全文获取类型
收费全文 | 2493篇 |
免费 | 76篇 |
国内免费 | 9篇 |
专业分类
化学 | 1861篇 |
晶体学 | 36篇 |
力学 | 32篇 |
数学 | 141篇 |
物理学 | 508篇 |
出版年
2022年 | 17篇 |
2021年 | 21篇 |
2020年 | 28篇 |
2019年 | 33篇 |
2018年 | 23篇 |
2017年 | 22篇 |
2016年 | 35篇 |
2015年 | 54篇 |
2014年 | 61篇 |
2013年 | 125篇 |
2012年 | 113篇 |
2011年 | 137篇 |
2010年 | 69篇 |
2009年 | 72篇 |
2008年 | 134篇 |
2007年 | 135篇 |
2006年 | 127篇 |
2005年 | 151篇 |
2004年 | 118篇 |
2003年 | 118篇 |
2002年 | 110篇 |
2001年 | 37篇 |
2000年 | 30篇 |
1999年 | 34篇 |
1998年 | 26篇 |
1997年 | 25篇 |
1996年 | 27篇 |
1995年 | 27篇 |
1994年 | 31篇 |
1993年 | 24篇 |
1992年 | 37篇 |
1991年 | 17篇 |
1990年 | 20篇 |
1989年 | 25篇 |
1988年 | 18篇 |
1987年 | 18篇 |
1986年 | 24篇 |
1985年 | 27篇 |
1984年 | 43篇 |
1983年 | 26篇 |
1982年 | 27篇 |
1981年 | 34篇 |
1980年 | 20篇 |
1979年 | 32篇 |
1977年 | 26篇 |
1976年 | 28篇 |
1975年 | 31篇 |
1974年 | 29篇 |
1973年 | 22篇 |
1972年 | 19篇 |
排序方式: 共有2578条查询结果,搜索用时 328 毫秒
31.
Bile acids, such as cholic, chenodeoxycholic, deoxycholic, lithocholic and ursodeoxycholic acids, were allowed to react with hexafluoroisopropanol and tri-fluoracetic anhydride at 37 for 30 min. The resulting derivatives were gas chromatographed on QF-1, with flame ionization detection, and were identified by gas chromatography-mass spectrometry. Separation was good. By using this method, these acids were detected in samples of human duodenal fluid; the ratios of each were 24.4, 41.5, 24.9, 2.3 and 6.9%, respectively. 相似文献
32.
The nitro group in tertiary or secondary aliphatic nitro compounds is replaced by hydrogen or deuterium on treatment with tributyltin hydride or tributyltin deuteride, respectively. 相似文献
33.
Liu J Raveendran P Shervani Z Ikushima Y 《Chemical communications (Cambridge, England)》2004,(22):2582-2583
Ag2S nanocrystals with a mean diameter of 5.9 nm (sigma= 1.65 nm) and characteristic surface plasmon resonance absorption at 330 nm have been synthesized in water-in-supercritical CO2 reverse microemulsion using the commonly used AOT surfactant with 2,2,3,3,4,4,5,5-octafluoro-1-pentanol (F-pentanol) as cosurfactant. 相似文献
34.
Tsuguo Yamaoka Nobuko Nakajima Ken'ichi Koseki Yutaka Maruyama 《Journal of polymer science. Part A, Polymer chemistry》1990,28(9):2517-2532
A series of novel photosensitive polybenzoxazole precursors were prepared from polycondensation of 2,2-bis(3,3′-amino-4,4′-hydroxyphenyl)hexafluoropropane with photosensitive dicarboxylic acid chlorides such as p-phenylenediacryloyl chloride and benzophenone-4,4′-dicarboxylic chloride. The precursors are soluble in common organic solvents owing to the presence of perfluoromethyl groups in the chain structure, and insolubilized in the solvents on irradiation with the light. Polybenzoxazole patterns with high resolution as well as high aspect ratio were reproduced by baking the precursor patterns at 300°C. The pattern shrinkage on the conversion to polybenzoxazole was slight. The polybenzoxazole films offered good heat-resistance up to 400°C in addition to good electrical properties. 相似文献
35.
Murahashi T Higuchi Y Katoh T Kurosawa H 《Journal of the American Chemical Society》2002,124(48):14288-14289
The linear sandwich tripalladium complexes [Pd3{Ar(CH=CH)4Ar}2[BArf]2 (Ar = Ph, p-t-Bu-C6H4, p-styryl-C6H4) undergo photoinduced isomerization involving face-inversion of the tetraene ligands. Irradiation of these complexes with visible light (>510 nm) resulted in rac (staggered sandwich) to meso (eclipsed sandwich) isomerization. The structures of rac and meso isomers are determined by X-ray crystallographic analyses. 相似文献
36.
