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Regulation And Localization Of Endogenous Human Tristetraprolin, Anna-Marie Fairhurst, John E. Connolly, Katharine A Hintz, Nicolas J Goulding May 2003

Regulation And Localization Of Endogenous Human Tristetraprolin, Anna-Marie Fairhurst, John E. Connolly, Katharine A Hintz, Nicolas J Goulding

Dartmouth Scholarship

Tumor necrosis factor (TNF) has been implicated in the development and pathogenicity of infectious diseases and autoimmune disorders, such as septic shock and arthritis. The zinc-finger protein tristetraprolin (TTP) has been identified as a major regulator of TNF biosynthesis. To define its intracellular location and examine its regulation of TNF, a quantitive intracellular staining assay specific for TTP was developed. We establish for the first time that in peripheral blood leukocytes, express


Kinetic And Spectroscopic Characterization Of The H178a Methionyl Aminopeptidase From Escherichia Coli, Alicja J. Copik, Sabina I. Swierczek, W. Todd Lowther, Ventris M. D'Souza, Brian W. Matthews, Richard C. Holz May 2003

Kinetic And Spectroscopic Characterization Of The H178a Methionyl Aminopeptidase From Escherichia Coli, Alicja J. Copik, Sabina I. Swierczek, W. Todd Lowther, Ventris M. D'Souza, Brian W. Matthews, Richard C. Holz

Chemistry Faculty Research and Publications

To gain insight into the role of the strictly conserved histidine residue, H178, in the reaction mechanism of the methionyl aminopeptidase from Escherichia coli (EcMetAP-I), the H178A mutant enzyme was prepared. Metal-reconstituted H178A binds only one equivalent of Co(II) or Fe(II) tightly with affinities that are identical to the WT enzyme based on kinetic and isothermal titration calorimetry (ITC) data. Electronic absorption spectra of Co(II)-loaded H178A EcMetAP-I indicate that the active site divalent metal ion is pentacoordinate, identical to the WT enzyme. These data indicate that the metal binding site has not been affected by altering H178. …


Synthesis Of Novel [3, 2-B] Indole Fused Oleanolic Acids As Potential Inhibitors Of Cell Proliferation, Heather J. Finlay, Tadashi Honda, Gordon W. Gribble May 2003

Synthesis Of Novel [3, 2-B] Indole Fused Oleanolic Acids As Potential Inhibitors Of Cell Proliferation, Heather J. Finlay, Tadashi Honda, Gordon W. Gribble

Dartmouth Scholarship

Seven new indole-fused oleanolic acid derivatives were synthesized from oleanolic acid for their ability to inhibit cell proliferation in NRP. 152 cells.


Preparation Of 2s,3s-N-Isobutyl-N-(2-Hydroxy-3-Amino-4-Phenylbutyl)-P-Nitrobenzenesulfonylamide Hydrochloride And Other Derivatives Of 2-Hydroxy-1,3-Diamines, Aslam A. Malik, Hasan Palandoken, Joy A. Stringer, Roland P. Carlson, John Leach, Thomas G. Archibald, Robert G. Miotke Apr 2003

Preparation Of 2s,3s-N-Isobutyl-N-(2-Hydroxy-3-Amino-4-Phenylbutyl)-P-Nitrobenzenesulfonylamide Hydrochloride And Other Derivatives Of 2-Hydroxy-1,3-Diamines, Aslam A. Malik, Hasan Palandoken, Joy A. Stringer, Roland P. Carlson, John Leach, Thomas G. Archibald, Robert G. Miotke

Chemistry and Biochemistry

The present invention provides a new process for the preparation of 2S,3S-N-isobutyl-N-(2-hydroxy-3-amino-4phenylbutyl)- p-nitrobenzenesulfonylamide hydrochloride, wherein this compound is prepared directly from the chloromethylalcohol. Importantly, the process of the present invention results in higher yields of 2S,3S-N-isobutyl-N-(2hydroxy -3 -amino -4-phenylbutyl) -pnitrobenzenesulfonylamide hydrochloride without sacrificing its purity. The processes of the present inventin can be used to prepare not only the 2S,3S-derivative, but also the 2R,3S-, 2S,2R- and the 2R,3R-derivatives.


