首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   301篇
  免费   7篇
  国内免费   2篇
化学   150篇
晶体学   1篇
力学   8篇
数学   99篇
物理学   52篇
  2023年   2篇
  2021年   2篇
  2020年   4篇
  2019年   4篇
  2018年   5篇
  2017年   5篇
  2016年   2篇
  2015年   4篇
  2014年   6篇
  2013年   18篇
  2012年   3篇
  2011年   7篇
  2010年   9篇
  2009年   11篇
  2008年   20篇
  2007年   12篇
  2006年   16篇
  2005年   16篇
  2004年   17篇
  2003年   15篇
  2002年   12篇
  2000年   7篇
  1999年   5篇
  1998年   5篇
  1997年   6篇
  1996年   7篇
  1995年   10篇
  1994年   5篇
  1993年   8篇
  1992年   3篇
  1991年   3篇
  1989年   2篇
  1987年   2篇
  1985年   3篇
  1984年   4篇
  1983年   3篇
  1982年   3篇
  1981年   8篇
  1980年   2篇
  1979年   2篇
  1978年   2篇
  1977年   7篇
  1976年   4篇
  1974年   4篇
  1973年   4篇
  1970年   1篇
  1967年   2篇
  1966年   2篇
  1960年   1篇
  1941年   1篇
排序方式: 共有310条查询结果,搜索用时 15 毫秒
1.
Asymmetric platinum donor–acceptor complexes [(pimp)Pt(Q2−)] are presented in this work, in which pimp=[(2,4,6-trimethylphenylimino)methyl]pyridine and Q2−=catecholate-type donor ligands. The properties of the complexes are evaluated as a function of the donor ligands, and correlations are drawn among electrochemical, optical, and theoretical data. Special focus has been put on the spectroelectrochemical investigation of the complexes featuring sulfonyl-substituted phenylendiamide ligands, which show redox-induced linkage isomerism upon oxidation. Time-dependent density functional theory (TD-DFT) as well as electron flux density analysis have been employed to rationalize the optical spectra of the complexes and their reactivity. Compound 1 ([(pimp)Pt(Q2−)] with Q2−=3,5-di-tert-butylcatecholate) was shown to be an efficient photosensitizer for molecular oxygen and was subsequently employed in photochemical cross-dehydrogenative coupling (CDC) reactions. The results thus display new avenues for donor–acceptor systems, including their role as photocatalysts for organic transformations, and the possibility to introduce redox-induced linkage isomerism in these compounds through the use of sulfonamide substituents on the donor ligands.  相似文献   
2.
La3B6O13(OH) was obtained by a high-pressure/high-temperature experiment at 6 GPa and 1673 K. The compound crystallizes in the space group P21 (no. 4) with the lattice parameters a=4.785(2), b=12.880(4), c=7.433(3) Å, and β=90.36(10)°, and is built up of corner- as well as edge-sharing BO4 tetrahedra. It represents the first acentric high-pressure borate containing these B2O6 entities. The compound develops borate layers of „sechser“-rings with the La3+ cations positioned between the layers. Single-crystal and powder X-ray diffraction, vibrational and MAS NMR spectroscopy, second-harmonic generation (SHG) and thermoanalytical measurements, as well as computational methods were used to affirm the proposed structure and the B2O6 entities.  相似文献   
3.
As a consequence of the static Jahn-Teller effect of the 5E ground state of MnIII in cubic structures with octahedral parent geometries, their octahedral coordination spheres become distorted. In the case of six fluorido ligands, [MnF6]3− anions with two longer and four shorter Mn−F bonds making elongated octahedra are usually observed. Herein, we report the synthesis of the compound K3[MnF6] through a high-temperature approach and its crystallization by a high-pressure/high-temperature route. The main structural motifs are two quasi-isolated, octahedron-like [MnF6]3− anions of quite different nature compared to that met in ideal octahedral MnIII Jahn-Teller systems. Owing to the internal electric field of Ci symmetry dominated by the next-neighbour K+ ions acting on the MnIII sites, both sites, the pseudo-rhombic (site 1) and the pseudo-tetragonally elongated (site 2) [MnF6]3− anions are present in K3[MnF6]. The compound was characterized by single-crystal and powder X-ray diffraction, and magnetometry as well as by FTIR, Raman, and ligand field spectroscopy. A theoretical interpretation of the electronic structure and molecular geometry of the two Mn sites in the lattice is given by using a vibronic coupling model with parameters adjusted from multireference ab-initio cluster calculations.  相似文献   
4.
