Search results for "conformation"
showing 10 items of 1414 documents
A cocrystal of two Mo(VI) complexes bearing different diastereomers of the 2,4-di-tert-butyl-6-{[(1-oxido-1-phenylpropan-2-yl)(methyl)amino]methyl}ph…
2013
The title cocrystal contains two chiral conformational diastereomers,viz.(1S,2R,RN)- and (1S,2R,SN)-, of [2,4-di-tert-butyl-6-{[(1-oxido-1-phenylpropan-2-yl)(methyl)amino]methyl}phenolato](methanol)-cis-dioxidomolybdenum(VI), [Mo(C25H35NO2)O2(CH3OH)], representing the first example of a structurally characterized molybdenum complex with enantiomerically pure ephedrine derivative ligands. The MoVIcations exhibit differently distorted octahedral coordination environments, with two oxide ligands positionedcisto each other. The remainder of the coordination comprises phenoxide, alkoxide and methanol O atoms, with an amine N atom completing the octahedron. The distinct complexes are linked by st…
Novel Biocompatible Cationic Copolymers Based on Polyaspartylhydrazide Being Potent as Gene Vector on Tumor Cells
2007
Introduction. The reaction between !,"-poly(aspartylhydrazide) (PAHy), a water soluble synthetic polymer and 3-(carboxypropyl)trimethyl-ammonium chloride (CPTACl) produced copolymers bearing permanent positive charges (PAHy–CPTA) with molecular weight of 10 kDa and PAHy–CPTA copolymers differing in positive charge amount (18–58%) were chosen for biological investigations. Materials and methods. Biophysical properties of DNA/PAHy–CPTA polyplexes were evaluated in terms of DNA condensation, zeta potential and size distribution. Cytotoxicity studies on Neuro2A murine neuroblastoma cells evidenced absence of toxicity of these copolymers up to 300 2g/ml unlike linear polyethylenimine (LPEI) that…
Hemoglobin dynamics in rat erythrocytes investigated by M�ssbauer spectroscopy
1991
Rats have been enriched in 57Fe and erythrocytes were isolated from the blood. Mössbauer absorption spectroscopy on the hemoglobin of these erythrocytes has shown rather similar dynamics as found earlier in crystals of myoglobin, in frozen solutions of human hemoglobin and in a number of other proteins. The results strongly indicate that the motion of the heme and presumably some part of the F-helix is mainly influenced by the average viscosity of the sample determined by a network of hydrogen bridges and other weak interactions. Extrapolations of Mössbauer results from protein crystals to proteins in their physiological surroundings seem to be suitable for heme proteins.
Expression of Active Streptolysin O in Escherichia coli as a Maltose-Binding-Protein-Streptolysin-O Fusion Protein. The N-Terminal 70 Amino Acids are…
1996
Streptolysin 0 (SLO) is the prototype of a family of cytolysins that consists of proteins which bind to cholesterol and form very large transmembrane pores. Structure/function studies on the pore-forming cytolysin SLO have been complicated by the proteolytic inactivation of a substantial portion of recombinant SLO (rSLO) expressed in Escherichia coli. To overcome this problem, translational fusions between the E. coli maltose-binding protein (MBP) gene and SLO were constructed, using the vectors pMAL-p2 and pMAL-c2. MBP-SLO fusion proteins were degraded if secreted into the E. coli periplasm, but intact, soluble MBP-SLO fusion proteins were produced at high levels in the cytoplasm. Active S…
Conformational polymorphs of 1,1,2,2-tetrachloroethane: pressure vs. temperature.
2011
Directional Cl···Cl type I and II interactions govern the low-density aggregation of 1,1,2,2-tetrachloroethane molecules in synclinal conformation in the crystalline state at low temperature, whereas the dense molecular packing in high-pressure is achieved for the antiperiplanar conformers and electrostatically less favored Cl···Cl contacts. The mechanism of transformation between loose and dense associations involves the collapse of Cl···Cl contacts and conformational conversion.
Diastereo- and enantioselective synthesis of orthogonally protected 2,4-diaminocyclopentanecarboxylates: a flip from beta-amino- to beta,gamma-diamin…
2007
Conformationally restricted, orthogonally protected 2,4-diaminocarboxylates with a cyclopentane skeleton were efficiently synthesized from beta-lactam 6, the syntheses involving strategies of diastereoselective epoxidation of the beta-lactam and the corresponding monoprotected amino esters with opposite selectivities followed by regioselective opening of the oxirane ring with sodium azide. The enantiomers were also prepared. This new class of compounds can be regarded not only as conformationally constrained beta,gamma-diamino acid derivatives but also as potential functionalized carbocyclic nucleoside precursors.
Reactions at Interfaces: Oxygenation of n-Butyl Ligands Anchored on Silica Surfaces with Methyl(trifluoromethyl)dioxirane
2011
The oxygenation of n-butyl and n-butoxy chains bonded to silica with methyl(trifluoromethyl)dioxirane (1) revealed the ability of the silica matrix to release electron density toward the reacting C(2)-H σ-bond through the Si-C(1) and Si-O(1) σ-bonds connecting the alkyl chain to the surface (silicon β-effect). The silica surface impedes neither the alkyl chain adopting the conformation required for the silicon β-effect nor dioxirane 1 approaching the reactive C(2) methylene group. Reaction regioselectivity is insensitive to changes in the solvation of the reacting system, the location of organic ligands on the silica surface, and the H-bonding character of the silica surface. Reaction rates…
First principles investigations of Pd-on-Au nanostructures for trichloroethene catalytic removal from groundwater
2010
Catalytic groundwater remediation from chlorinated organic solvents like trichloroethene (TCE) has been found to be more effective and sustainable than traditional non-destructive methods. Among the experimentally studied catalyst materials, Pd-decorated Au nanoparticles show the highest activity and selectivity combined with the best resistance towards poisoning by chemicals present in groundwater. In this study the thermochemistry and adsorption geometries of TCE and its hydrodechlorination products are investigated via density functional theory calculations. Various model systems for Pd-supported Au nanoparticles are addressed. The adsorption of TCE is endothermic on bare Au(111), almost…
Analysis of Vibrational Circular Dichroism Spectra of Peptides
2020
Vibrational circular dichroism (VCD) is one of the major spectroscopic tools to study peptides. Nevertheless, a full understanding of what determines the signs and intensities of VCD bands of these compounds in the amide I and amide II spectral regions is still far from complete. In the present work, we study the origin of these VCD signals using the general coupled oscillator (GCO) analysis, a novel approach that has recently been developed. We apply this approach to the ForValNHMe model peptide in both α-helix and β-sheet configurations. We show that the intense VCD signals observed in the amide I and amide II spectral regions essentially have the same underlying mechanism, namely, the th…
Stereoelectronic Properties of N-acetyl-α,β-dehydroamino acid N′-methylamides
1998
α,β-Dehydroamino acids are useful peptide modifiers. However, their stereoelectronic properties still remain insufficiently recognized. Based on FTIR experiments in the range of νs(N-H), AI, AII and νs(Cα=Cβ) and ab initio calculations with B3LYP/6-31G*, we studied the solution conformational preferences and the amide electron density perturbation of Ac-ΔXaa-NHMe, where ΔXaa = ΔAla, (E)-ΔAbu, (Z)-ΔAbu, (Z)-ΔLeu, (Z)-ΔPhe and ΔVal. Each of these dehydroamides adopts a C5 structure, which in Ac-ΔAla-NHMe is fully extended and accompanied by the strong C5 hydrogen bond. Interaction with bond Cα=Cβ lessens the amidic resonance within the flanking amide groups. The N-terminal C=O bond is noticea…