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Probing The Electronic And Structural Properties Of Doped Aluminum Clusters: Mal12- (M=Li, Cu, And Au), R. Pal, Li-Feng Cui, Satya S. Bulusu, Hua-Jin Zhai, Lai-Sheng Wang, Xiao Cheng Zeng Jan 2008

Probing The Electronic And Structural Properties Of Doped Aluminum Clusters: Mal12- (M=Li, Cu, And Au), R. Pal, Li-Feng Cui, Satya S. Bulusu, Hua-Jin Zhai, Lai-Sheng Wang, Xiao Cheng Zeng

Xiao Cheng Zeng Publications

Photoelectron spectroscopy (PES) is combined with theoretical calculations to investigate the electronic and atomic structures of three doped aluminum clusters, MAl12- (M=Li, Cu, and Au). Well-resolved PES spectra have been obtained at two detachment photon energies, 266 nm (4.661 eV) and 193 nm (6.424 eV). Basin-hopping global optimization method in combination with density-functional theory calculations has been used for the structural searches. Good agreement between the measured PES spectra and theoretical simulations helps to identify the global minimum structures. It is found that LiAl12- (C5v) can be viewed as replacing a surface Al …


Modulation Of Water Exchange In Europium(Iii) Dota–Tetraamide Complexes Via Electronic Substituent Effects, S. James Ratnakar, Mark Woods, Angelo J.M. Lubag, Zoltan Kovacs, A. Dean Sherry Jan 2008

Modulation Of Water Exchange In Europium(Iii) Dota–Tetraamide Complexes Via Electronic Substituent Effects, S. James Ratnakar, Mark Woods, Angelo J.M. Lubag, Zoltan Kovacs, A. Dean Sherry

Chemistry Faculty Publications and Presentations

The chemical exchange saturation transfer (CEST) efficiency for a series Eu3+-based tetraamide complexes bearing p-substituents on a single coordinating pendant arm is highly sensitive to water exchange rates. The CEST effect increases in the order Me < MeO < F ∼ CO2tBu < CN ≪ H. These results show that CEST contrast can be modulated by changes in electron density at a single ligating atom, and this forms the basis of creating imaging agents that respond to chemical oxidation and reduction.


A Polarizable Force-Field Model For Quantum-Mechanical-Molecular-Mechanical Hamiltonian Using Expansion Of Point Charges Into Orbitals, P. K. Biswas, Valentin Gogonea Jan 2008

A Polarizable Force-Field Model For Quantum-Mechanical-Molecular-Mechanical Hamiltonian Using Expansion Of Point Charges Into Orbitals, P. K. Biswas, Valentin Gogonea

Chemistry Faculty Publications

We present an ab initio polarizable representation of classical molecular mechanics (MM) atoms by employing an angular momentum-based expansion scheme of the point charges into partial wave orbitals. The charge density represented by these orbitals can be fully polarized, and for hybrid quantum-mechanical-molecular-mechanical (QM/MM) calculations, mutual polarization within the QM/MM Hamiltonian can be obtained. We present the mathematical formulation and the analytical expressions for the energy and forces pertaining to the method. We further develop a variational scheme to appropriately determine the expansion coefficients and then validate the method by considering polarizations of ions by the QM system employing the …


Role Of Transcription Factor Mef2a In Development Of Coronary Artery Disease (Cad) And Myocardial Infarction (Mi), Maniragava Sai Bhagavatula Jan 2008

Role Of Transcription Factor Mef2a In Development Of Coronary Artery Disease (Cad) And Myocardial Infarction (Mi), Maniragava Sai Bhagavatula

ETD Archive

Coronary artery disease (CAD) and myocardial infarction (MI) are the leading cause of death in developed countries. Genetic factors play an important role in the pathogenesis of CAD and MI. The revolutionary advances in molecular genetics have provided new insights into the genetic pathways involved in this disease. Recently, our laboratory used linkage analysis to map the first disease-causing gene for CAD and MI to chromosome 15q26 in a large family and subsequently mutation analysis identified a 7-amio acid deletion in MEF2A, a gene encoding a transcription factor. Later we identified three novel mutations N263S, P279L, G283D in four other …


