全文获取类型
收费全文 | 1091篇 |
免费 | 102篇 |
国内免费 | 4篇 |
专业分类
化学 | 884篇 |
晶体学 | 3篇 |
力学 | 23篇 |
数学 | 113篇 |
物理学 | 174篇 |
出版年
2023年 | 31篇 |
2022年 | 25篇 |
2021年 | 51篇 |
2020年 | 73篇 |
2019年 | 83篇 |
2018年 | 29篇 |
2017年 | 23篇 |
2016年 | 79篇 |
2015年 | 59篇 |
2014年 | 47篇 |
2013年 | 78篇 |
2012年 | 57篇 |
2011年 | 72篇 |
2010年 | 32篇 |
2009年 | 28篇 |
2008年 | 50篇 |
2007年 | 26篇 |
2006年 | 43篇 |
2005年 | 37篇 |
2004年 | 25篇 |
2003年 | 17篇 |
2002年 | 18篇 |
2001年 | 12篇 |
2000年 | 14篇 |
1999年 | 12篇 |
1998年 | 5篇 |
1997年 | 5篇 |
1996年 | 10篇 |
1995年 | 11篇 |
1994年 | 8篇 |
1993年 | 3篇 |
1992年 | 14篇 |
1991年 | 5篇 |
1988年 | 4篇 |
1987年 | 5篇 |
1986年 | 5篇 |
1985年 | 6篇 |
1984年 | 5篇 |
1983年 | 3篇 |
1982年 | 4篇 |
1979年 | 4篇 |
1978年 | 7篇 |
1977年 | 5篇 |
1976年 | 4篇 |
1975年 | 3篇 |
1972年 | 4篇 |
1964年 | 6篇 |
1960年 | 4篇 |
1934年 | 3篇 |
1875年 | 2篇 |
排序方式: 共有1197条查询结果,搜索用时 31 毫秒
1.
H. Tietze-Jaensch D. Sieger R. Geick W. Zulehner A. de Geyer 《Applied Physics A: Materials Science & Processing》1992,54(1):19-21
The formation of silicon oxide precipitates from Czochralski grown silicon depends on the time and temperature of the heat treatment as well as on the initial content of interstitially dissolved oxygen. Samples containing between 5×1017 Oi/cm3 and 13×1017 Oi/cm3 have been heated at 750° C for 96 h. SiO2 precipitates of various shape and size have been obtained and investigated by means of small angle neutron scattering (SANS) in the Q-range 0.05 Å–1<Q<0.2 Å–1. The obtained SANS patterns reveal a typical anisotropy of their intensity distribution, which splits into a central peak at Q<0.1 Å–1 due to the shape of the individual particles and a number of weak intensities for large Q-values, originating from a correlation between defects, possibly between the precipitates. While these correlation peaks in the SANS patterns are seen best for rather low values of about (5–7)×1017 Oi/cm3 oxygen content, the central peak anisotropy is most pronounced for higher values of ca 10×1017 Oi/cm3. The integrated intensity of the central peak increases with increasing initial oxygen content. For comparison, untreated samples of the same initial oxygen content do not reveal any anisotropic SAN scattering or a broadened central peak beam. 相似文献
2.
Wulf-Dieter Geyer 《Israel Journal of Mathematics》1989,68(1):102-108
It is shown that any algebraic curveC over a finite field has a separable cover of some degreen over the projective lineP
1 such that the geometric Galois group of the Galois hull ofC |P
1 is the full symmetric groupS
n.
This work was partially supported by a grant from G.I.F. (German Israeli Foundation for Scientific Research and Development). 相似文献
3.
4.
5.
6.
Maximilian W. Kuntze-Fechner Hendrik Verplancke Lukas Tendera Martin Diefenbach Ivo Krummenacher Holger Braunschweig Todd B. Marder Max C. Holthausen Udo Radius 《Chemical science》2020,11(40):11009
The reaction of [Ni(Mes2Im)2] (1) (Mes2Im = 1,3-dimesityl-imidazolin-2-ylidene) with polyfluorinated arenes as well as mechanistic investigations concerning the insertion of 1 and [Ni(iPr2Im)2] (1ipr) (iPr2Im = 1,3-diisopropyl-imidazolin-2-ylidene) into the C–F bond of C6F6 is reported. The reaction of 1 with different fluoroaromatics leads to formation of the nickel fluoroaryl fluoride complexes trans-[Ni(Mes2Im)2(F)(ArF)] (ArF = 4-CF3-C6F42, C6F53, 2,3,5,6-C6F4N 4, 2,3,5,6-C6F4H 5, 2,3,5-C6F3H26, 3,5-C6F2H37) in fair to good yields with the exception of the formation of the pentafluorophenyl complex 3 (less than 20%). Radical species and other diamagnetic side products were detected for the reaction of 1 with C6F6, in line with a radical pathway for the C–F bond activation step using 1. The difluoride complex trans-[Ni(Mes2Im)2(F)2] (9), the bis(aryl) complex trans-[Ni(Mes2Im)2(C6F5)2] (15), the structurally characterized nickel(i) complex trans-[NiI(Mes2Im)2(C6F5)] (11) and the metal radical trans-[NiI(Mes2Im)2(F)] (12) were identified. Complex 11, and related [NiI(Mes2Im)2(2,3,5,6-C6F4H)] (13) and [NiI(Mes2Im)2(2,3,5-C6F3H2)] (14), were synthesized independently by reaction of trans-[Ni(Mes2Im)2(F)(ArF)] with PhSiH3. Simple electron transfer from 1 to C6F6 was excluded, as the redox potentials of the reaction partners do not match and [Ni(Mes2Im)2]+, which was prepared independently, was not detected. DFT calculations were performed on the insertion of [Ni(iPr2Im)2] (1ipr) and [Ni(Mes2Im)2] (1) into the C–F bond of C6F6. For 1ipr, concerted and NHC-assisted pathways were identified as having the lowest kinetic barriers, whereas for 1, a radical mechanism with fluoride abstraction and an NHC-assisted pathway are both associated with almost the same kinetic barrier.A combined experimental and theoretical study on the mechanism of the C–F bond activation of C6F6 with [Ni(NHC)2] is provided. 相似文献
7.
