全文获取类型
收费全文 | 238篇 |
免费 | 4篇 |
国内免费 | 5篇 |
专业分类
化学 | 133篇 |
力学 | 2篇 |
数学 | 23篇 |
物理学 | 89篇 |
出版年
2024年 | 3篇 |
2023年 | 8篇 |
2022年 | 3篇 |
2021年 | 7篇 |
2020年 | 4篇 |
2019年 | 8篇 |
2018年 | 5篇 |
2017年 | 3篇 |
2016年 | 10篇 |
2015年 | 11篇 |
2014年 | 9篇 |
2013年 | 7篇 |
2012年 | 9篇 |
2011年 | 11篇 |
2010年 | 7篇 |
2009年 | 7篇 |
2008年 | 9篇 |
2007年 | 20篇 |
2006年 | 17篇 |
2005年 | 16篇 |
2004年 | 13篇 |
2003年 | 8篇 |
2002年 | 2篇 |
2001年 | 6篇 |
2000年 | 5篇 |
1999年 | 2篇 |
1998年 | 1篇 |
1997年 | 2篇 |
1996年 | 4篇 |
1995年 | 6篇 |
1994年 | 2篇 |
1993年 | 5篇 |
1992年 | 3篇 |
1991年 | 2篇 |
1990年 | 3篇 |
1989年 | 2篇 |
1988年 | 1篇 |
1987年 | 2篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1979年 | 1篇 |
1977年 | 1篇 |
排序方式: 共有247条查询结果,搜索用时 0 毫秒
231.
The classical problem of testing the equality of the covariance matrices from k ? 2 p-dimensional normal populations is reexamined. The likelihood ratio (LR) statistic, also called Bartlett’s statistic, can be decomposed in two ways, corresponding to two distinct component-wise decompositions of the null hypothesis in terms of the covariance matrices or precision matrices, respectively. The factors of the LR statistic that appear in these two decompositions can be interpreted as conditional and unconditional LR statistics for the component-wise null hypotheses, and their mutual independence under the null hypothesis allows the determination of the overall significance level. 相似文献
232.
Osman Tiryaki 《Accreditation and quality assurance》2006,11(10):514-513
Method validation is an important requirement in the practice of pesticide residue analysis and is the process of verifying that a method is fit for its purpose. To make a correct decision on the validity of the method, the following method performance parameters have to be taken into consideration: scope, specificity, limit of detection, limit of quantification, linear range, accuracy, precision, repeatability, reproducibility, recovery, ruggedness and robustness. The goal of this study was to validate previously adapted thin-layer chromatographic methods for the pesticide residue analysis in grain. Confirmation of validation parameters for some compounds was also performed by gas chromatographic analysis. 相似文献
233.
T. M. El‐Gogary A. El‐Dissouky A. S. Hilali 《International journal of quantum chemistry》2003,91(6):685-694
The geometry of metal ions (La3+, Ce3+, UO, and Th4+) complexes with 5‐azorhodanine derivatives was optimized at the level of molecular mechanics. Two stoichiometric ratios of metal to ligand (i.e., 1:1 and 1:2) were investigated. Tetracoordinate and hexacoordinate of each stoichiometric ratio have been studied. Effect of substitution in the ligand on the geometry of the complexes was discussed in the light of electron donating–accepting properties of these substituents. The influence of the nuclear effective charge of the central metal ions on the metal–ligand (M–L) bonding was discussed and the effect of the number of ligands on the M–L bond length was also discussed and correlated to the experimental results. The total energies of the different metal complexes were computed using the extended Huckel method. The effect of substituents in ligand, metal type, and stoichiometry of the complexes on the complex total energies were discussed. Stability constant of (La3+, Ce3+, UO, and Th4+) metal ions with 5‐azorhodanine derivaties have been determined potentiometrically in 0.1 M KCl and 50% (v/v) ethanol–water mixture. The order of the stability constants of the formed complexes was found to be La3+ < Ce3+ < UO < Th4+. The influence of substituents on the stability of the complexes was examined on the basis of electron‐repelling property of the substituent. The effect of temperature on the stability of the complexes formed was studied and the corresponding thermodynamic parameters (ΔG, ΔH, and ΔS) were derived and discussed. The stoichiometries of these complexes were determined conductometrically and indicated the formation of 1:1 and 1:2 (metal:ligand) complexes. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem, 2003 相似文献
234.
针对自动光学检测(AOI)平台运行过程中的定位精度控制问题,提出了一种基于速度和加速度前馈控制与PID反馈控制的复合控制算法,该算法对输入量进行跟踪补偿控制以消除系统稳态误差,用于提高AOI平台定位精度。基于开放式的数控系统设计方法设计了AOI平台。在Matlab/Simulink环境下,构建了基于该复合控制算法的定位精度控制仿真模型,仿真结果验证了复合控制算法的有效性。将该复合控制算法作为ACR9000控制器的控制算法,并基于ACR9000控制器进行AOI平台实验研究。应用该AOI平台进行了印刷电路板(PCB)检测实验,实验结果表明文中复合控制算法能够提高AOI平台定位精度,AOI平台的定位精度满足印刷电路板检测要求,可以将该AOI平台用于印刷电路板检测。 相似文献
235.
Interactions Between Alkyl Triphenyl Phosphonium Bromides and Polyvinylpyrrolidones in Aqueous Media
Rebecca Dean Maryjo Doiron Kate Dunlop 《Journal of Dispersion Science and Technology》2013,34(7):1018-1023
The interactions of polyvinylpyrrolidones with alkyl triphenyl phosphonium bromide in aqueous media were investigated with conductometric, fluorimetric and tensiometric techniques. Formation of surfactant-polymer aggregates was detected in the case of C16 and C14 surfactant by these techniques. Tensiometric technique proved to be very sensitive to detect the early stage of association at very low concentrations. The Gibbs free energy of micellization and the dielectric constant values of the micellar interface values were obtained and discussed in terms of strength of interaction between the polymers and surfactants. 相似文献
236.
