全文获取类型
收费全文 | 351篇 |
免费 | 19篇 |
国内免费 | 5篇 |
专业分类
化学 | 261篇 |
晶体学 | 1篇 |
力学 | 15篇 |
数学 | 39篇 |
物理学 | 59篇 |
出版年
2023年 | 2篇 |
2022年 | 3篇 |
2021年 | 17篇 |
2020年 | 22篇 |
2019年 | 11篇 |
2018年 | 19篇 |
2017年 | 7篇 |
2016年 | 18篇 |
2015年 | 11篇 |
2014年 | 14篇 |
2013年 | 27篇 |
2012年 | 21篇 |
2011年 | 20篇 |
2010年 | 16篇 |
2009年 | 7篇 |
2008年 | 24篇 |
2007年 | 19篇 |
2006年 | 15篇 |
2005年 | 15篇 |
2004年 | 10篇 |
2003年 | 7篇 |
2002年 | 14篇 |
2000年 | 3篇 |
1999年 | 3篇 |
1998年 | 5篇 |
1997年 | 2篇 |
1996年 | 5篇 |
1995年 | 5篇 |
1994年 | 4篇 |
1993年 | 2篇 |
1992年 | 1篇 |
1990年 | 1篇 |
1987年 | 1篇 |
1986年 | 1篇 |
1985年 | 2篇 |
1984年 | 7篇 |
1983年 | 2篇 |
1982年 | 4篇 |
1981年 | 4篇 |
1978年 | 1篇 |
1972年 | 2篇 |
1971年 | 1篇 |
排序方式: 共有375条查询结果,搜索用时 312 毫秒
21.
Rafael M. de Almeida Victoria C. Ferrari Dr. Juliana dos S. Souza Dr. Flavio L. Souza Wendel A. Alves 《Chemphyschem》2020,21(6):476-483
Herein, a detailed investigation of the surface modification of a zinc oxide (ZnO) nanorod electrode with FeOOH nanoparticles dispersed in glycine was conducted to improve the water oxidation reaction assisted by sunlight. The results were systematically analysed in terms of the general parameters (light absorption, charge separation, and surface for catalysis) that govern the photocurrent density response of metal oxide as photoanode in a photoelectrochemical (PEC) cell. ZnO electrodes surface were modified with different concentration of FeOOH nanoparticles using the spin-coating deposition method, and it was found that 6-layer deposition of glycine-FeOOH nanoparticles is the optimum condition. The glycine plays an important role decreasing the agglomeration of FeOOH nanoparticles over the ZnO electrode surface and increasing the overall performance. Comparing bare ZnO electrodes with the ones modified with glycine-FeOOH nanoparticles an enhanced photocurrent density can be observed from 0.27 to 0.57 mA/cm2 at 1.23 VRHE under sunlight irradiation. The impedance spectroscopy data aid us to conclude that the higher photocurrent density is an effect associated with more efficient surface for chemical reaction instead of electronic improvement. Nevertheless, the charge separation efficiency remains low for this system. The present discovery shows that the combination of glycine-FeOOH nanoparticle is suitable and environmentally-friend cocatalyst to enhance the ZnO nanorod electrode activity for the oxygen evolution reaction assisted by sunlight irradiation. 相似文献
22.
