全文获取类型
收费全文 | 3750篇 |
免费 | 142篇 |
国内免费 | 71篇 |
专业分类
化学 | 2114篇 |
晶体学 | 43篇 |
力学 | 394篇 |
综合类 | 4篇 |
数学 | 639篇 |
物理学 | 769篇 |
出版年
2024年 | 4篇 |
2023年 | 52篇 |
2022年 | 100篇 |
2021年 | 92篇 |
2020年 | 117篇 |
2019年 | 97篇 |
2018年 | 78篇 |
2017年 | 113篇 |
2016年 | 85篇 |
2015年 | 95篇 |
2014年 | 134篇 |
2013年 | 316篇 |
2012年 | 203篇 |
2011年 | 187篇 |
2010年 | 161篇 |
2009年 | 245篇 |
2008年 | 242篇 |
2007年 | 239篇 |
2006年 | 233篇 |
2005年 | 175篇 |
2004年 | 128篇 |
2003年 | 135篇 |
2002年 | 105篇 |
2001年 | 73篇 |
2000年 | 94篇 |
1999年 | 73篇 |
1998年 | 68篇 |
1997年 | 34篇 |
1996年 | 25篇 |
1995年 | 25篇 |
1994年 | 31篇 |
1993年 | 27篇 |
1992年 | 28篇 |
1991年 | 14篇 |
1990年 | 12篇 |
1989年 | 7篇 |
1988年 | 8篇 |
1987年 | 20篇 |
1986年 | 14篇 |
1985年 | 15篇 |
1984年 | 17篇 |
1983年 | 3篇 |
1982年 | 13篇 |
1981年 | 7篇 |
1980年 | 4篇 |
1979年 | 7篇 |
1978年 | 5篇 |
1977年 | 3篇 |
排序方式: 共有3963条查询结果,搜索用时 15 毫秒
1.
When dealing with simple phenols such as caffeic acid (CA) and ferulic acid (FA), found in a variety of plants, it is very important to have control over the most important factors that accelerate their degradation reactions. This is the first report in which the stabilities of these two compounds have been systematically tested by exposure to various different factors. Forced degradation studies were performed on pure standards (trans-CA and trans-FA), dissolved in different solvents and exposed to different oxidative, photolytic and thermal stress conditions. Additionally, a rapid, sensitive, and selective stability-indicating gas chromatographic-mass spectrometric method was developed and validated for determination of trans-CA and trans-FA in the presence of their degradation products. Cis-CA and cis-FA were confirmed as the only degradation products in all the experiments performed. All the compounds were perfectly separated by gas chromatography (GC) and identified using mass spectrometry (MS), a method that additionally elucidated their structures. In general, more protic solvents, higher temperatures, UV radiation and longer storage times led to more significant degradation (isomerization) of both trans-isomers. The most progressive isomerization of both compounds (up to 43%) was observed when the polar solutions were exposed to daylight at room temperature for 1 month. The method was validated for linearity, precision as repeatability, limit of detection (LOD) and limit of quantitation (LOQ). The method was confirmed as linear over tested concentration ranges from 1−100 mg L−1 (r2s were above 0.999). The LOD and LOQ for trans-FA were 0.15 mg L−1 and 0.50 mg L−1, respectively. The LOD and LOQ for trans-CA were 0.23 mg L−1 and 0.77 mg L−1, respectively. 相似文献
2.
We give a sheaf theoretic interpretation of Potts models with external magnetic field, in terms of constructible sheaves and their Euler characteristics. We show that the polynomial countability question for the hypersurfaces defined by the vanishing of the partition function is affected by changes in the magnetic field: elementary examples suffice to see non-polynomially countable cases that become polynomially countable after a perturbation of the magnetic field. The same recursive formula for the Grothendieck classes, under edge-doubling operations, holds as in the case without magnetic field, but the closed formulae for specific examples like banana graphs differ in the presence of magnetic field. We give examples of computation of the Euler characteristic with compact support, for the set of real zeros, and find a similar exponential growth with the size of the graph. This can be viewed as a measure of topological and algorithmic complexity. We also consider the computational complexity question for evaluations of the polynomial, and show both tractable and NP-hard examples, using dynamic programming. 相似文献
3.
A string of four new hetero binuclear Ru(III) complexes of ferrocenecarboxaldehyde-4(N)-substituted thiosemicarbazones were synthesized and characterized by various spectral (infrared, ultraviolet–visible, Electron Paramagnetic Resonance (EPR) and High Resolution Mass Spectrometry (HR-MS) techniques. The binding abilities of the ligands/complexes with nucleic acid (calf thymus DNA, CT-DNA) and bovine serum albumin (BSA) were analyzed by absorption and emission titration methods. The complexes exhibited better DNA binding affinity than their parent ligands. The interaction with CT-DNA was found to be intercalative and with BSA static quenching mechanism was observed. All the synthesized Ru(III) complexes were subjected to study their in vitro cytotoxicity against MCF-7 (human breast cancer) and HT-29 (human colon cancer) cell lines. Among the four complexes, complex 3 [RuCp (FF-etsc)PPh3]Cl exhibited the highest cytotoxicity in MCF-7 cells and complex 4 [RuCp (FF-ptsc)PPh3]Cl was the most active on HT-29 cells. 相似文献
4.
