全文获取类型
收费全文 | 815篇 |
免费 | 36篇 |
国内免费 | 3篇 |
专业分类
化学 | 501篇 |
晶体学 | 38篇 |
力学 | 4篇 |
数学 | 82篇 |
物理学 | 229篇 |
出版年
2022年 | 5篇 |
2021年 | 10篇 |
2020年 | 10篇 |
2019年 | 16篇 |
2017年 | 7篇 |
2016年 | 20篇 |
2015年 | 15篇 |
2014年 | 29篇 |
2013年 | 37篇 |
2012年 | 26篇 |
2011年 | 26篇 |
2010年 | 18篇 |
2009年 | 24篇 |
2008年 | 22篇 |
2007年 | 26篇 |
2006年 | 20篇 |
2005年 | 29篇 |
2004年 | 28篇 |
2003年 | 26篇 |
2002年 | 20篇 |
2001年 | 15篇 |
2000年 | 11篇 |
1999年 | 19篇 |
1998年 | 8篇 |
1997年 | 14篇 |
1996年 | 8篇 |
1995年 | 20篇 |
1994年 | 13篇 |
1993年 | 16篇 |
1992年 | 15篇 |
1991年 | 17篇 |
1990年 | 21篇 |
1989年 | 6篇 |
1988年 | 8篇 |
1987年 | 9篇 |
1985年 | 10篇 |
1984年 | 14篇 |
1983年 | 14篇 |
1982年 | 10篇 |
1981年 | 13篇 |
1980年 | 8篇 |
1979年 | 11篇 |
1978年 | 17篇 |
1977年 | 17篇 |
1976年 | 16篇 |
1975年 | 16篇 |
1974年 | 8篇 |
1973年 | 6篇 |
1967年 | 7篇 |
1933年 | 5篇 |
排序方式: 共有854条查询结果,搜索用时 15 毫秒
1.
Synthesis of Highly Substituted γ‐Butyrolactones by a Gold‐Catalyzed Cascade Reaction of Benzyl Esters 下载免费PDF全文
Maria Camila Blanco Jaimes Alexander Ahrens Daniel Pflästerer Dr. Matthias Rudolph Prof. Dr. A. Stephen K. Hashmi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(1):427-433
Easily accessible benzylic esters of 3‐butynoic acids in a gold‐catalyzed cyclization/rearrangement cascade reaction provided 3‐propargyl γ‐butyrolactones with the alkene and the carbonyl group not being conjugated. Crossover experiments showed that the formation of the new C?C bond is an intermolecular process. Initially propargylic–benzylic esters were used, but alkyl‐substituted benzylic esters worked equally well. In the case of the propargylic–benzylic products, a simple treatment of the products with aluminum oxide initiated a twofold tautomerization to the allenyl‐substituted γ‐butyrolactones with conjugation of the carbonyl group, the olefin, and the allene. The synthetic sequence can be conducted stepwise or as a one‐pot cascade reaction with similar yields. Even in the presence of the gold catalyst the new allene remains intact. 相似文献
2.
3.
In this article, we present results of an empirical study with 500 German students of grades 7 and 8. The study focussed on students' mathematics achievement and their interest in mathematics as well as on the relation between these two constructs. In particular, the results show that the development of an individual student's achievement between grade 7 and grade 8 depends on the achievement level of the specific classroom and therefore on the specific mathematics instruction Interest in mathematics could be regarded a predictor for mathematics achievement Moreover, our findings suggest that the students show hardly any fear of mathematics independent of their achievement level. 相似文献
4.
5.
6.
