全文获取类型
收费全文 | 2103篇 |
免费 | 60篇 |
国内免费 | 9篇 |
专业分类
化学 | 1515篇 |
晶体学 | 22篇 |
力学 | 20篇 |
数学 | 149篇 |
物理学 | 466篇 |
出版年
2023年 | 15篇 |
2022年 | 13篇 |
2021年 | 20篇 |
2020年 | 15篇 |
2019年 | 35篇 |
2018年 | 26篇 |
2017年 | 19篇 |
2016年 | 32篇 |
2015年 | 50篇 |
2014年 | 42篇 |
2013年 | 104篇 |
2012年 | 113篇 |
2011年 | 169篇 |
2010年 | 69篇 |
2009年 | 75篇 |
2008年 | 136篇 |
2007年 | 116篇 |
2006年 | 89篇 |
2005年 | 117篇 |
2004年 | 103篇 |
2003年 | 93篇 |
2002年 | 93篇 |
2001年 | 41篇 |
2000年 | 36篇 |
1999年 | 17篇 |
1998年 | 11篇 |
1997年 | 16篇 |
1996年 | 37篇 |
1995年 | 24篇 |
1994年 | 25篇 |
1993年 | 23篇 |
1992年 | 22篇 |
1991年 | 17篇 |
1990年 | 18篇 |
1989年 | 12篇 |
1988年 | 15篇 |
1987年 | 16篇 |
1986年 | 23篇 |
1985年 | 40篇 |
1984年 | 29篇 |
1983年 | 13篇 |
1982年 | 18篇 |
1981年 | 21篇 |
1980年 | 15篇 |
1979年 | 28篇 |
1978年 | 17篇 |
1977年 | 29篇 |
1976年 | 16篇 |
1975年 | 11篇 |
1973年 | 9篇 |
排序方式: 共有2172条查询结果,搜索用时 843 毫秒
101.
102.
Tomoko Nagao Masayoshi Isozaki Tetsuya Fujimoto Iwao Yamamoto 《Phosphorus, sulfur, and silicon and the related elements》2013,188(8-9):1975-1976
The reaction of a cyclic phosphonium ylide [ 1 ] with enoate 2 gives a hydroazulene derivative with stereoselectivity. 相似文献
103.
Yoshio Aso Shoji Nishiguchi Tetsuya Jigami Tetsuo Otsubo Fumio Ogura 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1):417-418
Several well-defined 3,4-thienylene-ethynylene oligomers with different chain lengths have been synthesized and characterized. X-Ray crystallographic analyses proved their unique, totally helical conformations. 相似文献
104.
105.
Tetsuya Tsuda Susumu Kuwabata Gery R. Stafford Charles L. Hussey 《Journal of Solid State Electrochemistry》2013,17(2):409-417
The electrochemistry of Hf(IV) and the electrodeposition of Al–Hf alloys were examined in the Lewis acidic 66.7–33.3 mol% aluminum chloride-1-ethyl-3-methylimidazolium chloride molten salt containing HfCl4. When cyclic staircase voltammetry was carried out at a platinum disk electrode in this melt, the deposition and stripping waves for Al shifted to negative and positive potentials, respectively, suggesting that aluminum stripping is more difficult due to the formation of Al–Hf alloys. Al–Hf alloy electrodeposits containing ~13 at.% Hf were obtained on Cu rotating wire and cylinder electrodes. The Hf content in the Al–Hf alloy deposits depended on the HfCl4 concentration in the melt, the electrodeposition temperature, and the applied current density. The deposits were composed of dense crystals and were completely chloride-free. The chloride-induced pitting corrosion potential of the resulting Al–Hf alloys was approximately +0.30 V against pure aluminum when the Hf content was above 10 at.%. 相似文献
106.
