全文获取类型
收费全文 | 385篇 |
免费 | 30篇 |
国内免费 | 4篇 |
专业分类
化学 | 322篇 |
晶体学 | 1篇 |
力学 | 9篇 |
数学 | 54篇 |
物理学 | 33篇 |
出版年
2023年 | 4篇 |
2022年 | 3篇 |
2021年 | 13篇 |
2020年 | 20篇 |
2019年 | 12篇 |
2018年 | 29篇 |
2017年 | 13篇 |
2016年 | 27篇 |
2015年 | 27篇 |
2014年 | 30篇 |
2013年 | 47篇 |
2012年 | 18篇 |
2011年 | 32篇 |
2010年 | 22篇 |
2009年 | 22篇 |
2008年 | 25篇 |
2007年 | 15篇 |
2006年 | 14篇 |
2005年 | 12篇 |
2004年 | 9篇 |
2003年 | 9篇 |
2002年 | 7篇 |
1999年 | 3篇 |
1998年 | 1篇 |
1997年 | 2篇 |
1996年 | 1篇 |
1993年 | 1篇 |
1992年 | 1篇 |
排序方式: 共有419条查询结果,搜索用时 31 毫秒
411.
Cu2+-mediated salbutamol-imprinted polymer nanoparticles, synthesized by precipitation polymerization, were mixed with graphite powder and n-eicosane in order to fabricate a modified carbon paste electrode. This electrode was then applied for indirect differential pulse voltammetry determination of salbutamol. In the presence of Cu2+ ions, the formed Cu2+–salbutamol complex was adsorbed in to the pre-designed cavities of the MIP particles, situated on the electrode surface. Since the electrochemical signal of salbutamol was intrinsically small, the oxidation peak of the participant Cu2+, after reduction step, was recorded and used as an indication of salbutamol amount, adsorbed in the electrode. Different variables influencing the sensor performance were studied and the best conditions were chosen for the determination purpose. Correlation between the sensor response to salbutamol and its concentration was linear in the range of 1.0 × 10−9–5.5 × 10−8 M. Detection limit was calculated equal to 6.0 × 10−10 M (S/N). Five replicated determination of salbutamol (1 × 10−8 M) resulted in standard error of 3.28%, meaning a satisfactory precision of the determination method. The prepared sensor was applied for real sample analysis. In order to minimize the interference effect, the synthesized polymer was successfully used as a solid phase sorbent for salbutamol extraction, before analysis of real samples by the developed sensor. 相似文献
412.
In this account, a detailed computational study is conducted to verify the geometric, energetic, and electronic properties of the planar cyclic (B 6C) (-2) (as the simplest carrier of hexacoordinate carbon) within some metal complexes. The [M(B 6C)] ((-)) (M = Li, Na, K) and [M(B 6C)] (M = Be, Mg, Ca) series are employed for this purpose. Relevant ab initio calculations at both DFT and post-HF levels vividly demonstrate that this dianion is stabilized considerably in the electric field generated by cations, whereas the geometrical and electronic properties of this ring remain almost intact in these complexes. The complementary topological analysis of charge densities confirms that cyclic (B 6C) (-2) within these complexes exhibits the same topological patterns as the naked dianion, thus confirming the presence of an unusual charge density distribution in this dianion. An electrostatic model is proposed that not only qualitatively but also quantitatively explains the observed computational trends in these complexes. This model successfully traces the polarization of the central carbon atom of the ring in the presence of a hard, multiply charged cation. To facilitate experimental detection, the photoelectron spectra of the [M(B 6C)] ((-)) (M = Li, Na, K) series are computed and the dominant features are extracted. Although considered species are not global minima on their potential energy hypersurfaces, their kinetic stabilities are verified and demonstrated unequivocally. 相似文献
413.
Catalytic Behaviour of Transition Metal Cations In Electrosynthesis and Growth of Nanostructure Conducting Polypyrrole Films On/Between the Passive Cu Interdigital Electrodes: Application In Gas Sensors 下载免费PDF全文
The electrosynthesis of nanostructured polypyrrole (PPy) on copper interdigital electrodes (Cu‐IDEs) surfaces was performed by anodic oxidation of pyrrole in the presence of oxalic acid in aqueous solution (passivation technique) by potentiostatic method. Some divalent transition metal ions (Fe(II), Co(II), Ni(II), Cu(II), Zn(II)) as catalyst can be used to polymers growth on/between spacing between passive Cu‐IDEs by using potentiostatic technique. The morphology of the conducting films was examined by field emission scanning electron microscope, indicating a dependence of the film morphology to catalyst type. The PPy films on Cu‐IDEs were used to investigate the properties of the gas sensing ability. 相似文献
414.
Elham Ghaemi Naader Alizadeh 《International Journal for Ion Mobility Spectrometry》2014,17(3-4):117-124
Ion mobility spectrometry (IMS) was applied to determine the influence of structural features of nanocluster formation of picoline isomers in ion mobility spectrometry. Since the results of our studies show that different isomers have the same mobilities in pure nitrogen buffer gas and their corresponding peaks are totally overlapped, 2-butanol vapor was introduced into buffer gas by means of an online system from 0 to 300 mL min?1. We found different structural features of these isomeric compounds which cause distinct differences in ion mobility spectra. These differences result from the formation of different nanocluster product ions (~1 nm3) with different cross section areas formed depending on the occurrence of certain structural features (position of the methyl group on the pyridine ring). The size of cluster product ions formed was determined using cross section area measurements. The effects of temperature in the range from 80 to 200 °C and electric field strength have also been investigated. At 140–160 °C and 636 V cm?1, optimum peak-to-peak resolution can be obtained. 相似文献
415.
An effective route to hydantoins is described, based on the 2 : 1 : 1 addition of arylsulfonyl isocyanates, dialkyl acetylenedicarboxylates, and dialkyl trialkylsilyl phosphites. The resulting tetrasubstituted, stable hydantoins 4 / 4′ (Table) were obtained in excellent yields, and their structures were corroborated spectroscopically (IR, 1H‐, 13C‐, 31P‐NMR, EI‐MS) and by elemental analyses. A plausible mechanism for this type of cyclization is proposed (Scheme 2). 相似文献
416.
Annals of Operations Research - Transportation sector with the consumption of 25% of energy play a major role in Iranian economy. This sector produces 27% of total undesirable greenhouse gases in... 相似文献
417.
We present a summary of methods based on semidefinite programming for estimating arrival rate of nonhomogeneous Poisson processes from a finite set of observed data. Both one-dimensional time dependent, and multi-dimensional time and location dependent rates are considered. The arrival rate is a nonnegative function of time (or time and location). We also assume that it is a smooth function with continuous derivatives of up to certain order k. We estimate the rate function by one or multi-dimensional splines, with the additional condition that the underlying rate function is nonnegative. This approach results in an optimization problem over nonnegative polynomials, which can be modeled and solved using semidefinite programming. We also describe a method which requires only linear constraints. Numerical results based on e-mail arrival and highway accidents are presented. 相似文献
418.
Mediterranean Journal of Mathematics - In this paper, we introduce a new modified Ishikawa iteration for finding a common element of the set of solutions of an equilibrium problem and the set of... 相似文献
419.