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Articles 931 - 960 of 1131

Full-Text Articles in Physical Sciences and Mathematics

Semiclassical Application Of The Mo”Ller Operators In Reactive Scattering, Sophya Garashchuk, John C. Light Jan 2001

Semiclassical Application Of The Mo”Ller Operators In Reactive Scattering, Sophya Garashchuk, John C. Light

Faculty Publications

Mo\ller operators in the formulation of reaction probabilities in terms of wave packet correlation functions allow us to define the wave packets in the interaction region rather than in the asymptotic region of the potential surface. We combine Mo\ller operators with the semiclassical propagator of Herman and Kluk. This does not involve further approximations and can be used with any initial value representation (IVR) semiclassical propagator. Time propagation in asymptotic regions of the potential due to Mo\ller operators reduces the oscillations of the propagator integrand and improves convergence of the results with respect to the number of trajectories. The effectiveness …

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Self-Assembly Of A Bis-Urea Macrocycle Into A Columnar Nanotube, Linda S. Shimizu, Mark D. Smith, A. D. Hughes, Ken D. Shimizu Jan 2001

Self-Assembly Of A Bis-Urea Macrocycle Into A Columnar Nanotube, Linda S. Shimizu, Mark D. Smith, A. D. Hughes, Ken D. Shimizu

Faculty Publications

A bis-urea macrocycle 1 was synthesized and shown to form extended nanotubular columns byX-ray crystallography.

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Structure Determination Of Ba8Corh6O21, A New Member Of The 2h-Perovskite Related Oxides, Hans Conrad Zur Loye, M. D. Smith, K. E. Stitzer, A. El Abed, J. Darriet Jan 2001

Structure Determination Of Ba8Corh6O21, A New Member Of The 2h-Perovskite Related Oxides, Hans Conrad Zur Loye, M. D. Smith, K. E. Stitzer, A. El Abed, J. Darriet

Faculty Publications

Single crystals of Ba8CoRh6O21 were grown out of a potassium carbonate flux. The structure was solved by a general method using the superspace group approach. The superspace group employed was R3m(00γ)0s with a = 10.0431(1) Å, c1 = 2.5946(1) Å and c2 = 4.5405(1) Å, V = 226.60(1) Å3. Ba8CoRh6O21 represents the first example of an m = 5, n = 3 member of the A3n+3mA'nB3m+nO9m+6n family of 2H hexagonal perovskite related oxides and contains chains consisting of six …

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Simplified Calculation Of The Stability Matrix For Semiclassical Propagation, Sophya Garashchuk, John C. Light Dec 2000

Simplified Calculation Of The Stability Matrix For Semiclassical Propagation, Sophya Garashchuk, John C. Light

Faculty Publications

We present a simple method of calculation of the stability (monodromy) matrix that enters the widely used semiclassical propagator of Herman and Kluk and almost all other semiclassical propagators. The method is based on the unitarity of classical propagation and does not involve any approximations. The number of auxiliary differential equations per trajectory scales linearly rather than quadratically with the system size. Just the first derivatives of the potential surface are needed. The method is illustrated on the collinear H[sub 3] system.

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Conductivity Of Irradiated Pure Water, Jerry Goodisman, Rick Blades Sep 2000

Conductivity Of Irradiated Pure Water, Jerry Goodisman, Rick Blades

Chemistry - All Scholarship

The conductivity of water having parts per billion concentrations of oxygen, hydrogen, and bicarbonate was measured while the water was irradiated by a low-pressure mercury vapor lamp, which was turned on and off periodically. A cell normally used for measurement of dissolved oxidizable carbon was modified for use in these measurements. When the lamp is turned on, the conductivity increases (sometimes decreases) with a time constant of about 50 ms; when the lamp is turned off, the conductivity changes in the opposite direction with a time constant of about 275 ms, but does not return to its value before the …

