全文获取类型
收费全文 | 6340篇 |
免费 | 418篇 |
国内免费 | 31篇 |
专业分类
化学 | 4889篇 |
晶体学 | 28篇 |
力学 | 158篇 |
综合类 | 1篇 |
数学 | 1021篇 |
物理学 | 692篇 |
出版年
2022年 | 35篇 |
2021年 | 52篇 |
2020年 | 64篇 |
2019年 | 109篇 |
2018年 | 65篇 |
2017年 | 63篇 |
2016年 | 211篇 |
2015年 | 236篇 |
2014年 | 231篇 |
2013年 | 386篇 |
2012年 | 301篇 |
2011年 | 318篇 |
2010年 | 282篇 |
2009年 | 286篇 |
2008年 | 325篇 |
2007年 | 274篇 |
2006年 | 259篇 |
2005年 | 233篇 |
2004年 | 270篇 |
2003年 | 216篇 |
2002年 | 277篇 |
2001年 | 151篇 |
2000年 | 143篇 |
1999年 | 73篇 |
1998年 | 65篇 |
1997年 | 77篇 |
1996年 | 87篇 |
1995年 | 63篇 |
1994年 | 73篇 |
1993年 | 71篇 |
1992年 | 67篇 |
1991年 | 43篇 |
1990年 | 46篇 |
1989年 | 47篇 |
1988年 | 42篇 |
1987年 | 42篇 |
1986年 | 39篇 |
1985年 | 47篇 |
1984年 | 66篇 |
1983年 | 56篇 |
1982年 | 71篇 |
1981年 | 73篇 |
1980年 | 74篇 |
1979年 | 82篇 |
1978年 | 79篇 |
1977年 | 83篇 |
1976年 | 77篇 |
1975年 | 75篇 |
1974年 | 75篇 |
1973年 | 54篇 |
排序方式: 共有6789条查询结果,搜索用时 10 毫秒
51.
A method is presented to reduce the memory requirement of normal mode analysis applied to systems containing two or more large proteins when these systems exhibit symmetry properties. We use a rigid geometry model (i.e., only the dihedral angles of the polypeptide chain are considered as variables). This model allows a reduction by a factor of 8 on average of the number of variables with a concomitant freezing of the high-frequency modes. The symmetry properties of the system are used to reduce further the number of variables that must be considered in the computation. Application of group theory leads to a factorization of the matrices of interest (the coefficient and the Hessian matrices) into independent blocks along the diagonal. The initial, reducible representation is thus transformed into a number of irreducible representations of smaller dimensions. In the case of the C2 symmetry group, the method leads to a reduction of the size of the matrices that must be manipulated during the computation (coefficient matrix, Hessian matrix, and eigenvectors matrix) by a factor of 256 compared with the usual normal mode analysis in Cartesian coordinate space. The method is particularly well adapted to the study of the dynamics of oligomeric proteins because these proteins often display symmetry properties (e.g., virus coat proteins, immunoglobulins, hemoglobin, etc.). In favorable cases, in conjunction with X-ray diffuse scattering data, the study of systems showing allosteric properties might be considered. © 1994 by John Wiley & Sons, Inc. 相似文献
52.
Jean M. J. Tronchet Bernard Gentile Alain P. Bonenfant Olivier R. Martin 《Helvetica chimica acta》1979,62(3):696-699
Further examples of O-isopropylidenaldehydosugars in the furanose series Formyl-bearing furanose derivatives 1–3 (α-D -xylo or α-D -erythro configurations) and 5–8 (configurations α-D -ribo, α-D -lyxo, β-L -threo and D -arabino) have been prepared by classical synthetic steps and their properties mainly spectroscopic, reported. The coupling constant between the formyl and the vicinal proton is always small. Like other members of the series, these new aldehydosugars constitute very useful and flexible synthetic intermediates. 相似文献
53.
Marfisi S Rodríguez MP Alvarez G Celis MT Forgiarini A Lachaise J Salager JL 《Langmuir : the ACS journal of surfaces and colloids》2005,21(15):6712-6716
Commercial ethoxylated nonionic surfactant mixtures containing alcohol cosurfactant exhibit a three-phase behavior whose formulation strongly varies with the water/oil ratio. As a consequence, a change in water/oil ratio can result in a sequence of up to three different emulsion inversion processes, through a combination of formulation and composition effects. 相似文献
54.
We describe a versatile, efficient method for the preparation of ether analogues of (S,S)-lysobisphosphatidic acid (LBPA) and its enantiomer from (S)-solketal. Phosphorylation of a protected sn-2-O-octadecenyl glyceryl ether with 2-cyanoethyl bis-N,N-diisopropylamino phosphine and subsequent deprotection generated the bisether LBPA analogues. By simply changing the sequence of deprotection steps, we obtained the (R,R)- and (S,S)-enantiomers of 2,2'-bisether LBPA. An ELISA assay with anti-LBPA monoclonal antibodies showed that the bisether LBPAs were recognized with the same affinity as the natural 2,2'-bisoleolyl LBPA. [reaction: see text] 相似文献
55.
