全文获取类型
收费全文 | 2609篇 |
免费 | 51篇 |
国内免费 | 16篇 |
专业分类
化学 | 1564篇 |
晶体学 | 18篇 |
力学 | 39篇 |
数学 | 556篇 |
物理学 | 499篇 |
出版年
2021年 | 23篇 |
2020年 | 38篇 |
2019年 | 22篇 |
2018年 | 22篇 |
2017年 | 25篇 |
2016年 | 49篇 |
2015年 | 34篇 |
2014年 | 49篇 |
2013年 | 116篇 |
2012年 | 89篇 |
2011年 | 96篇 |
2010年 | 67篇 |
2009年 | 53篇 |
2008年 | 95篇 |
2007年 | 99篇 |
2006年 | 106篇 |
2005年 | 102篇 |
2004年 | 105篇 |
2003年 | 82篇 |
2002年 | 70篇 |
2001年 | 44篇 |
2000年 | 33篇 |
1999年 | 22篇 |
1998年 | 22篇 |
1997年 | 27篇 |
1996年 | 49篇 |
1995年 | 37篇 |
1994年 | 30篇 |
1993年 | 30篇 |
1992年 | 42篇 |
1991年 | 30篇 |
1990年 | 22篇 |
1989年 | 19篇 |
1988年 | 20篇 |
1987年 | 19篇 |
1986年 | 24篇 |
1985年 | 32篇 |
1984年 | 34篇 |
1983年 | 20篇 |
1982年 | 41篇 |
1981年 | 31篇 |
1980年 | 45篇 |
1979年 | 42篇 |
1978年 | 36篇 |
1977年 | 41篇 |
1976年 | 52篇 |
1975年 | 44篇 |
1974年 | 38篇 |
1973年 | 27篇 |
1971年 | 22篇 |
排序方式: 共有2676条查询结果,搜索用时 31 毫秒
61.
The thermally stable, terminal phosphinidene complexes [CpM(CO)2(eta1-PNiPr2)]AlCl4(Cp= Cp, Cp*; M = Fe) and [Cp*M(CO)3(eta1-PNiPr2)]AlCl4 (M = Cr, Mo, W) react with Ph2C=N=N to form terminal P-coordinated eta1-phosphaazine and eta3-diazaphosphaallene ligands, respectively, whereas [CpFe(CO)2(eta1-PNiPr2)]AlCl4 reacts with Me3SiCHN2 affording a terminal phosphorus bound eta1-phosphaalkene complex. 相似文献
62.
Cai H Chen T Wang X Schultz AJ Koetzle TF Xue Z 《Chemical communications (Cambridge, England)》2002,(3):230-231
Reactions of Ta(NMe2)5 with D2SiR'Ph (R' = Me, Ph) were found to give a dideuteride eta 2-imine complex (Me2N)3Ta(mu-D)2(mu-N-eta 2-N,C-CH2NMe)Ta(NMe2)3(1-d2) through C-H activation of an amide ligand via beta-H abstraction, and the structure of 1 was confirmed by single crystal neutron and X-ray diffraction. 相似文献
63.
A two-state Markov noise process for lattice fluctuations and chemical exchange dynamics is used to derive a stochastic Liouville equation describing the evolution of the spin-density operator in nuclear magnetic resonance spectroscopy. Relaxation through lattice fluctuations and chemical exchange processes is incorporated into the theory at the same fundamental level, and the results are valid for all time scales provided that lattice fluctuations are much faster than chemical exchange kinetics. Time-scale separation emerges as an essential feature from the lowest-order perturbation expansion of the average resolvent in the Laplace domain. 相似文献
64.
K. A. Zaklika Thomas Kissel Arthur L. Thayer Paul A. Burns A. Paul Schaap 《Photochemistry and photobiology》1979,30(1):35-44
Abstract— The chemiluminescence from the cleavage of a number of 1,6-diaryl-2,5,7,8-tetraoxabicyclo[4.2.0]octanes 1 has been examined. The ease of oxidation of (object) the aryl moiety strongly influences both the stability and chemiluminescence efficiency of these 1,2-dioxetanes. When Ar is difficult to oxidize, 1 is comparable in stability to simple. alkyl-substituted 1,2-dioxe-tanes and affords triplet excited states in moderate yield. Both biradical and concerted cleavage mechanisms have been suggested to explain this behavior. However, when Ar is a readily oxidized group, 1 is substantially destahilized and gives excited singlet states in high yield. In this instance 1 is analogous to a number of bioluminescent systems. Cleavage mechanisms involving intramolecular electron transfer are proposed to account for this observation. In certain cases thermolysis of 1 occurs by both types of mechanism in competition, and the electron transfer mechanism may be selectively catalyzed by polar, protic media. 相似文献
65.
