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991.
A numerical technique and a computer program based on the method of orthogonal collocation on finite elements for solving steady state carrier-mediated transport problems is presented. The method is especially suitable in solving boundary layer type of problems as arise in carrier-mediated transport. The method uses an efficient LU decomposition of a blockdiagonal matrix. A residual criterion is used for the placement of elements which can be easily implemented using an interactive feature in the computer program. Numerical results for three different systems; a system with simple kinetics and equal diffusivities for carrier and its complex, a system with simple kinetics and unequal diffusivities and a system with complex kinetics and equal diffusivities, indicate that the method is very versatile and has very good convergence properties. The method can be used very easily for all these systems by making minor modifications to the computer program. 相似文献
992.
J. M. Schultz E. W. Fischer O. Schaumburg H. A. Zachmann 《Journal of Polymer Science.Polymer Physics》1980,18(2):239-245
The course of melting of melt-crystallized polyethylene fractions and of a poly(ethylene oxide)-polystyrene-poly(ethylene oxide) triblock copolymer has been followed by small-angle x-ray scattering (SAXS). Changes in the intensity and shape of the SAXS curves indicated that both surface melting and melting over the full crystallite thickness (full-strand melting) take place. Full strand melting is the final, irreversible process. Comparison with an analytical model indicates that in the earlier stages of the irreversible, full-strand process the crystallites melt out randomly throughout the bulk. Later stages may occur by the simultaneous melting of a larger stack of crystallites. 相似文献
993.
J. Petermann R. M. Gohil J. M. Schultz R. W. Hendricks J. S. Lin 《Journal of Polymer Science.Polymer Physics》1982,20(3):523-534
Polypropylene films were produced by solidification during high-rate (>104s?1) melt drawing. Small-angle x-ray scattering (SAXS) data were collected during interruptions of the annealing of these films. Fibrillar crystallization took place during the melt-drawing process. The fibrils exhibit an axial density modulation as determined by SAXS and transmission electron microscopy. Annealing increases the amplitude of the density modulation. Detailed examination of the SAXS curves shows that the modulation is approximately sinusoidal and that the amplification of the density modulation occurs with no change in periodicity. Comparison of SAXS curves taken at different times during annealing suggests a process similar to spinodal decomposition. It is proposed that the microstructural change within a fibril takes place by the axial motion and clustering of chain defects. 相似文献
994.
Park HS Blewitt G Cortez BG Foster GW Gajewski W Haines TJ Kielczewska D LoSecco JM Bionta RM Bratton CB Casper D Chrysicopoulou P Claus R Errede S Ganezer KS Goldhaber M Jones TW Kropp WR Learned JG Lehmann E Reines F Schultz J Seidel S Shumard E Sinclair D Sobel HW Stone JL Sulak LR Svoboda R van der Velde JC Wuest C 《Physical review letters》1985,54(1):22-25
995.
996.
Schultz MJ Adler RS Zierkiewicz W Privalov T Sigman MS 《Journal of the American Chemical Society》2005,127(23):8499-8507
The experimental and computational mechanistic details of the Pd(OAc)(2)/TEA-catalyzed aerobic alcohol oxidation system are disclosed. Measurement of various kinetic isotope effects and the activation parameters as well as rate law derivation support rate-limiting deprotonation of the palladium-coordinated alcohol. Rate-limiting deprotonation of the alcohol is contrary to the majority of related kinetic studies for Pd-catalyzed aerobic oxidation of alcohols, which propose rate-limiting beta-hydride elimination. This difference in the rate-limiting step is supported by the computational model, which predicts the activation energy for deprotonation is 3 kcal/mol higher than the activation energy for beta-hydride elimination. The computational features of the similar Pd(OAc)(2)/pyridine system were also elucidated. Details of the study illustrate that the use of TEA results in an active catalyst that has only one ligand bound to the Pd, resulting in a significant lowering of the activation energy for beta-hydride elimination and, therefore, a catalyst that is active at room temperature. 相似文献
997.
998.
A simple device was developed for in-vial liquid-liquid extraction using a polymer membrane (nonporous polypropylene) to separate an aqueous sample from an organic extractant. The membrane consisted of tubing with an internal diameter of 6 mm and a wall thickness of 0.05 mm, which was heat-sealed at the lower end and filled with 500 microl hexane. This membrane bag was incorporated into a conventional 20 ml headspace vial suitable for a multi-purpose sampler (MPS 2, Gerstel, Mülheim, Germany) directly interfaced to a gas chromatograph with a mass-selective detector. The sampler enabled the extraction vial to be mixed at a defined temperature with subsequent large-volume injection of the organic extract taken from the membrane bag. The method was evaluated using several triazines, 2,4-dichloroaniline, alpha-hexachlorocyclohexane and phenanthrene as model compounds. Extraction parameters such as temperature, agitation speed, and extraction time were optimised. Recoveries of 60-90% were achieved after 30 min extraction. By increasing the injection volume to 100 microl, detection limits of 1-10 ng/l were determined. 相似文献
999.
Baldwin EP Martin SS Abel J Gelato KA Kim H Schultz PG Santoro SW 《Chemistry & biology》2003,10(11):1085-1094
The basis for the altered DNA specificities of two Cre recombinase variants, obtained by mutation and selection, was revealed by their cocrystal structures. The proteins share similar substitutions but differ in their preferences for the natural LoxP substrate and an engineered substrate that is inactive with wild-type Cre, LoxM7. One variant preferentially recombines LoxM7 and contacts the substituted bases through a hydrated network of novel interlocking protein-DNA contacts. The other variant recognizes both LoxP and LoxM7 utilizing the same DNA backbone contact but different base contacts, facilitated by an unexpected DNA shift. Assisted by water, novel interaction networks can arise from few protein substitutions, suggesting how new DNA binding specificities might evolve. The contributions of macromolecular plasticity and water networks in specific DNA recognition observed here present a challenge for predictive schemes. 相似文献
1000.
W. C. Burnett D. R. Corbett M. Schultz E. P. Horwitz R. Chiarizia M. Dietz Anil Thakkar M. Fern 《Journal of Radioanalytical and Nuclear Chemistry》1997,226(1-2):121-127
The analysis of environmental samples for low levels of U, Pu, Am and other actinide elements is often hampered by sample-dependent problems involving the composition and/or mineralogy of specific samples. While relatively small samples (1–2 g of soil or 1–2 of water) are required to reach the extremely low detection limits occasionally mandated for environmental monitoring. One approach to avoid the troublesome and often inexplicable problems collectively referred to as matrix effects is to pre-concentrate actinides into a common form that would then behave uniformly and predictably during a subsequent separation scheme. Recently, a new extraction chromatographic resin based on diphosphonate chemistry was developed at Argonne National Laboratory. This resin commercialized as Eichrom's Actinide Resin, exhibits extremely high affinity for actinide elements even in the presence of high concentrations of salts. We have measured the uptake of actinides by the Dipex® extractant from natural waters and natural matrix soil standards. Water samples have been analyzed for gross -activities and gave results that compared favorably to the traditional approach. In addition, we have obtained good recoveries and excellent separations for soil samples as judged by resolution on the -spectra and the complete absence of interfering energies. 相似文献