemical composition of the head louse's nit sheath. The pyrolyzate of the female insect's secretions, which form a cement-like cylinder holding the egg onto the hair, is dominated by amino acid derivatives and fatty acids. No chitin-specific compounds were detected in the sheath. These results, contrary to previous reports, show that the polymeric complex of the sheath is composed of proteinaceous moieties, possibly cross-linked to aliphatic components. This study constitutes the first chemical characterization of the pyrolysis products of insect (louse) glue and unequivocally confirms that louse sheaths are not chitinous, …

A Biogeochemical Comparison Of Fossil (Carboniferous) And Modern Crustose Red Algae, Michael A. Kruge, John E. Utgaard, William Ferry

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

The nature of the contribution of the various types of algae to sedimentary organic matter continues to be a topic of research interest. Crustose red algae have however received less attention than other types. The fossil calcareous red algae (Rhodophyta) analyzed in this study are two relatively unrecrystallized specimens of Parachaetetes (Family Solenoporacea) from the lower part of the Ste. Genevieve Formation (Carboniferous, Visean) in Union County, Illinois, USA. They occurred in the patch reef phase of a small carbonate mudmound-patchreef. The three modern specimens (collected and identified by F. Collier) are the crustose algae Lithothamnion, Clathromorphum and Phymatolithon …

Chemistry Of Maceral And Groundmass Density Fractions Of Torbanite And Cannel Coal, Zhiwen Han, Michael A. Kruge

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

Microscopically, torbanite and cannel coal are composed of coarser macerals set in a fine-grained to amorphous groundmass. It is often assumed that the amorphous groundmass is genetically related to the distinct macerals. The separation of macerals and groundmass from 14 late Paleozoic torbanite, cannel, and humic coals permits the analysis of individual constituents using elemental analysis and flash pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). Cluster and principal component analyses of the Py-GC/MS data further reveal the chemical similarities and differences between the various constituents. Pyrolyzates of Botryococcus-related alginites are characterized by an abundance of normal alkadienes, alkenes, and alkanes. Even their …

Some Aspects Of The Adsorption Of A Lennard-Jones Gas On A Rough Surface, Douglas Henderson, Pawel Bryk, Stefan Sokolowski

Faculty Publications

We study the adsorption, including wetting, of a Lennard-Jones gas on a rough surface consisting of rough layer on a smooth substrate with which the gas interacts via a 9-3 potential. The rough layer is two molecular diameters thick and consists of a disordered quenched matrix of hard spheres. As well as interacting with the other matrix spheres by the hard-sphere potential, the matrix molecules interact with the gas molecules by the hard-sphere potential. Hence, on average, the degree to which the gas molecules can approach the substrate depends only on the density of the matrix layer. The density of …

New Polyether Toxins From Shellfish And Marine Phytoplankton: Isolation Studies And Development Of Analytical Methods, Alan G. Bishop

Theses

There are three classes of polyether toxins responsible for Diarrhetic Shellfish Poisoning (DSP) world-wide. The causative toxins are okadaic acid (OA) and derivatives (DTXs), pectenotoxins (PTXs) and yessotoxins (YTXs). The origin of these toxins are phytoplankton from Dinophysis or Prorocentrum spp. OA has been demonstrated for most outbreaks in Europe and more recently a new isomer DTX-2 has been reported in Ireland.

Marine phytoplankton biomass samples consisting predominantly of Dinophysis acuta, were acquired using a large double plankton net from waters off the South-west coast of Ireland. Analysis of unialgal samples using high performance liquid chromatography (HPLC) with fluorescence and …

Characterisation And Optimisation Of Gypsum Crystallization, Catherine H. Shannon

Theses

Gypsum is produced as a by-product during the citric acid production process at ADM Ringaskiddy. The particle size and filterability of the gypsum has a critical bearing on the overall citric acid production rate. Prior to August 1996, research in the area of gypsum crystal optimisation at ADM had concentrated on the application of vortex mixing to perform the gypsum formation reaction. While the gypsum crystals produced with vortex mixing were found to be desirably clear of microcrystalline gypsum, the crystals were considerably smaller and more difficult to filter and wash. This research project sought to retain the advantages conferred …

Optimisation Studies In A Batch Pharmaceutical Company, Sarah Fitzgerald

Theses

This thesis outlines a collaborative project between industry and academia based on a short term research contract.

