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51.
Ab initio supermolecular SCF calculations at the STO-3G level are reported for the diacetylene-hydrogen fluoride complexes. The reverse
σ-complex is predicted to have somewhat higher stability and H-bond strength than the π-complexes. 相似文献
52.
Complexes of W(CO)(5) with neutral diatomic pnictogen ligands N(2), P(2), As(2), Sb(2), and Bi(2) and anionic Group 14 ligands Si(2) (2-), Ge(2) (2-), Sn(2) (2-), and Pb(2) (2-) coordinated in both side-on and end-on fashion have been optimized by using density functional theory at the BP86 level with valence sets of TZP quality. The calculated bond energies have been used to compare the preferential binding modes of each respective ligand. The results were interpreted by analyzing the nature of the interaction between the ligands and the metal fragment using an energy partitioning method. This yields quantitative information regarding the strength of covalent and electrostatic interactions between the metal and ligand, as well as the contributions by orbitals of different symmetry to the covalent bonding. Results show that all the ligands studied bind preferentially in a side-on coordination mode, with the exception of N(2), which prefers to coordinate in an end-on mode. The preference of the heavier homologues P(2)-Bi(2) for binding in a side-on mode over the end-on mode in the neutral complexes [(CO)(5)WE(2)] comes mainly from the much stronger electrostatic attraction in the former species. The energy difference between the side-on and end-on isomers of the negatively charged complexes with the ligands Si(2) (2-), Ge(2) (2-), Sn(2) (2-), and Pb(2) (2-) is much less and it cannot be ascribed to a particular bonding component. 相似文献
53.
54.
O. D. Bonner 《Journal of solution chemistry》1980,9(11):877-884
Osmotic and activity coefficients, determined from isopiestic measurements, are presented for aqueous solutions of eight tetramethylguanidinium salts. It is proposed that both hydronium and tetramethylguanidinium ions are capable of forming stable ion pairs with many anions by means of bridged hydrogens forming six-membered rings and that these ion pairs are stable in rather dilute aqueous solutions. 相似文献
55.
In the context of the density functional theory of the local electron density the valence and differential density distribution in crystalline sulfates of M2SO4 (M is Li, Rb, and Cs) and double sulfates of MLiSO4 were calculated using the pseudopotential method in the basis set of numerical atomic pseudo-orbitals. It is shown that in lithium sulfate crystallographically inequivalent oxygen atoms are in different charge states and have a different force of chemical bonding with sulfur. Anions are bonded to each other through lithium atoms that form tetrahedral complexes with oxygen. In rubidium sulfates the electron clouds of the anions overlap and chain structures form. Chemical bonding between the anion and the cation has an ionic nature. These features of the electron structure manifest themselves in double sulfates, where LiO4 complexes that link the anionic chains also form, and heavy metals serve as cations. 相似文献
56.
Brahmananda?Ghosh David A.?LightnerEmail author Antony F.?McDonaghEmail author 《Monatshefte für Chemie / Chemical Monthly》2004,135(9):1189-1199
Summary. A symmetrical C(10)-selena-bilirubin analog, 8,12-bis(2-carboxyethyl)-7,13-dimethyl-2,3,17,18-tetraethyl-10-selenabiladiene-ac-1,19(21H,24H)-dione was synthesized from 8-(2-carboxyethyl)-2,3-diethyl-7-methyl-(10H)-dipyrrin-1-one in one step by reaction with diselenyl dichloride. The selena-rubin exhibited UV-vis and NMR spectroscopic properties similar to those of the parent mesobilirubin, and like bilirubin and mesobilirubin, it adopts an intramolecularly hydrogen-bonded conformation, shaped like a ridge-tile but with a steeper pitch. The longer C–Se bond lengths (2.2Å) and smaller bond angles at C–Se–C (88°), as compared to C–CH2–C (1.5Å, 106°), lead to an interplanar angle between the two dipyrrinones of only 72°, which is considerably less than that of bilirubin (100°) and close to that (74°) of its 10-thia-rubin analog. Despite the conformational distortion, the sensitivity of Se toward oxidation and the typically weak C–Se bond, the selena-rubin is metabolized in normal rats, like bilirubin, to acyl glucuronides, which are secreted into bile. In mutant (Gunn) rats lacking bilirubin glucuronosyl transferase (UGT1A1), glucuronide or other metabolites of the selena-rubin were not detected in bile, demonstrating the importance of hepatic glucuronidation for its biliary excretion. 相似文献
57.
