全文获取类型
收费全文 | 542篇 |
免费 | 12篇 |
国内免费 | 6篇 |
专业分类
化学 | 373篇 |
晶体学 | 4篇 |
力学 | 7篇 |
数学 | 33篇 |
物理学 | 143篇 |
出版年
2021年 | 4篇 |
2020年 | 4篇 |
2019年 | 9篇 |
2018年 | 10篇 |
2017年 | 4篇 |
2016年 | 7篇 |
2015年 | 7篇 |
2014年 | 8篇 |
2013年 | 36篇 |
2012年 | 28篇 |
2011年 | 21篇 |
2010年 | 15篇 |
2009年 | 12篇 |
2008年 | 54篇 |
2007年 | 40篇 |
2006年 | 25篇 |
2005年 | 24篇 |
2004年 | 10篇 |
2003年 | 16篇 |
2002年 | 14篇 |
2001年 | 12篇 |
2000年 | 10篇 |
1999年 | 7篇 |
1997年 | 9篇 |
1996年 | 7篇 |
1995年 | 9篇 |
1994年 | 7篇 |
1993年 | 9篇 |
1992年 | 9篇 |
1991年 | 9篇 |
1990年 | 6篇 |
1987年 | 7篇 |
1986年 | 4篇 |
1985年 | 6篇 |
1984年 | 8篇 |
1983年 | 3篇 |
1982年 | 4篇 |
1981年 | 8篇 |
1980年 | 6篇 |
1979年 | 15篇 |
1978年 | 4篇 |
1977年 | 6篇 |
1976年 | 3篇 |
1975年 | 5篇 |
1974年 | 5篇 |
1973年 | 4篇 |
1972年 | 3篇 |
1971年 | 5篇 |
1970年 | 3篇 |
1967年 | 4篇 |
排序方式: 共有560条查询结果,搜索用时 15 毫秒
551.
A possible human carcinogen, 1,4-dioxane, was investigated as to its concentration levels in household detergents and cleaners currently sold in Japan. A solid-phase extraction combined with stable isotope dilution and gas chromatographic/mass spectrometric determination was evaluated for the determination of 1,4-dioxane in household products. The evaluation of the method was performed using a recovery study of 1,4-dioxane-d8 from detergent and cleaner samples. The mean overall recovery and relative standard deviation were 78 and 15%, respectively. The limit of quantitation was 0.05 mg/kg. This method was satisfactorily applied to the determination of 1,4-dioxane in household products. 1,4-Dioxane was detected in 40 out of the 51 investigated samples. The concentrations ranged from 0.05 to 33 mg/kg, and the mean was 2.7 mg/kg. The mean of the products that included anionic surfactants, i.e., alkylpoly(oxyethylene)sulfates, was 7.2 mg/kg, which was higher than the 0.39 mg/kg mean for the other surfactants. Moreover, the 1,4-dioxane load/person was estimated to be 0.061 mg/day/person in Japan, which was 27% of the load from the domestic effluent. 相似文献
552.
553.
An efficient, two-stage, continuous-flow synthesis of 1α,25-(OH)(2)-vitamin D(3) (activated vitamin D(3)) and its analogues was achieved. The developed method afforded the desired products in satisfactory yields using a high-intensity and economical light source, i.e., a high-pressure mercury lamp. In addition, our method required neither intermediate purification nor high-dilution conditions. 相似文献
554.
Tanabe T Bi B Hu L Maurer K Moeller KD 《Langmuir : the ACS journal of surfaces and colloids》2012,28(3):1689-1693
A new amino acid derived fluorescent linker for attaching molecules to the surface of a microelectrode array has been developed. Molecules to be monitored on an array are attached to the C-terminus of the linker, the N-terminus is then used to attach the linker to the array, and the side chain is used to synthesize a fluorescent tag. The fluorescent group is made with a one-step oxidative cycloaddition reaction starting from a hydroxyindole group. The linker is compatible with site-selective Cu(I)-chemistry on the array, it allows for quality control assessment of the array itself, and it is compatible with the electrochemical impedance experiments used to monitor binding events on the surface of the array. 相似文献
555.
H Aiso T Kochi H Mutsutani T Tanabe S Nishiyama F Kakiuchi 《The Journal of organic chemistry》2012,77(17):7718-7724
Palladium-catalyzed electrochemical iodination and one-pot arylation of arylpyridines are described. Ortho-selective C-H iodination proceeded via dual activation of each substrate by a palladium catalyst and an electrode. Various aryl groups were introduced at the ortho positions of arylpyridines by ON/OFF switching of two different catalytic cycles using the same palladium catalyst in a one-pot fashion. 相似文献
556.
