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61.
Abstract— Some photochemical reactions of bacteriorhodopsin (BR) embedded in NaCl pellets (BR-NaCI) in the visible region are described here. BR in these preparations is a mixture of two classes of species: a drastically blue-shifted form and the unchanged purple pigment. Depending on the illumination history of the BR before being immobilized, both kinds of BR could be demonstrated in light-adapted (LA) and dark-adapted (DA) forms, but light adaptation was not possible once the pellets were made. Analogously to BR suspensions, the light-adapted blue-shifted BRexhibited an a/l-trans type photocycle, but the thermal steps were greatly slowed down (time constants 1 to 5 min). The parent species absorb at 506 nm. The DA blue-shifted BR exhibited absorption changes resolved into two photoreactions, one all-(rans- like (as in LA-BR) and another, 13-cw like, whose decay rate is also greatly slowed down (recovery time several hours). The parent species of the 13-cis like cycle absorb at 480 nm. That pigment fraction in the pellets whose absorption was not blue-shifted, also exhibited similar photoreactions to BR in suspension, but with an overall turnover rate only one order of magnitude slower. From a previous report (Lazarev and Terpugov, Biochim. Biophys. Acta 590 ,324–338,1980) and this one, it appears that the very slow photocycles in NaCl-BR of low moisture content originate from blue-shifted chromophores rather than from unchanged BR. 相似文献
62.
63.
Jean-Marc Martel Belaïd Aouni 《The Journal of the Operational Research Society》1990,41(12):1121-1132
Many algorithms have been developed for multiple-criteria decision-making problems. Goal programming (GP) is one of these algorithms. This model is a special extension of linear programming. Usually, it is not easy for the decision-maker to choose his aspiration levels a priori. Moreover, the incommensurability of the measurement units of the various objectives creates an aggregation problem. However, in the standard GP formulation, the decision-maker is not required to arbitrate among conflicting objectives. To deal with these difficulties, we explicitly introduce the structure of the decision-maker's preferences into the GP model in order to evaluate the impact of deviations from the decision-maker's aspirations levels. Easily and naturally, the idea of a generalized criterion, as introduced in the Promethee outranking method, will be used to build this structure of preferences. 相似文献
64.
Chass GA Mirasol RS Setiadi DH Tang TH Chin W Mons M Dimicoli I Dognon JP Viskolcz B Lovas S Penke B Csizmadia IG 《The journal of physical chemistry. A》2005,109(24):5289-5302
Computational and experimental determinations were carried out in parallel on the conformational probability of N-Acetyl-Phenylalanine-NH2 (NAPA). Ab initio computations were completed at the BLYP/6-311G(df,p), B3LYP/6-31G(d), B3LYP/6-31G(d,p), and B3LYP/6-31+G(d) levels of theory, labeled L/61fp, B/6, B/6p, and B/6+, respectively. Three experimentally identified conformers were compared with theoretical data, confirming their identities as the betaLanti, gammaLgauche+, and gammaLgauche- (BACKBONESIDECHAIN) conformers. Evidence comes from matching experimental and theoretical data for all three constituent N-H stretches of NAPA, with a Delta(Experimental-Theoretical) = approximately 1-3 cm(-1), approximately 0-5 cm(-1), and approximately 1-6 cm(-1), at the L/61fp and B/6+ levels, respectively. Corrected-ZPE relative energies were computed to be 0.14, 0.00, 0.26 and 0.00, 0.67, 0.57 (kcal*mol(-1)) for the betaLanti, gammaLgauche+, and gamma(Lgauche- conformers, respectively, at the L/61fp and B/6+ levels, respectively. The MP2/6-31+G(d) level of theory was subsequently found to give similar relative energies. Characterization of the intramolecular interactions responsible for red and blue shifting of the N-H stretches showed the existence of the following intramolecular interactions: C=O[i]- - -HN[i], (Ar[i])-Cgamma- - -HN[i+1], (Ar[i])-Cdelta-H- - -O=C[i-1] for betaLanti; C=O[i-1]- - -HN[i+1], (Ar[i])-Cgamma- - -HN[i+1], (Ar[i])-C-H- - -O=C[i] for gammaLgauche+; and C=O[i-1]- - -HN[i+1] for gammaLgauche-. Each of these interactions were further investigated and subsequently characterized by orbital population and Atoms-In-Molecules (AIM) analyses, with the identity of overlap and bond critical points (BCP) serving as 'scoring criteria', respectively. Experimental and theoretical carbonyl stretches were also compared and showed good agreement, adding further strength to the synergy between experiment and theory. 相似文献
65.
