首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   791篇
  免费   3篇
  国内免费   19篇
化学   258篇
力学   57篇
数学   237篇
物理学   261篇
  2016年   10篇
  2015年   7篇
  2013年   43篇
  2012年   18篇
  2011年   29篇
  2010年   6篇
  2009年   14篇
  2008年   20篇
  2007年   27篇
  2006年   23篇
  2005年   26篇
  2004年   17篇
  2003年   8篇
  2002年   15篇
  2001年   12篇
  2000年   8篇
  1999年   14篇
  1998年   10篇
  1997年   12篇
  1996年   13篇
  1995年   23篇
  1994年   11篇
  1993年   21篇
  1992年   12篇
  1991年   11篇
  1990年   16篇
  1989年   17篇
  1988年   9篇
  1987年   10篇
  1986年   18篇
  1985年   23篇
  1984年   14篇
  1983年   15篇
  1982年   15篇
  1981年   23篇
  1980年   23篇
  1979年   17篇
  1978年   19篇
  1977年   18篇
  1976年   14篇
  1975年   16篇
  1974年   13篇
  1973年   21篇
  1972年   12篇
  1971年   9篇
  1969年   9篇
  1968年   5篇
  1967年   6篇
  1966年   6篇
  1965年   5篇
排序方式: 共有813条查询结果,搜索用时 15 毫秒
11.
The nucleus23Na has been investigated by studying the primary γ-rays emitted from 53 keV neutron capture in it using a high resolution and high efficiency (100%) HPGe detector and NaI(T1) detector for anti-Compton. 24 primary γ-rays were placed in the24Na, in which 3 primary γ-rays were new ones from a (n, γ) reaction, and reported for the first time. In order to obtain an exact energy calibration within 7 MeV,56Fe(n,γ)57Fe reaction was used at thermal neutron energy. Intensity calibration was obtained from the27Al(p,γ)28Si reaction atE p=2046 keV. The neutron binding energy of24Na was determined to be 6959.75 keV.  相似文献   
12.
In den Jahren seiner Tätigkeit am Weizmann Institut of Science begann G. M. J. Schmidt seine Arbeiten über die Beziehungen zwischen der Struktur organischer Kristalle und der in ihnen stattfindenden chemischen Reaktionen, ein Forschungsvorhaben, das sich in der Folge als außergewöhnlich fruchtbar erwiesen hat. So wuchs seine ?Festkörper-Gruppe”? und wurde divergenter - Röntgenstrukturanalytiker, Organiker, Spektroskopiker und schließlich sogar Theoretiker wirkten mit. Professor Schmidt starb 1971. Als eines der Mitglieder dieser Gruppe folge ich nun der Einladung, über neuere Entwicklungen auf meinem Interessengebiet zu berichten. Ein Großteil der bisher untersuchten Reaktionen organischer Kristalle wird durch Licht oder andere Strahlung induziert. Dies ist eine natürliche Folge davon, daß Strahlung, ungleich den meisten chemischen Reaktanden, leicht die Oberfläche des Kristalls durchdringen und so die zu aktivierenden Orte erreichen kann. In diesem Beitrag sollen einige der in der Photochemie organischer Kristalle wirksamen Prinzipien aufgezeigt und anhand von Beispielen verdeutlicht werden, wobei nicht beabsichtigt ist, alle bisher untersuchten unterschiedlichen Reaktionstypen und Systeme zu erfassen. Es ist geboten, hier in Anerkennung auch eines anderen großen Wissenschaftlers zu gedenken, der vor kurzer Zeit verschied - Theodor Förster. Manche der Ideen, auf die ich im folgenden eingehe, wurzeln, wie so vieles in der jüngsten Entwicklung der Photochemie, in Professor Försters früheren Arbeiten.  相似文献   
13.
Abstract– The isomer composition and spectral properties of 15 artificial bacteriorhodopsin (bR) pigments, based on a series of retinal analogs with polyene residue modified below C9 are determined for both dark-adapted (DA) and light-adapted (LA) forms. Similarly to native bR, in all cases only two isomers, C13=C14cis (13-cis) and M-trans, are observed. However, the artificial DA pigments have a lower 13-d.s content than native DA bR (? 66%) while the corresponding LA pigments have a much higher 13-cis content (11-69%) than native LA bR (<2%). Thus, in variance with the native pigment, in all of the artificial systems light also induced the reversed all-trans13-cis process. The data are accounted for in terms of specific steric interactions between the polyene and the protein binding site which allow a (C15-anti)(Cls-syn) isomerization during the photocycle of the artificial pigments, but not in the case of native bR. This accounts for the high proton pumping efficiency of the natural pigment. The nature of a highly red shifted light-adapted form of two of the artificial pigments is investigated and discussed. It is also shown that, in variance with native bR, several artificial pigments exhibit identical absorption spectra for their 13-cis and all-trans isomers. It is concluded that the spectral data for the above species of artificial pigments do not lead to a clear molecular model for the origin of the spectral shift between 13-cis and all-trans bR.  相似文献   
14.
