全文获取类型
收费全文 | 819篇 |
免费 | 6篇 |
国内免费 | 1篇 |
专业分类
化学 | 626篇 |
晶体学 | 4篇 |
力学 | 11篇 |
数学 | 88篇 |
物理学 | 97篇 |
出版年
2022年 | 8篇 |
2021年 | 11篇 |
2020年 | 14篇 |
2019年 | 10篇 |
2018年 | 8篇 |
2017年 | 10篇 |
2016年 | 20篇 |
2015年 | 16篇 |
2014年 | 16篇 |
2013年 | 33篇 |
2012年 | 47篇 |
2011年 | 46篇 |
2010年 | 22篇 |
2009年 | 30篇 |
2008年 | 41篇 |
2007年 | 31篇 |
2006年 | 18篇 |
2005年 | 19篇 |
2004年 | 14篇 |
2003年 | 15篇 |
2002年 | 9篇 |
2001年 | 6篇 |
2000年 | 8篇 |
1999年 | 7篇 |
1997年 | 15篇 |
1996年 | 7篇 |
1994年 | 9篇 |
1993年 | 7篇 |
1991年 | 7篇 |
1990年 | 6篇 |
1989年 | 12篇 |
1988年 | 7篇 |
1987年 | 7篇 |
1986年 | 15篇 |
1985年 | 12篇 |
1984年 | 10篇 |
1983年 | 10篇 |
1982年 | 16篇 |
1981年 | 12篇 |
1980年 | 12篇 |
1979年 | 12篇 |
1978年 | 15篇 |
1977年 | 15篇 |
1976年 | 14篇 |
1975年 | 8篇 |
1974年 | 22篇 |
1973年 | 15篇 |
1972年 | 15篇 |
1970年 | 12篇 |
1957年 | 6篇 |
排序方式: 共有826条查询结果,搜索用时 734 毫秒
21.
Alexander Apelblat Emanuel Manzurola Zoya Orekhova 《Journal of solution chemistry》2007,36(8):1023-1035
Conductivity measurements of glutaric acid and disodium glutarate in dilute aqueous solutions were performed in the 288.15
to 323.15 K temperature range. The limiting equivalent conductances of glutarate anions, λ
o(HGlut−,T) and λ
o(1/2Glut2−,T), and the dissociation constants of glutaric acid, K
1(T) and K
2(T), were derived by the use of the Onsager and the Quint and Viallard conductivity equations. The applied molecular model was
successfully confirmed by analyzing the conductivities of sodium hydrogen glutarate at 298.15 K. 相似文献
22.
Josef Scharf Karl Schlögl Michael Widhalm Johann Lex Werner Tückmantel Emanuel Vogel Franz Pertlik 《Monatshefte für Chemie / Chemical Monthly》1986,117(2):255-267
2,7-Dibromo-1,6-methano[10]anulene (3) and 2,9-Dibromo-syn-1,6:8,13-diimino[14]anulene (9) were quantitatively separated into their enantiomers by chromatography on triacetylcellulose (TAC) in ethanol. X-ray structure analysis (Bijvoet technique) established the chiralities (+)(R)-3 and (+)(S)-9 for the dextrorotatory enantiomers.Comparison of the CD spectra allowed the configurational assignment to further optically active [10] and [14] anulenes which were also accessible by chromatography onTAC. Conversion of (+)(R)-2-bromo-1,6-methano[10]anulene (2) into the corresponding methylester (–)-4 confirmed its previously proposed chirality (–)(R).2,7-Dibromo-1,6-oxido[10]anulene (7) and 2,9-dibromo-syn-diimino[14]anulene (9) are in contrast to the 2,9-dibromo-syn-dioxido[14]anulene (10) optically stable until 250°C. Consequently their inversion barriers are higher than 42 kcal (176 kJ) mol–1.The CD spectra of mono and disubstituted anulenes (with C1 and C2 symmetry, resp.) are compared: For the [10]anulenes theCotton effect around 330 nm seems to be specific for their configuration with a positive effect indicating (S)-chirality and vice versa. Some regularities concerning the chromatographic resolutions are discussed.
Stereochemie planar chialer Verbindungen, 10. Mitt.: Röntgenkristallstruktur und absolute Chiralität überbrückter [10]- und [14] Anulene
Zusammenfassung 2,7-Dibrom-1,6-methano[10]anulen (3) und 2,9-Dibrom-syn-1,6:8,13-diimino[14]anulen (9) wurden durch Chromatographie an Triacetylcellulose (TAC) in Ethanol quantitativ in ihre Enantiomeren getrennt. Röntgenstruktur-analyse (Bijvoet-Technik) bewies für die rechtsdrehenden Enantiomeren die Chiralität (+)(R)-3 bzw. (+)(S)-9.Ein Vergleich der CD-Spektren ermöglichte die Konfigurationszuordnung weiterer optisch aktiver [10]- und [14]Anulene, die gleichfalls durch Chromato-graphie anTAC erhalten worden waren. Umwandlung von (+)(R)-2-Brom-1,6-methano[10]anulen (2) in den entsprechenden Methylester (–)-4 bestätigte dessen schon früher vorgeschlagene Chiralität (–)(R).Dibrom-1,6-oxido[10]anulen (7) und Dibrom-diimino[14]anulen (9) sind im Gegensatz zum Dioxido[14]anulen (10) bis 250°C optisch stabil. Ihre Inver-sionsbarrieren liegen somit über 42 kcal (176kJ) mol–1.Die CD-Spektren von mono- und disubstituierten Anulenen (mit C1 bzw. C2-Symmetrie) werden verglichen: Für die [10]Anulene scheint derCottoneffekt um 330 nm konfigurationsspezifisch zu sein, wobei ein positiver Effekt (S)-Chiralität anzeigt — und vice versa. Einige Regelmäßigkeiten bezüglich der chromatographischen Enantiomerentrennung werden diskutiert.相似文献
23.
