全文获取类型
收费全文 | 14616篇 |
免费 | 401篇 |
国内免费 | 322篇 |
专业分类
化学 | 9112篇 |
晶体学 | 100篇 |
力学 | 405篇 |
综合类 | 30篇 |
数学 | 1886篇 |
物理学 | 3806篇 |
出版年
2022年 | 158篇 |
2021年 | 187篇 |
2020年 | 175篇 |
2019年 | 176篇 |
2018年 | 171篇 |
2017年 | 141篇 |
2016年 | 329篇 |
2015年 | 298篇 |
2014年 | 365篇 |
2013年 | 779篇 |
2012年 | 623篇 |
2011年 | 722篇 |
2010年 | 519篇 |
2009年 | 497篇 |
2008年 | 659篇 |
2007年 | 698篇 |
2006年 | 562篇 |
2005年 | 577篇 |
2004年 | 575篇 |
2003年 | 577篇 |
2002年 | 611篇 |
2001年 | 440篇 |
2000年 | 398篇 |
1999年 | 307篇 |
1998年 | 223篇 |
1997年 | 203篇 |
1996年 | 221篇 |
1995年 | 236篇 |
1994年 | 227篇 |
1993年 | 177篇 |
1992年 | 168篇 |
1991年 | 175篇 |
1990年 | 191篇 |
1989年 | 154篇 |
1988年 | 138篇 |
1987年 | 135篇 |
1986年 | 123篇 |
1985年 | 216篇 |
1984年 | 233篇 |
1983年 | 159篇 |
1982年 | 178篇 |
1981年 | 147篇 |
1980年 | 151篇 |
1979年 | 139篇 |
1978年 | 115篇 |
1977年 | 162篇 |
1976年 | 142篇 |
1975年 | 118篇 |
1974年 | 110篇 |
1973年 | 114篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
992.
An eco-friendly tandem tosylation/Ferrier N-glycosylation of amines catalyzed by Er(OTf)3 in 2-MeTHF
Monica Nardi Natividad Herrera Cano Antonio De Nino Maria Luisa Di Gioia Loredana Maiuolo Manuela Oliverio Ana Santiago Diletta Sorrentino Antonio Procopio 《Tetrahedron letters》2017,58(18):1721-1726
Er(OTf)3 in 2-MeTHF provides a new and eco-friendly process for Ferrier glycosylation of sulfonamides and amino acids with various N-nucleophiles.The stereoselective synthesis of 2,3-unsaturated-N-pseudoglycals was carried out with 3,4,6-tri-O-acetyl-d-glucal and different nucleophiles affording good results in a short time. 相似文献
993.
A metal-free synthesis of symmetrical anhydrides has been developed starting from aldehydes, both aliphatic and aromatic or primary benzylic alcohols. The reaction occurs at room temperature and makes use of trichloroisocyanuric acid (TCCA) as an oxidant providing the desired carboxylic anhydrides in satisfactory yields. 相似文献
994.
Fengxiang Li Junlin Xie De Fang Feng He Kai Qi Pijun Gong 《Research on Chemical Intermediates》2017,43(10):5413-5432
A series of Ce–MnO x /TiO2 catalysts were prepared using a novel sol–gel template method and investigated for low-temperature selective catalytic reduction (SCR) of NO with NH3 at temperatures ranging from 353 to 473 K. The 0.07Ce–MnO x /TiO2 catalyst showed the highest activity and best resistance to SO2 poisoning. The structure and properties of the catalysts were characterized using X-ray diffraction (XRD) analysis, thermogravimetric analysis (TGA), thermogravimetry (TG)–differential scanning calorimetry (DSC)–mass spectroscopy (MS), high-resolution transmission electron microscopy (HRTEM), Brunauer–Emmett–Teller (BET) measurements, H2-temperature-programmed reduction (TPR), and NH3-temperature-programmed desorption (TPD). The superior catalytic activity of the 0.07Ce–MnO x /TiO2 catalyst was probably due to a change in the active components, an increase in surface active oxygen and surface acid sites, and lower crystallinity and larger surface area with Ce doping. Furthermore, the reduction ability also became stronger. The SO2 poisoning resistance of the 0.07Ce–MnO x /TiO2 catalyst improved because doping with Ce can effectively decrease the formation of ammonium salt on the catalyst surface and the sulfation of MnO x . In situ diffuse-reflectance infrared Fourier-transform (DRIFT) spectroscopy experiments indicated that addition of Ce could promote adsorption of NH3 and inhibit generation of some nitryl species. The SCR reactions over the catalysts mainly followed the Eley–Rideal mechanism accompanied with a partial Langmuir–Hinshelwood mechanism. 相似文献
995.
