全文获取类型
收费全文 | 1262篇 |
免费 | 29篇 |
国内免费 | 8篇 |
专业分类
化学 | 985篇 |
晶体学 | 9篇 |
力学 | 8篇 |
数学 | 79篇 |
物理学 | 218篇 |
出版年
2023年 | 5篇 |
2022年 | 11篇 |
2021年 | 9篇 |
2020年 | 17篇 |
2019年 | 18篇 |
2018年 | 15篇 |
2017年 | 11篇 |
2016年 | 31篇 |
2015年 | 32篇 |
2014年 | 27篇 |
2013年 | 60篇 |
2012年 | 72篇 |
2011年 | 72篇 |
2010年 | 40篇 |
2009年 | 45篇 |
2008年 | 75篇 |
2007年 | 67篇 |
2006年 | 68篇 |
2005年 | 75篇 |
2004年 | 78篇 |
2003年 | 59篇 |
2002年 | 68篇 |
2001年 | 30篇 |
2000年 | 19篇 |
1999年 | 18篇 |
1998年 | 13篇 |
1997年 | 10篇 |
1996年 | 14篇 |
1995年 | 11篇 |
1994年 | 19篇 |
1993年 | 20篇 |
1992年 | 11篇 |
1991年 | 7篇 |
1990年 | 8篇 |
1989年 | 12篇 |
1988年 | 4篇 |
1987年 | 6篇 |
1986年 | 8篇 |
1985年 | 16篇 |
1984年 | 9篇 |
1983年 | 13篇 |
1982年 | 7篇 |
1981年 | 11篇 |
1980年 | 10篇 |
1979年 | 10篇 |
1978年 | 14篇 |
1977年 | 13篇 |
1976年 | 8篇 |
1975年 | 8篇 |
1974年 | 6篇 |
排序方式: 共有1299条查询结果,搜索用时 10 毫秒
111.
Yasuhiro Matsuda Takefumi Kawata Shinji Sugihara Sadahito Aoshima Takahiro Sato 《Journal of Polymer Science.Polymer Physics》2006,44(8):1179-1187
The aqueous solution of a thermoresponsive polymer, poly[2‐(2‐ethoxy) ethoxyethyl vinyl ether] poly(EOEOVE), contains a tiny amount of large polymer aggregates at low polymer concentrations far below the lower critical solution temperature (~40 °C). The molar mass Mw,slow, radius of gyration 〈S2〉, and hydrodynamic radius RH,slow of the aggregating component of poly(EOEOVE) were obtained by simultaneous static and dynamic light scattering as functions of the polymer concentration and temperature, while the weight fraction wslow of the component was estimated by size‐exclusion chromatography. The Mw,slow dependencies of 〈S2〉 and RH,slow, as well as the ratio 〈S2〉/RH,slow, indicated that the poly(EOEOVE) aggregate takes a sparsely branched polymer‐like conformation. We have analyzed the structure of the aggregate, using the branched polymer model of random type. The Mw,slow dependence of 〈S2〉 obtained was favorably compared with this model with reasonable structural parameters. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1179–1187, 2006 相似文献
112.
113.
Harada S Kumagai N Kinoshita T Matsunaga S Shibasaki M 《Journal of the American Chemical Society》2003,125(9):2582-2590
Full details of our direct Michael addition of unmodified ketones using new asymmetric zinc catalysis are described. Et(2)Zn/(S,S)-linked-BINOL complexes were successfully applied to direct 1,4-addition reactions of hydroxyketones. The first generation Et(2)Zn/(S,S)-linked-BINOL 1 = 2/1 system was effective for 1,4-addition of 2-hydroxy-2'-methoxyacetophenone (3). Using 1 mol % of (S,S)-linked-BINOL 1 and 2 mol % of Et(2)Zn, we found that a 1,4-addition reaction of beta-unsubstituted enone proceeded smoothly at 4 degrees C to afford products in high yield (up to 90%) and enantiomeric excess (up to 95%). In the case of beta-substituted enones, however, the first generation Et(2)Zn/(S,S)-linked-BINOL 1 = 2/1 system was not at all effective. The second generation Et(2)Zn/(S,S)-linked-BINOL 1 = 4/1 with MS 3A system was developed and was effective for various beta-substituted enones to afford products in good dr, yield (up to 99%), and high enantiomeric excess (up to 99% ee). With the Et(2)Zn/1 = 4/1 systems, catalyst loading for beta-unsubstituted enone was reduced to as little as 0.01 mol % (substrate/chiral ligand = 10 000). The new system was also effective for 1,4-addition reactions of 2-hydroxy-2'-methoxypropiophenone (9) to afford chiral tert-alcohol in high enantiomeric excess (up to 96% ee). Mechanistic investigations as well as transformations of the Michael adducts into synthetically versatile intermediates are also described. 相似文献
114.
