全文获取类型
收费全文 | 121227篇 |
免费 | 19298篇 |
国内免费 | 12733篇 |
专业分类
化学 | 83039篇 |
晶体学 | 1471篇 |
力学 | 7602篇 |
综合类 | 785篇 |
数学 | 13685篇 |
物理学 | 46676篇 |
出版年
2024年 | 393篇 |
2023年 | 2240篇 |
2022年 | 3957篇 |
2021年 | 4313篇 |
2020年 | 4623篇 |
2019年 | 4541篇 |
2018年 | 3908篇 |
2017年 | 3623篇 |
2016年 | 5734篇 |
2015年 | 5560篇 |
2014年 | 6746篇 |
2013年 | 8863篇 |
2012年 | 10648篇 |
2011年 | 10979篇 |
2010年 | 7411篇 |
2009年 | 7104篇 |
2008年 | 7708篇 |
2007年 | 7087篇 |
2006年 | 6497篇 |
2005年 | 5436篇 |
2004年 | 4226篇 |
2003年 | 3398篇 |
2002年 | 3260篇 |
2001年 | 2679篇 |
2000年 | 2292篇 |
1999年 | 2461篇 |
1998年 | 2081篇 |
1997年 | 1964篇 |
1996年 | 2091篇 |
1995年 | 1686篇 |
1994年 | 1617篇 |
1993年 | 1316篇 |
1992年 | 1217篇 |
1991年 | 1081篇 |
1990年 | 886篇 |
1989年 | 647篇 |
1988年 | 513篇 |
1987年 | 432篇 |
1986年 | 408篇 |
1985年 | 351篇 |
1984年 | 263篇 |
1983年 | 172篇 |
1982年 | 153篇 |
1981年 | 117篇 |
1980年 | 86篇 |
1979年 | 47篇 |
1978年 | 45篇 |
1976年 | 44篇 |
1974年 | 50篇 |
1973年 | 38篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
超临界NaCl水溶液的分子动力学模拟 总被引:7,自引:0,他引:7
采用分子动力学模拟的方法对超临界NaCl水溶液的微观结构进行了研究.模拟发现在所研究超临界条件下,密度的变化比温度的变化对超临界NaCl水溶液的微观结构影响更大.温度及密度对Cl- H2O径向分布函数的影响比对Na+ H2O径向分布函数的影响要大.超临界条件下,各gNa+-Cl-在0.261 nm处出现峰值,表明Na+、Cl-之间发生了离子的缔合.超临界条件下,随温度增加,缔合作用增强;随密度增加,缔合作用减弱.本文工作为建立可适用于超临界条件下的电解质热力学模型提供了依据. 相似文献
992.
Two methods, e.g. initial rate method and thermokinetic reduced extent method were presented for studies on non-competitive
inhibition. Arginase-catalyzed the hydrolysis of L-arginine toL-ornithine and urea and the inhibition of this reaction by sodium fluoride were studied in the absence and presence of exogenous
of Mn2+at 37°C in 40 mM sodium barbiturate-hydrochloric acid buffer solution (pH 7.4). Both methods were successively used to determine
the values of K1. The advances and disadvantages of each method were compared in this paper. Exogenous Mn2+ could result in more sensitivity of arginase to F-1. Since the inhibition of arginase by F-1 depends on the pH values of the reaction system and behave as a non-competitive inhibition, it probably due to its small
volume and high electronic density allow it access to the activity site of the enzyme and replaces of μ-OH2 (or μ-OH) as the bridge ligand with Mn(II, II) cluster. However, further studies are necessary to determine the modes of
interaction of F-1 with bovine liver arginase.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
993.
Fan CA Hu XD Tu YQ Wang BM Song ZL 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(18):4301-4310
A novel and highly diastereoselective samarium-catalyzed tandem rearrangement/reduction of secondary alpha-hydroxy epoxides, which involves a C1 to C3 carbon migration rearrangement and a very interesting hetero-Tishchenko reduction of the intermediate aldehyde and the reductant aldehyde, has been reported. This reaction could be developed to provide a facile and stereoselective construction of 2-quarternary 1,3-diol units with an hydroxymethyl moiety attached to the diastereogenic quaternary carbon center. Detailed investigations have been carried out concerning the screening of the aldehydes as a reductant, the optimization of reaction conditions, and the substrate scope of this tandem reaction. A catalytic cycle for this reaction, the electronic and steric effects of the reductant aldehydes, and the mechanism for the acyl migration of 1,3-diol monoesters are proposed. 相似文献
994.
