全文获取类型
收费全文 | 1971篇 |
免费 | 118篇 |
国内免费 | 7篇 |
专业分类
化学 | 1697篇 |
晶体学 | 11篇 |
力学 | 22篇 |
数学 | 165篇 |
物理学 | 201篇 |
出版年
2024年 | 3篇 |
2023年 | 28篇 |
2022年 | 33篇 |
2021年 | 105篇 |
2020年 | 82篇 |
2019年 | 58篇 |
2018年 | 41篇 |
2017年 | 41篇 |
2016年 | 81篇 |
2015年 | 71篇 |
2014年 | 89篇 |
2013年 | 132篇 |
2012年 | 194篇 |
2011年 | 139篇 |
2010年 | 90篇 |
2009年 | 69篇 |
2008年 | 113篇 |
2007年 | 120篇 |
2006年 | 94篇 |
2005年 | 88篇 |
2004年 | 81篇 |
2003年 | 58篇 |
2002年 | 49篇 |
2001年 | 21篇 |
2000年 | 12篇 |
1999年 | 11篇 |
1998年 | 7篇 |
1997年 | 10篇 |
1996年 | 16篇 |
1995年 | 7篇 |
1994年 | 7篇 |
1993年 | 4篇 |
1992年 | 10篇 |
1991年 | 12篇 |
1990年 | 10篇 |
1989年 | 12篇 |
1988年 | 12篇 |
1987年 | 14篇 |
1986年 | 5篇 |
1985年 | 11篇 |
1984年 | 8篇 |
1983年 | 6篇 |
1982年 | 7篇 |
1980年 | 3篇 |
1979年 | 3篇 |
1978年 | 3篇 |
1977年 | 3篇 |
1931年 | 2篇 |
1914年 | 2篇 |
1911年 | 2篇 |
排序方式: 共有2096条查询结果,搜索用时 15 毫秒
1.
Susana Estopiñá-Durán Liam J. Donnelly Euan B. Mclean Bryony M. Hockin Prof. Alexandra M. Z. Slawin Dr. James E. Taylor 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(15):3950-3956
A combination of pentafluorophenylboronic acid and oxalic acid catalyses the dehydrative substitution of benzylic alcohols with a second alcohol to form new C−O bonds. This method has been applied to the intermolecular substitution of benzylic alcohols to form symmetrical ethers, intramolecular cyclisations of diols to form aryl-substituted tetrahydrofuran and tetrahydropyran derivatives, and intermolecular crossed-etherification reactions between two different alcohols. Mechanistic control experiments have identified a potential catalytic intermediate formed between the aryl boronic acid and oxalic acid. 相似文献
2.
Alexandra Shlapentokh 《Monatshefte für Mathematik》2002,110(4):59-67
Let F be a function field of characteristic over a finite field . Then for any finite set of F-primes S and any , there exists a set of F-primes W of density greater than such that and has a Diophantine definition over . (Here and is defined analogously.) 相似文献
3.
R. Hildebrand 《Journal of Mathematical Sciences》2004,121(2):2178-2220
4.
Alexander G. Ramm Alexandra B. Smirnova Angelo Favini 《Annali di Matematica Pura ed Applicata》2003,182(1):37-52
A nonlinear operator equation F(x)=0, F:H→H, in a Hilbert space is considered. Continuous Newton’s-type procedures based on a construction of a dynamical system with
the trajectory starting at some initial point x
0 and becoming asymptotically close to a solution of F(x)=0 as t→+∞ are discussed. Well-posed and ill-posed problems are investigated.
Received: June 29, 2001; in final form: February 26, 2002?Published online: February 20, 2003
This paper was finished when AGR was visiting Institute for Theoretical Physics, University of Giessen. The author thanks
DAAD for support 相似文献
5.
Alexandra Shlapentokh 《Compositio Mathematica》2002,132(1):99-120
Let F be a function field of characteristic p > 2, finitely generated over a field C algebraic over a finite field C
p
and such that it has an extension of degree p. Then Hilbert's Tenth Problem is not decidable over F. 相似文献
6.