New Insights Into Molecular Mechanisms Of Fludarabine, Alina D. Bulgar Jan 2008

New Insights Into Molecular Mechanisms Of Fludarabine, Alina D. Bulgar

ETD Archive

Nucleotide analogs (e.g. fludarabine) are antimetabolites used in the treatment of a wide variety of hematological malignancies and solid tumors. Upon being metabolized to their active triphosphate form, these agents are incorporated into DNA. Among other molecular targets, their incorporation may lead to activation of base excision repair (BER) pathway. The molecular mechanism of BER recognition and repair of the incorporated fludarabine has not yet been elucidated. The main focus of this research was to study the involvement of BER pathway in the response to fludarabine induced DNA damage. Also, the possibility of enhancing antineoplastic activity of fludarabine by inhibition …


Quadrupole Magnetic Field-Flow Fractionation;A Novel Technique For The Characterization Of Magnetic Particles, Francesca Carpino Jan 2008

Quadrupole Magnetic Field-Flow Fractionation;A Novel Technique For The Characterization Of Magnetic Particles, Francesca Carpino

ETD Archive

In the last few decades, the development and use of nanotechnology has become of increasing importance. Magnetic nanoparticles, because of their unique properties, have been employed in many different areas of application. They are generally made of a core of magnetic material coated with some other material to stabilize them and to help disperse them in suspension. The unique feature of magnetic nanoparticles is their response to a magnetic field. They are generally superparamagnetic, in which case they become magnetized only in a magnetic field and lose their magnetization when the field is removed. It is this feature that makes …


Hydrogenase Inhibition By O2: Density Functional Theory/Molecular Mechanics Investigation, Daniela Dogaru Jan 2008

Hydrogenase Inhibition By O2: Density Functional Theory/Molecular Mechanics Investigation, Daniela Dogaru

ETD Archive

[Fe-Fe]-hydrogenases are enzymes that reversibly catalyze the reduction of protons to molecular hydrogen, which occurs in anaerobic media. In living systems, [Fe-Fe]-hydrogenases shift the reversible reaction towards H2 formation. The [Fe-Fe]-hydrogenase H-cluster is the active site, which contains two iron atoms (Fep-Fed, i.e., proximal and distal iron). Because most experimental and theoretical investigations confirm that the structure of di-iron air inhibited species is FepII-FedII-O-O-H-, O2 has to be prevented from binding to Fed in all di-iron subcluster oxidation states in order to retain a catalytically active enzyme. By understanding the catalytic processes of metalloenzymes, researches are enabled to produce an …


Identification And Analysis Of Prohibitin In B16 Mouse Melanoma Cells, Christopher Francis Jan 2008

Identification And Analysis Of Prohibitin In B16 Mouse Melanoma Cells, Christopher Francis

Theses, Dissertations and Capstones

Prohibitin, a highly conserved protein found in eukaryotic cells, has been found in recent years to possess a wide variety of functions in the cell. Whereas the mechanisms by which the protein functions are still largely unknown, it is clear that prohibitin possesses very strong anti-proliferative properties in the cell, as well as potentially both nuclear and mitochondrial functions based upon its movement and localization upon apoptotic signaling. Upon treatment with retinoic acid, transformed B16 mouse melanoma cells also indicate a differential expression of prohibitin in which production of the protein is increased. The purpose of this work was to …


Polystyrene As A Medium In Reverse-Phase Separation Of Polycyclic Aromatic Hydrocarbons, Madhavi Mantha Jan 2008

Polystyrene As A Medium In Reverse-Phase Separation Of Polycyclic Aromatic Hydrocarbons, Madhavi Mantha

Browse all Theses and Dissertations

The purpose of the research was to design a method using high-performance liquid chromatography (HPLC) that would separate the sixteen polycyclic aromatic hydrocarbons (PAHs) designated by Environmental Protection Agency (EPA) as priority pollutants on two different kinds of polystyrene (PS) in the reversed phase. One was a zirconia-based column coated with polystyrene. The other was a polystyrene divinylbenzene (PS-DVB) column. The idea behind using these columns was to take advantage of extreme retention of PAHs by these columns by using high temperatures or temperature programming in order to reduce the amount of organic modifier in the mobile phases to perform …