O. Gabriel Rosa Ganser Monika Geyer C. Jungwirth A. Orleanski G. Stehlik O. Hoffmann-Ostenhof 《Monatshefte für Chemie / Chemical Monthly》1956,87(6):695-700
Scheinbare Divergenzen zwischen den seinerzeit aufgestellten Phosphatbilanzen in Säureextrakten aus phosphatangereicherter und-verarmter Hefe und den in der letzten Mitteilung dieser Reihe erhobenen Befunden über den Gehalt an freien Nucleotiden in demselben Material, veranlaßten eine genauere Überprüfung der Frage, inwieweit die Extraktionsmethoden die Ergebnisse der Nucleotidbestimmung und der Phosphatbilanzen beeinflussen. Es zeigte sich, daß bei Bestimmung der freien Nucleotide, trotz Verwendung verschiedener Extraktionsmittel, sowohl qualitativ als auch quantitativ weitgehend entsprechende Ergebnisse erhalten wurden.Die Resultate können wieder in dem Sinne erklärt werden, daß während der Phosphatanreicherung eine Synthese von Nucleinsäure auf Kosten der freien Nucleotide erfolgt.Gleichzeitig durchgeführte Phosphatbilanzen in den Säureextrakten aus phosphat-verarmter und-angereicherter Hefe ergaben je nach den Extraktionsbedingungen starke, zur Zeit noch schwer deutbare Konzentrationsunterschiede in den einzelnen Phosphatfraktionen.
Mit 2 Abbildungen 相似文献
Mit 2 Abbildungen 相似文献
8.
Scherer LJ Merz L Constable EC Housecroft CE Neuburger M Hermann BA 《Journal of the American Chemical Society》2005,127(11):4033-4041
We describe the synthesis and a novel approach to the conformational analysis of 2,2'-bipyridines (bpy) bearing aromatic rich Frechet-type dendritic wedges of the first and second generation as substituents. The evaporation of solutions of these new ligands on graphite surfaces under ambient conditions results in the formation of self-organized monolayers. Scanning tunneling microscopy (STM) investigations of the monolayers under ambient conditions (air, 298 K) gave images at submolecular and near-atomic resolution. The analysis of the STM images includes the following processes: (i) identification and reproduction of potential homoconformational domains, (ii) exclusion of improper data using quality criteria for drift and feedback artifacts, (iii) compilation of running averages and checking for averaging artifacts, (iv) analysis of three-dimensional and contour plots, (v) calculation of the HOMO properties of the free molecules, and (vi) final conformational assignment based on all accessible information. Following this procedure, two different conformations could be assigned to domains observed in the monolayers of the first-generation (G1) and second-generation (G2) dendritic compounds. Homoconformational domains are observed side-by-side. The different conformations arise from syn or anti arrangements at the ether substituents. An additional conformational effect is found upon treating the G1 domains with HCl gas, when a partial rearrangement of the bpy from trans to cis occurs, concomitant with protonation. 相似文献
9.
Wagner J Andres H Rohrbach S Wagner D Oberer L France J 《The Journal of organic chemistry》2005,70(23):9588-9590
[Reaction: see text]. Sanglifehrin A is a novel complex natural product showing strong immunosuppressive activity and remarkably high affinity for cyclophilin A. To assess its pharmacokinetic properties in vivo, an efficient synthetic route was developed to introduce a tritium label in position C35 of sangliferin A via an oxidation/reduction strategy. The synthetic approach is particularly attractive, because the C35-oxo intermediate 7 is available in good yield on large scale and the reducing agent, lithium tri-sec-butylborotritide, is readily available. An attempt to apply a similar strategy to the alcohol in position C31 led primarily to C31-epi-hydroxy sanglifehrin A under a variety of conditions. 相似文献
10.
Glycosylations are notoriously difficult reactions that require extensive optimization regarding the type of anomeric leaving group, solvent, reaction temperature, and reaction time. Described is the use of a silicon‐based microreactor to screen reaction conditions and to scale‐up synthetic procedures. For the first time, glycosyl phosphates were employed in a microreactor. The optimized reaction conditions were successfully transferred to a batch process. 相似文献