Clean, High-Yield Preparation Of S,S- And R,S- Amino Acid Isosteres, Aslam A. Malik, Todd E. Clement, Hasan Palandoken, James Robinson Iii, Joy A. Stringer Apr 2003

Clean, High-Yield Preparation Of S,S- And R,S- Amino Acid Isosteres, Aslam A. Malik, Todd E. Clement, Hasan Palandoken, James Robinson Iii, Joy A. Stringer

Chemistry and Biochemistry

The present invention provides compounds and methods that can be used to convert the intermediate halomethyl ketones (HMKs), e.g., chloromethyl ketones, to the corresponding S,S- and R,S-diastereomers. More particularly, the present invention provides: (1) reduction methods; (2) inversion methods; and (3) methods involving the epoxidation of alkenes. Using the various methods of the present invention, the R,S-epoxide and the intermediary compounds can be prepared reliably, in high yields and in high purity.


Tropospheric Carbon Monoxide Measurements From The Scanning High-Resolution Interferometer Sounder On 7 September 2000 In Southern Africa During Safari 2000, W. W. Mcmillan, M. L. Mccourt, H. E. Revercomb, R. O. Knuteson, Ted J. Christian, B. G. Doddridge, Peter V. Hobbs, J. V. Lukovich, P. C. Novelli, S. J. Piketh, L. Sparling, D. Stein, R. J. Swap, Robert J. Yokelson Apr 2003

Tropospheric Carbon Monoxide Measurements From The Scanning High-Resolution Interferometer Sounder On 7 September 2000 In Southern Africa During Safari 2000, W. W. Mcmillan, M. L. Mccourt, H. E. Revercomb, R. O. Knuteson, Ted J. Christian, B. G. Doddridge, Peter V. Hobbs, J. V. Lukovich, P. C. Novelli, S. J. Piketh, L. Sparling, D. Stein, R. J. Swap, Robert J. Yokelson

Chemistry and Biochemistry Faculty Publications

[1] Retrieved tropospheric carbon monoxide (CO) column densities are presented for more than 9000 spectra obtained by the University of Wisconsin-Madison (UWis) Scanning High-Resolution Interferometer Sounder (SHIS) during a flight on the NASA ER-2 on 7 September 2000 as part of the Southern African Regional Science Initiative (SAFARI 2000) dry season field campaign. Enhancements in tropospheric column CO were detected in the vicinity of a controlled biomass burn in the Timbavati Game Reserve in northeastern South Africa and over the edge of the river of smoke in south central Mozambique. Relatively clean air was observed over the far southern coast …


Chemistry & Biochemistry Newsletter, Department Of Chemistry & Biochemistry, South Dakota State University Apr 2003

Chemistry & Biochemistry Newsletter, Department Of Chemistry & Biochemistry, South Dakota State University

Chemistry & Biochemistry Newsletter: 2002-2015

Inside:

Page 2 2003 Graduates; Bonneman Scholarship in Medical Technology Awarded; Dean’s List–Spring 2003

Page 3 Update of Sophomore Organic Chemistry Lab; Halaweish Receives Governor’s Grant

Page 4 A Mini-sized Antarctic in Shepard Hall

Page 5 Alumni News; Faculty and Staff News; Foundation Donors

Page 6 Recent Faculty Publications


Teachers' Resource For Materials And Environmental Chemistry, Carnetta Skipworth Apr 2003

Teachers' Resource For Materials And Environmental Chemistry, Carnetta Skipworth

Masters Theses & Specialist Projects

In many secondary education chemistry classrooms, teachers have a difficult time introducing chemistry topics in a way that will be interesting to the high school student. The development of a materials and environmental chemistry teacher's manual will help teachers introduce a variety of selected topics in an interesting fashion to the students. This manual focuses on the subjects covered for freshman and sophomore level students. The manual uses five separate experiments to introduce topics such as the electromagnetic spectrum and solubility. The five experiments include a test on tennis shoe stiffness and energy dissipation ability, pesticides in water, grease in …


Peptide−Protein Interactions: Photoinduced Electron-Transfer Within The Preformed And Encounter Complexes Of A Designed Metallopeptide And Cytochrome C, Robin C. Lasey, Liu Liu, Ling Zang, Michael Y. Ogawa Apr 2003

