全文获取类型
收费全文 | 4862篇 |
免费 | 134篇 |
国内免费 | 13篇 |
专业分类
化学 | 2672篇 |
晶体学 | 47篇 |
力学 | 149篇 |
数学 | 495篇 |
物理学 | 1646篇 |
出版年
2023年 | 38篇 |
2022年 | 78篇 |
2021年 | 81篇 |
2020年 | 97篇 |
2019年 | 97篇 |
2018年 | 97篇 |
2017年 | 74篇 |
2016年 | 132篇 |
2015年 | 89篇 |
2014年 | 127篇 |
2013年 | 289篇 |
2012年 | 253篇 |
2011年 | 299篇 |
2010年 | 185篇 |
2009年 | 168篇 |
2008年 | 241篇 |
2007年 | 239篇 |
2006年 | 252篇 |
2005年 | 210篇 |
2004年 | 155篇 |
2003年 | 137篇 |
2002年 | 112篇 |
2001年 | 93篇 |
2000年 | 87篇 |
1999年 | 59篇 |
1998年 | 46篇 |
1997年 | 45篇 |
1996年 | 52篇 |
1995年 | 54篇 |
1994年 | 49篇 |
1993年 | 62篇 |
1992年 | 50篇 |
1991年 | 42篇 |
1990年 | 56篇 |
1989年 | 43篇 |
1988年 | 43篇 |
1987年 | 42篇 |
1985年 | 53篇 |
1984年 | 48篇 |
1983年 | 43篇 |
1982年 | 40篇 |
1981年 | 46篇 |
1980年 | 51篇 |
1979年 | 35篇 |
1978年 | 44篇 |
1977年 | 38篇 |
1976年 | 40篇 |
1975年 | 33篇 |
1974年 | 40篇 |
1973年 | 40篇 |
排序方式: 共有5009条查询结果,搜索用时 0 毫秒
41.
Witte PT Chowdhury SR ten Elshof JE Sloboda-Rozner D Neumann R Alsters PL 《Chemical communications (Cambridge, England)》2005,(9):1206-1208
A "sandwich" type polyoxometalate catalyst ([MeN(n-C8H17)3]12[WZn3(ZnW9O34)2]) was very efficiently recycled by nanofiltration with almost quantitative retention, using an alpha-alumina supported mesoporous gamma-alumina membrane. 相似文献
42.
An efficient and practical one-pot method for the synthesis of novel diversified sugar derived dihydro-quinazolino[4,3-b]quinazolin-8-ones has been reported. Various protected sugar hemiacetals were used to synthesize the hybrid tetracyclic ring system. The one-step reductive transformation of 2-(2-nitrophenyl)-3H-quinazolin-4-one with different sugar hemiacetals furnished the desired tetracyclic product in good yields and with high purity. 相似文献
43.
Summary N-(orthovanillidene)L-alanine (OVAlaH2), N-(salicylidene)L-valine (SValH2), N-(orthovanillidene)L-valine (OVValH2), N-(orthovanillidene)L-tyrosine (OVTyrH3) and N-(salicylidene)L-glutamic acid (SGluH3) react with LaIII, PrIII, NdIII and SmIII to yield new chiral complexes. Their dominant conformers were determined from c.d. spectra supported by1H n.m.r. data, except for the L-glutamic acid derived complexes which were insoluble. 相似文献
44.
The regio– and stereoselective synthesis of the keto-esters 20 and 22 are described, the latter being a potential intermediate to several diterpenes. The key steps involve the Diels-Alder cycloaddition between the benzocycloheptenone 5 and cyclopentadiene followed by a regioselective functionalisation of the adduct 6. A remarkable reversal of regioselectivity was observed during oxymercuration of the unsymmetric double bond in 6 and its reduced product 11 leading to 8 and 12 which were subsequently transformed to 20 and 22 respectively. 相似文献
45.
The selenium analogues of anti-thyroid drugs exhibit their anti-thyroid action by a mechanism different from that of MMI. The selenium analogue of MMI and related selenium compounds exhibit high GPx activity, providing a novel method for the reversible inhibition of thyroid hormone biosynthesis. 相似文献
46.
