全文获取类型
收费全文 | 1634篇 |
免费 | 52篇 |
国内免费 | 8篇 |
专业分类
化学 | 964篇 |
晶体学 | 9篇 |
力学 | 101篇 |
数学 | 237篇 |
物理学 | 383篇 |
出版年
2023年 | 9篇 |
2022年 | 47篇 |
2021年 | 54篇 |
2020年 | 40篇 |
2019年 | 33篇 |
2018年 | 34篇 |
2017年 | 31篇 |
2016年 | 59篇 |
2015年 | 52篇 |
2014年 | 60篇 |
2013年 | 116篇 |
2012年 | 127篇 |
2011年 | 133篇 |
2010年 | 88篇 |
2009年 | 103篇 |
2008年 | 129篇 |
2007年 | 94篇 |
2006年 | 91篇 |
2005年 | 80篇 |
2004年 | 51篇 |
2003年 | 48篇 |
2002年 | 45篇 |
2001年 | 16篇 |
2000年 | 15篇 |
1999年 | 13篇 |
1998年 | 12篇 |
1997年 | 9篇 |
1996年 | 18篇 |
1995年 | 7篇 |
1994年 | 6篇 |
1993年 | 8篇 |
1992年 | 5篇 |
1991年 | 4篇 |
1990年 | 4篇 |
1989年 | 4篇 |
1988年 | 3篇 |
1986年 | 3篇 |
1985年 | 5篇 |
1984年 | 3篇 |
1983年 | 4篇 |
1982年 | 4篇 |
1981年 | 3篇 |
1979年 | 3篇 |
1978年 | 2篇 |
1976年 | 2篇 |
1975年 | 2篇 |
1961年 | 1篇 |
1956年 | 1篇 |
1955年 | 2篇 |
1953年 | 2篇 |
排序方式: 共有1694条查询结果,搜索用时 15 毫秒
1.
The influence of different referencing methods on the accuracy of δ13C value measurement of ethanol fuel by gas chromatography/combustion/isotope ratio mass spectrometry 下载免费PDF全文
2.
João Marcos G. Barbosa Milenna K. Fernandes Rodrigues Lurian C. David Taynara C. e Silva Danielly A. Fortuna Lima Naiara Z. Pereira Emmanuel B. D'Alessandro Anselmo E. de Oliveira Paulo H. Jorge da Cunha Maria Clorinda S. Fioravanti Nelson R. Antoniosi Filho 《Biomedical chromatography : BMC》2020,34(11):e4935
An innovative volatolomic approach employs the detection of biomarkers present in cerumen (earwax) to identify cattle intoxication by Stryphnodendron rotundifolium Mart., Fabaceae (popularly known as barbatimão). S. rotundifolium is a poisonous plant with the toxic compound undefined and widely distributed throughout the Brazilian territory. Cerumen samples from cattle of two local Brazilian breeds (‘Curraleiro Pé-Duro’ and ‘Pantaneiro’) were collected during an experimental intoxication protocol and analyzed using headspace (HS)/GC–MS followed by multivariate analysis (genetic algorithm for a partial least squares, cluster analysis, and classification and regression trees). A total of 106 volatile organic metabolites were identified in the cerumen samples of bovines. The intoxication by S. rotundifolium influenced the cerumen volatolomic profile of the bovines throughout the intoxication protocol. In this way, it was possible to detect biomarkers for cattle intoxication. Among the biomarkers, 2-octyldecanol and 9-tetradecen-1-ol were able to discriminate all samples between intoxicated and nonintoxicated bovines. The cattle intoxication diagnosis by S. rotundifolium was accomplished by applying the cerumen analysis using HS/GC–MS, in an easy, accurate, and noninvasive way. Thus, the proposed bioanalytical chromatography protocol is a useful tool in veterinary applications to determine this kind of intoxication. 相似文献
3.
Dr. Felipe L. Coelho Eduarda S. Gil Dr. Paulo F. B. Gonçalves Dr. Leandra F. Campo Dr. Paulo H. Schneider 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(34):8157-8162
In this work, a series of 2-chalcogenylindoles was synthesized by an efficient methodology, starting from chalcogenoalkynes, including a previously unreported tellurium indole derivative. For the first time, these 2-substituted chalcogenylindoles were obtained in the absence of metal catalyst or base, under thermal conditions only. In addition, the results described herein represent a methodology with inverse regioselectivity for the chalcogen functionalization of indoles. 相似文献
4.
5.
Calibration of the relationship between height and phase is of uttermost importance to perform accurate 3D measurements in phase measurement profilometry. This work reports a different approach to this problem by first looking at the analytical expression for this relationship and determining the regime spanned by the fringe analysis method. The conclusions thus ascertained, amply justify confronting the analytical expression with a simple normalization procedure of the experimental data, with a remarkable matching between both results. In light of this, a linear calibration procedure with just one plane is proposed and verified experimentally. 相似文献
6.
Nadir Arada Paulo Correia Adélia Sequeira 《Numerical Methods for Partial Differential Equations》2007,23(6):1468-1500
This article is concerned with the equations governing the steady motion of a viscoelastic incompressible second‐order fluid in a bounded domain. A new proof of existence and uniqueness of strong solutions is given. In addition, using appropriate finite element methods to approximate a coupled equivalent problem, sharp error estimates are obtained using a fixed point argument. The method is applied to the two‐dimensional lid‐driven cavity problem, at low Reynolds number and in a certain range of values of the viscoelastic parameters, to analyze the combined effects of inertia and viscoelasticity on the flow. © 2007 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq, 2007 相似文献
7.
