全文获取类型
收费全文 | 1716篇 |
免费 | 71篇 |
国内免费 | 6篇 |
专业分类
化学 | 1439篇 |
晶体学 | 24篇 |
力学 | 16篇 |
数学 | 70篇 |
物理学 | 244篇 |
出版年
2023年 | 4篇 |
2022年 | 15篇 |
2021年 | 13篇 |
2020年 | 18篇 |
2019年 | 37篇 |
2018年 | 20篇 |
2017年 | 13篇 |
2016年 | 44篇 |
2015年 | 35篇 |
2014年 | 59篇 |
2013年 | 72篇 |
2012年 | 101篇 |
2011年 | 118篇 |
2010年 | 77篇 |
2009年 | 53篇 |
2008年 | 119篇 |
2007年 | 113篇 |
2006年 | 115篇 |
2005年 | 128篇 |
2004年 | 115篇 |
2003年 | 98篇 |
2002年 | 68篇 |
2001年 | 22篇 |
2000年 | 19篇 |
1999年 | 16篇 |
1998年 | 29篇 |
1997年 | 20篇 |
1996年 | 18篇 |
1995年 | 10篇 |
1994年 | 7篇 |
1993年 | 4篇 |
1992年 | 16篇 |
1991年 | 10篇 |
1990年 | 6篇 |
1988年 | 7篇 |
1986年 | 4篇 |
1985年 | 17篇 |
1984年 | 15篇 |
1983年 | 8篇 |
1982年 | 17篇 |
1981年 | 18篇 |
1980年 | 13篇 |
1979年 | 21篇 |
1978年 | 9篇 |
1977年 | 8篇 |
1976年 | 8篇 |
1975年 | 7篇 |
1974年 | 8篇 |
1973年 | 9篇 |
1972年 | 3篇 |
排序方式: 共有1793条查询结果,搜索用时 12 毫秒
61.
Chatani N Oshita M Tobisu M Ishii Y Murai S 《Journal of the American Chemical Society》2003,125(26):7812-7813
A GaCl3-catalyzed reaction of alpha,beta-unsaturated ketones with isocyanides leading to the formation of unsaturated lactone derivatives is described. This is the first example of the catalytic [4+1] cycloaddition of alpha,beta-unsaturated ketones and isocyanides. GaCl3 is an excellent catalyst due to its lower oxophilicity, which is desirable for all of the key steps, such as E/Z isomerization, cyclization, and deattachment from the products. 相似文献
62.
In bacteriorhodopsin (bR), Arg-82bR has been proven to be a very important residue for functional role of this light-driven proton pump. The arginine residue at this position is a super-conserved residue among archaeal rhodopsins. pharaonis phoborhodopsin (ppR; or called as "pharaonis sensory rhodopsin II") has its absorption maximum at 498 nm and acts as a sensor in the membrane of Natronobacterium pharaonis, mediating the negative phototaxis from the light of wavelength shorter than 520 nm. To investigate the role of the arginine residue (Arg-72ppR) of ppR corresponding to Arg-82bR, mutants whose Arg-72ppR was replaced by alanine (R72A), lysine (R72K), glutamine (R72Q) and serine (R72S) were prepared. These mutants were unstable in low concentrations of NaCl and lost their color gradually when the proteins were solubilized with 0.1% n-dodecyl-beta-D-maltoside. The order of instability was R72S > R72A > R72K > R72Q > the wild type. The rates of denaturation were reduced in a solution of high concentrations of monovalent anions. 相似文献
63.
Merrilactone A (1) has been shown to possess neurotrophic activity and thus is expected to hold therapeutic potential in the treatment of neurodegeneration diseases. In this paper, we report the total synthesis of (+/-)-1, employing, as key steps, a novel desymmetrization protocol of meso-diketone to construct the core cis-bicyclo[3.3.0]octyl system of 1 (3 --> 2) and a radical cyclization to install the highly congested C9-quaternary carbon (16 --> 17). 相似文献
64.
