全文获取类型
收费全文 | 989篇 |
免费 | 80篇 |
国内免费 | 123篇 |
专业分类
化学 | 1084篇 |
晶体学 | 6篇 |
力学 | 2篇 |
综合类 | 11篇 |
数学 | 8篇 |
物理学 | 81篇 |
出版年
2024年 | 1篇 |
2023年 | 28篇 |
2022年 | 45篇 |
2021年 | 110篇 |
2020年 | 70篇 |
2019年 | 42篇 |
2018年 | 38篇 |
2017年 | 33篇 |
2016年 | 62篇 |
2015年 | 45篇 |
2014年 | 51篇 |
2013年 | 72篇 |
2012年 | 62篇 |
2011年 | 52篇 |
2010年 | 36篇 |
2009年 | 44篇 |
2008年 | 41篇 |
2007年 | 29篇 |
2006年 | 53篇 |
2005年 | 36篇 |
2004年 | 31篇 |
2003年 | 33篇 |
2002年 | 20篇 |
2001年 | 14篇 |
2000年 | 20篇 |
1999年 | 19篇 |
1998年 | 16篇 |
1997年 | 17篇 |
1996年 | 10篇 |
1995年 | 12篇 |
1994年 | 9篇 |
1993年 | 8篇 |
1992年 | 10篇 |
1991年 | 9篇 |
1990年 | 2篇 |
1989年 | 3篇 |
1988年 | 2篇 |
1987年 | 1篇 |
1986年 | 2篇 |
1985年 | 2篇 |
1984年 | 1篇 |
1982年 | 1篇 |
排序方式: 共有1192条查询结果,搜索用时 31 毫秒
11.
Lionel Joucla Florence Popowycz Olivier Lozach Laurent Meijer Benoît Joseph 《Helvetica chimica acta》2007,90(4):753-763
The syntheses of paullone ( 1a ) and three paullone derivatives, including a sulfur analogue ( 2a ), a tricyclic derivative ( 2b ), and a ring‐enlarged variant ( 2c ), are described, Pd‐catalyzed intramolecular Heck reaction being the key step. The kinase‐inhibitory properties of the novel paullone analogues were investigated. 相似文献
12.
离子表面活性剂胶团对阿斯匹林碱水解反应的影响 总被引:3,自引:0,他引:3
离子表面活性剂胶团对阿斯匹林碱水解反应的影响史振民*刘生昆张祝莲巩育军(延安大学化学系延安716000)关键词表面活性剂,阿斯匹林,碱水解反应,胶团,抑制作用1996-05-04收稿,1996-08-12修回阿斯匹林(ASP),学名为乙酰水杨酸,有较... 相似文献
13.
Allison K. O'Brien Neil B. Cramer Christopher N. Bowman 《Journal of polymer science. Part A, Polymer chemistry》2006,44(6):2007-2014
The overall effects of oxygen on thiol–acrylate photopolymerizations were characterized. Specially, the choice of thiol monomer chemistry, functionality, and concentration on the extent of oxygen inhibition were considered. As thiol concentration was increased, the degree of oxygen inhibition was greatly reduced because of chain transfer from the peroxy radical to the thiol. When comparing the copolymerization of 1,6‐hexanediol diacrylate with the alkane‐based thiol (1,6‐hexane dithiol) to the copolymerization with the propionate thiol (glycol dimercaptopropionate), it was found that the propionate system was much more reactive and polymerized to a greater extent in the presence of oxygen. In addition, the functionality was considered where the glycol dimercaptopropionate was compared to a tetrafunctional propionate of similar chemistry (pentaerythritol tetrakis(mercaptopropionate)). Given the same thiol concentration, the higher functionality thiol imparted a faster polymerization rate, due to the increased polymer system viscosity, which limited oxygen diffusion and decreased the extent of overall oxygen inhibition. Thus, preliminary insight is provided into how thiol monomer choice affects the extent of oxygen inhibition in thiol–acrylate photopolymerization. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2007–2014, 2006 相似文献
14.
The corrosion inhibition of 1-(2-pyridylazo)-2-naphthol (PAR) on the corrosion of cold rolled steel in 0.5 M sulfuric acid (H2SO4) was studied using weight loss method and potentiodynamic polarization method. Results obtained revealed that together with chloride ion, PAR is an effective corrosion inhibitor for steel corrosion in sulfuric acid. It was found that for steel corrosion inhibition in the presence of single PAR in sulfuric acid the Temkin adsorption isotherm may be used to explain the adsorption phenomenon. For the mixture of PAR and NaCl used as corrosion inhibitor, however, the Langmuir adsorption isotherm can be used to satisfactorily elucidate the adsorption of mixture of PAR and NaCl. Potentiodynamic polarization studies showed that single PAR mainly acts as a cathodic inhibitor for the corrosion of steel in 0.5 M sulfuric acid. The mixture of PAR and chloride ion, however, acts as a mixed type inhibitor that mainly inhibits cathodic reaction of the steel corrosion in sulfuric acid. By means of electrochemical polarization tests, a desorption potential at ca. −370 mV was observed for the adsorption of mixture of PAR and chloride ion, when potential reaches this value, adsorbed inhibitor molecule heavily departs from the steel surface. For the mixture of PAR and chloride ion, thermodynamic parameters such as adsorption heat, adsorption entropy and adsorption free energy were obtained from experimental data of the temperature studies of the inhibition process at four temperatures ranging from 30 to 45 °C, the kinetic data such as apparent activation energies and pre-exponential factors at different concentrations of the inhibitor were calculated, and the effect of the apparent activation energies and pre-exponential factors on the corrosion rates of cold rolled steel was discussed. The most suitable range of inhibitor concentration was discussed. The inhibitive action was satisfactorily explained by using both thermodynamic and kinetic models. Synergism between chloride ion and PAR was proposed. The results obtained from weight loss and potentiodynamic polarization were in good agreement. 相似文献
15.