Flavio Antonio Franchina Delphine Zanella Eliane Lazzari Pierre‐Hugues Stefanuto Jean‐Franois Focant 《Journal of separation science》2020,43(9-10):1790-1799
Headspace gas chromatography is frequently used for aroma profiling thanks to its ability to naturally exploit the volatility of aroma compounds, and also to provide chemical information on sample composition. Its main advantages rely on simplicity, no use of solvent, amenability to automation, and the cleanliness of the extract. In the present contribution, the most effective sampling (dynamic extraction), separation (multidimensional gas chromatography), and detection (mass spectrometry) techniques for untargeted analysis are exploited in combination, showing their potential in unraveling aroma profiles in fruit beers. To complete the overall analytical process, a neat workflow for data analysis is discussed and used for the successful characterization and identification of five different beer flavors (berries, cherry, banana, apple, and peach). From the technical viewpoint, the coupling of purge‐and‐trap, comprehensive two‐dimensional gas chromatography, and mass spectrometry makes the global methodology unique, and it is for the first time discussed. A (low‐)flow modulation approach allowed for the full transfer into the second dimension with mass‐spectrometry compatible flow (< 7 mL/min), avoiding the need of splitting before detection and making the overall method sensitive (1.2–5.2‐fold higher signal to noise ratio compared to unmodulated gas chromatography conditions) and selective. 相似文献
23.
Amyloglucosidase from Novo (Copenhagen, Denmark) was immobilized in controlled pore silica particles with the silane-glutaraldehyde
covalent method. Thermal stability of the free and immobilized enzyme (IE) was determined with 30% (w/v) α-amylase liquefied
cassava starch, pH 4.5, temperatures from 35 to 75°C. Free amyloglucosidase maintained its activity practically constant for
240 min and temperatures up to 50°C. The IE has shown higher stability retaining its activity for the same period up to 60°C.
Half-life for free enzyme was 20.6, 6.44, 2.07, 0.69, and 0.24 h for 55, 60, 65, 70, and 75°C, respectively, whereas the IE
at the same temperatures had half-lives of 116.4, 30.88, 8.52, 2.44, and 0.73 h. The energy of thermal deactivation was thus
50.6 and 57.6 kcal/mol, respectively for the free and IE, confirming stabilization by immobilization. 相似文献
24.
Yun Zou Meriem Gaida Flavio A. Franchina Pierre-Hugues Stefanuto Jean-Franois Focant 《Molecules (Basel, Switzerland)》2022,27(6)
Coffee, one of the most popular beverages in the world, attracts consumers by its rich aroma and the stimulating effect of caffeine. Increasing consumers prefer decaffeinated coffee to regular coffee due to health concerns. There are some main decaffeination methods commonly used by commercial coffee producers for decades. However, a certain amount of the aroma precursors can be removed together with caffeine, which could cause a thin taste of decaffeinated coffee. To understand the difference between regular and decaffeinated coffee from the volatile composition point of view, headspace solid-phase microextraction two-dimensional gas chromatography time-of-flight mass spectrometry (HS-SPME-GC×GC-TOFMS) was employed to examine the headspace volatiles of eight pairs of regular and decaffeinated coffees in this study. Using the key aroma-related volatiles, decaffeinated coffee was significantly separated from regular coffee by principal component analysis (PCA). Using feature-selection tools (univariate analysis: t-test and multivariate analysis: partial least squares-discriminant analysis (PLS-DA)), a group of pyrazines was observed to be significantly different between regular coffee and decaffeinated coffee. Pyrazines were more enriched in the regular coffee, which was due to the reduction of sucrose during the decaffeination process. The reduction of pyrazines led to a lack of nutty, roasted, chocolate, earthy, and musty aroma in the decaffeinated coffee. For the non-targeted analysis, the random forest (RF) classification algorithm was used to select the most important features that could enable a distinct classification between the two coffee types. In total, 20 discriminatory features were identified. The results suggested that pyrazine-derived compounds were a strong marker for the regular coffee group whereas furan-derived compounds were a strong marker for the decaffeinated coffee samples. 相似文献
25.
26.
27.
We prove that given a compact n-dimensional boundaryless manifold M, n?2, there exists a residual subset R of Diff1(M) such that if f∈R admits a spectral decomposition (i.e., the non-wandering set admits a partition into a finite number of transitive compact sets), then this spectral decomposition is robust in a generic sense (tame behavior). This implies a C1-generic trichotomy that generalizes some aspects of a two-dimensional theorem of Mañé [Topology 17 (1978) 386-396].Lastly, Palis [Astérisque 261 (2000) 335-347] has conjectured that densely in Diffk(M) diffeomorphisms either are hyperbolic or exhibit homoclinic bifurcations. We use the aforementioned results to prove this conjecture in a large open region of Diff1(M). 相似文献
28.
