全文获取类型
收费全文 | 2951篇 |
免费 | 98篇 |
国内免费 | 23篇 |
专业分类
化学 | 1784篇 |
晶体学 | 16篇 |
力学 | 83篇 |
数学 | 451篇 |
物理学 | 738篇 |
出版年
2023年 | 27篇 |
2022年 | 53篇 |
2021年 | 57篇 |
2020年 | 69篇 |
2019年 | 82篇 |
2018年 | 61篇 |
2017年 | 63篇 |
2016年 | 102篇 |
2015年 | 61篇 |
2014年 | 77篇 |
2013年 | 145篇 |
2012年 | 178篇 |
2011年 | 204篇 |
2010年 | 116篇 |
2009年 | 89篇 |
2008年 | 154篇 |
2007年 | 193篇 |
2006年 | 170篇 |
2005年 | 134篇 |
2004年 | 109篇 |
2003年 | 88篇 |
2002年 | 66篇 |
2001年 | 40篇 |
2000年 | 33篇 |
1999年 | 52篇 |
1998年 | 26篇 |
1997年 | 34篇 |
1996年 | 35篇 |
1995年 | 22篇 |
1994年 | 16篇 |
1993年 | 27篇 |
1992年 | 26篇 |
1991年 | 15篇 |
1990年 | 20篇 |
1989年 | 20篇 |
1988年 | 21篇 |
1987年 | 13篇 |
1986年 | 15篇 |
1985年 | 21篇 |
1984年 | 22篇 |
1982年 | 11篇 |
1981年 | 22篇 |
1980年 | 19篇 |
1979年 | 18篇 |
1978年 | 20篇 |
1977年 | 23篇 |
1976年 | 17篇 |
1975年 | 13篇 |
1974年 | 13篇 |
1972年 | 12篇 |
排序方式: 共有3072条查询结果,搜索用时 15 毫秒
41.
The complete assignment of 19F, 1H and 13C NMR spectra for a monosubstituted octafluoro[2.2]paracyclophane derivative is described for the first time. The unambiguous assignments were achieved through the combination of 19F--1H HOESY, 1H COSY and 19F COSY techniques and then further confirmed employing a complementary approach using a Karplus-dependent 3JCF interaction. Interesting aspects of the coupling patterns for various JHH, JHF, JCF and JFF interactions are also discussed. 相似文献
42.
Alex Berlin Neil Gilkes Douglas Kilburn Vera Maximenko Renata Bura Alexander Markov Anton Skomarovsky Alexander Gusakov Arkady Sinitsyn Oleg Okunev Irina Solovieva John N. Saddler 《Applied biochemistry and biotechnology》2006,130(1-3):528-545
Seven cellulase preparations from Penicillium and Trichoderma spp. were evaluated for their ability to hydrolyze the cellulose fraction of hardwoods (yellow poplar and red maple) pretreated by organosolv extraction, as well as model cellulosic substrates such as filter paper. There was no significant correlation among hydrolytic performance on pretreated hardwood, based on glucose release, and filter paper activity. However, performance on pretreated hardwood showed significant correlations to the levels of endogenous β-glucosidase and xylanase activities in the cellulase preparation. Accordingly, differences in performance were reduced or eliminated following supplementation with a crude β-glucosidase preparation containing both activities. These results complement a previous investigation using softwoods pretreated by either organosolv extraction or steam explosion. Cellulase preparations that performed best on hardwood also showed superior performance on the softwood substrates. 相似文献
43.
44.
Ruifeng Liu Paula R. Moody Alex S. Vanburen Jeffrey A. Clark Joel A. Krauser Dennis R. Tate 《Vibrational Spectroscopy》1996,10(2):325-329
Results of ab initio and density functional theory calculations on the structure and vibrational frequencies of hypophosphite anion indicate earlier experimental assignments of the fundamental vibrational modes are correct while the recent reassignments of several modes proposed by Bickley et al. are inconsistent with the calculated results. 相似文献
45.
Lee LF Adronov A Schaller RD Fréchet JM Saykally RJ 《Journal of the American Chemical Society》2003,125(2):536-540
Near-field scanning optical microscopy (NSOM) has been used to investigate the photophysical characteristics of first- to fourth-generation (G1 to G4) light-harvesting dendrimer thin films containing coumarin-343 and coumarin-2 as the core and peripheral chromophores, respectively. Thin film photoluminescence (PL) spectra exhibit a significant red shift in the lower generations (G1, G2, and G3) as compared to their respective solution PL spectra, implying the formation of excimers. Spatially resolved PL NSOM images exhibit pronounced nanoscopic domains in G1, which become more homogeneous in higher generations due to site-isolation of the core chromophore. G4 exhibits complete site-isolation for these light-harvesting dendrimer films. 相似文献
46.
The aim of this work was the preparation of enantiomerically pure bis(pinene-bipyridine) ligands containing the ferrocenyl moiety. Several such ligands (1-3) were synthesized and completely characterized. These molecules can be diastereoselectively deprotonated at the acidic methylene group of the pinene moiety using a strong and sterically hindered base such as LDA. Subsequent reaction of the formed anion with alkyl halides yield the family of C(2)-symmetric enantiopure compounds (1a-c). Copper(I), silver(I), or zinc(II) complexes with several ligands (C1-C8) were prepared and structurally characterized in the solid state and in solution. Self-assembled helical species are formed in several cases. It became evident that the chiral groups present in the ligand do not completely determined the helical configuration of the assemblages. Diastereoselectivity is thus not complete with this type of ligands, contrary to other, similar ligands studied before. 相似文献
47.
