全文获取类型
收费全文 | 4368篇 |
免费 | 106篇 |
国内免费 | 28篇 |
专业分类
化学 | 2773篇 |
晶体学 | 30篇 |
力学 | 121篇 |
数学 | 830篇 |
物理学 | 748篇 |
出版年
2022年 | 32篇 |
2021年 | 54篇 |
2020年 | 48篇 |
2019年 | 56篇 |
2018年 | 43篇 |
2017年 | 34篇 |
2016年 | 77篇 |
2015年 | 78篇 |
2014年 | 65篇 |
2013年 | 219篇 |
2012年 | 169篇 |
2011年 | 206篇 |
2010年 | 123篇 |
2009年 | 87篇 |
2008年 | 160篇 |
2007年 | 179篇 |
2006年 | 208篇 |
2005年 | 235篇 |
2004年 | 179篇 |
2003年 | 171篇 |
2002年 | 144篇 |
2001年 | 78篇 |
2000年 | 68篇 |
1999年 | 45篇 |
1998年 | 41篇 |
1997年 | 54篇 |
1996年 | 57篇 |
1995年 | 61篇 |
1994年 | 52篇 |
1993年 | 56篇 |
1992年 | 69篇 |
1991年 | 50篇 |
1990年 | 41篇 |
1989年 | 48篇 |
1988年 | 54篇 |
1986年 | 38篇 |
1985年 | 86篇 |
1984年 | 73篇 |
1983年 | 63篇 |
1982年 | 73篇 |
1981年 | 68篇 |
1980年 | 78篇 |
1979年 | 52篇 |
1978年 | 69篇 |
1977年 | 56篇 |
1976年 | 57篇 |
1975年 | 56篇 |
1974年 | 62篇 |
1973年 | 58篇 |
1972年 | 31篇 |
排序方式: 共有4502条查询结果,搜索用时 62 毫秒
61.
Peter V. Broadhurst Brian F.G. Johnson Jack Lewis A.Guy Orpen Paul R. Raithby John R. Thornback 《Journal of organometallic chemistry》1980,187(1):141-145
Reaction of CS2 with H2Os3(CO)8(MeCN)S in cyclohexane yields a product H2Os3(CO)7(CS)S2. this has been characterised by NMR and mass spectroscopy, and by X-ray analysis, and has been shown to contain a terminal thiocarbonyl ligand. 相似文献
62.
Alastair C. Lewis Sarah A. Askey Krystyna M. Holden Keith D. Bartle Michael J. Pilling 《Journal of separation science》1997,20(2):109-114
The composition and concentration of polycyclic aromatic compounds (PAC) in fuels. Theier combustion products and in the atmosphere remains a topic of considerable interest. Despite the wealth of literature on the identification of PAC, speciation at low concentrations remains difficult due to instrument limitation and the complexity of fuel and environmental samples. Consequently on line sample preparation procedures (SPE, SFE, LC, etc.) are becomeing an increasingly important step in the analysis procedure particularly where sample clean-up and fractionation are essential for improving analytical resolution. In this study a normal phase high pressure analytical resolution. In this study a normal phase high pressure liquid chromatography-gas chromatography (LC-GC) system has been developed to provide quantitative analysis of samples, as diverse as coal liquids, petroleum fuels, diesel exhaust particulates, and urban air particulates. Separation and identification of parent and alkylated PAH, hetercycline nitro-and oxy-PAC can be achieved by direct coupling to an atomic emission detector and a bech top mass spectrometer. For both systems the primary LC separation combined with the large sample volume transferred to GC vastly improves detection limits. Furthermore the complimentary nature of the two detectors used enables the positive indentification of many unknowns. 相似文献
63.
Certain marine organisms produce calcium-activated photoproteins that allow them to emit light for a variety of purposes, such as defense, feeding, breeding, etc. Even though there are many bioluminescent organisms in nature, only a few photoproteins have been isolated and characterized. The mechanism of emission of light in the blue region is the result of an internal chemical reaction. Because there is no need for excitation through external irradiation for the emission of bioluminescence, the signal produced has virtually no background. This allows for the detection of the proteins at extremely low levels, making these photoproteins attractive labels for analytical applications. In that regard, the use of certain photoproteins, namely, aequorin, obelin, and the green fluorescent protein as labels in the design and development of binding assays for biomolecules has been reviewed. In addition, a related fluorescent photoprotein, the green fluorescent protein (GFP), has been recently employed in bioanalysis. The use of GFP in binding assays is also discussed in this review. 相似文献
64.
