全文获取类型
收费全文 | 1782篇 |
免费 | 126篇 |
国内免费 | 29篇 |
专业分类
化学 | 1219篇 |
晶体学 | 1篇 |
力学 | 221篇 |
综合类 | 4篇 |
数学 | 145篇 |
物理学 | 347篇 |
出版年
2024年 | 1篇 |
2023年 | 14篇 |
2022年 | 79篇 |
2021年 | 65篇 |
2020年 | 56篇 |
2019年 | 55篇 |
2018年 | 44篇 |
2017年 | 86篇 |
2016年 | 85篇 |
2015年 | 87篇 |
2014年 | 49篇 |
2013年 | 124篇 |
2012年 | 116篇 |
2011年 | 106篇 |
2010年 | 85篇 |
2009年 | 137篇 |
2008年 | 104篇 |
2007年 | 113篇 |
2006年 | 97篇 |
2005年 | 66篇 |
2004年 | 75篇 |
2003年 | 47篇 |
2002年 | 24篇 |
2001年 | 31篇 |
2000年 | 25篇 |
1999年 | 19篇 |
1998年 | 27篇 |
1997年 | 23篇 |
1996年 | 14篇 |
1995年 | 14篇 |
1994年 | 12篇 |
1993年 | 8篇 |
1992年 | 9篇 |
1991年 | 4篇 |
1990年 | 9篇 |
1989年 | 2篇 |
1988年 | 9篇 |
1987年 | 4篇 |
1986年 | 3篇 |
1984年 | 2篇 |
1983年 | 1篇 |
1982年 | 2篇 |
1979年 | 1篇 |
1978年 | 1篇 |
1977年 | 1篇 |
1971年 | 1篇 |
排序方式: 共有1937条查询结果,搜索用时 46 毫秒
171.
In the present paper, we have synthesized a biomorphic ceramic material from oak wood as biological template structure and infiltration with zirconia-sol. After the material characterization, we have optimized the sample dissolution by acid attack in an oven under microwave irradiation. Experimental designs were used as a multivariate strategy for the effect's evaluation of varying several variables. This article describes the development by response surface methodology (RSM) of a procedure for zirconium determination, and other ions, such as copper and nickel by inductively coupled plasma mass spectrometry (ICP-MS) and others, such as iron, calcium and magnesium determination by flame atomic absorption spectrometry (FAAS) in the synthesized sample after digestion. A full factorial design (33) was used to find optimal conditions for the procedure through response surface study. Three variables (time, HNO3 volume and HF volume) were regarded as factors and as response to the concentration of different metal ions in the optimization study. 相似文献
172.
Sengupta P Sarkar AK Bhaumik U Chatterjee B Roy B Chakraborty US Pal TK 《Biomedical chromatography : BMC》2010,24(12):1342-1349
A simple, high‐throughput and specific high‐performance liquid chromatography tandem mass spectrometry method has been developed and validated according to the FDA guidelines for simultaneous quantification of olmesartan and pioglitazone in rat plasma. The bioanalytical method consists of liquid–liquid extraction and quantitation by triple quadrupole mass spectrometry using electrospray ionization technique, operating in multiple reaction monitoring and positive ion modes. The compounds were eluted isocratically on a C18 column with a mobile phase consisting of a mixture of methanol and water (containing 0.5% formic acid) in a ratio of 9:1. The response to olmesartan and pioglitazone was linear over the range 0.01–10 µg/mL. The validation results demonstrated that the method had satisfactory precision and accuracy across the calibration range. Intra‐ and inter‐day precisions ranged from 0.66 to 3.32 and from 0.94 to 2.93% (%CV), respectively. The accuracy determined at three quality control levels was within 91.27–107.28%. There was no evidence of instability of the analytes in rat plasma following the stability studies. The method proved highly reproducible and sensitive and was successfully applied in a pharmacokinetic study after single dose oral administration of olmesartan and pioglitazone to the rat. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
173.