In the past in Eli Lilly, process optimisation in a multi-purpose, modular building had been mainly confined to equipment commissioning and new product development. It was necessary to embark upon an exercise to develop an optimisation programme m order to meet the increased requirements and demands of the building. Increased market demands, through the introduction of over-the-counter (OTC) drugs, and the demand for cycle time reduction through the expiry of existing patents, made the need for optimisation inevitable.

The purpose of this thesis …

Trans-Resveratrol Inhibits Calcium Influx In Thrombin-Stimulated Human Platelets, Yuliya Dobrydneva, Roy L. Williams, Peter F. Blackmore

Chemistry & Biochemistry Faculty Publications

1 The phytoestrogenic compound trans-resveratrol (trans-3,5,4'-trihydroxystilbene) is found in appreciable quantities in grape skins and wine. It has been shown that both products rich in trans-resveratrol and pure trans-resveratrol inhibit platelet aggregation both in vivo and in vitro. However the mechanism of this action still remains unknown.

2 An essential component of the aggregation process in platelets is an increase in intracellular free Ca²⁺ ([Ca²⁺]_i). Ca²⁺ must enter the cell from the external media through specific and tightly regulated Ca²⁺ channels in the plasma membrane. The objective …

Autocatalytic Reduction Of Dichloro 5, 10, 15, 20 Tetraphenylporphinatoplatinum(Iv) By 1-Methylimidazole, F. Ece Bulak

Turkish Journal of Chemistry

It was observed that in toluene solution, excess 1-methyl-imidazole (Melm) reduces dichloro 5, 10, 15, 20 tetraphenyl-porphinatoplatinum(IV) (PtTPPCl_2) to tetraphenylporphinato-platinum(II) (PtTPP) autocatalytically (Fig. 1). There was no Pt(III) intermediate or 1-methylimidazole radical detected by Electron Resonance Spectroscopy (ESR) at 25°C. The reaction was found to be autocatalyzed by the PtTPP product when the 1-methylimidazole to PtTPPCl_2 concentration ratio is about 10^4 or more. From the data obtained it is reasonable to suppose that aggregation of the PtTPP product with PtTPPCl_2 plays an important role in this reduction process.

A Modified Potentiometric Method For The Estimation Of Phenol In Aqueous Systems, Farhat Huma, Muhammad Jaffar, Khalid Masud

Turkish Journal of Chemistry

A modified potentiometric titration is proposed for the estimation of phenol in aqueous systems. The method is evolved on the basis of a critical dependence of pH on log V rather than simple V, as used in conventional potentiometric titrations. The method incorporates titrants in a concentration range several orders of magnitude greater than that of phenol in the aqueous phase. Derivative potentiometric curves so obtained provide a clear exposition of the equivalence point and the overall error is found to be between \pm 1.0 and 1.5%. The range of phenol concentration investigated was from 10^{-2} to 10^{-3} M. and …

Synthesis, Structural And Thermal Studies Of Titanium(Iv) Complexes Of N-Alkyl Phenothiazines, Jaldappa Seetharamappa, Boregowda Keshavan

Turkish Journal of Chemistry

New coordination compounds of the type [Ti(C_2O_4)_2L]2H_2O where L=N-alkyl phenothiazines (NAPs) were synthesised and characterised by elemental analyses, molar conductance, magnetic, thermal and spectral data. The spectral data suggest the bidentate nature of NAPs in the complexes. An octahedral structure is proposed for all the complexes. Thermal studies were used to evaluate the kinetic and thermodynamic parameters.