全文获取类型
收费全文 | 410篇 |
免费 | 4篇 |
国内免费 | 3篇 |
学科分类
数理化 | 417篇 |
出版年
2023年 | 3篇 |
2022年 | 12篇 |
2021年 | 17篇 |
2020年 | 4篇 |
2019年 | 9篇 |
2018年 | 7篇 |
2017年 | 3篇 |
2016年 | 7篇 |
2015年 | 10篇 |
2014年 | 6篇 |
2013年 | 24篇 |
2012年 | 14篇 |
2011年 | 27篇 |
2010年 | 21篇 |
2009年 | 22篇 |
2008年 | 25篇 |
2007年 | 27篇 |
2006年 | 18篇 |
2005年 | 20篇 |
2004年 | 14篇 |
2003年 | 10篇 |
2002年 | 18篇 |
2001年 | 4篇 |
2000年 | 6篇 |
1999年 | 2篇 |
1998年 | 3篇 |
1996年 | 4篇 |
1995年 | 4篇 |
1994年 | 3篇 |
1992年 | 2篇 |
1991年 | 4篇 |
1990年 | 6篇 |
1989年 | 3篇 |
1988年 | 4篇 |
1987年 | 2篇 |
1986年 | 4篇 |
1985年 | 4篇 |
1982年 | 2篇 |
1981年 | 3篇 |
1980年 | 4篇 |
1979年 | 3篇 |
1978年 | 7篇 |
1977年 | 2篇 |
1976年 | 3篇 |
1975年 | 3篇 |
1974年 | 3篇 |
1973年 | 4篇 |
1968年 | 3篇 |
1964年 | 1篇 |
1963年 | 1篇 |
排序方式: 共有417条查询结果,搜索用时 15 毫秒
101.
Antiochia R Lavagnini I Pastore P Magno F 《Bioelectrochemistry (Amsterdam, Netherlands)》2004,64(2):157-163
Cyclic voltammetry was successfully applied to study the oxidation of nicotinamide adenine dinucleotide (NADH) both in homogeneous and heterogeneous phase. The first case was realized with a solution containing p-methylamino-phenolsulphate (MAP) as redox mediator and the diaphorase (DI) from Clostridium kluveri as enzyme while the second one by using both a glassy carbon (GC) and a carbon nanotube paste (CNTP) electrode modified with electrodeposited films derived from 3,4-dihydroxybenzaldehyde (3,4-DHB). Such systems were successively coupled with glucose dehydrogenase (GDH) reaction to realize the redox chain present in glucose biosensors. A critical comparison of the two systems was also reported. 相似文献
102.
Cyclic voltammetry has been successfully used to study the oxidation of nicotinamide adenine dinucleotide (NADH) at single-wall carbon-nanotube-paste (CNTP) electrodes modified with p-methylaminophenolsulfate (p-MAP) and 3,4-dihydroxybenzaldehyde (3,4-DHB). Diffusion-like behaviour was observed for p-MAP-modified electrodes, and a diffusion coefficient of 2.4×10–6 cm2 s–1 was calculated for p-MAP in the paste. The behaviour of 3,4-DHB-modified CNTP electrodes was typical of that of surface-confined mediators. p-MAP electrocatalytic activity was first checked in solution, and a rate constant of 9.2 mol–1 L s–1 was obtained for the reaction between NADH and the mediator. The p-MAP-modified electrode did not have significant electrocatalytic activity for electro-oxidation of NADH, probably because of the formation of a complex between NADH and the confined mediator. In contrast, the 3,4-DHB-modified electrode had very good NADH electrocatalytic activity, with a heterogeneous rate constant of approximately 20×102 mol–1 L s–1. 相似文献
103.
104.
