全文获取类型
收费全文 | 187篇 |
免费 | 11篇 |
专业分类
化学 | 165篇 |
晶体学 | 1篇 |
数学 | 6篇 |
物理学 | 26篇 |
出版年
2023年 | 3篇 |
2022年 | 2篇 |
2021年 | 1篇 |
2020年 | 4篇 |
2019年 | 3篇 |
2018年 | 3篇 |
2017年 | 1篇 |
2016年 | 6篇 |
2015年 | 6篇 |
2014年 | 10篇 |
2013年 | 11篇 |
2012年 | 11篇 |
2011年 | 12篇 |
2010年 | 8篇 |
2009年 | 8篇 |
2008年 | 8篇 |
2007年 | 9篇 |
2006年 | 11篇 |
2005年 | 15篇 |
2004年 | 16篇 |
2003年 | 13篇 |
2002年 | 14篇 |
2001年 | 2篇 |
2000年 | 1篇 |
1999年 | 1篇 |
1998年 | 2篇 |
1997年 | 2篇 |
1996年 | 2篇 |
1992年 | 1篇 |
1987年 | 2篇 |
1986年 | 1篇 |
1985年 | 1篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1981年 | 1篇 |
1980年 | 1篇 |
1979年 | 1篇 |
1976年 | 3篇 |
排序方式: 共有198条查询结果,搜索用时 0 毫秒
41.
Shinobu Tsutsui Hiromasa Tanaka Shigeki Matsumoto 《Journal of organometallic chemistry》2006,691(4):595-603
The reduction of p-anisyl(1,2,3-tri-tert-butylcycloprop-2-en-1-yl)dichlorogermane (1) with potassium in the presence of an excess of tert-butyldimethylsilane in benzene under reflux gave p-anisyl(tert-butyldimethylsilyl)(1,2,3-tri-tert-butylcycloprop-2-en-1-yl)germane (4) in 15% yield. The formation of 4 indicates that p-anisyl(1,2,3-tri-tert-butylcycloprop-2-en-1-yl)germylene (2), which is the first example of a (cycloprop-2-en-1-yl)germylene derivative, was generated and trapped by the hydrosilane. The DFT calculations revealed that the cis-2-p-anisyl-1,3,4-tri-tert-butyl-2-germabicyclo[1.1.0]butane-2,4-diyl structure cis-5 is 8.0 kJ/mol more stable than cis-2. The NBO analysis revealed that cis-5 has a 2-germabicyclo[1.1.0]butane diradical character. 相似文献
42.
Hiroaki Kakiuchi Hiromasa Ohmi Takahiro Yamada Keiji Yokoyama Kohei Okamura Kiyoshi Yasutake 《Plasma Chemistry and Plasma Processing》2012,32(3):533-545
Silicon oxide films are deposited in atmospheric-pressure (AP) He/O2/HMDSO plasma excited by a 150?MHz VHF power using a cylindrical rotary electrode. The atomic bonding configurations and deposition rate are studied by controlling the O2 concentration (O2/HMDSO source ratio) and VHF power density, the other parameters being maintained constant. Under the addition of 0.03?% O2 to the process gas mixture (O2/HMDSO????0.09), AP-VHF plasma greatly enhances the fragmentation and oxidation of HMDSO, so that an almost inorganic film is obtained at a very high deposition rate of 33?nm?s?1. A silicon oxide coating on a polycarbonate pane is demonstrated with no significant thermal deformation of the pane, showing that AP-VHF plasma would be an efficient coating tool for polymer substrates. 相似文献
43.
Yong Li Meng-Chu Zhu Man-Li Zhang Yu-Fang Wang Mei Dong Qing-Wen Shi Chang-Hong Huo Françoise Sauriol Hiromasa Kiyota Yu-Cheng Gu Bin Cong 《Tetrahedron letters》2012,53(21):2601-2603
Two novel sesquiterpene dimers, achillinin B and C, were isolated from the flowers of Achillea millefolium. The structures were elucidated by extensive spectroscopic analysis. A plausible biosynthetic pathway of achillinin B and C by Diels–Alder reaction of the corresponding guaiane sesquiterpenoids is also discussed. 相似文献
44.
Hiromasa Nishikiori Nobuaki Tanaka Tsuneo Fujii 《Research on Chemical Intermediates》2000,26(5):469-482
Dip-coated thin films including rhodamine B have been prepared using the sol-gel reaction of tetraethyl orthosilicate under
relative humidity of 30% and 60%. They have been aged under relative humidity of 20%, 60%, and 95% for 5 days. According to
the absorption spectra, just after the preparation of the films and under higher humidity, a larger amount of the dimers (H-and
J-types) were formed in the films. Five days after the preparation of the films and aged under higher humidity, the H-dimer
increased. On the other hand, the J-dimer increased, regardless of humidity under which the films were aged. 相似文献
45.
A fully optical remote detection system for propane gas was realized in real time by a near-infrared absorption method employing a 2-km long low-loss silica optical-fibre link in conjunction with an InGaAs light emitting diode at 1.68 μm. The detection sensitivity for propane gas in air, which was achieved to lower than 2 torr, i.e. nearly 12% of the lower explosion limit for propane, demonstrates the practical feasibility and reliability of this kind of fibre-optic remote gas sensor system with electrical and thermal safety. 相似文献
46.