Kei Fujise Eiji Tsurumaki Gaku Fukuhara Nobuyuki Hara Yoshitane Imai Shinji Toyota 《化学:亚洲杂志》2020,15(16):2456-2461
Polycyclic aromatic hydrocarbons consisting of three fused anthracene units were designed as new π‐conjugated compounds having helical structures. These expanded helicenes were synthesized by Pt‐catalyzed cycloisomerization of the corresponding ethynyl‐substituted precursors. The nonplanar and helical structure was confirmed by X‐ray analysis and DFT calculations, and the barrier to helical inversion was estimated to be 34 kJ mol?1. The enantiomers of the diphenyl derivative were successfully resolved by chiral HPLC. Enantiopure samples showed good chiroptical performance in the CD (|Δ?| 1380 L mol?1 cm?1) and CPL (|glum| 0.013) spectra, and these values were considerably large for simple organic molecules. The unique chiroptical properties are discussed on the basis of the molecular structure and the electronic state with the aid of time‐dependent DFT calculations. 相似文献
115.
The effect of oxygen isotope substitution on the transition temperature Tc of a superconducting (Nd1−xCex)2CuO4−δ system was studied, where the special synthetic method was taken to minimize ambiguous factors on the oxygen concentration and to guarantee the complete substitution of 16O by 18O. The isotope exponent in the relationship of Tc∝1/M was estimated to be less than 0.15 by magnetic susceptibility measurements. 相似文献
116.
Matsumoto T Itakura N Nakaya Y Tatsumi K 《Chemical communications (Cambridge, England)》2011,47(3):1030-1032
A S/SH bridged hetero-dinuclear Ru/Ge complex cation reacted with H(2) to afford the μ-S/μ-H complex. The reaction was considerably slower compared to that of the μ-S/μ-OH complex. Thus, the μ-S/μ-SH and μ-S/μ-OH complexes might provide models for the unready and ready states, respectively, of [NiFe] hydrogenase. 相似文献
117.
A new 20-membered macrolide designated exiguolide has been isolated from the marine sponge Geodia exigua, and its structure determined by interpretation of spectroscopic data. Exiguolide specifically inhibited fertilization of sea urchin (Hemicentrotus pulcherrimus) gametes but not embryogenesis of the fertilized egg. 相似文献
118.
Imai M Tanaka M Tanaka K Yamamoto Y Imai-Ogata N Shimowatari M Nagumo S Kawahara N Suemune H 《The Journal of organic chemistry》2004,69(4):1144-1150
Intermolecular hydroacylation between salicylaldehydes 1, 26-40 and 1,4-penta- or 1,5-hexadienes 4-13 by Rh-catalyst proceeded under mild reaction conditions to give a mixture of iso- and normal-hydroacylated products 14-25, 41-55, and 57-60. In the hydroacylation reaction, chelation of both salicylaldehyde and diene to the Rh-complex plays a crucial role. The ratio of iso- and normal-hydroacylated products could be regulated by the addition of salicylic acid or amines. The effects of various Rh-complexes, solvents, and additives were examined, and the plausible mechanisms of the catalytic cycle were proposed on the basis of the deuterium-labeling salicylaldehyde experiments. 相似文献
119.
Hiroaki Ohmukai Yasumasa Sugiyama Akira Hirota Mitsunori Kirihata Shinji Tanimori 《Journal of heterocyclic chemistry》2020,57(3):1090-1100
Phomapyrone B ( 1 ), the 2-pyrones isolated from the phytopathogenic fungus Leptosphaeria maculans, has been synthesized as the enantiomeric form starting from (S)-2-methylbutanol ( 4 ). Surugapyrone B ( 3 ) isolated from Streptmyces sp. USF-6280 as an antioxidant has also been synthesized as a natural form. The absolute configuration of phomapyrone B ( 1 ) was estimated to be the (R)-form and that of surugapyrone B ( 3 ) being the (S)-form. A series of 2-pyrone derivatives 17 have been synthesized through the established procedure and their DPPH radical-scavenging activities have also been evaluated. 相似文献
120.
Selective shielding of one side of the pyridinium face by way of intramolecular cation-pi complex formation enabled nucleophiles to attack only from the non-shielded side, and consequently, chiral 1,4-dihydropyridines were produced stereoselectively with up to 99% de. The structure of the cation-pi complex was elucidated by 1H NMR studies and X-ray analysis. 相似文献