全文获取类型
收费全文 | 666篇 |
免费 | 8篇 |
国内免费 | 1篇 |
专业分类
化学 | 398篇 |
晶体学 | 1篇 |
力学 | 10篇 |
数学 | 51篇 |
物理学 | 215篇 |
出版年
2020年 | 5篇 |
2019年 | 5篇 |
2017年 | 8篇 |
2016年 | 7篇 |
2014年 | 6篇 |
2013年 | 16篇 |
2012年 | 21篇 |
2011年 | 25篇 |
2010年 | 12篇 |
2009年 | 5篇 |
2008年 | 13篇 |
2007年 | 16篇 |
2006年 | 24篇 |
2005年 | 18篇 |
2004年 | 20篇 |
2003年 | 12篇 |
2002年 | 21篇 |
2001年 | 21篇 |
2000年 | 15篇 |
1999年 | 16篇 |
1998年 | 10篇 |
1997年 | 8篇 |
1996年 | 20篇 |
1995年 | 10篇 |
1994年 | 10篇 |
1993年 | 15篇 |
1992年 | 18篇 |
1991年 | 13篇 |
1990年 | 9篇 |
1989年 | 5篇 |
1988年 | 7篇 |
1987年 | 6篇 |
1986年 | 13篇 |
1985年 | 15篇 |
1984年 | 17篇 |
1983年 | 8篇 |
1982年 | 13篇 |
1981年 | 14篇 |
1980年 | 13篇 |
1979年 | 15篇 |
1978年 | 20篇 |
1977年 | 19篇 |
1976年 | 17篇 |
1975年 | 9篇 |
1974年 | 8篇 |
1973年 | 15篇 |
1972年 | 6篇 |
1969年 | 5篇 |
1968年 | 5篇 |
1894年 | 5篇 |
排序方式: 共有675条查询结果,搜索用时 15 毫秒
181.
With a variety of electrophilic reagents reaction occurs exclusively at the CH3Sn bonds of [(CH3)3Sn]4C and [(CH3)3Sn]3CH. While the inner SnC bonds remain intact, methyl groups may be progressively cleaved off, one from each of the trimethylstannyl groups; in the case of bromine a second Me group may be cleaved from each of the SnMe2Br groups. The various products were identified by 1H, 13C and 119Sn NMR spectroscopy. 相似文献
182.
W. H. Wells 《Fiber and Integrated Optics》1978,1(3):243-287
Full-duplex communications in a single optical fiber is both feasible and practical in certain applications. The main problem is crosstalk between the two directions. This paper reviews the sources of crosstalk, gives its magnitude, and describes techniques to reduce crosstalk. An example is a system that requires 75 optical dB of isolation between transmitted and received signals at each terminal. There are two sources of optical crosstalk. The first occurs in components such as couplers and connectors and can be held below 50 dB by careful design. The second is Rayleigh scattering within the fiber, which increases system noise as well as crosstalk between counterdirectional signals. 相似文献
183.
Measurement of bumetanide in plasma and urine by high-performance liquid chromatography and application to bumetanide disposition. 总被引:2,自引:0,他引:2
A high-performance liquid chromatographic method for the measurement of bumetanide in plasma and urine is described. Following precipitation of proteins with acetonitrile, bumetanide was extracted from plasma or urine on a 1-ml bonded-phase C18 column and eluted with acetonitrile. Piretanide dissolved in methanol was used as the internal standard. A C18 Radial Pak column and fluorescence detection (excitation wavelength 228 nm; emission wavelength 418 nm) were used. The mobile phase consisted of methanol-water-glacial acetic acid (66:34:1, v/v) delivered isocratically at a flow-rate of 1.2 ml/min. The lower limit of detection for this method was 5 ng/ml using 0.2 ml of plasma or urine. Nafcillin, but not other semi-synthetic penicillins, was the only commonly used drug that interfered with this assay. No interference from endogenous compounds was detected. For plasma, the inter-assay coefficients of variation of the method were 7.6 and 4.4% for samples containing 10 and 250 ng/ml bumetanide, respectively. The inter-assay coefficients of variation for urine samples containing 10 and 2000 ng/ml were 8.1 and 5.7%, respectively. The calibration curve was linear over the range 5-2000 ng/ml. 相似文献
184.
Five polybrominated oxydiphenol derivatives have been isolated from various Great Barrier Reef collections and one Fijian collection of the sponge Dysidea herbacea: 3,4',5,6,6'-hexabromo-2, 2'-oxydiphenol (11), 3,4',5,6,6'-pentabromo-2,2'-oxydiphenol (12), 3.4',5,6,6'-pentabromo-2,2'-oxydiphenol 1-methyl ether (13), 3,4,4',5,6'-pentabromo-2,2'-oxydiphenol 1,1'-dimethyl ether (14) and 3,4',5,6'-tetrabromo-2,2'-oxydiphenol 1'-methyl ether (15).The structure of the first member of this series is determined by a new method involving 13C spin-lattice relaxation data. The contributions of nearby hydrogens to quaternary carbon spin-lattice relaxation times are calculated for various possible structures and compared with the experimental data, leading to an unequivocal proof of structure. The structures of the remaining compounds in the series are established principally by analysis of 13C chemical shifts and 13C-1H coupling constants. 相似文献
185.
