全文获取类型
收费全文 | 2987篇 |
免费 | 267篇 |
国内免费 | 14篇 |
专业分类
化学 | 2226篇 |
晶体学 | 14篇 |
力学 | 63篇 |
数学 | 420篇 |
物理学 | 545篇 |
出版年
2024年 | 2篇 |
2023年 | 53篇 |
2022年 | 75篇 |
2021年 | 119篇 |
2020年 | 172篇 |
2019年 | 186篇 |
2018年 | 83篇 |
2017年 | 69篇 |
2016年 | 201篇 |
2015年 | 151篇 |
2014年 | 167篇 |
2013年 | 203篇 |
2012年 | 277篇 |
2011年 | 270篇 |
2010年 | 159篇 |
2009年 | 130篇 |
2008年 | 193篇 |
2007年 | 163篇 |
2006年 | 150篇 |
2005年 | 105篇 |
2004年 | 67篇 |
2003年 | 36篇 |
2002年 | 31篇 |
2001年 | 25篇 |
2000年 | 19篇 |
1999年 | 14篇 |
1998年 | 15篇 |
1997年 | 5篇 |
1996年 | 12篇 |
1995年 | 10篇 |
1994年 | 9篇 |
1993年 | 7篇 |
1992年 | 10篇 |
1991年 | 5篇 |
1990年 | 5篇 |
1989年 | 2篇 |
1988年 | 4篇 |
1987年 | 8篇 |
1986年 | 7篇 |
1984年 | 3篇 |
1983年 | 3篇 |
1981年 | 7篇 |
1980年 | 2篇 |
1979年 | 4篇 |
1978年 | 5篇 |
1975年 | 4篇 |
1974年 | 4篇 |
1973年 | 3篇 |
1971年 | 2篇 |
1932年 | 2篇 |
排序方式: 共有3268条查询结果,搜索用时 85 毫秒
21.
We present a novel algorithm of constrained, overdamped dynamics to study the long-time properties of peptides, proteins, and related molecules. The constraints are applied to an all-atom model of the molecule by projecting out all components of the nonbonding interactions which tend to alter fixed bond lengths and angles. Because the overdamped dynamical equations are first order in time, the constraints are satisfied by inversion of a banded matrix at each timestep, which is computationally efficient. Thermal effects are included through a Langevin noise term in the equation of motion. Because high-frequency components of the motion have been eliminated, the timestep of the algorithm is determined by the nonbonding forces, which are two to three orders of magnitude weaker than the bonding forces. Using polyalanine as a test example, we demonstrate that trajectories simulating a microsecond of motion can be run about 103 times faster than an equivalent molecular dynamics simulation. © 1994 by John Wiley & Sons, Inc. 相似文献
22.
Salama Tarek A. El-Ahl Abdel-Aziz S. Khalil Abdel-Galil M. Girges Margret M. Lackner Bernd Steindl Christian Elmorsy Saad S. 《Monatshefte für Chemie / Chemical Monthly》2003,134(9):1241-1252
Summary. Several new 1-aryl-, aralkyl-, and heteroaryl-5-(4-phenylbuta-1,3-dienyl)tetrazole derivatives and annulated tetrazole derivatives were efficiently and regiospecifically prepared in nearly quantitative yield via a facile one step reaction of dienones with a combination of tetrachlorosilane and sodium azide in acetonitrile under mild conditions. A complete structure assignment of three representative examples of the tetrazoles was achieved by advanced 2D NMR measurements including COSY, TOCSY, HSQC, HMBC, NOESY, and ROESY experiments.Received March 17, 2003; accepted March 18, 2003
Published online July 28, 2003 相似文献
23.
Bernd?Lackner Yulita?Popova Christoph?Etzlstorfer Andrija A.?Smelcerovic Christian W.?Klampfl Heinz?FalkEmail author 《Monatshefte für Chemie / Chemical Monthly》2005,136(5):777-793
Summary. The syntheses of the two heterocyclically substituted title hypericin derivatives were achieved starting either from 6-benzothiazolyl-tri-O-methyl-6-demethylemodin or 6-benzoxazolyl-tri-O-methyl-6-demethylemodin. The use of microwave assisted synthesis for the preparation of these anthraquinone synthons and the chemical as well as photochemical properties of the corresponding unique hypericin derivatives, which might constitute new photodynamic therapy agents, are reported. The tautomeric and stereochemical aspects of these hypericin derivatives were investigated by means of semiempirical calculations (AM1). 相似文献
24.
Tarek A. Salama Abdel-Aziz S. El-Ahl Abdel-Galil M. Khalil Margret M. Girges Bernd Lackner Christian Steindl Saad S. Elmorsy 《Monatshefte für Chemie / Chemical Monthly》2003,20(5):1241-1252
Several new 1-aryl-, aralkyl-, and heteroaryl-5-(4-phenylbuta-1,3-dienyl)tetrazole derivatives and annulated tetrazole derivatives were efficiently and regiospecifically prepared in nearly quantitative yield via a facile one step reaction of dienones with a combination of tetrachlorosilane and sodium azide in acetonitrile under mild conditions. A complete structure assignment of three representative examples of the tetrazoles was achieved by advanced 2D NMR measurements including COSY, TOCSY, HSQC, HMBC, NOESY, and ROESY experiments. 相似文献
25.