Alex B. Scholten Jan W. de Haan Hans-Gerd Janssen Leo J. M. van de Ven Carel A. Cramers 《Journal of separation science》1997,20(1):17-23
Retention gape deactivated with Silicone OV-1701-OH show good chromatographic performance and remarkable stability against water induced stationary phase degradrdation. In an attempt to better understand the findamentals off the deactivation process using silanol terminated polysiloxanes, a fumed silica was deactivated with Silicon OV-1701-OH. In contrast to fused silic capillaries, fumed silica (Aerosil A-200) can be studied by 29Si cross-polarization magic-angle-spinning (CPMAS) NMR, thus serving as a model substrate for fused silica. Retention data from inverse gas chromatography at infinite dilurion and 29Si CP MAS NMR data of five Aerosil phases, differing in residual silanol surface concentration, are correlated with the aim of validating this approach for stationary phase characterization. A comparatively detailed model of the deactivating polymer layer that explains the observed absorption activities is deduced. Surface silanols are shown to play a key role in the polymer layer, the structure of which is of primary importance for the absorption behavior after deactivation. Contrary to common belief, the absolute silanol surface concentration after deativation is only of secondary importance for the overall absorption activity. High silanol surface concentrations enhance degradation of the polysiloxane chains into small cyclic fragments as well as subsequent absorption and immobolization to the silica substrate surface. The mobility of linear polysiloxane chains in the kHz regime (as determined bby NMR cross-polarization dynamics) appears to determine the extent which the residual silanols are accessible for analytes. It is therefore anticipated that there is an optimum silanol surface concentration of fused silica surfaces to be deactivated with silanol terminated polysiloxanes; it should be lazrge enough to adsord polymer fragments, but not large to avoid excessive residual silanol activity. 相似文献
48.
Hughes RP Meyer MA Tawa MD Ward AJ Williamson A Rheingold AL Zakharov LN 《Inorganic chemistry》2004,43(2):747-756
Reaction of Pd(TMEDA)(CH(3))(2) [TMEDA = tetramethylethylenediamine] with fluoroalkyl iodides R(F)I affords a series of square planar Pd(II) complexes Pd(TMEDA)(CH(3))(R(F)) [R(F) = CF(2)CF(3) (9), CFHCF(3) (10), CH(2)CF(3) (11)], presumably by oxidative addition followed by reductive elimination of CH(3)I. The solid-state structures of each compound have been determined by single crystal X-ray diffraction studies, allowing the effect of increasing alpha-fluorination on the structural trans-influence of alkyl ligands to be examined. In these compounds there is no significant difference observed in the trans-influence of the three fluorinated alkyl ligands toward the trans-N atom, although a significant cis-influence on the neighboring methyl ligand is apparent. Oxidative addition of the same series of fluoroalkyl ligands to the corresponding Pt(TMEDA)(CH(3))(2) affords octahedral Pt(IV) complexes trans-Pt(TMEDA)(CH(3))(2)(R(F))I [R(F) = CF(2)CF(3) (12), CFHCF(3) (13), CH(2)CF(3) (14)] as the kinetic products. In each case, subsequent isomerization to the corresponding all cis-isomers is observed; in the case of 13, the stereocenter at the alpha-carbon results in two diastereomeric cis-isomers, which are formed at different rates. The molecular structures of 13 and its more stable all cis-isomer 16b have been crystallographically determined. Kinetic studies of the trans-cis isomerization reactions show the mechanism to involve a polar transition state, presumably involving iodide dissociation, followed by rearrangement of the cation, and iodide recombination. High dielectric solvents increase the rate, but solvent coordinating ability has no effect. Dissolved salts (LiI, LiOTf) show normal accelerative salt effects, with no inhibition in the case of added iodide, consistent with the formation of an intimate ion pair intermediate. The kinetic parameters show that the trans-effects of fluoroalkyl ligands in these compounds follow the order expected from the relative sigma-donor properties of the ligands, with CF(2)CF(3) < CFHCF(3) < CH(2)CF(3). 相似文献
49.
The perfect pairing (PP) approximation from generalized valence bond theory is formulated in an unrestricted fashion for both closed- and open-shell systems using a coupled cluster ansatz. In the model chemistry proposed here, active electron pairs are correlated, but the unpaired or radical electrons remain uncorrelated, leading to a linear number of decoupled cluster amplitudes which can be solved for analytically. The alpha and beta spatial orbitals are variationally optimized independently. This minimal treatment of electron-electron correlation noticeably improves upon symmetry-breaking problems and other pathologies in Hartree-Fock (HF) theory and may be computed using the resolution of the identity approximation at only a factor of several times more effort than HF itself. PP also generally predicts improved molecular structures over HF. This compact, correlated wave function potentially provides a useful starting point for dynamical correlation corrections. 相似文献
50.
In the preceding paper under the same title we have formulated a theorem which describes the set of states (i.e., probability measures on phase space of an infinite system of particles inR
v) corresponding to stationary solutions of the BBGKY hierarchy. We have proved the following statement: ifG is a Gibbs measure (Gibbs random point field) corresponding to a stationary solution of the BBGKY hierarchy, then its generating function satisfies a differential equation which is conjugated to the BBGKY hierarchy. The present paper deals with the investigation of the conjugated equation for the generating function in particular cases. 相似文献