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111.
112.
Abe F Albrow M Amidei D Anway-Wiese C Apollinari G Atac M Auchincloss P Azzi P Baden AR Bacchetta N Badgett W Bailey MW Bamberger A de Barbaro P Barbaro-Galtieri A Barnes VE Barnett BA Bauer G Baumann T Bedeschi F Behrends S Belforte S Bellettini G Bellinger J Benjamin D Benlloch J Bensinger J Beretvas A Berge JP Bertolucci S Biery K Bhadra S Binkley M Bisello D Blair R Blocker C Bodek A Bolognesi V Booth AW Boswell C Brandenburg G Brown D Buckley-Geer E Budd HS Busetto G Byon-Wagner A 《Physical review D: Particles and fields》1993,48(3):998-1008
113.
Emil Pop Marcus E. Brewster J. J. Kaminski Nicholas Bodor 《International journal of quantum chemistry》1989,35(2):315-324
9-Amino-1,2,3,4-tetrahydroacridine (THA ), a potent cholinesterase inhibitor, was recently used in the treatment of Alzheimer's disease. On attempting to prepare a dihydropyridine ? pyridinium salt-based redox chemical delivery system (CDS ) to enhance brain delivery of THA , several of the practical synthetic challenges were examined by using a theoretical MO approach. The structures, reactivities and stability of THA , derivatives of THA and a model compound, 4-aminopyridine, a simple dibasic heterocyclic amine, were studied in the framework of the AM -1 approximation. The study included the possible protonated forms of THA and 4-aminopyridine. The calculated heats of formation showed that ring nitrogen protonated forms are more stable for both THA and 4-aminopyridine. The calculated heats of formation showed that ring nitrogen protonated forms are more stable for both THA and 4-aminopyridine, consistent with experimental results. Electron delocalization is responsible for the remarkable stability of these molecules and for the observed lack of reactivity of the amino group, both in the basic and protonated forms. The site of N-alkylation of the 9-nicotinamide derivative of THA (an intermediate in the synthesis of THA -CDS ) is controlled by electronic, thermodynamic, and steric factors. 相似文献
114.
Sloutskin E Solutskin E Ocko BM Tamam L Taman L Kuzmenko I Gog T Deutsch M 《Journal of the American Chemical Society》2005,127(21):7796-7804
The surface structure and thermodynamics of two ionic liquids, based on the 1-alkyl-3-methylimidazolium cations, were studied by X-ray reflectivity and surface tensiometry. A molecular layer of a density approximately 18% higher than that of the bulk is found to form at the free surface of these liquids. In common with surface layering in liquid metals and surface freezing in melts of organic chain molecules, this effect is induced by the lower dimensionality of the surface. The concentrations of the oppositely charged ions within the surface layer are determined by chemical substitution of the anion. The temperature-dependent surface tension measurements reveal a normal, negative-slope temperature dependence. The different possible molecular arrangements within the enhanced-density surface layer are discussed. 相似文献
115.
Microcalorimetric measurements of excess molar enthalpies, at 298.15 K, are reported for the two ternary systems formed by mixing either diisopropyl ether or 2-methyltetrahydrofuran with binary mixtures of cyclohexane and n-heptane. Smooth representations of the results are presented and used to construct constant excess molar enthalpy contours on Roozeboom diagrams. It is shown that useful estimates of the ternary enthalpies can be obtained from the Liebermann and Fried model, using only the physical properties of the components and their binary mixtures. 相似文献
116.
Hünig I Painter AJ Jockusch RA Carçabal P Marzluff EM Snoek LC Gamblin DP Davis BG Simons JP 《Physical chemistry chemical physics : PCCP》2005,7(12):2474-2480
The gas phase structures of phenyl alpha- and beta-d-xylopyranoside (alpha- and beta-pXyl) and their mono-hydrates have been investigated using a combination of resonant two-photon ionization (R2PI), ultra-violet hole-burning and resonant infrared ion dip spectroscopy, coupled with density functional theory (DFT) and ab initio computation. The hole-burning experiments indicate the population of a single conformer only, in each of the two anomers. Their experimental and calculated infrared spectra are both consistent with a conformational assignment corresponding to the computed global minimum configuration. All three OH groups are oriented towards the oxygen atom (O1) on the anomeric carbon atom to form an all trans(ttt) counter-clockwise chain of hydrogen bonds. The mono-hydrates, alpha- and beta-pXyl(H(2)O) each populate two distinct structures in the molecular beam environment, with the water molecule inserted between OH4 and OH3 or between OH3 and OH2 in alpha-pXyl(H2O), and between OH2 and O1 in either of two alternative orientations, in beta-pXyl(H2O). In all of the mono-hydrated xyloside complexes, the water molecule inserts into the weakest link of the sugar molecules' hydrogen-bonded chain of hydroxy groups, creating a single extended chain, strengthened by co-operativity. The all-trans configuration of the xylose moiety is retained and the mono-hydrate structures correspond to those calculated to lie at the lowest relative energies. 相似文献
117.
