全文获取类型
收费全文 | 5416篇 |
免费 | 673篇 |
国内免费 | 766篇 |
专业分类
化学 | 3900篇 |
晶体学 | 45篇 |
力学 | 461篇 |
综合类 | 37篇 |
数学 | 665篇 |
物理学 | 1747篇 |
出版年
2024年 | 11篇 |
2023年 | 93篇 |
2022年 | 194篇 |
2021年 | 225篇 |
2020年 | 221篇 |
2019年 | 212篇 |
2018年 | 170篇 |
2017年 | 184篇 |
2016年 | 215篇 |
2015年 | 211篇 |
2014年 | 241篇 |
2013年 | 374篇 |
2012年 | 438篇 |
2011年 | 449篇 |
2010年 | 305篇 |
2009年 | 265篇 |
2008年 | 325篇 |
2007年 | 270篇 |
2006年 | 255篇 |
2005年 | 242篇 |
2004年 | 186篇 |
2003年 | 200篇 |
2002年 | 177篇 |
2001年 | 146篇 |
2000年 | 132篇 |
1999年 | 146篇 |
1998年 | 102篇 |
1997年 | 106篇 |
1996年 | 116篇 |
1995年 | 97篇 |
1994年 | 64篇 |
1993年 | 73篇 |
1992年 | 57篇 |
1991年 | 59篇 |
1990年 | 50篇 |
1989年 | 40篇 |
1988年 | 32篇 |
1987年 | 22篇 |
1986年 | 21篇 |
1985年 | 20篇 |
1984年 | 16篇 |
1983年 | 13篇 |
1982年 | 14篇 |
1981年 | 9篇 |
1980年 | 8篇 |
1976年 | 8篇 |
1975年 | 6篇 |
1973年 | 7篇 |
1972年 | 5篇 |
1970年 | 4篇 |
排序方式: 共有6855条查询结果,搜索用时 15 毫秒
1.
A lithium(I) coordination polymer has been formed from LiClO4 and the 2,2′‐bipyrimidine (bpym) ligand in which each square pyramidal lithium(I) atom is coordinated in the basal plane by four nitrogen donor atoms derived from two bpym ligands and one water molecule at the apical position. These are connected into a layer structure via hydrogen‐bonding interactions involving the perchlorate anions. Copyright © 2004 John Wiley & Sons, Ltd. 相似文献
2.
A novel mixed sol method was developed for the preparation of supported catalysts. Analyses by means of XRD and BET show that a 40%AgBiVMoO/γ-Al2O3 catalyst prepared by this method possessed high specific surface area and high dispersion of the active phase. As a result, high acrylic acid selectivity of 8.5% was obtained when the catalyst was used in the reaction of propane partial oxidation to acrylic acid in a fixed-bed reactor. 相似文献
3.
[reaction: see text] A catalyst for enolate formation was designed that incorporates an amine base along with a thiourea to bind to the oxygen atom of the substrate and enolate through hydrogen bonding. A computational model of the transition state was developed in which the thiourea (modeled initially as a urea) and amine were separate molecules. This model and models incorporating one or two methanol molecules in place of the urea showed an out-of-plane hydrogen bond, apparently to the carbonyl pi-bond, in addition to an in-plane hydrogen bond to an unshared electron pair. In contrast, optimized complexes of the ketone and the fully formed enolate showed only in-plane hydrogen bonding. The transition state model with the urea and amine was used to define a database search with the computer program CAVEAT to identify structures suitable for linking the amine and urea/thiourea moieties in the transition state. On the basis of a group of structures identified from this search, a flexible but conformationally biased linker was designed to connect the two catalytic moieties. The molecule having the amine and thiourea moieties connected by this linker was synthesized and was shown to catalyze proton exchange between methanol and deuterated acetone. The catalyst was about 5-fold more efficient than the amine and thiourea as separate molecules and relative to a similar but less conformationally biased catalyst. 相似文献
4.
Photoinduced shape deformation of colloidal spheres made of an amphiphilic azo polymer has been demonstrated in this work. The polymer contains the donor-and-acceptor-type azobenzene chromophores and can form uniform colloidal spheres by dropwise adding water into its THF solution. When the colloidal spheres obtained were exposed to the interfering p-polarized Ar+ laser beams (150 mW/cm2), the colloidal spheres changed to prolates (i.e., "rugby-balls"), "spindles", and finally "rods", depending on the irradiation times. The elongated direction of the spheres was observed to be the same as the polarization direction of the laser beam. The average major-to-minor ratio of the ellipsoids could be easily adjusted by controlling the irradiation time. The deformation effect observed in this work can offer a new way to prepare nonspherical colloids from colloidal spheres and will shed new light on the correlation between the photodriven shape deformation and photoinduced surface relief gratings for the same type of polymers. 相似文献
5.