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Effect Of Collagen Turnover On The Accumulation Of Advanced Glycation End Products, Nicole Verzijl, Jeroen Degroot, Suzanne R. Thorpe, Ruud A. Bank, J. Nikki Shaw, Timothy J. Lyons, Johannes Wj Bijlsma, Floris Pjg Lafeber, John W. Baynes, Johan M. Tekoppele Sep 2000

Effect Of Collagen Turnover On The Accumulation Of Advanced Glycation End Products, Nicole Verzijl, Jeroen Degroot, Suzanne R. Thorpe, Ruud A. Bank, J. Nikki Shaw, Timothy J. Lyons, Johannes Wj Bijlsma, Floris Pjg Lafeber, John W. Baynes, Johan M. Tekoppele

Faculty Publications

Collagen molecules in articular cartilage have an exceptionally long lifetime, which makes them susceptible to the accumulation of advanced glycation end products (AGEs). In fact, in comparison to other collagen-rich tissues, articular cartilage contains relatively high amounts of the AGE pentosidine. To test the hypothesis that this higher AGE accumulation is primarily the result of the slow turnover of cartilage collagen, AGE levels in cartilage and skin collagen were compared with the degree of racemization of aspartic acid (% D-Asp, a measure of the residence time of a protein). AGE (Ne- (carboxymethyl)lysine, Ne-(carboxyethyl)lysine, and pentosidine) and % D-Asp concentrations increased …

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Pyridoxamine, An Inhibitor Of Advanced Glycation Reactions, Also Inhibits Advanced Lipoxidation Reactions: Mechanism Of Action Of Pyridoxamine, Joelle M. Onorato, Alicia J. Jenkins, Suzanne R. Thorpe, John W. Baynes Jul 2000

Pyridoxamine, An Inhibitor Of Advanced Glycation Reactions, Also Inhibits Advanced Lipoxidation Reactions: Mechanism Of Action Of Pyridoxamine, Joelle M. Onorato, Alicia J. Jenkins, Suzanne R. Thorpe, John W. Baynes

Faculty Publications

Maillard or browning reactions lead to formation of advanced glycation end products (AGEs) on protein and contribute to the increase in chemical modification of proteins during aging and in diabetes. AGE inhibitors such as aminoguanidine and pyridoxamine (PM) have proven effective in animal model and clinical studies as inhibitors of AGE formation and development of diabetic complications. We report here that PM also inhibits the chemical modification of proteins during lipid peroxidation (lipoxidation) reactions in vitro, and we show that it traps reactive intermediates formed during lipid peroxidation. In reactions of arachidonate with the model protein RNase, PM prevented modification …

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Ac Susceptibility Of Sr3CuptXIr1-XO6: A Magnetic System With Competing Interactions And Dimensionality, S H. Irons, T D. Sangrey, K M. Beauchamp, M D. Smith, Hans Conrad Zur Loye May 2000

Ac Susceptibility Of Sr3CuptXIr1-XO6: A Magnetic System With Competing Interactions And Dimensionality, S H. Irons, T D. Sangrey, K M. Beauchamp, M D. Smith, Hans Conrad Zur Loye

Faculty Publications

Sr3CuPtxIr1-xO6 has been cited as an example of a one-dimensional quantum spin chain with competing ferromagnetic and antiferromagnetic interactions. We have measured the ac susceptibility of Sr3CuPtxIr1-xO6 with x=0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, and 0.7, in magnetic fields of 0–60 kOe, and at temperatures down to 0.275 K. Our data show that the x=endpoint Sr3CuIrO6, exhibits long-range ferromagnetic order at T=20.1 K, contrary to results from dc susceptibility studies which indicated that it remained a one-dimensional ferromagnet to below 4 …

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Fundamental Capillary Electrophoresis: An Evaluation Of Electrokinetic Sampling, Cindy Ann Mleziva Blake May 2000

Fundamental Capillary Electrophoresis: An Evaluation Of Electrokinetic Sampling, Cindy Ann Mleziva Blake

Seton Hall University Dissertations and Theses (ETDs)