Peptide−Protein Interactions: Photoinduced Electron-Transfer Within The Preformed And Encounter Complexes Of A Designed Metallopeptide And Cytochrome C, Robin C. Lasey, Liu Liu, Ling Zang, Michael Y. Ogawa

Chemistry Faculty Publications

Photoinduced electron-transfer (ET) occurs between a negatively charged metallopeptide, [Ru(bpy)2(phen-am)-Cys-(Glu)(5)-Gly](3-) = RuCE(5)G, and ferricytochrome c = Cyt c. In the presence of Cyt c, the triplet state lifetime of the ruthenium metallopeptide is shortened, and the emission decays via biexponential kinetics, which indicates the existence of two excited-state populations of ruthenium peptides. The faster decay component displays concentration-independent kinetics demonstrating the presence of a preformed peptide-protein complex that undergoes intra-complex electron-transfer. Values of K-b = (3.5 +/- 0.2) x 10(4) M-1 and k(ET)(obs) = (2.7 +/- 0.4) x 10(6) s(-1) were observed at ambient temperatures. The magnitude of k(ET)(obs) decreases …


Co-Catalytic Metallopeptidases As Pharmaceutical Targets, Richard C. Holz, Krzysztof P. Bzymek, Sabina I. Swierczek Apr 2003

Co-Catalytic Metallopeptidases As Pharmaceutical Targets, Richard C. Holz, Krzysztof P. Bzymek, Sabina I. Swierczek

Chemistry Faculty Research and Publications

Understanding the reaction mechanism of co-catalytic metallopeptidases provides a starting point for the design and synthesis of new molecules that can be screened as potential pharmaceuticals. Many of the enzymes that contain co-catalytic metallo-active sites play important roles in cellular processes such as tissue repair, protein maturation, hormone level regulation, cell-cycle control and protein degradation. Therefore, these enzymes play central roles in several disease states including cancer, HIV, stroke, diabetes, bacterial infections, neurological processes, schizophrenia, seizure disorders, and amyotrophic lateral sclerosis. The mechanism of AAP, an aminopeptidase from Aeromonas proteolytica, is one of the best-characterized examples of a metallopeptidase …


Emissions Of Trace Gases And Particles From Savanna Fires In Southern Africa, Parikhit Sinha, Peter V. Hobbs, Robert J. Yokelson, I. T. Bertschi, Donald R. Blake, Isobel J. Simpson, Song Gao, Thomas W. Kirschsetter, Tica Novakov Mar 2003

Emissions Of Trace Gases And Particles From Savanna Fires In Southern Africa, Parikhit Sinha, Peter V. Hobbs, Robert J. Yokelson, I. T. Bertschi, Donald R. Blake, Isobel J. Simpson, Song Gao, Thomas W. Kirschsetter, Tica Novakov

Chemistry and Biochemistry Faculty Publications

[1] Airborne measurements made on initial smoke from 10 savanna fires in southern Africa provide quantitative data on emissions of 50 gaseous and particulate species, including carbon dioxide, carbon monoxide, sulfur dioxide, nitrogen oxides, methane, ammonia, dimethyl sulfide, nonmethane organic compounds, halocarbons, gaseous organic acids, aerosol ionic components, carbonaceous aerosols, and condensation nuclei (CN). Measurements of several of the gaseous species by gas chromatography and Fourier transform infrared spectroscopy are compared. Emission ratios and emission factors are given for eight species that have not been reported previously for biomass burning of savanna in southern Africa (namely, dimethyl sulfide, methyl nitrate, …


Evolution Of Gases And Particles From A Savanna Fire In South Africa, Peter V. Hobbs, Parikhit Sinha, Robert J. Yokelson, Ted J. Christian, Donald R. Blake, Song Gao, Thomas W. Kirschsetter, Tica Novakov, Peter Pilewskie Mar 2003

Evolution Of Gases And Particles From A Savanna Fire In South Africa, Peter V. Hobbs, Parikhit Sinha, Robert J. Yokelson, Ted J. Christian, Donald R. Blake, Song Gao, Thomas W. Kirschsetter, Tica Novakov, Peter Pilewskie

