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71.
Aza-Michael addition of 4-aryl-1H-1,2,3-triazoles to 2-cycloalken-1-ones has been studied in the presence of DABCO as organic base. The reactions were carried out in acetonitrile at room temperature to provide 2,4-disubstituted 2H-1,2,3-triazoles as major adducts and 1,4-disubstituted 1H-1,2,3-triazoles as minor adducts. Though the reaction times are longer (4–8 days), the two regioisomers were separated by using column chromatography and the adducts were obtained in very good to excellent combined chemical yields. The electron-rich and electron-poor substituents on aryl moiety of 4-aryl-triazoles could tolerate the reaction conditions to afford the title adducts. 相似文献
72.
The addition of the N-pronucleophiles to 2- or 3-nitro-2-alkenoates in the presence of base provided Michael addition products. In the case of 3-nitro compounds, reaction occurred via the formation of α-adducts and the subsequent elimination of nitrous acid to produce olefins with high Z stereoselectivity. 3-Phthalimido-2-nitrocinnamate adduct 8a was converted into 2,3-diamino ester 11a. 相似文献
73.
Optimising time-varying gradient orientation for microstructure sensitivity in diffusion-weighted MR
Drobnjak I Alexander DC 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2011,212(2):344-354
Here we investigate whether varying the diffusion-gradient orientation during a general waveform single pulsed-field gradient sequence improves sensitivity to the size of coherently oriented pores over having a fixed orientation. The experiment optimises the shape and the orientation of the gradient waveform in each of a set of measurements to minimise the expected variance of estimates of the parameters of a simple model. A key application motivating the work is measuring the size of axons in white matter. Thus, we use a two compartment white matter model with impermeable, single-radius cylinders, and search for waveforms that maximise the sensitivity to axon radius, intra-cellular volume fraction and diffusion constants. Output of the optimisation suggests the only benefit of allowing the gradient orientation to vary in the plane perpendicular to the cylinders is that we can gain perpendicular gradient strength by maximising two orthogonal gradients simultaneously. This suggests that varying orientation in itself does not increase the sensitivity to model parameters. On the other hand, the variation in a plane containing the parallel direction increases the sensitivity significantly because parallel sensitivity improves the diffusion constant estimates. However, we also find that similar improvement in the estimates can be achieved without optimising the orientation, but by having one measurement in the parallel and the rest in the perpendicular direction. The optimisation searches a very large space where it cannot hope to find the global minimum so we cannot make a categorical conclusion. However, given the consistency of the results in multiple reruns and variations of the experiments reported here, we can suggest that for probing coherently oriented systems, pulse sequences with variable orientation, such as double-wave vector sequences, do not offer more advantage than fixed orientation sequences with optimised shape. The advantage of varying orientation is however likely to emerge for more complex systems with dispersed pore orientation. 相似文献
74.
乳清分离蛋白-葡聚糖接枝物性质的荧光光谱法分析 总被引:2,自引:0,他引:2
乳清分离蛋白与葡聚糖的混合物在干热处理条件下,发生了以褐变为特征的美拉德反应。当葡聚糖分子量由67kD增至150kD时,游离氨基含量分别下降了35.77%和30.53%,糖链越长,其接入到蛋白质肽链的难度越大。采用荧光光谱对乳清分离蛋白-葡聚糖接枝物的性质进行分析。内源荧光光谱图显示,接枝产物在405nm的最大荧光强度显著提高,且350~500nm范围内的荧光强度顺序为:G67>G150,这说明接枝物中有Maillard反应体系所特有的荧光物质生成;由外援荧光光谱图得出,接枝产物在470nm的最大荧光强度均有明显降低,各溶液体系中荧光强度高低顺序依次为:WPI>G150>G67。疏水性指数的测定进一步说明两种不同分子量的葡聚糖接入到蛋白质肽链中,对乳清分离蛋白的疏水性均有一定的屏蔽作用。 相似文献
75.
《合成通讯》2012,42(24):3510-3527
AbstractA series of novel indoline-(thio)urea were designed and prepared using indoline(s) as a new platform and tested as organocatalysts in the Michael and Morita–Baylis–Hillman reactions. Most of the compounds were found to be very active catalysts although they did not promote the enantioselectivity. As agents for the conversion of thiocarbonyl compounds into carbonyl compounds, potentials of PIFA and DDQ were also displayed. Furthermore, DFT calculations rationalized the experimentally observed non-enantioselectivity of the catalysts. 相似文献
76.
The covalent conjugates of cellulase from Aspergillus niger were prepared with various molar ratios by using dextran. The conjugate (nE/nD: 1/5) showed higher activity than purified enzyme at all temperatures after 1 h of incubation and its activity could also be measured at higher temperature. Also, this conjugate lost only 60% activity in 2 h at 70°C in comparison to the purified enzyme, which lost all its activity. In addition, conjugation protected cellulase against denaturation in the presence of sodium dodecylsulfate (residual activity of about 80%) and inactivation by air bubbles (residual activity of about 50% for 4 h). 相似文献
77.
Kazuki OsakamaMasaharu Sugiura Makoto Nakajima Shunsuke Kotani 《Tetrahedron letters》2012,53(32):4199-4201
An efficient method was developed for the enantioselective reductive aldol reaction of α,β-unsaturated ketones with aldehydes in the presence of a Lewis base catalyst; conjugate reduction using a tertiary amine and trichlorosilyl triflate, followed by an aldol reaction with BINAP dioxide (BINAPO) as an organocatalyst, gave the corresponding product in high yield with high stereoselectivity. 相似文献
78.
79.
Given an optimization problem with a composite of a convex and componentwise increasing function with a convex vector function as objective function, by means of the conjugacy approach based on the perturbation theory, we determine a dual to it. Necessary and sufficient optimality conditions are derived using strong duality. Furthermore, as special case of this problem, we consider a location problem, where the “distances” are measured by gauges of closed convex sets. We prove that the geometric characterization of the set of optimal solutions for this location problem given by Hinojosa and Puerto in a recently published paper can be obtained via the presented dual problem. Finally, the Weber and the minmax location problems with gauges are given as applications. 相似文献
80.
Triphenylphosphine and tributylphosphine are excellent catalysts for Michael additions. Many β-dicarbonyl compounds and electron-poor olefins, including sterically demanding partners, react successfully. The Michael addition catalyzed by phosphines deserves attention in its own right as a useful synthetic method. 相似文献