全文获取类型
收费全文 | 1160篇 |
免费 | 79篇 |
国内免费 | 3篇 |
专业分类
化学 | 1028篇 |
晶体学 | 5篇 |
力学 | 9篇 |
数学 | 90篇 |
物理学 | 110篇 |
出版年
2023年 | 22篇 |
2022年 | 12篇 |
2021年 | 27篇 |
2020年 | 44篇 |
2019年 | 34篇 |
2018年 | 29篇 |
2017年 | 23篇 |
2016年 | 37篇 |
2015年 | 51篇 |
2014年 | 50篇 |
2013年 | 66篇 |
2012年 | 96篇 |
2011年 | 108篇 |
2010年 | 54篇 |
2009年 | 40篇 |
2008年 | 83篇 |
2007年 | 82篇 |
2006年 | 91篇 |
2005年 | 69篇 |
2004年 | 60篇 |
2003年 | 53篇 |
2002年 | 30篇 |
2001年 | 4篇 |
2000年 | 2篇 |
1999年 | 3篇 |
1998年 | 12篇 |
1997年 | 11篇 |
1996年 | 12篇 |
1995年 | 3篇 |
1994年 | 1篇 |
1993年 | 3篇 |
1992年 | 5篇 |
1991年 | 3篇 |
1990年 | 2篇 |
1987年 | 4篇 |
1985年 | 4篇 |
1984年 | 1篇 |
1981年 | 3篇 |
1980年 | 1篇 |
1979年 | 3篇 |
1977年 | 1篇 |
1971年 | 1篇 |
1968年 | 1篇 |
1938年 | 1篇 |
排序方式: 共有1242条查询结果,搜索用时 140 毫秒
101.
Lee JJ Fuller RO Sobolev AN Clausen HF Overgaard J Koutsantonis GA Iversen BB Spackman MA 《Chemical communications (Cambridge, England)》2011,47(7):2029-2031
The title compound undergoes two order-disorder transitions between 15 and 299 K, dictated by ordering of the guest molecules in the host cages, and resulting in three related crystal structures. We anticipate behaviour of this kind to be widespread, and speculate that the concept of "the crystal structure" for individual Dianin's clathrates may be elusive. 相似文献
102.
103.
We show that arylpalladium(II) reagents linked to biotin and indocyanine dye residues can be prepared by decarboxylative palladation of appropriately substituted electron-rich benzoic acid derivatives. When prepared under the conditions described, these organometallic intermediates are tolerant of air and water, can be stored for several months in solution in dimethyl sulfoxide, and permit biotin- and indocyanine dye-labeling of functionally complex olefinic substrates in water by Heck-type coupling reactions. 相似文献
104.
The RNA world hypothesis requires that early translation be catalyzed by RNA enzymes. Here we show that a five-nucleotide RNA enzyme, reacting with a tetranucleotide substrate and elevated PheAMP, forms aminoacyl- and peptidyl-RNAs RNA-Phe through RNA-Phe(5). A second series of products is formed from RNA-Phe diesters, after trans migration of phenylalanine from the 2'- to the 3'-hydroxyl group of the substrate RNA, followed by reaminoacylation of the 2'-OH. While the ribozyme is required for initial attachment of phenylalanine to an RNA substrate, as well as reacylation (and thus for formation of all products), further extension into RNA-peptides appears to be an uncatalyzed, but RNA-stimulated reaction. The ribozyme readily turns over at high PheAMP and GCCU concentrations. Thus, GUGGC/GCCU comprises a true RNA enzyme. We define Michaelis-Menten parameters plus and minus divalent magnesium and characterize ca. 20 molecular species of aminoacyl-, peptidyl-, dipeptidyl-, and mixed peptidyl/aminoacyl-RNAs. 相似文献
105.
