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   1808篇
  免费   169篇
  国内免费   305篇
化学   1826篇
晶体学   40篇
力学   4篇
综合类   20篇
数学   2篇
物理学   390篇
  2024年   6篇
  2023年   38篇
  2022年   85篇
  2021年   64篇
  2020年   94篇
  2019年   68篇
  2018年   56篇
  2017年   78篇
  2016年   74篇
  2015年   80篇
  2014年   84篇
  2013年   142篇
  2012年   141篇
  2011年   98篇
  2010年   93篇
  2009年   104篇
  2008年   103篇
  2007年   142篇
  2006年   96篇
  2005年   92篇
  2004年   105篇
  2003年   79篇
  2002年   64篇
  2001年   42篇
  2000年   49篇
  1999年   32篇
  1998年   31篇
  1997年   28篇
  1996年   19篇
  1995年   25篇
  1994年   10篇
  1993年   18篇
  1992年   10篇
  1991年   7篇
  1990年   9篇
  1989年   7篇
  1988年   2篇
  1987年   3篇
  1986年   2篇
  1985年   2篇
排序方式: 共有2282条查询结果,搜索用时 15 毫秒
31.
阿利新蓝 (AlcianBlue)是一种从植物中提取出的天然物。于 1 944年由Haddock和Wood在实验室通过多次实验后所发现。它的水溶液呈天蓝色 ,着色性好而且吸光系数很大。又因它较好的水溶性。所以可以作为高效的生物染色剂[1,2 ] ,用于粘蛋白染色、细菌染色及聚酯、纤维素等人造和天然纤维的染料[3 ] 。基于它的重大应用前景和较高的商业价值 ,探索出一条合理的工业化合成路线就非常重要了。有关阿利新蓝的应用虽然有很多 ,但始终未见合成阿利新蓝的文献报道。在设计它的有机合成时必然涉及酞菁铜 (PcCu)的氯甲基化反…  相似文献   
32.
研究了溴酚蓝(BPB)·亚甲蓝(MB)等色染料离子对萃取光度测定银、汞和铜的方法。首先将被测金属离子形成[Me(phen)3]BPB的二氯乙烷萃取液,用KCN解析并反萃入水相,而后加入和溴酚蓝等色的亚甲蓝溶液继续萃取。由于等色染料离子对和Me(CN)nBPB三元络合物同时进入二氯乙烷中而提高了灵敏度、测定Ag、Hg和Cu的摩尔吸光系数均在105L·mol(-1)·cm(-1)以上。  相似文献   
33.
制备了普鲁士蓝修饰的丝网印刷过氧化氢传感器,研究了过氧化氢在该修饰电极上的电催化还原特性,考察了有关修饰膜制备和试验条件对传感器性能的影响。结果表明,pH4.0的0.2mol·L-1KH2PO4 K2HPO4缓冲溶液(PBS)中,修饰电极对过氧化氢显示出快速的电化学响应,较高的稳定性、重现性和催化活性,测定的线性范围为1.0×10-5~1.0×10-3mol·L-1,相关系数为0.999,检出限为6.0×10-6mol·L-1(3σ)。电极制作方法简便,可用于实际样品的测定。  相似文献   
34.
The analytical treatment of a model considering the electrooxidation of p-porous silicon layers under galvanostatic conditions is able to give account of experimental facts such as the shape and location of the electroluminescence peak as well as of the spectral shift of the electroluminescence peak produced by oxidation. The proposed model considers electroluminescence to be the result of electron injection into the conduction band by an adsorbed intermediate produced by electrooxidation of the surface coverage with hydrogen or siloxene of the silicon nanocrystallites. The access of holes to the surface is made possible by low accumulation layer conditions and is the rate determining step in the electroluminescence mechanism. In this way it is possible to give a satisfactory explanation to the shift towards the blue experimented by the electroluminiscence emission maximum as a consequence of electrooxidation.  相似文献   
35.
