全文获取类型
收费全文 | 1630篇 |
免费 | 209篇 |
国内免费 | 61篇 |
专业分类
化学 | 1851篇 |
晶体学 | 9篇 |
综合类 | 4篇 |
物理学 | 36篇 |
出版年
2024年 | 1篇 |
2023年 | 16篇 |
2022年 | 34篇 |
2021年 | 61篇 |
2020年 | 71篇 |
2019年 | 68篇 |
2018年 | 68篇 |
2017年 | 41篇 |
2016年 | 95篇 |
2015年 | 87篇 |
2014年 | 95篇 |
2013年 | 101篇 |
2012年 | 92篇 |
2011年 | 108篇 |
2010年 | 77篇 |
2009年 | 72篇 |
2008年 | 104篇 |
2007年 | 112篇 |
2006年 | 86篇 |
2005年 | 71篇 |
2004年 | 72篇 |
2003年 | 64篇 |
2002年 | 148篇 |
2001年 | 32篇 |
2000年 | 23篇 |
1999年 | 17篇 |
1998年 | 10篇 |
1997年 | 9篇 |
1996年 | 14篇 |
1995年 | 8篇 |
1994年 | 7篇 |
1993年 | 3篇 |
1992年 | 6篇 |
1991年 | 3篇 |
1990年 | 3篇 |
1989年 | 3篇 |
1988年 | 2篇 |
1987年 | 3篇 |
1986年 | 3篇 |
1985年 | 2篇 |
1984年 | 2篇 |
1983年 | 2篇 |
1982年 | 2篇 |
1980年 | 1篇 |
1979年 | 1篇 |
排序方式: 共有1900条查询结果,搜索用时 15 毫秒
51.
Panchaud P Chabaud L Landais Y Ollivier C Renaud P Zigmantas S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(15):3606-3614
A novel reaction for the introduction of an azide moiety by means of a mild radical process is currently under development. Sulfonyl azides are suitable azidating agents for nucleophilic radicals, such as secondary and tertiary alkyl radicals. More electrophilic radicals, such as enolate radicals, do not react with sulfonyl azides. This feature allowed the development of efficient intra- and intermolecular carboazidations of olefins. Due to the versatility of the azido group, this reaction has an important synthetic potential, as already demonstrated by the preparation of the core of several alkaloids, particularly those containing an amino-substituted quaternary carbon center, such as FR901483. 相似文献
52.
The oxidative cyclization of 5-(2-amino-5-methoxycarbonylphenyl)-substituted tricarbonyl[η4-cyclohexa-1,3-diene]iron complexes by air in protic medium provides the corresponding tricarbonyl[η4-4a,9a-dihydro-9H-carbazole]iron complexes. This procedure is applied to the total synthesis of the 3-methoxycarbonylcarbazole alkaloids mukonine and mukonidine. 相似文献
53.
Five new C19 diterpene alkaloids, leucanthumsines A ( 1 ), B ( 2 ), C ( 3 ), D ( 4 ), and E ( 5 ), were isolated from the Chinese medicinal herb Aconitum sungpanense var. leucanthum, together with the known C19 diterpene alkaloids pseudaconine, neoline, 1‐O‐methyldelphisine, crassicaudine, chasmanine, talatisamine, indaconitine, ezochansmanine, and leueantine D. The structures of these new alkaloids were elucidated by HR‐MS and advanced NMR methods, including 1H‐ and 13C‐NMR (DEPT), 1H,1H‐COSY, HMQC, and HMBC experiments. 相似文献
54.
An accurate and simple HPLC method for the simultaneous determination of three protoberberine alkaloids (columbamine, jatrorrhizine, and palmatine) contained in Chinese medicine Jin-Guo-Lan (Tinospora sagittata Oliv. and Tinospora capillipes Gagnep) is presented in this study. The herb samples from six main origins and three herb markets were investigated. The separation was performed on a YMC-C18 ODS column at 30°C with a gradient elution program. Acetonitrile and phosphate buffer (0.02 mol L−1 sodium dihydrogen phosphate and 0.01 mol L−1 triethylamine, pH 3) were used as mobile phases and the flow rate was set at 1 mL min−1. The recovery of the method was in the range of 99.43–100.96%, and all the alkaloids showed good linearity (r
2 > 0.9997) in the relatively wide concentration ranges. The developed method was applied to the determination of these alkaloids in the collected herb samples, and the results showed that the contents of these components in Jin-Guo-Lan varied greatly from habitat to habitat. It was demonstrated that the proposed method was helpful for the quality evaluation of Chinese medicine Jin-Guo-Lan. 相似文献
55.
