全文获取类型
收费全文 | 838篇 |
免费 | 31篇 |
国内免费 | 228篇 |
专业分类
化学 | 896篇 |
晶体学 | 12篇 |
力学 | 5篇 |
综合类 | 2篇 |
数学 | 2篇 |
物理学 | 180篇 |
出版年
2023年 | 18篇 |
2022年 | 8篇 |
2021年 | 20篇 |
2020年 | 11篇 |
2019年 | 18篇 |
2018年 | 11篇 |
2017年 | 17篇 |
2016年 | 21篇 |
2015年 | 17篇 |
2014年 | 31篇 |
2013年 | 70篇 |
2012年 | 34篇 |
2011年 | 26篇 |
2010年 | 42篇 |
2009年 | 44篇 |
2008年 | 54篇 |
2007年 | 63篇 |
2006年 | 50篇 |
2005年 | 67篇 |
2004年 | 65篇 |
2003年 | 35篇 |
2002年 | 42篇 |
2001年 | 32篇 |
2000年 | 28篇 |
1999年 | 27篇 |
1998年 | 32篇 |
1997年 | 19篇 |
1996年 | 21篇 |
1995年 | 25篇 |
1994年 | 18篇 |
1993年 | 17篇 |
1992年 | 22篇 |
1991年 | 17篇 |
1990年 | 10篇 |
1989年 | 9篇 |
1988年 | 15篇 |
1987年 | 4篇 |
1986年 | 4篇 |
1985年 | 7篇 |
1983年 | 3篇 |
1982年 | 5篇 |
1981年 | 4篇 |
1980年 | 1篇 |
1979年 | 4篇 |
1977年 | 1篇 |
1976年 | 1篇 |
1975年 | 1篇 |
1972年 | 2篇 |
1969年 | 1篇 |
1966年 | 1篇 |
排序方式: 共有1097条查询结果,搜索用时 15 毫秒
1.
荧光光谱法研究蛋白质构象的电磁-温度协同效应 总被引:1,自引:1,他引:0
长期以来电磁生物效应受到人们普遍关注,近年来从各个角度进行了相关研究。电磁-温度协同效应是当前的热点。本研究通过电磁场及温度协同对蛋白质影响的研究,发现蛋白质在电磁场作用下的不可逆变性,而且这种变性也遵循Arrhenius规律,并进一步得出电磁-温度协同作用的蛋白质变性模型。本文从分子反应动力学的角度解释了电磁-温度协同效应,并对非热效应作了一定的探讨。 相似文献
2.
3.
Pure gas sorption and transport properties of polyesters based on bisphenol-A and both pure isophthalic and pure terephthalic acid chloride were obtained for He, N2, O2, CH4, and CO2 at 35°C. The polymers were synthesized in our laboratory and amorphous films were prepared with a specialized solvent casting procedure. The polymer containing m-phenylene groups shows higher permselectivity for most of the gas pairs. The ideal selectivity of O2/N2 was increased by 33% when p-phenylene units were replaced by m-phenylene ones. On the other hand, the polyester containing only p-phenylene groups, shows higher permeability to all the gases studied. The polymer based on pure terephthalic acid chloride has a 75% higher oxygen permeability and a 1.1-fold higher carbon dioxide permeability than the isophthalic acid derivative. The polyester containing meta-phenylene units has lower Tg, higher permselectivity, lower permeability, lower fractional free volume (FFV), and lower d-spacing. The values of FFV, and lower d-spacing. The values of FFV and d-spacing were only slightly different between the two isomers. Moreover, for the sub-Tgγ transition the maximum in tan δ occured at essentially the same temperature (?55°C). The polymer with a higher concentration of p-phenylene units shows somewhat larger area under the γ-peak, indicating slightly more sub-Tg motion. The Distribution of FFV is considered to be the determining factor for the differences in transport properties observed. © 1993 John Wiley & Sons, Inc. 相似文献
4.
5.
Summary A variety of bilipeptides has been synthesized and investigated by UV-VIS and CD spectroscopy to explore the conformational influence of peptide ligands on the covalently bound tetrapyrrol moiety. The results obtained are complemented by those reported previously. From the comprehensive data thus available several features of the peptidic chain regulating interactions with the bilatriene moiety have been elucidated. Accordingly, the presence of three amide linkages at the ligand is prerequiste for induction of pronounced conformational changes consisting either in a complete transition ofM intoP helical bilatriene species by inversion of all torsional angles, or in a stretching of the chromophore. The kind of conformational influence can be controlled by varying the position of the prolyl entity within a given peptide.Dedicated to Prof. Dr. Kurt Schaffner on occasion of his 60th birthday 相似文献
6.
