全文获取类型
收费全文 | 2363篇 |
免费 | 279篇 |
国内免费 | 446篇 |
专业分类
化学 | 2052篇 |
晶体学 | 20篇 |
力学 | 58篇 |
综合类 | 53篇 |
数学 | 719篇 |
物理学 | 186篇 |
出版年
2024年 | 4篇 |
2023年 | 20篇 |
2022年 | 28篇 |
2021年 | 70篇 |
2020年 | 129篇 |
2019年 | 89篇 |
2018年 | 71篇 |
2017年 | 78篇 |
2016年 | 112篇 |
2015年 | 107篇 |
2014年 | 111篇 |
2013年 | 209篇 |
2012年 | 131篇 |
2011年 | 138篇 |
2010年 | 113篇 |
2009年 | 151篇 |
2008年 | 153篇 |
2007年 | 159篇 |
2006年 | 145篇 |
2005年 | 124篇 |
2004年 | 110篇 |
2003年 | 109篇 |
2002年 | 87篇 |
2001年 | 73篇 |
2000年 | 77篇 |
1999年 | 64篇 |
1998年 | 78篇 |
1997年 | 63篇 |
1996年 | 47篇 |
1995年 | 45篇 |
1994年 | 32篇 |
1993年 | 28篇 |
1992年 | 18篇 |
1991年 | 30篇 |
1990年 | 12篇 |
1989年 | 11篇 |
1988年 | 5篇 |
1987年 | 7篇 |
1986年 | 7篇 |
1985年 | 9篇 |
1984年 | 4篇 |
1983年 | 2篇 |
1982年 | 4篇 |
1981年 | 2篇 |
1980年 | 2篇 |
1979年 | 3篇 |
1978年 | 4篇 |
1976年 | 3篇 |
1974年 | 2篇 |
1973年 | 2篇 |
排序方式: 共有3088条查询结果,搜索用时 62 毫秒
1.
《Mendeleev Communications》2022,32(6):777-779
The reactions of aryllithium reagents o-LiC6H4CH2NR2 with (MeO)2CO afford two new tris(aryl)carbinols bearing pendant-NR2 donor groups in the side chain [o-R NCH C H ] COH [R = Me, R + R = (CH) ]. These alcohols feature helical chirality due to differently inclined aromatic fragments and are presented in a crystalline cell as two M and P enantiomers. Carbinol (R = Me) readily reacts with (Me3SiCH2)3Sc(THF)2 to give a scandium bis(alkyl) complex [(o-C6H4CH2NMe2)3CO]Sc(CH2SiMe3)2 featuring rigid binding of the alkoxy anion through a κ1-O, κ2-N chelating coordination mode 相似文献
2.
Edward G. Sheetz Zhao Zhang Alyssa Marogil Minwei Che Dr. Maren Pink Dr. Veronica Carta Prof. Dr. Krishnan Raghavachari Prof. Dr. Amar H. Flood 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(60):e202201584
The recognition of boron compounds is well developed as boronic acids but untapped as organotrifluoroborate anions (R−BF3−). We are exploring the development of these and other designer anions as anion-recognition motifs by considering them as substituted versions of the parent inorganic ion. To this end, we demonstrate strong and reliable binding of organic trifluoroborates, R−BF3−, by cyanostar macrocycles that are size-complementary to the inorganic BF4− progenitors. We find that recognition is modulated by the substituent's sterics and that the affinities are retained using the common K+ salts of R−BF3− anions. 相似文献
3.
The Effect of the Spacer of Bis(biurea) Ligands on the Structure of A2L3‐type (A=anion) Phosphate Complexes 下载免费PDF全文
Prof. Biao Wu Dr. Shaoguang Li Prof. Yibo Lei Prof. Huaiming Hu Dr. Nader de Sousa Amadeu Prof. Dr. Christoph Janiak Dr. Jennifer S. Mathieson Dr. De‐Liang Long Prof. Leroy Cronin Prof. Xiao‐Juan Yang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(6):2588-2593
By tuning the length and rigidity of the spacer of bis(biurea) ligands L, three structural motifs of the A2L3 complexes (A represents anion, here orthophosphate PO43?), namely helicate, mesocate, and mono‐bridged motif, have been assembled by coordination of the ligand to phosphate anion. Crystal structure analysis indicated that in the three complexes, each of the phosphate ions is coordinated by twelve hydrogen bonds from six surrounding urea groups. The anion coordination properties in solution have also been studied. The results further demonstrate the coordination behavior of phosphate ion, which shows strong tendency for coordination saturation and geometrical preference, thus allowing for the assembly of novel anion coordination‐based structures as in transition‐metal complexes. 相似文献
4.