Highly efficient methods for synthesizing metacyclophanes such as 2,6-bridged pyrones and pyridines are described. 4-Hydroxy-2-pyrone derivative 3 bridged at the 3 and 6-positions is readily available. This compound was transformed into 2,6-bridged 4-pyrone 4 on heating in ethanol or in hydrochloric acid. Heating 4 with ammonia or methylamine afforded the corresponding 2,6-bridged 4-pyrone 7 or 8. These pyridones were synthesized directly from 3 by treatment with ammonia or methylamine. These methods have a wide applicability to the bridge length of metacyclophane; compounds with a short bridge (n=8) as well as long bridge (n=18) are synthesized in satisfactory yields. 相似文献
65.
Masayuki Inoue 《Tetrahedron》2003,59(30):5645-5659
Ladder-shaped polyether natural products show diverse biological activities with extreme potency. As the initial phase of detailed SAR studies of bioactive polyethers, we set out to construct structurally simple mimics. This paper details the divergent synthesis of 6-X-7-6 tetracycles (X=7, 8, or 9) starting from a simple 6-membered ether. Key reactions in the synthesis include (i) the direct formation of an O,S-acetal by the coupling of an alcohol with an α-chlorosulfide, (ii) the construction of a 7-membered ring by radical cyclization, and (iii) cyclization to the 7, 8 or 9-membered ring via a ring-closing metathesis reaction. The neutral reaction conditions of our strategy enable the synthesis of a wide variety of substrates. The results of this study can be applied for the rapid construction of artificial polyether compounds with diversified molecular shapes and sizes. 相似文献
66.
Gebbink RJ Watanabe M Pratt RC Stack TD 《Chemical communications (Cambridge, England)》2003,(5):630-631
Cupric complexes of a novel phenanthroline-phenolate ligand have strongly distorted coordination geometries and electrochemical properties conducive to modeling the spectroscopy and reactivity of the enzyme galactose oxidase. 相似文献
67.
Ando M Takizawa M Suwabe S Yamato S Shimada K 《European journal of mass spectrometry (Chichester, England)》2003,9(6):619-622
Analysis of selenium in biological samples is very important and numerous analytical methods for the element have been developed. One of the most convenient and widely used methods for routine determination of serum selenium is a fluorometric method using 2,3-diaminonaphthalene (DAN); however, this method lacks specificity. We observed that 4,5-benzopiazselenol (BPS), a selenium derivative of DAN, is ionized with electron capture in an atmospheric pressure chemical ionization (APCI) interface, and subsequently established a method for determining total human serum selenium by means of liquid chromatography/atmospheric pressure chemical ionization mass spectrometry. All pretreatment procedures were carried out in a single test tube to minimize selenium loss. The recovery of organic or inorganic selenium spiked to human serum was 97-103%.The detection limit of BPS was equivalent to 0.2 ng of selenium and the lower quantitative limit of serum selenium was 10 ng mL(-1). The coefficient of variation of standard concentrations in control serum samples was 4.5%. The purity of the observed peak obtained from serum samples was confirmed using the ion cluster technique. 相似文献
68.
69.
Matsuda H Morikawa T Toguchida I Harima S Yoshikawa M 《Chemical & pharmaceutical bulletin》2002,50(7):972-975
Two new flavanone glycosides, (2S)- and (2R)-eriodictyol 7-O-beta-D-glucopyranosiduronic acids, and a new phenylbutanoid glycoside, (2S, 3S)-1-phenyl-2,3-butanediol 3-O-beta-D-glucopyranoside, were isolated from the flowers of Chrysanthemum indicum L. cultivated in China together with eight flavonoids. The absolute stereostructures of the new compounds were determined on the basis of chemical and physicochemical evidence. Both of the new flavanone glycosides were found to show inhibitory activity for rat lens aldose reductase. 相似文献