Author(s): Heidi M Muchall

Nitrilimines (R-CNN-R) can be described through a carbenic valence bond structure, and although intermolecular carbenic reactions from nitrilimines are unknown, intramolecular reaction products from ortho-vinyl MeCOO-CNN-Ph (1) and Ph-CNN-Ph (2) that seem to have followed two typical carbene reaction mechanisms, [1+2] cycloaddition and C-H insertion, have ...

Article GUID: 21974693

Author(s): Mak CC; Timerghazin QK; Peslherbe GH;

Upon photoexcitation of iodide-water clusters, I(-)(H(2)O)(n), an electron is transferred from iodide to a diffuse cluster-supported, dipole-bound orbital. Recent femtosecond photoelectron spectroscopy experiments have shown that, for photoexcited I(-)(H(2)O)(n) (n= 5), complex excited-state dynamics ultimately result in the stabilization of the transferr ...

Article GUID: 22466252

Author(s): Wang S; Orabi EA; Baday S; Bernèche S; Lamoureux G;

Proteins of the Amt/MEP family facilitate ammonium transport across the membranes of plants, fungi, and bacteria and are essential for growth in nitrogen-poor environments. Some are known to facilitate the diffusion of the neutral NH(3), while others, notably in plants, transport the positively charged NH(4)(+). On the basis of the structural data for Amt ...

Article GUID: 22631217

Author(s): Shadrina MS; English AM; Peslherbe GH;

The diffusion of small gases to special binding sites within polypeptide matrices pivotally defines the biochemical specificity and reactivity of proteins. We investigate here explicit O(2) diffusion in adult human hemoglobin (HbA) as a case study employing the recently developed temperature-controlled locally enhanced sampling (TLES) method and vary the ...

Article GUID: 22690872

Author(s): Varadwaj PR; Varadwaj A; Peslherbe GH;

The proton accepting and donating abilities of cyclopropenylidene (c-C(3)H(2)) on its complexation with hydrogen halides H-X (X = F, Cl, Br) are analyzed using density-functional theory with three functionals (PBE0, B3LYP, and B3LYP-D) and benchmarked against second-order Møller-Plesset (MP2) theory. Standard signatures including, inter alia, dipole momen ...

Article GUID: 22696309

Author(s): Varadwaj A; Varadwaj PR;

Based on an experimental observation, it has been controversially suggested in a study (Kurotobi et al., Science 2011, 33, 613) that a single molecule of water can completely be localized within the subnano-space inside the fullerene C(60) cage and, that neither the H atoms nor the O lone-pairs are linked, either via hydrogen bonding or through dative bon ...

Article GUID: 23090782

Author(s): Zhang L; Muchall HM; Peslherbe GH;

The ground-state equilibrium geometries, electronic structures and vertical excitation energies of methyl- and methoxyl-substituted phenol radical cations and phenoxyl radicals have been investigated using time-dependent density-functional theory (namely TD-B3LYP) and complete-active-space second-order perturbation theory (CASPT2). The "anomalous" large r ...

Article GUID: 23216064

Author(s): Jahangiri S; Mercer SM; Jessop PG; Peslherbe GH;

The solvation behavior of alkyl diammonium chlorides of varying alkyl chain length and the molecular details of their effect on the salting-out of organic molecules in aqueous phase have been investigated by classical molecular dynamics simulations. More specifically, systems containing water, tetrahydrofuran (THF), and their mixtures with a,?-alkyl diamm ...

Article GUID: 23789929

Author(s): Mak CC; Timerghazin QK; Peslherbe GH;

Photoexcitation of iodide-acetonitrile clusters, I(-)(CH3CN)n, to the charge-transfer-to-solvent (CTTS) state and subsequent cluster relaxation could result in the possible formation of cluster analogues of the bulk solvated electron. In this work, the relaxation process of the CTTS excited iodide-acetonitrile binary complex, [I(-)(CH3CN)]*, is investigat ...

Article GUID: 23819756

Author(s): Mak CC; Peslherbe GH;

Upon photoexcitation of iodide-methanol clusters, I(-)(CH3OH)n, to a charge-transfer-to-solvent (CTTS) excited state, extensive relaxation was found to occur, accompanied by a convoluted modulation of the stability of the excited electron, which ultimately decreases substantially. In order to develop a molecular-level understanding of the relaxation proce ...

Article GUID: 24922343

Author(s): Fürst O; Nichols CG; Lamoureux G; D' Avanzo N;

Cholesterol is the major sterol component of all mammalian plasma membranes. Recent studies have shown that cholesterol inhibits both bacterial (KirBac1.1 and KirBac3.1) and eukaryotic (Kir2.1) inward rectifier K(+) (Kir) channels. Lipid-sterol interactions are not enantioselective, and the enantiomer of cholesterol (ent-cholesterol) does not inhibit Kir ...

Article GUID: 25517146

Author(s): Bilkiss B Issack

While it has long been known that cholesterol reduces the permeability of biological membranes to water, the exact mechanism by which cholesterol influences transmembrane permeation is still unclear. The thermodynamic and kinetic contributions to the transport of water across mixed DPPC/cholesterol bilayers of different composition are thus examined by mo ...

Article GUID: 25679811