Chemistry and Biochemistry Faculty Publications

[1] Airborne measurements of particles and gases from a 1000-ha savanna fire in South Africa are presented. These measurements represent the most extensive data set reported on the aging of biomass smoke. The measurements include total concentrations of particles (CN), particle sizes, particulate organic carbon and black carbon, light-scattering coefficients, downwelling UV fluxes, and mixing ratios for 42 trace gases and 7 particulate species. The ratios of excess nitrate, ozone, and gaseous acetic acid to excess CO increased significantly as the smoke aged over ∼40–45 min, indicating that these species were formed by photochemistry in the plume. For 17 other …


Analysis Of Heme Structural Heterogeneity In Mycobacterium Tuberculosis Catalase-Peroxidase (Katg), Salem Chouchane, Stefania Girotto, Sofia Kapetanaki, Johannes Schelvis, Shengwei Yu, Richard S. Magliozzo Mar 2003

Analysis Of Heme Structural Heterogeneity In Mycobacterium Tuberculosis Catalase-Peroxidase (Katg), Salem Chouchane, Stefania Girotto, Sofia Kapetanaki, Johannes Schelvis, Shengwei Yu, Richard S. Magliozzo

Department of Chemistry and Biochemistry Faculty Scholarship and Creative Works

Mycobacterium tuberculosis catalase-peroxidase (KatG) is a heme enzyme considered important for virulence, which is also responsible for activation of the anti-tuberculosis pro-drug isoniazid. Here, we present an analysis of heterogeneity in KatG heme structure using optical, resonance Raman, and EPR spectroscopy. Examination of ferric KatG under a variety of conditions, including enzyme in the presence of fluoride, chloride, or isoniazid, and at different stages during purification in different buffers allowed for assignment of spectral features to both five- and six-coordinate heme. Five-coordinate heme is suggested to be representative of "native" enzyme, since this species was predominant in the enzyme examined …


Analysis Of Anion Distributions In The Developing Strata Of A Constructed Wetland Used For Chlorinated Ethene Remediation, Joshua D. Kovacic Mar 2003

Analysis Of Anion Distributions In The Developing Strata Of A Constructed Wetland Used For Chlorinated Ethene Remediation, Joshua D. Kovacic

Theses and Dissertations

Perchloroethene (PCE), Trichloroethene (TCE) and their degradation products are among the most common organic groundwater contaminants in the United States. Constructed wetlands utilizing upward flow harbor reduction-oxidation conditions that have demonstrated the potential to promote both partial and total mineralization of PCE and TCE through the process of natural attenuation. Organic acid and inorganic anion concentrations are indicative of reduction-oxidation processes that drive chlorinated ethene degradation. These analytes were investigated to assess their development within three vertically stratified regions of a constructed wetland cell at Wright-Patterson Air Force Base fed by groundwater contaminated with PCE and TCE. Data collected during …


Cooperative Effects In One-Dimensional Chains Of Three-Center Hydrogen Bonding Interactions, Ruben D. Parra, Satya S. Bulusu, Xiao Cheng Zeng Feb 2003

Cooperative Effects In One-Dimensional Chains Of Three-Center Hydrogen Bonding Interactions, Ruben D. Parra, Satya S. Bulusu, Xiao Cheng Zeng

Xiao Cheng Zeng Publications

Cooperative effects in a one-dimensional network of intermolecular bifurcated hydrogen bonding interactions are investigated by means of ab initio calculations. The trans–trans conformation of the diformamide molecule is used as a basic motif to model a chain of bifurcated H bonds. In this model system, the two proton–acceptor atoms belong to the same molecule. The one-dimensional network is modeled then by periodically stacking up to 12 molecules of the unit motif. Different indicators of H-bond strength such as energetic, structural, dielectric, vibrational frequencies, and isotropic chemicals shifts consistently show significant cooperative effects in the chains. The dissociation energy in the …


Trace Gas And Particle Emissions From Fires In Large Diameter And Belowground Biomass Fuels, Isaac T. Bertschi, Robert J. Yokelson, Darold E. Ward, R. E. Babbitt, Ronald A. Susott, Jon G. Goode, Wei Min Hao Feb 2003

