全文获取类型
收费全文 | 7298篇 |
免费 | 265篇 |
国内免费 | 47篇 |
专业分类
化学 | 5249篇 |
晶体学 | 27篇 |
力学 | 252篇 |
数学 | 945篇 |
物理学 | 1137篇 |
出版年
2023年 | 64篇 |
2022年 | 74篇 |
2021年 | 129篇 |
2020年 | 122篇 |
2019年 | 152篇 |
2018年 | 94篇 |
2017年 | 87篇 |
2016年 | 211篇 |
2015年 | 171篇 |
2014年 | 213篇 |
2013年 | 403篇 |
2012年 | 477篇 |
2011年 | 527篇 |
2010年 | 291篇 |
2009年 | 256篇 |
2008年 | 457篇 |
2007年 | 477篇 |
2006年 | 430篇 |
2005年 | 393篇 |
2004年 | 370篇 |
2003年 | 336篇 |
2002年 | 281篇 |
2001年 | 103篇 |
2000年 | 104篇 |
1999年 | 83篇 |
1998年 | 67篇 |
1997年 | 73篇 |
1996年 | 88篇 |
1995年 | 62篇 |
1994年 | 48篇 |
1993年 | 44篇 |
1992年 | 49篇 |
1991年 | 48篇 |
1990年 | 53篇 |
1989年 | 32篇 |
1988年 | 25篇 |
1986年 | 30篇 |
1985年 | 41篇 |
1984年 | 60篇 |
1983年 | 39篇 |
1982年 | 51篇 |
1981年 | 42篇 |
1980年 | 58篇 |
1979年 | 37篇 |
1978年 | 45篇 |
1977年 | 43篇 |
1976年 | 36篇 |
1975年 | 42篇 |
1974年 | 26篇 |
1973年 | 31篇 |
排序方式: 共有7610条查询结果,搜索用时 31 毫秒
61.
The influence of a chiral surfactant and a polymer-supported chiral additive on reduction of ketones using sodium borohydride will be described. Initial preparations involved methylation of (S)-leucinol to give (2S)-N , N-dimethyl-2-amino-4-methyl-1-pentanol (1) (67%). The chiral surfactant (2) was synthesized by reacting (1) with bromohexadecane (71%). The functionalized styrene for the polymer-supported chiral additive (5) was synthesized by reacting (1) with 4-vinylbenzyl chloride. Polymerization was carried out with 10% of the functionalized monomer (4), 5% cross-linking agent divinylbenzene, and 85% styrene with AIBN as the initiator. The activity of the chiral surfactant and polymeric additive were examined by using them as additives in a standard reduction of 2-pentanone with sodium borohydride to yield (R)- and (S)-2-pentanol (3) (20%). The resulting alcohol was analyzed by polarimetry (ee 9.5%) and also esterified with (2S)-methylbutyric acid prior to characterization by NMR. 13C NMR indicated an enantiomeric excess of 5.2% when the chiral surfactant was used, and 7% when the polymeric additive was used. 相似文献
62.
Lamb pregastric lipase was purified from a commercial source using delipidation, solubilization with KSCN, acid-precipitation, pepsin-digestion, affinity chromatography with agarose-Cibacron Blue F3GA, gel filtration, and elution from a native 10% (w/v) polyacrylamide gel. The enzyme had a single subunit of 68,000 Da with maximum esterase activity when measured at pH 6.0 and 30 degrees C. The enzyme preferentially hydrolyzed short- and medium-chain (C4, C6, and C8) synthetic esters and short-chain (C4 and C6) monoacid triglycerides. The NH2-terminal sequence demonstrated high homology with gastric and lingual lipases. 相似文献
63.
64.
Anzalone PW Baru AR Danielson EM Hayes PD Nguyen MP Panico AF Smith RC Mohan RS 《The Journal of organic chemistry》2005,70(6):2091-2096
[reaction: see text] Three one-pot methods for the conversion of aldehydes to homoallyl ethers catalyzed by Bi(OTf)(3).xH(2)O (1 < x < 4) have been developed. The one-pot synthesis of homoallyl ethers can be achieved either by in situ generation of the acetal followed by its reaction with allyltrialkylsilane or by a three-component synthesis in which the aldehyde, trimethylorthoformate or an alkoxytrimethylsilane and allyltrimethylsilane are mixed together in the presence of bismuth triflate (0.1-1.0 mol %). In addition, a three-component synthesis of homoallyl acetates, which is achieved by reacting the aldehyde, acetic anhydride, and allyltrimethylsilane in the presence of bismuth triflate (3.0-5.0 mol %), has been developed. The use of a relatively nontoxic, easy to handle, and inexpensive catalyst adds to the versatility of these methods. 相似文献
65.