Using conductance measurements, an attempt has been made to gain detailed information about the specific molecular interactions of crown compounds with metal ions in a 1,4-dioxane/water binary system. Analyses of the transport data of dioxane/water mixtures yielded the mobility of the crown compound action complexes and the ion-pair dissociation constant of the crown compound–electrolyte complex. Binary mixed aqueous solvents are frequently employed in broad areas of chemistry. Their applicability ranges from synthetic and mechanistic studies in organic chemistry to biophysical chemistry, with emphasis on molecular interactions in biologically significant structures. Stability constants of crown compound complexes are determined by various methods, such as potentiometry (with ion selective electrodes), polarography, voltammetry, spectrophotometry, nuclear magnetic resonance, calorimetry and solubility. In this study the conductometry measurements have been carried out with high precision at optimal concentrations in dioxane/water systems. Structures of crown–cation complexes in dioxane/water mixtures are estimated from the conductance parameters (κ, Λ and α) as well as the complex formation constant, Ke = (ΛMAm − Λ) / (Λ − ΛMaLbAm) [L]. The conductance behavior of Na+, K+ chlorides and Na+ perchlorates with 18-crown-6, 15-crown-5, and 12-crown-4 have been studied in various dioxane/water systems (50%, 80%, and 85%) at 25°C. The all experimental studies have been made by the ratio 1 : 1 of the metal-ion and the crown ether, Ke. For the calculations, Excel. 5.0 was used as an application program. Copyright © 1998 John Wiley & Sons, Ltd. 相似文献
237.
Ana Cristina Soria Isabel Martínez-CastroJesús Sanz 《Journal of chromatography. A》2009,1216(15):3300-3304
Data precision in the analysis by purge-and-trap coupled on-line to gas chromatography–mass spectrometry (P&T-GC–MS) of honey volatiles has been studied by statistical analysis. The contribution of non-random factors to dispersion of quantitative results was proven by comparing several statistical parameters (correlation coefficients, principal component analysis (PCA) eigenvalues and loadings) from both experimental and simulated data. PCA was also useful for grouping volatiles with similar dispersion behaviour; these groups being generally related to compounds with common properties or structural features. The use of area ratios improves data precision for compounds within the same group. Results from this study could be used for a better selection of internal standards in quantitative analysis of volatiles by P&T-GC–MS. 相似文献
238.
Anas M. Abdel Rahman Judy Pawling Michael Ryczko Amy A. Caudy James W. Dennis 《Analytica chimica acta》2014
Metabolomics is the identification and quantitation of small bio-molecules (metabolites) in biological samples under various environmental and genetic conditions. Mass spectrometry provides the unique opportunity for targeted identification and quantification of known metabolites by selective reaction monitoring (SRM). However, reproducibility of this approach depends on careful consideration of sample preparation, chemical classes, and stability of metabolites to be evaluated. Herein, we introduce and validate a targeted metabolite profiling workflow for cultured cells and tissues by liquid chromatography–triple quadrupole tandem mass spectrometry. The method requires a one-step extraction of water-soluble metabolites and targeted analysis of central metabolites that include glycolysis, amino acids, nucleotides, citric acid cycle, and the hexosamine biosynthetic pathway. The sensitivity, reproducibility and molecular stability of each targeted metabolite were assessed under experimental conditions. Quantitation of metabolites by peak area ratio was linear with a dilution over a 4 fold dynamic range with minimal deviation R2 = 0.98. Inter- and intra-day precision with cells and tissues had an average coefficient of variation <15% for cultured cell lines, and somewhat higher for mouse liver tissues. The method applied in triplicate measurements readily distinguished immortalized cells from malignant cells, as well as mouse littermates based on their hepatic metabolic profiles. 相似文献
239.
Xiao Wang Zhihong Yu Zhihao Huang Nianchen Zhou Xiaoxiao Cheng Zhengbiao Zhang Wei Zhang Xiulin Zhu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2024,136(5):e202315686
Unraveling the chirality transfer mechanism of polymer assemblies and controlling their handedness is beneficial for exploring the origin of hierarchical chirality and developing smart materials with desired chiroptical activities. However, polydisperse polymers often lead to an ambiguous or statistical evaluation of the structure–property relationship, and it remains unclear how the iterative number of repeating units function in the helicity inversion of polymer assemblies. Herein, we report the macroscopic helicity and dynamic manipulation of the chiroptical activity of supramolecular assemblies from discrete azobenzene-containing oligomers (azooligomers), together with the helicity inversion and morphological transition achieved solely by changing the iterative chain lengths. The corresponding assemblies also differ from their polydisperse counterparts in terms of thermodynamic properties, chiroptical activities, and morphological control. 相似文献
240.
成像光谱技术在植物非生物胁迫表型高通量分析中的研究进展 总被引:1,自引:0,他引:1
植物非生物胁迫是指对植物产生不利影响的非生物因素,非生物胁迫威胁植物发芽、生长、发育和繁殖,是阻碍农作物高效栽培和农业可持续发展的主要因素.植物胁迫精准管理和抗逆植物育种是缓解和解决非生物胁迫的有效途径,其中植物表型分析是一个不可或缺的环节,但是传统滞后的如人工、破坏式表型测量方法很难满足高通量表型分析的需求,制约着植... 相似文献