Robin F. Weitkamp Beate Neumann Hans‐Georg Stammler Berthold Hoge 《Angewandte Chemie (International ed. in English)》2020,59(14):5494-5499
We report on the first examples of isolated silanol–silanolate anions, obtained by utilizing weakly coordinating phosphazenium counterions. The silanolate anions were synthesized from the recently published phosphazenium hydroxide hydrate salt with siloxanes. The silanol–silanolate anions are postulated intermediates in the hydroxide‐mediated polymerization of aryl and alkyl siloxanes. The silanolate anions are strong nucleophiles because of the weakly coordinating character of the phosphazenium cation, which is perceptible in their activity in polysiloxane depolymerization. 相似文献
5.
烷基硫酸盐表面张力的量子化学研究 总被引:1,自引:0,他引:1
用AMl量子化学计算法优化了十三烷基硫酸根阴离子和——CH3在不同取代位的十二烷基硫酸根阴离子的几何构型,得到最优构型时最高占据分子轨道能级EHOMO、最低空轨道能级ELUMO、电子能量Eele和偶极矩μ等数据.将这些电子结构数据分别与表面张力相拟合,得到很好的相关性。文中讨论了——CH3在不同位置取代对表面张力的影响。 相似文献
6.
本文讨论了每个元都有幂等元作为右单位元的左消半群与幂单半群N的Schuzenberger积M◇N的ρ类,证明了这种半群M与N的Schuzenberger积M◇N的ρ类是右E一半适合半群和弱E-headged半群. 相似文献
7.
Ernesto Quesada 《Tetrahedron letters》2004,45(25):4877-4881
The first syntheses of newly isolated members of the Preussomerin family, Preussomerins K and L, are reported. Key steps include the functionalisation of a 2-arylacetal anion, one-pot Friedel-Crafts cyclisation-deprotection and reductive opening of epoxides. 相似文献
8.
Cyclic Hypomonotonicity,Cyclic Submonotonicity,and Integration 总被引:9,自引:1,他引:8
Rockafellar has shown that the subdifferentials of convex functions are always cyclically monotone operators. Moreover, maximal cyclically monotone operators are necessarily operators of this type, since one can construct explicitly a convex function, which turns out to be unique up to a constant, whose subdifferential gives back the operator. This result is a cornerstone in convex analysis and relates tightly convexity and monotonicity. In this paper, we establish analogous robust results that relate weak convexity notions to corresponding notions of weak monotonicity, provided one deals with locally Lipschitz functions and locally bounded operators. In particular, the subdifferentials of locally Lipschitz functions that are directionally hypomonotone [respectively, directionally submonotone] enjoy also an additional cyclic strengthening of this notion and in fact are maximal under this new property. Moreover, every maximal cyclically hypomonotone [respectively, maximal cyclically submonotone] operator is always the Clarke subdifferential of some directionally weakly convex [respectively, directionally approximately convex] locally Lipschitz function, unique up to a constant, which in finite dimentions is a lower C2 function [respectively, a lower C1 function]. 相似文献
9.
H. R. Ebrahimi-Vishki M. A. Pourabdollah 《Proceedings of the American Mathematical Society》1997,125(7):2171-2174
The purpose of this paper is to introduce an algebra of functions on a semitopological semigroup and to study these functions from the point of view of universal semigroup compactification. We show that the corresponding semigroup compactification of this algebra is universal with respect to the property of being a nilpotent group.
10.
Rafał Bocian Thorsten Holm Andrzej Skowroński 《Central European Journal of Mathematics》2004,2(1):67-75
Auslander’s representation dimension measures how far a finite dimensional algebra is away from being of finite representation
type. In [1], M. Auslander proved that a finite dimensional algebra A is of finite representation type if and only if the representation dimension of A is at most 2. Recently, R. Rouquier proved that there are finite dimensional algebras of an arbitrarily large finite representation
dimension. One of the exciting open problems is to show that all finite dimensional algebras of tame representation type have
representation dimension at most 3. We prove that this is true for all domestic weakly symmetric algebras over algebraically
closed fields having simply connected Galois coverings. 相似文献