Yutaka Morita Manfred Hesse Hans Schmid Avijit Banerji Julie Banerji Asima Chatterjee Willi E. Oberhnsli 《Helvetica chimica acta》1977,60(4):1419-1434
Alstonia scholaris: The structure of the indole alkaloid nareline Besides the known akuammidine, picralinal, picrinine and pseudoakuammigine a new indole alkaloid called nareline (M=352) was isolated from Alstonia scholaris R. BR. , which belongs to the plant family of Apocynaceae. Its structure 2 was deduced by single crystal X-ray diffraction. 2 represents the absolute configuration. The spectroscopic data of 2 and its derivatives (Scheme 1) as well as their chemical behavior support this structure. In biogenetic sense nareline is related to the bases akuammiline ( 4 ) and picraline ( 5 ) (Scheme 2). In contrast to those the C-atom 5 is exocyclic and represents an aldehyde group which forms together with the oxygen atom of the N (4)-hydroxylamine group a cyclic half acetale. - By oxidation (CrO3/CH3COOH) of 2 the oxindol derivative 19 (oxonareline) is formed which contains a cyclic acetal as a partial structure element (Scheme 4). 相似文献
37.
A new optical CO2 sensor based on the luminescence intensity change of the europium(III) complex tris(thenoyltrifluoroacetonato) europium(III) dihydrate ([Eu(tta)3]) caused by the absorption change of various pH indicators—thymol blue, phenol red, or cresol red—with CO2 was developed and its CO2 sensing properties were investigated. For all the CO2 sensors using pH indicators the observed luminescence intensity from [Eu(tta)3] at 613 nm increased with increasing CO2 concentration. The linear calibration method based on the plot of (I100–I0)/(I–I0) versus the inverse of CO2 concentration was suggested, where I0 and I100 were luminescence intensities at 613 nm of the CO2 sensor film in 100% nitrogen and 100% gaseous CO2. In all cases the plots showed good linearity and the correlation factors of the plots, r2, were 0.991 for thymol blue, 0.990 for phenol red, and 0.998 for cresol red. The slopes of the plots (A/B) for thymol blue, phenol red, and cresol red were 2.2, 5.2, and 9.0%, respectively. The response times of the CO2 sensor film were 4.0 s for thymol blue, 4.4 s for phenol red, and 8.8 s for cresol red for switching from nitrogen to CO2, and the recovery times of films were 36 s for thymol blue, 39.2 s for phenol red, and 56.6 s for cresol red for switching from CO2 to nitrogen. The signal changes were fully reversible and hysteresis was not observed during the measurements. The highly sensitive CO2 sensor was developed using thymol blue as an indicator for the CO2-sensing probe. 相似文献
38.
Yutaka Nishiyama Hiroshi KawabataToshiki Nishino Kouji HashimotoNoboru Sonoda 《Tetrahedron》2003,59(34):6609-6614
It was found that lanthanum metal caused the dehalogenation of o-dihalogen substituted arenes and α,α′-dihalogen substituted o-xylenes to generate the corresponding benzynes and o-quinodimethanes. When o-dihalogen substituted arenes were allowed to react with lanthanum metal in the presence of dienes, the Diels-Alder products between benzyne and dienes were formed in moderate to good yields. Similarly, the Diels-Alder adducts of o-quinodimethane with dienophiles were obtained, in the reaction of α,α′-dibromo-o-xylenes with lanthanum metal in the presence of dienophiles. 相似文献
39.
40.
Tamura O Shiro T Ogasawara M Toyao A Ishibashi H 《The Journal of organic chemistry》2005,70(12):4569-4577
The 4-hydroxy 4-substituted glutamic acid moiety is a common substructure of biologically important natural products such as monatin [(2S,4S)-2], lycoperdic acid (3), and dysiherbaine (4). To develop methodology for syntheses of these natural products, cycloadditions of nitrone 5 with 2-substituted 2-propen-1-ols 6 and 2-substituted acrylates 8 were investigated. Reactions of nitrone 5 with alcohols 6 in the presence of MgBr2OEt2 gave cycloadducts 7 in a highly stereoselective manner, whereas noncatalyzed reactions of 5 with acrylates 8 afforded adducts 9. Using the former reaction, syntheses of monatin [(2S,4S)-2], monatin derivative 18, and lycoperdic acid (3) were accomplished. The C4-epimer of monatin [(2S,4R)-2)] was also synthesized by employing the latter cycloaddition. 相似文献