Pure rotational transitions of the weakly bound complex He-N(2)O and three minor isotopomers (He-(14)N(15)NO, He-(15)N(14)NO, and He-(15)N(15)NO) were measured in the frequency region from 6 to 20 GHz. Predictions for the microwave transition frequencies were based on the infrared work by Tang and McKellar [J. Chem. Phys. 117, 2586 (2002)]. In the case of (14)N containing isotopomers, nuclear quadrupole hyperfine structure of the rotational transitions was observed and analyzed. The resulting spectroscopic parameters were used to determine geometrical and dynamical information about the complex. An ab initio potential energy surface was calculated at the coupled cluster level of theory with single and double excitations and perturbative inclusion of triple excitations. This surface was constructed using the augmented correlation consistent polarized valence triple zeta basis set for all atoms with the inclusion of bond functions for the van der Waals bond. Bound state calculations were done to determine the energies of low-lying rovibrational levels that are supported by the potential energy surface. The resulting transition energies agree with the experimental values to 1% or better. 相似文献
47.
Useful procedures for preparing a novel tetraazacyclotetradecadiene and a pentaazacyclotetradecatriene are reported. J. Heterocyclic Chem., 14, 1097 (1977) 相似文献
48.
Tripathi SK Patel U Roy D Sunoj RB Singh HB Wolmershäuser G Butcher RJ 《The Journal of organic chemistry》2005,70(23):9237-9247
[Structure: see text]. The synthesis and characterization of a series of organochalcogen (Se, Te) compounds derived from benzyl alcohol 13 are described. The synthesis of the key precursor dichalcogenides 15, 22, and 29 was achieved by the ortho-lithiation route. Selenide 18 was obtained by the reaction of the dilithiated derivative 14 with Se(dtc)2. Oxidation of 15 and 22 with H2O2 afforded the corresponding cyclic ester derivatives 17 and 24, respectively. Oxidation of selenide 18 with H2O2 affords the spirocyclic compound 19. The presence of intramolecular interactions in dichalcogenides 15 and 22 has been proven by single-crystal X-ray studies. The cyclic compounds 17 and 19 have also been characterized by single-crystal X-ray studies. GP(X)-like antioxidant activity of selenium compounds has been evaluated by the coupled bioassay method. Density functional theory calculations at the mPW1PW91 level on ditelluride 22 have identified a fairly strong nonbonding interaction between the hydroxy oxygen and tellurium atom. The second-order perturbation energy obtained through NBO analysis conveys the involvement of n(O) --> sigma(Te-Te) orbital overlap in nonbonding interaction. Post wave function analysis with the Atoms in Molecules (AIM) method identified distinct bond critical point in 15 and 22 and also indicated that the nonbonding interaction is predominantly covalent. Comparison between diselenide 15 and ditelluride 22 using the extent of orbital interaction as well as the value of electron density at the bond critical points unequivocally established that a ditelluride could be a better acceptor in nonbonding interaction, when the hydroxy group acts as the donor. 相似文献
49.
The yellow complex of Pt(IV) with 1-pyridyl-4,4,6-trimethyl-1H,4H-pyrimidine-2-thiol (PyTPT) which has maximum absorbance at 430 nm, is studied for the spectrophotometric determination of the metal. Molar absorptivity is 5000 liters mol?1 cm?1 and Sandell's sensitivity is 0.039 μg/cm2. The determination of Pt(IV) (2.8–8.4 ppm) in the presence of diverse ions is described. 相似文献
50.
The physics of the two-photon absorption process is investigated for a three-state system. The density-matrix equations for the two-photon interaction are solved in the steady-state limit assuming that the pump laser radiation is monochromatic. Collisional broadening, saturation, and Stark shifting of the two-photon resonance are investigated in detail by numerical solution of the steady-state density-matrix equations. Analytical expressions for the saturation intensity and the Stark shift are derived for the case where the single-photon transitions between the intermediate state and the initial and final states are far from resonance with the pump laser. For this case, it is found that the direction of the Stark shift is dependent on the relative magnitudes of the dipole-moment matrix elements for the single-photon transitions that couple the intermediate state with the initial and final states. Saturation and Stark shifting are also investigated for the case where the single-photon transitions between the intermediate state and the initial and final states are close to resonance with the pump laser. 相似文献