全文获取类型
收费全文 | 2068篇 |
免费 | 102篇 |
国内免费 | 12篇 |
专业分类
化学 | 1444篇 |
晶体学 | 2篇 |
力学 | 61篇 |
数学 | 281篇 |
物理学 | 394篇 |
出版年
2023年 | 19篇 |
2022年 | 36篇 |
2021年 | 59篇 |
2020年 | 67篇 |
2019年 | 64篇 |
2018年 | 44篇 |
2017年 | 36篇 |
2016年 | 90篇 |
2015年 | 76篇 |
2014年 | 74篇 |
2013年 | 127篇 |
2012年 | 123篇 |
2011年 | 166篇 |
2010年 | 81篇 |
2009年 | 103篇 |
2008年 | 136篇 |
2007年 | 130篇 |
2006年 | 121篇 |
2005年 | 106篇 |
2004年 | 72篇 |
2003年 | 53篇 |
2002年 | 62篇 |
2001年 | 24篇 |
2000年 | 31篇 |
1999年 | 21篇 |
1998年 | 13篇 |
1997年 | 15篇 |
1996年 | 20篇 |
1995年 | 14篇 |
1994年 | 20篇 |
1993年 | 15篇 |
1992年 | 8篇 |
1991年 | 7篇 |
1990年 | 6篇 |
1989年 | 10篇 |
1988年 | 10篇 |
1987年 | 9篇 |
1986年 | 9篇 |
1985年 | 7篇 |
1984年 | 9篇 |
1981年 | 7篇 |
1979年 | 10篇 |
1976年 | 4篇 |
1975年 | 4篇 |
1973年 | 3篇 |
1942年 | 6篇 |
1940年 | 3篇 |
1931年 | 3篇 |
1912年 | 4篇 |
1896年 | 3篇 |
排序方式: 共有2182条查询结果,搜索用时 15 毫秒
41.
Fluorescence quenching of aromatic molecules by inorganic anions has been the subject of many investigations, yet the nature of the quenching mechanism is not fully understood. The fluorescence-quenching rate constants correlate with electrochemical data, but the radicals expected to form upon transfer of an electron to the excited aromatic molecules have escaped observation. We report the first observation of radical-ion species formed by electron-transfer quenching with inorganic anions in acetonitrile. A decisive step leading to formation of separated radical ions is the trapping of the primary charge-transfer complex by a second inorganic ion. 相似文献
42.
Ana C. D. Medeiros Lidiane P. Correia Mônica O. da S. Simões R. O. Macêdo 《Journal of Thermal Analysis and Calorimetry》2007,88(2):311-315
A number of disintegrants
are available on the market. They improve tablets’ disintegration. The
objective of this work is the comparison of the technological quality parameters
of disintegrants using different analytical techniques. Three batches of disintegrants
and their binary mixtures (water:disintegrants) were investigated. Cooling
experiments were used from –30 up to 200°C. The data obtained showed
calorimetric differences between the samples. In the binary mixtures water
showed different crystallization behaviour from the one found in the literature.
According to the results DSC technique helped the quality control of different
disintegrants. 相似文献
43.
A glassy carbon electrode was modified with an electropolymerized film of 1‐naphthylamine in aqueous solution. The electrocatalytic properties of this modified electrode (ME) were investigated using ascorbic acid (AA) as probe molecule. The electrochemical behavior of AA in buffer solution was examined by voltammetry and amperometry. The results showed that the ME exhibited good electrocatalytic activity towards the oxidation of AA, as a consequence, it can be used as amperometric sensor of this analyte in a flow injection system with good sensitivity. Calibration curves were linear over the concentration range 0.05–1.50 mM with a phosphate buffer solution pH 3 as the carrier, the detection limit was 1 ppm (S/N=3). The methods were applied to the determination of AA in beverages and pharmaceutical products. A good correlation with a reference method was attained. 相似文献
44.
The liquid membrane extraction (MX) and the solvent extraction (SX) of pertechnetate with Aliquat 336 as a carrier has been studied. From the results of SX the percentage of pertechnetate in the inner solution in experiment with LM was proposed. It has been found that the pertraction of pertechnetate depends on the inner solution used and the most effective solutions were those with ClO
4
–
and SCN–. Effects of the carrier concentration in membranes and outer phase composition have been studied too. The results of these experiments were kinetic curves with a minimum, which may be interpreted as a result of competing processes in the systems. 相似文献
45.
Alvarez-Lueje A Valenzuela C Squella JA Núñez-Vergara LJ 《Journal of AOAC International》2005,88(6):1631-1636
In this work, a liquid chromatography stability-indicating method was developed and applied to study the hydrolytic behavior of simvastatin in different pH values and temperatures. The selected chromatographic conditions were a C18 column; acetonitrile-28 mM phosphate buffer solution, pH 4 (65 + 35) as the mobile phase; 251 degrees C column temperature; and flow rate 1 mL/min. The developed method exhibited an adequate repeatability and reproducibility (coefficient of variation 0.54 and 0.74%, respectively) and a recovery higher than 98%. Furthermore, the detection and quantification limits were 9.1 x 10(-7) and 2.8 x 10(-6) M, respectively. The degradation of simvastatin fitted to pseudo-first order kinetics. The degradation was pH dependent, being much higher at alkaline pH than at acid pH. Activation energy, kinetic rate constants (k) at different temperatures, the half life (t1/2) and the time for 10% degradation to occur (t90) values are also reported. 相似文献
46.