66.
67.
68.
Polymeric molecules containing multiple thiol groups (polythiols) provide tenacious attachment to metal surfaces such as gold. Polythiol films are also well suited for subsequent derivatization with biomacromolecules through remnant free thiol groups of the film. In this study, 1-3 nm thick layers of a commercial polythiol, poly((mercaptopropyl)methylsiloxane) (PMPMS), are investigated with X-ray photoelectron spectroscopy (XPS) and electrochemical impedance spectroscopy. XPS is used to reveal the surface coverage of thiolate-Au bonds between the polythiol and the metal support, which is found to be approximately 30% lower than that in alkanethiol self-assembled monolayers. The surface density of thiolate-Au bonds did not depend on film thickness provided sufficient PMPMS material was present. Differential capacitance measurements show that the effective dielectric barrier presented by PMPMS films under aqueous environments corresponds closely to their physical thickness, with even approximately 1 nm films remaining impermeable to electrolyte species. Modification of the films with an oligoethylene glycol compound was also examined, in anticipation of future applications in label-free, impedance-based biomolecular diagnostics. 相似文献
69.
Abstract— In stationary-phase Escherichia coli B/r, photoreactivation (PR) at 313 nm of ultraviolet (u.v.) killing is inefficient compared with PR at 405 nm, and can be explained solely by photoenzymatic reversal of pyrimidine dimers. In Staphylococcus epidermidis, PR shows a maximum at 313 nm, suggesting that this organism shows the Type III PR proposed by Jagger et al.[5] for Streptomyces strains. Reversal of pyrimidine dimers is not sufficient to explain this PR. The mechanism of Type III PR remains unknown. With both S. epidermidis and E. coli B/r, the amount of uracil–thymine heteroadduct in DNA hydrolysates decreases if the cells are given a post-u.v. treatment at 313 nm, but no decrease is observed if the post-u.v. treatment is at 405 nm. The biological significance of this adduct and of its removal is not clear. It may play a role in Type III PR. 相似文献
70.
THE EFFECTS OF HOST-CELL REACTIVATION ON ASSAY OF U.V.-IRRADIATED HAEMOPHILUS INFLUENZAE TRANSFORMING DNA 总被引:4,自引:0,他引:4
Abstract— The host cell reactivation (HCR) mechanism in Haemophilus influenzae cells is inhibited by sub-microgram concentrations of acriflavine (as is already known to be true for Escherichia coli ). Exposure of these cells to similar concentrations of the drug during bacterial transformation increases the apparent ultraviolet light (u.v.) sensitivity of previously irradiated transforming DNA, indicating a repair of this DNA after uptake by the cells under normal conditions. Repair is inhibited by applying acriflavine at any time up to one hour after competent cells contact the irradiated transforming DNA. The fraction of the u.v. damage repaired by HCR is very different for different genetic markers. Those markers which are most u.v. sensitive when assayed in the absence of acriflavine are most poorly repaired, suggesting that this is the reason for their higher sensitivity. For all markers the fraction of the damage repairable by in vitro photoreactivation is approximately constant, and strongly overlaps the damage repairable by HCR. The degree of HCR achieved can be altered by experimental treatment of the H. influenzae DNA prior to transformation. Thus treatment of irradiated DNA with an enzyme from Micrococcus lysodeikticus –known to attack u.v. damaged, but not undamaged DNA–prevents subsequent intracellular repair of the same u.v. lesions whose repair is inhibited by acriflavine. Similarly, partial replacement of the thymine in transforming DNA by 5-bromouracil (BU) strongly inhibits repair of subsequent u.v. damage. As in bacteriophage, the BU effect is relieved if the u.v. exposure occurs in the presence of cysteamine. It is clear that intracellular repair must be considered in interpreting experiments with u.v.-irradiated transforming DNA. 相似文献