全文获取类型
收费全文 | 913篇 |
免费 | 29篇 |
国内免费 | 3篇 |
专业分类
化学 | 543篇 |
晶体学 | 3篇 |
力学 | 28篇 |
数学 | 147篇 |
物理学 | 224篇 |
出版年
2021年 | 12篇 |
2020年 | 8篇 |
2019年 | 17篇 |
2018年 | 9篇 |
2017年 | 10篇 |
2016年 | 17篇 |
2015年 | 20篇 |
2014年 | 20篇 |
2013年 | 42篇 |
2012年 | 60篇 |
2011年 | 57篇 |
2010年 | 40篇 |
2009年 | 29篇 |
2008年 | 55篇 |
2007年 | 47篇 |
2006年 | 45篇 |
2005年 | 62篇 |
2004年 | 46篇 |
2003年 | 33篇 |
2002年 | 36篇 |
2001年 | 12篇 |
2000年 | 16篇 |
1999年 | 9篇 |
1998年 | 7篇 |
1997年 | 8篇 |
1996年 | 14篇 |
1995年 | 16篇 |
1994年 | 11篇 |
1993年 | 7篇 |
1992年 | 6篇 |
1991年 | 5篇 |
1990年 | 5篇 |
1989年 | 7篇 |
1988年 | 7篇 |
1987年 | 7篇 |
1986年 | 6篇 |
1985年 | 8篇 |
1984年 | 13篇 |
1983年 | 10篇 |
1982年 | 13篇 |
1981年 | 7篇 |
1980年 | 8篇 |
1979年 | 12篇 |
1977年 | 8篇 |
1976年 | 9篇 |
1975年 | 4篇 |
1974年 | 8篇 |
1973年 | 8篇 |
1972年 | 3篇 |
1970年 | 4篇 |
排序方式: 共有945条查询结果,搜索用时 906 毫秒
21.
Jérémie Fournier Dit Chabert Stéphane Pellet-Rostaing Marc Lemaire 《Tetrahedron letters》2006,47(6):1015-1018
An original methodology starting from 3-aroyl-2-(2′-nitro-4′-methoxyphenyl)-benzo[b]thiophene allows the synthesis of unusual fused heterocycles. Direct hydrogenation with nickel catalysts followed by desulfurisation led to 2,3-diarylquinolines or 2,3-diaryltetrahydroquinolines. 相似文献
22.
23.
[reaction: see text] Anti alpha-amino-homopropargylic alcohols are prepared by addition of metallated propargylic amines to aldehydes. Among the four organometallic (LI, Zn, Ti, Cu) derivatives used, the most effective are the copper reagents. 相似文献
24.
A new method for injecting and driving fluids by means of a multi-port injection valve and syringe pumps in a micro-channel network is described. A structure composed of two micro-channels arranged as a cross is connected with capillary tubes to an external multi-port injection valve. The fluid flows are driven by pressure and the multi-port valve controls the direction of the flow within the different sections of the structure. The first position of the multi-port valve allows the preparation of the loading of the sample, which is pinched in the cross section of the two micro-channels. The second position allows the precise injection of nL volumes. No dead volume exists between injection and separation modes. The system can be used to prepare a sample plug by pressure in order to perform chromatography with a broad range of buffered or non-buffered solutions. Thanks to the insensitivity to the ionic strength of the sample, this injection method is useful for the injection of complex biological samples in microchip analysis. In order to demonstrate the feasibility of the method, different solutions of ionic or fluorescent molecules were injected and detected in a photoablated planar polymer device. 相似文献
25.
Mezzache S Afonso C Pepe C Karoyan P Fournier F Tabet JC 《Rapid communications in mass spectrometry : RCM》2003,17(14):1626-1632
The proton affinities of proline, cis-3-methylproline and cis-3-ethylproline have been measured by the kinetic method using an ion trap instrument; the values obtained are 936, 940.5, and 943 kJ mol(-1), respectively. The experimental values are consistent with those obtained by high-level ab initio calculations (B3LYP/6-31+G*//B3LYP/6-31G* and B3P86/6-31+G*//B3LYP/6-31G*). Several conformations of neutral and protonated proline were considered, in particular the endo and exo ring structure and the position of the carboxyl group. These results show the importance of the position of the hydrogen atom of the carboxyl group in determining the most stable protonated proline structure. 相似文献
26.
