全文获取类型
收费全文 | 655篇 |
免费 | 2篇 |
国内免费 | 2篇 |
专业分类
化学 | 396篇 |
晶体学 | 3篇 |
力学 | 25篇 |
数学 | 120篇 |
物理学 | 115篇 |
出版年
2023年 | 2篇 |
2022年 | 2篇 |
2020年 | 4篇 |
2019年 | 4篇 |
2018年 | 8篇 |
2017年 | 6篇 |
2016年 | 16篇 |
2015年 | 7篇 |
2014年 | 7篇 |
2013年 | 24篇 |
2012年 | 45篇 |
2011年 | 58篇 |
2010年 | 25篇 |
2009年 | 22篇 |
2008年 | 47篇 |
2007年 | 40篇 |
2006年 | 47篇 |
2005年 | 43篇 |
2004年 | 42篇 |
2003年 | 30篇 |
2002年 | 29篇 |
2001年 | 8篇 |
2000年 | 3篇 |
1999年 | 17篇 |
1998年 | 3篇 |
1997年 | 10篇 |
1996年 | 10篇 |
1995年 | 4篇 |
1994年 | 5篇 |
1993年 | 5篇 |
1992年 | 7篇 |
1991年 | 4篇 |
1990年 | 4篇 |
1989年 | 3篇 |
1988年 | 3篇 |
1987年 | 3篇 |
1986年 | 6篇 |
1985年 | 10篇 |
1984年 | 6篇 |
1983年 | 7篇 |
1982年 | 4篇 |
1981年 | 5篇 |
1980年 | 3篇 |
1979年 | 5篇 |
1977年 | 2篇 |
1976年 | 2篇 |
1975年 | 2篇 |
1974年 | 4篇 |
1973年 | 3篇 |
1972年 | 1篇 |
排序方式: 共有659条查询结果,搜索用时 0 毫秒
1.
Mathieu Boiret Anna de Juan Nathalie Gorretta Yves-Michel Ginot Jean-Michel Roger 《Analytica chimica acta》2015
Raman chemical imaging provides chemical and spatial information about pharmaceutical drug product. By using resolution methods on acquired spectra, the objective is to calculate pure spectra and distribution maps of image compounds. With multivariate curve resolution-alternating least squares, constraints are used to improve the performance of the resolution and to decrease the ambiguity linked to the final solution. Non negativity and spatial local rank constraints have been identified as the most powerful constraints to be used. 相似文献
2.
Jean Bellissard Anton Bovier Jean-Michel Ghez 《Communications in Mathematical Physics》1991,135(2):379-399
We study a one dimensional tight binding hamiltonian with a potential given by the period doubling sequence. We prove that its spectrum is purely singular continuous and supported on a Cantor set of zero Lebesgue measure, for all nonzero values of the potential strength. Moreover, we obtain the exact labelling of all spectral gaps and compute their widths asymptotically for small potential strength. 相似文献
3.
Robert R. Gamache Jean-Michel Hartmann 《Journal of Quantitative Spectroscopy & Radiative Transfer》2004,83(2):119-147
A complex semiclassical model for the calculation of line widths and shifts of H2O broadened by N2, derived from the Robert and Bonamy approach, is tested by comparisons with measurements for selected transitions in various vibrational bands. The lines retained, which involve rotational states with Kc=J or J−1 have been chosen for two reasons. The first is that they show large variations of the widths with J and thus enable a severe test of the model. The second is that, as explained in this paper, they are well-suited for the study of the effects of vibration on the collisional parameters. The measured values have been extracted from an updated version of a database built years ago (JQSRT 52 (1994) 481) that contains all available measurements. Comparisons between experimental and calculated widths and shifts at room temperature illustrate the quality of the model and clearly demonstrate, for the first time, that there is a vibrational dependence of the broadening. Values of collisional parameters are first studied in fundamental bands. This shows that the theoretical approach accounts for most of the dependence of broadening and shifting on rotational quantum numbers: the variations of γ, which reach a factor of nearly 20 from low to high J values, are correctly accounted for by the model as are some specific features of the shifts δ. Analysis confirms that the bending and stretching vibrations have significantly different effects on δ, due to the vibrational dependence of the intermolecular potential. On the other hand, differences on the widths are rather small with slightly smaller broadening for lines of the bending band. Calculations show that there is a spectroscopic effect, due to the larger rotational constant A in the v2=1 state. Calculations made for overtone bands involving numerous quanta of the stretching vibration are then presented. They predict that a significant dependence of the width should be observed for high J lines due to the effect of vibration on the interaction potential. This is confirmed by comparisons with measurements for lines involving a change of three and four quanta of stretching vibration. 相似文献
4.