Barluenga J Fernández MA Aznar F Valdés C 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(8):2276-2283
A novel approach for the synthesis of the important indole ring is described. Indoles are obtained from o-bromoanilines and alkenyl halides in a Pd-catalyzed cascade process that involves an alkenyl amination followed by an intramolecular Heck reaction. The overall process represents the first example of the participation of alkenyl amination reactions in Pd-catalyzed cascade reactions. Initially, the relative reactivity of aryl and alkenyl bromides and chlorides towards Pd-catalyzed amination was investigated. Competition experiments were carried out in the presence of primary and secondary amines, and these revealed the reactivity order alkenyl bromides > aryl bromides > alkenyl chlorides > aryl chlorides, as well as very high chemoselectivity; the more reactive halide was always favored. Thereafter, optimized reaction conditions for the sequential alkenyl amination/Heck cyclization to give indoles were investigated with the model reaction of o-bromoaniline with alpha-bromostyrene. An extensive screening of ligands, bases, and reaction conditions revealed that the [Pd2(dba)3]/DavePhos, NaOtBu, toluene combination at 100 degrees C were the optimized reaction conditions to carry out the cascade process (dba=dibenzylideneacetone, DavePhos=2-dicyclohexylphosphino-2'-N,N-dimethylaminobiphenyl). The reaction proceeds with aryl, alkyl, and functionalized substitutents in both starting reactants. The cyclization was also studied with N-substituted o-bromoanilines (which would give rise to N-substituted indoles); however, in this case, indole formation occurred only with 1-substituted-2-bromoalkenes. Finally, the application of this methodology to o-chloroanilines required further optimization. Although the catalyst based on DavePhos failed to promote the cascade process, a catalytic combination based on [Pd2(dba)3]/X-Phos promoted the formation of the indole ring also from the less reactive chloroanilines. 相似文献
47.
Crespo A Martí MA Estrin DA Roitberg AE 《Journal of the American Chemical Society》2005,127(19):6940-6941
A novel technique for computing free energy profiles in enzymatic reactions using the multiple steering molecular dynamics approach in the context of an efficient QM-MM density functional scheme is presented. The conversion reaction of chorismate to prephenate catalyzed by the Bacillus subtilis enzyme chorismate mutase has been chosen as an illustrative example. 相似文献
48.
M. Bouby H. J. Mac Cordick I. Billard 《Journal of Radioanalytical and Nuclear Chemistry》1996,210(1):161-169
The properties of mobile, 5% w/w cell suspensions ofMycobacterium phlei have been examined for their capacity to adsorb and retain uranyl(VI) and neptuny(V) cations from nitrate-buffered solutions at pH 1. Equilibrium conditions of sorption were attained after 3 hours for concentrations (C) in the range 0.015–18 mM cation and indicated a maximum specific adsorption capacity (Qe
max) of 182 mol/g dry biomass forC10 mM. NpO
2
+
generally showed higherQe values than UO
2
2+
at corresponding concentrations. Lixiviation tests with cation-loaded biomass in neutral and acidic media indicated that the extent of desorption did not vary extensively between pH 7 and pH 1 and did not exceed 3% for U and 1% for Np ions at pH 7 during 7-day periods of treatment. Analogous experiments with U-loaded biomass subjected to neutron activation prior to lixiviation enabled retention measurements for various fission-product isotopes produced in situ and showed that retention of239Np formed within the cellular matrix was >99% at pH 7 and 94% at pH 1. 相似文献
49.
Mercedes de Frutos Alejandro Cifuentes Jose Carlos Diez-Masa 《Journal of separation science》1997,20(1):29-33
The behavior of bovine whey proteins in Reversed-Phase High Performance Liquid Chromatography (RP-HPLC) systems has been investigated. The Linear Solvent Strength (LSS) model has been applied to the separation of these proteins studying how their retention time and band broadening change when different gradient parameters are modified. From our results it is deduced that the LSS model describes the behaviour of the whey proteins in RP-HPLC. Also, it seems that ts (the retention time for non-retained solutes) depends on the size of these proteins. The good fit observed between experimental data and the equations deduced from the LSS model allows the prediction of a gradient shape that permits a rapid analysis of the above mentioned proteins. 相似文献
50.
New physically adsorbed polymer coating for reproducible separations of basic and acidic proteins by capillary electrophoresis 总被引:1,自引:0,他引:1
In this work, a new physically adsorbed coating for capillary electrophoresis (CE) is presented. The coating is based on a N,N-dimethylacrylamide-ethylpyrrolidine methacrylate (DMA-EPyM) copolymer synthesized in our laboratory. The capillary coating is simple and easy to obtain as only requires flushing the capillary with a polymer aqueous solution for 2 min. It is shown that by using these coated capillaries the electrostatic adsorption of a group of basic proteins onto the capillary wall is significantly reduced allowing their analysis by CE. Moreover, the DMA-EPyM coating provides reproducible separations of the basic proteins with RSD values for migration times lower than 0.75% for the same day (n = 5) and lower than 3.90% for three different days (n = 15). Interestingly, the electrical charge of the coated capillary wall can be modulated by varying the pH of the running buffer which makes possible the analysis of basic and acidic proteins in the same capillary. The usefulness of this coating is further demonstrated via the reproducible separation of whey (i.e. acidic) proteins from raw milk. The coating protocol should be compatible with both CE in microchips and CE-MS of different types of proteins. 相似文献