全文获取类型
收费全文 | 170篇 |
免费 | 0篇 |
国内免费 | 2篇 |
专业分类
化学 | 141篇 |
数学 | 11篇 |
物理学 | 20篇 |
出版年
2022年 | 2篇 |
2021年 | 2篇 |
2019年 | 3篇 |
2018年 | 1篇 |
2014年 | 1篇 |
2013年 | 16篇 |
2012年 | 4篇 |
2011年 | 7篇 |
2010年 | 10篇 |
2009年 | 3篇 |
2008年 | 9篇 |
2007年 | 6篇 |
2006年 | 12篇 |
2005年 | 15篇 |
2004年 | 7篇 |
2003年 | 12篇 |
2002年 | 14篇 |
2001年 | 1篇 |
2000年 | 1篇 |
1998年 | 1篇 |
1997年 | 1篇 |
1996年 | 2篇 |
1995年 | 1篇 |
1994年 | 1篇 |
1993年 | 2篇 |
1990年 | 2篇 |
1988年 | 2篇 |
1987年 | 3篇 |
1986年 | 2篇 |
1985年 | 2篇 |
1984年 | 1篇 |
1982年 | 2篇 |
1981年 | 8篇 |
1980年 | 4篇 |
1979年 | 2篇 |
1978年 | 7篇 |
1977年 | 3篇 |
排序方式: 共有172条查询结果,搜索用时 31 毫秒
1.
The piston problem is investigated in the case where the length of the cylinder is infinite (on both sides) and the ratio m/M is a very small parameter, where m is the mass of one particle of the gaz and M is the mass of the piston. Introducing initial conditions such that the stochastic motion of the piston remains in the average at the origin (no drift), it is shown that the time evolution of the fluids, analytically derived from Liouville equation in a previous work, agrees with the Second Law of thermodynamics. We thus have a non equilibrium microscopical model whose evolution can be explicitly shown to obey the two laws of thermodynamics. 相似文献
2.
Nicholas I. M. Gould Dominique Orban Annick Sartenaer Phillipe L. Toint 《4OR: A Quarterly Journal of Operations Research》2005,3(3):227-241
In this paper, we examine the sensitivity of trust-region algorithms on the parameters related to the step acceptance and
update of the trust region. We show, in the context of unconstrained programming, that the numerical efficiency of these algorithms
can easily be improved by choosing appropriate parameters. Recommended ranges of values for these parameters are exhibited
on the basis of extensive numerical tests.
MSC classification:
65K05, 90C26, 90C30 相似文献
3.
The steric effect of alkyl groups as parameterized by E's covers a range of over seven powers of ten. In this article an attempt is made to portray in mechanism terms the manifold nature of the steric effect as a function of substitution, i.e. the composition of the steric effect. One most consider the contribution of the topological carbon sites as a function of the true coordinates of these atoms. To this end, we evaluate the geometry of these alkyl groups in carboxylic acid indirectly by a search for the probable conformations of these acids. The starting point in this study is the determination of the minimum energy conformations in carboxylic acids using the empirical force field method based on analogous alkylmethyl ketone models.This approach to the ground state behaviour of these acids leads directly to a division of the complete set of alkyl groups into two subsets within which a Conformational sequence or filitation is associated with the substitution process which generates the successive alkyl groups of that subset. It is shown that eclipsed conformations are preferred in the case of secondary and tertiary groups bearing Et and Me sub-groups, giving way to preferred bisected conformations when t-Bu and i-Pr sub-groups are present. For further elucidation of steric perturbation terms these two subsets must be considered independently. These important observations lead to an overall coherent interpretation of steric effects.Three regions of distinct behaviour as a function of substitution have been identified. In Region I (the so-called “mormal” region, where the contribution of the introduction of successive methyl groups to the overall E's increases monotonically), besides excellent topological site correlations, an excellent hybrid correlation is proposed. For a conformationally homogeneous (i.e. eclipsed) set of alkyl groups the overall E's of groups is well expressed by a linear combination of the weighted contribution of sub-groups and the Newman six-number. This correlation leads to an interpretation of the composition of the overall steric effect of an alkyl group, as measured by the E's parameter, in terms of conformationally defined sites and stresses the steric importance of certain privileged sites. This result is consistent with the molecular mechanics viewpoint of preferred conformations but at variance with previous assumptions.The levelling effect (Region II), in the light of conformational information, is understood in terms of sterically active and inactive sites, while the inversion effect (Region III) is considered to be the result of molecular distortion brought about by relief of local internal steric strain within the alkyl groups. The X-ray structure of i-Pr3CCO2H illustrates this point. 相似文献
4.
The reaction of PhSeCl and N-PSP with homogeranic acid () or homoneric acid () affords butanolides in a stereospecific way. Despite the large number of cyclic cases studied in the literature such acyclic systems were remained largely unexplored. PhSe+ was unable to realize polycyclization. 相似文献
5.
