全文获取类型
收费全文 | 1527篇 |
免费 | 29篇 |
国内免费 | 2篇 |
专业分类
化学 | 1150篇 |
晶体学 | 3篇 |
力学 | 17篇 |
数学 | 197篇 |
物理学 | 191篇 |
出版年
2021年 | 11篇 |
2020年 | 18篇 |
2019年 | 9篇 |
2016年 | 30篇 |
2015年 | 22篇 |
2014年 | 20篇 |
2013年 | 39篇 |
2012年 | 62篇 |
2011年 | 67篇 |
2010年 | 39篇 |
2009年 | 39篇 |
2008年 | 49篇 |
2007年 | 61篇 |
2006年 | 47篇 |
2005年 | 60篇 |
2004年 | 56篇 |
2003年 | 42篇 |
2002年 | 45篇 |
2001年 | 32篇 |
2000年 | 39篇 |
1999年 | 27篇 |
1998年 | 27篇 |
1997年 | 25篇 |
1996年 | 30篇 |
1995年 | 27篇 |
1994年 | 48篇 |
1993年 | 21篇 |
1992年 | 24篇 |
1991年 | 28篇 |
1990年 | 9篇 |
1989年 | 30篇 |
1988年 | 15篇 |
1987年 | 12篇 |
1986年 | 20篇 |
1985年 | 32篇 |
1984年 | 35篇 |
1983年 | 11篇 |
1982年 | 33篇 |
1981年 | 32篇 |
1980年 | 32篇 |
1979年 | 32篇 |
1978年 | 29篇 |
1977年 | 19篇 |
1976年 | 23篇 |
1975年 | 17篇 |
1974年 | 17篇 |
1973年 | 18篇 |
1972年 | 11篇 |
1971年 | 12篇 |
1970年 | 8篇 |
排序方式: 共有1558条查询结果,搜索用时 0 毫秒
51.
Roman Tkachov Lukas Stepien Aljoscha Roch Hartmut Komber Felix Hennersdorf Jan J. Weigand Ingmar Bauer Anton Kiriy Christoph Leyens 《Tetrahedron》2017,73(16):2250-2254
Herein, aiming at optimization of the polymerization process leading to a family of hole- and electron-conducting 1,1,2,2-ethenetetrathiolate-based polymers, such as poly(nickel-1,1,2,2-ethenetetrathiolate), poly[Kx(Ni-ett)], we investigated transformations of the monomer precursor 1,3,4,6-tetrathiapentalene-2,5-dione (TPD) occurring under polymerization conditions. We found that only one ring of TPD opens upon its reaction with potassium methoxide under inert conditions at room temperature which leads to the formation of potassium 2-oxo-1,3-dithiol-4,5-dithiolate (K2[3]). Heating of K2[3] under reflux in methanol solution under inert conditions opens the second ring, however the resulting product is not potassium ethenetetrathiolate (K4[2]), the product of an exhaustive methanolysis of TPD, but potassium tetrathiooxalate (K2[4]), the product of the decarbonylation of K2[3]. Preliminary experiments reveal that the involvement of K2[4] in the polymerization process is beneficial for reproducible formation of high quality 1,1,2,2-ethenetetrathiolate-based polymers suitable for thermoelectric applications. 相似文献
52.
The phosphonate analogue of α-N-benzoyl protected phenylalanine methylester has been prepared by catalytic synthesis. Commonly used Rh-complexes has been applied in asymmetric hydrogenation to check their usefulness in the standard reaction. 相似文献
53.
Nikolaus M. Loening Barth‐Jan van Rossum Hartmut Oschkinat 《Magnetic resonance in chemistry : MRC》2012,50(4):284-288
In nuclear magnetic resonance spectroscopy, experimental limits due to the radiofrequency transmitter and/or coil means that conventional radiofrequency pulses (“hard pulses”) are sometimes not sufficiently powerful to excite magnetization uniformly over a desired range of frequencies. Effects due to nonuniform excitation are most frequently encountered at high magnetic fields for nuclei with a large range of chemical shifts. Using optimal control theory, we have designed broadband excitation pulses that are suitable for solid‐state samples under magic‐angle‐spinning conditions. These pulses are easy to implement, robust to spinning frequency variations, and radiofrequency inhomogeneities, and only four times as long as a corresponding hard pulse. The utility of these pulses for uniformly exciting 13C nuclei is demonstrated on a 900 MHz (21.1 T) spectrometer. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
54.
Mahmoud Nasrollahzadeh Mohaddeseh Sajjadi Hartmut Komber Hossein Ali Khonakdar S. Mohammad Sajadi 《应用有机金属化学》2019,33(7)
In the present work, for the first time we have designed a novel approach for the synthesis of N‐benzyl‐N‐aryl‐5‐amino‐1H‐tetrazoles using reduced graphene oxide (rGO) decorated with Cu‐Ni bimetallic nanoparticles (NPs). In situ synthesis of Cu/Ni/rGO nanocomposite was performed by a cost efficient, surfactant‐free and environmentally benign method using Crataegus azarolus var. aronia L. leaf extract as a stabilizing and reducing agent. Phytochemicals present in the extract can be used to reduce Cu2+ and Ni2+ ions and GO to Cu NPs, Ni NPs and rGO, respectively. Analyses by means of FT‐IR, UV–Vis, EDS, TEM, FESEM, XRD and elemental mapping confirmed the Cu/Ni/rGO formation and also FT‐IR, NMR, and mass spectroscopy as well as elemental analysis were used to characterize the tetrazoles. The Cu/Ni/rGO nanocomposite showed the superior catalytic activity for the synthesis of N‐benzyl‐N‐aryl‐5‐amino‐1H‐tetrazoles within a short reaction time and high yields. Furthermore, this protocol eliminates the need to handle HN3. 相似文献
55.
