全文获取类型
收费全文 | 8497篇 |
免费 | 397篇 |
国内免费 | 1篇 |
专业分类
化学 | 5599篇 |
晶体学 | 94篇 |
力学 | 344篇 |
数学 | 1393篇 |
物理学 | 1465篇 |
出版年
2023年 | 58篇 |
2022年 | 73篇 |
2021年 | 114篇 |
2020年 | 162篇 |
2019年 | 148篇 |
2018年 | 219篇 |
2017年 | 174篇 |
2016年 | 337篇 |
2015年 | 271篇 |
2014年 | 274篇 |
2013年 | 625篇 |
2012年 | 575篇 |
2011年 | 652篇 |
2010年 | 349篇 |
2009年 | 311篇 |
2008年 | 567篇 |
2007年 | 583篇 |
2006年 | 508篇 |
2005年 | 505篇 |
2004年 | 364篇 |
2003年 | 338篇 |
2002年 | 265篇 |
2001年 | 111篇 |
2000年 | 104篇 |
1999年 | 84篇 |
1998年 | 61篇 |
1997年 | 49篇 |
1996年 | 88篇 |
1995年 | 59篇 |
1994年 | 52篇 |
1993年 | 55篇 |
1992年 | 44篇 |
1991年 | 33篇 |
1990年 | 28篇 |
1989年 | 29篇 |
1988年 | 16篇 |
1987年 | 25篇 |
1985年 | 51篇 |
1984年 | 39篇 |
1983年 | 20篇 |
1982年 | 51篇 |
1981年 | 39篇 |
1980年 | 50篇 |
1979年 | 41篇 |
1978年 | 31篇 |
1977年 | 31篇 |
1976年 | 41篇 |
1975年 | 41篇 |
1974年 | 26篇 |
1973年 | 26篇 |
排序方式: 共有8895条查询结果,搜索用时 31 毫秒
101.
Phosphine oxides with at least one aryl-P bond are reduced into the corresponding phosphines by stoechiometric amounts of Mg-Cp2TiCl2 in boiling THF. 相似文献
102.
Gérald Perron Jean-François Côté Daniel Lambert Johanne Pageau Jacques E. Desnoyers 《Journal of solution chemistry》1994,23(2):121-133
Blends of immiscible polymers are often stabilized by block copolymers which can form non-aqueous micelles and microemulsions in the liquid polymers. The phase diagrans, apparent volumes and apparent heat capacities of model non-aqueous binary and ternary systems were studied in order to investigate the conditions under which such self-assembly systems could form. 1,2-Hexanediol, which can cosolubilize hexane and ethyleneglycol, forms inverse micelles in hexane and weak microaggregates in ethyleneglycol. Genapol X-060, a commercial alcoholic surfactant containing on the average an aliphatic chain of 13 carbons and 6 oxyethylenes (C13E6), forms microaggregates in poly(ethyleneglycol) 400. These self-assembly systems are strengthen in the presence of a third component which has an affinity for the inner phase.Presented at the Symposium, 76th CSC Congress, Sherbrooke, Quebec, May 30–June 3, 1993, honoring Professor Donald Patterson on the occasion of his 65th birthday. 相似文献
103.
Ribeiro da Silva MD Gomes JR Gonçalves JM Sousa EA Pandey S Acree WE 《The Journal of organic chemistry》2004,69(8):2785-2792
The mean (N-O) bond dissociation enthalpies were derived for three 2-methyl-3-(R)-quinoxaline 1,4-dioxide (1) derivatives, with R = methyl (1a), ethoxycarbonyl (1b), and benzyl (1c). The standard molar enthalpies of formation in the gaseous state at T = 298.15 K for the three 1 derivatives were determined from the enthalpies of combustion of the crystalline solids and their enthalpies of sublimation. In parallel, accurate density functional theory-based calculations were carried out in order to estimate the gas-phase enthalpies of formation for the corresponding quinoxaline derivatives. Also, theoretical calculations were used to obtain the first and second N-O dissociation enthalpies. These dissociation enthalpies are in excellent agreement with the experimental results herewith reported. 相似文献
104.
Nathalie Laronze Jean-François Moisan Catherine Roch-Marchal Feng-Xian Liu Gilbert Hervé 《Journal of Cluster Science》2002,13(3):355-368
Transition metal salts of heteropolyacids have been prepared taking into account the strong acidic and cation exchanging properties of the solid heteropolyacids. The exchange between protons and the transition metal cation is carried out by stirring a suspension of the hydrated heteropolyacid in a solution of the metal acetylacetonate complex in toluene. The exchange occurs on the surface of the solid particles and diffusion of protons and metal cations into the hydrated lattice leads to the substitution of all the protons. The method can be utilized in order to prepare supported vanadyl and copper molybdophosphates from supported heteropolyacids and they have been studied in the catalysis of the oxidative dehydrogenation of isobutyric acid. The effect of vanadyl counter-ions on the catalytic behavior is the same as observed with bulk catalysts but, on the contrary, copper supported molybdophosphate shows an acid catalytic activity not observed with bulk catalysts. 相似文献
105.