We study the problem of asset and liability management of participating insurance policies with guarantees. We develop a scenario optimization model for integrative asset and liability management, analyze the tradeoffs in structuring such policies, and study alternative choices in funding them. The nonlinearly constrained optimization model can be linearized through closed form solutions of the dynamic equations. Thus large-scale problems are solved with standard methods. We report on an empirical analysis of policies offered by Italian insurers. The optimized model results are in general agreement with current industry practices. However, some inefficiencies are identified and potential improvements are highlighted. 相似文献
29.
Flavio S. Damos Rita C.S. Luz Auro A. Tanaka Lauro T. Kubota 《Analytica chimica acta》2010,664(2):144-10063
The development of a simple, efficient and sensitive sensor for dissolved oxygen is proposed using the host-guest binding of a supramolecular complex at a host surface by combining a self-assembled monolayer (SAM) of mono-(6-deoxy-6-mercapto)-β-cyclodextrin (βCDSH), iron (III) tetra-(N-methyl-4-pyridyl)-porphyrin (FeTMPyP) and cyclodextrin-functionalized gold nanoparticles (CDAuNP). The supramolecular modified electrode showed excellent catalytic activity for oxygen reduction. The reduction potential of oxygen was shifted about 200 mV toward less negative values with this modified electrode, presenting a peak current much higher than those observed on a bare gold electrode. Cyclic voltammetry and rotating disk electrode (RDE) experiments indicated that the oxygen reduction reaction involves probably 4-electrons with a rate constant (kobs) of 7 × 104 mol−1 L s−1. A linear response range from 0.2 up to 6.5 mg L−1, with a sensitivity of 5.5 μA L mg−1 (or 77.5 μA cm−2 L mg−1) and a detection limit of 0.02 mg L−1 was obtained with this sensor. The repeatability of the proposed sensor, evaluated in terms of relative standard deviation was 3.0% for 10 measurements of a solution of 6.5 mg L−1 oxygen. 相似文献
30.
Flavio Ceretta Alessandro Zaggia Lino Conte Bruno Ameduri 《Journal of polymer science. Part A, Polymer chemistry》2013,51(15):3202-3212
4′‐Nonafluorobutylstyrene (3) was synthesized and polymerized by conventional and controlled radical polymerization (iodine transfer polymerization (ITP)). Such an aromatic fluoromonomer was prepared from Ullmann coupling between 1‐iodoperfluorobutane and 4‐bromoacetophenone followed by a reduction and a dehydration in 50% overall yield. Two radical polymerizations of (3) were initiated by AIBN either under conventional or controlled conditions, with 1‐iodoperfluorohexane in 84% monomer conversion and in 50% yield. ITP of (3) featured a fast monomer conversion and a linear evolution of the ln([M]0/[M]) versus time. The kinetics of radical homopolymerization of (3) enabled one to assess its square of the propagation rate to the termination rate (kp2/kt) in ITP conditions (36.2·10?2 l·mol?2·sec?2 at 80 °C) from the Tobolsky's kinetic law. Polydispersity index (?) of the fluoropolymer achieved by conventional polymerization was 1.30 while it worthed 1.15 when synthesized by ITP. Thermal stabilities of these oligomers were satisfactory (10% weight loss under air occurred from 305 °C) whereas the melting point was 47 °C. Contact angles and surface energies assessed from spin‐coated poly(3) films obtained by conventional (hysteresis = 18°, surface energy 18 mN.m?1) and ITP (hysteresis = 47°, surface energy 15 mN.m?1) evidenced ? values' influence onto surface properties of the synthesized polymers. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3202–3212 相似文献