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   248篇
  免费   23篇
  国内免费   29篇
化学   179篇
晶体学   5篇
力学   11篇
综合类   7篇
数学   20篇
物理学   78篇
  2024年   4篇
  2023年   3篇
  2022年   11篇
  2021年   12篇
  2020年   16篇
  2019年   14篇
  2018年   7篇
  2017年   5篇
  2016年   15篇
  2015年   13篇
  2014年   7篇
  2013年   16篇
  2012年   22篇
  2011年   19篇
  2010年   10篇
  2009年   7篇
  2008年   19篇
  2007年   13篇
  2006年   8篇
  2005年   7篇
  2004年   5篇
  2003年   4篇
  2002年   5篇
  2001年   9篇
  2000年   5篇
  1999年   9篇
  1998年   3篇
  1997年   3篇
  1996年   6篇
  1995年   3篇
  1994年   4篇
  1993年   2篇
  1992年   3篇
  1991年   1篇
  1990年   5篇
  1989年   2篇
  1988年   1篇
  1985年   1篇
  1982年   1篇
排序方式: 共有300条查询结果,搜索用时 15 毫秒
251.
Poly(trimethylene terephthalate) (PTT) nanocomposites containing carbon nanotubes (CNTs) with different surface structure and aspect ratio were prepared by melt compounding for electrospinning. The dispersion state of the CNTs in the composites was then examined utilizing rheology tools. The results show that carboxylic surface functionalized CNTs present better dispersion in the matrix than hydroxy surface functionalized CNTs because the former has stronger affinity to the PTT. Besides surface functionalization, the aspect ratio of CNTs is also vital to their final dispersion. The CNTs with lower aspect ratio are dispersed as individuals or small bundles while those with higher aspect ratio are dispersed mainly as flocs with large hydrodynamic radius, showing higher effective volume fraction. The presence of CNTs has a large influence on the morphologies of electrospun fiber and on the appearances of CNTs in the fibers. In the presence of CNTs with lower aspect ratio, continuous composite fibers are obtained. But the structure of those continuous fibers highly depends on the surface group of CNTs. Carboxylic surface functionalized CNTs are well embedded by the PTT and oriented along the fiber axis during electrospinning, leading to bead-free and uniform fiber morphology; while hydroxy surface functionalized CNTs show tortuous conformations with less orientation in the fibers, and as a result, the obtained fibers show beaded and misshaped morphologies. In the case of higher aspect ratio, however, the CNTs prefer to exist as entanglements or knots in the streamlines, and thereby only beaded or even uncontinuous fibers are obtained. Therefore, the formation and fiber morphology of PTT/CNT composite fibers obtained by electrospinning strongly depend on the surface functional groups of the CNTs, as well as on the CNT structure.  相似文献   
252.
We employed CE to identify mixtures of the toxic alkaloids lappaconitine, bullatine A, atropine sulfate, atropine methobromide, scopolamine hydrobromide, anisodamine hydrobromide, brucine, strychnine, quinine sulfate, and chloroquine in human blood and urine, using procaine hydrochloride as an internal standard. The separation employed a fused-silica capillary of 75 microm id x 60 cm length (effective length: 50.2 cm) and a buffer containing 100 mM phosphate and 5% ACN (pH 4.0). The sample was injected in a pressure mode and the separation was performed at a voltage of 16 kV and a temperature of 25 degrees C. The compounds were detected by UV absorbance at wavelengths of 195 and 235 nm. All the ten alkaloids were separated within 16 min. The method was validated with regard to precision (RSD), accuracy, sensitivity, linear range, LOD, and LOQ. In blood and urine samples, the detection limits were 5-40 ng/mL and linear calibration curves were obtained over the range of 0.02-10 microg/mL. The precision of intra- and interday measurements was less than 15%. Electrophoretic peaks could be identified either by the relative migration time or by their UV spectrum.  相似文献   
253.
Two DendriMac polymers (Dendri‐hydr and Dendri‐click) are efficiently and conveniently synthesized via the combination of living anionic polymerization (LAP) and hydrosilylation/click chemistry. Based on the end‐capping of DPE derivatives (DPE‐SiH and DPE‐DA) toward polymeric anions, the polymeric core and arms are effectively synthesized, and the base polymers can be regarded as polymeric bricks. Hydrosilylation and click chemistry are used as coupling reactions to construct the DendriMac polymers with high efficiency and convenience. The numbers of branched arms are calculated by SEC as 5.84 and 6.08 for Dendri‐hydr and Dendri‐click, respectively, which indicate that the DendriMac architectures exhibit high structural integrity. Because of its independence, high efficiency, and convenience, the whole construction can be regarded as the “building of polymeric bricks.”

