全文获取类型
收费全文 | 3009篇 |
免费 | 244篇 |
国内免费 | 742篇 |
专业分类
化学 | 2419篇 |
晶体学 | 13篇 |
力学 | 261篇 |
综合类 | 22篇 |
数学 | 283篇 |
物理学 | 997篇 |
出版年
2024年 | 29篇 |
2023年 | 355篇 |
2022年 | 97篇 |
2021年 | 106篇 |
2020年 | 92篇 |
2019年 | 97篇 |
2018年 | 92篇 |
2017年 | 86篇 |
2016年 | 116篇 |
2015年 | 89篇 |
2014年 | 116篇 |
2013年 | 212篇 |
2012年 | 124篇 |
2011年 | 160篇 |
2010年 | 111篇 |
2009年 | 165篇 |
2008年 | 168篇 |
2007年 | 176篇 |
2006年 | 169篇 |
2005年 | 165篇 |
2004年 | 152篇 |
2003年 | 99篇 |
2002年 | 106篇 |
2001年 | 70篇 |
2000年 | 72篇 |
1999年 | 81篇 |
1998年 | 78篇 |
1997年 | 84篇 |
1996年 | 68篇 |
1995年 | 61篇 |
1994年 | 48篇 |
1993年 | 42篇 |
1992年 | 29篇 |
1991年 | 28篇 |
1990年 | 28篇 |
1989年 | 20篇 |
1988年 | 26篇 |
1987年 | 11篇 |
1986年 | 18篇 |
1985年 | 20篇 |
1984年 | 13篇 |
1983年 | 6篇 |
1982年 | 14篇 |
1981年 | 20篇 |
1980年 | 9篇 |
1977年 | 9篇 |
1976年 | 12篇 |
1975年 | 7篇 |
1973年 | 9篇 |
1972年 | 5篇 |
排序方式: 共有3995条查询结果,搜索用时 0 毫秒
71.
Paul G. Mezey 《Theoretical chemistry accounts》1985,67(1):43-61
The family of all possible reaction mechanisms on a potential surface has an algebraic structure with potential applications in quantum chemical molecular design and synthesis planning.Transformation properties and equivalence relations of reaction paths on potential energy hypersurfaces lead to a topological definition of reaction mechanisms. The family of all fundamental reaction mechanisms on the hypersurface has a group structure,the fundamental group of an appropriately defined topological space. Isomorphism and homomorphism relations between fundamental groups of reaction mechanisms are used to characterize the chemically important topological properties of various subsets of a hypersurface, or those of different excited state hypersurfaces. 相似文献
72.
Rudi van Eldik 《Angewandte Chemie (International ed. in English)》1986,25(8):673-682
In order to understand the dynamics of chemical reactions in general, detailed information on electronic, structural and kinetic properties is required. The key questions on how chemical reactions actually occur can in many cases only be answered in terms of information obtained from kinetic studies. In conventional kinetic studies of chemical reactions in solution, the variables usually selected include concentration, acidity, solvent, and temperature. In recent years, pressure has become an additional selected variable in such studies. It enables the measurement of the volume of activation and the construction of reaction volume profiles and thus assists in the elucidation of the underlying mechanism; it also completes the comprehension of reaction kinetics by adding another kinetic parameter that the suggested reaction mechanism must account for. Furthermore, the volume of activation is the only transition state property that can be correlated with the corresponding ground state property in an experimentally simple manner. In this paper, the insights so gained in our understanding of the dynamics of reactions involving coordination complexes will be presented. Such reactions are of fundamental interest to chemists since they often form the basis of catalytic, biological, environmental and energy related processes. Any additional information that will add to the understanding of the reaction dynamics is therefore of exceptional importance. 相似文献
73.