The geometry and energy of 1,3-butadiene have been calculated using the 6-311G** basis set as a function of the CCCC dihedral angle-0 ° (trans), 30 °, 60 °, 75 °, 90 °, 120 °, 135 °, 150 °, 165 ° and 180 ° (cis)-assuming that the vinyl groups remain planar. Potential minima are located at 0 ° and 141.4 °, with the trans structure more stable than the gauche by 13.2 kJ mol–1. Potential maxima are located at 76.7 °, giving a barrier height of 25.4 kJ mol–1 relative to the trans structure, and at 180 ° giving a barrier height of 3.0 kJ mol–1 relative to the 141.4 °-gauche structure. Using the 6-31G* basis set the inclusion of electron correlation, accounting for about 52% of the correlation energy, was found to produce no significant change in the shape of the potential energy curve. The magnitude of the expectation energy differences is such that both barriers with respect to the 14l.4 °-gauche maximum structure can be categorized unequivocally as attractive-dominant, whereas the values for the energy barrier with respect to the trans structure, although characteristic of a repulsive-dominant barrier at the 6–311G** level, are sufficiently small that higher level calculations might give the opposite result. Analysis of V nn for the conversion reactions cis 150 °-gauche, trans 60 °-gauche, and trans 90 °-gauche in terms of the individual contributions from the various internuclear interactions shows that nonbonded interactions are important, not only in initiating the destabilization of the crowded cis structure, but also through-out the entire range of CCCC dihedral angles, 0 ° to 180 °.  相似文献   
15.
The back photoreaction of the M intermediate in the photocycle of bacteriorhodopsin is investigated both for the native pigment and its D96N mutant. The experimental setup is based on creating the M intermediate by a first pulse, followed by a (blue) laser pulse which drives the back photoreaction of M. Experiments are carried out varying the delay between the two pulses, as well as the temperature over the -25 degrees C-20 degrees C range. It is found that the kinetic patterns of the M back photoreaction change with time after the generation of this intermediate. The data provide independent evidence for the suggestion of a photocycle mechanism based on two distinct M intermediates. They are thus in keeping with the consecutive model of Varo and Lanyi (Biochemistry 30, 5016-5022; 1991), although they cannot exclude other models such as those based on branched or parallel cycles. More generally, we offer a "photochemical" approach to discriminating between intermediate stages in the photocycle which does not depend on spectroscopic and/or kinetic data. While markedly affecting the rate of the M --> N transition in the photocycle, the rate of the thermal step in back photoreaction of M, at both room and low temperatures, is not significantly affected by the D96N mutation. It is proposed that while Asp 96 is the Schiff-base protonating moiety in the M --> N transition, another residue (most probably Asp 85) reprotonates the Schiff base following light absorption by M.  相似文献   
16.
Reactions are described that employ 90°-1,3-butadiene as a reference structure for the evaluation of the stabilization energyof the benzenoid and other cyclic conjugated hydrocarbons. The unique benefits of this rotamer of butadiene as a reference molecule within the homodesmotic conceptual framework are discussed. Experimental stabilization energies are presented for a number of cyclic hydrocarbons.  相似文献   
17.
18.
19.
20.
Tendon functions by transmitting tensile loads from muscle to bone. Morphologically, it can be described as a macromolecular multicomposite material, basically consisting of collagen fibrils held together by a soft, hydrated matrix material. Recently, tendon has been deformed beyond the "in vivo" elastic limit and by cyclical loading systematically damaged. Using high-resolution electron microscopy, decomposition of the collagen fibril into subfibrils (15 nm diameter) and microfibrils (3.5 nm diameter) has been noted. The interfacial adhesion between such units is strongly dependent on age, and is probably related with crosslinking phenomena observed by biochemical methods. In addition, tendon collagen contains a considerable amount of water throughout the entire structure which strongly affects its overall mechanical behavior. The various bound states of water have been identified using primarily dynamic mechanical spectroscopy coupled with more conventional methods of structural characterization.Published in Mekhanika Polimerov, No. 4, pp. 693–701, July–August, 1976.  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号