N. M. Emanuel Z. K. Maizus V. G. Vinogradova 《Reaction Kinetics and Catalysis Letters》1981,17(1-2):77-82
The dependence of inhibiting properties of M(dtc) on M for the complexes of M(II) and n M(III) has been studied. Inhibition is due to the interaction of M(dtc)n with RO2.
M(dtc)n M M(II) M(III). M(dtc)n RO2.相似文献
24.
Mohammad A. Hai Nigel W. Preston Rolf Kyburz Emanuel Schpp I. Ralph C. Bick Manfred Hesse 《Helvetica chimica acta》1980,63(7):2130-2134
Aristoserratine, a New Indole Alkaloid from Aristotelia serrata W.R.B. OLIVER and from A. peduncularis (LABILL .) HOOK . F. The new indole alkaloid aristoserratine (2) has been isolated from Aristotelia. Its structure and absolute configuration were elucidated on the basis of spectroscopic data. 相似文献
25.
Fowler CJ Sessler JL Lynch VM Waluk J Gebauer A Lex J Heger A Zuniga-Y-Rivero F Vogel E 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(15):3485-3496
Porphyrin (P), porphycene (Pc), corrphycene (Cn), and hemiporphycene (Hpc) represent a series of well defined "4-N in" constitutional porphyrin isomers. These isomers, in the form of their octaethyl derivatives, represent a congruent set of porphyrinoids whose properties can be compared. In this study we report how variations in electronic structure and nitrogen-core size in the free-base forms of these four systems are reflected in the properties of their corresponding metal complexes. Specifically, the effects that these differences have on the axial ligation properties of the Zn(II), Mg(II), Ni(II), and Co(II) complexes of P, Pc, Cn, and Hpc in toluene using pyridine as the axial ligand are detailed. Also reported are the relative stabilities of these complexes under acidic conditions. It is shown that for the zinc, magnesium, and cobalt complexes, there are distinct differences in the ability to maintain four-, five-, or six-coordinate geometries in the presence of similar concentrations of pyridine. By contrast, no apparent differences in axial ligand binding affinity are seen for the four nickel complexes. Little difference in stability was likewise seen when these same complexes were subject to acid-mediated demetallation, with all four falling into stability class II, according to the accepted porphyrin stability ranking system. High stabilities were also seen in the case of the cobalt complexes, with the Pc and Cn complexes being of stability class III and the P and Hpc derivatives falling into stability class II. The Zn(II) and Mg(II) complexes were all far less stable than the corresponding Ni(II) and Co(II) complexes. In this case, semiquantitative analyses of the rate of acid-induced decomposition revealed the following stability sequence P>Cn>Hpc>Pc for both the Zn(II) and Mg(II) complexes. Single-crystal X-ray diffraction structures were solved for the Zn(II), Mg(II), and Ni(II) complexes of the octaethyl derivatives of Hpc, Cn, and Pc as well as a Co(II) octamethylcorrphycene and are reported as part of this study. These solid-state structures confirm four-coordinate species for the Ni(II) complexes, four- and five-coordinate species for the Mg(II) and Zn(II) complexes, and a six-coordinate species for the lone Co(II) complex. 相似文献
26.
Zoya?Orekhova Yonit?SambiraEmail author Emanuel?Manzurola Alexander?Apelblat 《Journal of solution chemistry》2005,34(7):853-867
Conductivity measurements of DL-pyroglutamic acid and sodium pyroglutamate in dilute aqueous solutions were performed in the 288.15–323.15 K temperature range. The limiting molar conductances of pyroglutamate anion, λo(pGlu−, T) and the dissociation constants of pyroglutamic acid, K(T) were derived from the Onsager, and the Quint and Viallard conductivity equations. Densities of aqueous solutions with molalities lower than 0.5 mol-kg−1 were determined at 5 K intervals from T = 288.15 K to 333.15 K. Densities served to evaluate the apparent molar volumes, V2,φ(m, T), the cubic expansion coefficients, α (m,T) and the changes of the isobaric heat capacities with respect to pressure, (∂ CP/∂ P)T,m. They were correlated qualitatively with the changes in the structure of water when pyroglumatic acid is dissolved in it. 相似文献
27.
28.
29.