C_(20)-二萜生物碱结构复杂,环上大多有含氧的基团。利用NMR、MS等确定羟基、羰基在分子中的位置往往不够有力。特別是对于C_1~3或C_(11)位上羰基,没有可靠而简便的光谱鉴別方法。我们通过对几个Atisine型含羰基化合物的圆二色谱研究发现,由CD谱确定羰基在C_6位、C_(11)位及C_(13)位是一种简便有效的方法。 相似文献
56.
Francesca CardonaEnrico Faggi Francesca LiguoriMartina Cacciarini Andrea Goti 《Tetrahedron letters》2003,44(11):2315-2318
Practical syntheses of nitrone 8 by two different approaches from sugars are reported. Its use as a versatile intermediate in highly selective 1,3-dipolar cycloaddition reactions constitutes the key step for novel total syntheses of hyacinthacine A2 (3) and 7-deoxycasuarine (20) by simple transformations of a common isoxazolidine adduct. 相似文献
57.
58.
Madhuri Manpadi 《Tetrahedron letters》2005,46(26):4433-4437
Various substituted arylcuprates undergo stereocontrolled additions to a d-mannitol-derived γ-alkoxy-α,β-enoate with exclusive anti-selectivity. The method is well suited for the preparation of a broad range of biologically active Amaryllidaceae alkaloids and their aromatic analogues. A model accounting for the stereochemical outcome of this process is presented. 相似文献
59.
Takashi Tozawa Dr. Hitoshi Nagao Yoshinobu Yamane Teruaki Mukaiyama Prof. Dr. 《化学:亚洲杂志》2007,2(1):123-134
Chiral quaternary ammonium phenoxides were readily prepared from commercially available cinchona alkaloids and proved to be useful new asymmetric organocatalysts. Among various chiral quaternary ammonium phenoxides, a cinchonidine‐derived catalyst that bears both a sterically hindered N1‐9‐anthracenylmethyl group and a strongly electron withdrawing 9‐O‐3,5‐bis(trifluoromethyl)benzyl group were found to be highly effective for the Michael addition of ketene silyl acetals (derived from phenyl carboxylates) and α,β‐unsaturated ketones followed by lactonization. Optically active 3,4‐dihydropyran‐2‐one derivatives were obtained in high yields with excellent control of enantio‐ and diastereoselectivity. This catalyst can be handled in air and stored at room temperature in a sealed bottle without decomposition for at least one month. 相似文献
60.
Xi Chen Changqing YiMeijin Li Xin LuZhen Li Peiwei LiXiaoru Wang 《Analytica chimica acta》2002,466(1):79-86
Electrogenerated chemiluminescences (ECLs) based on tris(2,2′-bipyridine)ruthenium(II) (Ru(bpy)32+) and lupin alkaloids, for instance, sophoridine (SRI), matrine (MT), sophoranol (SR) and sophocarpine (SC) in an aqueous alkaline buffer solution (pH 9.0) are studied. The light emission is mainly caused by an electro-oxidation reaction between tertiary amino group on the alkaloid compounds and Ru(bpy)32+ in a thin layer flow cell equipped with a glassy carbon disc electrode (22.1 mm2) at the potential of +1.50 V (versus Ag/AgCl). The luminescence wavelength of 610 nm confirmed that ECL is caused by Ru(bpy)32+∗ to its ground state. ECL intensities of these lupin alkaloids are affected by the substituent character, three-dimensional conformation of hydrogen on β-carbon atom. Ionization potentials taken from calculation data further confirm the experimental results. In addition, the factors affecting the determination and HPLC separation of the four alkaloids are also investigated. 相似文献