The composition, overall stability constant and molar absorptivity of the chelate of gallium(III) ion with semimethylthymol blue, SMTB, were determined spectrophotometrically in acetate buffer (pH 4.5–5). A violet Ga(SMTB) chelate was formed with logarithmic overall stability constant of 18.0±0.1 (I=0.1) and molar absorptivity of 4.25×104l mol–1cm–1 (max 580 nm). SMTB is proposed as a new reagent for the spectrophotometric determination of micro-molar amounts of gallium(III). The colour development depends on time, temperature, pH and buffer species. The interference of different cations, anions and organic acids on gallium(III) determination was also investigated. Beer's law was obeyed for 3.5–31.3 gGa(III)/25ml (0.14–1.25 g ml–1). SMTB was used for the spectrophotometric determination of gallium in different grade minerals and ores and the results were of acceptable error and relative standard deviation. Comparison between the two suggested methods and atomic absorption spectrometry for Ga(III) determination was carried out.  相似文献   
36.
Toluidine blue(TB) is a good sensitizer for the polymerization of acrylnmide(AM) induced by He-Ne laser. With TB as a sensitizer and various alcoholamine as donors, the photoredox of TB and the polymerization kinetics of AM induced by He-Ne laser were investigated. It was found that either for the photoredox of TB or for the polymerization of AM, the activity of alcoholamine increases in the order of EOA相似文献   
37.
Sol-gel-derived prussian blue-silicate amperometric glucose biosensor   总被引:1,自引:0,他引:1  
A new type of inorganic biosensor is introduced. The sensor comprises glucose oxidase enzymes encapsulated in a sol-gel-derived Prussian blue-silicate hybrid network. Glucose is detected by the biocatalytic reduction of oxygen followed by catalytic reduction of hydrogen peroxide by the Prusian blue catalyst. The sol-gel silicate entails a rigid encapsulating matrix, the Prussian blue provides chemical catalysis and charge mediation from the reduction site to the supporting electrode, and the enzyme is responsible for the biocatalysis. The feasibility of a dual optical/electrochemical mode of analysis is also demonstrated.  相似文献   
38.
Three highly sensitive spectrophotometric methods for the determination of platinum(IV) have been developed, based on its colour reactions with molybdate and basic dyes (BD) in aqueous solution in the presence of poly(vinyl alcohol). Platinum(IV) reacts with molybdate and BD to form ion — association complexes of composition (BD)2[Pt (MoO4)3]. The molar absorptivities are between 6.83 × 105 and 9.51 × 105 dm3mol–1cm–1, the highest value being found with nile blue. Suitable conditions for the reactions and the effects of foreign ions were investigated. The methods can be applied to the spectrophotometric determination of trace amounts of platinum(IV) in some catalysts and ores.  相似文献   
39.
《Electroanalysis》2005,17(3):210-222
Presented in this work is the first step towards an enzymeless/mediatorless glucose sensor. We first observed remarkable electrocatalytic oxidation of glucose using combinative ruthenium oxide (RuOx)‐Prussian blue (PB) analogues (designated as mvRuOx‐RuCN, mv: mixed valent) at ca. 1.1 V (vs. Ag/AgCl) in acidic media (pH 2 Na2SO4/H2SO4). Individual RuOx and PB analogs failed to give any such catalytic response. A high ruthenium oxidation state (i.e., oxy/hydroxy‐RuVII, E°≈1.4 V vs. RHE), normally occurring in strong alkaline conditions at RuOx‐based electrodes, was electrogenerated and stabilized (without any conventional disproportionation reaction) in the mvRuOx‐RuCN matrix for glucose catalysis. Detail X‐ray photoelectron spectroscopic studies can fully support the observation. The catalyst was chemically modified onto a disposable screen‐printed carbon electrode and employed for the amperometric detection of glucose via flow injection analysis (FIA). This system has a linear detection range of 0.3–20 mM with a detection limit and sensitivity of 40 μM (S/N=3) and 6.2 μA/(mM cm2), respectively, for glucose. Further steps towards the elimination of interference and the extendibility to neutral pHs were addressed.  相似文献   
40.
Ab initio molecular orbital and density functional theory (DFT) in conjunction with different basis sets calculations were performed to study the N? H…O and S? H…O blue‐shifted H‐bonds in the HNO…HFSO2 complex. The geometric structures, vibrational frequencies, and interaction energies were calculated by both standard and CP‐corrected methods. Natural bond orbital (NBO) analysis was used to investigate the origin of blue‐shifted H‐bonds, showing that the decrease in the σ*(N? H) and σ*(S? H) is due to the electron density redistribution effect. The structure reorganization effect on the blue‐shifted hydrogen bonds was discussed in detail. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007  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