  相似文献   

254.
以LiTi2(PO4)3为母体,以天然高岭石为起始原料,经高温固相反应制得了一系列新的锂快离子导体Li1.2+x-yYxTi1.9-xAl0.1Si0.1SyP2.9-yO12(以下简称Y-S-Lisicon).X射线粉末衍射分析结果表明在x≤0.3,y<(0.2+x)的组成范围内均能得到类似于Nasicon三方结构的相,同时还存在其他杂相.应用交流阻抗技术测定电导率的结果表明起始组成为x=0.1,y=0.15的合成物电导率最高,其在室温下的电导率为2.93×10-5 S·cm-1,在673 K时可达3.62×10-2 S·cm-1,其在473~673 K间的活化能为37.19 kJ·mol-1,分解电压为3.0 V.  相似文献   
255.
染料敏化太阳电池(DSC)是一种新型光伏电池。本文从高效率化和长期耐久性两方面分析了目前制约DSC产业化的因素,并综述了解决这些问题的最新研究成果。重点论述了世界DSC产业化研究的最新动态,并对这一新型太阳电池产业化的未来发展方向及发展前景进行了展望。  相似文献   
256.
Li  Shengqiang  Yan  Yurong  Zhong  Liang  Liu  Ping  Sang  Ye  Cheng  Wei  Ding  Shijia 《Mikrochimica acta》2015,182(11):1917-1924

We describe a new kind of electrochemical immunoassay for the peptide hormone prolactin. A glassy carbon electrode (GCE) was modified with a hybrid material consisting of graphene, single walled carbon nanotubes and gold nanoparticles (AuNPs) in a chitosan (CS) matrix. The graphene and the single wall carbon nanotubes were first placed on the GCE, and the AuNPs were then electrodeposited on the surface by cyclic voltammetry. This structure results in a comparably large surface for immobilization of the capturing antibody (Ab1). The modified electrode was used in a standard sandwich-type of immunoassay. The secondary antibody (Ab2) consisted of AuNPs with immobilized Ab2 and modified with biotinylated DNA as signal tags. Finally, alkaline phosphatase was bound to the biotinylated DNA-AuNPs-Ab2 conjugate via streptavidin chemistry. The enzyme catalyzes the hydrolysis of the α-naphthyl phosphate to form α-naphthol which is highly electroactive at an operating voltage as low as 180 mV (vs. Ag/AgCl). The resulting immunoassay exhibits high sensitivity, wide linear range (50 to 3200 pg∙mL‾1), low detection limit (47 pg∙mL‾1), acceptable selectivity and reproducibility. The assay provides a pragmatic platform for signal amplification and has a great potential for the sensitive determination of antigens other than prolactine.

The immunoassay for prolactin is based on a glassy carbon electrode modified with SWCNTs, graphene and antibody-coated gold nanoparticles, and a secondary antibody conjugated to other gold nanoparticles via a biotinylated DNA linker

