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The stereoselective acylation of meso polyol 2 by vinyl acetate (solvent and acyl donor) in the presence of porcine pancreas lipase gave the corresponding monoester 5 in good yield (76%) and high enantiomeric purity (ee > 98%). The enzymatic reaction was also highly regioselective for a primary alcohol end group, and the two unprotected secondary alcohols were not involved. Compound 5 corresponds to the C(19)-C(27) fragment of rifamycin S. 相似文献
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Jean-Charles Boutonnet Francoise Rose-Munch Eric Rose Gilles Precigoux 《Journal of organometallic chemistry》1985,284(2):C25-C30
The complex CpV(CO)3THF has been prepared in THF solution (i) photochemically from CpV(CO)4, and (ii) from [CpV(H)(CO)3]?/[Ph3C]+ at low temperatures. THF is replaced by [CpV(H)(CO)3]? to form [{CpV(CO)3}2-μ-H]?, and by various ligands L with C, η2-CC, Sn, N, O, S, Se or Te functionality to yield CpV(CO)3L and cis-[CpV(CO)2LL] (LL = bipy, o-phen, tolane). The δ (51V) values range over ca. 1400 ppm and allow the assignment of distinct coordination modes for ambidentate ligands. The temperature gradient is ca. +1.2 ppm/deg. For [CpV(SnCl3)(CO)3]? (δ ?1340 ppm rel. to VOCl3), 1J(51V-117,119Sn) is 900 Hz. The isotope effect on introducing 12CO for 13CO in CpV(CO)4 is ?0.48(2) ppm; 1J(51V-13C) 107 Hz. 相似文献
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Frdric Tronc Warner Chen Mitchell A. Winnik Sarah T. Eckersley Gene D. Rose J. M. Weishuhn D. M. Meunier 《Journal of polymer science. Part A, Polymer chemistry》2002,40(22):4098-4116
This article describes the results of experiments examining the competition between the polymer diffusion rate and the crosslinking rate in low‐glass‐transition‐temperature, epoxy‐containing latex films in the presence of a diamine. We examined films formed from donor‐ and acceptor‐labeled poly(butyl acrylate‐co‐methyl methacrylate‐co‐glycidyl methacrylate) copolymer latex and studied the influence of several parameters on the growth rate of gel content and the rate of polymer diffusion. These factors include the molecular weight of the latex polymer, the presence or absence of a diamine crosslinking agent, and the cure protocol. The results were compared to the predictions of a recent theory of the competition between crosslinking and polymer diffusion across interfaces. In the initially formed films, polymer diffusion occurs more rapidly than the chemical reaction rate. Therefore, these films fall into the fast‐diffusion category of this model. In our system (unlike in the model), the latex polymer has a broad distribution of molecular weights and a distribution of diffusivities. The shortest chains contribute to the early time diffusion that we measure. At later stages of our experiment, slower diffusing species contribute to the signal that we measure. The diffusion time decreases substantially, and we observe a crossover to a regime in which the chemical reaction dominates. The increases in chain branching and gel formation bring polymer diffusion to a halt. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4098–4116, 2002 相似文献
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Traditional methodologies for the characterization of volatile organic compounds (VOCs) in subsurface soil are expensive, time-consuming processes that are often conducted on samples collected at random. The determination of VOCs in near-surface soils and vegetation is the foundation for a more efficient sampling strategy to characterize subsurface soil and improve understanding of environmental problems.In the absence of a standard methodology for the determination of VOCs in vegetation and in view of the high detection limits of the method for soils, we developed a methodology using headspace gas chromatography with an electron capture detector for the determination of low levels (parts-per-billion to parts-per-trillion) of VOCs in soils and vegetation. The technique demonstrates good sensitivity, good recoveries of internal standards and surrogate compounds, good performance, and minimal waste. A case study involving application of this technique as a first-step vadose-zone characterization methodology is presented. 相似文献
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TRANSIENT INTERMEDIATES IN INTRAMOLECULARLY PHOTOSENSITIZED PYRIMIDINE DIMER SPLITTING BY INDOLE DERIVATIVES 总被引:1,自引:0,他引:1
Tish Young Sang-Tae Kim John R. Van Camp Rosemarie F. Hartman Seth D. Rose 《Photochemistry and photobiology》1988,48(5):635-641
Abstract— Intramolecularly photosensitized pyrimidine dimer splitting can serve as a model for some aspects of the monomerization of dimers in the enzyme-substrate complex composed of a photolyase and UV-damaged DNA. We studied compounds in which a pyrimidine dimer was covalently linked either to indole or to 5-methoxyindole. Laser flash photolysis studies revealed that the normally observed photoejection of electrons from the indole or the 5-methoxyindole to solvent was diminished by an order of magnitude for indoles with dimer attached (dimer-indole and dimer-methoxyindole). The fluorescence lifetime of dimer-indole in aqueous methanol was 0.85 ns, whereas that of the corresponding indole without attached dimer (tryptophol) was 9.7 ns. Similar results were obtained for the dimer-methoxyindole (0.53 ns) and 5-methoxytryptophol (4.6 ns). The quantum yield of dimer splitting for the dimer-methoxyindole (φ287 K7 = 0.08) was only slightly greater than the value found earlier for the dimer bearing the unsubstituted indole (4>2K7 = 0.04). Transient absorption spectroscopy also revealed lower yields of indole radical cations following laser flash photolysis of dimer-indole compared to the indole without attached dimer. Dimer-methoxyindole behaved similarly. These results are interpreted in terms of an enhanced rate of radiationless relaxation of the indole and methoxyindole excited singlet states in dimer-indoles. The possible quenching of the indole and methoxyindole excited states via electron abstraction by the covalently linked dimer is discussed. 相似文献
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