Curing of diglycidyl ether of bisphenol-A (DGEBA) with phosphorus containing amide amines i.e. bis[3(3’-aminobenzamido phenyl)]methyl
phosphine oxide (MB),bis[3(4’-aminobenzamido phenyl)]methyl phosphine oxide (PB), tris[3(3’-aminobenzamidophenyl)] phosphine
oxide (MT) and tris[3(4’-aminobenzamido phenyl)] phosphine oxide (PT)and conventionally used curing agent 4,4’-diaminodiphenyl
sulfone (D) was studied by DSC. The amines MB, PB, MT and PT were synthesised in the laboratory and were characterized by
determining elemental composition, melting point, and amine equivalent. Structural characterization was done by 1H-NMR and FTIR. The onset temperature of curing depended on the nucleophilicity of the amines and was in the orderMT≈MB<PT<PB<D.
The exothermic peak temperatures were in the orderD>PB>PT>MT≈MB. The char residue of cured epoxy resin was significantly higher
when phosphorus was incorporated in the cured network. Using mixed amine formulations based on amine D and P-containing amines
and the molar ratio of these amines could easily control the curing characteristics. A linear relationship between char yield
and P-content was observed in such formulations.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
74.
Andriy B. Zaborovskiy Ruslan E. Prystansky Vitaliy I. Timokhin 《Journal of organometallic chemistry》2004,689(18):2912-2919
The interaction of (Me3Si)3SiH with O2 is known to afford (Me3SiO)2Si(H)SiMe3 in which the two oxygen atoms arise from the same oxygen molecule. In order to investigate the mechanism of this unusual reaction, the oxidation rates were measured in the temperature range 30-70 °C by following oxygen uptake in the presence and absence of hydroquinone as inhibitor. The rate constant for the spontaneous reaction of (Me3Si)3SiH with O2 was determined at 70 °C to be ∼3.5 × 10−5 M−1 s−1. A sequence of the propagation steps is proposed by combining the previous and present experimental findings with some theoretical results obtained at the semiempirical level. These calculations showed that the silylperoxyl radical (Me3Si)3SiOO undergoes three consecutive unimolecular steps to give (Me3SiO)2Si()SiMe3. Evidence has been obtained that the rate determining step is the rearrangement of silylperoxyl radical to a dioxirand-like pentacoordinated silyl radical. Our findings are of considerable importance for the understanding of the oxidation of hydrogen-terminated silicon surfaces. 相似文献
75.
An efficient synthetic method for the preparation of (E)- and (Z)-3(5)-(2-hydroxyphenyl)-4-styrylpyrazoles has been developed. The reaction of (E)- and (Z)-3-styrylchromones with hydrazine hydrate afforded the corresponding (E)- and (Z)-4-styrylpyrazoles, respectively, saved 4′-nitro-derivatives where both (E)- and (Z)-4′-nitro-3-styrylchromones afforded (E)-3(5)-(2-hydroxyphenyl)-4-(4-nitrostyryl)pyrazoles. The reaction mechanism for these transformations was discussed and the stereochemistry of all products was assigned by NMR experiments. 相似文献
76.
Simultaneous thermogravimetry–differential thermal analysis (TG–DTA) and gas and liquid chromatography with mass spectrometry detection have been used to study the kinetics and decomposition of 2-hydroxybenzoic acid, 2-carboxyphenyl ester, commercially known as salsalate. Samples of salsalate were heated in the TG–DTA apparatus in an inert atmosphere (100 ml min−1 nitrogen) in the temperature range 30–500 °C. The data indicated that the decomposition of salsalate is a two-stage process. The first decomposition stage (150–250 °C) had a best fit with second-order kinetics with Ea=191–198 kJ/mol. The second decomposition stage (300–400 °C) is described as a zero-order process with Ea=72–80 kJ/mol. The products of the decomposition were investigated in two ways:
- (a)Salsalate was heated in a gas chromatograph at various isothermal temperatures in the range 150–280 °C, and the exit gas stream analyzed by mass spectrometry (GC–MS). This approach suggested that salsalate decomposes with the formation of salicylic acid, phenol, phenyl salicylate, and cyclic oligomers of salicylic acid di- and tri-salicylides.
- (b)One gram samples of salsalate were heated in a vessel under nitrogen to 150 °C, and the residues were analyzed by liquid chromatography–mass spectrometry (LC–MS). The major compound detected was a linear tetrameric salicylate ester.