BAI Quan KONG Yu DONG Cuihua & GENG Xindu Institute of Modern Separation Science Shaanxi Key Laboratory of Modern Separation Science Northwest University Xi''''an China 《中国科学B辑(英文版)》2005,48(Z1)
The refolding of the reduced-denatured insulin from bovine pancreas was investigated with the size exclusion chromatography (SEC). It was shown that the reduced-denatured insulin originally denatured with 7.0 mol·L-1 guanidine hydrochloride (GuHCI) or 8.0 mol·L-1 urea could not be refolded with a non-oxidized mobile phase. Although the oxidized and reduced glutathione (GSSG and GSH) were employed in the oxidized mobile phase, the reduced-denatured insulin still could not be renatured. However, in the presence of 2.0 mol·L-1 urea in the oxidized mobile phase employed, the reduced-denatured insulin can be refolded with SEC, and the aggregation of denatured insulin can be diminished by urea. In addition, the disul-fide exchange of reduced-denatured insulin also can be accelerated with GSSG/GSH in the oxidized mobile phase. The three disulfide bridges of insulin were formed correctly and the reduced-unfolded insulin can be renatured completely. The results were further tested with re-versed-phase liquid chromatography (RPLC) and hydrophobic interaction chromatography (HIC). 相似文献
58.
Y. Marcus 《Journal of solution chemistry》1991,20(9):929-944
Taft and Kamlet's -scale of solvent hydrogen bond donation ability is reexamined with regard to its correlations with three widely used polarity scales: Dimroth and Reichardt's E
T
(30), Kosower's Z and Mayer's A
N
, as well as with the m values of the solvents when present as monomeric solutes. The correlation with E
T
serves to extend the solvent -scale according to the expression:
相似文献
59.
The evidence for the stabilizing nature of the H–H bonding in planar biphenyl is succinctly reviewed. The stabilizing nature
of the H–H bonding is revealed through a comparison of the atomic energy of every atom in planar biphenyl with the same atom
in the twisted equilibrium structure. It is shown that the barrier to rotation via the planar transition state is the net
resultant of a stabilisation of the four ortho-hydrogen atoms (by 8 kcal/mol each), a stabilisation of the two para-carbon atoms (by 3 kcal/mol each) and by the dominant destabilisation of the two carbon atoms joining the two rings—the two
junction carbon atoms—(by 22 kcal/mol each). The energetic stabilisation of the four ortho-hydrogen atoms is further shown to be in large proportion due to the formation of the hydrogen–hydrogen interatomic surface.
Furthermore, neither the “bond order” between the two junction carbon atoms nor the total electron delocalisation between
the two rings exhibit a significant change in going from the planar to the twisted equilibrium geometry. These findings are
in contrast with the classical view of a balance between “steric non-bonded repulsion” and better electron delocalisation
as a function of the twist dihedral angle. Similar conclusions have been recently reached by Pacios and Gómez through a study
of the electrostatic potential at the position of the hydrogen nuclei.
We dedicate this article to Professor TM Krygowski on the occasion of his 70th birthday wishing him a long and productive
life. 相似文献
60.
The composition range and (composite modulated) structure of compounds within the wide range non-stoichiometric LaSb2Snx, 0.1?x?0.75, solid solution is carefully investigated via a combined electron diffraction, XRD and electron probe microanalysis study. Evidence for metastability of the LaSb2Snx phase at the low x composition end of the solid solution is presented. Direct evidence is found for a reasonably (although by no means perfectly) well ordered Sn sub-structure which is, in general, mutually incommensurable with respect to a very well ordered underlying LaSb2 sub-structure along both a and c directions. The overall (3+2)-d superspace group symmetry is given along with a discussion of the consequences as regards the arrangement of the Sn atoms. The Sn sub-structure c-axis cell dimension shows very little variation with composition x providing direct experimental evidence of the importance of Sn-Sn metallic bonding (along one-dimensional [001] Sn strings) for the stability of the phase. 相似文献
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