Capillary electrophoresis has become a powerful separation technique in fields of biochemical separations, inorganic ions, and chiral separations. The technique has experienced exponential growth since the historic publication of Zone Electrophoresis in Open-Tubular Glass Capillaries by Lukacs and Jorgenson in 1981. However, the use of capillary electrophoresis as a primary research analysis tool still remains to be seen in many pharmaceutical laboratories. One of the main reasons for this is that it remains difficult to validate CE methods using the criteria of quantitation and accuracy posed by the current government regulating agencies, as developed for high performance liquid chromatography and …

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Synthesis Of The Fungicide Propiconazole A Systemic Foliar Fungicide., Hazel Delaney Mar 2000

Synthesis Of The Fungicide Propiconazole A Systemic Foliar Fungicide., Hazel Delaney

Masters

Propiconazole, 1-[[2-(2,4-dichlorophenyl)-4-propyl-1, 3-dioxol-2-yl[methyl]-1H-1,2,4-triazole, commercially know as “Tilt” is a systemic foliar fungicide for cereals and is widely used in agriculture. The aim of this project was to develop an economically feasible process for the production of propiconazole and to maximise the yields of the intermediates in the developed process. Processes investigated included the original Ciba-Geigy process. In addition an investigation into the synthesis and characterisation of the impurities formed, and reported to be formed in each step of the reaction process was carried out and seven of the reported impurities were synthesised. One impurity was shown not to be present …

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New Rare Cave Minerals From The Perolas-Santana Karst System (São Paulo State, Brazil), Paolo Forti, Ermanno Galli, Antonio Rossi Jan 2000

New Rare Cave Minerals From The Perolas-Santana Karst System (São Paulo State, Brazil), Paolo Forti, Ermanno Galli, Antonio Rossi

International Journal of Speleology

The Perolas-Santana karst system (São Paulo State, Brazil) has been partially studied from the mineralogical point of view. The present paper will contribute to the knowledge of the minerals in these caves, describing the occurrence of euhedral celestite crystals and of a rather rare mineral for a cavern environment: lithiophorite. Thanks to these new discoveries the Perolas-Santana karst system becomes one of the most important in Brazil from a mineralogical point of view. Finally, the result of the chemical analyses carried out on this newly discovered Monoxyhydroxide put in evidence a zonation in the distribution of the different elements which …

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Monomer-Dimer Equilibrium Constants Of Rna In The Dimer Initiation Site Of Human Immunodeficiency Virus Type 1, Michael F. Shubsda, Mark P. Mcpike, Jerry Goodisman, James C. Dabrowiak Mar 1999

Monomer-Dimer Equilibrium Constants Of Rna In The Dimer Initiation Site Of Human Immunodeficiency Virus Type 1, Michael F. Shubsda, Mark P. Mcpike, Jerry Goodisman, James C. Dabrowiak

Chemistry - All Scholarship

The genome of the human immunodeficiency virus (HIV) exists as a dimer of two identical RNA molecules hydrogen bonded to each other near their 5' ends. The dimer, known to be important for viral infectivity, is formed by two monomers interacting through a stem-loop structure called the dimer initiation site (DIS). An initially formed intermediate, the "kissing" dimer, is unstable and rearranges to the stable, duplex form. In this report we use nondenaturing polyacrylamide gel electrophoresis to measure the monomer-dimer equilibrium constant of three RNA sequences, 41-, 27-, and 19-mers, located in the DIS of the MAL isolate of HIV-1. …

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Clinopyroxene Compositions Of The Isotropic Gabbros From The Sarıkaraman Ophiolite: New Evidence On Supra-Subduction Zone Type Magma Genesis In Central Anatolia, Kenan M. Yaliniz, M. Cemal Göncüoğlu Jan 1999

Clinopyroxene Compositions Of The Isotropic Gabbros From The Sarıkaraman Ophiolite: New Evidence On Supra-Subduction Zone Type Magma Genesis In Central Anatolia, Kenan M. Yaliniz, M. Cemal Göncüoğlu

