全文获取类型
收费全文 | 41856篇 |
免费 | 2902篇 |
国内免费 | 2251篇 |
专业分类
化学 | 19777篇 |
晶体学 | 250篇 |
力学 | 1956篇 |
综合类 | 112篇 |
数学 | 15525篇 |
物理学 | 9389篇 |
出版年
2024年 | 163篇 |
2023年 | 1126篇 |
2022年 | 851篇 |
2021年 | 888篇 |
2020年 | 2116篇 |
2019年 | 1842篇 |
2018年 | 1672篇 |
2017年 | 1430篇 |
2016年 | 1531篇 |
2015年 | 1536篇 |
2014年 | 2113篇 |
2013年 | 4888篇 |
2012年 | 1965篇 |
2011年 | 2322篇 |
2010年 | 1805篇 |
2009年 | 2218篇 |
2008年 | 2357篇 |
2007年 | 2100篇 |
2006年 | 1739篇 |
2005年 | 1464篇 |
2004年 | 1339篇 |
2003年 | 1188篇 |
2002年 | 1334篇 |
2001年 | 735篇 |
2000年 | 692篇 |
1999年 | 687篇 |
1998年 | 552篇 |
1997年 | 452篇 |
1996年 | 502篇 |
1995年 | 489篇 |
1994年 | 416篇 |
1993年 | 330篇 |
1992年 | 283篇 |
1991年 | 198篇 |
1990年 | 193篇 |
1989年 | 193篇 |
1988年 | 131篇 |
1987年 | 141篇 |
1986年 | 115篇 |
1985年 | 145篇 |
1984年 | 131篇 |
1983年 | 68篇 |
1982年 | 115篇 |
1981年 | 113篇 |
1980年 | 56篇 |
1979年 | 51篇 |
1978年 | 41篇 |
1977年 | 54篇 |
1976年 | 38篇 |
1971年 | 26篇 |
排序方式: 共有10000条查询结果,搜索用时 19 毫秒
941.
Quantum equations of motion describing the energy transfer dynamics via intramolecular anharmonic coupling are presented and solved numerically. Dynamical features of the average excitations of a homogeneous system (SF6) and a heterogeneous system (H/W) are quantitatively discussed in terms of the intramolecular vibrational relaxation (IVR) rates. Possible mechanisms of surface-enhanced desorption via low-power laser radiation are proposed.This work was supported in part by the Office of Naval Research, the Air Force Office of Scientific Research (AFSC), United States Air Force, under Grant AFOSR-82-0046 and the National Science Foundation under Grant No. CHE-8022874Camille and Henry Dreyfus Teacher-Scholar (1975–82) 相似文献
942.
Robert Kolodziuk Mustapha Tollabi Catherine Goux-Henry Denis Sinou 《Journal of organometallic chemistry》2003,687(2):384-391
Carbohydrate-substituted phosphines are easily obtained in quite good yields by coupling of protected or non-protected d-glucosamine with the corresponding diphenylphosphino acid. These neutral ligands, in association with palladium acetate, are very active catalysts in the Suzuki cross-coupling reaction. The polyhydroxy phosphines are more active than the peracetylated phosphines. The process tolerates electron-rich as well as electron-poor substituents. Excellent turnovers, up to 97?000 are observed. 相似文献
943.
Balandina A Kalinin A Mamedov V Figadère B Latypov S 《Magnetic resonance in chemistry : MRC》2005,43(10):816-828
(1)H, (13)C and (15)N NMR chemical shifts for a variety of novel quinoxalines were determined by different 2D methods and were calculated using the GIAO DFT approach. Comparison with experimental data shows good correlations in the case of (1)H, (13)C and (15)N chemical shifts. Different combinations of basis sets were tested. In non-polar solvents quinoxalines exist as dimers owing to strong hydrogen bonding. Calculations for dimers improve the correlation between experiment and theory. Additive empirical methods for estimating chemical shifts have drawbacks and have to be used with a great care for this type of compound. 相似文献
944.
Giancarlo Cravotto Marina Beggiato Giovanni Palmisano Stefano Tollari Werner Bonrath 《Tetrahedron letters》2005,46(13):2267-2271
Pd-catalyzed homo- and cross-couplings of boronic acids and aryl halides were successfully carried out both in aqueous media under high-intensity ultrasound (US) and in DME under microwave (MW). Heterogeneous catalysis with Pd/C was employed, avoiding phosphine ligands and phase-transfer catalysts. In a trial series involving 15 different iodo- and bromoaryls and 7 boronic acids, both energy sources drastically reduced reaction times affording biaryls in acceptable to good yields. With palladium(II) acetate as catalyst, electron-deficient aryl chlorides also reacted, affording a few biaryls in acceptable yields. Ullmann-type zinc-mediated homocoupling of iodo- and bromoaryls in the presence of Pd/C under CO2 atmosphere was achieved in aqueous media under US, though not under MW. Suzuki homo- and cross-couplings were also carried out in a new reactor developed in our laboratory, featuring combined US and MW irradiation, further improving a green synthetic method. 相似文献
945.
