全文获取类型
收费全文 | 5942篇 |
免费 | 322篇 |
国内免费 | 28篇 |
专业分类
化学 | 4755篇 |
晶体学 | 20篇 |
力学 | 114篇 |
数学 | 575篇 |
物理学 | 828篇 |
出版年
2024年 | 6篇 |
2023年 | 62篇 |
2022年 | 94篇 |
2021年 | 109篇 |
2020年 | 135篇 |
2019年 | 155篇 |
2018年 | 124篇 |
2017年 | 106篇 |
2016年 | 242篇 |
2015年 | 186篇 |
2014年 | 196篇 |
2013年 | 306篇 |
2012年 | 523篇 |
2011年 | 596篇 |
2010年 | 269篇 |
2009年 | 204篇 |
2008年 | 444篇 |
2007年 | 441篇 |
2006年 | 447篇 |
2005年 | 412篇 |
2004年 | 291篇 |
2003年 | 253篇 |
2002年 | 209篇 |
2001年 | 61篇 |
2000年 | 33篇 |
1999年 | 27篇 |
1998年 | 31篇 |
1997年 | 32篇 |
1996年 | 28篇 |
1995年 | 23篇 |
1994年 | 16篇 |
1993年 | 22篇 |
1992年 | 15篇 |
1991年 | 16篇 |
1990年 | 11篇 |
1989年 | 9篇 |
1988年 | 8篇 |
1987年 | 9篇 |
1986年 | 8篇 |
1985年 | 18篇 |
1984年 | 13篇 |
1983年 | 6篇 |
1982年 | 7篇 |
1981年 | 10篇 |
1980年 | 6篇 |
1979年 | 10篇 |
1978年 | 7篇 |
1977年 | 12篇 |
1976年 | 7篇 |
1967年 | 5篇 |
排序方式: 共有6292条查询结果,搜索用时 15 毫秒
81.
FitzGerald PA Carr MW Davey TW Serelis AK Such CH Warr GG 《Journal of colloid and interface science》2004,275(2):649-658
Dimeric poly(ethylene oxide) surfactants (or nonionic gemini surfactants) with the structure (Cn-2H2n-3CHCH2O(CH2CH2O)mH)2(CH2)6 (or GemnEm), where n is the alkyl length and m is the average number of ethylene oxides per head group, were synthesized. Surfactants were synthesized with alkyl chain lengths n = 12, 14, and 20 and m = 5, 10, 15, 20, and 30. Water solubilities and cloud temperatures at 1 wt% were determined by measuring turbidity as a function of temperature. Cloud temperatures increase with m and decrease with n, as observed for conventional surfactants. For large m the cloud temperatures were all above 100 degrees C. Surfactants with small m (i.e., n = 12, 14, m = 5 and n = 20, m = 10) were insoluble at room temperature, forming two-phase mixtures. Critical micelle concentrations (CMCs) were measured using a pyrene fluorescence method and are all in the range of 10(-7) to 10(-6) M, with the lowest values from the surfactants with large n and small m. CMCs of mixtures with both anionic and nonionic conventional (monomeric) surfactants were well described by an ideal mixing model. 相似文献
82.
We construct a rigid-body (five-dimensional) potential-energy surface for the water-hydrogen complex using scaled perturbation theory (SPT). An analytic fit of this surface is obtained, and, using this, two minima are found. The global minimum has C2v symmetry, with the hydrogen molecule acting as a proton donor to the oxygen atom on water. A local minimum with Cs symmetry has the hydrogen molecule acting as a proton acceptor to one of the hydrogen atoms on water, where the OH bond and H2 are in a T-shaped configuration. The SPT global minimum is bound by 1097 microEh (Eh approximately 4.359744 x 10(-18) J). Our best estimate of the binding energy, from a complete basis set extrapolation of coupled-cluster calculations, is 1076.1 microEh. The fitted surface is used to calculate the second cross virial coefficient over a wide temperature range (100-3000 K). Three complementary methods are used to quantify quantum statistical mechanical effects that become significant at low temperatures. We compare our results with experimental data, which are available over a smaller temperature range (230-700 K). Generally good agreement is found, but the experimental data are subject to larger uncertainties. 相似文献
83.