Tarek A.?SalamaEmail author Bernd?Lackner Heinz?Falk 《Monatshefte für Chemie / Chemical Monthly》2003,134(8):1113-1119
Summary. An efficient synthesis of tri-O-methylemodin aldehyde was achieved via bromination of tri-O-methylemodin utilizing N-bromosuccinimide yielding the monobromo and dibromo derivatives. Sommelet reaction of the monobromomethyl derivative as well as hydrolysis of the dibromomethyl analog with aqueous silver nitrate afforded the protected aldehyde in good yield. Accordingly, both bromo derivatives can be used even when they are obtained as a mixture of the bromination reaction, which could not be controlled easily to yield the bromo products selectively. From the aldehyde the tri-O-methylemodin nitrile was prepared in a one-pot reaction using hydroxylamine-O-sulfonic acid.Received February 18, 2003; accepted March 3, 2003
Published online June 2, 2003 相似文献
26.
K. Lochner H. Bassler L. Sebastian G. Weiser G. Wegner V. Enkelmann 《Chemical physics letters》1981,78(2):366-370
The photoconductivity of DCHD displays a maximum near 3.6 eV coinciding with the maximum of the So → S1 absorption of the carbazole group. It is attributed to a sensitization involving charge transfer from the excited chromophore to the chain. The rate constant for non-radiative decay of the carbazole singlet due to energy transfer to the chain is 1.6 × 1013 s?1, and for charge transfer ≈ 3 × 1011 s?1. 相似文献
27.
28.
A set of highly preorganized pyrazolate-bridged dimanganese complexes L(Mn)MnX have been prepared and structurally characterized. They can be described as hybrid organometallic/Werner-type systems that consist of a low-spin CpMn(I)(CO)2 subunit (Mn1) and a proximate tripodal tetradentate {N4} binding pocket accommodating a high-spin Mn(II) ion (Mn2), with Mn...Mn distances of approximately 4.3 A and different coligands bound to Mn2. Density functional theory (DFT) calculations (both the hybrid B3LYP and the pure BP86 functionals and the all-electron basis sets 6-311G and 6-311G*) confirm that the valence alpha and beta Kohn-Sham molecular orbitals (MOs) of these mixed-valent Mn(I)Mn(II) compounds have predominant Mn(3d) character and an almost perfectly localized nature: all five unpaired electrons are essentially localized at the Werner-type Mn2, whereas Mn1 possesses an effective closed-shell structure with the MOs of highest energy centered there. One-electron oxidation occurs in a clean process at approximately E(1/2) = -0.6 V (versus ferrocene/ferrocinium), giving the low-spin/high-spin Mn(II)Mn(II) species. UV/vis and IR spectroelectrochemistry as well as a detailed theoretical analysis reveal that the redox process takes place with strict site control at the organometallic subunit, while it does not significantly influence the spin and charge distribution on the Werner-type site. Positions and shifts of the nu(C[triple bond]O) absorptions are largely reproduced by the DFT calculations. These systems thus represent an exceptional example of the effect the unsymmetry of a dinucleating ligand scaffold has on the spin and charge distribution in homobimetallic complexes and might offer interesting prospects for the study of the cooperative effects of bimetallic arrays. 相似文献
29.
Sebastian G. Spain Matthew I. Gibson Neil R. Cameron 《Journal of polymer science. Part A, Polymer chemistry》2007,45(11):2059-2072
Glycopolymers are receiving increasing interest due to their application in areas, such as glycomics, medicine, biotechnology, sensors, and separation science. Consequently, new methods for their synthesis are constantly being developed, with an increasing emphasis on the preparation of well-defined polymers and on the production of complex macromolecular architectures such as stars. This review covers recent developments in the synthesis of glycopolymers, with a particular emphasis on (i) the use of controlled radical polymerization to prepare well-defined glycopolymers from unprotected monomers and (ii) postpolymerization modification strategies using reactive polymer precursors (including “click” reactions). Recent work on the production of glycosylated polypeptides, which are under investigation as mimics of naturally occurring glycoproteins, is also included. The authors offer some suggestions as to future developments and remaining challenges in this topical area of polymer chemistry. © 2007 Wiley Periodicals, Inc. J Polym Sci PartA: Polym Chem45: 2059–2072, 2007 相似文献
30.
The three-dimensional structure of a complex tubular uranyl phosphonate, (UO(2))(3)(HO(3)PC(6)H(5))(2)(O(3)PC(6)H(5))(2).H(2)O, was determined ab initio from laboratory X-ray powder diffraction data and refined by the Rietveld method. The crystals belong to the space group P2(1)2(1)2(1), with a = 17.1966(2) ?, b = 7.2125(2) ?, c = 27.8282(4) ?, and Z = 4. The structure consists of three independent uranium atoms, among which two are seven-coordinated and the third is eight-coordinated. These metal atoms are connected by four different phosphonate groups to form a one-dimensional channel structure along the b axis. The phenyl groups are arranged on the outer periphery of the channels, and their stacking forces keep the channels intact in the lattice. The determination of this structure which contains 50 non-hydrogen atoms in the asymmetric unit, from conventional X-ray powder data, represents significant progress in the application of powder techniques to structure solution of complex inorganic compounds, including organometallic compounds. 相似文献