Kinetic Evaluation Of Highly Active Supported Gold Catalysts Prepared From Monolayer-Protected Clusters: An Experimental Michaelis-Menten Approach For Determining The Oxygen Binding Constant During Co Oxidation Catalysis, Cormac G. Long, John D. Gilbertson, G. Vijayaraghavan, K. J. Stevenson, Christopher J. Pursell, Bert D. Chandler Jan 2008

Kinetic Evaluation Of Highly Active Supported Gold Catalysts Prepared From Monolayer-Protected Clusters: An Experimental Michaelis-Menten Approach For Determining The Oxygen Binding Constant During Co Oxidation Catalysis, Cormac G. Long, John D. Gilbertson, G. Vijayaraghavan, K. J. Stevenson, Christopher J. Pursell, Bert D. Chandler

Chemistry Faculty Research

Thiol monolayer-protected Au clusters (MPCs) were prepared using dendrimer templates, deposited onto a high-surface-area titania, and then the thiol stabilizers were removed under H2/N2. The resulting Au catalysts were characterized with transmission electron microscopy, X-ray photoelectron spectroscopy, and infrared spectroscopy of adsorbed CO. The Au catalysts prepared via this route displayed minimal particle agglomeration during the deposition and activation steps. Structural data obtained from the physical characterization of the Au catalysts were comparable to features exhibited from a traditionally prepared standard Au catalyst obtained from the World Gold Council (WGC). A differential kinetic study of CO oxidation catalysis by the …


Protein Adsorption Onto Organically-Modified Silica Glass Leads To A Different Structure Than Sol-Gel Encapsulation, Daryl K. Eggers, B, Menaa, C. Torres, M. Herrero, V. Rives, A. R.W Gilbert Jan 2008

Protein Adsorption Onto Organically-Modified Silica Glass Leads To A Different Structure Than Sol-Gel Encapsulation, Daryl K. Eggers, B, Menaa, C. Torres, M. Herrero, V. Rives, A. R.W Gilbert

Faculty Publications, Chemistry

The secondary structures of two proteins were examined by circular dichroism spectroscopy after adsorption onto a series of organically modified silica glasses. The glasses were prepared by the sol-gel technique and were varied in hydrophobicity by incorporation of 5% methyl, propyl, trifluoropropyl, or n-hexyl silane. Both cytochrome c and apomyoglobin were found to lose secondary structure after adsorption onto the modified glasses. In the case of apomyoglobin, the α-helical content of the adsorbed protein ranged from 21% to 28%, well below the 62% helix found in solution. In contrast, these same glasses led to a striking increase in apomyoglobin structure …


A Promising Change In The Selection Of The Circular Polarization Excitation Used In The Measurement Of Eu(Iii) Circularly Polarized Luminescence, K. Do, F. C. Muller, Gilles Muller Jan 2008

A Promising Change In The Selection Of The Circular Polarization Excitation Used In The Measurement Of Eu(Iii) Circularly Polarized Luminescence, K. Do, F. C. Muller, Gilles Muller

Faculty Publications, Chemistry

A judicious change in the selected transition used for circular polarization excitation will overcome the low oscillator strength limitation of the currently allowed magnetic-dipole 5D1 ← 7F2 (Eu(III)) transition chosen for circularly polarized luminescence (CPL) measurement. The proposed allowed magnetic-dipole 5D1 ← 7F0 (Eu(III)) transition will facilitate the detection of CPL from the Eu(III) systems of interest. CPL on the acetonitrile solution of the chiral tris complex of Eu(III) with (R,R)-N,N′-bis(1-phenylethyl)-2,6-pyridinedicarboxamide ([Eu((R,R)-1)3]3+), recently suggested as an effective and reliable CPL calibrating agent, confirms the feasibility of the proposed experimental procedure. A comparable CPL activity exhibited by the acetonitrile solution of …


Flash: A Rapid Method For Prototyping Paper-Based Microfluidic Devices, Andres W. Martinez, Scott T. Phillips, Benjamin J. Wiley, Malancha Gupta, George M. Whitesides Jan 2008

Flash: A Rapid Method For Prototyping Paper-Based Microfluidic Devices, Andres W. Martinez, Scott T. Phillips, Benjamin J. Wiley, Malancha Gupta, George M. Whitesides