Trace Gas And Particle Emissions From Fires In Large Diameter And Belowground Biomass Fuels, Isaac T. Bertschi, Robert J. Yokelson, Darold E. Ward, R. E. Babbitt, Ronald A. Susott, Jon G. Goode, Wei Min Hao

Chemistry and Biochemistry Faculty Publications

[1] We adopt a working definition of residual smoldering combustion (RSC) as biomass combustion that produces emissions that are not lofted by strong fire-induced convection. RSC emissions can be produced for up to several weeks after the passage of a flame front and they are mostly unaffected by flames. Fuels prone to RSC include downed logs, duff, and organic soils. Limited observations in the tropics and the boreal forest suggest that RSC is a globally significant source of emissions to the troposphere. This source was previously uncharacterized. We measured the first emission factors (EF) for RSC in a series of …


Examination Of The Role Of The Clamp-Loader And Atp Hydrolysis In The Formation Of The Bacteriophage T4 Polymerase Holoenzyme, Michael A. Trakselis, Anthony J. Berdis, Stephen J. Benkovic Feb 2003

Examination Of The Role Of The Clamp-Loader And Atp Hydrolysis In The Formation Of The Bacteriophage T4 Polymerase Holoenzyme, Michael A. Trakselis, Anthony J. Berdis, Stephen J. Benkovic

Chemistry Faculty Publications

Transient kinetic analyses further support the role of the clamp-loader in bacteriophage T4 as a catalyst which loads the clamp onto DNA through the sequential hydrolysis of two molecules of ATP before and after addition of DNA. Additional rapid-quench and pulse-chase experiments have documented this stoichiometry. The events of ATP hydrolysis have been related to the opening/closing of the clamp protein through fluorescence resonance energy transfer (FRET). In the absence of a hydrolysable form of ATP, the distance across the subunit interface of the clamp does not increase as measured by intramolecular FRET, suggesting gp45 cannot be loaded onto DNA. …


Trace Gas Emissions From The Production And Use Of Domestic Biofuels In Zambia Measured By Open-Path Fourier Transform Infrared Spectroscopy, Isaac T. Bertschi, Robert J. Yokelson, Darold E. Ward, Ted J. Christian, Wei Min Hao Feb 2003

Trace Gas Emissions From The Production And Use Of Domestic Biofuels In Zambia Measured By Open-Path Fourier Transform Infrared Spectroscopy, Isaac T. Bertschi, Robert J. Yokelson, Darold E. Ward, Ted J. Christian, Wei Min Hao

Chemistry and Biochemistry Faculty Publications

[1] Domestic biomass fuels (biofuels) were recently estimated to be the second largest source of carbon emissions from global biomass burning. Wood and charcoal provide approximately 90% and 10% of domestic energy in tropical Africa. In September 2000, we used open-path Fourier transform infrared (OP-FTIR) spectroscopy to quantify 18 of the most abundant trace gases emitted by wood and charcoal cooking fires and an earthen charcoal-making kiln in Zambia. These are the first in situ measurements of an extensive suite of trace gases emitted by tropical biofuel burning. We report emission ratios (ER) and emission factors (EF) for (in order …


Efficient Incorporation Of Coa, Nad And Fad Into Rna By In Vitro Transcription, Faqing Huang Feb 2003

Efficient Incorporation Of Coa, Nad And Fad Into Rna By In Vitro Transcription, Faqing Huang

Faculty Publications

Protein enzymes frequently recruit small molecule coenzymes to perform a variety of biochemical reactions. While the catalytic activities of RNA have been expanding rapidly, a similar strategy for RNA to utilize coenzymes and to increase its functional capabilities has yet to be demonstrated. A general in vitro transcription procedure has been developed to efficiently prepare RNA with coenzymes CoA, NAD and FAD covalently attached to the 5' end. These adenosine-containing coenzymes initiate transcription under the T7 class II promoter by T7 RNA polymerase. In addition to the three coenzymes, other adenosine-containing molecules may be incorporated into the first nucleotide position …


Phosphoproteomic Studies Of Smooth Muscle Contraction: Investigation Of Differential Phosphorylation In Relaxed/Contracted Rat Aortic Smooth Muscle Tissue Using Maldi-Tof Ms, Tonya M. Pekar Jan 2003

