全文获取类型
收费全文 | 2924篇 |
免费 | 94篇 |
国内免费 | 16篇 |
专业分类
化学 | 2248篇 |
晶体学 | 25篇 |
力学 | 28篇 |
数学 | 113篇 |
物理学 | 620篇 |
出版年
2023年 | 18篇 |
2022年 | 26篇 |
2021年 | 31篇 |
2020年 | 32篇 |
2019年 | 49篇 |
2018年 | 26篇 |
2017年 | 23篇 |
2016年 | 70篇 |
2015年 | 44篇 |
2014年 | 79篇 |
2013年 | 161篇 |
2012年 | 154篇 |
2011年 | 165篇 |
2010年 | 65篇 |
2009年 | 98篇 |
2008年 | 179篇 |
2007年 | 164篇 |
2006年 | 175篇 |
2005年 | 165篇 |
2004年 | 123篇 |
2003年 | 140篇 |
2002年 | 117篇 |
2001年 | 55篇 |
2000年 | 66篇 |
1999年 | 44篇 |
1998年 | 30篇 |
1997年 | 38篇 |
1996年 | 30篇 |
1995年 | 16篇 |
1994年 | 31篇 |
1993年 | 27篇 |
1992年 | 52篇 |
1991年 | 26篇 |
1990年 | 26篇 |
1989年 | 28篇 |
1988年 | 29篇 |
1987年 | 31篇 |
1986年 | 21篇 |
1985年 | 44篇 |
1984年 | 35篇 |
1983年 | 19篇 |
1982年 | 28篇 |
1981年 | 29篇 |
1980年 | 31篇 |
1979年 | 40篇 |
1978年 | 32篇 |
1977年 | 20篇 |
1976年 | 15篇 |
1975年 | 16篇 |
1973年 | 25篇 |
排序方式: 共有3034条查询结果,搜索用时 15 毫秒
171.
Ninomiya Kazuhiko Kudo Takuto Strasser Patrick Terada Kentaro Kawai Yosuke Tampo Motonobu Miyake Yasuhiro Shinohara Atsushi Kubo Kenya M. 《Journal of Radioanalytical and Nuclear Chemistry》2019,320(3):801-805
Journal of Radioanalytical and Nuclear Chemistry - Elemental isotopic ratios are measured in various research fields and provide useful information regarding age, origin, geological and biological... 相似文献
172.
Yuki Sato Dr. Shin-ichi Kawaguchi Dr. Akihiro Nomoto Prof. Dr. Akiya Ogawa 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(9):2295-2302
Bis-phosphanated compounds are regarded as the most ubiquitous privileged ligand structures in transition-metal catalysis. The development of highly atom economical reactions is of great importance for their syntheses because less atom economical methods often require complicated purification procedures under inert atmospheres to remove excess starting materials and byproducts. Herein, the photoinduced addition reactions of diphosphane monosulfides bearing PV(S)−PIII single bonds to alkenes is disclosed. These reactions require only equimolar amounts of the diphosphane monosulfide relative to the alkene and facilitate highly selective introduction of two different types of phosphorus-containing groups, such as thiophosphoryl and phosphanyl groups, into a variety of alkenes without any catalyst, base, or additive. 相似文献
173.
Hisanobu Ogoshi Kazurni Saita Ken-ichi Sakurai Takamichi Watanabe Hiroo Toi Yasuhiro Aoyama 《Tetrahedron letters》1986,27(52):6365-6368
Described is the preparation of chiral octaethylporphyrin derivatives having two 2-substituted naphthyl groups in a trans orientation at the 5- and 15-meso positions and formyl or hydroxymethyl or alkoxymethyl group derived therefrom at the 10-meso position. One of the derivatives has been successfully resolved into enantiomers by means of HPLC. 相似文献
174.
Tsuneyuki Sato Tsuyoshi Yamamoto Tetsuo Ogawa Takayuki Otsu 《Journal of polymer science. Part A, Polymer chemistry》1986,24(7):1519-1528
Poly[acryloyl-L-valine (ALV)] microspheres containing peroxy ester groups were prepared by radical copolymerization of ALV with a small amount of di-tert-butyl peroxyfumarate. When the microspheres were irradiated in the presence of second vinyl monomers, long-lived propagating radicals of the second monomers were formed in the microspheres by the reaction of microsphere polymer radicals with the monomers. The presence of a minute quantity of ethyl alcohol served to soften the microspheres and made the polymer radicals more mobile in the microspheres. As a result, sharper ESR spectra of the propagating radicals were observed although their lifetimes became shorter. This microsphere method also yielded easily the stable propagating radicals of a-methylstyrene and 1,1-diphenylethylene which have no homopolymerizability in usual radical polymerization. When N-n-propyldimethacroylamide and N,N′-dimethyl-N,N′-dimethacroylhydrazine, which undergo cyclopolymerization, were used as second monomer, uncyclized polymer radicals were only observed. Some discussions were given on the propagation mechanism of the cyclopolymerization. 相似文献
175.
176.
Toshio Ogawa Masakazu Sakai Wataru Ishitobi 《Journal of polymer science. Part A, Polymer chemistry》1986,24(1):109-118
Molecular weight distribution of Nylon 12 was determined with hexafluoroisopropanol/toluene mixture as eluent by gel permeation chromatography. Calibration curve for Nylon 12 was easily obtained from that of polystyrene because the method of universal calibration was applicable among these polymers. The molecular weight distributions of Nylon 12 were always broader than expected by the theory of polymerization, i.e., most probable distribution. This result was not caused by broadening effect in gel permeation chromatography, but by polymerization itself. 相似文献
177.
178.
