全文获取类型
收费全文 | 257篇 |
免费 | 11篇 |
专业分类
化学 | 177篇 |
晶体学 | 5篇 |
力学 | 2篇 |
数学 | 14篇 |
物理学 | 70篇 |
出版年
2023年 | 3篇 |
2021年 | 3篇 |
2020年 | 3篇 |
2019年 | 2篇 |
2018年 | 5篇 |
2017年 | 3篇 |
2016年 | 10篇 |
2015年 | 4篇 |
2014年 | 3篇 |
2013年 | 19篇 |
2012年 | 19篇 |
2011年 | 30篇 |
2010年 | 11篇 |
2009年 | 9篇 |
2008年 | 18篇 |
2007年 | 21篇 |
2006年 | 17篇 |
2005年 | 20篇 |
2004年 | 15篇 |
2003年 | 7篇 |
2002年 | 7篇 |
2001年 | 6篇 |
2000年 | 5篇 |
1999年 | 8篇 |
1998年 | 4篇 |
1997年 | 2篇 |
1996年 | 3篇 |
1994年 | 1篇 |
1992年 | 1篇 |
1990年 | 1篇 |
1987年 | 2篇 |
1979年 | 2篇 |
1978年 | 1篇 |
1975年 | 1篇 |
1974年 | 1篇 |
1966年 | 1篇 |
排序方式: 共有268条查询结果,搜索用时 15 毫秒
41.
Boydston AJ Pecinovsky CS Chao ST Bielawski CW 《Journal of the American Chemical Society》2007,129(47):14550-14551
A new series of highly photoluminescent benzobis(imidazolium) salts with tunable electronic and physical properties is described. Systematic structural manipulations provided a set of materials that were not only fluorescent in the condensed state but also displayed tunable glass transition temperatures ranging from -0.3 to 113 degrees C. Upon heating, these robust materials flowed while maintaining their emissive properties. Further phase tuning was demonstrated through the synthesis of two thermotropic liquid-crystalline fluorescent benzobis(imidazolium) salts. 相似文献
42.
Karp E Pecinovsky CS McNevin MJ Gin DL Schwartz DK 《Langmuir : the ACS journal of surfaces and colloids》2007,23(15):7923-7927
An amphiphilic photoisomerizable macrocycle has been prepared that forms stable Langmuir monolayers at the air-water interface. The hydrophilic core of the molecule switches between closed and open isomers upon irradiation by the appropriate wavelengths of light. Isotherm measurements, Brewster angle microscope images, and atomic force micrographs (of transferred Langmuir-Blodgett films) suggest a phase transition between a face-on to a tilted edge-on molecular orientation as a function of surface concentration. In the face-on phase, in situ photoisomerization results in a reversible increase in surface pressure due to greater molecular crowding in the open configuration. 相似文献
43.
Sharon Peled Ching-Hua Tseng Aaron A. Sodickson Ross W. Mair Ronald L. Walsworth David G. Cory 《Journal of magnetic resonance (San Diego, Calif. : 1997)》1999,140(2):320-324
A single-shot pulsed gradient stimulated echo sequence is introduced to address the challenges of diffusion measurements of laser polarized 3He and 129Xe gas. Laser polarization enhances the NMR sensitivity of these noble gases by >10(3), but creates an unstable, nonthermal polarization that is not readily renewable. A new method is presented which permits parallel acquisition of the several measurements required to determine a diffusive attenuation curve. The NMR characterization of a sample's diffusion behavior can be accomplished in a single measurement, using only a single polarization step. As a demonstration, the diffusion coefficient of a sample of laser-polarized 129Xe gas is measured via this method. 相似文献
44.
Thomas M. Cooper Lalgudi V. Natarajan Cory G. Miller 《Photochemistry and photobiology》1999,69(2):173-176
Abstract— In order to develop new systems that couple photochromism with molecular conformation change, a series of spiropyrans having different ring substituents were attached to poly(L-glutamic acid). The polypeptides were dissolved in hexafluoroisopropanol and dark adapted so that the dye was in the merocyanine form. Following adaptation by white light and dye photoconversion from the merocyanine to spiropyran forms, polypeptide dark-adaptation kinetics were monitored by circular dichroism (CD) and dye dark adaptation was monitored by UV/ visible. Light adaptation caused a light-induced coil-to-helix transition, with dark adaptation resulting in relaxation back to the coil. The dark-adaptation rate constant measured by UV/visible was equal to that measured by CD, demonstrating close coupling between dye state and polypeptide conformation. By varying the substituents on the spiropyran ring, dark-adaptation half lives were varied from less than a minute to 2 h, representing nearly three orders of magnitude. 相似文献
45.