Phosphoproteomic Studies Of Smooth Muscle Contraction: Investigation Of Differential Phosphorylation In Relaxed/Contracted Rat Aortic Smooth Muscle Tissue Using Maldi-Tof Ms, Tonya M. Pekar

Theses, Dissertations and Capstones

Many human disorders are associated with the malfunction of smooth muscle tissue, or are related to the capabilities of its proper function—asthma, glaucoma, renal inefficiency, hypertension, and cardiovascular disease. Dysfunctional proteins are frequently implicated as the source of such disorders. As the second highest cause of death in the United States, the epidemic of cardiovascular disease makes the study of smooth muscle of utmost concern.

The capabilities of proteomics and mass spectrometry allow the entire proteome complement of a cell or tissue type to be analyzed at once. This investigation employs such techniques in an effort to better understand the …


Investigations Of Supramolecular And Catalytic Properties Of Ppi Dendrimers, Aaron K. Holley Jan 2003

Investigations Of Supramolecular And Catalytic Properties Of Ppi Dendrimers, Aaron K. Holley

Theses, Dissertations and Capstones

The research reported in this thesis focused on supramolecular and catalytic properties of poly(propylene imine) (PPI) dendrimers. Analytical techniques used in this research included high resolution NMR spectroscopy, as well as UV-vis and fluorescence spectroscopies and scanning electron microscopy. This investigation showed that: (1) PPI dendrimers interact with diacids to form interlock self-assemblies by electrostatic interactions (with an increase in dendrimer generation, smaller diacids are required to form the most efficient self-assembly); (2) PPI/diacid self-assemblies are able to encapsulate fluorescent dyes within the void spaces of the PPI/diacid moieties; (3) PPI-3 can chelate many types of metal cations, and these …


Tetratricopeptide Repeat Motif-Mediated Hsc70-Msti1 Interaction Molecular Characterization Of The Critical Contacts For Successful Binding And Specificity*, Odutayo O. Odunuge, Judith A. Hornby, Chrisiane Bies, Richard Zimmermann, David J. Pugh, Gregory L. Blatch Jan 2003

Tetratricopeptide Repeat Motif-Mediated Hsc70-Msti1 Interaction Molecular Characterization Of The Critical Contacts For Successful Binding And Specificity*, Odutayo O. Odunuge, Judith A. Hornby, Chrisiane Bies, Richard Zimmermann, David J. Pugh, Gregory L. Blatch

Faculty Publications

Murine stress-inducible protein 1 (mSTI1) is a cochaperone that is homologous with the human Hsp70/ Hsp90-organizing protein (Hop). Guided by Hop structural data and sequence alignment analyses, we have used site-directed mutagenesis, co-precipitation assays, circular dichroism spectroscopy, steady-state fluorescence, and surface plasmon resonance spectroscopy to both qualitatively and quantitatively characterize the contacts necessary for the N-terminal tetratricopeptide repeat domain (TPR1) of mSTI1 to bind to heat shock cognate protein 70 (Hsc70) and to discriminate between Hsc70 and Hsp90. We have shown that substitutions in the first TPR motif of Lys8 or Asn12 did not affect binding of mSTI1 to Hsc70, …


Fluorescence Determination Of Tryptophan Side-Chain Accessibility And Dynamics In Triple-Helical Collagen-Like Peptides, K. V. Simon-Lukasik, A. V. Persikov, B. Brodsky, J. A. M. Ramshaw, William Laws, J. B. A. Ross, R. D. Ludescher Jan 2003

Fluorescence Determination Of Tryptophan Side-Chain Accessibility And Dynamics In Triple-Helical Collagen-Like Peptides, K. V. Simon-Lukasik, A. V. Persikov, B. Brodsky, J. A. M. Ramshaw, William Laws, J. B. A. Ross, R. D. Ludescher