Zouhair Asfari Rym Abidi Françoise Arnaud Jacques Vicens 《Journal of inclusion phenomena and macrocyclic chemistry》1992,14(2):163-169
The template synthesis of copper(II) phthalocyanine by the condensation of dicyanobenzene within the supercages of Cu(II) exchanged X and Y type zeolites was studied using differential scanning calorimetry. The exotherms for intrazeolite and surface complexation have been resolved. These thermal events exhibit a dependence on the copper loading and hydration level which has been interpreted as a pressure effect. 相似文献
106.
Cantat T Jaroschik F Nief F Ricard L Mézailles N Le Floch P 《Chemical communications (Cambridge, England)》2005,(41):5178-5180
New samarium carbene complexes have been synthesized and characterized by X-ray diffraction analysis; the carbenic nature was assessed by reactivity studies. 相似文献
107.
A laboratory information management system (LIMS) can make a major contribution to the quality and therefore to the efficiency
and competitiveness of a laboratory. Since it can impact all aspects of a laboratory's organization it must be the key if
not the principal player of the laboratory's quality system. It should support the laboratory in establishing, maintaining
and applying quality procedures thereby enabling the laboratory to achieve its quality goals. As a tool, LIMS permits the
laboratory to input and use its own know-how and experience to optimize the total organization (internal and external) and
workflow of generated information. However, perceived "quality" in the context of an LIMS, can be viewed as being made up
of different facets such as the security, reliability and accessibility of information as well as its turn around time and
production cost. This paper reviews the role of a LIMS in the laboratory and the contribution that both system design and
functionality can have on "building quality ".
Received: 5 October 1998 · Accepted: 20 October 1998 相似文献
108.
Menezes PH Gonçalves SM Hallwass F Silva RO Bieber LW Simas AM 《Organic letters》2003,5(10):1601-1604
[reaction: see text] Several (77)Se NMR experiments were performed by titrating a sample of selenides with the chiral shift reagent methylbenzylamine (MBA), followed by acquisition of (77)Se NMR spectra. Eventually, we observed the appearance of two anisochronous resonances, with a relatively large separation, from 37 to 56 Hz, corresponding to the formation of the diastereomeric complexes. This methodology avoids derivatization processes, and the studied compound can be easily recovered from the NMR tube. 相似文献
109.
The importance of natural antioxidants principally relates to their health-promoting properties. The discovery of new sources of established compounds or more potent compounds is a costly exercise and any technique capable of aiding this procedure would be highly significant. An approach combining chromatographic separation, component analysis and post-column identification of free radical scavenging has been reported. However, its effectiveness is dependent upon various factors and the number of samples analyzed without operator intervention is restricted. A more applicable technique using a 10% to 100% methanol with 2% acetic acid mobile phase and a citric acid-sodium citrate buffered methanolic 1,1-diphenyl-2-picrylhydrazyl free radical reagent is presented, whereby free radical scavengers can be detected within crude extracts of variable polarity without special considerations. As an illustration, acetone, 70% (aq.) methanol and acetonitrile-soluble extracts were prepared from sage (Salvia officinalis L.) for extraction of polar and non-polar radical scavengers and analyzed. Radical scavenging components were identified as carnosic, caffeic and rosmarinic acids and luteolin-7-O-glycoside. Others radical scavengers were tentatively identified as benzoic and hydroxycinnamic acid derivatives, flavonoids and diterpenoids. Through the application of this technique, carnosic acid and rosmarinic acid were identified as the principal free radical scavengers. 相似文献
110.
The scope of catalytic enantioselective tandem carbonyl ylide formation-intramolecular [3 + 2] cycloadditions 总被引:1,自引:0,他引:1
Hodgson DM Labande AH Pierard FY Expósito Castro MA 《The Journal of organic chemistry》2003,68(16):6153-6159
Catalytic enantioselective tandem carbonyl ylide formation-intramolecular 1,3-dipolar cycloaddition reactions of 2-diazo-3,6-diketoesters show promising scope in terms of asymmetric induction as the tethered alkene/alkyne dipolarophile component is varied. Cycloadditions were found to occur in moderate to very good yields, with a difference in ee exhibited by the electronically different 2-diazo-3,6-diketoesters 1, 25 and 33, 34. Values for ee of up to 90% for alkene dipolarophiles and up to 86% for alkyne dipolarophiles were obtained. 相似文献