全文获取类型
收费全文 | 34845篇 |
免费 | 1266篇 |
国内免费 | 265篇 |
专业分类
化学 | 24665篇 |
晶体学 | 280篇 |
力学 | 684篇 |
综合类 | 1篇 |
数学 | 5964篇 |
物理学 | 4782篇 |
出版年
2023年 | 167篇 |
2022年 | 324篇 |
2021年 | 431篇 |
2020年 | 611篇 |
2019年 | 599篇 |
2018年 | 417篇 |
2017年 | 389篇 |
2016年 | 943篇 |
2015年 | 831篇 |
2014年 | 1005篇 |
2013年 | 1706篇 |
2012年 | 2180篇 |
2011年 | 2462篇 |
2010年 | 1329篇 |
2009年 | 1181篇 |
2008年 | 2275篇 |
2007年 | 2093篇 |
2006年 | 2117篇 |
2005年 | 1968篇 |
2004年 | 1687篇 |
2003年 | 1380篇 |
2002年 | 1335篇 |
2001年 | 486篇 |
2000年 | 469篇 |
1999年 | 409篇 |
1998年 | 397篇 |
1997年 | 418篇 |
1996年 | 449篇 |
1995年 | 314篇 |
1994年 | 368篇 |
1993年 | 335篇 |
1992年 | 303篇 |
1991年 | 279篇 |
1990年 | 245篇 |
1989年 | 210篇 |
1988年 | 210篇 |
1987年 | 221篇 |
1986年 | 180篇 |
1985年 | 376篇 |
1984年 | 331篇 |
1983年 | 280篇 |
1982年 | 342篇 |
1981年 | 277篇 |
1980年 | 288篇 |
1979年 | 240篇 |
1978年 | 227篇 |
1977年 | 217篇 |
1976年 | 208篇 |
1975年 | 186篇 |
1974年 | 160篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
831.
Several scenarios were evaluated to explain the large "dendrimer effect" observed in the bromination of cyclohexene with H(2)O(2) and NaBr catalyzed by the addition of Frechét-type dendrimers terminating in -O(CH(2))(3)SePh groups. Although phenylseleninic acid was an efficient catalyst for the oxidation of NaBr with H(2)O(2), first-order rate constants for the selenoxide elimination were too small to produce PhSeO(2)H at a rate sufficient to explain the rates of catalysis and no dendrimer effect was observed in the rates of selenoxide elimination. An induction period was observed using 1-SePh as a catalyst for the oxidation of Br(-) with H(2)O(2). The addition of preformed selenoxide 1-Se(=O)Ph gave immediate catalysis with no induction period. However, rates of oxidation of the selenides with H(2)O(2) under homogeneous or biphasic conditions or with t-BuOOH under homogeneous conditions were too slow to account for the rates of catalysis, and no dendrimer effect was observed in the rates of oxidation. The primary oxidant for converting selenides to selenoxides was "Br(+)" produced initially by the uncatalyzed background reaction of H(2)O(2) with NaBr and then produced catalytically following formation of selenoxide groups. Autocatalysis is observed, and the rate of oxidation increases with the number of SePh groups. Autocatalysis is the source of the large dendrimer effect observed with the SePh series of catalysts. 相似文献
832.
Michael J. Kurylo 《Chemical physics letters》1978,58(2):238-242
Rate constants for the reaction of OH radicals with OCS and CS2 have been determined at 296 K using the flash photolysis resonance fluorescence technique. The values derived from this study are kOH + OCS = (5.66 ± 1.21) × 10?14 cm3 molecule?1 s?1 and kOH + CS2 = (1.85 ± 0.34) × 10?13 cm3 molecule?1 s?1, where the uncertainties are 95% confidence limits making allowance for possible systematic errors. 相似文献
833.
Michael Widom 《Communications in Mathematical Physics》1983,92(1):121-136
Analytic maps of the form \(f(z) = e^{2\pi i\Omega } z + \mathcal{O}(z^2 )\) display quasiperiodicity when Ω satisfies a diophantine condition. Quasiperiodic motion is confined to a neighborhood of the origin known as a Siegel domain. The boundary of this domain obeys universal scaling relations. In this paper we investigate these scaling relations through a renormalization group analysis, and we discuss singularities and asymptotic form of the scaling function. 相似文献
834.
The vibrational population distribution of X 1Σ(υ′' = 0 through ν′' = 7) BaO formed in the reaction Ba + O2 at 0.3 torr has been measured by laser induced photoluminescence intensities. On the basis of the assumed similarity between the Ba + O2 and Ba + N2O reactions, these data suggest that a population inversion may exist between A 1Σ(ν′ = 1) and X 1Σ(υn = 7) BaO formed in the latter reaction at ≈ 16 torr. 相似文献
835.