Chemistry and Biochemistry Faculty Publications

We report tryptophan fluorescence measurements of emission intensity, iodide quenching, and anisotropy that describe the environment and dynamics at X and Y sites in stable collagen-like peptides of sequence (Gly-X-Y)(n). About 90% of tryptophans at both sites have similar solvent exposed fluorescence properties and a lifetime of 8.5-9 ns. Analysis of anisotropy decays using an associative model indicates that these long lifetime populations undergo rapid depolarizing motion with a 0.5 ns correlation time; however, the extent of fast motion at the Y site is considerably less than the essentially unrestricted motion at the X site. About 10% of tryptophans at …


Constrained Analysis Of Fluorescence Anisotropy Decay: Application To Experimental Protein Dynamics, E. Feinstein, G. Deikus, E. Rusinova, E. L. Rachofsky, J. B. A. Ross, William Laws Jan 2003

Constrained Analysis Of Fluorescence Anisotropy Decay: Application To Experimental Protein Dynamics, E. Feinstein, G. Deikus, E. Rusinova, E. L. Rachofsky, J. B. A. Ross, William Laws

Chemistry and Biochemistry Faculty Publications

Hydrodynamic properties as well as structural dynamics of proteins can be investigated by the well-established experimental method of fluorescence anisotropy decay. Successful use of this method depends on determination of the correct kinetic model, the extent of cross-correlation between parameters in the fitting function, and differences between the timescales; of the depolarizing motions and the fluorophore's fluorescence lifetime. We have tested the utility of an independently measured steady-state anisotropy value as a constraint during data analysis to reduce parameter cross correlation and to increase the timescales over which anisotropy decay parameters can be recovered accurately for two calcium-binding proteins. Mutant …


Comparison Between Hydrogen And Dihydrogen Bonds Among H3bnh3, H2bnh2, And Nh3, T. Kar, Steve Scheiner Jan 2003

Comparison Between Hydrogen And Dihydrogen Bonds Among H3bnh3, H2bnh2, And Nh3, T. Kar, Steve Scheiner

Chemistry and Biochemistry Faculty Publications

Several possible binary complexes among ammonia-borane, aminoborane, and ammonia, via hydrogen and/or dihydrogen bonds, have been investigated to understand the effect of different hybridization. Møller–Plesset second-order perturbation theory with aug-cc-pVDZ basis set was used. The interaction energy is corrected for basis set superposition error, and the Morokuma–Kitaura method was employed to decompose the total interaction energy. Like H3BNH3, the sp2 hybridized H2BNH2 also participates in H- and dihydrogen bond formation. However, such bonds are weaker than their sp3 analogs. The contractions of BN bonds are associated with blueshift in …


Self-Aggregates Of Cationic Meso-Tetratolylporphyrins In Aqueous Solutions, Pavel Kubat, Kamil Lang, Kristina Prochazkova, Pavel Anzenbacher Jr. Jan 2003

Self-Aggregates Of Cationic Meso-Tetratolylporphyrins In Aqueous Solutions, Pavel Kubat, Kamil Lang, Kristina Prochazkova, Pavel Anzenbacher Jr.

Chemistry Faculty Publications

Aggregation properties of meso-tetratolylporphyrins bearing cationic substituents of a lipophilic nature such as ammonium, pyridinium, phosphonium, sulfonium, and isothiouronium were studied by UV/vis and resonance light scattering spectroscopy. The exciton point-dipole approximation was used to predict the structural alignment of the porphyrin units within the aggregate. The contribution of various types of aggregates depends on the porphyrin substitution, ionic strength, and temperature of aqueous solution of the porphyrin. In general, the preferred structure of an aggregate formed by temperature-induced aggregation is the J-aggregate exhibiting the characteristically narrow, red-shifted Soret band indicating a parallel "side-by-side" arrangement of the porphyrin units. The …


Photoinduced Electron-Transfer Along Α-Helical And Coiled-Coil Metallopeptides, Anna Fedorova, Anita Chaudhari, Michael Y. Ogawa Jan 2003

Photoinduced Electron-Transfer Along Α-Helical And Coiled-Coil Metallopeptides, Anna Fedorova, Anita Chaudhari, Michael Y. Ogawa