Gloria Brusotti Tatiana Adrienne Ngueyem Raffaela Biesuz Gabriele Caccialanza 《Journal of separation science》2010,33(11):1692-1697
Euphorbiaceae barks are known to contain an appreciable amount of polyphenolic compounds responsible for several biological activities. Preliminary extraction from Bridelia grandis stem bark afforded high content of polyphenols, determined by spectrophotometric methods such as Folin–Ciocalteu (for total phenols, TP) and n‐butanol‐HCl (for condensed tannins, CT). A preliminary Plackett–Burman screening design was used to identify the key factors that influence the TP and CT extraction. Between all the variables known to influence the extraction from vegetable matrixes, six were selected; maceration was chosen as traditional extraction methodology. To investigate the effect of solvents and extraction method, methanol, acetone 70% (v/v in water), centrifugation and ultrasound were chosen. A full factorial design 23 was applied to optimize the extraction procedure. The responses were obtained analyzing the extracts for their TP and CT contents determined by the above‐mentioned spectrophotometric methods. The results confirm that, within the explored domain, the optimum solvent is methanol and the optimum method is one‐cycle centrifugation. Finally, it was also compared with the effect of maceration on the considered responses. It has never given results better than centrifugation, whereas in the case of CT it represents an advantage to employ a three‐cycle centrifugation instead of one. 相似文献
174.
A new fluorinated stationary phase was prepared through thermal immobilization of poly(methyl‐3,3,3‐trifluoropropylsiloxane) onto 5 μm Kromasil silica particles. The best conditions of immobilization time and temperature were determined through a central composite design and response surface methodologies. Physical–chemical characterization using solid‐state 29Si NMR measurements, infrared spectroscopy and elemental analysis showed that the immobilization process was effective to promote a coating of the support that corresponds to a monolayer of polymer. The stationary phase presents selectivity for positional isomers and good peak shape for basic compounds. 相似文献
175.
J. Pablo Lamas Lucia Sanchez-PradoMarta Lores Carmen Garcia-JaresMaria Llompart 《Journal of chromatography. A》2010,1217(33):5307-5316
Exposure to fragrance substances is exponentially increasing in our daily life due to the enhanced use of scented products. Some fragrances are known to be important sensitizers, inhalation being an important exposure pathway in indoor environments. A simple and sensitive method based on solid-phase enrichment and solid-phase microextraction (SPME) followed by gas chromatography–mass spectrometry (GC–MS) has been developed for the analysis of 24 volatile fragrance allergens in indoor air. Suspected allergens present in the air (0.2 m3) were adsorbed onto a very small quantity of florisil (25 mg) and then transferred to a SPME fiber in the headspace mode (HS). To the best of our knowledge, this paper describes the first application of SPME for the determination of these compounds in air samples. The experimental parameters affecting the microextraction process have been optimized using a multifactor experimental design strategy. Accuracy, linearity, precision and detection limits (LODs) were evaluated to assess the performance of the proposed method. External calibration, using spiked sorbent standards, and not requiring the complete sampling process (only the SPME step), demonstrated to be suitable for the quantification of all suspected allergens. Recovery studies were performed at three concentration levels (0.04, 1.00 and 50 μg m−3), obtaining quantitative recoveries (≥85%) in most cases. LOD values at the low ng m−3 level were achieved for all the target compounds. The application of the method to daily home air samples demonstrated the ubiquity of this kind of fragrance ingredients in quotidian indoor environments, finding 18 of the 24 considered compounds in concentrations ranging from 0.01 to 56 μg m−3. Benzyl alcohol, linalool, citronellol, ionone and lilial were found in most analyzed samples. 相似文献
176.
Lamas JP Sanchez-Prado L Garcia-Jares C Lores M Llompart M 《Journal of chromatography. A》2010,1217(52):8087-8094
A new method based on solid phase dispersion-pressurized liquid extraction (PLE) followed by gas chromatography-mass spectrometry (GC-MS) has been developed for the determination of 26 suspected fragrance allergens (all the regulated in the EU Cosmetics Directive amenable by GC, as well as pinene and methyleugenol) in cosmetic samples. The effects of the temperature, extraction time and solvent, and dispersing sorbent, affecting the whole proposed procedure, have been evaluated using a multifactor strategy. The optima conditions after the analysis of main and second order effects entailed the extraction at 120°C for 15 min, using hexane/acetone as solvent, and florisil as dispersing sorbent. The method performance has been studied, showing good linearity (R≥0.996) as well as good precision (RSD≤10%). Detection limits (S/N=3) ranged from 0.000001 to 0.0002% (w/w), values far below the established restrictions as regard labelling in the European Cosmetics Regulation. Reliability was demonstrated through the quantitative recoveries of all the studied compounds. The absence of matrix effects allowed quantification of the compounds by calibration with standard solutions. The analysis of 10 samples (several moisturizing and anti-wrinkle creams and lotions, hand creams, and sunscreen and after-sun creams), covering very different matrices, showed the presence of suspected allergens in all the analyzed samples; in fact, half of the samples contained an elevated number of them. Although the ubiquity of these compounds was demonstrated, labelling was in all cases in consonance with the European Cosmetics Regulation. 相似文献
177.