Chemistry and Biochemistry

This article describes FLASH (Fast Lithographic Activation of Sheets), a rapid method for laboratory prototyping of microfluidic devices in paper. Paper-based microfluidic devices are emerging as a new technology for applications in diagnostics for the developing world, where low cost and simplicity are essential. FLASH is based on photolithography, but requires only a UV lamp and a hotplate; no clean-room or special facilities are required (FLASH patterning can even be performed in sunlight if a UV lamp and hotplate are unavailable). The method provides channels in paper with dimensions as small as 200 μm in width and 70 μm in …


Favourable Influence Of Hydrophobic Surfaces On Protein Structure In Porous Organically-Modified Silica Glasses, Daryl K. Eggers, B. Menaa, M. Herrero, V. Rives, M. Lavrenko Jan 2008

Favourable Influence Of Hydrophobic Surfaces On Protein Structure In Porous Organically-Modified Silica Glasses, Daryl K. Eggers, B. Menaa, M. Herrero, V. Rives, M. Lavrenko

Faculty Publications, Chemistry

Organically-modified siloxanes were used as host materials to examine the influence of surface chemistry on protein conformation in a crowded environment. The sol–gel materials were prepared from tetramethoxysilane and a series of monosubstituted alkoxysilanes, RSi(OR′)3, featuring alkyl groups of increasing chain length in the R-position. Using circular dichroism spectroscopy in the far-UV region, apomyoglobin was found to transit from an unfolded state to a native-like helical state as the content of the hydrophobic precursor increased from 0 to 15%. At a fixed molar content of 5% RSi(OR′)3, the helical structure of apomyoglobin increased with the chain length of the R-group, …


Singlet Oxygen Chemistry In Water:  A Porous Vycor Glasssupported Photosensitizer, David Aebisher, Nikolay S. Azar, Matibur Zamadar, Naveen Gandra, Harry D. Gafney, Roumei Gao, Alexander Greer Jan 2008

Singlet Oxygen Chemistry In Water:  A Porous Vycor Glasssupported Photosensitizer, David Aebisher, Nikolay S. Azar, Matibur Zamadar, Naveen Gandra, Harry D. Gafney, Roumei Gao, Alexander Greer

Faculty Publications

Singlet molecular oxygen [1O2 (1Δg)] is generated cleanly in aqueous solution upon irradiation of a heterogeneous complex, meso-tetra(N-methyl-4-pyridyl)porphine (1) adsorbed onto porous Vycor glass (PVG). The cationic photosensitizer 1 tightly binds onto PVG and gives a stable material, which does not dissociate 1 into the surrounding aqueous phase. The production of 1O2 was measured by monitoring the time-resolved 1O2 (1Δg) phosphorescence at 1270 nm. Indirect analysis of 1O2 generation was also carried out with the photooxidation oftrans-2-methyl-2-pentenoate anion, which afforded the corresponding hydroperoxide. Sensitizer-1-impregnated PVG gives rise to a new singlet …


Synthesis Of Phenoxides With Pendant Amines And Catalytic Intramolecular Hydroaminations, Kenneth Awasung Jan 2008

Synthesis Of Phenoxides With Pendant Amines And Catalytic Intramolecular Hydroaminations, Kenneth Awasung

Undergraduate Review

One core focus of my research project, (my 2007 summer research) is to make structural analogs of substituted phenols to support the titanium catalysis of organic compounds. The synthesis and study of these and related ligands, (pyrrolyls, aldimines, salens, and other nitrogen/oxygen heterocycles) is a major field of organometallic chemistry. Bulky phenols and their analogs serve as highly effective ligands to support catalysis due to their sterics and electronics. I have been designing and have begun synthesizing phenol analogs using a series of aldol condensations and michael additions and other organic chemistry methodology to generate new substituted phenols. Our method …


The Tropical Forest And Fire Emissions Experiment: Laboratory Fire Measurements And Synthesis Of Campaign Data, Robert J. Yokelson, Ted J. Christian, T. G. Karl, Alex Guenther Jan 2008

The Tropical Forest And Fire Emissions Experiment: Laboratory Fire Measurements And Synthesis Of Campaign Data, Robert J. Yokelson, Ted J. Christian, T. G. Karl, Alex Guenther

