首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   1007篇
  免费   75篇
  国内免费   21篇
化学   793篇
晶体学   2篇
力学   64篇
数学   105篇
物理学   139篇
  2024年   2篇
  2023年   6篇
  2022年   33篇
  2021年   48篇
  2020年   85篇
  2019年   63篇
  2018年   81篇
  2017年   50篇
  2016年   91篇
  2015年   70篇
  2014年   88篇
  2013年   124篇
  2012年   86篇
  2011年   73篇
  2010年   63篇
  2009年   40篇
  2008年   36篇
  2007年   19篇
  2006年   13篇
  2005年   6篇
  2004年   4篇
  2003年   5篇
  2002年   4篇
  2001年   1篇
  2000年   2篇
  1996年   1篇
  1995年   1篇
  1994年   1篇
  1993年   2篇
  1990年   2篇
  1988年   1篇
  1981年   2篇
排序方式: 共有1103条查询结果,搜索用时 15 毫秒
41.
Metal-free electrocatalysts for oxygen reduction reaction (ORR) are key to the development of efficient, durable, and low-cost alternatives to noble-metal-based electrocatalysts in fuel cell cathodes. In recent years, many efforts are directed to the metal-free catalyst based on heteroatom-doped graphene. In this work, we demonstrate that the graphene surface can be converted into the catalyst for the oxygen reduction by chemical functionalization. In this context, we first synthesized malononitrile-functionalized graphene oxide. Amidoximation of nitrile group and reduction in graphene oxide were then carried out by hydroxylamine in one step. The electrochemical behavior of functionalized graphene-modified electrode for the reduction in oxygen was studied. The results showed that the electrocatalyst fabricated by this method exhibited striking catalytic activities in alkaline solution. In alkaline solution, this catalyst showed a competitive activity to the commercial Pt catalyst via four-electron transfer pathway with better ORR selectivity and stability. In addition, this metal-free electrocatalyst exhibited tolerance to methanol crossover effect. Based on its outstanding performance, this functionalized graphene electrocatalyst showed the promising prospect of a metal-free catalyst for fuel cell with much lower cost than currently used Pt/C catalyst.  相似文献   
42.
43.
44.
The viability and a number of morphological properties of in situ astrocytes of rat spinal cord cultures including changes in surface area and migration of both cell body and nucleus were investigated at magnetic field intensities comparable to those currently used for magnetic resonance imaging. Viability of rat spinal astrocytes was studied after up to 72 hours of 2.1T static magnetic field exposure. Surface areas and two-dimensional centroids of both soma and nucleus after 2 hours of magnetic field exposure were determined and compared with those of the same cells before magnetic field exposure. Cell membrane ruffling was quantified using fractal analysis.  相似文献   
45.
Abstract

The oxidation of thiocyanate to polythiocyanic acid by peroxydisulfate was carried out in an aqueous solution at room temperature. The primary step is the decomposition of peroxydisulfate into sulfate-free radicals. At room temperature in the presence of peroxydisulfate as a oxidizing agent, HSCN polymerizes to (HSCN)n. The oxidation of thiocyanate in an aqueous solution is often complicated, but here we obtained the polythiocyanic acid as a major product. The products were characterized by elemental analysis, IR, UV- visible, H-NMR spectroscopy, and X-ray powder diffraction.  相似文献   
46.
Two new symmetrical diamines were designed and synthesized having different functional groups such as a pair of phenyl ether linkages, 2,3-diaryl substituted imidazole rings and CF3 groups as pendant, and characterized by FT-IR, 1H and 13C-NMR spectroscopy and elemental analysis. A series of new fluorescent poly(imide-ether)s (PIEs) was prepared by polymerization of the diamines with commercial tetracarboxylic dianhydrides such as pyromellitic dianhydride and 3,3′,4,4′-benzophenone tetracarboxylic dianhydride. The resulting PIEs were amorphous and had intrinsic viscosity [η] in the range of 0.42–0.51 dL/g. The weight average molecular weights (Mw) of these polymers were measured by GPC and were in the range of 28658–35595 g/mol with molecular weight distribution (MWD) of 2.12–2.27. These polymers were readily soluble in a variety of organic solvents and formed low-colored and flexible thin films with cut-off wavelength (λ0) in the range of 385–420 nm, and all PIEs films exhibited high optical transparency. They also possessed good thermal stability with 10% weight loss temperatures (T10%) in the range 486–537°C in N2. The glass transition temperatures (Tg) of PIEs are in the range 251–324°C. These polymers showed fluorescence emission in film and in solution at 459–476 nm with the quantum yields in the range 4–12%.  相似文献   
47.