Turkish Journal of Earth Sciences

The Sarıkaraman Ophiolite is one of the least dismembered ophiolitic units of the allochthonous Central Anatolian Ophiolites, which retains its recognizable pseudostratigraphy. The Sarıkaraman Ophiolite is represented in its lowermost part by isotropic gabbros. Within the isotropic gabbro sequence, clinopyroxenes are observed as small, colorless relicts with a cloudy appearance. In most of the samples, they are completely replaced by a successive generation of green to brown amphiboles. Clinopyroxenes display diopsitic to augitic compositions within the range of En 45 Fs 5 Wo 49 to En 50 Fs 9 Wo 41 . They are Ca-rich and Na-poor (Na 2 O

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Investigation Of Peptide-Dna Interactions: Synthesis, Characterization And Applications Of Lysyl-Fluorophenylalaninamides, Teresita T. Ortega Dec 1998

Investigation Of Peptide-Dna Interactions: Synthesis, Characterization And Applications Of Lysyl-Fluorophenylalaninamides, Teresita T. Ortega

Seton Hall University Dissertations and Theses (ETDs)

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Correlation Function Formulation For The State Selected Total Reaction Probability, Sophya Garashchuk, David J. Tannor Aug 1998

Correlation Function Formulation For The State Selected Total Reaction Probability, Sophya Garashchuk, David J. Tannor

Faculty Publications

Investigates the correlation function formulation for the state selected total reaction probability. Discussion of the wave packet propagation; Derivation of the correlation function expression for the N[sub alpha](E); Application of quantum-mechanical and Herman-Kluk propagation methods.

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Role Of The Maillard Reaction In Aging Of Tissue Proteins: Advanced Glycation End Product-Dependent Increase In Imidazolium Cross-Links In Human Lens Proteins, Elisabeth Brinkmann Frye, Thorsten P. Degenhardt, Suzanne R. Thorpe, John W. Baynes Jul 1998

Role Of The Maillard Reaction In Aging Of Tissue Proteins: Advanced Glycation End Product-Dependent Increase In Imidazolium Cross-Links In Human Lens Proteins, Elisabeth Brinkmann Frye, Thorsten P. Degenhardt, Suzanne R. Thorpe, John W. Baynes

Faculty Publications

Dicarbonyl compounds such as glyoxal and methylglyoxal are reactive dicarbonyl intermediates in the nonenzymatic browning and cross-linking of proteins during the Maillard reaction. We describe here the quantification of glyoxal and methylglyoxal-derived imidazolium cross-links in tissue proteins. The imidazolium salt cross-links, glyoxal-lysine dimer (GOLD) and methylglyoxal-lysine dimer (MOLD), were measured by liquid chromatography/mass spectrometry and were present in lens protein at concentrations of 0. 02-0.2 and 0.1-0.8 mmol/mol of lysine, respectively. The lens concentrations of GOLD and MOLD correlated significantly with one another and also increased with lens age. GOLD and MOLD were present at significantly higher concentrations than the …

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Quadratic Electro-Optic Effects In Bacteriorhodopsin: Measurement Of Γ(-Ω;0,0,Ω) In Dried Gelatin Thin Films, Mikio Yamazaki, Jerry Goodisman, Robert R. Birge Apr 1998

Quadratic Electro-Optic Effects In Bacteriorhodopsin: Measurement Of Γ(-Ω;0,0,Ω) In Dried Gelatin Thin Films, Mikio Yamazaki, Jerry Goodisman, Robert R. Birge

Chemistry - All Scholarship

Quadratic electro-optic effects (dc or low frequency Kerr effect) of bacteriorhodopsin dispersed in dried gelatin thin films are examined in the near resonance region at three wavelengths: 633, 647, and 676 nm. The films show relatively large quadratic electro-optic effects compared to other molecular dispersed systems. The purple membrane is fixed within the polymerized gelatin matrix, and we show that the electronic contribution to γ dominates over possible orientational contributions. At 676 nm. the quadratic electro-optic coefficient s1133( - ω;0,0,ω) is 6.7 × 10-20 m2/V2 and the third order nonlinear susceptibility X1133(3) …