Chemistry and Biochemistry Faculty Publications

As part of the Tropical Forest and Fire Emissions Experiment (TROFFEE), tropical forest fuels were burned in a large. biomass-fire simulation facility and the smoke was characterized with open-path Fourier transform infrared spectroscopy (FTIR), proton-transfer reaction mass spectrometry (PTR-MS), gas chromatography (GC), GC/PTR-MS, and filter sampling of the particles. In most cases, about one-third of the fuel chlorine ended up in the particles and about one-half remained in the ash. About 50% of the mass of non-methane organic compounds (NMOC) emitted by these fires could be identified with the available instrumentation. The lab fire emission factors (EF, g compound emitted …


A Theoretical Study For The Reactivation Of O2 Inhibited [Fe-Fe]-Hydrogenase, Stefan Motiu Jan 2008

A Theoretical Study For The Reactivation Of O2 Inhibited [Fe-Fe]-Hydrogenase, Stefan Motiu

ETD Archive

The current investigation presents a reactivation pathway of the exogenously inhibited H-cluster (viz., by O2, or OH-, which metabolizes to H2O), for both vacuum and aqueous enzyme phase. The H-cluster is the catalytic site of [Fe-Fe]-hydrogenase, with the latter extracted from Desulfovibrio desulfuricans (Dd) bacteria. It consists of proximal iron, Fep, and distal Fed subunit, [Fep-Fed], which is bridged by di(thiomethyl)amine (DTMA) ligand, and a proximal cubane subunit, [Fe4-S4]2+p. [Fep-Fed] is coordinated by two cyanides (CN-), two terminal carbonyls (COt), and a bridging carbonyl (COb)*. An Fe atom from [Fe4-S4]2+p connects Fep through a cysteinyl sulfur (of Cys382). Density functional …


Mass Spectrometric Analysis Of Environmental Contaminants, Protein Structure And Expression, Ian E. Atkinson Jan 2008

Mass Spectrometric Analysis Of Environmental Contaminants, Protein Structure And Expression, Ian E. Atkinson

ETD Archive

There are a wide array of sciences at our disposal to further our understanding of the roles of toxins in the environment and their effects on living organisms. Of these disciplines, the field of mass spectrometry offers a powerful analytical means to identify compounds in varying and complex sample media. The presence of altered expressions of biomolecules upon exposure to toxins, the effects that these toxins may have on biomolecule structure and the identity of toxins in the sample all can be determined by mass spectrometry. In this study mass spectrometric analysis has been applied to environmental toxicological problems. First, …


Factor Va Directs Catalysis By Factor Xa During Prothrombin Activation, Michael Anthony Bukys Jan 2008

Factor Va Directs Catalysis By Factor Xa During Prothrombin Activation, Michael Anthony Bukys

ETD Archive

Hemostasis occurs through the controlled activation and inactivation of clotting factors resulting in the arrest of bleeding without blockage to the vasculature, while thrombosis is the undesired formation of vascular blood clots, which adversely affects millions of people annually. Clotting factors circulate in blood as inactive zymogens, which are proteolytically activated in response to vascular injury, assembled into enzymatic complexes and in turn activate additional coagulation factors culminating in the production of thrombin from the enzymatic complex prothrombinase. The prothrombinase complex is composed of the activated enzymatic component factor Xa (fXa) complexed to the activated cofactor portion factor Va (fVa) …


A Case In Kinase 2 Inhibitor Is A Potent Anti-Cancer Drug Candidate, Alieta Ciocea Jan 2008

A Case In Kinase 2 Inhibitor Is A Potent Anti-Cancer Drug Candidate, Alieta Ciocea

ETD Archive

Cancer is so widespread and lethal that it can be considered the biggest health problem of our century. Cancer drug development is a real challenge. Efforts outlined in this work were directed towards showing solid evidence that casein kinase 2 inhibitors can be used as a starting point for the development of potential cancer therapy. We first studied the effect of a specific CK2 inhibitor, DMAT, in a malignant megakaryoblastic leukemia cell line (MEG-01). Treated cells grew at a significantly lower rate than non-treated cells. Apoptosis was induced by DMAT in MEG-01 cells, dose and time dependent. When stimulated with …


