全文获取类型
收费全文 | 1301篇 |
免费 | 24篇 |
专业分类
化学 | 714篇 |
晶体学 | 22篇 |
力学 | 11篇 |
数学 | 195篇 |
物理学 | 383篇 |
出版年
2021年 | 11篇 |
2020年 | 10篇 |
2019年 | 18篇 |
2018年 | 44篇 |
2017年 | 30篇 |
2016年 | 64篇 |
2015年 | 43篇 |
2014年 | 52篇 |
2013年 | 138篇 |
2012年 | 39篇 |
2011年 | 76篇 |
2010年 | 50篇 |
2009年 | 47篇 |
2008年 | 64篇 |
2007年 | 49篇 |
2006年 | 44篇 |
2005年 | 42篇 |
2004年 | 47篇 |
2003年 | 47篇 |
2002年 | 27篇 |
2001年 | 36篇 |
2000年 | 20篇 |
1999年 | 17篇 |
1998年 | 19篇 |
1997年 | 20篇 |
1996年 | 12篇 |
1995年 | 14篇 |
1994年 | 8篇 |
1993年 | 12篇 |
1992年 | 13篇 |
1991年 | 10篇 |
1990年 | 10篇 |
1989年 | 10篇 |
1988年 | 8篇 |
1987年 | 17篇 |
1986年 | 9篇 |
1985年 | 10篇 |
1984年 | 15篇 |
1983年 | 6篇 |
1982年 | 12篇 |
1981年 | 14篇 |
1980年 | 13篇 |
1979年 | 9篇 |
1978年 | 5篇 |
1977年 | 6篇 |
1975年 | 5篇 |
1973年 | 5篇 |
1972年 | 4篇 |
1929年 | 5篇 |
1927年 | 5篇 |
排序方式: 共有1325条查询结果,搜索用时 15 毫秒
71.
Robert Piech Bogusław Baś 《International journal of environmental analytical chemistry》2013,93(5):410-420
Simple cyclic renewable silver amalgam film electrode (Hg(Ag)FE), applied for the determination of gallium(III) using differential pulse anodic stripping voltammetry (DP ASV), is presented. The effects of various factors such as: preconcentration potential and time, pulse height, step potential and supporting electrolyte composition are optimised. The calibration graph is linear from 5?nM (0.35?µg?L?1) to 80?nM (5.6?µg?L?1) for a preconcentration time of 60?s, with correlation coefficient of 0.995. For a Hg(Ag)FE with a surface area of 9.9?mm2 the detection limit for a preconcentration time of 120?s is as low as 0.1?µg?L?1. The repeatability of the method at a concentration level of the analyte as low as 3.5?µg?L?1, expressed as RSD is 3.2% (n?=?5). The proposed method was successfully applied by studying the synthetic samples and simultaneously recovery of Ga(III) from spiked aluminium samples. 相似文献
72.
Thien Y Vu Prof. Anna Chrostowska Prof. Thi Kieu Xuan Huynh Prof. Saïd Khayar Prof. Alain Dargelos Katarzyna Justyna Dr. Beata Pasternak Prof. Stanisław Leśniak Prof. Curt Wentrup 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(44):14983-14988
Thermal reactions of N‐benzylidene‐ and N‐(2‐pyridylmethylidene)‐tert‐butylamines ( 5 and 13 ) under FVT conditions have been investigated. Unexpectedly, at 800 °C, compound 5 yields 1,2‐dimethylindole and 3‐methylisoquinoline. In the reaction of 13 at 800 °C, 3‐methylimidazo[1,5‐a]pyridine was obtained as the major product. Mechanisms of these reactions have been proposed on the basis of DFT calculations. Furthermore, UV‐photoelectron spectroscopy combined with FVT has been applied for direct monitoring and characterization of the thermolysis products in situ. 相似文献
73.
Dr. Jacek Cieślak Dr. Cristina Ausín Dr. Andrzej Grajkowski Dr. Serge L. Beaucage 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(14):4623-4632
The reaction of 2‐cyano‐2‐methyl propanal with 2′‐O‐aminooxymethylribonucleosides leads to stable and yet reversible 2′‐O‐(2‐cyano‐2,2‐dimethylethanimine‐N‐oxymethyl)ribonucleosides. Following N‐protection of the nucleobases, 5′‐dimethoxytritylation and 3′‐phosphitylation, the resulting 2′‐protected ribonucleoside phosphoramidite monomers are employed in the solid‐phase synthesis of three chimeric RNA sequences, each differing in their ratios of purine/pyrimidine. When the activation of phosphoramidite monomers is performed in the presence of 5‐benzylthio‐1H‐tetrazole, coupling efficiencies averaging 99 % are obtained within 180 s. Upon completion of the RNA‐chain assemblies, removal of the nucleobase and phosphate protecting groups and release of the sequences from the solid support are carried out under standard basic conditions, whereas the cleavage of 2′‐O‐(2‐cyano‐2,2‐dimethylethanimine‐N‐oxymethyl) protective groups is effected (without releasing RNA alkylating side‐products) by treatment with tetra‐n‐butylammonium fluoride (0.5 m) in dry DMSO over a period of 24–48 h at 55 °C. Characterization of the fully deprotected RNA sequences by polyacrylamide gel electrophoresis (PAGE), enzymatic hydrolysis, and matrix‐assisted laser desorption/ionization (MALDI) mass spectrometry confirmed the identity and quality of these sequences. Thus, the use of 2′‐O‐aminooxymethylribonucleosides in the design of new 2′‐hydroxyl protecting groups is a powerful approach to the development of a straightforward, efficient, and cost‐effective method for the chemical synthesis of high‐quality RNA sequences in the framework of RNA interference applications. 相似文献
74.