Maria A Girault JP Saatov Z Harmatha J Dinan L Lafont R 《Journal of chromatographic science》2005,43(3):149-157
Ecdysteroid glycosides are found in both animals and plants. The chromatographic behavior of these molecules is characteristic, as they appear much more polar than their corresponding free aglycones when analyzed by normal-phase high-performance liquid chromatography (HPLC), whereas the presence of glycosidic moieties has a very limited (if any) impact on polarity when using reversed-phase HPLC. Biological activity is greatly reduced because the presence of this bulky substituent probably impairs the interaction with ecdysteroid receptor(s). 2-Deoxy-20-hydroxyecdysone 22-O-beta-D-glucopyranoside, which has been isolated from the dried aerial parts of Silene nutans (Caryophyllaceae), is used as a model compound to describe the rationale of ecdysteroid glycoside purification and identification. 相似文献
6.
Sirockin F Sich C Improta S Schaefer M Saudek V Froloff N Karplus M Dejaegere A 《Journal of the American Chemical Society》2002,124(37):11073-11084
There has recently been considerable interest in using NMR spectroscopy to identify ligand binding sites of macromolecules. In particular, a modular approach has been put forward by Fesik et al. (Shuker, S. B.; Hajduk, P. J.; Meadows, R. P.; Fesik, S. W. Science 1996, 274, 1531-1534) in which small ligands that bind to a particular target are identified in a first round of screening and subsequently linked together to form ligands of higher affinity. Similar strategies have also been proposed for in silico drug design, where the binding sites of small chemical groups are identified, and complete ligands are subsequently assembled from different groups that have favorable interactions with the macromolecular target. In this paper, we compare experimental and computational results on a selected target (FKBP12). The binding sites of three small ligands ((2S)1-acetylprolinemethylester, 1-formylpiperidine, 1-piperidinecarboxamide) in FKBP12 were identified independently by NMR and by computational methods. The subsequent comparison of the experimental and computational data showed that the computational method identified and ranked favorably ligand positions that satisfy the experimental NOE constraints. 相似文献
7.
Petit L Baraige F Bertheau Y Brunschwig P Diolez A Duhem K Duplan MN Fach P Kobilinsky A Lamart S Schattner A Martin P 《Journal of AOAC International》2005,88(2):654-664
The fate of DNA and protein transgenic sequences in products derived from animals fed transgenic crops has recently raised public interest. Sensitive molecular tests targeting the Bt176 genetic construct and the transgenic Cry1Ab protein were developed to determine whether plant sequences, especially transgenic sequences, are present in animal products. A protocol for total DNA extraction and purification from cow whole blood samples was first drawn up and assessed by spiking with known amounts of DNA from Bt176 maize. The limit of detection for transgenic sequences (35S promoter and Bt176-specific junction sequence) was determined by both the polymerase chain reaction-enzyme-linked immunosorbent assay (PCR-ELISA) and the 5'-nuclease PCR assay. Four additional PCR systems were built to substantiate the results. The first detects a mono-copy maize-specific sequence (ADH promoter). Two others target multi-copy sequences from plant nucleus (26S rRNA gene) and chloroplast (psaB gene). The last one, used as a positive control, targets a mono-copy animal sequence (alpha(s1)-casein gene). Both methods detected a minimum spiking at 25 copies of Bt176 maize/mL in 10 mL whole blood samples. The sandwich ELISA kit used detected down to 1 ng transgenic Cry1Ab protein/mL spiked whole blood. 相似文献
8.
Jourdain V Paillet M Almairac R Loiseau A Bernier P 《The journal of physical chemistry. B》2005,109(4):1380-1386
Sequential catalytic growth provides an efficient tool for the synthesis of carbon nanotubes periodically inserted with catalyst nanoparticles. Several synthesis parameters were found crucial in order to induce this particular growth mechanism. The presence of phosphorus is required to form metal phosphide particles active for the formation of carbon nanotubes with a matchstick morphology. The metal composition (Ni/Fe ratio) and the carbon supply have no influence on the nanofilament type but strongly affect the nanotube yield. The synthesis temperature induces important changes on both the nanofilament type and yield, which are correlated with important transformations of the catalyst layer in terms of composition, particle size, and physical state. 相似文献
9.
Ravelet C Boulkedid R Ravel A Grosset C Villet A Fize J Peyrin E 《Journal of chromatography. A》2005,1076(1-2):62-70
In this paper, we report for the first time an aptamer-based chiral stationary phase (CSP) able to resolve racemates of both target and various related compounds. The enantiomers of tyrosine and analogues (11 enantiomeric pairs) were separated using an immobilized tyrosine-specific L-RNA aptamer as CSP and an aqueous buffer (8 mM Tris-HCl buffer, 25 mM NaCl, 5 mM MgCl2; pH 7.4) as mobile phase, at a column temperature of 10 degrees C. It appeared that the carboxylic and amino groups as well as the aromatic side chain of amino acid controlled the stereospecific recognition. Modifications on the polar groups were strongly detrimental for enantioselectivity while the replacement of the phenolic group by some bicyclic aromatic residues of different polarity, size or shape did not impair the enantioselective interaction. In addition, the effects of the mobile phase composition and column temperature upon the retention and stereoselective properties of the CSP were assessed. Finally, it was found that the immobilized RNA aptamer could be used under hydro-organic mobile phase conditions without alteration of the stationary phase stability. 相似文献
10.