In the framework of ARMA models, we consider testing the reliability of the standard asymptotic covariance matrix (ACM) of the least-squares estimator. The standard formula for this ACM is derived under the assumption that the errors are independent and identically distributed, and is in general invalid when the errors are only uncorrelated. The test statistic is based on the difference between a conventional estimator of the ACM of the least-squares estimator of the ARMA coefficients and its robust HAC-type version. The asymptotic distribution of the HAC estimator is established under the null hypothesis of independence, and under a large class of alternatives. The asymptotic distribution of the proposed statistic is shown to be a standard χ2 under the null, and a noncentral χ2 under the alternatives. The choice of the HAC estimator is discussed through asymptotic power comparisons. The finite sample properties of the test are analyzed via Monte Carlo simulation. 相似文献
5.
6.
Jean-Michel NavarreDominique Guianvarc'h Audrey Farese-Di GiorgioRoger Condom Rachid Benhida 《Tetrahedron letters》2003,44(10):2199-2202
A short route to novel α-(2-aminothiazolyl)-C-nucleosides has been developed. The key step was the high diastereoselective reduction of the hemiacetal intermediates using L-Selectride, which afforded the corresponding R-diols in quantitative yields. These diols were converted, after C4-C1 ring closure and protecting groups cleavage, to their corresponding free α-C-nucleosides. 相似文献
7.
8.
Variants of the beta-aminophosphine L(1) [Ph(2)PCH(2)CH(Ph)NHPh] containing additional nitrogen donor functions have been prepared. These functions are branched off the C atom adjacent to the P atom, or the P atom itself. Ligand [Ph(2)PCH(o-C(6)H(4)NMe(2))CH(Ph)NHPh] has been obtained as a mixture of two diastereomers L(3A) and L(3B) by lithiation of L(2) [Ph(2)PCH(2)(o-C(6)H(4)NMe(2))] with n-BuLi followed by PhCH=NPh addition and hydrolysis. The diastereomers have been separated by fractional crystallization from ethanol. Ligand Et(2)NCH(2)P(Ph)CH(2)CH(Ph)NHPh has been obtained as a mixture of two diastereomers L(5A) and L(5B)(starting with P-Ph reductive cleavage of L(1) by lithium and subsequent hydrolysis to give PhP(H)CH(2)CH(Ph)NHPh (mixture of two diastereomers L(4A) and L(4B)). The latter reacts with diethylamine and formaldehyde to afford the L(5) diastereomeric mixture. Complexes RhCl(CO)(L) (L = L(3A), 1(A); L(3B), 1(B); L(5A/B), 2(A/B)) were obtained by reaction of [RhCl(CO)(2)](2) and the appropriate ligand or ligand mixture. Complexes 1(A), 1(B), and 2(A) have been isolated in pure form and characterized by classical techniques and by single-crystal X-ray diffraction. All structures exhibit a bidentate kappa-P,kappa-N(NHPh) mode similar to the complex containing L(1). While complexes 1(A) or 1(B) are stable in CDCl(3) solution, complex 2(A) slowly converts to its diastereomer 2(B). This unexpected epimerization appears to take place by inversion at the Rh-coordinated P center, an apparently unprecedented phenomenon. A mechanism based on a reversible P-C bond oxidative addition is proposed. The influence of the pendant nitrogen function of the diaminophosphines L(3A) and L(5A/B) on the rhodium catalytic activity in styrene hydroformylation has been examined and compared to that of the aminophosphines L(1) or L(2). The observed trends are related to the basicity of the dangling amine function and to its proximity to the metal center. 相似文献
9.
Grandjean C Boutonnier A Guerreiro C Fournier JM Mulard LA 《The Journal of organic chemistry》2005,70(18):7123-7132
[reaction: see text] The nature of a linker used for preparing glycoconjugate vaccines is of utmost importance as it may lead to immunogenic biomolecules. We report the conjugation of carbohydrate haptens to protein carriers leading to potential vaccines using the traceless Staudinger ligation. The ligation relies on the selective transfer of a phosphane substituent to an azide to form a native amide bond in the final product upon release of an oxidized phosphane byproduct. We designed new phosphino-functionalized cross-linkers suitable for protein carrier derivatization. We evaluated their utility in preparing conjugates using both synthetic and purified bacterial carbohydrates. The use of a borane-protected phosphane which is deprotected at the time of the ligation reaction led to the best results observed thus far in terms of stability toward oxidation and reactivity. 相似文献
10.
Guilard R Gryko DT Canard G Barbe JM Koszarna B Brandès S Tasior M 《Organic letters》2002,4(25):4491-4494
[reaction: see text] We have developed a new method that affords regioisomerically pure corroles possessing up to three different substituents at the meso positions. The corrole formation reaction involves the acid-catalyzed condensation of a dipyrromethane-dicarbinol with pyrrole followed by oxidation with DDQ. ABC-Type corroles were synthesized for the first time according to this procedure. 相似文献