5.
1‐n‐Butyl‐2,3‐dimethylimidazolium (BMMI) ionic liquids (ILs) associated with different anions undergo H/D exchange preferentially at 2‐Me group of the imidazolium in deuterated solvents. This process is mainly related to the existence of ion pairs rather than the anion basicity. The H/D exchange occurs in solvents (CDCl3 and MeCN for instance) in which intimate contact ion pairs are present and the anion possesses a labile H in its structure, such as hydrogen carbonate and prolinate. In D2O, separated ion pairs are formed and the H/D exchange does not occur. A plausible catalytic cycle is that the IL behaves as a neutral base in the course of all H/D exchange processes. NMR experiments, density functional calculations, and molecular dynamics simulations corroborate these hypotheses.  相似文献   
6.
The molecular chaperone Hsp90 undergoes an ATP‐driven cycle of conformational changes in which large structural rearrangements precede ATP hydrolysis. Well‐established small‐molecule inhibitors of Hsp90 compete with ATP‐binding. We wondered whether compounds exist that can accelerate the conformational cycle. In a FRET‐based screen reporting on conformational rearrangements in Hsp90 we identified compounds. We elucidated their mode of action and showed that they can overcome the intrinsic inhibition in Hsp90 which prevents these rearrangements. The mode of action is similar to that of the co‐chaperone Aha1 which accelerates the Hsp90 ATPase. However, while the two identified compounds influence conformational changes, they target different aspects of the structural transitions. Also, the binding site determined by NMR spectroscopy is distinct. This study demonstrates that small molecules are capable of triggering specific rate‐limiting transitions in Hsp90 by mechanisms similar to those in protein cofactors.  相似文献   
7.
The present paper proposes a new strategy for probabilistic (often called model-based) clustering. It is well known that local maxima of mixture likelihoods can be used to partition an underlying data set. However, local maxima are rarely unique. Therefore, it remains to select the reasonable solutions, and in particular the desired one. Credible partitions are usually recognized by separation (and cohesion) of their clusters. We use here the p values provided by the classical tests of Wilks, Hotelling, and Behrens–Fisher to single out those solutions that are well separated by location. It has been shown that reasonable solutions to a clustering problem are related to Pareto points in a plot of scale balance vs. model fit of all local maxima. We briefly review this theory and propose as solutions all well-fitting Pareto points in the set of local maxima separated by location in the above sense. We also design a new iterative, parameter-free cutting plane algorithm for the multivariate Behrens–Fisher problem.  相似文献   
8.
9.
10.
We consider a continuous time random walk X in a random environment on ?+ such that its potential can be approximated by the function V:?+→? given by $V(x)=\sigma W(x) -\frac {b}{1-\alpha}x^{1-\alpha}$ where σW a Brownian motion with diffusion coefficient σ>0 and parameters b, α are such that b>0 and 0<α<1/2. We show that P-a.s. (where P is the averaged law) $\lim_{t\to\infty} \frac{X_{t}}{(C^{*}(\ln\ln t)^{-1}\ln t)^{\frac{1}{\alpha}}}=1$ with $C^{*}=\frac{2\alpha b}{\sigma^{2}(1-2\alpha)}$ . In fact, we prove that by showing that there is a trap located around $(C^{*}(\ln\ln t)^{-1}\ln t)^{\frac{1}{\alpha}}$ (with corrections of smaller order) where the particle typically stays up to time t. This is in sharp contrast to what happens in the “pure” Sinai’s regime, where the location of this trap is random on the scale ln2 t.  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号