  相似文献   
257.
A series of donor‐acceptor conjugated polymers incorporating benzodithiophene (BDT) as donor unit and phenanthrenequnioxaline as acceptor unit with different side chains have been designed and synthesized. For polymer P1 featuring the BDT unit and alkoxy chains substituted phenanthrenequnioxaline unit in the backbone, serious steric hindrance resulted in quite low molecular weight. The implementation of thiophene ring spacer in polymer P2 greatly suppressed the interannular twisting to extend the effective conjugation length and consequently gave rise to improved absorption property and device performance. In addition, utilizing the alkylthienyl side chains to replace the alkyl side chains at BDT unit in polymer P3 further enhanced the photovoltaic performance due to the increased conjugation length. For polymer P4, translating the alkoxy side chains at the phenanthrenequnioxaline ring into the alkyl side chains at thiophene linker group enhanced molecular planarity and strengthened π?π stacking. Consequently improved absorption property and increased hole mobility were achieved for polymer P4. Our results indicated that side chain engineering not only can influence the solubility of polymer but also can determine the polymer backbone planarity and hence the photovoltaic properties. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1915–1926  相似文献   
258.
Recent controversy over the discovery of clouding agents containing the banned chemical di(2-ethylhexyl) phthalate in beverages in 2011 in Taiwan has caused public concerns. For the detection of dimethyl phthalate (DMP) in environment water samples, an indirect competitive enzyme-linked immunosorbent assay (ic-ELISA) was developed in this paper. Dimethyl 4-aminophthalate (4-DMAP) was covalently attached to bovine serum albumin as immunogen by a diazotization method. The conjugation of DMAP and ovalbumin as coating antigen was obtained in the same way. Polyclonal antibody was obtained from New Zealand white rabbits. Under the optimized conditions, DMP was detected in the concentration range of 0.02–419 ng/mL with a detection limit of 0.01 ng/mL. The proposed method has been applied to the analysis of river water, lake water, and rain water samples. Satisfactory recoveries were obtained ranging from 90.6% to 105.5%. The cross-reactivities of the anti-DMP antibody to seven structurally related phthalate esters were below 10%. The data demonstrated that the ic-ELISA method described in our study is a simple, sensitive, and specific method and showed that this assay is a reliable tool to detect DMP in water samples.  相似文献   
259.
Here we developed a rapid method to detect acetylcholinesterase (AChE) activity by matrix‐assisted laser desorption/ionization Fourier transform mass spectrometry (MALDI‐FTMS) for screening irreversible AChE inhibitors. Due to its good salt‐tolerance and low sample consumption, MALDI‐FTMS could facilitate rapid detection, especially detection in real application. AChE activity was determined through calculating abundance of substrate and product in mass spectrometry. By this approach, we investigated the relation of organophosphorous (OP) concentrations and AChE inhibition. Shown in different inhibition curves from different OP pesticides, enzyme inhibitions still kept good correlation with concentration of OPs. Finally, this AChE‐inhibited method was applied to screen whole bloods of four decedents and discuss their death reason. In contrast to healthy persons, three of decedents showed low AChE activity, and probably died for irreversible AChE inhibitors. Through the following detecting in GC‐MS/MS, the possible death reason of these three decedents was confirmed, and another decedent actually died for sumicidin, a non‐AChE inhibitor. It demonstrated that screening irreversible AChE inhibitors by detecting enzyme activity in MALDI‐FTMS provided fast and accurate analysis results and excluded another toxicants not functioning on AChE. This method offered alternative choices for indicating the existence of enzyme inhibitors.  相似文献   
260.
Molecularly imprinted polymers (MIPs) are tailor-made polymers with high selectivity for a given analyte, or group of structurally related compounds. The influence of the process parameters (the moles of functional monomer and cross-linker, the selection of functional monomer and solvent) on the preparation of oseltamivir (OS)-imprinted polymers was investigated. A mathematical method for uniform design to optimize these selected parameters and to increase the MIP selectivity for template molecules was applied. The optimal conditions to synthesize MIP were 0.69 mmol 30% acrylamide (AA) + 70% 4-Vinylpyridine (4-VP) and 5.0 mmol ethylene glycol dimethacrylate (EGDMA) copolymerized in 5 ml toluene in the presence of 0.1 mmol OS. MIP showed high affinity and selectivity for separation of the template molecule from other compounds. In the present study, we have established an effective LC-MS/MS method to identify and quantify OS with good sensitivity, accuracy and precision.  相似文献   
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