Masanobu Yamamoto Ryoko Maruyama Yoko Murakami Yuki Sakamoto Rei Yamakawa Tetsu Ando 《Analytical and bioanalytical chemistry》2013,405(23):7405-7414
trans-11,12-Epoxy-(6Z,9Z)-6,9-henicosadiene (posticlure) has been identified from a pheromone gland of the lymantriid species, Orgyia postica. Since the diversity of Lepidoptera suggests that some species utilize the structure-related epoxy compound as a sex pheromone component, epoxydienes and epoxytrienes derived from (6Z,9Z,11E)-6,9,11-trienes and (3Z,6Z,9Z,11E)-3,6,9,11-tetraenes with a C19–C21 chain were systematically synthesized and the chemical data were accumulated in order to contribute to a new pheromone research. Peracid oxidation of each triene and each tetraene produced, respectively, a mixture of three epoxydienes (cis-6,7-epoxy-9,11-diene; cis-9,10-epoxy-6,11-diene; and trans-11,12-epoxy-6,9-diene) and four epoxytrienes (cis-3,4-epoxy-6,9,11-triene; cis-6,7-epoxy-3,9,11-triene; cis-9,10-epoxy-3,6,11-triene; and trans-11,12-epoxy-3,6,9-triene). While the 9,10-epoxy compounds were unstable and, interestingly, converted into 9-ketone derivatives after chromatography over SiO2, each positional isomer was isolated by HPLC equipped with an ODS column, and the chemical structure was determined by NMR analysis. On the GC-MS analysis with a DB-23 column, the positional isomers were also eluted separately and characteristic mass spectra were proposed. By comparing the spectral data of the epoxy compounds with a different carbon chain, diagnostic fragment ions reflecting the chemical structure were determined as follows: m/z 79, 109, 113, and M-114 for the 6,7-epoxydienes; m/z 69, 97, 111, 139, and M-111 for the 9,10-epoxydienes; m/z 57, 79, 109, 136, M-151, and M-111 for the 11,12-epoxydienes; m/z 79, 91, 105, and 119 for the 3,4-epoxytrienes; m/z 79, 124, M-124, M-96, and M-69 for the 6,7-epoxytrienes; m/z 79, 95, 109, 137, and M-108 for the 9,10-epoxytrienes; and m/z 79, 134, M-149, M-109, and M-95 for the 11,12-epoxytrienes. 相似文献
107.
Daisuke Saeki Takeshi Yamada Yasuko In Tetsuya Kajimoto Reiko Tanaka Yota Iizuka Takahisa Nakane Akihito Takano Kazuo Masuda 《Tetrahedron》2013,69(5):1583-1589
Novel 5 lupane-type of triterpenois, i.e., 3β-acetoxy-18α,19α-epoxylupan-21β-ol (1), 18α,19α-epoxy-21β-hydroxylupan-3-one (2), lup-18-ene-3,21-dione (3), lupa-18,21-dien-3β-yl acetate (4), and (17S)-17,18-seco-lup-19(21)-ene-3,18,22-trione (5), named officinatrione, as well as 16 known compounds from the roots of Taraxacum officinale collected in Takatsuki city, Osaka, Japan. Of the above compounds, 5 was the first lupane-type triterpene, of which the D-ring was open to form a nine-membered ring. Compounds 2 and 5 exhibited moderate cytotoxic activities against L1210 cell line (IC50 10.5 and 10.1 μM). 相似文献
108.
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
109.
Tetsuya Yamamoto 《Colloid and polymer science》2013,291(11):2741-2744
Methacrylic monomer was used in soap-free emulsion polymerization in order to obtain a stable dispersion containing particles of the polymerized monomer. 2,2′-Azobis(2-methylpropionitrile) (AIBN) or 1,1′-azobis(1-acetoxy-1-phenylethane) (OTAZO-15) were used as the radical initiator. Although particles with a size of about 1.0 μm were obtained when using methyl methacrylate as the monomer and AIBN as the initiator, the particles did not exhibit good dispersion stability. When OTAZO-15, which has phenyl rings, was used as the initiator, the monomer phase solidified instead of forming particles in the aqueous phase. Benzyl methacrylate (BMA) monomer, which contains a phenyl ring, was polymerized using AIBN. Negatively charged particles with a size of 0.90 μm were formed. These particles exhibited good dispersion stability probably because of the pi electrons of the phenyl ring in the BMA monomer. The method in this study allows the synthesis of nearly micron-sized particles without surfactant, organic solvent, and electrolyte. 相似文献
110.
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