David F.V. Lewis 《Journal of computational chemistry》1987,8(8):1084-1089
Molecular orbital calculation by the MINDO/3 method are reported for 50 compounds used as solvents in chemical reactions. Relationships between various parameters of electronic structure and molecular properties such as dipole moment, polarizability and Taft solvent parameters are presented. Comparison between experimental values of π* and calculated values is given. 相似文献
65.
Gas chromatographic (GC) optimization studies are conducted for the 10 methylenedioxyphenethylamine regioisomeric substances related to the drug of abuse 3,4-methylenedioxymethamphetamine (MDMA, Ecstasy). These 10 compounds, having the same molecular weight and equivalent major mass spectral fragments, are not completely resolved using typical GC-mass spectrometry screening methods for illicit drugs. MDMA coelutes with at least one nondrug regioisomer under standard drug screening conditions. Separation of the 10 regioisomers is studied using stationary phases of varying polarities. Resolution optimization shows that very slow program rates give the best separation for the nonpolar stationary phases, requiring analysis times of as much as 85 min. Narrow-bore columns containing the same nonpolar stationary phases improve the analysis time to approximately 29 min. The polar stationary phase DB-35MS allows high-temperature programming rates, yielding complete resolution of all 10 compounds in less than 7 min. Temperature program optimization studies on the DB-35MS phase allow the separation time to be reduced to approximately 4.5 min. 相似文献
66.
Jack B. Campbell Edward R. Lavagnino Jonathan W. Paschal 《Journal of heterocyclic chemistry》1986,23(3):767-768
The spectral similarities of 10 and 11 substituted 7H-benzimidazo[2,1-a]benz[de]isoquinolin-7-ones hinder the identification of the individual isomers. Preparation of the 13-methyl p-toluenesulfonate salts of these compounds has allowed the assignment by the use of NOE techniques. Saturation of the N-methyl caused an NOE at H-12. The coupling pattern of H-12 then provides identification of the compound. 相似文献
67.
Brian F.G. Johnson Jack Lewis William J.H Nelson Maria D. Vargas Dario Braga Mary McPartlin 《Journal of organometallic chemistry》1983,246(2):c69-c73
The high nuclearity mixed metal cluster monoanions [Os10C(CO)24Cu(NCMe)]? (I) and [Os10C(CO)24AuPPh3]? (II) have been obtained by reaction of the carbido-dianion [Os10C(CO)24]2? (III) with one equivalent of [Cu(NCMe)4] [BF4] and Ph3PAuCl, respectively, in CH2Cl2. X-ray analysis of the [PPh3Me]+ salts of I and II show that the Cu and Au ligands have added to capping tetrahedra of the dianion III in μ3- and μ2-bridging positions, respectively. 相似文献
68.
Douglas X. West Collin P. Galloway Catherine A. Paulson Roger K. Bunting Lewis K. Pannell 《Transition Metal Chemistry》1989,14(6):420-424
Summary CoII complexes of various stoichiometries have been isolated from reactions of the metal chlorides and bromides withN-2-(4-picolyl)-,N-2-(6-picolyl)- andN-2-(4,6-lutidyl)-N-phenylthioureas. 相似文献
69.
The synthesis and properties of a perylenediamide diol linker and several DNA hairpins possessing this linker are described. The diol linker absorbs and fluoresces strongly in the visible. Hairpins having poly(dA)-poly(dT) stems have fluorescence quantum yields and decay times similar to those of the linker, indicating that hole injection does not occur from the singlet excited linker into the base pair domain. Fluorescence quenching by dG or dZ bases is observed when these bases are located near the linker. The strong distance dependence of fluorescence quenching is consistent with a superexchange mechanism for electron transfer. Failure to observe formation of the linker anion radical by means of femtosecond time resolved absorption spectroscopy is attributed to fast charge recombination. The properties and behavior of the perylene linker and its hairpins are compared to those of other arenedicarboxamide linkers. 相似文献
70.
Novel pyrimidine to pyrimidine transformation reactions are described. 1,3-Dimethyl-(or diethyl)-uracil(1) are converted into isocytosine, 2-thiouracil or uracil derivatives by treatment with guanidine, thiourea or urea, respectively. The latter two cases require base catalysis. The effects of some substituents at C-5 and C-6 of 1,3-dialkylated uracils (1a → 1e) on this transformation were examined and a plausible mechanism is offered for their reaction. The utility of this reaction is exemplified by the facile two-step conversion of pseudouridine into the anlileukemic agent, pseudoisocytidine, in good overall yield. 相似文献