全文获取类型
收费全文 | 8070篇 |
免费 | 715篇 |
国内免费 | 758篇 |
专业分类
化学 | 5843篇 |
晶体学 | 92篇 |
力学 | 306篇 |
综合类 | 77篇 |
数学 | 1264篇 |
物理学 | 1961篇 |
出版年
2023年 | 112篇 |
2022年 | 180篇 |
2021年 | 212篇 |
2020年 | 265篇 |
2019年 | 285篇 |
2018年 | 224篇 |
2017年 | 239篇 |
2016年 | 302篇 |
2015年 | 340篇 |
2014年 | 386篇 |
2013年 | 607篇 |
2012年 | 611篇 |
2011年 | 625篇 |
2010年 | 459篇 |
2009年 | 432篇 |
2008年 | 556篇 |
2007年 | 466篇 |
2006年 | 467篇 |
2005年 | 347篇 |
2004年 | 297篇 |
2003年 | 199篇 |
2002年 | 227篇 |
2001年 | 122篇 |
2000年 | 114篇 |
1999年 | 97篇 |
1998年 | 74篇 |
1997年 | 69篇 |
1996年 | 70篇 |
1995年 | 48篇 |
1994年 | 64篇 |
1993年 | 53篇 |
1992年 | 49篇 |
1991年 | 33篇 |
1990年 | 35篇 |
1989年 | 56篇 |
1988年 | 46篇 |
1987年 | 32篇 |
1985年 | 41篇 |
1984年 | 42篇 |
1983年 | 39篇 |
1982年 | 50篇 |
1981年 | 46篇 |
1980年 | 49篇 |
1979年 | 40篇 |
1978年 | 49篇 |
1977年 | 55篇 |
1976年 | 43篇 |
1975年 | 34篇 |
1974年 | 36篇 |
1973年 | 44篇 |
排序方式: 共有9543条查询结果,搜索用时 46 毫秒
131.
对近期发展的固体圆二色(CD)光谱测试方法进行了概述、评价和比较, 着重探讨了“浓度效应”的存在使固体CD光谱失真的原因. 通过对本课题组和其他作者已报道的四种化合物的固体CD谱再测试的反思, 强调了依手性化合物的手性光谱学性质不同, 根据浓度梯度实验选择其合适测试浓度的必要性. 对固有手性的阻转异构化合物(S)-1,1'-联二萘酚(S-BINOL)进行了成膜法固体CD谱浓度梯度测试, 发现所得固体薄膜CD谱中也存在着“浓度效应” 相似文献
132.
对近期发展的固体圆二色(CD)光谱测试方法进行了概述、评价和比较, 着重探讨了“浓度效应”的存在使固体CD光谱失真的原因. 通过对本课题组和其他作者已报道的四种化合物的固体CD谱再测试的反思, 强调了依手性化合物的手性光谱学性质不同, 根据浓度梯度实验选择其合适测试浓度的必要性. 对固有手性的阻转异构化合物(S)-1,1'-联二萘酚(S-BINOL)进行了成膜法固体CD谱浓度梯度测试, 发现所得固体薄膜CD谱中也存在着“浓度效应” 相似文献
133.
对近期发展的固体圆二色(CD)光谱测试方法进行了概述、评价和比较, 着重探讨了“浓度效应”的存在使固体CD光谱失真的原因. 通过对本课题组和其他作者已报道的四种化合物的固体CD谱再测试的反思, 强调了依手性化合物的手性光谱学性质不同, 根据浓度梯度实验选择其合适测试浓度的必要性. 对固有手性的阻转异构化合物(S)-1,1'-联二萘酚(S-BINOL)进行了成膜法固体CD谱浓度梯度测试, 发现所得固体薄膜CD谱中也存在着“浓度效应” 相似文献
134.
Wilkie GD Elliott GI Blagg BS Wolkenberg SE Soenen DR Miller MM Pollack S Boger DL 《Journal of the American Chemical Society》2002,124(38):11292-11294
The scope of intramolecular Diels-Alder and a novel tandem Diels-Alder/1,3-dipolar cycloaddition cascade of 1,3,4-oxadiazoles is disclosed. In the cases examined, the tandem cycloadditions construct three new rings with formation of four new C-C bonds and set all six stereocenters about a central six-membered ring in a single step including three contiguous and four total quaternary centers without a trace of a second diastereomer. 相似文献
135.