C. Andreoiu D. Rudolph I. Ragnarsson C. Fahlander R.A.E. Austin M.P. Carpenter R.M. Clark J. Ekman R.V.F. Janssens T.L. Khoo F.G. Kondev T. Lauritsen T. Rodinger D.G. Sarantites D. Seweryniak T. Steinhardt C.E. Svensson O. Thelen J.C. Waddington 《The European Physical Journal A - Hadrons and Nuclei》2002,14(3):317-348
High-spin states in 59Cu were populated using the fusion-evaporation reaction 28Si + 40Ca at a beam energy of 122 MeV. The Gammasphere Ge-detector array in conjunction with the 4π charged-particle detector array
Microball allowed for the detection of γ-rays in coincidence with evaporated light particles. The resulting extensive high-spin
decay scheme of 59Cu is presented, which comprises more than 320 γ-ray transitions connecting about 150 excited states. Their spins and parities
have been assigned via directional correlations of γ-rays emitted from oriented states. Average quadrupole moments of rotational
bands have been determined from the analysis of residual Doppler shifts. Shell model calculations in the fp shell are invoked to study some of the low-spin states, while the experimental characteristics of the rotational bands are
analyzed in the configuration-dependent cranked Nilsson-Strutinsky (CNS) approach.
Received: 15 February 2002 / Accepted: 23 April 2002 相似文献
7.
8.
From the highly refined proton-NMR spectra of monocyclic and bicyclic aminopolyethers, signal shifts have been observed which indicate conformation changes in the ligand moiety. Their dependence on solvent, coordinated cation and anion is discussed, and an interpretation of the spectra is put forward on the basis of dynamic symmetry patterns. 相似文献
9.
F. Gutbrod G. Kramer G. Rudolph G. Schierholz 《Zeitschrift fur Physik C Particles and Fields》1987,35(4):543-549
TheO(α s 2 ) QCD corrections to the thrust distribution for three-jet production ine + e ? annihilation are found to depend on the algorithm for recombining four partons into three jets. Several recombination schemes are discussed and results are compared. Results of the recombination approach are compared also to recent direct calculations of three-jet thrust distributions. The importance of terms proportional to jet resolution parameters is stressed. 相似文献
10.
Breher F Rüegger H Mlakar M Rudolph M Deblon S Schönberg H Boulmaâz S Thomaier J Grützmacher H 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(3):641-653
The formation of adducts of the square-planar 16-electron complexes trans-[M(tropp(ph))(2)](+) and cis-[M(tropp(ph))(2)](+) (M=Rh, Ir; tropp(Ph)=5-diphenylphosphanyldibenzo[a,d]cycloheptene) with acetonitrile (acn) and Cl(-), and the redox chemistry of these complexes was investigated by various physical methods (NMR and UV-visible spectroscopy, square-wave voltammetry), in order to obtain some fundamental thermodynamic and kinetic data for these systems. A trans/cis isomerization cannot be detected for [M(tropp(ph))(2)](+) in non-coordinating solvents. However, both isomers are connected through equilibria of the type trans-[M(tropp(ph))(2)](+)+L<==>[ML(tropp(ph))(2)](n)<==>cis-[M(tropp(ph))(2)](+)+L, involving five-coordinate intermediates [ML(tropp(ph))(2)](n) (L=acn, n=+1; L=Cl(-), n=0). Values for K(d) (K(f)), that is, the dissociation (formation) equilibrium constant, and k(d) (k(f)), that is, the dissociation (formation) rate constant, were obtained. The formation reactions are fast, especially with the trans isomers (k(f)>1x10(5) m(-1) s(-1)). The reaction with the sterically more hindered cis isomers is at least one order of magnitude slower. The stability of the five-coordinate complexes [ML(tropp(ph))(2)](n) increases with Ir>Rh and Cl(-)>acn. The dissociation reaction has a pronounced influence on the square-wave (SW) voltammograms of trans/cis-[Ir(tropp(ph))(2)](+). With the help of the thermodynamic and kinetic data independently determined by other physical means, these reactions could be simulated and allowed the setting up of a reaction sequence. Examination of the data obtained showed that the trans/cis isomerization is a process with a low activation barrier for the four-coordinate 17-electron complexes [M(tropp(ph))(2)](0) and especially that a disproportionation reaction 2 trans/cis-[M(tropp(ph))(2)](0)-->[M(tropp(ph))(2)](+)+[M(tropp(ph))(2)](-) may be sufficiently fast to mask the true reactivity of the paramagnetic species, which are probably less reactive than their diamagnetic equilibrium partners. 相似文献