全文获取类型
收费全文 | 626篇 |
免费 | 10篇 |
国内免费 | 4篇 |
专业分类
化学 | 514篇 |
晶体学 | 8篇 |
力学 | 12篇 |
数学 | 12篇 |
物理学 | 94篇 |
出版年
2019年 | 5篇 |
2018年 | 4篇 |
2016年 | 7篇 |
2015年 | 7篇 |
2014年 | 13篇 |
2013年 | 27篇 |
2012年 | 22篇 |
2011年 | 28篇 |
2010年 | 30篇 |
2009年 | 18篇 |
2008年 | 32篇 |
2007年 | 31篇 |
2006年 | 34篇 |
2005年 | 29篇 |
2004年 | 35篇 |
2003年 | 26篇 |
2002年 | 32篇 |
2001年 | 13篇 |
2000年 | 9篇 |
1999年 | 13篇 |
1998年 | 6篇 |
1997年 | 3篇 |
1996年 | 3篇 |
1995年 | 3篇 |
1994年 | 11篇 |
1993年 | 5篇 |
1992年 | 5篇 |
1991年 | 3篇 |
1990年 | 8篇 |
1989年 | 6篇 |
1987年 | 3篇 |
1986年 | 5篇 |
1985年 | 19篇 |
1984年 | 13篇 |
1983年 | 6篇 |
1982年 | 9篇 |
1981年 | 13篇 |
1980年 | 13篇 |
1979年 | 7篇 |
1978年 | 10篇 |
1977年 | 6篇 |
1976年 | 6篇 |
1975年 | 7篇 |
1974年 | 12篇 |
1973年 | 14篇 |
1972年 | 4篇 |
1971年 | 4篇 |
1970年 | 6篇 |
1967年 | 3篇 |
1966年 | 2篇 |
排序方式: 共有640条查询结果,搜索用时 0 毫秒
61.
[see reaction]. A new triphase catalyst has been developed. When an aqueous solution of H3PW12O40 (1) was added to a solution of the amphiphilic chain copolymer 2, a new self-assembled and macroporous complex 3 was formed. This complex was effective as a catalyst in the epoxidation of allylic alcohols. Even in the use of 2.7 x 10(-5) mole equiv of the catalyst, the epoxidation with aqueous H2O2 proceeded without organic solvents to give the corresponding epoxy alcohols in high yields. 相似文献
62.
Bose fluids restricted in one dimension (1D) are realized by adsorbing 4He atoms on the 1D pore walls with a diameter of about 18 A. The Bose fluid appears above an adsorbed amount after the pore walls are coated with the inert 4He atoms. Heat capacity of the fluid was observed to have a temperature-linear term at low temperatures. This corresponds to the phonon heat capacity of the Bose fluid in the 1D pores. We estimate the phonon velocity and the interaction of the 1D Bose fluid. 相似文献
63.
Motokawa M Kobayashi H Ishizuka N Minakuchi H Nakanishi K Jinnai H Hosoya K Ikegami T Tanaka N 《Journal of chromatography. A》2002,961(1):53-63
Reduction of through-pore size and skeleton size of a monolithic silica column was attempted to provide high separation efficiency in a short time. Monolithic silica columns were prepared to have various sizes of skeletons (approximately 1-2 microm) and through-pores (approximately 2-8 microm) in a fused-silica capillary (50-200 microm I.D.). The columns were evaluated in HPLC after derivatization to C18 phase. It was possible to prepare monolithic silica structures in capillaries of up to 200 microm I.D. from a mixture of tetramethoxysilane and methyltrimethoxysilane. As expected, a monolithic silica column with smaller domain size showed higher column efficiency and higher pressure drop. High external porosity (> 80%) and large through-pores resulted in high permeability (K = 8 x 10(-14) -1.3 x 10(-12) m2) that was 2-30 times higher than that of a column packed with 5-mirom silica particles. The monolithic silica columns prepared in capillaries produced a plate height of about 8-12 microm with an 80% aqueous acetonitrile mobile phase at a linear velocity of 1 mm/s. Separation impedance, E, was found to be as low as 100 under optimum conditions, a value about an order of magnitude lower than reported for conventional columns packed with 5-microm particles. Although a column with smaller domain size generally resulted in higher separation impedance and the lower total performance, the monolithic silica columns showed performance beyond the limit of conventional particle-packed columns under pressure-driven conditions. 相似文献
64.
Loftus N Miseki K Iida J Gika HG Theodoridis G Wilson ID 《Rapid communications in mass spectrometry : RCM》2008,22(16):2547-2554
High mass accuracy electrospray ionisation multistage tandem mass spectrometry (MS(n)) was applied to metabolite profiling studies on plasma samples derived from two strains of rat (the Zucker (fa/fa) obese strain and the normal wild type). Using a quadrupole ion trap time-of-flight (QIT-TOF) mass spectrometer, metabolite profiling software was applied to locate components of biological significance that could account for the differences between the two strains of rat and a formula prediction software tool was used to help identify individual components. The primary factor discriminating between the two populations was the concentration of endogenous lipids. In the Zucker (fa/fa) obese strain, the dominant ion signals and MS(n) spectra were in agreement with lysoglycerophosphocholine components such as palmitoyllysophosphatidylcholine, 1-oleoylglycerophosphocholine, 1-octadecyl-sn-glycero-3-phosphocholine and 1-stearoylglycerophosphocholine and these were found in relatively higher concentrations compared to the normal wild type. Components were identified using high mass accuracy MS(n) data, formula prediction software and by agreement with published mass spectra through internet databases, rather than using a conventional approach with authentic standards. This application shows that the use of high mass accuracy electrospray ionisation MS(n) together with a software tool can be used effectively to detect and characterise unknown analytes in complex matrices, and represents a promising approach for future profiling studies. 相似文献
65.
66.
67.
68.
69.
Yoichiro Hoshina Satoru Ikegami Kyoko Fujimoto Akihiko Okuyama Tatsuhiro Harada Susan James Peter G. Griffiths Zemin Wu Michael Lilly Andrew M. Bray 《Tetrahedron letters》2005,46(52):9035-9038
2,3-Diphenylpropionic acid library for VLA-4 antagonist was synthesized on solid-phase. Comparison of the two synthetic routes via an orthogonal generation of two aromatic amino functional groups are discussed. From this work, several compounds were identified as potent VLA-4 antagonists. 相似文献
70.
Frans C. Mijlhoff Gerrit H. Renes Kunio Kohata Kazuko Oyanagi Kozo Kuchitsu 《Journal of Molecular Structure》1977,39(2):241-252
The structure of 1,1-difluoroethylene was determined, from gas phase electron diffraction data obtained independently in Leiden and Tokyo and the rotational constants of F2CCH2, F2CCHD and F2CCD2 derived from the microwave study by Chauffoureaux. The two electron diffraction data agreed without significant discrepancy. From a joint least squares analysis of the diffraction and microwave data, the following rg bond distances and rz bond angles were derived: CC = 1.340 ± 0.006 Å, C-F = 1.315 ± 0.003 Å, C-H = 1.091 ± 0.010 Å, ∠C-C-F = 124.7 ± 0.3°, ∠C-C-H = 119.0 ± 0.4°, where the uncertainties represent estimated limits of error. 相似文献