Exact rotamer optimization for protein design 总被引:1,自引:0,他引:1
Computational methods play a central role in the rational design of novel proteins. The present work describes a new hybrid exact rotamer optimization (HERO) method that builds on previous dead-end elimination algorithms to yield dramatic performance enhancements. Measured on experimentally validated physical models, these improvements make it possible to perform previously intractable designs of entire protein core, surface, or boundary regions. Computational demonstrations include a full core design of the variable domains of the light and heavy chains of catalytic antibody 48G7 FAB with 74 residues and 10(128) conformations, a full core/boundary design of the beta1 domain of protein G with 25 residues and 10(53) conformations, and a full surface design of the beta1 domain of protein G with 27 residues and 10(60) conformations. In addition, a full sequence design of the beta1 domain of protein G is used to demonstrate the strong dependence of algorithm performance on the exact form of the potential function and the fidelity of the rotamer library. These results emphasize that search algorithm performance for protein design can only be meaningfully evaluated on physical models that have been subjected to experimental scrutiny. The new algorithm greatly facilitates ongoing efforts to engineer increasingly complex protein features. 相似文献
118.
Chin W Dognon JP Piuzzi F Tardivel B Dimicoli I Mons M 《Journal of the American Chemical Society》2005,127(2):707-712
Laser desorption of model peptides coupled to laser spectroscopic techniques enables the gas-phase observation of genuine secondary structures of biology. Spectroscopic evidence for the formation of beta-turns in gas-phase peptide chains containing glycine and phenylalanine residues establishes the intrinsic stability of these forms and their ability to compete with other stable structures. The precise characterization of local minima on the potential energy surface from IR spectroscopy constitutes an acute assessment for the state-of-the-art quantum mechanical calculations also presented. The observation of different types of beta-turns depending upon the residue order within the sequence is found to be consistent with the residue propensities in beta-turns of proteins, which suggests that the prevalence of glycine in type II and II' turns stems essentially from an energetic origin, already at play under isolated conditions. 相似文献
119.
Cheng Zhang Laurence Bensaid Donna McGregor Xikui Fang Robertha C. Howell Benjamin Burton-Pye Qunhui Luo Louis Todaro Lynn C. Francesconi 《Journal of Cluster Science》2006,17(2):389-425
Lanthanide complexes of polyoxometalates, including the α2-P2W17O61
10− ligand, have been pioneered by Michael T. Pope, to whom this paper is dedicated. Examination of the solid-state and solution behavior of lanthanide complexes of the α2-P2W17O61
10− ligand are reported here to identify trends that will facilitate rational synthesis of hybrid organic lanthanide polyoxometalate complexes. Therefore, combining our data with that obtained by Pope and others a number of trends come into view. It is clear that there are two structural types for the 1:1 or 2:2 [Ln(H2O)X(α2-P2W17O61)]2
14− species. The early lanthanides show a “cap to cap” structure that allows the Ln ion to be 9 coordinate and accommodates the longer bond lengths. The mid-late lanthanides show a “cap to belt” structure that allows the lanthanides to be 8 coordinate; this structural type is appropriate for the shorter bond lengths of the later lanthanides. The 1:1⇌1:2 equilibrium, that was observed by Pope for the Ce(III) analog is prevalent for the early- mid lanthanides. This equilibrium is slightly dependent on pH; however, cations have a major influence on this equilibrium. Larger, poorly hydrated cations appear to favor the 1:2 species for the early to mid lanthanides. Cations do not appear to influence the equilibrium for the later lanthanides; for all counterions, the 1:1 species was stable with no trace of the 1:2 species. Stability constants, K1 and K2, for the early to mid lanthanides were measured in this study by a competitive method and compared well with other published stability constant determinations. We suggest that the stability constants are not only dependent on the strength of interaction of the Ln with the α2-P2W17O61
10− ligand, but are also significantly influenced by the medium. The medium may bias the equilibria of the early-mid lanthanides and later lanthanides. The log K1/log K2 ratios are very close, suggesting that it is difficult to separate the 1:1 and 1:2 Ln: α2-P2W17O61
10− species.Electronic Supplementary Material Supplementary material for this article is available at and is accessible for authorized users.This paper is dedicated to Professor Michael T. Pope in honor of his substantial and sustained contributions to polyoxometalate chemistry and his inspiration to scientists working in the field. 相似文献
120.
Y. Marcus 《Journal of solution chemistry》1987,16(9):735-744
The translational entropy loss on the association of two ions to form an ion pair or 11 complex is overcompensated by a rotational entropy gain, an electrostatic entropy gain, and an entropy gain due to solvent release from translational immobilization. The first three effects can be calculated, leaving the fourth as a difference from the experimental entropy change on association. The ratio of the solvent release entropy gain to the entropy change on melting of the solvent indicates the number of solvent molecules released on the association. A similar value is obtained from data for the volume change on association.Presented as a poster at the 10th International Conference on Non-Aqueous Solvents (ICNAS) at Leuven, Belgium, August 1986, and at the 24th International Congress on Coordination Chemistry (ICCC) at Athens, Greece, August 1986. 相似文献