Nanocomposite membranes based on polyelectrolyte complex (PEC) of chitosan/phosphotungstic acid (PWA) and different types of montmorillonite (MMT) were prepared as alternative membranes to Nafion for direct methanol fuel cell (DMFC) applications. Fourier transform infrared spectroscopy (FTIR) revealed an electrostatically fixed PWA within the PEC membranes, which avoids a decrease in proton conductivity at practical condition. Various amounts of pristine as well as organically modified MMT (OMMT) (MMT: Cloisite Na, OMMT: Cloisite 15A, and Cloisite 30B) were introduced to the PEC membranes to decrease in methanol permeability and, thus, enhance efficiency and power density of the cells. X-ray diffraction patterns of the nanocomposite membranes proved that MMT (or OMMT) layers were exfoliated in the membranes at loading weights of lower than 3 wt.%. Moreover, the proton conductivity and the methanol permeability as well as the water uptake behavior of the manufactured nanocomposite membranes were studied. According to the selectivity parameter, ratio of proton conductivity to methanol permeability, the PEC/2 wt.% MMT 30B was identified as the optimum composition. The DMFC performance tests were carried out at 70 °C and 5 M methanol feed and the optimum membrane showed higher maximum power density as well as acceptable durability compared to Nafion 117. The obtained results indicated that owing to the relatively high selectivity and power density, the optimum nanocomposite membrane could be considered as a promising polyelectrolyte membrane (PEM) for DMFC applications.  相似文献   
48.
The aim of this work was to prepare lactose imprinted polymer and study of its selectivity for the recognition of different mono- and disaccharides. A series of molecularly imprinted polymers (MIPs) against lactose were synthesized and their binding properties were compared with a Blank non-imprinted polymer. Methacrylamide (MAAM) and ethylene glycol dimethacrylate were used as functional monomer and cross-linker, respectively. Dimethylsulfoxide was also applied as polymerization solvent. Different lactose:MAAM ratios were applied and optimized MIP was selected in a conventional batch adsorption study. The dissociation constant and maximum binding sites of polymer were determined using the Scatchard analysis. The selectivity of MIP for different mono- and disaccharides was also evaluated. The results indicated that the shape of cavity and orientation of functional monomers in binding sites and the spatial arrangement of hydroxyl groups in saccharide structure were responsible for the selectivity of lactose imprinted polymer.  相似文献   
49.
Fe(NO3)3·9H2O is used as an efficient and effective catalyst for the one‐pot three‐component synthesis of highly functionalized piperidines from aromatic aldehydes, anilines and b–ketoesters in ethanol at ambient temperature. This procedure includes some important aspects like the easy work‐up, no need to column chromatography, simple and readily available precursors, and good to high yields.  相似文献   
50.
We report on a competitive immunoassay for the determination of aflatoxin B1 using fluorescence resonance energy transfer (FRET) from anti-aflatoxin B1 antibody (immobilized on the shell of CdTe quantum dots) to Rhodamine 123 (Rho 123-labeled aflatoxin B1 bound to albumin). The highly specific immunoreaction between the antibody against aflatoxin B1 on the QDs and the labeled-aflatoxin B1 brings the Rho 123 fluorophore (acting as the acceptor) and the QDs (acting as the donor) in close spatial proximity and causes FRET to occur upon photoexcitation of the QDs. In the absence of unlabeled aflatoxin B1, the antigen-antibody complex is stable, and strong emission resulting from the FRET from QDs to labeled aflatoxin B1 is observed. In the presence of aflatoxin B1, it will compete with the labeled aflatoxin B1-albumin complex for binding to the antibody-QDs conjugate so that FRET will be increasingly suppressed. The reduction in the fluorescence intensity of the acceptor correlates well with the concentration of aflatoxin B1. The feasibility of the method was established by the detection of aflatoxin B1 in spiked human serum. There is a linear relationship between the increased fluorescence intensity of Rho 123 with increasing concentration of aflatoxin B1 in spike human serum, over the range of 0.1–0.6 μmol·mL?1. The limit of detection is 2?×?10?11 M. This homogeneous competitive detection scheme is simple, rapid and efficient, and does not require excessive washing and separation steps.
Figure
A nanobiosensor has been fabricated based on a competitive immunoassay for the determination of aflatoxin B1 using fluorescence resonance energy transfer (FRET). In the presence of aflatoxin B1, it will compete with the labeled aflatoxin B1-albumin complex for binding to the antibody-QDs conjugate so that FRET will be increasingly suppressed.  相似文献   
[首页] « 上一页 [1] [2] [3] [4] 5 [6] [7] [8] [9] [10] [11] 下一页 » 末  页»
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号