Viana FA Pouliquen YB Andrade-Neto M Santiago GM Pessoa OD Rodrigues-Filho E Braz-Filho R 《Magnetic resonance in chemistry : MRC》2004,42(8):695-699
A detailed NMR study and full assignments of the 1H and 13C spectral data for two novel triterpenoid saponins isolated from the stem bark of Pentaclethra macroloba (Willd.) Kuntze are described. Their structures were established using a combination of 1D and 2D NMR techniques including 1H,1H-COSY, TOCSY, NOESY, gs-HMQC and gs-HMBC, and also electrospray ionization mass spectrometry and chemical methods. The structures were established as 3beta-O-([O-beta-D-glucopyranosyl-(1-->2)-O-beta-D-glucopyranosyl-(1-->4)-O-beta-D-glucopyranosyl-(1-->3)-O-alpha-L-rhamnopyranosyl-(1-->2)]-[O-beta-D-glucopyranosyl-(1-->3)-O-beta-D-glucopyranosyl-(1-->4)])-alpha-L-arabinopyranosylhederagenin (1) and 3beta-O-)[O-beta-D-glucopyranosyl-(1-->2)-O-beta-D-glucopyranosyl-(1-->4)-O-beta-D-glucopyranosyl-(1-->3)-O-alpha-L-rhamnopyranosyl-(1-->2)]-[O-beta-D-glucopyranosyl-(1-->3)-O-beta-D-glucopyranosyl-(1-->4)])-alpha-L-arabinopyranosyloleanolic acid (2). 相似文献
946.
Jorge Antonio Guerrero-Alvarez 《Tetrahedron letters》2007,48(5):795-798
The relationship between the 13C and 17O NMR chemical shifts and the dihedral energies (non-bonding interactions) of 1,4-dioxaspiro[4.4]nonane, 1,4-dioxa- and 6,10-dioxaspiro[4.5]decane, 1,4-dioxa- and 6,11-dioxaspiro[4.6]undecane, 1,5-dioxaspiro[5.5]undecane, 1,5-dioxa and 7,12-dioxaspiro[5.6]dodecane and 1,6-dioxaspiro[6.6]tridecane were analyzed. These data showed correlation of the non-bonding interactions with the chemical shift of the spiranic carbon, as well as a linear relationship between 13C and 17O. 相似文献
947.
Stereochemistry of 7-aryl-1,7,8,8a-tetrahydro-3(2H)-indolizinones was studied by1H and13C NMR. Complete assignment of1H NMR signals and analysis of1H-1H coupling constants were performed using the iterative PANIC program. Values of3
J
6,7,3
J
7,8endo, and4
J
5,7 allow one to unambiguously identify the correspondingexo- andendo-stereoisomers. For stereoisomers with exo-orientation of H(7), complete assignment of13C NMR signals was performed on the basis of analysis of the13C-1H coupling constants using two dimensional heteronuclear shift-correlating spectroscopy.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 591–593, March, 1996. 相似文献
948.
949.
Synthesis and spectral characterization of some complexes of platinum(II) containing η-methyleugenol
Several complexes of the formula trans-[Pt(Meug)(Am)Cl2], Meug: methyleugenol (4-allyl-1,2-dimethoxybenzene), a η2-coordinated olefin, and Am: ammine, methylamine, diethylamine, o-toluidine, m-toluidine, p-toluidine, o-anisidine, m-anisidine and p-anisidine have been prepared. UV, IR, Raman, 1H NMR, 13C NMR and 2D NMR spectra of the complexes were recorded and analyzed. 相似文献
950.
Cellulose-based hydrogel materials were prepared and modified with tannic acid and l-methionine using ionic liquid as the solvent. The gels were prepared to develop a sustained release medium for selenourea (SeU). The drug delivery characteristics of selenourea-loaded cellulose (CSeU), selenourea-loaded tannic acid-modified cellulose (CTSeU), and selenourea-loaded L-methionine-modified cellulose (CMSeU) were investigated in aqueous media and simulated gastric fluid (SGF) media. This modified gel beads have been characterized using field emission scanning electron microscope, X-ray energy-dispersive spectroscopy, Fourier transform infrared spectroscopy, thermogravimetry–differential thermal analysis and swelling properties and compared with those of the unmodified ones. We also investigated the inhibitory effects of SeU released from these gels on the activity of mushroom tyrosinase. Out of all the gel materials, CTSeU showed maximum SeU release both in water and SGF media. However, tyrosinase inhibitory action in PBS medium was comparable for all the three gel materials. 相似文献