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Age-Dependent Increase In Ortho-Tyrosine And Methionine Sulfoxide In Human Skin Collagen Is Not Accelerated In Diabetes: Evidence Against A Generalized Increase In Oxidative Stress In Diabetes, Mary C. Wells-Knecht, Timothy J. Lyons, David R. Mccance, Suzanne R. Thorpe, John W. Baynes Aug 1997

Age-Dependent Increase In Ortho-Tyrosine And Methionine Sulfoxide In Human Skin Collagen Is Not Accelerated In Diabetes: Evidence Against A Generalized Increase In Oxidative Stress In Diabetes, Mary C. Wells-Knecht, Timothy J. Lyons, David R. Mccance, Suzanne R. Thorpe, John W. Baynes

Faculty Publications

The glycoxidation products Nepsilon-(carboxymethyl)lysine and pentosidine increase in skin collagen with age and at an accelerated rate in diabetes. Their age-adjusted concentrations in skin collagen are correlated with the severity of diabetic complications. To determine the relative roles of increased glycation and/or oxidation in the accelerated formation of glycoxidation products in diabetes, we measured levels of amino acid oxidation products, distinct from glycoxidative modifications of amino acids, as independent indicators of oxidative stress and damage to collagen in aging and diabetes. We show that ortho-tyrosine and methionine sulfoxide are formed in concert with Nepsilon-(carboxymethyl)lysine and pentosidine during glycoxidation of collagen …

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Carboxymethylethanolamine, A Biomarker Of Phospholipid Modification During The Maillard Reaction In Vivo, Jesus R. Requena, Mahtab U. Ahmed, C. Wesley Fountain, Thorsten P. Degenhardt, Sharanya Reddy, Cliff Perez, Timothy J. Lyons, Alicia J. Jenkins, John W. Baynes, Suzanne R. Thorpe May 1997

Carboxymethylethanolamine, A Biomarker Of Phospholipid Modification During The Maillard Reaction In Vivo, Jesus R. Requena, Mahtab U. Ahmed, C. Wesley Fountain, Thorsten P. Degenhardt, Sharanya Reddy, Cliff Perez, Timothy J. Lyons, Alicia J. Jenkins, John W. Baynes, Suzanne R. Thorpe

Faculty Publications

Nepsilon-(Carboxymethyl)lysine (CML) is a stable chemical modification of proteins formed from both carbohydrates and lipids during autoxidation reactions. We hypothesized that carboxymethyl lipids such as (carboxymethyl)phosphatidylethanolamine (carboxymethyl-PE) would also be formed in these reactions, and we therefore developed a gas chromatography-mass spectrometry assay for quantification of carboxymethylethanolamine (CME) following hydrolysis of phospholipids. In vitro, CME was formed during glycation of dioleoyl-PE under air and from linoleoylpalmitoyl-PE, but not from dioleoyl-PE, in the absence of glucose. In vivo, CME was detected in lipid extracts of red blood cell membranes, approximately 0.14 mmol of CME/mol of ethanolamine, from control and diabetic subjects, …

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Quantitation Of Ethidium-Stained Closed Circular Dna In Agarose Gels, Michael F. Shubsda, Jerry Goodisman, James C. Dabrowiak Feb 1997

Quantitation Of Ethidium-Stained Closed Circular Dna In Agarose Gels, Michael F. Shubsda, Jerry Goodisman, James C. Dabrowiak