Gerhard Gompper Clemens Bechinger Stephan Herminghaus Rolf Isele-Holder U. Benjamin Kaupp Hartmut Löwen Holger Stark Roland G. Winkler 《The European physical journal. Special topics》2016,225(11-12):2061-2064
Locomotion of autonomous microswimmers is a fascinating field at the cutting edge of science. It combines the biophysics of self-propulsion via motor proteins, artificial propulsion mechanisms, swimming strategies at low Reynolds numbers, the hydrodynamic interaction of swimmers, and the collective motion and synchronisation of large numbers of agents. The articles of this Special Issue are based on the lecture notes of an international summer school, which was organized by the DFG Priority Programme 1726 “Microswimmers – From Single Particle Motion to Collective Behaviour” in the fall of 2015. The minireviews provide a broad overview of the field, covering both elementary and advanced material, as well as selected areas from current research. 相似文献
56.
Hartmut B. Stegmann Hansjörg V. Dumm Klaus Scheffler 《Phosphorus, sulfur, and silicon and the related elements》2013,188(2):159-170
Abstract Pentakoordinierte Phosphorverbindungen vom Typ der 2.3-Dihydro-1.3.2-benzoxazaphosphole entstehen bei der Umsetzung von 2-Amino-phenolen oder N-Äthyl-2-hydroxy-anilinen mit Diphenyl-trifluorphosphoran unter Verwendung von Triäthylamin als Fluorwasserstoff-Akzeptor. Die Synthese einer großen Anzahl verschieden substituierter Spezies zeigt die Allgemeingültigkeit dieses Verfahrens. Die isolierbaren Substanzen werden durch NMR-Spektren (1H, 31P, 19F) und die üblichen analytischen Methoden charakterisiert. Die Markierung einer Verbindung mit 15N trägt wesentlich zur Struktursicherung bei. Bei den 3-H-2-Fluor-2.2-diphenyl-1.3.2-benzoxazaphospholen wurde ein bemerkenswerter Zusammenhang zwischen P–F-Kopplungskonstante und dem F-shift aufgefunden, der eine lineare Korrelation dieser beiden Größen erkennen läßt. Pentacoordinated phosphorus compounds of the type of 2,3-dihydro-1,3,2-benzoxazaphospholes originate from reaction of 2-aminophenol or N-ethyl-2-hydroxyaniline with diphenyl-trifluorophosphorane using triethylamine as an HF-acceptor. The described synthesis of a great number of differently substituted species indicates the wide field of application. The substances are characterized by nmr spectroscopy (1H, 31P, 19F) and the usual analytical methods. By marking one compound with 15N the structure assignment is proved. Remarkably, the compounds of the type 3-H-2-fluoro-2,2-diphenyl-1,3,2-benzoxazaphospholes exhibit a nearly linear correlation between the P–F-coupling constants and the F-chemical shift. 相似文献
57.
Oliver Brücher Uwe Bergsträßer Harald Kelm Jens Hartung Marco Greb Ingrid Svoboda Hartmut Fuess 《Tetrahedron》2012,68(34):6968-6980
A cascade, composed of (i) oxovanadium(V)-catalyzed oxidation of bromide by tert-butyl hydroperoxide and (ii) stereoselective 6-endo-bromocyclization, affords 3-bromo-2-aryl-2,6,6-trimethyltetrahydropyrans from styrene-type tertiary alkenols in synthetically useful yields. (E)-Alkenols add the bromo- and the alkoxy substituent anti-selectively across the double bond, indicating a bromonium ion-mechanism for the ring closure. 6-endo-control of the alkenol cyclization thereby arises from the polar effect of the aryl substituent. Two methyl substituents bound to the alkene terminus are not similarly able to favor 6-endo-cyclization, because strain arising from methyl group repulsion, as the bromonium-activated π-bond and the hydroxyl oxygen approach, directs bromocyclization of tertiary prenyl-type substrates toward tetrahydrofuran formation. A hexasubstituted bromotetrahydropyran prepared from the oxidation/bromocyclization cascade served as starting material for synthesis of racemic aplysiapyranoid A, in a sequence of free radical and polar functional group interconversion. 相似文献
58.
59.
This paper discusses stationary rotordynamics of synchronous electric machinery, considering different load cases. The model comprises the electrical operation in a rigid network and in an isolated condition. The mechanical part is modelled as a Laval Rotor (Jeffcott Rotor) with a noncircular shaft, accounting for both static- and dynamic rotor eccentricities. The results show, that the machine's electrical operation may influence the occurence of mechanical vibrations significantly and therefore demonstrate the importance of analysing the electromechanical interaction. (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
60.
This contribution discusses the non-linear dynamic behaviour of a rotor system equipped with a compliant seal. The investigated model consists of a Laval-Rotor and a stiff seal ring which is visco-elastically supported. The fluid forces stemming from the turbulent incompressible lubricant film are accounted for by the non-linear Muszynska model. The added compliance leads to an improved stability behaviour of the steady state. Within the post-critical regime the additional compliance gives rise to bifurcations of the stationary vibration: Hopf bifurcations lead to limit cycles which can loose their stability via Neimark-Sacker bifurcations. (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献