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291.
The complexation of tetramethylresorc[4]arene with primary and secondary amines in acetonitrile was investigated spectrophotometrically. The stoichiometry of the complexes formed was shown to depend on the amine concentration. Based on the proposed complexation models, the formation constants of the complexes as well as their thermodynamical parameters were determined and discussed. Depending on the amine concentration, two types of solid complexes of tetramethylresorc[4]arene with amines were obtained. The composition of these complexes was confirmed by 1H NMR. 相似文献
292.
Two series of interpenetrating sulfonic acid resins (ISAR), 10×n and n×10, were prepared by means of the wet method, and the physicochemical, thermodynamic and kinetic properties of the ISAR were measured. The results show: 10×n resins exhibit better properties than n×10 ones, mainly in higher apparent degree of crosslinking and larger conformational entropy effect, among which, 10×1 resin exhibits the best thermodynamic and kinetic properties. In the DTA graphs of n×10 resins, there are two T_g and two T_(ox), but in those of 10×n, only one T_g and one T_(ox). This result well supports the conclusion that 10×n resins have much better interpenetrating structural aspects. 相似文献
293.
Yu. A. Zolotarev E. V. Laskatelev V. S. Kozik E. M. Dorokhova S. G. Rozenberg Yu. A. Borisov N. F. Myasoedov 《Russian Chemical Bulletin》1997,46(10):1726-1729
The solid-phase catalytic hydrogenation of (R-4tert-butoxy-Δ1-pyrroline-2-carboxylic) acid under the action of hydrogen spillover was studied. The reaction proceeds stereoselectively
with the predominant formation of thel-amino acid. The configuration of the asymmetric center formed is determined by that of the asymmetric C(4) atom. The major
portion of the isotope label is incorporated into the allylic C(3) and C(5) positions, and the β-H atoms are more mobile.
Using quantum-chemical calculations, the geometric structure of thel-hydroxyproline molecule was calculated, and the spin-spin coupling constants for this tritium-labeled amino acid were determined.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1820–1823, October, 1997. 相似文献
294.
V.?I.?VigdorovichEmail author L.?E.?Tsygankova O.?V.?Alekhina T.?P.?D'yachkova 《Russian Journal of Electrochemistry》2005,41(10):1046-1052
The effect of thiourea (0.5–10 mM) on the kinetics of the hydrogen evolution reaction (HER) at iron and the hydrogen transport through a steel membrane out of ethylene glycol (containing 2 and 10 wt % H2O) and aqueous solutions containing HCl (0.1–0.99 M) with a constant ionic strength equal to unity is studied in parallel experiments. The presence of 0.5 mM of thiourea in the solutions raises the overvoltage of hydrogen evolution, while a subsequent increase in its concentration does not effect the HER kinetics. The dependence of the flux of hydrogen diffusion through the membrane on the thiourea content passes through a maximum. 相似文献
295.
A. G. Matveeva E. I. Matrosov Z. A. Starikova G. V. Bodrin S. V. Matveev P. V. Petrovskii E. E. Nifant’ev 《Russian Chemical Bulletin》2005,54(11):2519-2534
The trifunctional ligand, 2,6-bis(diphenylphosphorylmethyl)-4-methylphenol (L
2), forms complexes with cerium(III) nitrate having a ligand to metal ratio of 1: 1, 2: 1, and 3: 1. The structures of these complexes in the solid state and
in solution were studied by X-ray diffraction, IR and NMR (1H and 31P) spectroscopy, and conformational analysis (molecular mechanics). The 2: 1 complexes of L
2 with lanthanum(III) and neodymium(III) nitrates were synthesized and characterized. In all complexes, the neutral ligand is coordinated through both phosphoryl
oxygen atoms. The hydroxy oxygen atom is coordinated only in some complexes, and the hydrogen atom of the hydroxy group is
involved in hydrogen bonding. The compositions and structures of the resulting complexes depend on the method of synthesis
and the nature of solvent. The ligand was found to undergo easy inner-sphere oxidation. The structure of one of the transformation
products was established by X-ray diffraction. Unlike the coordinated ligand, the free ligand is very stable to oxidation.
Dedicated to Corresponding Member of the Russian Academy of Sciences T. A. Mastryukova.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2440–2454, November, 2005. 相似文献
296.
FANG Fang ZHU Yu ZHAO Qian JIANG Gang WANG Hong-Yan 《结构化学》2007,26(9):1092-1096
Geometric and electronic properties of Pdn–1Pb and Pdn (n≤8) clusters have been studied by using density functional theory with effective core potentials, focusing on the differences between mono- and bimetallic clusters. The average bond length of Pdn–1Pb (n≤8) bimetallic clusters is longer than that of pure palladium clusters except for n = 2 and 3. The most stable structure of Pdn–1Pb (n≤7) is the singlet where there is at least a Pd or Pb atom on its excited state. The energy gaps of Pd–Pb binary clusters are narrower than those of Pdn clusters, and then the chemical activity is strengthened when Pdn clusters are doped with Pb. 相似文献
297.