Chemistry Faculty Publications

A peptide-based electron-transfer system has been designed in which the specific positions of redox-active metal complexes appended to either an a-helix, or an a-helical coiled-coil, can be reversed to test the effect of the helix dipole in controlling photoinduced electron-transfer rates. Two 30-residue apopeptides were prepared having the following sequences: (1) Ac-K-(IEALEGK)(ICALEGK)(IEALEHK)-(IEALEGK)-G-amide, and (II) Ac-K-(IEALEGK)(IHALEGK)-(IEALECK)(IEALEGK)-G-amide. Each apopeptide was reacted first with [Ru(bpy)(2)(phen-ClAc)](2+), where bpy = 2,2'-bipyridine and phen-ClAc = 5-chloroacetamido-1,10-phenanthroline, to attach the ruthenium polypyridyl center to the cysteine side-chain of the polypeptide. The isolated products were then reacted with [Ru(NH3)(5)(H2O)](2+) to yield the binuclear electron-transfer metallopeptides ET-I and ET-II. …


Synthesis Of Some New Substituted 1,2,4-Triazole And 1,3,4-Thiadiazole And Their Derivatives, Khosrow Zamani, Khalil Faghihi, M. Reza Sangi, Javad Zolgharnein Jan 2003

Synthesis Of Some New Substituted 1,2,4-Triazole And 1,3,4-Thiadiazole And Their Derivatives, Khosrow Zamani, Khalil Faghihi, M. Reza Sangi, Javad Zolgharnein

Turkish Journal of Chemistry

Several 5-(isomeric pyridyl)-4-aryl-1,2,4-triazole-3-thiol/yl-thiomethyl/yl-thioethyl/yl-thiobenzyl and yl-thioglycolic acids were prepared as possible biologically active agents. The infrared, nuclear magnetic resonance (^{1}H-NMR and ^{13}C-NMR), mass spectra and elemental analysis of these compounds are reported


Hypothalamic Proopiomelanocortin Neurons Are Glucose Responsive And Express Katp Channels, Nurhadi Ibrahim, Martha A. Bosch, James L. Smart, Jian Qiu, Marcelo Rubinstein, Oline K. Rønnekleiv, Malcolm J. Low, Martin J. Kelly Jan 2003

Hypothalamic Proopiomelanocortin Neurons Are Glucose Responsive And Express Katp Channels, Nurhadi Ibrahim, Martha A. Bosch, James L. Smart, Jian Qiu, Marcelo Rubinstein, Oline K. Rønnekleiv, Malcolm J. Low, Martin J. Kelly

Faculty Publications - Department of Biological & Molecular Science

Hypothalamic proopiomelanocortin (POMC) neurons are critical for controlling homeostatic functions in the mammal. We used a transgenic mouse model in which the POMC neurons were labeled with enhanced green fluorescent protein to perform visualized, whole-cell patch recordings from prepubertal female hypothalamic slices. The mouse POMC-enhanced green fluorescent protein neurons expressed the same endogenous conductances (a transient outward K current and a hyperpolarization-activated, cation current) that have been described for guinea pig POMC neurons. In addition, the selective -opioid receptor agonist DAMGO induced an outward current (maximum of 12.8 1.2 pA), which reversed at K equilibrium potential (EK), in the majority …


The Anorexigenic Fatty Acid Synthase Inhibitor, C75, Is A Nonspecific Neuronal Activator, Kanji A. Takahashi, James L. Smart, Hongyan Liu, Roger D. Cone Jan 2003

The Anorexigenic Fatty Acid Synthase Inhibitor, C75, Is A Nonspecific Neuronal Activator, Kanji A. Takahashi, James L. Smart, Hongyan Liu, Roger D. Cone

Faculty Publications - Department of Biological & Molecular Science

C75, a recently derived compound that potently suppresses feeding and induces weight loss, has been proposed to act mainly by inhibiting fatty acid synthase (FAS) in central neurons that control feeding. For example, normal, fasting- associated, hypothalamic increases in neuropeptide Y (NPY)/Agouti-related protein (AGRP) expression and decreases in proopiomelanocortin (POMC)/cocaine and amphetamine regulated transcript (CART) expression were reported to be blocked by C75. Using loose-patch extracellular recording in acute slices, we tested the effect of C75 on anorexigenic POMC neurons and orexigenic NPY neurons of the hypothalamic arcuate nucleus, which were identified by promoter-driven GFP expression, as well as on …