The surface modification of tire rubber after treatment with saturated NaOH aqueous solution was investigated by HATR infrared analysis, potentiometric titration, and contact angle measurements. Infrared analysis of the powdered treated rubber showed a decrease in absorption at 1540, 1450, and 1395 cm(-1). This decrease is attributed to the removal of zinc stearate, an additive present in tire formulations that often migrates and diffuses to the surface, resulting in poor adhesion between the rubber and other materials. The potentiometric titration of the suspension of powdered rubber in 0.1 M NaCl showed that more hydrochloric acid was consumed by the untreated rubber, most likely a result of the hyrdrolysis of the zinc stearate to the organic acid. Contact angles of flat tire pieces showed an homogeneity enhancement of the treated rubber surface. The decrease of the zinc stearate on the treated rubber surface explains the improvement in the adhesion of this material to the cement matrix, observed in a previous research. The promising results of this study are a starting point for future research on incorporating rubber particles into cementitious materials as a means of successfully utilizing the vast amounts of tire waste currently in landfills. 相似文献
8.
Fonseca GS Umpierre AP Fichtner PF Teixeira SR Dupont J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(14):3263-3269
Stable transition-metal nanoparticles of the type [M(0)](n) are easily accessible through the reduction of Ir(I) or Rh(III) compounds dissolved in "dry" 1-n-butyl-3-methylimidazolium hexafluorophosphate ionic liquid by molecular hydrogen. The formation of these [M(0)](n) nanoparticles is straightforward; they are prepared in dry ionic liquid whereas the presence of the water causes the partial decomposition of ionic liquid with the formation of phosphates, HF and transition-metal fluorides. Transmission electron microscopy (TEM) observations and X-ray diffraction analysis (XRD) show the formation of [Ir(0)](n) and [Rh(0)](n) nanoparticles with 2.0-2.5 nm in diameter. The isolated [M(0)](n) nanoparticles can be redispersed in the ionic liquid, in acetone or used in solventless conditions for the liquid-liquid biphasic, homogeneous or heterogeneous hydrogenation of arenes under mild reaction conditions (75 degrees C and 4 atm). The recovered iridium nanoparticles can be reused several times without any significant loss in catalytic activity. Unprecedented total turnover numbers (TTO) of 3509 in 32 h, for arene hydrogenation by nanoparticles catalysts, have been achieved in the reduction of benzene by the [Ir(0)](n) in solventless conditions. Contrarily, the recovered Rh(0) nanoparticles show significant agglomeration into large particles with a loss of catalytic activity. The hydrogenation of arenes containing functional groups, such as anisole, by the [Ir(0)](n) nanoparticles occurs with concomitant hydrogenolysis of the C-O bond, suggesting that these nanoparticles behave as "heterogeneous catalysts" rather than "homogeneous catalysts". 相似文献
9.
Chemical, structural, and thermal properties of Zn(II)-Cr(III) layered double hydroxides intercalated with sulfated and sulfonated surfactants 总被引:1,自引:0,他引:1
Crepaldi EL Pavan PC Tronto J Valim JB 《Journal of colloid and interface science》2002,248(2):429-442
Zn(II)-Cr(III)-LDHs (layered double hydroxides) containing sulfated or sulfonated surfactants as the interlamellar anion were synthesized by the coprecipitation method. The syntheses were conducted under various different experimental conditions, such as the Zn : Cr ratio, pH, and aging time. In each of the prepared materials, unlike previously reported data, the interlayer anion arrangement did not change, being consistent with a perpendicular monolayer. The thermal decomposition process of the prepared materials was studied by a set of analysis methods, such as TG/DTA, TG/MS, PXRD, and FT-IR. From the results obtained it was possible to conclude that, in an air atmosphere, the anions decomposed by a partial combustion, leading to the formation of sulfide. The results also showed that sulfonated surfactants containing LDHs are much more stable than those containing sulfated surfactants. A mechanism was proposed for the thermal decomposition of such LDHs based on the experimental results. 相似文献
10.
Elizabeth P.G. Arêas José A.G. Arêas James Hamburger Warner L. Peticolas Paulo S. Santos 《Journal of colloid and interface science》1996,180(2):578
A remarkably high viscosity has been induced in protein aqueous solutions by the addition of certain structurally related organic solvents. The effect has been observed for lysozyme aqueous solutions containing tetramethylurea (TMU), dimethylsulfoxide (DMSO), dimethylformamide, and hexamethylphosphortriamide. The effect has also been induced in ferrocytochrome c aqueous solutions by TMU. Critical concentrations for both the protein and organic solvent were verified for the onset of the viscosity increase. A common feature of the solvents which were able to induce the effect is a dipolar moiety (C=O, S → O and P → O) and a nonpolar region represented by the methyl groups. The resulting fluids show an extremely restricted flow and a typical non-Newtonian, pseudoplastic behavior. Use was made of1H nuclear magnetic resonance (NMR) and Raman spectroscopy to characterize protein structural modifications and of13C NMR to investigate changes in relaxation times and chemical shifts in the solvent/water solutions. A systematic rheological characterization of the systems was undertaken for some of the solvents, and unusual patterns of viscous effects were identified for the solvent/water systems both with and without protein. The process was found to be at least partially reversible, as concluded from the recovered original solution rheological characteristics and the original protein1H NMR spectrum, after eliminating the organic solvent by ultrafiltration. The whole process was characterized as consisting of two mutually independent stages. The first involves an extensive conformational transition of the polypeptide backbone, from a predominantly α-helical to increased random coiled and β-sheet structures, with the occurrence of nonorthodox protein secondary structures at regions above the solvent critical point. The second stage consists of short-lived interchain contacts leading to an entanglement of the macromolecular system as a whole. A microphase reversion in the organic solvent/water mixture, supported by13C NMR and rheological results, is proposed as the driving force causing the observed behavior. 相似文献