We study the minimum number of weights assigned to the edges of a graph G with no component K2 so that any two adjacent vertices have distinct sets of weights on their incident edges. The best possible upper bound on this parameter is proved. 相似文献
46.
X-ray crystallography and solid-state NMR techniques were used to determine the structure and 195Pt NMR chemical shift (CS) tensor of Pt[S2C2(CF3)2]2. This is the first reported crystal structure of a highly oxidizing (CN- or CF3-substituted) neutral bis(dithiolene) complex of a Ni triad metal in its pure form. The 195Pt NMR CS tensor is highly anisotropic and asymmetric; the latter property is attributed to the noninnocent nature of the ligand. The tensor components and orientation are determined with density functional theory calculations. 相似文献
47.
Organ MG Avola S Dubovyk I Hadei N Kantchev EA O'Brien CJ Valente C 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(18):4749-4755
We have developed the first user-friendly Negishi protocol capable of routinely cross-coupling all combinations of alkyl and aryl centers. The use of an easily synthesized, air stable, highly active, well-defined precatalyst PEPPSI-IPr (1; PEPPSI=pyridine-enhanced precatalyst preparation, stabilization and initiation; IPr=diisopropylphenylimidazolium derivative) substantially increases the scope, reliability, and ease-of-use of the Negishi reaction. All organohalides and routinely used pseudohalides were excellent coupling partners, with the use of chlorides, bromides, iodides, triflates, tosylates, and mesylates resulting in high yield of the coupled product. Furthermore, all reactions were performed by using general laboratory techniques, with no glove-box necessary as the precatalyst was weighed and stored in air. Utilization of this methodology allowed for the easy synthesis of an assortment of sterically encumbered biaryls and druglike heteroaromatics, demonstrating the value of the PEPPSI-IPr system. Furthermore, this is also the first time Pd-NHC (NHC=N-heterocyclic carbene) methodology has surpassed the related phosphine-ligated Negishi processes both in activity and use. 相似文献
48.
O'Brien CJ Kantchev EA Valente C Hadei N Chass GA Lough A Hopkinson AC Organ MG 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(18):4743-4748
The synthesis of NHC-PdCl(2)-3-chloropyridine (NHC=N-heterocyclic carbene) complexes from readily available starting materials in air is described. The 2,6-diisopropylphenyl derivative was found to be highly catalytically active in alkyl-alkyl Suzuki and Negishi cross-coupling reactions. The synthesis, ease-of-use, and activity of this complex are substantial improvements over in situ catalyst generation and all current Pd-NHC complexes. The utilization of complex 4 led to the development of a reliable, easily employed Suzuki-Miyama protocol. Employing various reaction conditions allowed a large array of hindered biaryl and drug-like heteroaromatic compounds to be synthesized without difficulty. 相似文献
49.
A variety of dipyrromethanes and dipyrromethenes have been prepared, and their 15N NMR chemical shifts have been measured by two-dimensional correlation to 1H NMR signals. The nitrogen atoms in five examples of dipyrromethanes consistently exhibit chemical shifts around -231 ppm, relative to nitromethane. Seven examples of hydrobromide salts of meso-unsubstituted dipyrromethenes consistently display 15N chemical shifts around -210 ppm, while their corresponding zinc(II) complexes exhibit chemical shifts around -170 ppm. The presence of electron-withdrawing substituents on one of the pyrrolic rings of dipyrromethenes affects the chemical shifts of both of the nitrogen nuclei in the molecule. Boron difluoride complexes of meso-unsubstituted dipyrromethenes display 15N chemical shifts around -190 ppm. Two examples of free-base dipyrromethenes bearing substituents at the meso-position exhibit 15N chemical shifts at approximately -156 ppm, and for the zinc complexes of these compounds at -162 ppm. One-bond nitrogen-hydrogen coupling constants, when measurable, were consistently in the range of -96 Hz. Since the measured 15N chemical shifts have such a high regularity correlated to structure, they can be used as diagnostic indications for identifying the structure of dipyrrolic compounds. 相似文献
50.
Jasmine Regourd Ian M. Comeau Cory S. Beshara Alison Thompson 《Journal of heterocyclic chemistry》2006,43(6):1709-1714