Chemistry - All Scholarship

The fluorescence of ethidium bromide (EB) bound to equimolar amounts of supercoiled form I and unstrained linear form III pBR322, SV40 and PM2 DNA in agarose gels has been measured by scanning a photographic negative of the gel with a microdensitometer. For SV40 and PM2 DNA, commonly used staining conditions cause both forms, i.e. linear and supercoiled, to fluoresce to the same extent. This obviates the need to use a correction factor for the fluorescence of form I DNA when measuring the amount of this form relative to the amounts of unstrained forms in agarose gels. In the case of …

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Kinetics Of Cleavage Of Intra- And Extracellular Simian Virus 40 Dna With The Enediyne Anticancer Drug C- 1027, Jerry Goodisman, James C. Dabrowiak, Christopher A. Kirk, Terry A. Beerman, Loretta S. Gawron Jan 1997

Kinetics Of Cleavage Of Intra- And Extracellular Simian Virus 40 Dna With The Enediyne Anticancer Drug C- 1027, Jerry Goodisman, James C. Dabrowiak, Christopher A. Kirk, Terry A. Beerman, Loretta S. Gawron

Chemistry - All Scholarship

A kinetic analysis of cleavage of simian virus DNA (SV40 DNA) inside and outside green monkey BSC-I cells by the enediyne-protein antibiotic C-1027 and its free chromophore is described. Information on rate constants was obtained by fitting populations of forms I (closed circular DNA), II (nicked circular DNA) and III (linear DNA) of SV4f.J DNA as a function of drug concentration to a kinetic model which includes: cutting of form I to give form II with rate constant k1. cutting of form I to give form III with rate constant k4, and cutting of form II to give form III …

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The Resolution Of Chiral Dialkylarylsufonium Ions By 1h Nmr Spectroscopy, Johnathan Whetstine Jan 1997

The Resolution Of Chiral Dialkylarylsufonium Ions By 1h Nmr Spectroscopy, Johnathan Whetstine

Mahurin Honors College Capstone Experience/Thesis Projects

The goal of this research was to design a rapid Nuclear Magnetic Resonance method to measure enantiomeric excess of chiral sulfonium ions by using chiral lanthanide shift reagents. The sulfonium ions studied were dialkylarylsulfonium ions. The shift reagent that was employed was Europium (III) surrounded by chiral ligands of 3-trifluoroacetyl-d-camphor (tfc), which is derived from (+)-camphor. Ethylmcthylphenylsulfonium ion was synthesized for study as a racemic and enantiomerically enriched mixture. The sulfonium ion was then ion-paired with the shift reagent for resolution of R and S enantiomers. The best resolution was obtained with the Eu(fod)4- shift reagent, with nearly baseline resolution …

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Solvent Impregnated Resins For The Recovery Of Gold From Gold(I)Thiourea Solutions, Fiona Fitzpatrick Jan 1997

Solvent Impregnated Resins For The Recovery Of Gold From Gold(I)Thiourea Solutions, Fiona Fitzpatrick

Masters

Solvent Impregnated Resins (SIRs) are high surface area, macroporous, polymeric resins which have been physically impregnated with an organic solvent. In this research, three resins have been impregnated with Di-2-ethylhexyl phosphoric acid, a solvent which has shown selectivity to gold. The ability of the resins to recover gold (1) thiourea perchlorate from solution has been investigated. The resins have been studied both bare and when impregnated with the solvent and their efficiency was seen to increase upon impregnation. The overall efficiency of the resins was found to be pH dependent. It is also related to the level of impregnation of …

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Efficient And General Synthesis Of Novel Β-Polyfluoroalkoxy Vinamidinium Salts, Koichiro Kase, Mitsuyoshi Katayama, Takashi Ishihara, Hiroki Yamanaka, John T. Gupton Jan 1997

Efficient And General Synthesis Of Novel Β-Polyfluoroalkoxy Vinamidinium Salts, Koichiro Kase, Mitsuyoshi Katayama, Takashi Ishihara, Hiroki Yamanaka, John T. Gupton

Chemistry Faculty Publications

Novel β-polyfluoroalkoxy vinamidinium salts 3 and/or 4 were synthesized in good yields by the reaction of N-(2- polyfluoroalkoxy-3 ,3-difluoro-1-propenyI)trimethylammonium iodides (2), prepared from N-(2,3,3-trifluoro-1-propenyl)trimethylammonium iodide (1), with secondary amines in MeCN at 70 °C for 1 h. The salts were also obtainable in comparable yields by the one-pot reaction of 1 with sodium polyfluoroalkoxide followed by treatment with amines.

