全文获取类型
收费全文 | 25222篇 |
免费 | 672篇 |
国内免费 | 149篇 |
专业分类
化学 | 17124篇 |
晶体学 | 127篇 |
力学 | 591篇 |
数学 | 4399篇 |
物理学 | 3802篇 |
出版年
2022年 | 182篇 |
2021年 | 263篇 |
2020年 | 317篇 |
2019年 | 324篇 |
2018年 | 238篇 |
2017年 | 200篇 |
2016年 | 492篇 |
2015年 | 463篇 |
2014年 | 502篇 |
2013年 | 1334篇 |
2012年 | 1176篇 |
2011年 | 1465篇 |
2010年 | 742篇 |
2009年 | 727篇 |
2008年 | 1281篇 |
2007年 | 1341篇 |
2006年 | 1321篇 |
2005年 | 1264篇 |
2004年 | 1090篇 |
2003年 | 940篇 |
2002年 | 848篇 |
2001年 | 366篇 |
2000年 | 309篇 |
1999年 | 252篇 |
1998年 | 284篇 |
1997年 | 315篇 |
1996年 | 368篇 |
1995年 | 250篇 |
1994年 | 292篇 |
1993年 | 279篇 |
1992年 | 252篇 |
1991年 | 246篇 |
1990年 | 205篇 |
1989年 | 237篇 |
1988年 | 247篇 |
1987年 | 208篇 |
1986年 | 202篇 |
1985年 | 301篇 |
1984年 | 341篇 |
1983年 | 222篇 |
1982年 | 377篇 |
1981年 | 344篇 |
1980年 | 327篇 |
1979年 | 328篇 |
1978年 | 332篇 |
1977年 | 296篇 |
1976年 | 292篇 |
1975年 | 261篇 |
1974年 | 256篇 |
1973年 | 245篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
931.
Robert Cogburn 《Probability Theory and Related Fields》1982,61(2):153-160
Summary We consider birth and death in a random environment, having probabilitiesp(,x) andq(,x) of a step to the right or left, respectively, from statex in environment. Under several sets of conditions involving the existence of limp(,x) and limq(,x) asx, we give conditions for certain extinction or escape to when 0 is absorbing, corresponding to recurrence or transience when 0 is reflecting. The environmental sequence is assumed to be stationary ergodic, and for some results stronger assumptions are required. 相似文献
932.
Max F. Bechtold Walter Mahler Robert A. Schunn 《Journal of polymer science. Part A, Polymer chemistry》1980,18(9):2823-2855
Linear relationships among molecular weight, polymerization time, and gelation for the condensation of any monomer, including those of unknown size and functionality, are developed and applied to data on soluble silicic acids generated from tetraethyl silicate and from sodium silicate. The results suggest the formation of monomers containing ca. 12–15 ? OSi units with functionality of ca. 2.05 that condense with a rate constant of ca. 10?4 liter/mole sec and an activation energy of 40–70 kJ/mole. One model compatible with these characteristics and the stoichiometry involved is a ladder polymer ca. 3 ? SiO units wide. Polymer isolation was achieved by replacing residual ? OH with (CH3)3Sio? , as well as by freezing of of aqueous solutions, which yielded fibers under special conditions. Solutions of the uncapped and capped polymers and melts of the latter had low viscosity even for fractions with M?n ~100,000. This implies a coiled or globular nature for the polymers, which is supported by their limited propensity for film and fiber formation. Attemps to improve this situation by copolymerization, the use of other capping agents, and by the polymerization of precapped monomers were unsuccessful. 相似文献
933.
The 13P and 13C spectra of the triply 13C labelled molecules (CH3)3P, (CH3)3PO, (CH3)3PS and (CH3)3PSe oriented in a nematic phase are reported. The CPC bond angles have been measured. The 13P chemical shift tensor shows a large anisotropy except in the case of (CH3)3P. The abnormal large value observed for the PSe bond length suggests a large anisotropy of the 1J(PSe) spin coupling. 相似文献
934.
A general synthetic approach to strained 1,4-annulated cyclooctatetraene-based cyclophanes is described. A key feature in this approach is exploitation of the cubane core as a masked cyclooctatetraene synthon. Thus, 1,4-disubstituted cubanes 3 and 4 used as precursors to cyclooctatetraenophanes have been prepared in four steps from the readily available 1,4-cubanedicarboxaldehyde (5). The synthesis of 3 was effected by palladium/copper-mediated coupling of 1,4-bis[(Z,Z)-2-iodovinyl]cubane (6) and 1,4-bis[(Z,Z)-but-1-en-3-ynyl]cubane (8). For the synthesis of 4, on the other hand, modified Eglington-Glaser coupling was applied for the macrocyclization step. The general characteristic of Rh(I) to induce [2 + 2] cycloreversion of the cubane core to syn-tricyclo[4.2.0.0(2,5)]octa-3,7-diene followed by thermal rearrangement to cyclooctatetraene was applied as a key structural transformation toward targeted cyclooctatetraenophanes 1 and 2. 相似文献
935.