Darensbourg DJ Maynard EL Holtcamp MW Klausmeyer KK Reibenspies JH 《Inorganic chemistry》1996,35(9):2682-2684
84.
85.
86.
Conformations of cyclopropyl methyl ketone have been studied using ab initio methods in an effort to quantify the effects of conjugative overlap between the cyclopropane ring and an adjacent ketone carbonyl. Results were comparable with previous experimental and theoretical studies. Cyclopropyl methyl ketone exhibits a global energy minimum in the s-cis conformer and a local energy minimum near the s-trans conformer. The potential energy curve obtained was used to derive torsion parameters which were employed in molecular mechanics studies of the conformations of the set of bicyclo[m.1.0]alkan-2-ones having larger ring sizes from five- to 16-membered. Similar conformations for the cyclopropyl ketone substructure are observed for all the medium and large ring systems examined. Possible synthetic ramifications of local conformational anchoring by this functional group array are discussed. 相似文献
87.
5-Methyl-4-phenyl-2-styryipyridine has been oxidized to 5-methyl-4-phenylpyridinie-2-carboxylic acid. The decarboxylation of this acid has given 3-methyl-4-phenylpyrldine. To prove the structure of -(5-methyl-4-phenyl-2-pyridyl)acetophenone, it has been converted into 2, 5-dimethyl-4-phenylpyridine. The reaction of benzyl chloride with the lithium derivative of 2, 5-dimethyl-4-phenylpyridine has been studied. 3,7-Dimethyl-2-azafluorene has been obtained from 2,5-dimethyl-4-p-tolylpyridine. 相似文献
88.
Carrillo-Marquez T Caggiano L Jackson RF Grabowska U Rae A Tozer MJ 《Organic & biomolecular chemistry》2005,3(22):4117-4123
Two distinct routes to beta-cycloalkylalanine derivatives have been developed. The first route employs the reaction of the iodoalanine-derived zinc-copper reagent 2 with cycloalk-1-en-3-yl phosphates, and the second uses the palladium-catalysed coupling of the iodoalanine-derived zinc reagent 1 with cycloalkenyl triflates; in each case, catalytic hydrogenation of the unsaturated product leads to the protected beta-cycloalkylalanine. The latter route allows access to a range of cycloalkyl derivatives, with ring sizes of 5-8. beta-(1-Methyl-1-cyclohexyl)alanine may be prepared using reaction of the zinc-copper reagent 2 with 3-methyl-2-cyclohexenyl chloride, followed by hydrogenation. The corresponding cyclopentyl derivative may be prepared by reaction of the same zinc-copper reagent 2 with diethyl geranylphosphate, followed by ring-closing metathesis and hydrogenation. 相似文献
89.
A response equation for conductivity detection in ion chromatography has been derived. This equation is applicable to non-suppressed ion chromatography using both fully ionised and partially ionised eluents. A prime assumption of this equation is that when partially ionised eluents are used (such as benzoic acid), both the ionised and neutral components of the eluent species contribute to the detector response of anionic analytes. Experimental evidence is provided to support this assumption in that pH changes accompanying the elution of an analyte have been measured. These pH changes are proportional to the concentration of analyte injected onto the column, in accordance with predictions from the response equation. Furthermore, it is shown that protonated eluents (such as benzoic acid) give more sensitive detection than equivalent ionised eluents (such as potassium benzoate) and the signal enhancement achieved using a protonated eluent species is in accordance with theory. 相似文献
90.
The reactions of benzocyclic ketones and α-ketoacids as carbonyl components in the Biginelli reaction were investigated. These unusual Biginelli substrates furnished novel drug-like dihydropyrimidinone scaffolds suitable for further elaboration. 相似文献