全文获取类型
收费全文 | 206篇 |
免费 | 2篇 |
国内免费 | 5篇 |
专业分类
化学 | 142篇 |
晶体学 | 2篇 |
数学 | 48篇 |
物理学 | 21篇 |
出版年
2022年 | 1篇 |
2019年 | 2篇 |
2018年 | 5篇 |
2017年 | 2篇 |
2016年 | 3篇 |
2015年 | 3篇 |
2014年 | 1篇 |
2013年 | 10篇 |
2012年 | 10篇 |
2011年 | 20篇 |
2010年 | 10篇 |
2009年 | 7篇 |
2008年 | 14篇 |
2007年 | 13篇 |
2006年 | 12篇 |
2005年 | 12篇 |
2004年 | 7篇 |
2003年 | 9篇 |
2002年 | 4篇 |
2001年 | 1篇 |
2000年 | 8篇 |
1999年 | 2篇 |
1998年 | 3篇 |
1997年 | 2篇 |
1996年 | 1篇 |
1995年 | 1篇 |
1994年 | 2篇 |
1993年 | 2篇 |
1992年 | 6篇 |
1990年 | 2篇 |
1988年 | 1篇 |
1987年 | 2篇 |
1986年 | 1篇 |
1985年 | 2篇 |
1984年 | 2篇 |
1983年 | 5篇 |
1982年 | 4篇 |
1981年 | 3篇 |
1980年 | 2篇 |
1978年 | 4篇 |
1977年 | 3篇 |
1976年 | 1篇 |
1975年 | 2篇 |
1974年 | 1篇 |
1973年 | 3篇 |
1970年 | 1篇 |
1969年 | 1篇 |
排序方式: 共有213条查询结果,搜索用时 15 毫秒
81.
Zhan Jie Wang Hirokazu Usuki Toshihide Kumagai Hiroyuki Kokawa 《Journal of Sol-Gel Science and Technology》2007,42(3):375-379
(La0.7Sr0.3)MnO3 thin films were deposited on SiO2/Si substrates by a metal-organic decomposition (MOD) method, and then Pb(Zr0.52Ti0.48)O3 (PZT) thin films were grown on (La0.7Sr0.3)MnO3-coated SiO2/Si substrates by a sol-gel method. The effects of annealing temperature on the crystalline phases, microstructures and electrical
properties of the PZT films were investigated. X-ray diffraction analysis results indicated that the PZT films with a perovskite
single phase could be obtained by annealing at 650°C. The dielectric constant and the remnant polarization of the PZT films
increased with increasing annealing temperature. The remnant polarization and the coercive field of the films annealed at
650°C were 18.3 μC/cm2 and 35.5 kV/cm, respectively, whereas the dielectric constant and loss value measured at 1 kHz were approximately 1100 and
0.81, respectively. 相似文献
82.
Toshihide Kawanaka 《Tetrahedron letters》2007,48(11):1973-1976
Oligodeoxyribonucleotides and their backbone-modified analogs were synthesized in good yields by the boranophosphotriester method in solution. The oligodeoxyriobonucleoside boranophosphates, fully protected with 2-(azidomethyl)benzoyl groups, were converted to the various backbone-modified DNA analogs via the corresponding H-phosphonate intermediates. A new efficient protecting group for the O6-position of 2′-deoxyguanosine, 4-[(2-azidomethyl)benzoyloxy]benzyl (AZBn) group, was also developed. The AZBn group was found to be quickly removed by treatment with MePPh2 in dioxane-2-mercaptoethanol-H2O. 相似文献
83.
Role of copper ion in bacterial copper amine oxidase: spectroscopic and crystallographic studies of metal-substituted enzymes 总被引:1,自引:0,他引:1
Kishishita S Okajima T Kim M Yamaguchi H Hirota S Suzuki S Kuroda S Tanizawa K Mure M 《Journal of the American Chemical Society》2003,125(4):1041-1055
The role of the active site Cu(2+) of phenylethylamine oxidase from Arthrobacter globiformis (AGAO) has been studied by substitution with other divalent cations, where we were able to remove >99.5% of Cu(2+) from the active site. The enzymes reconstituted with Co(2+) and Ni(2+) (Co- and Ni-AGAO) exhibited 2.2 and 0.9% activities, respectively, of the original Cu(2+)-enzyme (Cu-AGAO), but their K(m) values for amine substrate and dioxygen were comparable. X-ray crystal structures of the Co- and Ni-AGAO were solved at 2.0-1.8 A resolution. These structures revealed changes in the metal coordination environment when compared to that of Cu-AGAO. However, the hydrogen-bonding network around the active site involving metal-coordinating and noncoordinating water molecules was preserved. Upon anaerobic mixing of the Cu-, Co-, and Ni-AGAO with amine substrate, the 480 nm absorption band characteristic of the oxidized form of the topaquinone cofactor (TPQ(ox)) disappeared rapidly (< 6 ms), yielding the aminoresorcinol form of the reduced cofactor (TPQ(amr)). In contrast to the substrate-reduced Cu-AGAO, the semiquinone radical (TPQ(sq)) was not detected in Co- and Ni-AGAO. Further, in the latter, TPQ(amr) reacted reversibly with the product aldehyde to form a species with a lambda(max) at around 350 nm that was assigned as the neutral form of the product Schiff base (TPQ(pim)). Introduction of dioxygen to the substrate-reduced Co- and Ni-AGAO resulted in the formation of a TPQ-related intermediate absorbing at around 360 nm, which was assigned to the neutral iminoquinone form of the 2e(-)-oxidized cofactor (TPQ(imq)) and which decayed concomitantly with the generation of TPQ(ox). The rate of TPQ(imq) formation and its subsequent decay in Co- and Ni-AGAO was slow when compared to those of the corresponding reactions in Cu-AGAO. The low catalytic activities of the metal-substituted enzymes are due to the impaired efficiencies of the oxidative half-reaction in the catalytic cycle of amine oxidation. On the basis of these results, we propose that the native Cu(2+) ion has essential roles such as catalyzing the electron transfer between TPQ(amr) and dioxygen, in part by providing a binding site for 1e(-)- and 2e(-)-reduced dioxygen species to be efficiently protonated and released and also preventing the back reaction between the product aldehyde and TPQ(amr). 相似文献
84.