Goto M Yamamoto Y Sumimoto M Tsuruda N Kurosaki H 《Chemical & pharmaceutical bulletin》2003,51(10):1157-1162
Square-planar complexes with the formula [Pt(L(2))(L(1))](X)(2) x nH(2)O, where L(1) is S-2-aminomethylpyrrolidine (S-pyrda) or 2-aminomethylpiperidine (pipda) and L(2) is diammine (X=Cl), cyclobutane-1,1-dicarboxylato (cbdca) (X=none), 2,2'-bipyridine (bpy) (X=NO(3)), or 1,10-phenanthroline (phen) (X=Cl), were prepared and the nature of the coordination of L(1) was examined by (1)H-NMR spectroscopy and X-ray crystallography. These 2-aminomethylazacycloalkane derivatives form five-membered chelate rings condensed with an azacycloalkane ring in cis- or trans-configurations. The (1)H-NMR spectrum of complexes with S-pyrda as L(1) were consistent with cis-condensed rings in an S(N) conformation with any of L(2) group. However, (1)H-NMR spectra of the complexes with pipda as L(1) indicated trans-fused successive rings for the diammine and cbdca as L(2), but spectra for bpy and phen as L(2) were consistent with a conformation having cis-fused successive rings. X-Ray crystallography data for the two complexes with pipda as L(1) and cbdca (1) and bpy (2) as L(2) confirms the different coordination behavior in the solid state. 相似文献
47.
Horikiri H Hirano N Tanaka Y Oishi J Hatakeyama H Kawamura K Nagase H 《Chemical & pharmaceutical bulletin》2004,52(6):664-669
Syntheses of 10-oxo, 10alpha-hydroxy, and 10beta-hydroxy derivatives of a potent kappa-opioid receptor selective agonist, TRK-820, are described. These derivatives were supposed to be potential degradation products in formulation of TRK-820 as a result of autoxidation. 10-Oxo-TRK-820 11 was derived from 10-oxo-4,5-epoxymorphinan 14 in 10 steps in 32% overall yield. Reduction of the 10-oxo group in 4,5-epoxymorphinan with NaBH(4) gave 10beta-hydroxy-4,5-epoxymorphinan, exclusively. A stepwise inversion method of the 10beta-hydroxy group to produce 10alpha-hydroxy-4,5-epoxymorphinan was established. By HPLC analyses, 10alpha-hydroxy-TRK-820 12 was confirmed to be one of the degradation products in developing formulation of TRK-820. 相似文献
48.
Takashi Hayashita Norio Teramae Toshiharu Kuboyama Shigeo Nakamura Hiromasa Yamamoto Hiroshi Nakamura 《Journal of inclusion phenomena and macrocyclic chemistry》1998,32(2-3):251-265
Recent progress in chromoionophores based on (1) spherand and hemispherand, (2) cryptand, and (3) dibenzo-16-crown-5 and calix[4]crown which selectively respond to alkali metal ions in aqueous media is reviewed in relation to their molecular structure and photometric function. The design concept of the chromoionophores for colorimetry in aqueous media is discussed in the light of their acid dissociation and metal complex formation equilibria. 相似文献
49.
Kawamura K Horikiri H Hayakawa J Seki C Yoshizawa K Umeuchi H Nagase H 《Chemical & pharmaceutical bulletin》2004,52(6):670-674
Chemical syntheses of three kinds of potential metabolites of TRK-820, a potent kappa-opioid receptor agonist, were described. One of the potential metabolites 2, 17-N-dealkylated TRK-820, was synthesized starting from noroxycodone through 8 steps in 21% total yield. Glucuronidation of intermediate 10 and compound 1, the free base of TRK-820, was carried out stereoselectively to give 3-O-beta-D-glucuronides 15 and 16 in good yields, respectively. Syntheses of potential conjugated metabolites 3 and 4 were accomplished through 10 steps and 2 steps in 11% and 43% total yields, respectively. Among the potential metabolites of TRK-820, compounds 2 and 4 were identified as metabolites in human hepatocytes. The results of pharmacological studies of compounds 2, 3, and 4 are described. 相似文献
50.
Hiromasa Goto 《Journal of polymer science. Part A, Polymer chemistry》2007,45(11):2085-2090
The electrochemically driven control of the natural optical activity of polyanilines bearing chiral camphorsulfonic acid is reported. Aniline was polymerized in the presence of camphorsulfonic acid by oxidative electrochemical polymerization in water to afford polyanilines containing (+)- or (−)-camphorsulfonic acid. This research elucidated that the polymerization, with cyclic voltammetry scanning up to 1.1 V, produced consistent optically active polyanilines. The polyaniline films thus prepared showed intense and tunable optical activity based on electrochemical reduction/oxidation in a 0.1 M sulfuric acid aqueous solution. The circular dichroism and optical rotation angle of the polymer were tunable by the appropriate adjustment of an externally applied potential as a form of optical modulation. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2085–2090, 2007 相似文献