Development Of Oligonucleotide Microarray For High Throughput Dna Methylation Analysis, Xiaopeng Li Jan 2008

Development Of Oligonucleotide Microarray For High Throughput Dna Methylation Analysis, Xiaopeng Li

ETD Archive

DNA methylation is a key event regulating gene expression. DNA methylation analysis plays a pivotal role in unlocking association of epigenetic events with cancer. However, simultaneous evaluation of the methylation status of multiple genes is still a technical challenge. Microarray is a promising approach for high-throughput analysis of the methylation status at numerous CpG sites within multiple genes of interest. In this dissertation study, we conducted a systematic study to examine the use of microarray methods for methylation analysis. First, a robust universal microarray was established with more flexible in design and content, and potential cost saving over commercial arrays. …


Technologies For Proteomic And Genomic Biomarker Analysis, Yiding Liu Jan 2008

Technologies For Proteomic And Genomic Biomarker Analysis, Yiding Liu

ETD Archive

In the first part of this dissertation, we systematically validated the application of molecular weight cut-off ultrafiltration in separation and enrichment of low-molecular-weight peptides from human serum. Under optimized conditions, both free-phase and bound LMW peptides could be separated and enriched. The method proved to be highly efficient and reproducible coupled with MALDI-TOF MS proteomic pattern analysis. Three marker peaks were found to be eligible for distinguishing normal and ovarian cancer samples. A novel organic solvent precipitation method coupled with enzymatic deglycosylation was also developed for biomarker detection from human serum. This method allowed us to generate reproducible free-phase peptide …


Inhibition Of The Nf-Kb Signaling Pathway And Its Effects On Apoptosis And Cancer, Joseph A. Lupica Jan 2008

Inhibition Of The Nf-Kb Signaling Pathway And Its Effects On Apoptosis And Cancer, Joseph A. Lupica

ETD Archive

The Rel/NF-kB family of inducible transcription factors are evolutionarily conserved structurally and functionally, from insects to humans. They are ubiquitously expressed in a number of mature cell types, playing a pivotal role regulating cell growth, differentiation and apoptosis. Under normal circumstances, the proliferation of new cells is tightly regulated, as is the programmed lifespan of most cells, occasionally however cells loose their responsiveness to growth control mechanisms, resulting in a tumor or neoplasm. Sustained or chronic inflammation has been linked to a number of pathological conditions that destroy tissue and facilitate neoplastic growth. NF-kB in part mediates the opposing signals …


Modeling The Human Prothrombinase Complex Components, Tivadar Orban Jan 2008

Modeling The Human Prothrombinase Complex Components, Tivadar Orban

ETD Archive

Thrombin generation is the culminating stage of the blood coagulation process. Thrombin is obtained from prothrombin (the substrate) in a reaction catalyzed by the prothrombinase complex (the enzyme). The prothrombinase complex is composed of factor Xa (the enzyme), factor Va (the cofactor) associated in the presence of calcium ions on a negatively charged cell membrane. Factor Xa, alone, can activate prothrombin to thrombin however, the rate of conversion is not physiologically relevant for survival. Incorporation of factor Va into prothrombinase accelerates the rate of prothrombinase activity by 300,000-fold, and provides the physiological pathway of thrombin generation. The long-term goal of …


Synthesis And Characterization Of Acylphosphine Oxide Photoinitiators, Hany F. Sobhi Jan 2008

Synthesis And Characterization Of Acylphosphine Oxide Photoinitiators, Hany F. Sobhi

ETD Archive

Recently, polymerization science has assumed an increasing relevance in many applications, including orthopedic and dental biomaterials. Current technologies are based on the use of photochemically reactive systems, which are suited to absorb light to produce primary radical species capable of initiating polymerization. Acylphosphine oxides and acylphosphonates are known to be very effective photoinitiators for various unsaturated polymeric systems. The high reactivity observed was ascribed to the phosphinyl and phosphinoyl radicals generated. Because of the poor qualities of other initiators, we examined new routes to synthesize acylphosphine oxide initiators to achieve compatibility with aqueous media and improved performance. The preparation and …


