Search results for "molecular conformation"
showing 10 items of 376 documents
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…
Estimation of formamide harmonic and anharmonic modes in the Kohn-Sham limit using the polarization consistent basis sets.
2010
Formamide harmonic and anharmonic frequencies of fundamental vibrations in the gas phase and in several solvents were successfully estimated in the B3LYP Kohn-Sham complete basis set limit (KS CBS). CBS results were obtained by extrapolating a power function (two-parameter formula) to the results calculated with polarization-consistent basis sets. Anharmonic corrections using the second order perturbation treatment (PT2) and hybrid B3LYP functional combined with polarization consistent pc-n (n = 0, 1, 2, 3, 4) and several Pople’s basis sets were analyzed for all fundamental formamide vibrational modes in the gas phase and solution. Solvent effects were modeled within a PCM method. The anhar…
Conformation resolved induced infrared activity: trans- and cis-formic acid isolated in solid molecular hydrogen
2011
We report combined experimental and theoretical studies of infrared absorptions induced in solid molecular hydrogen by different conformers of formic acid (HCOOH, FA). FTIR spectra recorded in the H(2) fundamental region (4120-4160 cm(-1)) reveal a number of relatively strong trans-FA induced Q-branch absorptions that are assigned by studying both FA-doped parahydrogen (pH(2)) and normal hydrogen (nH(2)) samples. The induced H(2) absorptions are also studied for HCOOD doped nH(2) crystals for both the trans and cis conformers that show resolvable differences. Samples containing90% of the higher energy cis-HCOOD conformer are produced by in situ IR pumping of the OD stretching overtone of tr…
The Important Role of the Nuclearity, Rigidity, and Solubility of Phosphane Ligands in the Biological Activity of Gold(I) Complexes
2018
A series of 4-ethynylaniline gold(I) complexes containing monophosphane (1,3,5-triaza-7-phosphaadamantane (pta; 2), 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane (3), and PR3 , with R=naphthyl (4), phenyl (5), and ethyl (6)) and diphosphane (bis(diphenylphosphino)acetylene (dppa; 7), trans-1,2-bis(diphenylphosphino)ethene (dppet; 8), 1,2-bis(diphenylphosphino)ethane (dppe; 9), and 1,3-bis(diphenylphosphino)propane (dppp; 10)) ligands have been synthesized and their efficiency against tumor cells evaluated. The cytotoxicity of complexes 2-10 was evaluated in human colorectal (HCT116) and ovarian (A2780) carcinoma as well as in normal human fibroblasts. All the complexes showed a hi…
Formation and transformation of carbon nanoparticles under electron irradiation.
2004
This article reviews the phenomena occurring during irradiation of graphitic nanoparticles with high–energy electrons. A brief introduction to the physics of the interaction between energetic electrons and solids is given with particular emphasis on graphitic materials. Irradiation effects are discussed, starting from microscopic mechanisms that lead to structural alterations of the graphite lattice. It is shown how random displacements of the atoms and their subsequent rearrangements eventually lead to topological changes of the nanoparticles. Examples are the formation of carbon onions, morphological changes of carbon nanotubes, or the coalescence of fullerenes or nanotubes under electron…
Computing Metal-Binding Proteins for Therapeutic Benefit
2021
Over one third of biomolecules rely on metal ions to exert their cellular functions. Metal ions can play a structural role by stabilizing the structure of biomolecules, a functional role by promoting a wide variety of biochemical reactions, and a regulatory role by acting as messengers upon binding to proteins regulating cellular metal-homeostasis. These diverse roles in biology ascribe critical implications to metal-binding proteins in the onset of many diseases. Hence, it is of utmost importance to exhaustively unlock the different mechanistic facets of metal-binding proteins and to harness this knowledge to rationally devise novel therapeutic strategies to prevent or cure pathological st…
Hybrid Organic-Inorganic Nanostructures Fabricated from Layer-by-Layer Self-Assembled Multilayers of Hyperbranched Polyglycerols and Phosphorus Dendr…
2007
Multilayer thin films of cationic phosphorous dendrimers and anionic hyperbranched polyglycerols were fabricated by electrostatic layer-by-layer (LbL) self-assembly (SA). The film formation was monitored by surface plasmon resonance (SPR) spectroscopy and UV-visible spectroscopy, and it was found that the stepwise, alternating deposition results in a linear growth up to four bilayers. Hybrid organic-TiO2 nanostructures were generated by exposing the supramolecular multilayers to TiCl4 precursors. The amounts of TiO2 incorporated inside the scaffolds could be tuned by controlling the porosity of the multilayers with the addition of a small amount of salts. The resulting hybrid films exhibit …