全文获取类型
收费全文 | 446篇 |
免费 | 19篇 |
国内免费 | 47篇 |
专业分类
化学 | 347篇 |
晶体学 | 6篇 |
力学 | 30篇 |
综合类 | 11篇 |
数学 | 30篇 |
物理学 | 88篇 |
出版年
2024年 | 1篇 |
2022年 | 7篇 |
2021年 | 5篇 |
2020年 | 9篇 |
2019年 | 11篇 |
2018年 | 11篇 |
2017年 | 12篇 |
2016年 | 13篇 |
2015年 | 16篇 |
2014年 | 23篇 |
2013年 | 26篇 |
2012年 | 10篇 |
2011年 | 19篇 |
2010年 | 13篇 |
2009年 | 28篇 |
2008年 | 21篇 |
2007年 | 30篇 |
2006年 | 29篇 |
2005年 | 28篇 |
2004年 | 33篇 |
2003年 | 22篇 |
2002年 | 26篇 |
2001年 | 22篇 |
2000年 | 19篇 |
1999年 | 19篇 |
1998年 | 20篇 |
1997年 | 11篇 |
1996年 | 9篇 |
1995年 | 3篇 |
1994年 | 8篇 |
1993年 | 2篇 |
1992年 | 1篇 |
1991年 | 2篇 |
1990年 | 1篇 |
1959年 | 2篇 |
排序方式: 共有512条查询结果,搜索用时 8 毫秒
1.
Teresa uczak Radosaw Pankiewicz Bogusawa ska Grzegorz Schroeder Maria Betowska-Brzezinska Bogumil Brzezinski 《Journal of Molecular Structure》2006,800(1-3):140-145
Novel self-assembled monolayers were obtained on silver using 4,7-diazaheptyl-trimethoxy-silane (SiN) and vinyl-trialkoxy-silane (SiVA, where the alkyl group is 3,6,9,12,15,18,21,24,27,30,33,36,39,42,45,48,51,54,57,60-eicozaoxa- hexaheptaconan). It was shown that thus modified metal surface was protected against electrooxidation. A densely packed monolayer remained stable and did not desorb from the Ag electrode on the potential cycling. The structure of SiN and SiVA as well as their complexes with Li+ cations were calculated and visualised by the AM1d and PM5 semi-empirical methods. 相似文献
2.
3.
Analysis of changes in 35Cl NQR frequency of complexes MCl4.L and MCl4.2L for M = Si, Ge, Sn and Ti was performed. The population of the atomic orbitals was calculated by the quantum chemistry methods PM3 and INDO. The results provided an explanation of the changes in 35Cl NQR frequency and the asymmetry parameter upon complex formation. In the complexes of non-transition elements, a decrease in 35Cl NQR frequency is first of all related to increasing population of pz orbitals on Cl atoms. In the complexes of Ti, the increase in 35Cl NQR frequency depends on a decrease in the pπ to dπ electron density transfer. 相似文献
4.
Static second-order nonlinear optical effects of amino acid zinc(Ⅱ) porphyrins 1, 2,3 and 4 were calculated by the TDHF/PM3 method based on the molecular structures optim.zed at the semiempirical PM3 quantum chemistry level, showing due to the cancellation of symmetric center, these amino acid zinc(H) porphyrins exhibit second order nonlinear optical response. The analysis of β components indicated that these amino acid zinc(Ⅱ) porphyrins are of multipolarizabilities, and they may be ascribed as the “mixture” of octupolar and dipoar molecules with ||βJ=3||/||βJ=1||≈5. It is found that there are no significant differences between the static β values of non-chiral and chiral amino acid zinc(Ⅱ) porphyrins. However, the βxyz component, which is quite important to quadratic macroscopic X^(2) susceptibility of chiral material, is increased significantly with the increase of side chain group of amino acids. 相似文献
5.
A. G. Taranto J. W. de M. Carneiro F. G. de Oliveira M. T. de Araujo C. R. Correa 《Journal of Molecular Structure》2002,580(1-3):207-215
Artemisinin is a sesquiterpene lactone with an endoperoxide function that is essential for its antimalarial activity. Endoperoxides are supposed to act on heme leading to the reduction of the peroxide bond and production of radicals, which can be responsible for killing the parasite. The geometries of artemisinin, radical anions and neutral species generated by rearrangement after reduction of the peroxide bond were fully optimized with the AM1 and PM3 semi-empirical methods, in order to characterize the intermediates formed during the process. Among the radicals calculated along the pathway for reductive decomposition of artemisinin, the secondary radical centered on carbon C4 has the highest stability when compared to other radicals that can be achieved either by hydrogen migration to the original O-centered radical or by homolytic break of C–C bond. This suggests that the C4-centered radical may be the species responsible for killing the parasite, as has been indicated previously in experimental studies. 相似文献
6.