W. Grüner R. Giegerich D. Strothmann C. Reidys J. Weber I. L. Hofacker P. F. Stadler P. Schuster 《Monatshefte für Chemie / Chemical Monthly》1996,127(4):355-374
Summary Global relations between RNA sequences and secondary structures are understood as mappings from sequence space into shape space. These mappings are investigated by exhaustive folding of allGC andAU sequences with chain lengths up to 30. The computed structural data are evaluated through exhaustive enumeration and used as an exact reference for testing analytical results derived from mathematical models and sampling based on statistical methods. Several new concepts of RNA sequence to secondary structure mappings are investigated, among them that ofneutral networks (being sets of sequences folding into the same structure). Exhaustive enumeration allows to test several previously suggested relations: the number of (minimum free energy) secondary structures as a function of the chain length as well as the frequency distribution of structures at constant chain length (commonly resulting in generalized forms ofZipf's law).
Analyse der Beziehungen zwischen RNA-Sequenzen und Sekundärstrukturen durch vollständige Faltung, 1. Mitt. Faltung, Neutrale Netzwerke
Zusammenfassung Die globalen Benziehungen zwischen RNA-Sequenzen und Sekundärstrukturen werden als Abbildungen aus einem Raum aller Sequenzen in einen Raum aller Strukturen aufgefaßt. Diese Abbildungen werden durch Falten aller binären Sequenzen desGC-undAU-Alphabets mit Kettenlängen bis zun=30 untersucht. Die berechneten Strukturdaten werden durch vollständiges Abzählen ausgewertet und als eine exakte Referenz zum Überprüfen analytischer Resultate aus mathematischen Modellen sowie zum Testen statistisch erhobener Proben verwendet. Einige neuartige Konzepte zur Beschreibung der Beziehungen zwischen Sequenzen und Strukturen werden eingehend untersucht, unter ihnen der Begriff derneutralen Netzwerke. Ein neutrales Netzwerk besteht aus allen Sequenzen, die eine bestimmte Struktur ausbilden. Vollständiges Abzählen ermöglicht beispielsweise die Bestimmung aller Strukturen minimaler freier Energie in Abhängigkeit von der Kettenlänge ebenso wie die Bestimmung der Häufigkeitsverteilungen der Strukturen bei konstanten Kettenlängen. Die letzteren folgen einer verallgemeinerten FormZipfschen Gesetzes.相似文献
298.
A. A. Vedenyapin M. D. Baturova G. I. Ioseliani G. Kh. Areshidze 《Russian Chemical Bulletin》1997,46(1):76-80
The anodic oxidation of the carbon felt Carbonetcalon results in the formation of surface defects which serve as centers of
strong adsorption of PdII, NiII, and CuII ions. The electrochemical reduction of adsorbed ions makes it possible to obtain metallic catalysts, which undergo multiple
redox cycles without loss of metal. The catalysts are characterized by high dispersity of the reduced phase, high adsorption
capacity with respect to hydrogen, and 100% selectivity in hydrogenation of acetophenone.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 81–85, January 1997 相似文献
299.
Vesselin Dimitrov 《Journal of solid state chemistry》2005,178(3):831-846
A classification of binary oxide glasses has been proposed taking into account the values obtained on their refractive index-based oxide ion polarizability αO2−(n0), optical basicity Λ(n0), metallization criterion M(n0), interaction parameter A(n0), and ion's effective charges as well as O1s and metal binding energies determined by XPS. Four groups of oxide glasses have been established: glasses formed by two glass-forming acidic oxides; glasses formed by glass-forming acidic oxide and modifier's basic oxide; glasses formed by glass-forming acidic and conditional glass-forming basic oxide; glasses formed by two basic oxides. The role of electronic ion polarizability in chemical bonding of oxide glasses has been also estimated. Good agreement has been found with the previous results concerning classification of simple oxides. The results obtained probably provide good basis for prediction of type of bonding in oxide glasses on the basis of refractive index as well as for prediction of new nonlinear optical materials. 相似文献
300.
Alison T. Ung Roger Bishop Donald C. Craig Ian G. Dance A. David Rae Marcia L. Scudder 《Journal of inclusion phenomena and macrocyclic chemistry》1993,15(4):385-398
The inclusion compounds of 2,8-dimethyltricyclo[5.3.1.13,9]dodecane-syn-2,syn-8-diol,3, with ferrocene and with squalene have been prepared. The crystal structures of these helical tubulate compounds: (3)3·(ferrocene)0.75 [P3121,a=b=13.7480(6),c=7.0312(5) Å,Z=1,R=0.038] and (3)3·(squalene)0.23 [P3121,a=b=13.677(1),c=7.0533(9) Å,Z=1,R=0.042] are described.
Supplementary Data relating to this article are deposited with the British Library as supplementary publication No. SUP 82151 (16 pages). 相似文献