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Cleavage Of Dna By The Insulin-Mimetic Compound, Nh4[Vo(O2)2(Phen)], Catharina Hiort, Jerry Goodisman, James C. Dabrowiak Jun 1996

Cleavage Of Dna By The Insulin-Mimetic Compound, Nh4[Vo(O2)2(Phen)], Catharina Hiort, Jerry Goodisman, James C. Dabrowiak

Chemistry - All Scholarship

The kinetics and mechanism of cleavage of DNA by the insulin-mimetic peroxo-vanadate NH4[VO(O2)2(phen)], pV, are described. In the presence of low energy UV radiation or biologically common reducing agents, pV decomposes into the monomer, dimer, and tetramer of vanadate and an uncharacterized compound of V4+ as shown by 51V NMR, ESR, and absorption spectra. The rate of photodecomposition of pV is reduced in the presence of calf thymus DNA, indicating that a decomposition product of the peroxo-vanadate, that is important in the destruction pathway of the complex, is interacting with DNA. This species, probably a short-lived complex of V4+, may …

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The Advanced Glycation End Product, NE-(Carboxymethyl)Lysine, Is A Product Of Both Lipid Peroxidation And Glycoxidation Reactions, Min-Xin Fu, Jesus R. Requena, Alicia J. Jenkins, Timothy J. Lyons, John W. Baynes, Suzanne R. Thorpe Apr 1996

The Advanced Glycation End Product, NE-(Carboxymethyl)Lysine, Is A Product Of Both Lipid Peroxidation And Glycoxidation Reactions, Min-Xin Fu, Jesus R. Requena, Alicia J. Jenkins, Timothy J. Lyons, John W. Baynes, Suzanne R. Thorpe

Faculty Publications

Nepsilon-(Carboxymethyl)lysine (CML) is an advanced glycation end product formed on protein by combined nonenzymatic glycation and oxidation (glycoxidation) reactions. We now report that CML is also formed during metal-catalyzed oxidation of polyunsaturated fatty acids in the presence of protein. During copper-catalyzed oxidation in vitro, the CML content of low density lipoprotein increased in concert with conjugated dienes but was independent of the presence of the Amadori compound, fructoselysine, on the protein. CML was also formed in a time-dependent manner in RNase incubated under aerobic conditions in phosphate buffer containing arachidonate or linoleate; only trace amounts of CML were formed from …

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Interaction Of Cationic Porphyrins With Dna, Ulrica Sehlstedt, Pamela Carter, Jerry Goodisman, James C. Dabrowiak, Seog K. Kim Oct 1993

Interaction Of Cationic Porphyrins With Dna, Ulrica Sehlstedt, Pamela Carter, Jerry Goodisman, James C. Dabrowiak, Seog K. Kim

Chemistry - All Scholarship

Utilizing linear dichroism (LD), circular dichroism (CD), and fluorescence energy transfer, the binding geometries of a series of Co3+-porphyrins and their free ligands were examined. The compounds studied were Co-meso-tetrakis(N-methylpyridinium-4-yl)porphyi(nC oTMPyP) and its free ligand (H2- TMPyP), Co-meso-tetrakis(N-n-butylpyridinium-4-yl)porphyrin( CoTBPyP) and its free ligand (H2TBPyP), and Co-meso-tetrakis(N-n-octylpyridinium-4-yl)porphyrin (CoTOPyP). The two non-metalloporphyrins exhibit negative LD, having angles of roughly 75' relative to the DNA helix axis. They also display negative CD and a significant contact energy transfer from the DNA bases. On the other hand, the three metalloporphyrins display orientation angles of roughly 45' between the porphyrin plane and the helix axis …