Arthur G. Werschulz 《Aequationes Mathematicae》1985,29(1):183-203
It is widely believed that order of exactness is a good measure of the quality of an algorithm for numerical quadrature. We show that this is not the case, by exhibiting a situation in which the optimal algorithm does not even integrate constants exactly. We also show that there are situations in which the penalty for using equidistant nodes is unbounded. Finally, we show that the complexity of obtaining an -approximation can be an arbitrary function of , i.e., there is no hardest quadrature problem. 相似文献
66.
Gutiérrez MC Sleegers A Simpson HD Alphand V Furstoss R 《Organic & biomolecular chemistry》2003,1(20):3500-3506
The first fluorogenic assay allowing for detection of microbial enzymes able to perform Baeyer-Villiger oxidation is described. This is based on the use of 4-oxopentyl umbelliferyl ether 1 as a fluorogenic substrate. When Baeyer-Villigerases active against this test ketone are present in the selected whole cells, 1 is transformed into 3-hydroxypropyl umbelliferyl ether 3, which, in a subsequent step, releases the fluorescent product umbelliferone. Different microorganisms, known to be endowed with Baeyer-Villigerase activity, were assayed. 相似文献
67.
Arthur J. Banister Anthony W. Luke 《Journal of polymer science. Part A, Polymer chemistry》1992,30(12):2653-2656
Mono-, bis- and tris-(1,3,2,4-dithiadiazolium) salts [R-(CNSNS +)n]n+[AsF-6]n (R = aryl, n = 1, 2, 3) were found to initiate the cationic ring-opening polymerization of tetrahydrofuran (THF) at room temperature to give clear gels from which the pure polymer was precipitated. 1,3,2,4-Dithiadiazolium cations associated with the hard [AsF6]- anion thus constitute a new class of cationic polymerization initiators. The poly(THF) formed by initiation with 1,3,2,4-dithiadiazolium cation was characterized by gel permeation chromatography, infrared spectrophotometry, and 13C-NMR spectroscopy. Number-average molecular weights of 198 700 g mol-1 (polydispersity 1.96) and 190 000 g mol-1 (polydispersity 1.61) were obtained using [PhCNSNS ] [AsF6] and [C6H3-1,3,5-(CNSNS )3][AsF6]3, respectively, as initiators. The use of multifunctional dithiadiazolium salts as initiators suggests that they may be useful in the preparation of starburst and dendritic polymers. © 1992 John Wiley & Sons, Inc. 相似文献
68.
A fundamental difficulty in theoretical physics is the dual and apparently incompatible interpretations of radiation as showing both continuous and extensive wave properties but also those of discrete atomic or smaller individual particles. Some of these contradictions are outlined. The explanation offered is of a quantized nature of time; units to=h/moc2 for a particle at rest, and of similar interval unit so when in relative motion, with conventional relativistic corrections.
For many purposes this form of quantization replaces the need for a wave concept which then appears as a mathematical approach, chosen to avoid the physical concept of an intrinsicc time for any particle, just as we have for its intrinsic mass, spin and electrical charge. to and so are directly related to its frequency, energy and mass. The uncertainty principle and interference relations follow directly from this model, without any physical wave concept. 相似文献
69.
Carbon-supported catalysts were phosphonated using 2-aminoethylphosphonic acid, and the resulting catalysts with largely enhanced proton conductivity performed substantially better than the untreated counterparts in proton-exchange membrane fuel cells. 相似文献
70.
B.M.Ratnayake Bandara Arthur J. Birch Brian Chauncy Lawrence F. Kelly 《Journal of organometallic chemistry》1981,208(2):C31-C35
Complexation commencing with some substituted 1,3- or 1,4-cyclohexadienes with Fe(CO)5 indicates that the steric direction is controlled by classical hindrance with groups such as alkyl, but probably involves transmission of the entering group through intermediate complexation with CO2Me. The results help to define methods of obtaining desired stereoisomers in the series. 相似文献