全文获取类型
收费全文 | 661篇 |
免费 | 8篇 |
国内免费 | 8篇 |
专业分类
化学 | 365篇 |
晶体学 | 2篇 |
力学 | 30篇 |
数学 | 68篇 |
物理学 | 212篇 |
出版年
2020年 | 4篇 |
2018年 | 6篇 |
2016年 | 6篇 |
2015年 | 8篇 |
2014年 | 11篇 |
2013年 | 33篇 |
2012年 | 27篇 |
2011年 | 36篇 |
2010年 | 26篇 |
2009年 | 29篇 |
2008年 | 42篇 |
2007年 | 26篇 |
2006年 | 30篇 |
2005年 | 24篇 |
2004年 | 29篇 |
2003年 | 23篇 |
2002年 | 20篇 |
2001年 | 12篇 |
2000年 | 19篇 |
1999年 | 7篇 |
1998年 | 7篇 |
1997年 | 7篇 |
1996年 | 12篇 |
1995年 | 9篇 |
1994年 | 5篇 |
1993年 | 9篇 |
1992年 | 12篇 |
1991年 | 16篇 |
1990年 | 14篇 |
1989年 | 8篇 |
1988年 | 7篇 |
1987年 | 6篇 |
1986年 | 5篇 |
1984年 | 11篇 |
1983年 | 5篇 |
1981年 | 9篇 |
1980年 | 11篇 |
1979年 | 8篇 |
1978年 | 7篇 |
1977年 | 9篇 |
1976年 | 12篇 |
1975年 | 7篇 |
1974年 | 4篇 |
1973年 | 5篇 |
1972年 | 4篇 |
1970年 | 3篇 |
1968年 | 3篇 |
1967年 | 3篇 |
1935年 | 3篇 |
1933年 | 4篇 |
排序方式: 共有677条查询结果,搜索用时 390 毫秒
101.
Boren BC Narayan S Rasmussen LK Zhang L Zhao H Lin Z Jia G Fokin VV 《Journal of the American Chemical Society》2008,130(28):8923-8930
The catalytic activity of a series of ruthenium(II) complexes in azide-alkyne cycloadditions has been evaluated. The [Cp*RuCl] complexes, such as Cp*RuCl(PPh 3) 2, Cp*RuCl(COD), and Cp*RuCl(NBD), were among the most effective catalysts. In the presence of catalytic Cp*RuCl(PPh 3) 2 or Cp*RuCl(COD), primary and secondary azides react with a broad range of terminal alkynes containing a range of functionalities selectively producing 1,5-disubstituted 1,2,3-triazoles; tertiary azides were significantly less reactive. Both complexes also promote the cycloaddition reactions of organic azides with internal alkynes, providing access to fully-substituted 1,2,3-triazoles. The ruthenium-catalyzed azide-alkyne cycloaddition (RuAAC) appears to proceed via oxidative coupling of the azide and alkyne reactants to give a six-membered ruthenacycle intermediate, in which the first new carbon-nitrogen bond is formed between the more electronegative carbon of the alkyne and the terminal, electrophilic nitrogen of the azide. This step is followed by reductive elimination, which forms the triazole product. DFT calculations support this mechanistic proposal and indicate that the reductive elimination step is rate-determining. 相似文献
102.
Cariton Kubwabo Xinghua Fan Pat E. Rasmussen Fang Wu Ivana Kosarac 《International journal of environmental analytical chemistry》2016,96(7):667-681
Phthalates have been used as plasticisers for several decades in various industry and consumer products. A method was developed for the determination of 13 not commonly monitored phthalates in household dust. The method was based on solvent extraction using sonication, sample clean-up by solid phase extraction (SPE), and analysis using isotope dilution gas chromatography-tandem mass spectrometry (GC/MS/MS). The method was applied to the analysis of dust samples collected using two vacuum sampling techniques from 38 urban Canadian homes: a sample of fresh or ‘active’ dust (FD) collected by technicians and a composite sample taken from the household vacuum cleaner (HD). Spearman rank correlations between HD and FD samples were significant for six phthalates with median concentrations above their method detection limits (MDLs), suggesting that the HD samples provide comparable results with FD samples. Seven phthalates were detected and quantified in a Canada-wide set of 126 household dust samples, among which six phthalates were detected at frequencies higher than 87%, with median (range) concentrations of 1.9 (<0.42–240) (μg/g) for diisohexyl phthalate (DIHxP), 3.8 (<0.16–260) (μg/g) for di-n-heptyl phthalate (DHepP), 6.6 (<1.1–1170) (μg/g) for diisooctyl phthalate (DIOP), 1.1 (<0.12–390) (μg/g) for di-n-octyl phthalate (DOP), 6.3 (<0.16–430) (μg/g) for dinonyl phthalate (DNP), and 1.8 (<0.18–850) (μg/g) for di-n-decyl phthalate (DDP). High detection frequencies and widely scattered concentration levels of these phthalates in this preliminary set of 126 samples suggested a high variability in potential exposure to phthalates in Canadian homes. NIST SRM 2585 (organic contaminants in house dust) was also analysed; eight phthalates were detected, with concentrations ranging from 6.0 μg/g for DOP to 79 μg/g for DIHxP. The results from SRM 2585 may contribute to the certification of phthalate concentration values in this SRM. 相似文献
103.
Ruthenium-catalyzed cycloaddition of aryl azides and alkynes 总被引:2,自引:0,他引:2
The formation of 1,5-disubstituted 1,2,3-triazoles from aryl azides and alkynes was readily accomplished using [Cp*RuCl]4 catalyst in dimethylformamide. It was also demonstrated that the reaction provided higher yields, cleaner product, and shorter reaction times when carried out under microwave irradiation. 相似文献
104.