Radial basis function method is an effective tool for solving differential equations in engineering and sciences. Many radial basis functions contain a shape parameter c which is directly connected to the accuracy of the method. Rippa [1] proposed an algorithm for selecting good value of shape parameter c in RBF-interpolation. Based on this idea, we extended the proposed algorithm for selecting a good value of shape parameter c in solving time-dependent partial differential equations. 相似文献
178.
Saikou Y. Diallo Jose J. Padilla Ross Gore Heber Herencia‐zapana Andreas Tolk 《Complexity》2014,19(3):56-63
This article proposes a Modeling and Simulation (M&S) formalism using Model Theory. The article departs from the premise that M&S is the science that studies the nature of truth using models and simulations. Truth in models and simulations is relative as they seek to answer specific modeling questions. Consequently, truth in M&S is relative because every model is a purposeful abstraction of reality. We use Model Theory to express the proposed formalism because it is built from the premise that truth is relative. The proposed formalism allows us to: (1) deduce formal definitions and explanations of areas of study in M&S, including conceptual modeling, validity, and interoperability, and (2) gain insight into which tools can be used to semi‐automate validation and interoperation processes. © 2013 Wiley Periodicals, Inc. Complexity 19: 56–63, 2014 相似文献
179.
Density and viscosity were determined for the binary mixtures containing the ionic liquid 1-butyl-3-methylimidazolium thiocyanate
([BMIM][SCN]) and 1-alcohols (1-butanol, 1-pentanol and 1-hexanol) at six temperatures (298.15, 308.15, 318.15, 328.15, 338.15
and 348.15) K and ambient pressure. The density and viscosity correlation for these systems was tested by an empirical second-order
polynomial and by the Vogel-Fucher-Tammann equation in wide ranges of temperatures. Excess molar volumes were described by
the Redlich-Kister polynomial expansions. The density and viscosity variations with composition were described by polynomials.
A qualitative analysis of the trend of the properties with solvent and temperature was performed. The obtained results indicate
that ionic liquid interactions with 1-alcohols are strongly dependent on the special trend of packing of this ionic liquid
into hydroxylic solvents. As previously observed, an increase of the 1-alcohol carbon-chain length leads to lower interactions
on mixing.
Electronic Supplementary Material The online version of this article () contains supplementary material, which is available to authorized users. 相似文献
180.
Joana Sousa Gilberto Alves Ana Fortuna Angelina Pena Celeste Lino Amílcar Falcão 《Biomedical chromatography : BMC》2011,25(5):535-541
A simple and fast liquid chromatographic method coupled with fluorescence detection (LC‐FD) is reported, for the first time, for the simultaneous quantification of norfloxacin (NOR), ciprofloxacin (CIP) and lomefloxacin (LOM) in human plasma, using levofloxacin as internal standard (IS). Sample preparation consists of a single‐step precipitation of plasma proteins followed by vortex‐mixing and centrifugation. Chromatographic separation was achieved within 7 min on a reversed‐phase C18 column with a mobile phase consisting of 0.1% aqueous formic acid (pH = 3.0, triethylamine)–methanol (82:18, v/v) pumped isocratically at 1.2 mL/min. The detector was set at excitation/emission wavelengths of 278/450 nm. Calibration curves were linear (r2 ≥ 0.994) in the range of 0.02–5.0 µg/mL, and the limit of quantification was established at 0.02 µg/mL for all analytes (NOR, CIP and LOM). The overall precision did not exceed 8.19% and accuracy was within ±10.91%. NOR, CIP and LOM were extracted from human plasma with an overall mean recovery ranged from 90.1 to 111.5%. No interferences were observed at the retention times of the analytes and IS. This novel LC‐FD method enables the reliable determination of NOR, CIP and LOM in a single chromatographic run, which may be suitable to support human pharmacokinetic‐based studies with those antimicrobial agents. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献