Standard JM Copack BA Johnson TK Przybyla DE Graham SR Steidl RJ 《The journal of physical chemistry. A》2008,112(2):336-341
Sulfur ylides are useful synthetic intermediates that are formed from the interaction between singlet carbenes and sulfur-containing molecules. Partial double-bond character frequently has been proposed as a key contributor to the stability of sulfur ylides. Calculations at the B3LYP, MP2, and CCSD(T) levels of theory employing various basis sets have been performed on the sulfur ylides H(2)S-CH(2) and (CH(3))(2)S-CH(2) in order to investigate the structure and bonding of these systems. The following general properties of sulfur ylides were observed from the computational studies: C-S bond distances that are close in length to that of a typical C-S double bond, high charge transfer from the sulfide to the carbene, and large torsional rotation barriers. Analysis of the sulfur ylide charge distribution indicates that the unusually short C-S bond distance can be attributed in part to the electrostatic attraction between highly oppositely charged carbon and sulfur atoms. Furthermore, n --> sigma* stabilization arising from donation of electron density from the carbon lone pair orbital into S-H or S-C antibonding orbitals leads to larger than expected torsional barriers. Finally, natural resonance theory analysis indicates that the bond order of the sulfur ylides H(2)S-CH(2) and (CH(3))(2)S-CH(2) is 1.4-1.5, intermediate between a single and double bond. 相似文献
106.
The improvement in amplitude modulation (AM) detection thresholds with increasing level of a sinusoidal carrier has been attributed to listening on the high-frequency side of the excitation pattern, where the growth of excitation is more linear, or to an increase in the number of "channels" via spread of excitation. In the present study, AM detection thresholds were measured using a 1000-Hz sinusoidal carrier. Thresholds for modulation frequencies of 4-64 Hz improved by about 10-20 dB as the carrier level increased from 10 dB SL (14.5 dB SPL on average) to 80 dB SPL. To minimize the use of spread of excitation with an 80-dB carrier, tonal "restrictors" with frequencies of 501, 801, 1210, and 1510 Hz were used alone and in combination. High-frequency restrictors elevated AM detection thresholds, whereas low-frequency restrictors did not, indicating that excitation on the high side is more important for detecting AM. Results of modeling suggest that the improvement in AM detection thresholds at high levels is likely due to the use of a relatively linear growth of response on the high-frequency side of the excitation pattern. 相似文献
107.
Claridge TD Davies SG Lee JA Nicholson RL Roberts PM Russell AJ Smith AD Toms SM 《Organic letters》2008,10(23):5437-5440
An experimentally simple protocol for the very highly (E)-selective Wadsworth-Emmons reaction [(E):(Z) selectivities in excess of 180:1 in some cases] of a range of straight-chain and branched aliphatic, substituted aromatic, and base-sensitive aldehydes via reaction with an alkyl diethylphosphonoacetate and MeMgBr is reported. 相似文献
108.
A versatile synthesis leading to either C-linked alpha- or beta-glucopyranosyl serines is presented from a common, advanced synthetic intermediate. Cyclization of the penultimate carbinol onto the alkene and methanolysis of the lactone yields selectively the alpha-linkage. A transposition of these last steps leads to the beta-linked isomer selectively. 相似文献
109.
Jacob R Tate M Banti Y Rix C Mainwaring DE 《The journal of physical chemistry. A》2008,112(2):322-331
Despite the complex phenomena involved in encoding template molecule information within stable synthetic polymers to yield selective and efficient molecular recognition processes, molecularly imprinted polymers (MIP) are increasingly finding broad areas of application. Molecular interactions, both during the polymerization of the functional monomers in the presence of the template and during the processes of specific recognition after template removal, are key determinants of an effective MIP. Covalent and noncovalent template imprinting have been employed to achieve specific recognition sites. In the present study, a molecularly imprinted biocompatible polymer, having a high capacity and affinity for the dye template, nickel(II) phthalocyanine tetrasulfonic acid, has been prepared. UV-visible spectroscopy, FTIR spectroscopy, and ICP analysis were used to investigate the aspects of the synthesis, binding capacity, and adsorption kinetics of the system. Poly(allylamine) cross-linked with epichlorohydrin has been used to represent an amino-functional receptor. Binding isotherms and capacities were correlated with the degree of template removal. Kinetic studies of binding allowed diffusion mechanisms to be evaluated for the fine particulate MIP. Ab initio molecular orbital calculations were performed using Hartree-Fock, MP2, and density functional theory methods to determine the most likely mechanisms of molecular imprinting. Suitable theoretical models have been constructed to mimic the interactions between the template molecule and the polymer. Simulation of the vibrational spectra was also undertaken to make meaningful assignments to experimentally determined spectral bands resulting from these template MIP receptor interactions. 相似文献
110.