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201.
We describe a large scale synthesis of secramine A. Consistent with its ability to inhibit activation of the small GTPase Cdc42, we find that secramine A inhibits cell spreading, a process previously shown to be Cdc42-dependent. 相似文献
202.
Photoemission from sodium deposited on ice films is described. Deposition of 0.02 ML of sodium is found to dramatically reduce the threshold for photoemission from the ice film to (2.3+/-0.2) eV. Thus, the cross-section for photoemission reaches >10(-18) cm2 in the visible region of the spectrum. It is proposed that the initial state is a solvated electron on the ice surface, which is supported by optical transmission spectroscopy. The potential significance of these results in understanding unexplained charging phenomena in the mesosphere is discussed. 相似文献
203.
Otyepka M Sklenovský P Horinek D Kubar T Hobza P 《The journal of physical chemistry. B》2006,110(9):4423-4429
The folding free energy of the INK4c tumor suppressor core, consisting of 10 helices, was determined as the sum of gas-phase interaction enthalpy, gas-phase interaction entropy, and dehydration and hydration free energy. The interaction energy and the hydration free energy were determined using the nonempirical density functional theory (DFT) method, augmented by a dispersion-energy correction term, the semiempirical density-functional tight-binding method covering the dispersion energy, and the density functional theory/conductor-like screening model (DFT/COSMO) procedure, whereas the interaction entropy was calculated with the empirical Cornell et al. force field. Alternatively, all contributions were evaluated consistently using empirical methods. All the values of the interaction energy of helix pairs are stabilizing, and the dominant stabilizing terms stem from the London dispersion energy and, in the case of charged systems, the electrostatic energy. The stabilization energy of the core, determined as the difference of the energy of the core and 10 separate helices, amounts to approximately 450 kcal/mol. Systematically, the difference in the hydration free energy of a helix pair and its separate components is smaller in magnitude than the interaction energy, and it is negative for some pairs while positive for others. The average total free energy of a core formation amounts to -29.6 kcal/mol (yielded by scaled quantum-chemical methods) and +13.9 kcal/mol (resulting from empirical methods). These values are considerably smaller than their single components, which are dominated by the interaction energy. The computationally predicted interval encloses the experimental value of the folding free energy (-2.8 kcal/mol). 相似文献
204.
205.
Merino P Tejero T Laguna M Cerrada E Moreno A Lopez JA 《Organic & biomolecular chemistry》2003,1(13):2336-2342
The cycloaddition reaction of N-benzyl C-(2-pyridyl) nitrone with allylic alcohol has been carried out to obtain the corresponding 2-benzyl-3-(2-pyridyl)-5-hydroxymethylisoxazolidine. The influence of Lewis acids in the reaction has been studied and a complete 3,5-regioselectivity and cis diastereoselectivity was observed when the reaction was carried out with 1.0 equiv of AgOTf, [Ag(OClO3)(PPh2Me)] or Zn(OTf)2. Insight into the mechanism of the reaction has been obtained by isolating and characterizing (X-ray) the intermediate complexes. Also, a model based on both experimental and theoretical results is proposed. 相似文献
206.
Certain meromorphic matrix valued functions on , the so-called boundary coefficients, are characterized in terms of a standard symmetric operator S in a Pontryagin space with finite (not necessarily equal) defect numbers, a meromorphic mapping into the defect subspaces of S, and a boundary mapping for S. Under some simple assumptions the boundary coefficients also satisfy a minimality condition. It is shown that these assumptions hold if and only if for S a generalized von Neumann equality is valid. 相似文献
207.
A C-linked analogue of beta-D-galactosylthreonine has been prepared from 2,3,4,6-tetra-O-benzyl-D-galactopyranolactone (1) in 14 steps. Three stereogenic centers were created during the synthesis, with the anomeric center of the C-glycoside being generated first by addition of a Grignard reagent to 1 and subsequent reduction of the intermediate hemiacetal with triethylsilane. The two stereogenic centers in the threonine moiety were both established by alkylation of Evans' chiral N-acyloxazolidinone enolates. 相似文献
208.
Bernadó P Akerud T García de la Torre J Akke M Pons M 《Journal of the American Chemical Society》2003,125(4):916-923
We describe a novel method for determining weak association constants of oligomeric protein complexes formed transiently under equilibrium conditions. This type of equilibrium process is recognized as being biologically important, but generally hard to study. Heteronuclear spin relaxation rates measured at multiple protein concentrations are analyzed using relaxation rates predicted from hydrodynamic calculations, yielding equilibrium constants and structural characterization of the protein complexes. The method was used to study the oligomerization equilibrium of bovine low molecular weight protein tyrosine phosphatase. X-ray structures of monomeric and dimeric forms of the protein have been reported previously. Using longitudinal and transverse (15)N relaxation rates measured at four different protein concentrations, we detected the monomer, dimer, and a previously unknown tetramer and measured the dissociation constants of the equilibria involving these species. A comparison of experimental and predicted relaxation rates for individual backbone amide (15)N spins enabled delineation of the tetramerization interface. The results suggest a novel concept for substrate modulation of enzymatic activity based on a "supramolecular proenzyme". The fast and reversible switching of the "supramolecular proenzyme" would have obvious advantages for the regulation of enzymes involved in cell signaling pathways. 相似文献
209.
Summary The reductive amination of octan-1-ol by ammonia in the gas phase has been studied. From the shape of the conversion curve
it was shown that in a certain conversion interval the amount of secondary and tertiary amines is higher than the equilibrium
composition of disproportionation reactions. 相似文献
210.
CP/MAS 13C-NMR spectroscopy in combination with spectral fitting was used to study the supermolecular structure of the cellulose fibril in spruce wood and spruce kraft pulp. During pulping, structures contributing to inaccessible surfaces in the wood cellulose are converted to the cellulose I allomorph, that is, the degree of order is increased. This increase is also accompanied by a conversion of cellulose I to cellulose I. Cellulose from wood composed of different cell types, that is, compression wood, juvenile wood, earlywood, latewood and normal wood exhibited a similar supermolecular structure. Assignments were made for signals from hemicellulose which contribute significantly to the spectral C-4 region (80–86 ppm) in kraft pulp spectra but substantially less to the corresponding region in wood spectra. 相似文献