全文获取类型
收费全文 | 144篇 |
免费 | 2篇 |
专业分类
化学 | 123篇 |
力学 | 9篇 |
数学 | 6篇 |
物理学 | 8篇 |
出版年
2023年 | 1篇 |
2022年 | 1篇 |
2021年 | 3篇 |
2020年 | 2篇 |
2019年 | 1篇 |
2016年 | 1篇 |
2015年 | 2篇 |
2014年 | 3篇 |
2013年 | 2篇 |
2012年 | 9篇 |
2011年 | 10篇 |
2010年 | 1篇 |
2009年 | 4篇 |
2008年 | 11篇 |
2007年 | 10篇 |
2006年 | 8篇 |
2005年 | 11篇 |
2004年 | 10篇 |
2003年 | 5篇 |
2002年 | 6篇 |
2001年 | 5篇 |
2000年 | 2篇 |
1999年 | 1篇 |
1998年 | 3篇 |
1996年 | 4篇 |
1995年 | 2篇 |
1993年 | 1篇 |
1992年 | 1篇 |
1990年 | 5篇 |
1989年 | 1篇 |
1988年 | 3篇 |
1987年 | 4篇 |
1986年 | 3篇 |
1985年 | 3篇 |
1982年 | 1篇 |
1978年 | 1篇 |
1974年 | 1篇 |
1970年 | 1篇 |
1964年 | 1篇 |
1937年 | 2篇 |
排序方式: 共有146条查询结果,搜索用时 31 毫秒
91.
Ahuja M Chiang YM Chang SL Praseuth MB Entwistle R Sanchez JF Lo HC Yeh HH Oakley BR Wang CC 《Journal of the American Chemical Society》2012,134(19):8212-8221
Genome sequencing has revealed that fungi have the ability to synthesize many more natural products (NPs) than are currently known, but methods for obtaining suitable expression of NPs have been inadequate. We have developed a successful strategy that bypasses normal regulatory mechanisms. By efficient gene targeting, we have replaced, en masse, the promoters of nonreducing polyketide synthase (NR-PKS) genes, key genes in NP biosynthetic pathways, and other genes necessary for NR-PKS product formation or release. This has allowed us to determine the products of eight NR-PKSs of Aspergillus nidulans, including seven novel compounds, as well as the NR-PKS genes required for the synthesis of the toxins alternariol (8) and cichorine (19). 相似文献
92.
Yu X Mailman A Lekin K Assoud A Robertson CM Noll BC Campana CF Howard JA Dube PA Oakley RT 《Journal of the American Chemical Society》2012,134(4):2264-2275
Semiquinone-bridged bisdithiazolyls 3 represent a new class of resonance-stabilized neutral radical for use in the design of single-component conductive materials. As such, they display electrochemical cell potentials lower than those of related pyridine-bridged bisdithiazolyls, a finding which heralds a reduced on-site Coulomb repulsion U. Crystallographic characterization of the chloro-substituted derivative 3a and its acetonitrile solvate 3a·MeCN, both of which crystallize in the polar orthorhombic space group Pna2(1), revealed the importance of intermolecular oxygen-to-sulfur (CO···SN) interactions in generating rigid, tightly packed radical π-stacks, including the structural motif found for 3a·MeCN in which radicals in neighboring π-stacks are locked into slipped-ribbon-like arrays. This architecture gives rise to strong intra- and interstack overlap and hence a large electronic bandwidth W. Variable-temperature conductivity measurements on 3a and 3a·MeCN indicated high values of σ(300 K) (>10(-3) S cm(-1)) with correspondingly low thermal activation energies E(act), reaching 0.11 eV in the case of 3a·MeCN. Overall, the strong performance of these materials as f = ? conductors is attributed to a combination of low U and large W. Variable-temperature magnetic susceptibility measurements were performed on both 3a and 3a·MeCN. The unsolvated material 3a orders as a spin-canted antiferromagnet at 8 K, with a canting angle φ = 0.14° and a coercive field H(c) = 80 Oe at 2 K. 相似文献
93.
Mailman A Winter SM Yu X Robertson CM Yong W Tse JS Secco RA Liu Z Dube PA Howard JA Oakley RT 《Journal of the American Chemical Society》2012,134(24):9886-9889
The layered-sheet architecture of the crystal structure of the fluoro-substituted oxobenzene-bridged bisdithiazolyl radical FBBO affords a 2D π-electronic structure with a large calculated bandwidth. The material displays high electrical conductivity for a f = 1/2 system, with σ(300 K) = 2 × 10(-2) S cm(-1). While the conductivity is thermally activated at ambient pressure, with E(act) = 0.10 eV at 300 K, indicative of a Mott insulating state, E(act) is eliminated at 3 GPa, suggesting the formation of a metallic state. The onset of metallization is supported by infrared measurements, which show closure of the Mott-Hubbard gap above 3 GPa. 相似文献
94.
Aromatic 4-tetrahydropyranyl and 4-quinuclidinyl cations. Linking Prins with Cope and Grob 总被引:1,自引:0,他引:1
The chair 4-tetrahydropyranyl cation and the 4-quinuclidinyl cation are shown to be energy minima and to be delocalized, with exceptionally long CH2CH2 bonds, according to B3LYP/6-31G* calculations; the implications for Prins cyclizations, Cope rearrangements, and Grob fragmentations are discussed. 相似文献
95.
Beer L Britten JF Cordes AW Clements OP Oakley RT Pink M Reed RW 《Inorganic chemistry》2001,40(18):4705-4709
The S-Se-N-based heterocycle benzo[2,1-c:3,4-c']bis(1,2,3-thiaselenazole) (BSe) can be prepared by the condensation of 1,4-diaminobenzene-2,3-dithiol with selenium tetrachloride. Crystals of this compound are not isomorphous with the related benzo[2,1-c:3,4-c']bis(1,2,3-dithiazole) (BT); a structure is adopted that allows for more extensive intermolecular Se- - -Se contacts. Electro-oxidation of BSe in the presence of [n-Bu4N][ClO4] affords metallic green needles of the charge transfer salt [BSe]3[ClO4]2, which exhibit a pressed pellet conductivity sigma(RT) = 10(-1) S cm(-1). The crystal structure of [BSe]3[ClO4]2 consists of slipped pi-stacks based on the triple-decker closed shell [BSe]3(2+) building block. The packing is analogous to that found for the charge transfer salt [BT]3[FSO3]2, for which sigma(RT) = 10(-2) S cm(-1). Extended Hückel band structure calculations on these two (sulfur- and selenium-based) 3:2 salts reveal more extensive intermolecular interactions in the selenium compound. As a result, the latter has a more two-dimensional electronic structure. Crystal data for Se2S2N2C6H2, a = 4.103(2) A, b = 12.159(2) A, c = 16.171(2) A, orthorhombic, Pbnm, Z = 4. Crystal data for Se6S6N6C18H6Cl2O4, a =17.00(1) A, b = 18.36(1) A, c = 10.679(4) A, 110.27(3), monoclinic, C2/c, Z = 4. 相似文献
96.
97.
98.
The methylene-linked bicyclic guanidine based on the 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine (hppH) framework provides a versatile platform able to support trigonal-planar, tetrahedral, and square-planar metal centers. 相似文献
99.
Beer L Haddon RC Itkis ME Leitch AA Oakley RT Reed RW Richardson JF VanderVeer DG 《Chemical communications (Cambridge, England)》2005,(9):1218-1220
The resonance stabilized bis-thiadiazinyl framework holds potential as a stable and versatile building block for the design of radical-based conductors and magnetic materials. 相似文献