The source of the effect of N-alkylation on the redox properties of Ni(II/I) and Cr(III/II) cyclam complexes has been investigated using DFT calculations. The structures of the anhydrous and hydrated complexes were optimized in the gas phase, and single point calculations were performed in a polarized continuum. The main results are the following: the decrease in outer sphere solvation upon N-alkylation is the major source of the relative stabilization of the lower oxidation state complexes by the tertiary amine ligands; tertiary amine nitrogen donors are stronger sigma-donors than the secondary amines, as predicted from the inductive effect of alkyls; steric strain elongates the metal-nitrogen bonds in the tertiary complexes and decreases the ligand strain energies; and the site of water binding to the complexes differs because of their different electronic structures (i.e., in the Ni complexes, the water molecules bind to the M[bond]N[bond]H sites, whereas in the Cr complexes they bind to the central metal cation). Outer sphere hydrogen bonding of water to the ligands in the coordination sphere lowers the ionization potentials by charge delocalization. 相似文献
136.
137.
In noncommutative probability theory independence can be based on free products instead of tensor products. This yields a highly noncommutative theory: free probability theory (for an introduction see [9]). The analogue of entropy in the free context was introduced by the second named author in [8]. Here we show that Shannon's entropy power inequality ([6, 1]) has an analogue for the free entropy (X) (Theorem 2.1).The free entropy, consistent with Boltzmann's formulaS=klogW, was defined via volumes of matricial microstates. Proving the free entropy power inequality naturally becomes a geometric question.Restricting the Minkowski sum of two sets means to specify the set of pairs of points which will be added. The relevant inequality, which holds when the set of addable points is sufficiently large, differs from the Brunn-Minkowski inequality by having the exponent 1/n replaced by 2/n. Its proof uses the rearrangement inequality of Brascamp-Lieb-Lüttinger ([2]). Besides the free entropy power inequality, note that the inequality for restricted Minkowski sums may also underlie the classical Shannon entropy power inequality (see 3.2 below).Research supported in part by grants from the National Science Foundation. 相似文献
138.
Gribble GW Switzer FL Bushweller JH Jewett JG Brown JH Dion JL Bushweller CH Byrn MP Strouse CE 《The Journal of organic chemistry》1996,61(13):4319-4327
The (1)H NMR spectra of 10-benzyl-9,11-diphenyl-10-azatetracyclo[6.3.0.0.(4,11)0.(5,9)]undecane (BnPh(2)()) and 10-methyl-9,11-diphenyl-10-azatetracyclo[6.3.0.0.(4,11)0.(5,9)]undecane (MePh(2)()) decoalesce due to slowing inversion at nitrogen and to slowing isolated bridgehead phenyl rotation. The high nitrogen inversion barriers in MePh(2)() (DeltaG() = 12.2 +/- 0.1 kcal/mol at 250 K) and BnPh(2)() (DeltaG() = 10.6 +/- 0.1 kcal/mol at 215 K) are typical of tertiary amines in which at least one C-N-C bond angle is constrained to a small value. Compared to the minuscule rotation barriers about sp(2)-sp(3) carbon-carbon bonds in simple molecular systems, the bridgehead phenyl rotation barriers in MePh(2)() (DeltaG() = 9.8 +/- 0.1 kcal/mol at 210 K) and BnPh(2)() (DeltaG() = 9.8 +/- 0.1 kcal/mol at 210 K) are unusually high. Molecular mechanics calculations (MMX force field) suggest that the origin of the high phenyl rotation barriers lies in the close passage of an o-phenyl proton and a methyl (or benzylmethylene) proton in the transition state. BnPh(2)() crystallized from hexane as white needles in the monoclinic system Pn. Unit cell dimensions are as follows: a = 12.198(1) ?, b = 6.1399(6) ?, c = 14.938(2) ?, beta = 107.470(4) degrees, V = 1067.1(2) ?(3), Z = 2. In the crystal molecular structure, the imine bridge CNC bond angle in BnPh(2)() is constrained to a small value (96 degrees ). The benzylic phenyl group is oriented gauche to the nitrogen lone pair. 相似文献
139.
140.
Y. A. Gordon V. Jakšić S. Molčanov B. Simon 《Communications in Mathematical Physics》1993,157(1):23-50
We investigate spectral properties of random Schrödinger operators H = - + n()(1 + |n|) acting onl
2(Z
d), where n are independent random variables uniformly distributed on [0, 1].Research partially supported by a Sloan Doctoral Dissertation Fellowship and NSERC under grant OGP-0007901Research partially supported by NSF grant DMS-9101716 相似文献