全文获取类型
收费全文 | 1808篇 |
免费 | 34篇 |
国内免费 | 4篇 |
专业分类
化学 | 1351篇 |
晶体学 | 4篇 |
力学 | 32篇 |
数学 | 214篇 |
物理学 | 245篇 |
出版年
2021年 | 18篇 |
2020年 | 26篇 |
2019年 | 22篇 |
2018年 | 22篇 |
2016年 | 30篇 |
2015年 | 16篇 |
2014年 | 24篇 |
2013年 | 44篇 |
2012年 | 51篇 |
2011年 | 51篇 |
2010年 | 28篇 |
2009年 | 31篇 |
2008年 | 53篇 |
2007年 | 63篇 |
2006年 | 55篇 |
2005年 | 44篇 |
2004年 | 49篇 |
2003年 | 40篇 |
2002年 | 47篇 |
2001年 | 27篇 |
2000年 | 27篇 |
1999年 | 16篇 |
1997年 | 31篇 |
1996年 | 32篇 |
1995年 | 25篇 |
1994年 | 27篇 |
1993年 | 28篇 |
1992年 | 15篇 |
1991年 | 34篇 |
1990年 | 26篇 |
1989年 | 27篇 |
1988年 | 26篇 |
1987年 | 28篇 |
1986年 | 29篇 |
1985年 | 37篇 |
1984年 | 34篇 |
1983年 | 17篇 |
1982年 | 30篇 |
1981年 | 36篇 |
1980年 | 36篇 |
1979年 | 36篇 |
1978年 | 32篇 |
1977年 | 23篇 |
1976年 | 16篇 |
1975年 | 22篇 |
1972年 | 15篇 |
1962年 | 25篇 |
1961年 | 26篇 |
1960年 | 64篇 |
1959年 | 23篇 |
排序方式: 共有1846条查询结果,搜索用时 31 毫秒
61.
Fazil O. Gülaar Franois Mermound F. Johann Winkler Armand Vuchs 《Helvetica chimica acta》1984,67(2):488-501
Ammonia chemical ionization (CI) mass spectra of various open-chain, cyclic and unsaturated C5- to C10-alcohols were obtained at source temperatures ranging from 60° to 250°C. The reactivity of the ammonia adduct ion MNH and its fragmentation channels are characteristic for substrate structure. Although strongly temperature-dependent, the spectra give nevertheless information on the OH-group environment as well as on the C-skeleton at any source temperature. Primary, secondary and tertiary alcohols as well as allylic and simple olefinic alcohols can be distinguished by their spectra, which show ammonium adduct ions [MNH4]+, adduct dehydrogenation ions [MNH4-H2], ammonium substitution ions [MNH4-H2O]+ and [M-OH]+-ions as the main characteristic peaks. Moreover, konfigurational assignments of stereoisomeric alcohols are possible for larger substrate-size and source-temperature ranges than with isobutane CI mass spectrometry. Homologous M NH-ions show molecular-size control of fragmentation and linear MNH-ions are less stable than branched isomers due to incomplete energy randomization. 相似文献
62.
Shigang Zhang Brigitte Schindler Graham Nicholson Ernst Bayer 《Journal of separation science》1995,18(9):579-581
Residual adsorptive activity of reversed phase (RP) column packings used in supercritical fluid chromatography (SFC) can be significantly reduced by a dynamic in-situ silanization with diphenyltetramethyldisilazane (DPTMDS). RP-materials thus deactivated were characterized both chromatographically and by solid-phase 29Si NMR. 相似文献
63.
64.
Summary A method for the separation of substituted tetraphenylporphyrins by preparative liquid chromatography is reported. The quality of the columns formed by axial compression of various stationary phases is tested. 相似文献
65.
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
66.
Polymorphism of SrTa2O6 Orthorhombic SrTa2O6 is a new low temperature modification related to orthorhombic CaTa2O6. SrTa2O6(orh.) was obtained when the wellknown modification SrTa2O6(TTB) which is related to the tetragonal tungsten bronzes was heated in the presence of a transporting agent (chlorine) or a mineralizer (melt of B2O3) at temperatures below 1150°C. It could be prepared by the reaction of a 1:1 mixture of Sr(NO3)2 or SrCO3 with Ta2O5 in a sealed quartz glass tube as well. SrTa2O6(orh.) also occurred as an intermediate phase of the reaction of the corresponding 1:2 mixture at temperatures below 900°C (e. g. 840°C). Indexing of Guinier powder patterns led to the following unit cell: a = 11.006 Å, b = 7.638 Å, c = 5.622 Å. At temperatures above 1220°C SrTa2O6(orh.) changes (in air) to SrTa2O6(TTB). A reversal of this transition could not be achieved without the presence of a mineralizer or a transporting agent. CaxSr1?xTa2O6 solid solutions of the low temperature form could not definitely be established. However, at 1300°C solid TTB solutions of CaxSr1?xTa2O6 were formed. For x > 0.05 the TTB unit cells are orthorhombically distorted. For x ≥ 0.85 the x-ray powder patterns of the solid solutions looked like the one of CaTa2O6(orh.) and no TTB-structure was observed at 1300°C. 相似文献
67.