995.
Gene‐Hsiang Lee Hsin‐Ta Wang 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(5):m216-m219
N,N′‐Bis(4‐pyridylmethyl)oxalamide, C14H14N4O2, exists as a dimer which is extended into a two‐dimensional network with other dimers through pyridine–amide hydrogen bonds. The crystal structure of the title coordination polymer, {[CoCl2(C14H14N4O2)]·0.5H2O}n, features a one‐dimensional zigzag chain, in which the cobalt ion sits at a twofold symmetry position and adopts a tetrahedral geometry, and the bridging ligand lies on an inversion center and connects to CoII ions in a bis‐monodentate mode. Furthermore, two interwoven chains create a cavity of ca 8.6 × 8.6 Å, which produces a three‐dimensional channel. Water molecules are held in the channel by hydrogen bonds. 相似文献
996.
Chun‐Xiang Wang Chen‐Xia Du Zhi‐Feng Li 《Acta Crystallographica. Section C, Structural Chemistry》2006,62(10):m488-m490
In the title compound, [Zn(C17H10N5O)2(H2O)2]·4H2O, cyclic water hexamers forming one‐dimensional metal–water chains are observed. The water clusters are trapped by the co‐operative association of coordination interactions and hydrogen bonds. The ZnII ion resides on a centre of symmetry and is in an octahedral coordination environment comprising two O atoms and two N atoms from two 2′‐(4,5‐diazafluoren‐9‐ylidene)picolinohydrazidate ligands and two water molecules. 相似文献
997.
Sadowsky JD Schmitt MA Lee HS Umezawa N Wang S Tomita Y Gellman SH 《Journal of the American Chemical Society》2005,127(34):11966-11968
Molecules that bind to specific surface sites on proteins are of great interest from both fundamental and practical perspectives. We are exploring a ligand development strategy that is based on oligomers with discrete folding propensities ("foldamers"); we target a specific cleft on the cancer-associated protein Bcl-xL because this system is well characterized structurally. In vivo, this cleft binds to alpha-helical segments (BH3 domains) of other proteins. We evaluated several types of helical foldamer, built entirely from beta-amino acid residues or from mixtures of alpha- and beta-amino acid residues, and ultimately identified foldamers in the latter class that bind very tightly to Bcl-xL. Our results suggest that combining different types of foldamer backbones will be an effective and general strategy for creating high-affinity and specific ligands for protein surface sites. 相似文献
998.
A series of 1-(2,4-dichlorophenoxyacetoxy)alkylphosphonic acid dimethyl esters 5 and its corresponding phosphonate monosalts 6 were synthesized as potential herbicide. The phosphonate monosalts can be prepared from 1-(2,4-dichlorophenoxyacetoxy)alkylphosphonic acid dimethyl esters 5, which were synthesized by the condensation of O,O-dimethyl-1-hydroxyalkylphosphonates with dichlorophenoxyacetic chloride. This method provides a simple and efficient procedure for the synthesis of phosphonate derivatives containing sensitive groups to acid, base or water such as carboxylate ester bond; and the herbicidal activity of title compounds was evaluated in a set of experiments in greenhouse. Most of the compounds exhibited notable herbicidal activity. 相似文献
999.
Bose G Nguyen VT Ullah E Lahiri S Görls H Langer P 《The Journal of organic chemistry》2004,69(26):9128-9134
The Lewis acid mediated domino "[3+3]-cyclization-homo-Michael" reaction of 1,3-bissilyl enol ethers with 1,1-diacylcyclopropanes allows an efficient one-pot synthesis of functionalized salicylates containing a halogenated side chain. A great variety of substitution patterns could be realized by variation of the starting materials and of the Lewis acid. The mechanism of the domino process was studied. 相似文献
1000.
Wang Li Duan Liying Wang Enbo Xiao Dongrong Li Yangguang Lan Yang Xu Lin Hu Changwen 《Transition Metal Chemistry》2004,29(2):212-215
The novel complex, Co(H2O)5[Co(2,6-pydc)2] (1) has been prepared in aqueous solution and characterized by single-crystal X-ray diffraction, elemental analyses and i.r. spectra. X-ray structural analysis revealed that three novel compounds each possess both – stacking and hydrogen-bonding interaction three-dimensional (3-D) networks. 相似文献