Hans‐Ruedi Mürner Rosario Scopelliti Jean‐Claude G. Bünzli 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(8):m434-m435
In the title compound, [TbCl(C27H35N3)2(H2O)](ClO4)2·2C2H6O, the TbIII ion has a coordination number of eight, composed of two tridentate substituted‐terpyridine ligands, a water molecule and a bound Cl? anion. The first coordination shell can be described as a distorted bicapped trigonal prism. The dihedral angles between pyridine rings belonging to the same tpy ligand range from 5.2 (5) to 16.8 (5)°. 相似文献
56.
Regioselectivite de la reaction des dialkyl cuprates de magnesium sur des aldehydes α,β-ethyleniques
Monique Bourgain-Commerçon Jean-Pierre Foulon Jean François Normant 《Journal of organometallic chemistry》1982,228(3):321-326
Various magnesium organocuprates give conjugative addition products with α,β-ethylenic aldehydes, and even with acrolein. The enolates may be trapped with bromine or trimethylsilyl chloride. 相似文献
57.
The ultraviolet absorption spectrum of the neopentyl peroxy radical (CH3)3CCH2O2, and the kinetics and products of its self reaction have been studied in the gas phase at 298 K. Absorption cross sections were quantified over the wavelength range 230–290 nm. The measured cross section at 250 nm was; Errors represent statistical (2σ) together with our estimate of potential systematic errors(15%). The kinetics of the decay of the UV absorption following the generation of the neopentyl peroxy radicals was complicated by the rapid decomposition of the (CH3)3CCH2O radicals formed in channel (4a). By measuring the yield of t-butyl peroxy radicals, the branching ratio k4a/(k4a + k4b) was determined to be 0.39 ± 0.03. The rate constant for the self reaction of neopentyl peroxy radicals was k4 = (1.07 ± 0.22) × 10?12 cm3 molecule?1 s?1. Quoted errors represent 2σ. These results are discussed with respect to the available literature data. © John Wiley & Sons, Inc. 相似文献
58.
Jean -Paul Malrieu 《Theoretical chemistry accounts》1982,62(2):163-174
Using the canonical problem of N separate electron pairs, theN dependence of approximate multireference CI schemes is analyzed. When the DCI is taken as multireference space, the second order Quasi Degenerate Many Body Perturbation Theory (QD(MB)PT) gives twice the expected correction, while the CIPSI algorithm gives 66% of it, and the MRDCI a vanishing part of it. A modified QDPT effective hamiltonian, and a combination of CIPSI and QDPT algorithms seem to give better trends. 相似文献
59.
Claude Balny Jennifer Canva Pierre Douzou Jean Bourdon 《Photochemistry and photobiology》1969,10(6):375-382
Abstract— Chemiluminescence and photochemiluminescence of systems generating excited (singlet) molecular oxygen has been studied at low temperature in fluid media. A possible interpretation is proposed: that dimers of singlet oxygen are directly or indirectly responsible for the observed emission, the species [1 δg +1 σg+ ] predominating. Energy transfer to a fluorescent molecule is possible only when conditions of spectral overlap, required for transfer by inductive resonance, are fulfilled. Evidence is also presented for the formation of a transient complex between oxygen and a sensitiser or acceptor molecule [S…O2 ], which is the precursor of singlet oxygen in these systems. However, other possible mechanisms cannot be excluded. 相似文献
60.
The gas-phase decomposition of diallylvinylphosphine 1 into C5H5P 12 is studied by DFT/6-311+G(d,p) calculations with the B3LYP functional, followed by single-point energy-only calculations at the CCSD(T)/6-311+G(d,p) level. According to these calculations, the first step involves a retro-ene elimination that yields 3-phosphahexatrienes 2Z and 2E. Both compounds equilibrate through the formation of 1,2- and 3,4-dihydrophosphetes 3 and 4, and it is shown that the formation of 2Z is favored by the exothermic formation of the 3,4-dihydrophosphinine 5 through a 6pi-electrocyclization. Though 5 can easily isomerize into 2,3- (6) and 1,2-diyhydrophosphinines (7) by successive 1,5-hydrogen shifts, the formation of 12 from 5, 6, or 7 through an elimination of H2 is found to be a high energy process. It is also shown that the elimination of H2 from lambda5-phosphinine 8 following a C2v pathway is a symmetry-forbidden process. Finally, 1,4-dihydrophosphinine 9, which can be formed through a 1,4-hydrogen shift from lambda5-phosphinine 8, is found to be a convenient precursor of 12 through a 1,4-elimination of H2. The formation of 9 from 5 involves the intermediary formation of 3-phosphabicyclo[3.1.0]hex-2-ene 10. The mechanism eventually proposed for the formation of 12 from 2Z is given in Scheme 16 at the CCSD(T) level. 相似文献