Stefano Mortara Daniele Fregonese Silvano Bresadola Rita Boaretto Silvana Sostero 《Journal of polymer science. Part A, Polymer chemistry》2001,39(24):4243-4248
Cyclopentadienyl magnesium chloride (MgClCp) and its functionalized derivatives represent original and interesting supporting materials to heterogenize metallocene catalysts for olefin polymerizations. The synthesis of MgClCp, its functionalization, and the preparation of a catalytic system in which the ZrCl2(Flu)+ moiety is joined on the support through a cyclopentadienyl ligand are reported. This catalyst was tested in ethene polymerization, and both the catalytic activity and properties of the produced polymer were measured. Its performance was compared with that shown by the catalyst ZrCl2CpFlu employed under the same conditions for both unsupported and conventional supports, such as MgCl2. The results showed a remarkable improvement in terms of the activity and polymer properties with these heterogenized catalysts. Moreover, this system showed stability toward leaching processes and was characterized by good morphological control of the growing polymer. Finally, catalysts in which [HB(3,5‐Me2pyrazolyl)3]ZrCl and [HB(3,5‐Me2pyrazolyl)3]ZrClOtBu+ moieties were bonded to a functionalized MgClCp? support were also synthesized and tested. The results showed that the proposed supports could be usefully used to heterogenize tailored metallocene homogeneous catalysts. In fact, new catalysts were prepared that combined the peculiar advantages of both heterogeneous and homogeneous catalysts and overcame the disadvantages of the latter, such as a lack of morphology and reactor fouling. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 4243–4248, 2001 相似文献
105.
Mathematical and computational modeling are key tools in analyzing important biological processes in cells and living organisms. In particular, stochastic models are essential to accurately describe the cellular dynamics, when the assumption of the thermodynamic limit can no longer be applied. However, stochastic models are computationally much more challenging than the traditional deterministic models. Moreover, many biochemical systems arising in applications have multiple time-scales, which lead to mathematical stiffness. In this paper we investigate the numerical solution of a stochastic continuous model of well-stirred biochemical systems, the chemical Langevin equation. The chemical Langevin equation is a stochastic differential equation with multiplicative, non-commutative noise. We propose an adaptive stepsize algorithm for approximating the solution of models of biochemical systems in the Langevin regime, with small noise, based on estimates of the local error. The underlying numerical method is the Milstein scheme. The proposed adaptive method is tested on several examples arising in applications and it is shown to have improved efficiency and accuracy compared to the existing fixed stepsize schemes. 相似文献
106.
Gabriela de Matuoka e Chiocchetti Elisabete A. De Nadai Fernandes Márcio Arruda Bacchi Rogério Augusto Pazim Silvana Regina Vicino Sarriés Thaís Melega Tomé 《Journal of Radioanalytical and Nuclear Chemistry》2013,297(3):399-404
Brazil is one of the largest producers of fruits cropping 40 million tons per year. In agro-food processing, approximately 50 % of raw material is discarded generating large amounts of by-products. The lack of information on the nutritional quality of agroindustrial by-products precludes their potential use in the manufacture of food products accessible to all. In this context, the objective of this work was to investigate the nutritional quality of by-products of the industrial processing of fruits. Samples of bagasse, peel and seeds of several fruits (banana, camu camu, coconut, cupuaçu, guava, jackfruit, mango, orange, papaya, pineapple, and soursop) were analysed by neutron activation analysis for the determination of Br, Ca, Co, Cr, Cs, Fe, K, La, Na, Rb, Sc and Zn. In general, higher levels of minerals were found in the by-products rather than in the pulps of fruits. This indicates that the use of the by-products should be encouraged, thereby reducing the economic and environmental impact of waste generated by agroindustrial processing. 相似文献
107.
Irma Lavagnini Bruno Fedrizzi Giuseppe Versini Franco Magno 《Rapid communications in mass spectrometry : RCM》2009,23(8):1167-1172
The effectiveness of isotopically and non‐isotopically labelled internal standards in reducing matrix‐induced effects is evaluated. The question is addressed in the quantitative analysis by gas chromatography/mass spectrometry (GC/MS) of dimethyl sulphide, chosen as a typical example of volatile sulphur compounds, in wine matrices. When matrix/run effects are not cancelled out the use of a variance component model (VCM) to handle the linear calibrations obtained by regression technique is successful. The method implies the estimation of an overall calibration straight line, which properly takes into account the uncertainty due to different matrices, the calibration run and the measurement error, making the use of an isotopically labelled internal standard not necessary. The obtained results show that the benefits of lowering times and costs for routine analyses compensate for the small increase in uncertainty in the concentration values obtained in the regression analysis and the slight increase in the detection limit. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
108.