Dupont A Eastoe J Martin L Steytler DC Heenan RK Guittard F Taffin de Givenchy E 《Langmuir : the ACS journal of surfaces and colloids》2004,20(23):9960-9967
Hybrid fluorocarbon-hydrocarbon (F-H) sulfate surfactants are shown to be efficient stabilizers in water-in-CO2 (w/c) microemulsions. The chain structure and F-H ratio affect the regions of P-T phase stability and aggregation structure in these w/c phases. High-pressure near-infrared spectroscopy and small-angle neutron scattering measurements of microemulsified water provide evidence for the stabilization of w/c microemulsion droplets. The relative lengths of the two chains were found to influence the favored aggregation structure: for symmetric chain surfactants (F8H8, F7H7) spherical reverse micelles are present, but for asymmetric chain surfactants (F7H4, F8H4) extended cylinder aggregates form. These changes in aggregation are consistent with different surfactant packing parameters owing to the controlled variations in molecular structure. Furthermore, the general order of w/c phase transition pressures (F8H8 < F7H7 and F8H4 < F7H4) is in line with estimations of surfactant fractional free volume, as proposed by Johnston et al. (J. Phys. Chem. B 2004, 108, 1962-1966). Studies of adsorption at the poly(dimethylsiloxane)-water interface are shown to be valuable for assessing the CO2-philicity of new surfactants. All in all, the symmetric F8H8 and F7H7 analogues are seen to be the most efficient compounds from this class for applications in CO2. 相似文献
27.
Over the past few years, a large number of studies have been prepared that describe the analysis of peptides and proteins using capillary electrophoresis (CE) and laser-induced fluorescence (LIF). These studies have focused on two general goals: (i) development of automatic, selective and quick separation and detection of mixtures of peptides or proteins; (ii) generation of new methods of quantitation for very low concentrations (nm and subnanomolar) of peptides. These two goals are attained with the use of covalent labelling reactions using a variety of dyes that can be readily excited by the radiation from a commonly available laser or via the use of noncovalent labelling (immunoassay using a labelled antibody or antigen or noncovalent dye interactions). In this review article, we summarize the works which were performed for protein and peptide analysis via CE-LIF. 相似文献
28.
This paper presents the construction of amperometric biosensors for the highly sensitive detection of carbamate insecticides based on the inhibition of acetylcholinesterase (AChE). This enzyme was immobilised by entrapment in an optimised sol-gel matrix on TCNQ-modified screen-printed electrodes. The enzyme activity was estimated by measuring the thiocholine produced by the enzymatic hydrolysis of the acetylthiocholine using TCNQ as mediator. Wild and genetically engineered AChEs from Drosophila melanogaster (Dm) were chosen for their high sensitivity towards insecticides, which substantially improves the LOD compared with cholinesterases from other sources. The wild type and three mutant enzymes were tested against three carbamate insecticides: carbaryl, carbofuran and pirimicard. The best LOD were obtained with the Y370A mutant for carbaryl (1 × 10−8 M), the E69W mutant for pirimicarb (2 × 10−8 M) and the I161V mutant for carbofuran (8 × 10−10 M). The biosensors were applied to the analysis of two potable water samples. 相似文献
29.
Molecules with multiple sites that induce strong directional association tend to form open networks with significant volumes available for the inclusion of guests. Such molecules can be conveniently synthesized by grafting diverse sticky sites onto geometrically suitable cores. The characteristic inability of 9,9'-spirobifluorene to form close-packed crystals suggests that it should serve as a particularly effective core for the elaboration of molecules designed to form highly porous networks. To test this hypothesis, various new tetrasubstituted 9,9'-spirobifluorenes with hydrogen-bonding sites at the 3,3',6,6'-positions or 2,2',7,7'-positions were synthesized by multistep routes. Four of these compounds were crystallized, and their structures were determined by X-ray crystallography. In all cases, the compounds form extensively hydrogen-bonded networks with high porosity. In particular, 43% of the volume of crystals of 3,3',6,6'-tetrahydroxy-9,9'-spirobifluorene (28) is available for the inclusion of guests, whereas the porosity is only 28% in crystals of tetrakis(4-hydroxyphenyl)methane, a close model that lacks the spirobifluorene core. Similarly, the porosities found in crystals of 2,2',7,7'-tetra(acetamido)-9,9'-spirobifluorene (33) and 2,2',7,7'-tetrasubstituted tetrakis(diaminotriazine) 39 are 33% and 60%, respectively. Moreover, the porosity of crystals of 2,2',7,7'-tetrasubstituted tetrakis(triaminotriazine) 40 is 75%, the highest value yet observed in crystals built from small molecules. These observations demonstrate that a particularly effective strategy for engineering molecules able to form highly porous networks is to graft multiple sticky sites onto spirobifluorenes or other cores intrinsically resistant to close packing. 相似文献
30.
The preparation and thermal analysis of metal chelates of benzohydroxarnic acid (BHA) with Al(III), Cd(II), Co(II), Cu(II) (two compounds), Fe(III), La(III), Pb(II), Mn(II), Ni(II), U(VI) and Zn(II) is discussed. The Al(III), La(III), Pb(II) and Mn(II) chelates are new compounds. DTA and TGA curves of the chelates and of BHA are presented, and the heats of decomposition of the chelates are estimated. 相似文献