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Full-Text Articles in Physical Sciences and Mathematics

Synthesis And Characterization Of A Water-Soluble Metallopeptide That Resembles A Parallel Beta-Pleated Sheet, Michael Y. Ogawa, Alexei B. Gretchikhine, Sunil-Datta Soni, Steven M. Davis Dec 1995

Synthesis And Characterization Of A Water-Soluble Metallopeptide That Resembles A Parallel Beta-Pleated Sheet, Michael Y. Ogawa, Alexei B. Gretchikhine, Sunil-Datta Soni, Steven M. Davis

Chemistry Faculty Publications

The title metallopeptide consists of two divalinyl peptides attached to the carboxylate groups of the ruthenium polypyridyl complex. [Ru(bpy)(2)L](2+): bpy = 2,2'-bipyridine; L = 3,5-dicarboxy-2,2'-bipyridine. The charged ruthenium complex is water soluble and is shown by variable temperature, and 2-D NMR to consist a parallel arrangement of interacting, extended peptide strands that ir reminiscent of the beta-sheet structure. Circular dichroism results support this assignment.


Relative Stabilities Of Dna 3-Way, 4-Way And 5-Way Junctions (Multi-Helix Junction Loops) - Unpaired Nucleotides Can Be Stabilizing Or Destabilizing, Neocles B. Leontis, Julie L. Kardmas, Amy J. Ravin Jun 1995

Relative Stabilities Of Dna 3-Way, 4-Way And 5-Way Junctions (Multi-Helix Junction Loops) - Unpaired Nucleotides Can Be Stabilizing Or Destabilizing, Neocles B. Leontis, Julie L. Kardmas, Amy J. Ravin

Chemistry Faculty Publications

Competition binding and UV melting studies of a DNA model system consisting of three, four or five mutually complementary oligonucleotides demonstrate that unpaired bases at the branch point stabilize three- and five-way junction loops but destabilize four-way junctions. The inclusion of unpaired nucleotides permits the assembly of five-way DNA junction complexes (5WJ) having as few as seven basepairs per arm from five mutually complementary oligonucleotides. Previous work showed that 5WJ, having eight basepairs per arm but lacking unpaired bases, could not be assembled I[Wang,Y.L., Mueller,J.E., Kemper,B. and Seeman,N.C. (1991) Biochemistry, 30, 5667-5674]. Competition binding experiments demonstrate that four-way junctions (4WJ) …


Acid-Base Chemical Mechanism Of Aspartase From Hafnia Alvei, Moon Young Yoon, Kim A. Thayer-Cook, Anthony J. Berdis, William E. Karsten, Klaus D. Schnackerz, Paul F. Cook Jun 1995

Acid-Base Chemical Mechanism Of Aspartase From Hafnia Alvei, Moon Young Yoon, Kim A. Thayer-Cook, Anthony J. Berdis, William E. Karsten, Klaus D. Schnackerz, Paul F. Cook

Chemistry Faculty Publications

An acid-base chemical mechanism is proposed for Hafnia alvei aspartase in which a proton is abstracted from C-3 of the monoanionic form of L-aspartate by an enzyme general base with a pK of 6.3-6.6 in the absence and presence of Mg2+. The resulting carbanion is presumably stabilized by delocalization of electrons into the β-carboxyl with the assistance of a protonated enzyme group in the vicinity of the β-carboxyl. Ammonia is then expelled with the assistance of a general acid group that traps an initially expelled NH3 as the final NH+4 product. In agreement with the function of the general acid …


Electrochemical Carbonylation Of Organoiron Methyl Complex: A Study Of Reaction Intermediates, C. Amatore, Mekki Bayachou, J. N. Verpeaux, L. Pospisil, J. Fiedler May 1995

Electrochemical Carbonylation Of Organoiron Methyl Complex: A Study Of Reaction Intermediates, C. Amatore, Mekki Bayachou, J. N. Verpeaux, L. Pospisil, J. Fiedler

Chemistry Faculty Publications

The one-electron reduction of CpFe(CO)2CH3 has been investigated by voltammetry and Fourier transform IR spectroelectrochemistry. The reduction initiates the insertion of CO ligand in the FeCH3 bond. The dissociation of a CO group proceeds in a parallel reaction. Reaction intermediates, the acyl derivative and released CO, form the radical anion of a complex CpFe(CO)2(COCH3) which is able to reduce the parent compound. The reversible redox potential − 1.8 V of CpFe(CO)2(COCH3) allows the regeneration of its radical anion which drives a catalytic cycle. The lifetime of intermediates is shortened by side reactions, one of which is the migration of the …


Helical Stacking In Dna 3-Way Junctions Containing 2 Unpaired Pyrimidines - Proton Nmr-Studies, Neocles B. Leontis, Michael T. Hills, Martial Piotto, Igor V. Ouporov, Arun Malhotra, David G. Gorenstein Jan 1995

Helical Stacking In Dna 3-Way Junctions Containing 2 Unpaired Pyrimidines - Proton Nmr-Studies, Neocles B. Leontis, Michael T. Hills, Martial Piotto, Igor V. Ouporov, Arun Malhotra, David G. Gorenstein

Chemistry Faculty Publications

The proton NMR spectra of DNA three-way junction complexes (TWJ) having unpaired pyrimidines, 5'-TT- and 5'-TC- on one strand at the junction site were assigned from 2D NOESY spectra acquired in H2O and D2O solvents and homonuclear 3D NOESY-TOCSY and 3D NOESY-NOESY in D2O solvent. TWJ are the simplest branched structures found in biologically active nucleic acids. Unpaired nucleotides are common features of such structures and have been shown to stabilize junction formation. The NMR data confirm that the component oligonucleotides assemble to form conformationally homogeneous TWJ complexes having three double-helical, B-form arms. Two of the helical arms stack upon …


Refinement Of The Solution Structure Of A Branched Dna Three-Way Junction, Neocles B. Leontis, Igor V. Ouporov Jan 1995

Refinement Of The Solution Structure Of A Branched Dna Three-Way Junction, Neocles B. Leontis, Igor V. Ouporov

Chemistry Faculty Publications

We have refined the structure of the DNA Three-Way Junction complex, TWJ- TC, described in the companion paper by quantitative analysis of two 2D NOESY spectra (mixing times 60 and 200 ms) obtained in D2O solution. NOESY crosspeak intensities extracted from these spectra were used in two kinds of refinement procedure: 1) distance-restrained energy minimization (EM) and molecular dynamics (MD) and 2) full relaxation matrix back calculation refinement. The global geometry of the refined model is very similar to that of a published, preliminary model (Leontis, 1993). Two of the helical arms of the junction are stacked. These are Helix …


Cs2ga2o(Bo3)2, Robert W. Smith Jan 1995

Cs2ga2o(Bo3)2, Robert W. Smith

Chemistry Faculty Publications

The structure of dicaesium digallium diorthoborate oxide constitutes a new type of oxide borate. It consists of a three-dimensional gallium-oxide-orthoborate lattice with Cs atoms occupying large cavities in the lattice. This lattice is made from pairs of Ga atoms connected through a shared O atom along the [001] direction; these Ga dimers are interconnected through shared O vertices to trigonal BO3 groups along the [010], [110] and [i10] directions, completing the tetrahedral coordination environment of each Ga atom.