Mass Spectrometry-Based High Throughput Approach For Identification Of Molecular Modification Of Oxidative Process In Respiratory Diseases, Wei Song Jan 2008

Mass Spectrometry-Based High Throughput Approach For Identification Of Molecular Modification Of Oxidative Process In Respiratory Diseases, Wei Song

ETD Archive

Eosinophil peroxidase (EPO) and myeloperoxidase (MPO) have been implicated in generating reactive species and promoting oxidative modifications in numerous diseases. The detection and identification of potential pathways has been proven extremely challenge due to evanescence nature of these reactive species. An alternative approach to study the involvement of oxidative modification is to detect and quantify the stable molecular fingerprints, like oxidized tyrosine species, in biological matrices. Previously reported analytical methods for quantifying oxidized amino acids have typically been limited by: low sensitivity, specificity and the failure of detection potential oxidation products generated during sample handling. Using GC/MS in combination with …


Study Of 3'-Untranslated Region Of Inducible Nitric Oxide Synthase And Identification Of Other Targets Of Gaitpathway, Sirisha Vadlamani Jan 2008

Study Of 3'-Untranslated Region Of Inducible Nitric Oxide Synthase And Identification Of Other Targets Of Gaitpathway, Sirisha Vadlamani

ETD Archive

Macrophages and other leukocytes play a vital role during inflammation. IFN-Îđ which is secreted by Th1 cells activates monocyte-macrophages and this activation leads to induction as well as suppression of certain genes expressed during inflammation. This suppression of genes may be potentially vital for resolution of inflammation. Upon IFN-Îđ stimulation, a Gamma-activated inhibitor of translation complex (GAIT) is formed, which binds to 3'-UTR of target mRNAs thereby silencing their translation. VEGF-A and ceruloplasmin are two proteins whose translation is suppressed by this pathway. The GAIT complex proteins have been identified as ribosomal protein L13a, glutamyl-prolyl tRNA synthatase (EPRS), NS-1 associated …


Interactions Of Cis-Bis Ruthenium Complexes With Monosaccharides, Lindsay Mcdonald Jan 2008

Interactions Of Cis-Bis Ruthenium Complexes With Monosaccharides, Lindsay Mcdonald

Undergraduate Review

Molecular recognition and binding of oligosaccharides play an essential role in many biological processes including cell-cell recognition, signaling and adhesion. Our group is currently involved in the development of metal based receptors that can effectively bind specific glycoconjugates. Species that can selectively bind and chemically alter membrane glycoconjugates have the potential to inhibit tumor cell metastasis, inflammation and fibrosis. As an initial step towards our goal the interactions of cis-Ru(bpy)2(DMF)22+ (bpy = bipyridine, DMF = dimethylformamide) and cis-Ru(acac)2(CH3CN)2+ (acac = acetylacetonate) with the monosaccharides glucose and mannose have been examined …


Phosphorylation Of Claudin-5 And Occludin By Rho Kinase In Brain Endothelial Cells, Masaru Yamamoto, Servio H. Ramirez, Shinji Sato, Tomomi Kiyota, Ronald Cerny, Kozo Kaibuchi, Yuri Persidsky, Tsuneya Ikezu Jan 2008

Phosphorylation Of Claudin-5 And Occludin By Rho Kinase In Brain Endothelial Cells, Masaru Yamamoto, Servio H. Ramirez, Shinji Sato, Tomomi Kiyota, Ronald Cerny, Kozo Kaibuchi, Yuri Persidsky, Tsuneya Ikezu

Ronald Cerny Publications

Critical to the proper maintenance of blood-brainbarrier (BBB) integrity are the endothelial tight junctions (TJs). Posttranslational modifications of essential endothelial TJ proteins, occludin and claudin-5, contribute and possibly disrupt BBB integrity. Our previous work has shown that Rho kinase (RhoK) activation mediates occludin and claudin-5 phosphorylation resulting in diminished barrier tightness and enhanced monocyte migration across BBB in the setting of human immunodeficiency virus-1 encephalitis (HIVE). To determine whether RhoK can directly phosphorylate TJ proteins, we examined phosphorylation of cytoplasmic domains of recombinant claudin- 5 and occludin by RhoK. We found that RhoK predominately phosphorylated two sites on occludin (T382 …