Michels JJ O'Connell MJ Taylor PN Wilson JS Cacialli F Anderson HL 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(24):6167-6176
A series of conjugated polyrotaxane insulated molecular wires are synthesised by aqueous Suzuki polymerisation, using hydrophobic binding to promote threading of the cyclodextrin units. These polyrotaxanes have conjugated polymer cores based on poly(para-phenylene), polyfluorene, and poly(diphenylene-vinylene), threaded through 0.9-1.6 cyclodextrins per repeat unit. Bulky naphthalene-3,6-disulfonate endgroups prevent the macrocycles from slipping off the conjugated polymer chains. Dialysis experiments show that the cyclodextrins become unthreaded only if smaller stoppers are used. MALDI TOF mass spectra detect oligomers with up to ten threaded cyclodextrins, and reveal the presence of some defects that result for oxidative homo-coupling of boronic acids. Weight-average molecular weights were determined by analytical ultracentrifugation, demonstrating that step-growth polymerisation is efficient enough to achieve degrees of polymerisation up to approximately 20 repeat units (84 para-phenylenes). The fluorescence spectra of these polyrotaxanes indicate that the presence of the threaded cyclodextrin macrocycles reduces the flexibility of the conjugated polymer pi-systems. Both the solution and the solid-state photoluminescence quantum yields are enhanced upon threading of the conjugated polyaromatic cores through alpha- or beta-cyclodextrins, and the emission spectra of the polyrotaxanes are blue-shifted compared to the corresponding unthreaded polymers. The greater weight of the 0-0 transition in the emission spectra, as well as the smaller Stokes shift, indicate that the polyrotaxanes are more rigid than the unthreaded polymers. 相似文献
836.
Chiu-Hong Lin Michael D. Ennis Robert L. Hoffman Gillian Phillips Susanne R. Haadsma-Svensson Nabil B. Ghazal Connie G. Chidester 《Journal of heterocyclic chemistry》1994,31(1):129-139
An efficient synthesis of the potent and orally active 5-HT1A agonists, (R)-(+)- and (S)-(-)-1-formyl-6,7,8,9-tetrahydro-N,N-dipropyl-3H-benz[e]indol-8-amines 1a and 1b , is described. This synthesis was accomplished in twelve steps from commercially available 1,5,6,7-tetrahydro-4H-indol-4-one ( 5 ). The key step involved a regio-controlled Friedel-Crafts acylation of 1-(p-toluenesulfonyl)indol-4-acetyl chloride with ethylene to yield a versatile synthon, 3-(p-toluenesulfonyl)-6,7,8,9-tetrahydro-3H-benz[e]indol-8-one ( 10 ). Subsequent coupling of this ketone with chiral α-methylbenzylamine under reductive amination conditions yielded a mixture of diastereomers. These diastereomers were efficiently separated by either chromatography or fractional recrystallization of the derived hydrochloride salts. Debenzylation of the pure diastereomers was followed by alkylation and formylation to yield (R)-(+)- and (S)-(-)-enantiomers 1a and 1b with >99% purity. 相似文献
837.
We have exactly enumerated all sequences and conformations of hydrophobic-polar (HP) proteins with chains of up to 19 monomers on the simple cubic lattice. For two variants of the HP model, where only two types of monomers are distinguished, we determined and statistically analyzed designing sequences, i.e., sequences that have a nondegenerate ground state. Furthermore we were interested in characteristic thermodynamic properties of HP proteins with designing sequences. In order to be able to perform these exact studies, we applied an efficient enumeration method based on contact sets. 相似文献
838.
A one-dimensional, two-state model problem with two well-separated avoided crossing points is employed to test the efficiency and accuracy of a semiclassical surface hopping technique. The use of a one-dimensional model allows for the accurate numerical evaluation of both fully quantum-mechanical and semiclassical transition probabilities. The calculations demonstrate that the surface hopping procedure employed accounts for the interference between different hopping trajectories very well and provides highly accurate transition probabilities. It is, in general, not computationally feasible to completely sum over all hopping trajectories in the semiclassical calculations for multidimensional problems. In this case, a Monte Carlo procedure for selecting important trajectories can be employed. However, the cancellation due to the different phases associated with different trajectories limits the accuracy and efficiency of the Monte Carlo procedure. Various approaches for improving the accuracy and efficiency of Monte Carlo surface hopping procedures are investigated. These methods are found to significantly reduce the statistical sampling errors in the calculations, thereby increasing the accuracy of the transition probabilities obtained with a fixed number of trajectories sampled. 相似文献
839.
Rate constants for the removal of Cl atoms in the reaction Cl + O3 → ClO + O2 were measured by the flash photolysis resonance fluorescence technique over the temperature range 213–298 K. The rate constant is given by the Arrhenius expression (2.94 ± 0.49) × 10?11 exp[?(298 ± 39)/T] in units of cm3 molecule?1 s?1. Comparison with recent results from other laboratories are presented. 相似文献
840.
The extended Hückel model is applied to porphyrin systems with metals Mn, Fe, Co, Ni, Cu, Zn and to the diprotic acid. A single method for choosing parameters is detailed. The model is used to discuss magnetic state, coupling of ring and metal, electronic transitions, and the effect of non-planarity.
National Institutes of Health Pre-Doctoral Fellow. 相似文献
Zusammenfassung Die erweiterte Hückel Theorie wird auf das Porphyrin-System mit den Metallen. Mn, Fe, Co, Ni, Cu und Zn sowie auf die zweifach protonierte Säure angewendet. Die Parameter werden dabei einheitlich gewählt. Anhand dieses Modells werden magnetische Eigenschaften, Kopplung zwischen Ring und Metall, Elektronenübergänge und der Einfluß der Abweichung von planarer Anordnung diskutiert.
Résumé Le modèle étendu de Hückel est appliqué aux complexes du porphyrine avec les métaux Mn, Fe, Co, Ni, Cu et Zn, et à l'acide diprotonique. On présente en détail une méthode unifiée pour obtenir les paramètres. L'état magnétique, le couplage cycle-métal, les transitions électroniques et l'effet de la non-planeïté sont discutés à l'aide de ce modèle.
National Institutes of Health Pre-Doctoral Fellow. 相似文献