66.
Abigail E. Watts Magdalena M. Lozinska Alexandra M. Z. Slawin Alvaro Mayoral Daniel M. Dawson Sharon E. Ashbrook Bela E. Bode A. Iulian Dugulan Mervyn D. Shannon Paul A. Cox Alessandro Turrina Paul A. Wright 《Angewandte Chemie (International ed. in English)》2020,59(35):15186-15190
An AlPO4 zeotype has been prepared using the aromatic diamine 1,10‐phenanthroline and some of its methylated analogues as templates. In each case the two template N atoms bind to a specific framework Al site to expand its coordination to the unusual octahedral AlO4N2 environment. Furthermore, using this framework‐bound template, Fe atoms can be included selectively at this site in the framework by direct synthesis, as confirmed by annular dark field scanning transmission electron microscopy and Rietveld refinement. Calcination removes the organic molecules to give large pore framework solids, with BET surface areas up to 540 m2 g?1 and two perpendicular sets of channels that intersect to give pore space connected by 12‐ring openings along all crystallographic directions. 相似文献
67.
Dr. Abigail E. Watts Dr. Magdalena M. Lozinska Prof. Alexandra M. Z. Slawin Dr. Alvaro Mayoral Dr. Daniel M. Dawson Prof. Sharon E. Ashbrook Dr. Bela E. Bode Dr. A. Iulian Dugulan Prof. Mervyn D. Shannon Dr. Paul A. Cox Dr. Alessandro Turrina Prof. Paul A. Wright 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(35):15298-15302
An AlPO4 zeotype has been prepared using the aromatic diamine 1,10-phenanthroline and some of its methylated analogues as templates. In each case the two template N atoms bind to a specific framework Al site to expand its coordination to the unusual octahedral AlO4N2 environment. Furthermore, using this framework-bound template, Fe atoms can be included selectively at this site in the framework by direct synthesis, as confirmed by annular dark field scanning transmission electron microscopy and Rietveld refinement. Calcination removes the organic molecules to give large pore framework solids, with BET surface areas up to 540 m2 g−1 and two perpendicular sets of channels that intersect to give pore space connected by 12-ring openings along all crystallographic directions. 相似文献
68.
Venture capital has proven to be an essential resource for economic growth, especially in some technological clusters. The focus is on the way the venture capitalist makes the investment decision and the portfolio selection. The aim of this paper is to formulate the venture capital investment problem through the Goal Programming model where the Financial Decision-Maker’s preferences will be explicitly incorporated through the concept of satisfaction functions. The proposed model will be illustrated by using data from an Italian venture capital fund. 相似文献
69.
Thamarath SS Bode BE Prakash S Sai Sankar Gupta KB Alia A Jeschke G Matysik J 《Journal of the American Chemical Society》2012,134(13):5921-5930
Photo-CIDNP (photochemically induced dynamic nuclear polarization) can be observed in frozen and quinone-blocked photosynthetic reaction centers (RCs) as modification of magic-angle spinning (MAS) NMR signal intensity under illumination. Studying the carotenoidless mutant strain R26 of Rhodobacter sphaeroides, we demonstrate by experiment and theory that contributions to the nuclear spin polarization from the three-spin mixing and differential decay mechanism can be separated from polarization generated by the radical pair mechanism, which is partially maintained due to differential relaxation (DR) in the singlet and triplet branch. At a magnetic field of 1.4 T, the latter contribution leads to dramatic signal enhancement of about 80,000 and dominates over the two other mechanisms. The DR mechanism encodes information on the spin density distribution in the donor triplet state. Relative peak intensities in the photo-CIDNP spectra provide a critical test for triplet spin densities computed for different model chemistries and conformations. The unpaired electrons are distributed almost evenly over the two moieties of the special pair of bacteriochlorophylls, with only slight excess in the L branch. 相似文献
70.
Reduction and N-Alkylation of α-Methylene-indolines with Sodium Cyanoborohydride in Carboxylic Acids
The reaction of α-methylene-indolines with NaCNBH3 in carboxylic acids at room temperature can yield either 2β,3β-dihydro-indolines or their N-alkyl derivatives as main products with high selectivity, depending mainly on the carboxylic acid and on the reaction time when using a large excess of NaCNBH3. 相似文献