Hirotaka Kinoshita Susumu Yonezawa Jae-ho Kim Masayuki Kawai Masayuki Takashima Toshihide Tsukatani 《Journal of fluorine chemistry》2008,129(5):416-423
A Ni electroless plating process was used with polytetrafluoroethylene (PTFE) fine particles (25–500 μm). Using nonionic hydrocarbon surfactant, PTFE particles were dispersed in the plating bath. The PTFE hydrophobicity was sufficiently high that Ni was deposited partly on the PTFE surface in the initial step. The Ni-PTFE particles were formed into the Ni-PTFE plate by heat treatment at 350 °C after pressing. The Ni-PTFE plate had electrical conductivity and gas permeability, which were influenced by the pore distribution in the plate. Pores with 1 μm diameter might be especially important to impart high gas permeability to the Ni-PTFE plate. 相似文献
85.
The first catalyst that achieves Stille cross-couplings of secondary (as well as primary) alkyl halides has been developed. The method employs easily handled and inexpensive catalyst components (NiCl2 and 2,2'-bipyridine) and, through the use of monoorganotin reagents, avoids the formation of toxic and difficult-to-remove triorganotin side products. 相似文献
86.
Takehito Kodzasa Toshihide Kamata Hiro Matsuda Toshio Fukaya Fujio Mizukami Jun Matsunami Yuji Nagai Kazuko Matsumoto 《Journal of Sol-Gel Science and Technology》1997,8(1-3):1029-1033
The preparation of transparent films consisting of one-dimensional tetranuclear platinum complex and an alumina gel was attempted. Characterization of the composite films obtained was performed by UV-Vis-NIR spectroscopy. From the redox behavior of the complex in films, it was confirmed that the complex maintains the tetranuclear structure in the alumina gel, when the content of the complex is low. However, it seems to turn into another complex with a longer platinum chain, as the content of complex in the gel increases. The third-order nonlinear susceptibility (3) values of composite films was estimated from the third harmonic generation (THG) Maker-fringe measurements of this preliminary study. 相似文献
87.
Cascade Synthesis of Five‐Membered Lactones using Biomass‐Derived Sugars as Carbon Nucleophiles 下载免费PDF全文
Dr. Sho Yamaguchi Takeaki Matsuo Dr. Ken Motokura Dr. Akimitsu Miyaji Prof. Toshihide Baba 《化学:亚洲杂志》2016,11(11):1731-1737
We report the cascade synthesis of five‐membered lactones from a biomass‐derived triose sugar, 1,3‐dihydroxyacetone, and various aldehydes. This achievement provides a new synthetic strategy to generate a wide range of valuable compounds from a single biomass‐derived sugar. Among several examined Lewis acid catalysts, homogeneous tin chloride catalysts exhibited the best performance to form carbon–carbon bonds. The scope and limitations of the synthesis of five‐membered lactones using aldehyde compounds are investigated. The cascade reaction led to high product selectivity as well as diastereoselectivity, and the mechanism leading to the diastereoselectivity was discussed based on isomerization experiments and density functional theory (DFT) calculations. The present results are expected to support new approaches for the efficient utilization of biomass‐derived sugars. 相似文献
88.
89.
Toshihide Matsuno Sachie Horii Takanobu Sato Yoshiki Matsumiya Motoki Kubo 《Applied biochemistry and biotechnology》2013,169(3):795-809
Accumulations of inorganic nitrogen (NH4 +, NO2 ?, and NO3 ?) were analyzed to evaluate the nitrogen circulation activity in 76 agricultural soils. Accumulation of NH4 + was observed, and the reaction of NH4 +?→?NO2 ? appeared to be slower than that of NO2 ??→?NO3 ? in agricultural soil. Two autotrophic and five heterotrophic ammonia-oxidizing bacteria (AOB) were isolated and identified from the soils, and the ammonia-oxidizing activities of the autotrophic AOB were 1.0?×?103–1.0?×?106 times higher than those of heterotrophic AOB. The relationship between AOB number, soil bacterial number, and ammonia-oxidizing activity was investigated with 30 agricultural soils. The ratio of autotrophic AOB number was 0.00032–0.26 % of the total soil bacterial number. The soil samples rich in autotrophic AOB (>1.0?×?104 cells/g soil) had a high nitrogen circulation activity, and additionally, the nitrogen circulation in the agricultural soil was improved by controlling the autotrophic AOBs. 相似文献
90.
Yamasaki T Ito Y Mito F Kitagawa K Matsuoka Y Yamato M Yamada K 《The Journal of organic chemistry》2011,76(10):4144-4148
Nitroxides have antioxidative activities toward lipid peroxidation, but the influence of steric factors is not known. We synthesized alkyl-substituted nitroxides at the α-position of the N-O moiety to enhance lipophilicity and the bulk effect. There was good correlation between the IC(50) and lipophilicity (log P(o/w)) of nitroxides with use of the thiobarbituric acid-reactive substances (TBARS) assay. Furthermore, an inhibitory effect on the TBARS assay was dependent upon the number and length of alkyl groups, though nitroxides had almost identical lipophilicity. 相似文献