Thermal properties of benzoic acids carrying one or two semiperfluorinated alkoxy tails on the aromatic core have been investigated in binary mixtures with the non-liquid crystalline bidirectional trans-1,2-bis(4-pyridyl)ethylene. The hydrogen bonded complexes built from the complementary molecular species show a significantly enhanced mesophase stability compared with the fluorinated acids in their pure states. The mesophase morphologies of the complexes are governed mainly by the number of the partially fluorinated chains grafted to the acid component. Mixed systems comprising the one-chain acids exhibit a smectic C phase followed by a smectic A phase at more elevated temperatures. Incorporation of a second semiperfluorinated chain into the acid leads to the formation of columnar mesophases. These columnar phases of the H-bonded complexes should represent ribbon phases resulting from the collapse of the smectic layers. 相似文献
7.
8.
– Halobacterium halobium , strain ET-15, which does not contain detectable amounts of bacteriorhodopsin (BR) shows behavioral responses to UV and yellow-green light. Attractant stimuli. i.e. light-increases in the yellow-green range or light-decreases in the UV, suppress the spontaneous reversals of the swimming direction for a certain time. Repellent stimuli, i.e. light-decreases in the yellow-green range or light-increases in the UV, elicit an additional reversal response after a few seconds. Action spectra of both sensory photosystems, PS 370 and PS 565, were measured with attractant as well as with repellent stimuli. As in BR-containing cells, maximal sensitivity was always found at 370 nm for the UV-system and at 565 nm for the long-wavelength system. Fluence-response curves at 370 and 565 nm obtained with strain ET-15 and with a BR-containing strain show that the sensitivity of both photosystems is not reduced in the absence of BR. It is concluded that BR is required neither for PS 565 nor for PS 370. Instead retinal-containing pigments different from BR have to be assumed to mediate photosensory behavior. 相似文献
9.
Briggs CR Allen MJ O'Hagan D Tozer DJ Slawin AM Goeta AE Howard JA 《Organic & biomolecular chemistry》2004,2(5):732-740
The energies of the gauche and anti conformers of 2-fluoroethylamine, 2-fluoroethanol and their protonated analogues are calculated using density functional theory. Unlike the non protonated systems, the protonated systems show a strong gauche effect where the C-F and the C-(+)NH(3) or C-F and C-(+)OH(2) bonds are gauche rather than anti to each other. Single crystal X-ray diffraction studies of 2-fluoroethylammonium compounds identify the same conformational preference. 相似文献
10.
Substituent effects on the rate constants for the photo-Claisen rearrangement of allyl aryl ethers 总被引:1,自引:0,他引:1
The photochemistry of 11 substituted allyl 4-X- and 3-X-aryl ethers 3 (ArOCH2-CH=CH2) has been examined in both methanol and cyclohexane as solvents. The ethers react by the photo-Claisen rearrangement to give allyl substituted phenols as the major primary photoproducts, as expected from the well-established radical pair mechanism. The excited singlet state properties (absorption spectra, fluorescence spectra, fluorescence quantum yields, and singlet lifetimes) were compared with a parallel set of unreactive 4-X- and 3-X-anisoles 4. The excited-state properties of three substituted 4-X-aryl 4-(1-butenyl) ethers 14 (ArOCH2CH2-CH=CH2) were also examined. The model compounds 4 and the reactive allyl ethers 3 have essentially identical rate constants for the excited-state processes with the exception of, the rate constant for homolytic cleavage from S(1) of the allyl ethers to give the radical pair. The difference between the fluorescence quantum yields and/or singlet lifetimes for 3 and 4 were used to obtain values of for all of the allyl ethers. These values exhibit a large substituent effect, spanning almost 2 orders of magnitude with electron-donating groups (CH3O, CH3) accelerating the reaction and electron-withdrawing ones (CN, CF3) slowing it down. The parallel range of rate constants observed in both methanol and cyclohexane indicates that ion pairs are not important intermediates in these rearrangements. Quantum yields of reaction (Phi(r)) for several of the more reactive ethers demonstrate that neither these values nor rate constants of reaction derived from them are reliable measures of the actual excited-state process. In fact, the values are significantly lower than the ones, indicating that the radical pairs undergo recombination to generate starting material. Finally, the rate constants were found to parallel a trend for the change in bond dissociation energy (deltaBDE) for the O-C (allyl) bond of the allyl ethers, indicating that other possible substituent effects are of minor importance. 相似文献