全文获取类型
收费全文 | 1662篇 |
免费 | 208篇 |
国内免费 | 60篇 |
专业分类
化学 | 1891篇 |
晶体学 | 4篇 |
综合类 | 3篇 |
物理学 | 32篇 |
出版年
2024年 | 1篇 |
2023年 | 15篇 |
2022年 | 71篇 |
2021年 | 63篇 |
2020年 | 72篇 |
2019年 | 66篇 |
2018年 | 69篇 |
2017年 | 41篇 |
2016年 | 88篇 |
2015年 | 85篇 |
2014年 | 95篇 |
2013年 | 97篇 |
2012年 | 91篇 |
2011年 | 107篇 |
2010年 | 74篇 |
2009年 | 71篇 |
2008年 | 103篇 |
2007年 | 107篇 |
2006年 | 92篇 |
2005年 | 74篇 |
2004年 | 72篇 |
2003年 | 70篇 |
2002年 | 153篇 |
2001年 | 28篇 |
2000年 | 22篇 |
1999年 | 17篇 |
1998年 | 11篇 |
1997年 | 13篇 |
1996年 | 10篇 |
1995年 | 8篇 |
1994年 | 5篇 |
1993年 | 2篇 |
1992年 | 5篇 |
1991年 | 4篇 |
1990年 | 3篇 |
1989年 | 4篇 |
1988年 | 2篇 |
1987年 | 3篇 |
1986年 | 3篇 |
1985年 | 2篇 |
1984年 | 3篇 |
1983年 | 3篇 |
1982年 | 2篇 |
1981年 | 1篇 |
1980年 | 1篇 |
1979年 | 1篇 |
排序方式: 共有1930条查询结果,搜索用时 15 毫秒
61.
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
62.
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
63.
Johannes Reisch Anura Wickramasinghe 《Monatshefte für Chemie / Chemical Monthly》1990,121(8-9):709-712
Summary Epoxidation of the acridone alkaloid acronycine (1) resulted in hydroxylation at the aromatic ring giving 5-hydroxyacronycine (3). The same reaction on 1,3-dimethoxy-10-methyl-9(10H)-acridinone (5) gave 1,3-dimethoxy-2-hydroxy-10-methyl-9(10H)-acridinone (6), 1,3-dimethoxy-2-hydroxy-4-peroxy-10-methyl-9(10H)-acridinone (8), and 1,3-dimethoxy-2,4-diperoxy-10-methyl-9(10H)-acridinone (9).
Naturstoffchemie, 137. Mitt.: Oxidierung von Acridonalkaloiden: Synthese des 5-Methoxyacronycins (Kurze Mitt.)
Zusammenfassung Die Epoxidierung des Acridonalkaloids Acronycin führte zu einer Hydroxylierung des aromatischen Rings, wobei 5-Hydroxyacronycin (3) entstand. Die gleiche Reaktion mit 1,3-Dimethoxy-10-methyl-9(10H)acridinon (5) ergab 1,3-Dimethoxy-2-hydroxy-10-methyl-9(10H)acridinon (6), 1,3-Dimethoxy-2-hydroxy-4-peroxy-10-methyl-9(10H)acridinon (8) und 1,3-Dimethoxy-2,4-diperoxy-10-methyl-9(10H)acridinon (9).相似文献
64.
Leyla Bitiş Sevda Süzgeç Ulaş Sözer Hasan Özçelik Josef Zapp Alexandra K. Kiemer Filiz Meriçli Ali H. Meriçli 《Helvetica chimica acta》2007,90(11):2217-2221
From the aerial parts of Delphinium buschianum Grossh ., collected in Turkey, a new diterpenoid alkaloid 1 , named budelphine, was isolated along with the known diterpenoid alkaloids karakoline ( 2 ), 18‐hydroxy‐14‐O‐methylgadesine ( 3 ), delsoline ( 4 ), lapaconidine ( 5 ), columbianine ( 6 ), 14‐benzoylneoline ( 7 ), and hetisine ( 9 ). The structure of 1 was established on the basis of 1H‐, 13C‐, DEPT, 1H,1H‐COSY, NOESY, HSQC, and HMBC NMR studies. 相似文献
65.
Andrés G. León Ana I. Olives M. Antonia Martín Benito del Castillo 《Journal of inclusion phenomena and macrocyclic chemistry》2007,57(1-4):577-583
The use of cyclodextrins (CDs) in HPLC as mobile phase additives provides a flexible alternative for the separation of chemically
related compounds because these separations can be performed on conventional columns and are economically advantageous over
the use of chiral stationary phases. The present paper describes the influence of the presence of β-cyclodextrin (β-CD) and
2-hydroxypropyl-β-cyclodextrin (HPβ-CD) on the separation of the β-carboline alkaloids norharmane, harmane and harmine. The
nature of the stationary phase (reverse phases C1 and C18) affects the chromatographic separations and also the stability of the inclusion complexes that are developed. The changes
in the proportion of the organic solvents at constant concentration of CDs (3 mM for β-CD and 15 mM for HPβ-CD) modify the
retention factors (k′) for all alkaloids studied. The nature of the organic solvent in the mobile phase also changes the chromatographic parameters.
The logarithm of the capacity factor (k′) is linearly increased with the proportion of water in the hydro-organic mobile phase (ethanolic or methanolic) but the
slopes obtained vary depending on the CD added to the mobile phase. The role of competitive equilibria, i.e., chromatographic
distribution and inclusion complexes formation is discussed.
This paper was presented at XIIIth International Cyclodextrin Symposium. Torino, Italy, May, 14–17, 2006 相似文献
66.
67.
68.
Ji‐Xin Tian Can Peng Lei Xu Yuan Tian Zun‐Jian Zhang 《Biomedical chromatography : BMC》2013,27(6):775-783
In this report, the in vitro metabolism of Strychnos alkaloids was investigated using liquid chromatography/high‐resolution mass spectrometry for the first time. Strychnine and brucine were selected as model compounds to determine the universal biotransformations of the Strychnos alkaloids in rat liver microsomes. The incubation mixtures were separated by a bidentate‐C18 column, and then analyzed by on‐line ion trap/time‐of‐flight mass spectrometry. With the assistance of mass defect filtering technique, full‐scan accurate mass datasets were processed for the discovery of the related metabolites. The structural elucidations of these metabolites were achieved by comparing the changes in accurate molecular masses, calculating chemical component using Formula Predictor software and defining sites of biotransformation based upon accurate MSn spectral information. As a result, 31 metabolites were identified, of which 26 metabolites were reported for the first time. These biotransformations included hydroxylation, N‐oxidation, epoxidation, methylation, dehydrogenation, de‐methoxylation, O‐demethylation, as well as hydrolysis reactions. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
69.
70.