全文获取类型
收费全文 | 1350篇 |
免费 | 28篇 |
国内免费 | 3篇 |
专业分类
化学 | 1003篇 |
晶体学 | 15篇 |
力学 | 6篇 |
数学 | 76篇 |
物理学 | 281篇 |
出版年
2023年 | 6篇 |
2022年 | 9篇 |
2021年 | 9篇 |
2020年 | 11篇 |
2019年 | 21篇 |
2018年 | 7篇 |
2017年 | 6篇 |
2016年 | 15篇 |
2015年 | 24篇 |
2014年 | 19篇 |
2013年 | 65篇 |
2012年 | 44篇 |
2011年 | 87篇 |
2010年 | 38篇 |
2009年 | 44篇 |
2008年 | 76篇 |
2007年 | 73篇 |
2006年 | 47篇 |
2005年 | 68篇 |
2004年 | 62篇 |
2003年 | 61篇 |
2002年 | 55篇 |
2001年 | 35篇 |
2000年 | 28篇 |
1999年 | 18篇 |
1998年 | 12篇 |
1996年 | 28篇 |
1995年 | 17篇 |
1994年 | 18篇 |
1993年 | 17篇 |
1992年 | 13篇 |
1991年 | 15篇 |
1990年 | 13篇 |
1989年 | 11篇 |
1988年 | 14篇 |
1987年 | 12篇 |
1986年 | 21篇 |
1985年 | 31篇 |
1984年 | 27篇 |
1983年 | 12篇 |
1982年 | 24篇 |
1981年 | 19篇 |
1980年 | 15篇 |
1979年 | 30篇 |
1978年 | 13篇 |
1977年 | 24篇 |
1976年 | 18篇 |
1975年 | 12篇 |
1974年 | 6篇 |
1973年 | 11篇 |
排序方式: 共有1381条查询结果,搜索用时 15 毫秒
31.
Ohno H Ando K Hamaguchi H Takeoka Y Tanaka T 《Journal of the American Chemical Society》2002,124(51):15255-15266
The base-mediated intramolecular amination of bromoallenes having an axial chirality is described. The treatment of (4S,aR)-4-alkyl-4-[N-(arylsulfonyl)amino]-1-bromobuta-1,2-dienes with NaH in DMF affords 2,3-cis-2-ethynylaziridines in good to excellent selectivity (2,3-cis:trans = 92:8-99:1). The reaction of (4S,aS)-bromoallenes with NaH/DMF also gives 2,3-cis-2-ethynylaziridines selectively (79:21-91:9). These experimental results have been rationalized by B3LYP density functional calculations together with the 6-31+G(d) basis set and the Onsager solvation model. The transition structures for cis-aziridine formation of both (4S,aR)- and (4S,aS)-bromoallenes in DMF are favored over the corresponding trans transition structures by 4.35 and 1.41 kcal/mol, respectively. Furthermore, the calculations predicted that a less polar solvent gives higher cis selectivity for (4S,aS)-bromoallenes. In fact, improvement of the cis selectivity to 99:1 has been realized by using a less polar solvent such as THF. The cyclization of bromoallenes bearing a beta- or gamma-amino group also affords four- and five-membered azacycles in a highly cis-selective manner. 相似文献
32.
Akasaka T Maeda Y Wakahara T Mizushima T Ando W Walchli M Suzuki T Kobayashi K Nagase S Kako M Nakadaira Y Fujitsuka M Ito O Sasaki Y Yamamoto K Erata T 《Organic letters》2000,2(17):2671-2674
[reaction: see text]In the photochemical bis-germylation of C60 with 1,1,2,2-tetrakis(2,6-diethylphenyl)-1,2-digermirane (1), a cycloadduct (2) is obtained in high yield for the first time. Spectroscopic analysis and theoretical investigation confirm that 2 (which has C1 symmetry) results from 1,4-cycloaddition. Control experiments and laser flash photolysis experiments suggest that an exciplex intermediate is responsible for the formation of 2. The redox properties of 2 were examined by differential pulse voltammetry. 相似文献
33.
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
34.