Silvia Bradamante Silvana Colombo Giorgio Vittadini 《Journal of heterocyclic chemistry》1981,18(7):1399-1403
The product obtained condensing l-methyl-5-nitroimidazole-2-aldehyde with 2-amino-4-trideuteriomethyl-pyrimidine and showing total deuterium incorporation at one of the olefinic carbons and partial deuterium incorporation para to the amino group, served to assign 13C and 1H resonances in the condensation products 3. The nature of the species undergoing condensation has been inferred from labelling experiments and from 1H and 13C nmr spectra of precursors and products in dimethylsulfoxide and trifluoroacetic acid. 相似文献
109.
Jamile Silva da Costa Waldemir Magno S. Andrade Raphael O. de Figueiredo Paulo Vinicius L. Santos Jofre Jacob da Silva Freitas William N. Setzer Joyce Kelly R. da Silva Jos Guilherme S. Maia Pablo Luis B. Figueiredo 《Molecules (Basel, Switzerland)》2022,27(7)
Myrciaria (Myrtaceae) species have been well investigated due to their chemical and biological relevance. The present work aimed to carry out the chemotaxonomic study of essential oils of the species M. dubia, M. floribunda, and M. tenella, sampled in the Brazilian Amazon and compare them with the volatile compositions from other Myrciaria species reported to Brazil and Colombia. The leaves of six Myrciaria specimens were collected (PA, Brazil) during the dry season, and their chemical compositions were analyzed by gas chromatography-mass spectrometer (GC-MS) and gas chromatography-flame ionization detector (GC-FID). The main compounds identified in the essential oils were monoterpenes with pinane and menthane skeletons, followed by sesquiterpenes with caryophyllane and cadinane skeletons. Among the sampled Myrciaria specimens, five chemical profiles were reported for the first time: profile I (M. dubia, α-pinene, 54.0–67.2%); profile II (M. floribunda, terpinolene 23.1%, α-phellandrene 17.7%, and γ-terpinene 8.7%); profile III (M. floribunda, γ-cadinene 17.5%, and an unidentified oxygenated sesquiterpene 15.0%); profile IV (M. tenella, E-caryophyllene 43.2%, and α-humulene 5.3%); and profile V (M. tenella, E-caryophyllene 19.1%, and caryophyllene oxide 41.1%). The Myrciaria chemical profiles showed significant variability in extraction methods, collection sites, plant parts, and genetic aspects. 相似文献
110.
Norma Sbarbati Nudelman Cecilia E. Silvana Alvaro 《Journal of Physical Organic Chemistry》2011,24(11):1067-1071
Inter‐ and intramolecular hydrogen bonding play an important role in determining the arrangement, physical properties, and reactivity of a great diversity of structures in chemical and biological systems. Several aromatic nucleophilic substitutions (ANS) in nonpolar aprotic, (non‐HBD), solvents recently studied in our laboratory have demonstrated the importance of self‐association of amines by hydrogen‐bond interactions. In this paper, we describe 1H‐NMR studies carried out at room temperature on bi‐ and polyfunctionalized amines, namely: N‐(3‐amino‐1‐propyl)morpholine (3‐APMo), histamine, 2‐guanidinobenzimidazole (2‐GB), 1,2‐diaminoethane (EDA), 3‐dimethylamino‐l‐propylamine (DMPA), and 1‐(2‐aminoethyl)piperidine (2‐AEPip). By 1H‐NMR measurements of amine solutions at variable concentrations we have shown that 3‐APMo, histamine and 2‐GB are able to form a six‐membered ring by intramolecular hydrogen bonding, while EDA, DMPA, and 2‐AEPip form dimers by intermolecular hydrogen bonds. Likewise, variable concentration 1H‐NMR studies allowed estimation of the corresponding equilibrium constants for the dimerization. These results are correlated with experimental kinetic results of ANS, confirming hereto the relevance of the “dimer mechanism” in reactions involving these amines. Copyright © 2011 John Wiley & Sons, Ltd. 相似文献