Effects of sugar inhibition on cellulases and β-glucosidase during enzymatic hydrolysis of softwood substrates 总被引:1,自引:0,他引:1
Zhizhuang Xiao Xiao Zhang David J. Gregg John N. Saddler 《Applied biochemistry and biotechnology》2004,115(1-3):1115-1126
A quantitative approach was taken to determine the inhibition effects of glucose and other sugar monomers during cellulase
and β-Glucosidase hydrolysis of two types of cellulosic material: Avicel and acetic acid-pretreated softwood. The increased
glucose content in the hydrolysate resulted in a dramatic increase in the degrees of inhibition on both β-Glucosidase and
cellulase activities. Supplementation of mannose, xylose, and galactose during cellobiose hydrolysis did not show any inhibitory
effects on β-Glucosidase activity. However, these sugars were shown to have significant inhibitory effects on cellulase activity
during cellulose hydrolysis. Our study suggests that high-substrate consistency hydrolysis with supplementation of hemicellulose
is likely to be a practical solution to minimizing end-product inhibition effects while producing hydrolysate with high glucose
concentration. 相似文献
16.
The ethanol effect on the Trichoderma reesei cellulases was studied to quantify and clarify this inhibition type. To determine inhibition parameters of crude cellulase
and purified exoglucanase Cel7A, integrated Michaelis-Menten equations were used assuming the presence of two inhibitors:
cellobiose as the reaction product and ethanol as a possible bioproduct of cellulose fermentation.
It was found that hydrolysis of cellulose by crude enzyme follows a model that considers noncompetitive inhibition by ethanol,
whereas Cel7A is very slightly competitively inhibited. Crude cellulase is much more inhibited (K
iul=K
icl=151.9 mM) than exoglucanase Cel7A (K
icl=1.6 × 1015 mM). Also, calculated inhibition constants showed that cellobiose inhibition is more potent than ethanol inhibition both for
the crude enzyme as well as exoglucanase Cel7A. 相似文献
17.
The production cost of cellulolytic enzymes is a major contributor to the high cost of ethanol production from lignocellulosics
using enzymatic hydrolysis. The aim of the present study was to investigate the cellulolytic enzyme production ofTrichoderma reesei Rut C 30, which is known as a good cellulase secreting micro-organism, using willow as the carbon source. The willow, which
is a fast-growing energy crop in Sweden, was impregnated with 1–4% SO2 and steam-pretreated for 5 min at 206°C. The pretreated willow was washed and the wash water, which contains several soluble
sugars from the hemicellulose, was supplemented with fibrous pretreated willow and used for enzyme production. In addition
to sugars, the liquid contains degradation products such as acetic acid, furfural, and 5-hydroxy-methylfurfural, which are
inhibitory for microorganisms. The results showed that 50% of the cellulose can be replaced with sugars from the wash water.
The highest enzyme activity, 1.79 FPU/mL and yield, 133 FPU/g carbohydrate, was obtained at pH 6.0 using 20 g/L carbon source
concentration. At lower pHs, a total lack of growth and enzyme production was observed, which probably could be explained
by furfural inhibition. 相似文献
18.
19.
The effects of five polyethylene glycol (PEG) compounds of different molecular weight on the thermal stability of penicillin
G acylase (PGA) obtained from a mutant ofEscherichia coli ATCC 11105 have been investigated. The molecular weights of PEG compounds were 400, 4000, 6000, 10,000, and 15,000. The thermal
inactivation mechanisms of both native and PEG-containing PGA were considered to obey first order inactivation kinetics during
prolonged heat treatments. Optimal concentrations of PEGs at molecular weights of 400,4000, 6000,10,000, and 15,000 were found
to be 250,150,150,100, and 50 mM, respectively. The greatest enhancement of thermostability was observed with PEG 4000 and
PEG 6000, as a nearly 20-fold increase above 50°C. PGA showed almost the same temperature activity profile and optimal temperature
values both in the presence and absence of PEG. The addition of PEGs did not cause any change in the optimal temperature value
of PGA, but the parametersV
m
,K
m
, the activation energy, and thek
cat
values of enzyme were markedly decreased because of the mixed inhibition by PEG compounds. The type of inhibition was found
to be hyperbolic uncompetitive. 相似文献
20.
Surface plasmon resonance (SPR) has been successfully applied for the simple, rapid, and label-free assay of various biomolecules. This assay evaluates a novel wavelength modulation SPR biosensor for the detection of tetanus toxin. The wavelength modulation SPR biosensor is designed based on fixing the incident angle of light and measuring the reflected intensities in the resonance wavelength range spanning 400-800 nm simultaneously. Tetanus toxin (TeNT), one of the most potent toxins known, is synthesized as a 150 kDa single polypeptide chain. The SPR biosensor has been shown to be capable of directly detecting concentration of tetanus toxin as low as 0.028 Lf ml−1. Under selected experimental conditions, the SPR biosensor has a good reproducibility, sensitivity and reversibility. The results illustrate how wavelength modulation SPR biosensor can be used to detect biomolecular interactions. 相似文献