In this paper, we will propose algorithms for calculating a minimal ellipsoid circumscribing a polytope defined by a system
of linear inequalities. If we know all vertices of the polytope and its cardinality is not very large, we can solve the problem
in an efficient manner by a number of existent algorithms. However, when the polytope is defined by linear inequalities, these
algorithms may not work since the cardinality of vertices may be huge. Based on a fact that vertices determining an ellipsoid
are only a fraction of these vertices, we propose algorithms which iteratively calculate an ellipsoid which covers a subset
of vertices. Numerical experiment shows that these algorithms perform well for polytopes of dimension up to seven. 相似文献
5.
6.
The cocrystal of 1,2-bis(diphenylphosphinoyl)ethane (DPPEO) with phenol (1:1) were studied theoretically with AM1, PM3, MNDO and MINDO/3 semi-empirical methods to elucidate its structure. The bond lengths and angles from theoretical studies of molecule DPPEO/phenol (1:1) were found to be as expected. Theoretical results, concerning with intermolecular van der Waals forces in cocrystal, were compared with the previously obtained experimental data and AM1 results were found to be the best fit for bond lengths and angles of DPPEO/phenol. 相似文献
7.
Franois Lavaud Michel Fontanille Yves Gnanou 《Journal of polymer science. Part A, Polymer chemistry》2004,42(19):4964-4975
Studies on the anionic polymerization of methyl methacrylate in tetrahydrofuran and in the presence of sparteine have revealed a beneficial effect due to this additive, resulting in a decrease in the extent of termination. Better control of the definition of the polymers formed can thus be achieved in the presence of this additive. On the other hand, macromolecular engineering requires a range of active species concentrations lower than 10?3 mol L?1 and particularly the synthesis of polymers of high molar masses. For a better understanding of the mechanism of chain growth under such concentration conditions, the kinetics of polymerization have been investigated with a technique based on adiabatic calorimetry. Sparteine has been found to lack sufficient cation‐binding power to prevent the propagating enolate ion pairs from aggregating. The rate constant of propagation of nonaggregated species has been estimated, as well as the aggregation constant of equilibrium. For very low initiator concentrations, termination reactions have been shown to profoundly alter the control of the polymerization and to prevent a quantitative monomer conversion. Theoretical maximal conversions have been calculated from kinetic data and compare well with the experimental values. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4964–4975, 2004 相似文献
8.
9.
H. William Bosch Sre
o D. kapin Egon Matijevi 《Colloids and surfaces. A, Physicochemical and engineering aspects》2004,250(1-3):43-50
Controlled precipitation of the diagnostic imaging agent ethyl 3,5-di(acetylamino)-2,4,6-triiodobenzoate has been used to produce fine particles of various sizes, morphologies, and degrees of crystallinity, which depended on experimental conditions. In addition, two distinct polymorphic forms of the drug have been fully characterized by single crystal X-ray diffraction studies, and evidence for a third polymorph was also observed. Some of the so prepared dry particles were coated with a thin layer of silica. 相似文献
10.
W. Kockelmann M. Hofmann O. Moze S.J. Kennedy K.H.J. Buschow 《The European Physical Journal B - Condensed Matter and Complex Systems》2002,30(1):25-32
The element distributions and the magnetic ordering behaviour of compounds RNi10Si2 (R
=
Tb, Dy, Ho, Er, Tm) have been studied by neutron powder diffraction down to temperatures of 1.6 K. The compounds crystallize
in an ordered variant of the ThMn12 structure type in the tetragonal space group P4/nmm. An ordered 1:1 distribution of Ni and Si on sites 4d and 4e, respectively,
corresponds to a modulation vector [0, 0, 1] with respect to the space group I4/mmm of the ThMn12 structure. TbNi10Si2 orders antiferromagnetically below T
N
= 4.5 K with a magnetic propagation vector of [0, 0, 1/2]. The magnetic Tb moments, 8.97(2) /Tb atom at 1.6 K, are aligned along the c-axis. The Ni sites in TbNi10Si2 do not carry any ordered magnetic moments. The compounds with R
=
Dy, Ho, Er, and Tm are paramagnetic down to 1.6 K and 3.0 K, respectively.
Received 10 July 2002 / Received in final form 12 September 2002 Published online 29 October 2002 相似文献