77.
Colin Eaborn Anna Kowalewska Wlodzimierz Stanczyk 《Journal of organometallic chemistry》1998,560(1-2)
The finding that compounds of the type (Me3Si)2(PhMe2Si)CSiMePhX react with electrophiles to give very predominantly rearranged products (Me3Si)2(Ph2MeSi)CSiMe2Y, which would be expected to be thermodynamically disfavoured, can be rationalized in terms of a mechanism in which the anchimerically-assisted departure of X− gives the Ph-bridged cation [(Me3Si)2
MePh]+ which is attacked by the nucleophile at the less hindered centre bearing two Me groups rather than that bearing one Me and one Ph group, with the outcome determined by kinetic rather than thermodynamic factors. Both (Me3Si)2(Ph2MeSi)CSiMe2Br and its isomer (Me3Si)2(PhMe2Si)CSiMePhBr react with AgBF4 in CH2Cl2 or Et2O to give >95% of the fluoride (Me3Si)2(Ph2MeSi)CSiMe2F. Reaction of the bromide (Me3Si)2(PhMe2Si)CSiMePhBr with AgO2CCF3 in Et2O, and that of the hydride (Me3Si)2(PhMe2Si)CSiMePhH with ICl in CCl4, likewise give >95% of the rearranged (Me3Si)2(Ph2MeSi)CSiMe2O2CCF3 and (Me3Si)2(Ph2MeSi)CSiMe2Cl, respectively. 相似文献
Full-size image
78.
Biomimetic formation of gramicidin S by dimerization-cyclization of pentapeptide precursor on solid support 总被引:1,自引:0,他引:1
The biomimetic formation of gramicidin S, cyclo(-d-Phe-Pro-Val-Orn-Leu-)2, by the dimerization and cyclization of pentapeptide precursor without the protection of δ-amino group of the Orn residue was examined on a solid support. The cyclization of H-d-Phe-Pro-Val-Orn-Leu-oxime on a resin with an oxime group of 0.62 mmol/g in 1,4-dioxane directly gave gramicidin S in a 50% yield. The dimerization-cyclization mode on the solid support was similar to that of the biosynthesis of gramicidin S on an enzyme. 相似文献
79.
Kunhye Lee 《Journal of organometallic chemistry》2005,690(19):4319-4329
The mechanism of the reaction of isothiocyanates with metal-azido complexes of Pt(II), Pd(II), and Sn as well as hydrazoic acid is studied using the density functional theory method. The relative stability between two possible product isomers (S-coordinated tetrazole-thiolato and N-coordinated tetrazolato complexes) does not directly relate to the experimentally synthesized product. The overall reaction proceeds via three steps. The first step is the approach of the S-atom of the organic isothiocyanate to the central metal atom followed by the nucleophilic attack of the coordinated N-atom of the azido group to the C-atom of the isothiocyanate. The activation barrier of this step is 22-24 kcal mol−1, and the resulting intermediate has the imidoyl azide form. In the second reaction step, electrophilic attack of the terminal N-atom of the azido group to the N-atom of the isothiocyanate transforms the intermediate to the S-coordinated tetrazole-thiolato product with a barrier of about 11 kcal mol−1. The N-coordinated tetrazole could be made from the S-coordinated tetrazole-thiolato complex only after the third step, in which the metal coordination migrates from the S- to the N-atom. 相似文献
80.
Ab initio molecular orbital calculations employing a 4-31G basis set have been used to study the minimum energy paths for the formation of HCO+, COH+, and HCOH2+ from CO by protonation. The protonation of N2 to give NNH+ and HNNH2+ and of NO+ to form HNO2+ and NOH2+ have also been investigated. All species formed have linear equilibrium geometries and the minimum energy path for approach of the proton is along the line-of-centers of the heavy atoms. Energy barriers to the formation of the various species are given, where appropriate, and changes in geometry, ordering of molecular orbitals and orbital occupancy are discussed. 相似文献