Tomoki Nishimura Yusuke Hatatani Mitsuru Ando Yoshihiro Sasaki Kazunari Akiyoshi 《Chemical science》2022,13(18):5243
Nanodiscs have attracted considerable attention as structural scaffolds for membrane-protein research and as biomaterials in e.g. drug-delivery systems. However, conventional disc-fabrication methods are usually laborious, and disc fabrication via the self-assembly of amphiphiles is difficult. Herein, we report the formation of polymer nanodiscs based on the self-assembly of amphiphilic graft copolymers by adjusting the persistence length of the main chain. Amphiphilic graft copolymers with a series of different main-chain persistence lengths were prepared and these formed, depending on the persistence length, either rods, discs, or vesicles. Notably, polymer nanodiscs were formed upon heating a chilled polymer solution without the need for any additives, and the thus obtained nanodiscs were used to solubilize a membrane protein during cell-free protein synthesis. Given the simplicity of this disc-fabrication method and the ability of these discs to solubilize membrane proteins, this study considerably expands the fundamental and practical scope of graft-copolymer nanodiscs and demonstrates their utility as tools for studying the structure and function of membrane proteins.A strategy for the fabrication of nanodiscs via the self-assembly of thermoresponsive amphiphilic graft copolymers is demonstrated. 相似文献
35.
36.
Atsushi Tarui Shoji Kondo Kazuyuki Sato Masaaki Omote Hideki Minami Yoshihisa Miwa Akira Ando 《Tetrahedron》2013,69(5):1559-1565
A highly diastereoselective cross-coupling reaction of an α-bromo-α-fluoro-β-lactam with a wide range of aryl Grignard reagents was catalyzed by Ni/bis(oxazoline) in yields of up to 98%. The product was obtained diastereoselectively as an anti-isomer. This is the first successful α-arylation of an α-fluoro-β-lactam to produce diverse α-aryl-α-fluoro-β-lactams. 相似文献
37.
Akira Hasegawa Takashi Ando Akihiko Kameyama Makoto Kiso 《Journal of carbohydrate chemistry》2013,32(5):645-658
Abstract Stereocontrolled synthesis of sialyl Lex epitope and its ceramide derivative with regard to the introduction of galactose or β-D-galactosyl ceramide into the terminal N-acetylglucosamine residue of sialyl Lex determinant is described. Königs-Knorr condensation of 2-(trimethylsilyl)ethyl 2, 4, 6-tri-O-benzyl-β-D-galactopyranoside (4) with 3, 4, 6-tri-O-acetyl-2-deoxy-2-phthalimido-D-glucopyranosyl bromide (5) gave the desired β-glycoside 6, which was converted into 2-(trimethylsilyl)ethyl O-(2-acetamido-4, 6-O-benzylidene-2-deoxy-β-D-glucopyranosyl)-(l→3)-2, 4, 6-tri-O-benzyl-β-D-galactopyranoside (8) via removal of the phthaloyl and O-acetyl groups, followed by N-acetylation and 4, 6-O-benzylidenation. Glycosylation of 8 with methyl 2, 3, 4-tri-O-benzyl-1-thio-β-L-fucopyranoside (9) gave the α-glycoside (10), which was transformed by reductive ring-opening of the benzyliderie acetal into the acceptor (11). Dimethyl(methylthio)sulfonium triflate (DMTST)-promoted coupling of 11 with methyl O-(methyl 5-acetamido-4, 7, 8, 9-tetra-O-acetyl-3, 5-dideoxy-D-glycero-α-D-galacto-2-nonulopyranosylonate)-(2→3)-2, 4, 6-tri-O-benzoyl-l-thio-β-D-galactopyra-noside (12) afforded the desired pentasaccharide (13), which was converted into the α-trichloroacetimidate 16 via reductive removal of the benzyl groups, then O-acetylation, removal of the 2-(trimethyIsilyl)ethyl group and treatment with trichloroacetonitrile. Condensation of 16 with (2S, 3R, 4E)-2-azido-3-O-benzoyl-4-octadecene-l, 3-diol (18) gave the β-glycoside 19, which was transformed into the title compound 21, via reduction of the azido group, coupling with octadecanoic acid, O-deacylation and hydrolysis of the methyl ester group. On the other hand, O-deacylation of 13 and subsequent hydrolysis of the methyl ester group gave the pentasaccharide epitope 17. 相似文献
38.
39.
40.