Ana Cristina Gmez-Herrero Carlos Snchez-Snchez Frdric Chrioux Jose Ignacio Martínez Jos Abad Luca Floreano Alberto Verdini Albano Cossaro Estelle Mazaleyrat Valrie Guisset Philippe David Simone Lisi Jos Angel Martín Gago Johann Coraux 《Chemical science》2021,12(6):2257
Catechols are ubiquitous substances often acting as antioxidants, thus of importance in a variety of biological processes. The Fenton and Haber–Weiss processes are thought to transform these molecules into aggressive reactive oxygen species (ROS), a source of oxidative stress and possibly inducing degenerative diseases. Here, using model conditions (ultrahigh vacuum and single crystals), we unveil another process capable of converting catechols into ROSs, namely an intramolecular redox reaction catalysed by a Cu surface. We focus on a tri-catechol, the hexahydroxytriphenylene molecule, and show that this antioxidant is thereby transformed into a semiquinone, as an intermediate product, and then into an even stronger oxidant, a quinone, as final product. We argue that the transformations occur via two intramolecular redox reactions: since the Cu surface cannot oxidise the molecules, the starting catechol and the semiquinone forms each are, at the same time, self-oxidised and self-reduced. Thanks to these reactions, the quinone and semiquinone are able to interact with the substrate by readily accepting electrons donated by the substrate. Our combined experimental surface science and ab initio analysis highlights the key role played by metal nanoparticles in the development of degenerative diseases.An antioxidant catechol transforms following intramolecular redox reactions into highly reactive oxygen species, a semiquinone and a quinone, on copper. 相似文献
68.
P. Unkel P. Buch J. Dembczyński W. Ertmer U. Johann 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1989,11(4):259-271
The hyperfine structure (hfs) of 18 metastable states of51V has been measured by laser induced fluorescence. 15 of these states have been measured additionally very precisely by the ABMR-LIRF method. Using results of earlier hfs measurements, the hfs of altogether 33 fine structure states is analyzed using a method of simultaneous parametrization of one- and two-body interactions in the atomic hfs of the model space 3d 3 +M 4s 2 ?M (M = 0, 1, 2). The hfs of these states is described by 16 parameters for the magnetic dipole interaction and 12 parameters for the electric quadrupole interaction. From these model space parameters corresponding configuration dependent parameters for the three configurations were determined. These parameters allow a prediction of the hfs constants of all states of the modelspace within an accuracy of 5 to 10%. The evaluation of the nuclear quadrupole moment of51V, free of Sternheimer corrections up to second order, yielded the value of -0.043(5) barn. 相似文献
69.
The purpose of the EROS 6.0 system is to predict the products of chemical reactions and to model reaction mechanisms. This is accomplished by elementary reaction steps that are selected through the rules that constitute the knowledge base of the EROS 6.0 system. These rules are derived by methods of machine learning. The learning process is based on reaction in data bases. An overview of the EROS 6.0 system is given and the structure of the knowledge as well as the generation of reaction rules are described. 相似文献
70.
Kronenburg CM Rijnberg E Jastrzebski JT Kooijman H Lutz M Spek AL Gossage RA van Koten G 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,11(1):253-261
(R)-[1-(Dimethylamino)ethyl]benzene reacts with nBuLi in a 1:1 molar ratio in pentane to quantitatively yield a unique hetero-aggregate (2 a) containing the lithiated arene, unreacted nBuLi, and the complexed parent arene in a 1:1:1 ratio. As a model compound, [Li(4)(C(6)H(4)CH(Me)NMe(2)-2)(2)(nBu)(2)] (2 b) was prepared from the quantitative redistribution reaction of the parent lithiated arene Li(C(6)H(4)CH(Me)NMe(2)-2) with nBuLi in a 1:1 molar ratio. The mono-Et(2)O adduct [Li(4)(C(6)H(4)CH(Me)NMe(2)-2)(2)(nBu)(2)(OEt(2))] (2 c) and the bis-Et(2)O adduct [Li(4)(C(6)H(4)CH(Me)NMe(2)-2)(2)(nBu)(2)(OEt(2))(2)] (2 d) were obtained by re-crystallization of 2 b from pentane/Et(2)O and pure Et(2)O, respectively. The single-crystal X-ray structure determinations of 2 b-d show that the overall structural motifs of all three derivatives are closely related. They are all tetranuclear Li aggregates in which the four Li atoms are arranged in an almost regular tetrahedron. These structures can be described as consisting of two linked dimeric units: one Li(2)Ar(2) dimer and a hypothetical Li(2)nBu(2) dimer. The stereochemical aspects of the chiral Li(2)Ar(2) fragment are discussed. The structures as observed in the solid state are apparently retained in solution as revealed by a combination of cryoscopy and (1)H, (13)C, and (6)Li NMR spectroscopy. 相似文献