Matej Babjak 《Tetrahedron》2005,61(9):2471-2479
A total synthesis of (+)-goniothalesdiol, a 3,4-dihydroxy-2,5-disubstituted tetrahydrofuran isolated from Goniothalamus borneensis (Annonaceae), and its 7-epimer is reported using oxycarbonylation methodology for construction of polyhydroxylated substituted heterocycles. Diastereoselectivity of addition of organometallic reagents to 2,3-O-isopropylidene-d-threose derivatives using theoretical calculations based on the semiempirical PM5 was studied. 相似文献
7.
V. Yu. Buz’ko I. V. Sukhno V. T. Panyushkin D. N. Ramazanova 《Journal of Structural Chemistry》2005,46(4):596-602
The structure and relative stability of 1,4-dioxane-water, (Diox)n·(H2O )m (n = 1, 2, m = 1–6), molecular complexes have been calculated by semiempirical MNDO/PM3 method. A considerable variety of (Diox)n·(H2O )m isomeric structures was stated. The mean energy of ODiox…HW-OW hydrogen bond in (Diox)n·(H2O)m complexes formed by 1,4-dioxane molecules in the chair conformation amounts to ?2.293 ± 0.210 kcal/mol with the average bond length 2.797 0.015 Å. 相似文献
8.
S. V. Shishkina T. G. Drushlyak L. A. Kutulya N. S. Pivnenko O. V. Shishkin 《Journal of Structural Chemistry》2004,45(5):889-895
X-ray analysis was carried out to study the molecular structure of β-hydroxyketone, which is one of the minor products of selective aldol condensation of (−)-menthone with 4-carbomethoxybenzaldehyde. The cyclohexanone ring of the compound has a practically undistorted chair conformation with an axial orientation of the 1-methyl group and the bulkiest 2-[1′-hydroxy-1′ -(4-carbomethoxyphenyl)]methyl substituent and the equatorial orientation of the isopropyl group in the 4 position. The stereochemical configuration was found to be (1R,2R,4 R, 1′ S), supporting that the compound belongs to the group of (+)-isomenthones; i.e., the starting (-)-menthone undergoes (to a certain extent) epimerization under the reaction conditions used. In crystal, there is intermolecular hydrogen bonding >C=O...HO- (the -O...H- bond length is 2.15 Å). The molecular conformation in hydroxyketone crystals differs from the one which prevails in solutions (according to previous NMR data) and which is characterized by an inverted cyclohexanone ring and intramolecular hydrogen bonding >C=O...HO.Original Russian Text Copyright © 2004 by S. V. Shishkina, T. G. Drushlyak, L. A. Kutulya, N. S. Pivnenko, and O. V. Shishkin__________Translated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 5, pp. 933–940, September–October, 2004. 相似文献
9.
Liqing Wu 《Analytica chimica acta》2003,482(2):175-181
In this report, with semi-empirical quantum method, we have studied the conformation and energy of supermolecule composed of picolinamide and its positional isomers with methacrylic acid. We tried to explore the reason why picolinamide was not likely to show imprinting effect when using methacrylic acid as functional monomer in our previous work. In order to produce imprinting effect, which was not achieved based on hydrogen bonding interaction, we have synthesized a molecular-imprinted polymer (MIP) based on copper ion coordination in prepolymerization. The complex in prepolymerization was composed of copper(II), acetate, picolinamide and 4-vinylpyridine (4-Vpy). Suprisingly, the MIP had high selectivity to picolinamide-copper acetate complex, and changes of either copper ion, picolinamide or acetate would result in decrease in the imprinting effect. This is also the first example where the high selective recognition of the MIP to its template was achieved mainly by inhibiting the binding of non-template rather than enhancing the binding of the template. And this report can be also looked upon as a first step towards the solution to the problem of imprinting of template that contains intramolecular hydrogen bond. 相似文献
10.
邻-甲氧基苯酚和α-,β-环糊精包合现象的理论与实验研究 总被引:1,自引:0,他引:1
通过紫外可见光谱法考察了水溶液中邻-甲氧基苯酚(o-Mop)和α-与β-环糊精(CD)的分子间相互作用, 利用Hildebrand-Benesi方程给出了两个包合物的稳定常数(Ks). 采用半经验PM3方法研究了α-,β-CD和o-Mop及其类似物苯酚(Phe)、丁香酚(Eug)之间的包络作用, 阐述了这些主客体包合作用过程中体系能量随主客体相对位置改变而变化的细节, 据此推断出主-客体包合物可能的分子结构, 计算了包合物的稳定化能(ΔEs). 研究结果表明, 本文所选主客体体系而言, 当客体和同一种主体分子作用时, 超分子包合物的ΔEs随着客体分子苯环上取代基团数目的增多而增加. 基于PM3方法优化得到的主-客体包合物在真空中的分子结构和通过实验方法在水溶液中测定的结构一致. 相似文献