全文获取类型
收费全文 | 3462篇 |
免费 | 184篇 |
国内免费 | 18篇 |
专业分类
化学 | 2420篇 |
晶体学 | 13篇 |
力学 | 76篇 |
数学 | 601篇 |
物理学 | 554篇 |
出版年
2023年 | 31篇 |
2022年 | 40篇 |
2021年 | 61篇 |
2020年 | 79篇 |
2019年 | 76篇 |
2018年 | 70篇 |
2017年 | 76篇 |
2016年 | 177篇 |
2015年 | 138篇 |
2014年 | 122篇 |
2013年 | 223篇 |
2012年 | 266篇 |
2011年 | 280篇 |
2010年 | 163篇 |
2009年 | 117篇 |
2008年 | 229篇 |
2007年 | 193篇 |
2006年 | 163篇 |
2005年 | 169篇 |
2004年 | 149篇 |
2003年 | 137篇 |
2002年 | 123篇 |
2001年 | 38篇 |
2000年 | 29篇 |
1999年 | 37篇 |
1998年 | 37篇 |
1997年 | 25篇 |
1996年 | 38篇 |
1995年 | 12篇 |
1994年 | 20篇 |
1993年 | 28篇 |
1992年 | 18篇 |
1991年 | 15篇 |
1990年 | 15篇 |
1989年 | 11篇 |
1988年 | 15篇 |
1987年 | 13篇 |
1986年 | 14篇 |
1985年 | 31篇 |
1984年 | 23篇 |
1983年 | 11篇 |
1982年 | 13篇 |
1981年 | 9篇 |
1980年 | 10篇 |
1979年 | 18篇 |
1978年 | 12篇 |
1977年 | 12篇 |
1975年 | 9篇 |
1974年 | 13篇 |
1973年 | 12篇 |
排序方式: 共有3664条查询结果,搜索用时 15 毫秒
91.
One-bond Pt-Pt nuclear spin-spin coupling constants J(Pt-Pt) for closely related dinuclear Pt complexes can differ by an order of magnitude without any obvious correlation with Pt-Pt distances. As representative examples, the spin-spin couplings of the dinuclear Pt(I) complexes [Pt(2)(CO)(6)](2+) (1) and [Pt(2)(CO)(2)Cl(4)](2-) (2) have been computationally studied with a recently developed relativistic density functional method. The experimental values are (1)J((195)Pt-(195)Pt) = 5250 Hz for 2 but 551 Hz for 1. Many other examples are known in the literature. The experimental trends are well reproduced by the computations and can be explained based on the nature of the ligands that are coordinated to the Pt-Pt fragment. The difference for J(Pt-Pt) of an order of magnitude is caused by a sensitive interplay between the influence of different ligands on the Pt-Pt bond, and relativistic effects on metal-metal and metal-ligand bonds as well as on "atomic orbital contributions" to the nuclear spin-spin coupling constants. The results can be intuitively rationalized with the help of a simple qualitative molecular orbital diagram. 相似文献
92.
Klaus Bieger Miguel Tomás José Barluenga Rafael Santiago Santiago García-Granda 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-4)
Abstract The title compound is the main product of the 2:1 reaction of DMAD with diazaphosphinines. The supposed mechanisms with intermediates and related products will be presented. 相似文献
93.
Bottleable Neutral Analogues of [B2H5]− as Versatile and Strongly Binding η2 Donor Ligands 下载免费PDF全文
Dr. Sunewang R. Wang Dominic Prieschl James D. Mattock Dr. Merle Arrowsmith Dr. Conor Pranckevicius Dr. Tom E. Stennett Dr. Rian D. Dewhurst Dr. Alfredo Vargas Prof. Dr. Holger Braunschweig 《Angewandte Chemie (International ed. in English)》2018,57(21):6347-6351
Herein we report the discovery that two bottleable, neutral, base‐stabilized diborane(5) compounds are able to bind strongly to a number of copper(I) complexes exclusively through their B?B bond. The resulting complexes represent the first known complexes containing unsupported, neutral σB?B diborane ligands. Single‐crystal X‐ray analyses of these complexes show that the X?Cu moiety (X=Cl, OTf, C6F5) lies opposite the bridging hydrogen atom of the diborane and is near perpendicular to the B?B bond, interacting almost equally with both boron atoms and causing a B?B bond elongation. DFT studies show that σ donation from and π backdonation to the pseudo‐π‐like B?B bond account for their formation. Astoundingly, these copper σB?B complexes are inert to ligand exchange with pyridine under either heating or photoirradiation. 相似文献
94.
Several methods are described for determining rate constants for second order reactions of the form U + V --> W using chemometrics and hard modelling to analyse UV absorption spectroscopic data, where all species absorb with comparable concentrations and extinctions. An interesting feature of this type of reaction is that the number of steps in the reaction is less than the number of absorbing species, resulting in a rank-deficient response matrix. This can cause problems when using some of the methods described in the literature. The approaches discussed in the paper depend, in part, on what knowledge is available about the system, including the spectra of the reactants and product, the initial concentrations and the exact kinetics. Sometimes some of this information may not be available or may be hard to estimate. Five groups of methods are discussed, namely use of multiple linear regression to obtain concentration profiles and fit kinetics information, rank augmentation using multiple batch runs, difference spectra based approaches, mixed spectral approaches which treat the reaction as two independent pseudospecies, and principal components regression. Two datasets are simulated, one where the spectra are quite different and the other where the spectrum of one reactant and the product share a high degree of overlap. Three sources of error are considered, namely sampling error, instrumental noise and errors in initial concentrations. The relative merits of each method are discussed. 相似文献
95.
96.
97.
98.
99.
L’ubomír Ježo Martin Palou Jana Kozánková Tomáš Ifka 《Journal of Thermal Analysis and Calorimetry》2010,101(2):585-593
Isothermal conduction calorimetry, differential thermal analysis (DTA)–thermogravimetric analysis (TG) analysis, and SEM observations have proved the activation effect of Ca(OH)2 released from the C3S hydration upon blast furnace slag (BFS). Five sample mixtures of BFS and C3S and two samples of pure BFS and C3S were submitted to reaction with water inside the calorimeter at room temperature. The values of hydration heat were recorded up to 7 days. Samples were stored in humidity during 28 days and then were submitted to DTA–TG and SEM analysis. The effect of Ca(OH)2 upon heat evolution of sample mixtures has been quantified and its influence upon the formation of new hydrates and microstructure of pastes was evidenced. 相似文献
100.