L.V. Natarajan Fredrick M. Stein Robert E. Blankenship Raymond Chang 《Chemical physics letters》1983,95(6):525-528
A study of the linear diehroism and fluorescence polarization of diphenylpolyenes (C6H5—(CH=CH)n—C6H5) with n = 1,2,3,4,6,8 in stretched polyethylene films shows that the polyenes orient in the anisotropic matrix with their transition dipole (emission and absorption, π → π*) aligned with the direction of stretch. The maximum dichroic ratio is observed for 1,6-diphenyl-1,3,5-hexatriene (DPH), with n = 3, whereas the values are substantially lower for n < 3 or n > 3. The high orientation of DPH and poor alignment of the higher polyenes may be accounted for in terms of the growing flexibility of the polyene chains with increasing chain length. The results justify the use of DPH as a convenient fluorescence probe for biological and synthetic membranes. 相似文献
936.
Daniel C. Brune Robert E. Blankenship Gilbert R. Seely 《Photochemistry and photobiology》1988,47(5):759-763
Abstract— Absorption and emission spectra of bacteriochlorophyll c dissolved in a variety of solvents were measured and fluorescence quantum yields determined from the integrated emission spectra. Values for the emission maxima calculated from the positions and bandwidths of the red absorption band using the Stepanov relationship agreed closely with the experimental values. Fluorescence quantum yields varied between 0.10 in methanol and 0.36 in tetrahydrofuran and in dibutylamine. Fluorescence lifetimes were also determined for bacteriochlorophyll c in four of the solvents, and ranged from 2.7 ns in methanol to 7.6 ns in dimethylsulfoxide. 相似文献
937.
Kenneth P. Ghiggino Louise E. Bennett Robert W. Henderson 《Photochemistry and photobiology》1988,47(1):65-72
Abstract— The absorption and fluorescence properties of porphyrin c (P c ), the porphyrin chromophore present in cytochrome c , have been determined in several solvents and micellar environments. In aqueous buffer solutions at pH 7.5 Pc may exist in both a fluorescent monomeric form with quantum yield of fluorescence, (Φf ,) ∼ 0.03, and fluorescence lifetime, (τf ) ∼ 8 ns, and as a non-fluorescent aggregate. The proportion of monomeric form is higher in organic solvents and micelles but is reduced with increasing porphyrin concentrations in aqueous solutions. Porphyrin c readily complexes with Zn2+ to produce a fluorescent chelate (Zn-P c ) with Φf , ∼ 0.02 and τf , ∼ 2 ns at pH 7.5. The yields of singlet excited oxygen formation from Pc and the Zn-P c complex are higher than observed for hematoporphyrin derivative (HpD). Both P c and Zn-P c are effective agents in tumor phototherapy and do not induce the prolonged cutaneous photosensitivity observed with the use of HpD. 相似文献
938.
A two-step, general synthesis of 1,4-benzodiazepine-2,5-diones (BZDs) is presented. This synthesis employs an Ugi four-component condensation using a convertible isocyanide (1-isocyanocyclohexene), followed by an acid-activated cyclization reaction. This synthesis represents a dramatically improved route to BZDs over those currently in the literature. In addition, since amino acids are not used as inputs, the potential for molecular diversity is much greater than that with existing syntheses. It was also found that BZDs substituted with methylenes at the C-3 and N-4 positions display conformational isomerism in the NMR spectra at room temperature. Variable-temperature NMR experiments support this observation and offer the interesting conclusion that the BZD core structure, in certain examples, might not be as rigid as previously supposed. 相似文献
939.
Minimal basis set (STO) molecular orbital and valence-bond calculations are reported for the3 B 1 and1 A 1 states of CH2. The open-shell molecular orbital calculations used the Roothaan formulation. The valence-bond calculations used the Prosser-Hagstrom biorthogonalisation technique to evaluate the cofactors required in using Löwdin's formulae. Optimisation of geometry and orbital exponents in the molecular orbital calculation on the3 B 1 state gave a geometry of RC-H=2.11 a.u. and H-C-H=123.2 °. The energy obtained was ?38.8355 a.u. The molecular orbital and valencebond calculations are compared. In the valence-bond calculations the variation with bond-length and bond-angle of the configuration energies was studied. Valence bond “build-up” studies are also reported. Valence-bond calculations using hybrid orbitals instead of natural atomic orbitals showed that the perfect-pairing approximation is not as good for CH2 as BeH2. The nature of the lone-pair and bonding orbitals is found to be significantly different between the3 B 1 and1 A 1 states. In the3 B 1 state the 2s and 2p orbitals are fairly equally mixed between both types of orbital. However in the1 A 1 state the bonding orbitals have mainly 2p character and the lone pair orbitals have mainly 2s character. As was found for H2O, the bonding hybrid orbitals do not follow the hydrogen nuclei as the bond angle varies but continue to point approximately in their equilibrium directions. 相似文献
940.
Protein tyrosine kinase Csk-catalyzed phosphorylation of Src containing unnatural tyrosine analogues
Using expressed protein ligation, five unnatural tyrosine analogues (amino-phenylalanine, homotyrosine, 2-methyl-tyrosine, (alphaS,betaR)-beta-methyl-tyrosine, and 2,6-difluoro-tyrosine) were incorporated into Src in place of the natural tail tyrosine residue. These semisynthetic substrates were evaluated as Csk substrates or allosteric activators. It appears that the tyrosine phenol hydroxyl is unlikely to be contributing significantly to Src's ground-state binding affinity for Csk. It has been observed that stabilizing tyrosine conformers can further optimize Src's already high substrate efficiency. These latter findings contrast similar studies with synthetic peptide substrates and highlight the value of investigation of protein kinase substrate selectivity with protein substrates. 相似文献