In the Tb3+–Yb3+ codoped glass ceramics with SrF2 nanocrystals precipitated, the energy transfer mechanism from Tb3+ to Yb3+ was investigated. The excitation power dependence of emission intensity study showed that the quantum cutting occurs during the energy transfer from Tb3+ to Yb3+ with the excitation of Tb3+ high energy level. However, the one-photon process is the main reason that is responsible for the Yb3+ infrared emission. The external quantum yields of Tb3+ and Yb3+ were evaluated by using an integrating sphere measurement system with the excitation of 377 and 488 nm lasers, which are much lower than the expected quantum efficiencies calculated from Tb3+ lifetimes. The external quantum yields in the glass ceramics and as-made glasses were also compared. 相似文献
557.
Obara S Itabashi M Okuda F Tamaki S Tanabe Y Ishii Y Nozaki K Haga MA 《Inorganic chemistry》2006,45(22):8907-8921
Novel mixed-ligand Ir(III) complexes, [Ir(L)(NwedgeC)X]n+ (L = N/\C/\N or N/\N/\N; X = Cl, Br, I, CN, CH3CN, or -CCPh; n = 0 or 1), were synthesized, where N/\CwedgeN = bis(N-methylbenzimidazolyl)benzene (Mebib) and bis(N-phenylbenzimidazolyl)benzene (Phbib), N/\N/\N = bis(N-methylbenzimidazolyl)pyridine (Mebip), and N/\C = phenylpyridine (ppy) derivatives. The X-ray crystal structures of [Ir(Phbib)(ppy)Cl] and [Ir(Mebib)(mppy)Cl] [mppy = 5-methyl-2-(2'-pyridyl)phenyl] indicate that the nitrogen atom of the ppy ligand is located trans to the coordinating carbon atom in Me- or Phbib, while the coordinating carbon atom in ppy occupies the trans position of Cl. [Ir(Mebip)(ppy)Cl]+ showed a quasireversible Ir(III/IV) oxidation wave at +1.05 V, while the Ir complexes, [Ir(Mebib)(ppy)Cl], were oxidized at +0.42 V versus Fc/Fc+. The introduction of an Ir-C bond in [Ir(Mebib)(ppy)Cl] induces a large potential shift of 0.63 V in a negative direction. Further, the oxidation potential of [Ir(Mebib)(Rppy)X] was altered by the substitution of R, R', and X groups. Compared to the oxidation potential, the first reduction potential revealed an almost constant value at -2.36 to -2.46 V for [Ir(L)(ppy)Cl] (L = Mebib and Phbib) and -1.52 V for [Ir(Mebip)(ppy)Cl. The UV-vis spectra of [Ir(Mebib)(R-ppy)X] show a clear singlet metal-to-ligand charge-transfer transition around 407 approximately 425 nm and a triplet metal-to-ligand charge-transfer transition at 498 approximately 523 nm. [Ir(Mebip)(ppy)Cl]+ emits at 610 nm with a luminescent quantum yield of Phi = 0.16 at room temperature. The phosphorescence of [Ir(Mebib)(ppy)X] was observed at 526 nm for X = CN and 555 nm for X = Cl with the high luminescent quantum yields, Phi = 0.77 approximately 0.86, at room temperature. [Ir(Phbib)(ppy)Cl] shows the emission at 559 nm with a luminescent quantum yield of Phi = 0.95, which is an unprecedentedly high value compared to those of other emissive metal complexes. Compared to the luminescent quantum yields of the Ir(ppy)2(L) derivatives and [Ir(Mebip)(ppy)Cl]+, the neutral Ir complexes, [Ir(L)(R-ppy)X] (L = Me- or Phbib), reveal very high quantum yields and large radiative rate constants (kr) ranging from 3.4 x 10(5) to 5.5 x 10(5) s(-1). The density functional theory calculation suggests that these Ir complexes possess dominantly metal-to-ligand charge-transfer and halide-to-ligand charge-transfer excited states. The mechanism for a high phosphorescence yield in [Ir(bib)(ppy)X] is discussed herein from the perspective of the theoretical consideration of radiative rate constants using perturbation theory and a one-center spin-orbit coupling approximation. 相似文献
558.
Laboratory experiments have been performed to investigate the physical processes that govern the interaction of a self-propagating barotropic cyclonic vortex with aligned circular cylinders. The motivation was to understand the dynamics which controls the interaction of North Brazil Current (NBC) rings with the Lesser Antilles (LA) in the Eastern Caribbean Sea. The geometrical parameter regulating the flow in the experiments was the ratio of the gap size to the diameter of the incident vortex, G /d. The range 0.03 ≤ G /d ≤ 0.4 was studied. Since the passages of the LA have values of 0.07 ≤ G /d ≤ 0.3 [2], the experimental results might explain recent oceanic observations [3]. (© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
559.
560.
The direct coupling reaction of D -ribosyl fluoride with typical π-excessive aromatic heterocycles such as furan, thiophene, pyrrole, benzofuran, benzothiophene, and indole and their trimethylsilyl derivatives was performed in the presence of boron trifluoride to afford the corresponding C-nucleosides in moderate to good yields. 相似文献