The present work has for the first time described and verified a theoretical model of the analytical extraction process electro-membrane extraction (EME), where target analytes are extracted from an aqueous sample, through a thin layer of 2-nitrophenyl octylether immobilized as a supported liquid membrane (SLM) in the pores in the wall of a porous hollow fibre, and into an acceptor solution present inside the lumen of the hollow fibre by the application of an electrical potential difference. The mathematical model was based on the Nernst-Planck equation, and described the flux over the SLM. The model demonstrated that the magnitude of the electrical potential difference, the ion balance of the system, and the absolute temperature influenced the flux of analyte across the SLM. These conclusions were verified by experimental data with five basic drugs. The flux was strongly dependent of the potential difference over the SLM, and increased potential difference resulted in an increase in the flux. The ion balance, defined as the sum of ions in the donor solution divided by the sum of ions in the acceptor solution, was shown to influence the flux, and high ionic concentration in the acceptor solution relative to the sample solution was advantageous for high flux. Different temperatures also led to changes in the flux in the EME system. 相似文献
105.
A well-known method of estimating the length of a parametric curve in is to sample some points from it and compute the length of the polygon passing through them. In this paper we show that for
uniform sampling of regular smooth curves, Richardson extrapolation can be applied repeatedly giving a sequence of derivative-free
length estimates of arbitrarily high orders of accuracy. A similar result is derived for the approximation of the area of
parametric surfaces.
相似文献
106.
Jonathan Masere Yuri Chekanov James R. Warren Felicia D. Stewart Rabih Al‐Kaysi Jerald K. Rasmussen John A. Pojman 《Journal of polymer science. Part A, Polymer chemistry》2000,38(21):3984-3990
Quaternary ammonium persulfates as free‐radical initiators for high‐temperature polymerization are synthesized and their shelf‐life stability investigated. These initiators do not have gaseous byproducts and are therefore ideal for frontal polymerization, a process in which polymeric materials are produced via a thermal front that propagates through the unreacted monomer/initiator solution. Quaternary ammonium persulfate initiators offer additional qualities such as high solubility in organic media and low volatility, which are desirable for frontal polymerization. The initiators are synthesized using two procedures, and the initiating efficacy of the respective products is compared to a peroxide initiator in the frontal polymerization of 1,6‐hexanediol diacrylate. Of all the quartenary ammonium persulfates synthesized, tricaprylmethylammonium (Aliquat) persulfate (APSO) is the best initiator for frontal polymerization because it is soluble in organic media, is very reactive, and does not produce volatile byproducts under decomposition. A study of the decomposition kinetics of APSO is performed, and frontal polymerization is proposed as a quicker analytical technique to assay the purity. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3984–3990, 2000 相似文献
107.
108.
ZHU Sheng-Jiang J.H. Hamilton A.V. Ramayya J.K. Hwang J.O. Rasmussen Y. X. Luo K. Li WANG Jian-Guo CHE Xing-Lai DING Huai-Bo S. Frauendorf V. Dimitrov XU Qiang GU Long YANG Yun-Yi 《中国物理C(英文版)》2009,33(Z1)
High spin states in A ~ 110 neutron-rich 106Mo, 110Ru and 112Ru nuclei have been reinvestigated by measuring the prompt γ-rays from the spontaneous fission of 252Cf. Two similar sets of bands are observed to high spins in each of three nuclei. Through analyzing of characters of the band structures, the chiral doublet bands are suggested in 106Mo, 110Ru and 112Ru. 相似文献
109.
YANG Yun-Yi ZHU Sheng-Jiang J.H. Hamilton A.V. Ramayya J. K. Hwang J.O. Rasmussen Y.X. Luo K. Li DING Huai-Bo WANG Jian-Guo XU Qiang GU Long 《中国物理C(英文版)》2009,33(Z1)
High-spin states in neutron-rich 102Mo nucleus have been studied by measuring the prompt γ-rays in the spontaneous fission of 252Cf. The previous level scheme has been updated and some new levels and transitions are identified. The one-phonon γ-band is expanded and a band head level of the two-phonon γ-band is proposed. The systematic characteristics of yrast bands, one-phonon γ-bands, two-phonon γ-bands and quasi-particle bands in 102Mo, 104Mo and 106Mo are discussed. 相似文献
110.
ZHU Sheng-jiang DING Huai-bo J.H.Hamilton A.V.Ramayya CHE Xing-lai J.K.Hwang Y.X.Luo J.O.Rasmussen K.Li WANG Jian-guo XU Qiang GU Long YANG Yun-yi S.Frauendorf V.Dimitrov 《原子核物理评论》2009,26(Z1)
The level structures of neutron-rich ~(105)Mo,~(106)Mo,~(108)Mo and 110Ru nuclei in A≈100 region have been carefully investigated by coincidence measurements of the prompt γ-rays populated in the spontaneous fission of ~(252)Cf with the Gammasphere detector array.In 105Mo,one-phonon K =9/2 and two-phonon K=13/2 γ-vibrational bands have been identified.In ~(108)Mo,one-phonon γ-vibrational band is expanded and two-phonon γ-vibrational band has been identified.Two similar sets of bands in ~(106)Mo and ~(110)Ru are observed to high spins,which have been proposed as the soft chiral γ-vibrational bands.The characteristics for these γ-vibrational bands and chiral doublet bands have been discussed. 相似文献