Y. C. Tong 《Journal of heterocyclic chemistry》1980,17(2):381-382
Methods for the preparations of 1H-imidazo[4,5-b]pyrazine-2-carboxylic acid and derivatives are reported. 相似文献
6.
An approach to comparative analysis of chromatographic fingerprints for assuring the quality of botanical drugs 总被引:4,自引:0,他引:4
The present study was focused on developing the chemometric methods for analysis of the chromatographic fingerprint to control the quality of botanical drugs, which has gained attention in Asia and other countries. We developed a novel approach to generate a set of fingerprint features, called Fisher components (FCs) that were extracted from the chromatographic fingerprint. The method greatly reduces the dimensionality of the fingerprint vector, and the resulting FCs still retain most discriminatory information of the original fingerprint. Choosing an example of relevance to contemporary botanical drugs, we applied the FCs to a set of Shenmai injection samples. We successfully identified the manufacturers of the samples using two classifiers, linear discriminant analysis (LDA) and k-Nearest Neighbor (k-NN) based on the FCs. We also applied a similarity assessment together with the visual analysis using the FCs to exam the products from different manufacturers. We found that the lot-to-lot consistency of products can be accurately determined using the FCs. Finally, we demonstrated that the application of chemometric methods for chromatographic fingerprinting offers reliability to detect suspected fraud samples. In summary, we demonstrated that the presented approaches could be useful to determine the identity, consistency, and authenticity of Shenmai injection through chromatographic fingerprinting. The methods are equally applicable to other botanical drugs. 相似文献
7.
Chlorpromazine hydrochloride is proposed as an indicator for the microtitration of iron(II), arsenic(III), ascorbic acid and hydroquinone with 0.0005–0.001 N ceric sulphate; the indicator blanks are small. The colorimetric déterminations of μg quantities of cerium(lV) and arsenic(III) using the same reagent are also described. 相似文献
8.
相转移催化元素硫的歧化反应 总被引:1,自引:0,他引:1
本工作将相转移催化(PTC)应用于元素硫歧化反应,大大降低了反应温度,提高了反应速度。该反应被证实与熔态硫在水溶液中的歧化相同,即4S+6OH~-=2S~(2-)+S_2O_3~(2-)+3H_2O。比较了四乙基铵、四丁基铵、十六烷基三甲基铵和三辛基甲基铵四种相转移催化剂及四氯乙烯、二甲苯和四氯乙烷三种溶剂的影响。讨论了本体系相转移催化的证据。为改进以元素硫歧化反应为基础的提取冶金过程提供了依据。 相似文献
9.
We introduce the concept of a twisting cochain and a twisted complex associated to a coherent sheaf. For sheaves of submanifolds these twisted complexes are used to construct on cochain level the Grothendieck theory of dual class and Gysin map. These explicit constructions give, for instance, a local formula for dual class of higher codimensional submanifolds. We prove a refined version of the Hirzebruch Riemann Roch using such local formulas. We also prove a theorem on when global analytic intersection classes can be computed from first order geometric data. This theory will be used to prove the Holomorphic Lefschetz formula (in Part II) and the Hirzebruch Riemann Roch for analytic coherent sheaves.The first author is supported in part by NSF grants GP-36418X1 and MCS 76-08478. The second by MCS 75-07986 and Sonderforschungsbereich Theoretische Mathematik at Bonn University 相似文献
10.
Metathesis reactions between Ru(2)(DMBA)(4)Cl(2) (DMBA = N,N'-dimethylbenzamidinate) and MX (M = Na and K) yielded bis-adduct derivatives Ru(2)(DMBA)(4)X(2) (X = CN (1), N(3) (2), N(CN)(2) (3)). Metathesis reactions between Ru(2)(DMBA)(4)(NO(3))(2) and KI resulted in Ru(2)(DMBA)(4)I(2) (4). Compound 1 is diamagnetic, while compounds 2-4 are paramagnetic (S = 1). Both compounds 1 and 2 undergo two reversible one-electron processes, an oxidation and a reduction, while compound 3 features a quasireversible reduction. Single-crystal X-ray diffraction studies revealed that the Ru-Ru bond lengths are 2.4508(9), 2.3166(7), 2.304[1], and 2.328(1) A for compounds 1-4, respectively. Structural and electrochemical data clearly indicate that the axial ligands impart a significant influence on the electronic structures of diruthenium species. 相似文献