Analyses of fatty acid (FA) composition in freshwater fishes promote understanding of the potential relationship between fish health or human nutrition and specific FAs. Therefore, the chemical identity of FAs in endemic fishes must be established. Paddlefish, sauger, and white bass were collected from the Ohio River. The structural identification of esterified FAs from fish-fillet lipids was conducted using gas chromatography-mass spectrometry (GC-MS). The same 13 FAs, composing more than 90% of the mass of FAs extracted by techniques used in this research, were found in all three species examined. Carbon chain length and degree and position of unsaturation were determined from the characteristic ionization and fragmentation of FA methyl esters (FAMEs) resulting from GC-MS electron impact (EI) and chemical ionization (CI) modes. Assignment of structure to the extracted FAs required complementary interpretation of both EI and CI MS. The EI spectra observed substantiate findings reported in the literature. The novelty of this research is in the thorough interpretation of CI spectra for which less data are available. The observations reported for analyses of fishes will be useful to all researchers studying FAs regardless of sample media. 相似文献
186.
The adsorption of Cd(II) and Co(II) onto goethite was measured at five temperatures between 10 and 70 degrees C. For both cations the amount adsorbed at any given pH increased as the temperature was increased. Cd(II) adsorbed at a slightly lower pH at each temperature than Co(II). Adsorption isotherms at pH 7.00 for Cd(II) could be fitted closely by a simple Langmuir model, but a two-site Langmuir model was needed for Co(II). Potentiometric titrations of goethite suspensions in the presence and absence of added cation could be modeled closely by a constant-capacitance surface complexation model that assumed the adsorption reactions M2+ + SOH ⇋ SOM+ + H+ and M2+ + SOH + H2O ⇋ SOMOH + 2H+, where M represents Cd or Co. This model also fitted the experimental data from the adsorption edge and adsorption isotherm experiments. Thermodynamic parameters estimated from both Langmuir and surface complexation models showed that the adsorption of both metals was endothermic. Values obtained for the adsorption enthalpies from both modeling schemes were similar for both cations. Estimates of the adsorption entropies were model-dependent: Langmuir parameters yielded positive entropies, while some of the surface complexation parameters generated negative adsorption entropies. Copyright 1999 Academic Press. 相似文献
187.
Application of pressurized liquid extraction technology to pharmaceutical solid dosage form analysis
Hoang TH Farkas R Wells C McClintock S Di Maso M 《Journal of chromatography. A》2002,968(1-2):257-261
The technique of pressurized liquid extraction has been evaluated for the extraction of active ingredients from pharmaceutical dosage forms using montelukast sodium oral chewable tablets as a model. The extraction method was optimized for the number of extraction cycles, extraction time, extraction solvent composition and temperature. Samples were extracted using two cycles of water for 2 min with a cell temperature of 40 degrees C and a pressure of 1.0 x 10(4) kPa, to disintegrate the tablet, followed by three cycles of methanol for 3 min at 70 degrees C and 1.0 x 10(4) kPa, to solubilize montelukast sodium. The method demonstrated an extraction efficiency of 98.2% of label claim and an RSD of 1.3% (n=10), as compared to 97.6% and an RSD of 0.9% obtained using a validated mechanical extraction method. 相似文献
188.
The reaction of the molecular transition metal iodate, Cs[CrO(3)(IO(3))], with UO(3) under mild hydrothermal conditions provides access to a new low-dimensional, mixed-metal U(VI) compound, Cs(2)[(UO(2))(CrO(4))(IO(3))(2)] (1). The structure of 1 is quite unusual and consists of one-dimensional (1)(infinity)[(UO(2))(CrO(4))(IO(3))(2)](2-) ribbons separated by Cs(+) cations. These ribbons are formed from [UO(7)] pentagonal bipyramids that contain a uranyl core, [CrO(4)] tetrahedra, and both monodentate and bridging iodate anions. Crystallographic data: 1, monoclinic, space group P2(1)/n, a = 7.3929(5) A, b = 8.1346(6) A, c = 22.126(2) A, beta = 90.647(1) degrees, Z = 4 (T = 193 K). 相似文献
189.
Rates of solvolysis of the complex cation [Co(4tBupy)4Cl2]+ have been determined in mixtures of water with the hydrophobic solvent, t-butyl alcohol. The solvent composition at which the extremum is found in the variation of the enthalpy H* and the entropy S* of activation correlates well with the extremum in the variation of the relative partial molar volume of t-butyl alcohol in the mixture and the straight line found for the variation of H* with S* is coincident with the same plot for water + 2-propanol mixtures. A free energy cycle is applied to the process initial state (C
n+) going to the transition state [M(n+1)+...Cl–] in water and in the mixture using free energies of transfer of the individual ionic species, G
t
o
(i), from water into the mixture. Values for G
t
o
(i) are derived from the solvent sorting method and from the TATB/TPTB method: using data from either method, changes in solvent structure on going from water into the mixture are found to stabilize the cation in the transition state, M(n+1)+, more than in the initial state, C
n+. This is compared with the application of the free energy cycle to the solvolysis of complexes [Co(Rpy)4Cl2]+ and [Coen2LCl]+ in mixtures of water with methanol, 2-propanol or t-butyl alcohol: the above conclusion regarding the relative stabilization of the cations holds for all these complexes in their solvolyses in water+alcohol mixtures using values of G
t
o
(Cl–) from either source. 相似文献
190.
Summary The kinetics of the solvolysis of the ions [Co(NH3)5Cl]2+ and [Co(CN)5Cl]3– have been investigated in a range of water-rich mixtures of water with n-PrOH at various temperatures. The variation of the enthalpies and entropies of activation with solvent composition show extrema in composition ranges where the physical properties of the mixtures, influenced by changes in solvent structure, also show extrema. From the application of a free energy cycle to the process of the initial state going to the transition state, it is concluded for the solvolyses of both complexes that the species of CoIII in the transition state is more stable in water + n-PrOH mixtures than the ionic complexes of CoIII in the initial state. The results are compared with those for the solvolysis of these and related complexes in mixtures of water with other alcohols. 相似文献