Rayne S. S. Magalhães Karina C. De Lima Diego S. G. de Almeida Joelma F. De Mesquita Elis C. A. Eleutherio 《Applied biochemistry and biotechnology》2017,181(3):914-924
In some pathogens, trehalose biosynthesis is induced in response to stress as a protection mechanism. This pathway is an attractive target for antimicrobials as neither the enzymes, Tps1, and Tps2, nor is trehalose present in humans. Accumulation of T6P in Candida albicans, achieved by deletion of TPS2, resulted in strong reduction of fungal virulence. In this work, the effect of T6P on Tps1 activity was evaluated. Saccharomyces cerevisiae, C. albicans, and Candida tropicalis were used as experimental models. As expected, a heat stress induced both trehalose accumulation and increased Tps1 activity. However, the addition of 125 μM T6P to extracts obtained from stressed cells totally abolished or reduced in 50 and 60 % the induction of Tps1 activity in S. cerevisiae, C. tropicalis, and C. albicans, respectively. According to our results, T6P is an uncompetitive inhibitor of S. cerevisiae Tps1. This kind of inhibitor is able to decrease the rate of reaction to zero at increased concentrations. Based on the similarities found in sequence and function between Tps1 of S. cerevisiae and some pathogens and on the inhibitory effect of T6P on Tps1 activity observed in vitro, novel drugs can be developed for the treatment of infectious diseases caused by organisms whose infectivity and survival on the host depend on trehalose. 相似文献
996.
997.
Dr. Yan Li Dr. Yuk-Chi Chan Bi-Xiang Leong Dr. Yongxin Li Dr. Emma Richards Indu Purushothaman Dr. Susmita De Dr. Pattiyil Parameswaran Dr. Cheuk-Wai So 《Angewandte Chemie (International ed. in English)》2017,56(26):7573-7578
The trapping of a silicon(I) radical with N-heterocyclic carbenes is described. The reaction of the cyclic (alkyl)(amino) carbene [cAACMe] (cAACMe=:C(CMe2)2(CH2)NAr, Ar=2,6-iPr2C6H3) with H2SiI2 in a 3:1 molar ratio in DME afforded a mixture of the separated ion pair [(cAACMe)2Si:.]+I− ( 1 ), which features a cationic cAAC–silicon(I) radical, and [cAACMe−H]+I−. In addition, the reaction of the NHC–iodosilicon(I) dimer [IAr(I)Si:]2 (IAr=:C{N(Ar)CH}2) with 4 equiv of IMe (:C{N(Me)CMe}2), which proceeded through the formation of a silicon(I) radical intermediate, afforded [(IMe)2SiH]+I− ( 2 ) comprising the first NHC–parent-silyliumylidene cation. Its further reaction with fluorobenzene afforded the CAr−H bond activation product [1-F-2-IMe-C6H4]+I− ( 3 ). The isolation of 2 and 3 confirmed the reaction mechanism for the formation of 1 . Compounds 1 – 3 were analyzed by EPR and NMR spectroscopy, DFT calculations, and X-ray crystallography. 相似文献
998.
R. Fausto L.A.E. Batista De Carvalho J.J.C. Teixeira-Dias 《Journal of computational chemistry》1992,13(7):799-809
The internal rotation in the HC(?X)YCH2CH3 (X, Y = O or S) series of molecules was studied by the ab initio SCF-MO method using 3-21G and 3-21G + d(ζ = 0.65S) basis sets. Energies and structures of several conformations of these molecules, determined by gradient geometry refinement, are reported and used to assess the effects of oxygen-by-sulphur substitution on molecular properties. The nature and relative importance of intramolecular interactions involving both the ? CH2CH3 and the HC(?X)Y (X, Y = O or S) fragments are also discussed. © 1992 by John Wiley & Sons, Inc. 相似文献
999.
Norbert Klempier Anna De Raadt Herfried Griengl Gottfried Heinisch 《Journal of heterocyclic chemistry》1992,29(1):93-95
Chemoselective hydrolysis of heterocyclic nitriles can be achieved by an easy to use immobilized biocatalyst prepared from Rhodococcus sp. Pyrimidine-2-carbonitrile ( 2a ) and 3-chloropyridazine-4-carbonitrile ( 4a ) were converted into the corresponding amides while from 2-ethoxycarbonyl-4-pyridinecarbonitrile ( 1a ), 6-methylpyridazine-3-carbonitrile ( 3a ), 3-chloropyridazine-4-carbonitrile ( 4a ), 3-ethoxycarbonyl-4,5-dihydroisoxazole-5-carbonitrile ( 8a ), indole-3-carbonitrile ( 9a ) and indole-3-ylacetonitrile ( 10a ) the acids were formed. 相似文献
1000.
Maria De Fenza Anna Esposito Daniele DAlonzo Annalisa Guaragna 《Molecules (Basel, Switzerland)》2021,26(6)
The de novo synthesis of piperidine nucleosides from our homologating agent 5,6-dihydro-1,4-dithiin is herein reported. The structure and conformation of nucleosides were conceived to faithfully resemble the well-known nucleoside drugs Immucillins H and A in their bioactive conformation. NMR analysis of the synthesized compounds confirmed that they adopt an iminosugar conformation bearing the nucleobases and the hydroxyl groups in the appropriate orientation. 相似文献