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Formation Of O-Tyrosine And Dityrosine In Proteins During Radiolytic And Metal-Catalyzed Oxidation, Thomas G. Huggins, Mary C. Wells-Knecht, Nicholas A. Detorie, John W. Baynes, Suzanna R. Thorpe Jun 1993

Formation Of O-Tyrosine And Dityrosine In Proteins During Radiolytic And Metal-Catalyzed Oxidation, Thomas G. Huggins, Mary C. Wells-Knecht, Nicholas A. Detorie, John W. Baynes, Suzanna R. Thorpe

Faculty Publications

To evaluate their usefulness as chemical indicators of cumulative oxidative damage to proteins, we studied the kinetics and extent of formation of ortho-tyrosine (0-Tyr), dityrosine (DT), and dityrosine-like fluorescence (Ex = 3 17 nm, E,,, = 407 nm) in the model proteins RNase and lysozyme exposed to radiolytic and metalcatalyzed (H20z/Cu2+) oxidation (MCO). Although there were protein-dependent differences, o-Tyr, DT, and fluorescence increased coordinately during oxidation of the proteins in both oxidation systems. The contribution of DT to total dityrosine-like fluorescence in oxidized proteins varied from 2-10070, depending on the protein, type of oxidation, and extent of oxidative damage. In …

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Oxidized Amino Acids In Lens Protein With Age: Measurement Of O-Tyrosine And Dityrosine In The Aging Human Lens, Mary C. Wells-Knect, Thomas G. Huggins, Daniel G. Dyer, Suzanne R. Thorpe, John W. Baynes Jun 1993

Oxidized Amino Acids In Lens Protein With Age: Measurement Of O-Tyrosine And Dityrosine In The Aging Human Lens, Mary C. Wells-Knect, Thomas G. Huggins, Daniel G. Dyer, Suzanne R. Thorpe, John W. Baynes

Faculty Publications

The concentrations of ortho-tyrosine (o-Tyr) and dityrosine (DT) were measured in noncataractous human lenses in order to assess the role of proteinoxidation reactions in the aging of lens proteins. The measurements were conducted by selected ion monitoring-gas chromatography/mass spectrometry using deuterium-labeled internal standards, which provided both high sensitivity and specificity for the quantitation of o-Tyr and DT. Between ages 1 and 78 years, the o-Tyr concentration in lens proteins varied from 0.3 to 0.9 mmol of o-Tyr/mol of Phe (n = 19), while DT ranged from 1 to 3 mumol of DT/mol of Tyr (n = 30). There were no …

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Accumulation Of Maillard Reaction Products In Skin Collagen In Diabetes And Aging, Daniel G. Dyer, John A. Dunn, Suzanne R. Thorpe, Karen E. Bailie, Timothy L. Lyons, David R. Mccance, John W. Baynes Jun 1993

Accumulation Of Maillard Reaction Products In Skin Collagen In Diabetes And Aging, Daniel G. Dyer, John A. Dunn, Suzanne R. Thorpe, Karen E. Bailie, Timothy L. Lyons, David R. Mccance, John W. Baynes

Faculty Publications

To investigate the contribution of glycation and oxidation reactions to the modification of insoluble collagen in aging and diabetes, Maillard reaction products were measured in skin collagen from 39 type 1 diabetic patients and 52 nondiabetic control subjects. Compounds studied included fructoselysine (FL), the initial glycation product, and the glycoxidation products, N epsilon-(carboxymethyl) lysine (CML) and pentosidine, formed during later Maillard reactions. Collagen-linked fluorescence was also studied. In nondiabetic subjects, glycation of collagen (FL content) increased only 33% between 20 and 85 yr of age. In contrast, CML, pentosidine and fluorescence increased five-fold, correlating strongly with age. In diabetic patients, …

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