合成了6种钨硅杂多配合物异构体α、βi-M3H2[SiW11(NbO2)O39]·H2O(M=Me4N+(TMA),Bu4N+(TBA),Et4N+(TEA);βi=β1,β2,β3)。IR光谱、UV光谱、极谱、I--S2O32-滴定证明合成的杂多配合物中有NbO2基存在, 183W NMR光谱证明其阴离子具有Keggin结构,催化实验结果表明,合成的化合物对烯烃环氧化反应具有催化活性,且过氧杂多配合物的催化活性高于非过氧杂多配合物,β异构体的催化活性高于α。 相似文献
7.
Brian D. Hudson Ashley R. George Martyn G. Ford David J. Livingstone 《Journal of computer-aided molecular design》1992,6(2):191-201
Summary Molecular dynamics simulations have been performed on a number of conformationally flexible pyrethroid insecticides. The results indicate that molecular dynamics is a suitable tool for conformational searching of small molecules given suitable simulation parameters. The structures derived from the simulations are compared with the static conformation used in a previous study. Various physicochemical parameters have been calculated for a set of conformations selected from the simulations using multivariate analysis. The averaged values of the parameters over the selected set (and the factors derived from them) are compared with the single conformation values used in the previous study. 相似文献
8.
Svein G. Dahl Peter A. Kollman Shashidhar N. Rao U. Chandra Singh 《Journal of computer-aided molecular design》1992,6(3):207-222
Summary The side-chain conformations of psychoactive phenothiazine drugs in crystals are different from those of biologically inactive ring sulfoxide metabolites. This study examines the potential energies, molecular conformations and electrostatic potentials in chlorpromazine, levomepromazine (methotrimeprazine), their sulfoxide metabolites and methoxypromazine. The purpose of the study was to examine the significance of the different crystal conformations of active and inactive phenothiazine derivatives, and to determine why phenothiazine drugs lose most of their biological activity by sulfoxidation. Quantum mechanics and molecular mechanics calculations demonstrated that conformations with the side chain folded over the ring structure had lowest potential energy in vacuo, both in the drugs and in the sulfoxide metabolites. In the sulfoxides, side chain conformations corresponding to the crystal structure of chlorpromazine sulfoxide were characterized by stronger negative electrostatic potentials around the ring system than in the parent drugs. This may weaken the electrostatic interaction of sulfoxide metabolites with negatively charged domains in dopamine receptors, and cause the sulfoxides to be virtually inactive in dopamine receptor binding and related pharmacological tests. 相似文献
9.
采用密度泛函方法,在DND基组水平上,对[GeMo12O40]^4-杂多阴离子最常见的α和β异构体进行了几何构型优化,得到了与X射线晶体衍射实验结果相一致的结构参数,并在此基础上进行了振动频率分析,得到了杂多阴离子的电子结构、热力学特性和振动光谱,通过定义α,β异构体异构化反应的Gibbs函变△Gα-β与温度的关系,研究了这两种异构体的相对稳定性.结果表明:低温时α异构体更稳定,高温时β异构体更稳定些,550K左右为转变点.振动频率分析得到2种异构体的最强峰位于4个频率位置,分别指认为vax(Mo-Od),vas(Mo-Od),vas(Mo-Oc-Mo),vas(Ge-Oa),vas(Mo-Ob-Mo)振动,与红外光谱(IR)的特征振动峰相对应,观察到了特征频率的振动模式,从理论计算角度说明了Rocchiccioli—Deltcheff关于振动模式的设想是合理的. 相似文献
10.
[Co(amp)2Cl2]2[ZnCl4]体系中两对称异构体的2D NMR研究 总被引:7,自引:0,他引:7
The two symmetrical isomers in [Co(amp)2Cl2]2[ZnCl4](amp=2-(Aminomethyl)pyridine) system were syn-thesized by general oxidation method and were separated by chromatography and recrystallization method. Their configurations were assigned by using 2D NMR techniques, particularly the NOESY NMR spectra. Solvent used was Me2SO-d6 with the central peak of the CD3 septet as the reference ( 13C,δ 39.37; 1H,δ 2.49 relative to SiMe4). Cation exchange media used was Dowex 50Wx 2(H+ form, 200~400mesh; Biorad). 相似文献