Tanase T Doi M Nouchi R Kato M Sato Y Ishida K Kobayashi K Sakurai T Yamamoto Y Yano S 《Inorganic chemistry》1996,35(17):4848-4857
Reactions of [Ni(tren)(H(2)O)(2)]X(2) (tren = tris(2-aminoethyl)amine; X = Cl (1a), Br (1b); X(2) = SO(4) (1c)) with mannose-type aldoses, having a 2,3-cis configuration (D-mannose and L-rhamnose), afforded {bis(N-aldosyl-2-aminoethyl)(2-aminoethyl)amine}nickel(II) complexes, [Ni(N,N'-(aldosyl)(2)-tren)]X(2) (aldosyl = D-mannosyl, X = Cl (2a), Br (2b), X(2) = SO(4) (2c); aldosyl = L-rhamnosyl, X(2) = SO(4) (3c)). The structure of 1c was confirmed by X-ray crystallography to be a mononuclear [Ni(II)N(4)O(2)] complex with the tren acting as a tetradentate ligand (1c.2H(2)O: orthorhombic, Pbca, a = 15.988(2) ?, b = 18.826(4) ?, c = 10.359(4) ?, V = 3118 ?(3), Z = 8, R = 0.047, and R(w) = 0.042). Complexes 2a,c and 3c were characterized by X-ray analyses to have a mononuclear octahedral Ni(II) structure ligated by a hexadentate N-glycoside ligand, bis(N-aldosyl-2-aminoethyl)(2-aminoethyl)amine (2a.CH(3)OH: orthorhombic, P2(1)2(1)2(1), a = 16.005(3) ?, b = 20.095(4) ?, c = 8.361(1) ?, V = 2689 ?(3), Z = 4, R = 0.040, and R(w) = 0.027. 2c.3CH(3)OH: orthorhombic, P2(1)2(1)2(1), a = 14.93(2) ?, b = 21.823(8) ?, c = 9.746(2) ?, V = 3176 ?(3), Z = 4, R = 0.075, and R(w) = 0.080. 3c.3CH(3)OH: orthorhombic, P2(1)2(1)2(1), a = 14.560(4) ?, b = 21.694(5) ?, c = 9.786(2) ?, V = 3091 ?(3), Z = 4, R = 0.072, and R(w) = 0.079). The sugar part of the complex involves novel intramolecular sugar-sugar hydrogen bondings around the metal center. The similar reaction with D-glucose, D-glucosamine, and D-galactosamine, having a 2,3-trans configuration, resulted in the formation of a mono(sugar) complex, [Ni(N-(aldosyl)-tren)(H(2)O)(2)]Cl(2) (aldosyl = D-glucosyl (4b), 2-amino-2-deoxy-D-glucosyl (5a), and 2-amino-2-deoxy-D-galactosyl (5b)), instead of a bis(sugar) complex. The hydrogen bondings between the sugar moieties as observed in 2 and 3 should be responsible for the assembly of two sugar molecules on the metal center. Reactions of tris(N-aldosyl-2-aminoethyl)amine with nickel(II) salts gave the tris(sugar) complexes, [Ni(N,N',N"-(aldosyl)(3)-tren)]X(2) (aldosyl = D-mannosyl, X = Cl (6a), Br (6b); L-rhamnosyl, X = Cl (7a), Br (7b); D-glucosyl, X = Cl (9); maltosyl, X = Br (10); and melibiosyl, X = Br (11)), which were assumed to have a shuttle-type C(3) symmetrical structure with Delta helical configuration for D-type aldoses on the basis of circular dichroism and (13)C NMR spectra. When tris(N-rhamnosyl)-tren was reacted with NiSO(4).6H(2)O at low temperature, a labile neutral complex, [Ni(N,N',N"-(L-rhamnosyl)(3)-tren)(SO(4))] (8), was successfully isolated and characterized by X-ray crystallography, in which three sugar moieties are anchored only at the N atom of the C-1 position (8.3CH(3)OH.H(2)O: orthorhombic, P2(1)2(1)2(1), a = 16.035(4) ?, b = 16.670(7) ?, c = 15.38(1) ?, V = 4111 ?(3), Z = 4, R = 0.084, and R(w) = 0.068). Complex 8 could be regarded as an intermediate species toward the C(3) symmetrical tris(sugar) complexes 7, and in fact, it was readily transformed to 7b by an action of BaBr(2). 相似文献
179.
Ogawa AK DeMattei JA Scarlato GR Tellew JE Chong LS Armstrong RW 《The Journal of organic chemistry》1996,61(18):6153-6161
We report our synthesis of the C(26)-C(37) fragment of serine/threonine protein phosphatase PP1 and PP2A inhibitor calyculin C (1). Outlined in this paper are synthetic approaches to the two components based on disconnection at the C(33)-N(3) amide bond. We report the successful synthesis of the C(33)-C(37) aza-sugar derived from D-lyxose which was coupled onto a C(26)-C(32) aminooxazole originating from L-pyroglutamic acid. Elaboration of the resulting amide to a fully deprotected C(26)-C(37) fragment of calyculin C completed our synthesis. This provided an appropriate phosphonium salt for use in a Wittig olefination for joining both halves of the natural product. 相似文献
180.
Yasuhiro Yamamoto Xiao-Hong Han Ken-ichiro Sugawara Saho Nishimura 《Angewandte Chemie (International ed. in English)》1999,38(9):1242-1244
Strongly electron withdrawing cyanoolefins tetracyanoethylene (tcne) and 7,7,8,8-tetracyano-p-quinodimethane (tcnq) react with [(η5-C5Me5)MCl(MDMPP-P,O)] (M=Rh, Ir; MDMPP-P,O=PPh2(2-O-6-MeO-C6H3), a P,O chelating phosphane) by insertion into the C−H bond adjacent to the M−O σ bond. The crystal structure of the iridium complex formed upon insertion of tcne is shown. 相似文献