75.
76.
A simple method for the synthesis of sugar-derived imines by a Schwartz's reagent reduction of easily available sugar lactams has been described. A direct addition of nucleophiles to the generated in situ cyclic imines and subsequent deprotection of hydroxyl function allows to convert sugar lactams in polyhydroxylated pyrrolidines and piperidines. 相似文献
77.
The t–J model is analysed in the limit of strong anisotropy, where the transverse components of electron spin are neglected. We propose a slave-particle-type approach that is valid, in contradiction to many of the standard approaches, in the low-doping regime and becomes exact for a half-filled system. We describe an effective method that allows to numerically study the system with the no-double-occupancy constraint rigorously taken into account at each lattice site. Then, we use this approach to demonstrate the destruction of the antiferromagnetic order by increasing the doping and formation of Nagaoka polarons in the strong interaction regime. 相似文献
78.
Ewa Ostrowska-Ligęza Ewa Jakubczyk Agata Górska Magdalena Wirkowska Joanna Bryś 《Journal of Thermal Analysis and Calorimetry》2014,118(2):911-918
The influence of adverse conditions of environment in the case of baby formulas, which are multiple mixtures, should be minimised. Water activity (a w) and moisture content, correlated through sorption isotherms, and glass transition temperature have been considered relevant parameters to describe food stability. The aim of the study was to analyse water activity and glass transition temperature as the function of water content for samples of baby formulas. Three types of baby formulas (mixture, agglomerate, coated agglomerate) were determined by sorption isotherms, DSC and MDSC. DSC curves of mixture, agglomerate and coated agglomerate did not show differences in shape and course. The glass transition temperature of powders stored at different water activities was measured and it decreased with the increase in moisture content, confirming the strong plasticising effect of water on this property. Critical water activities varied from 0.14 to 0.68 and critical moisture contents varied from 0.032 to 0.062 g g?1 powder. 相似文献
79.
Łukasz Wiśniewski Katarína Vaňková Pavel Ačai Milan Polakovič 《Chemical Papers》2014,68(12):1649-1655
Galacto-oligosaccharides are typically produced by an enzymatic reaction when the post-reaction mixture contains considerable amounts of lactose and glucose and a smaller amount of galactose. In order to develop a process of chromatographic removal of saccharide impurities, adsorption equilibria and kinetics of these di- and monosaccharides were investigated for Diaion UBK 530, an industrialgrade strong cation-exchanger in the Na+ form. Frontal chromatographic experiments were carried out in the temperature range of 30–70°C and a broad interval of saccharide concentrations up to 350 g L?1. Breakthrough curves were described using the equilibrium-dispersive model with the linear adsorption isotherm. Both the distribution and the axial dispersion coefficient values depended on the saccharide molecule type and size. No significant effect of temperature or concentration on the distribution coefficient was observed. The apparent dispersion coefficients of all saccharides exhibited some decrease with the temperature, which was caused by the decrease of the intraparticle mass transfer resistance. An analysis showed that both the intraparticle mass transfer and the axial dispersion had a significant influence on the front dispersion. 相似文献
80.
Denis Mashkovtsev Wataru Mizukami Jacek Korchowiec Anna Stachowicz-Kuśnierz Yuriko Aoki 《Journal of computational chemistry》2020,41(25):2203-2212
The elongation method with intermediate mechanical and electrostatic embedding (ELG-IMEE) is proposed. The electrostatic embedding uses atomic charges generated by a charge sensitivity analysis (CSA) method and parameterized for three different population analyses, namely, the Merz–Singh–Kollman scheme, the charge model 5, and the atomic polar tensor. The obtained CSA models were tested on two model systems. Test calculations show that the electrostatic embedding provides several times of decrease in the difference of energies of testing and reference calculations in comparison with the conventional elongation approach (ELG). The mechanical embedding is implemented in a combination of the conventional elongation method and the ONIOM approach. Moreover, it was demonstrated that the geometry optimization with the ELG-IMEE reduces the errors in the optimized structures by about one order in root-mean-square deviation, when compared to ELG. 相似文献