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81.
综述了含硅路易斯酸R3SiX [X=I, OTf, NTf2, C(C6F5)Tf2等]和(R3SiX+MLn)的发展、合成以及它们在有机合成中的应用. 它们主要被用来催化Aldol, 烯丙基化, Diels-Alder, Ene和Friedel-Crafts等反应. 催化剂的用量一般为0.5~20 mol%, 并随着催化剂的活性不同, 反应产率从一般到良好不等. 催化剂活性顺序为R3SiNTf2>R3SiOTf, (R3SiX+MLn)>R3SiX. 也对近年出现的手性含硅路易斯酸的发展和应用进行了概述, 当手性双-(多氟甲磺酰)-亚胺基硅烷用于催化环戊二烯和丙烯酸甲酯的Diels-Alder反应时, ee值高达54%. 相似文献
82.
Static second-order nonlinear optical effects of amino acid zinc(Ⅱ) porphyrins 1, 2,3 and 4 were calculated by the TDHF/PM3 method based on the molecular structures optim.zed at the semiempirical PM3 quantum chemistry level, showing due to the cancellation of symmetric center, these amino acid zinc(H) porphyrins exhibit second order nonlinear optical response. The analysis of β components indicated that these amino acid zinc(Ⅱ) porphyrins are of multipolarizabilities, and they may be ascribed as the “mixture” of octupolar and dipoar molecules with ||βJ=3||/||βJ=1||≈5. It is found that there are no significant differences between the static β values of non-chiral and chiral amino acid zinc(Ⅱ) porphyrins. However, the βxyz component, which is quite important to quadratic macroscopic X^(2) susceptibility of chiral material, is increased significantly with the increase of side chain group of amino acids. 相似文献
83.
84.
Kyoko Nozaki 《Journal of polymer science. Part A, Polymer chemistry》2004,42(2):215-221
Two examples of asymmetric alternating copolymerization, (1) the alternating copolymerization of α‐olefins (monosubstituted ethenes) with carbon monoxide and (2) the alternating copolymerization of meso‐epoxide with carbon dioxide, are described, and the meaning of chirality in polymer synthesis is emphasized. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 215–221, 2004 相似文献
85.
A new chiral aminophosphine ligand 6,6′-dimethoxy-2,2′-bis(diphenylphosphinoamino)biphenyl(DMBDPPABP) was prepared and its rhodium complex was found to be an effective catalyst for the asymmetric hydrogenation of amidoacrylic acid and its dervatives.The effects of solvent and reaction temperature on enantioselectivity were also studied. 相似文献
86.
87.
Boris GuintchinStefan Bienz 《Tetrahedron》2003,59(38):7527-7533
Enantiomerically enriched (E)- and (Z)-configured α-acetoxyallylsilanes have been prepared starting from a chiral acylsilane bearing an asymmetric unit at the silicon portion. Treatment of these compounds with organocuprates afforded the respective vinylogous substitution products in high yields and high stereoselectivities. The transformations proceed essentially by complete anti attack of the nucleophiles to the allylic acetates and predominantly via transition states leading to the (E)-configured vinylsilane products. By the proper choice of the double bond geometry in the starting material, the configuration of the newly formed stereogenic center can be controlled. The method represents a new and flexible entry into chiral vinylsilanes that can be used for subsequent transformations. As an example, the α,β-unsaturated γ-chiral, naturally occurring ketone (S)-(+)-bishomomanicone was synthesized with this method, which represents the first synthetic access to this compound. 相似文献
88.
用两种相似多糖类手性固定相拆分阿托品外消旋对映体的比较 总被引:1,自引:0,他引:1
分别涂敷纤维素-三(3,5-二甲基苯基氨基甲酸酯)(CDMPC)与直链淀粉-三(3,5-二甲基苯基氰基甲酸酯)(ADMPC)于自制的球形氨丙基硅胶上,制备了两种多糖类手性崮定相。用高效液相色谱法(HPLC)在正相条件下,用两种固定相直接拆分了阿托品(atmpine)外消旋体、在正己烷中加入了不同的醇类改性剂对阿托品进行拆分,并优化了流动相中醇类改性剂的比例:结果发现,阿托品在CDMPC固定相上可以得到基线拆分,而在ADMPC固定相上只能得到部分拆分。 相似文献
89.
在自制的硅基纤维素-三(3,5-二甲基苯基氨基甲酸酯)高效液相色谱手性固定相上(HPLC-CSP),优化了1-(6'-甲氧基萘)乙醇氢酯基化反应产物-萘普生甲酯手性分离的条件,测定了相应的一系列不对称氢酯基化反应产物的对映体过剩值(e.e.值)。结果表明,在CDMPC-CSP手性柱上用HPLC测定此类不对称催化反应的光学产率,评价催化剂体系的手性选择是一种非常理想的方法。 相似文献
90.
《Surface and interface analysis : SIA》2003,35(12):991-997
In x‐ray photoelectron spectroscopy (XPS) the Auger parameter is often used to study the electronic properties of elements, particularly in insulator materials, because this parameter is assumed to be independent of charging effects. In this paper we report on subtle differences in sample structure and experimental conditions for which the sample potential may not remain constant during the measurements for some spectrometers or experimental arrangements; for such conditions the Auger parameter is not independent of charging. We compare a series of measurements with insulating plate substrates of Al2O3 on which different amounts of SnO2 and Au were deposited. X‐ray photoelectron spectra were collected for different conditions of the sample that was placed either grounded or left floating on a metallic sample holder during measurement. It is found that the Auger parameter is independent of the experimental conditions for Au but substantial differences were found for deposited SnO2. Surprisingly, measurement artifacts due to charging appeared in the Auger parameter for Sn when the sample holder was grounded but not when it was left floating. In the grounded samples differences up to 0.6 eV in the Auger parameter for Sn were found with respect to the actual value of this parameter measured with substrates where charging effects were not significant. Because no differences in peak broadening have been observed under different measurement conditions, it has been assumed that the shift was not caused by a conventional differential charging phenomenon. Considering the different response of the substrate and the deposited layer on stabilizing the charge when the sample is grounded, we have worked out a possible explanation to account for the observed artifacts. Instrumental specifications should be optimized very carefully, especially if (as here) relatively high charging shifts point to a non‐optimum self‐biasing of the surface potential at the insulating samples. Copyright © 2003 John Wiley & Sons, Ltd. 相似文献