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1.
《Electroanalysis》2004,16(9):748-756
A strategy for constructing a global multivariate calibration model that includes calibration samples measured over time on different days is developed and applied in electroanalysis. Both synthetic and real samples (tap, extracted and river water) are analyzed by differential‐pulse anodic stripping voltammetry, showing the suitability of the global model constructed that provides successful results similar to those of the usual multivariate calibration. In addition the capability of discrimination of this model is evaluated in prediction for the mean of three replicates with estimation of probability of false noncompliance, α, and false compliance, β, being found 3.1, 11.2, 6.7 and 64.7 nM for nominal concentrations of zinc, cadmium, lead and copper of 96.0, 40.4, 37.3 and 328.0 nM respectively when α=β=0.05. It has been proven that the use of the global calibration does not imply a loss of multivariate analytical sensitivity, using this parameter as quality index of the analytical procedure. The viability of using calibration maintenance strategies with electroanalytical techniques is shown, providing a way to save time and experimental effort when these techniques are used in routine analysis. 相似文献
2.
To incorporate an acceptor type polythiophene segment onto a supramolecular block copolymer for potential light harvesting applications, effective synthetic routes for the end‐functionalized and acceptor‐substituted polythiophenes are critical. The Ullmann coupling reaction can be utilized to obtain electron‐deficient polythiophenes and to attach terminal thiophene units that carry functional groups. In this article, the reactions involving a 2,5‐dibromothiophene monomer containing an electron‐withdrawing fluorinated ester and 5‐bromo‐2‐thiophenecarboxaldehyde (the end‐capper) were studied in detail. It was found that the Ullmann coupling reaction of the dibromide is very fast (completed in a few minutes) and the terminal bromine group does not survive long under the reaction condition. These findings lead to the development of an effective procedure for aldehyde end‐capping of electron‐deficient polythiophenes. Polymers with molecular weights around 4000 Da are routinely obtained. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 41–47, 2007 相似文献
3.
A polymerized quaternary ammonium salt polydiallyldimethylammonium chloride, exhibiting high stability to heat and base, was prepared and applied as phase-transfer catalyst (PTC) in halogen-exchange (Halex) fluorination of chloronitrobenzenes to give excellent yields of corresponding fluoronitrobenzenes. Dimethyl sulfoxide was found to be the best solvent when microwave was applied as heating resource. 相似文献
4.
We wish to report synthesis of perfluorinated functionalized, branched ethers from their hydrocarbon analogues by direct fluorination. Yields up to 90%, with high purities, have been obtained at ambient temperature and pressure. This technique will likely develop into a new general method for producing perfluorinated, hyperbranched and dendritic polymers. 相似文献
5.
用光电化学电流法研究了铅、铅砷、铅锑和铅铋合金在4.5mol·L-1H2SO4溶液(22℃)中,以0.9V(vs.Hg/Hg2SO4)极化7h而形成的阳极膜中的氧化铅的半导体性质,合金添加剂砷、锑和铋对t-PbO(四方氧化铝)和o-PbO(斜方氧化铝)的禁带宽度没有影响,从量子效率和电位的关系可求Pb,Pb-lat%As(at%表示原子百分比,全文同),Pb-lat%Sb和Sb-lat%Bi上膜中t-Pbo的施主密度(ND)分别为9.3×1015,1.0×1016,3.1×1016和1.3×1017cm-3,平带位分别为-0.20,-0.22,-0.28和-0.08V(vs.Hg/Hg2SO4).比较VA元素砷、锑和铋对上述膜中t-Pbo的ND(从而自由电子密度)和膜中t-Pbo的生长速率的影响,可认为法添加剂砷、锑和铋对阳极膜中t-Pbo的作用符合Hauffe规则. 相似文献
6.
V. Riveros M. Gulppi M. Páez J. H. Zagal C. M. Rangel D. Huerta P. Skeldon G. E. Thompson 《Journal of Solid State Electrochemistry》2006,10(2):83-90
Using voltage-time responses and cyclic voltammetry, the initial stages of anodizing of Al–2.1 at.% Ag and Al–4 at.% Ag alloys
are shown to depend upon the heat treatment of the alloys and the pre-treatment of the alloy surfaces. Chemical polishing
of solution-treated alloys leads to relatively uniform anodic oxidation on a relatively smooth alloy surface, in the absence
of significant effects of coarse, silver-rich intermetallics. In contrast, losses of current to oxygen generation arise for
the roughened alloy surface from mechanical polishing. With ageing, secondary reactions at the relatively silver-rich intermetallics
are more prevalent, although the effects on the voltage-time response depend upon the balance between processes occurring
on the matrix and intermetallic regions, including film growth, oxygen generation within the anodic film, film damage due
to release of oxygen, dissolution of silver species and re-growth of damaged film. 相似文献
7.
用碳糊电极阳极溶出法测定桑色素的含量。在0.15mol·L-1NH4Cl 氨水缓冲溶液的介质中富集120s,桑色素在+0.10V(vs.SCE)左右出现阳极溶出峰。其峰电流的大小与桑色素的浓度呈线性关系。线性范围为4.00×10-6~1.40×10-5mol·L-1,相关系数为0.9996,检出限可达1.00×10-6mol·L-1,回收率为99.87%~102.01%。此法不用汞电极,灵敏度高,操作方便、快捷,成功地用于甘草提取物中桑色素的测定。 相似文献
8.
Andreas Charalambous 《Analytica chimica acta》2005,547(1):53-58
This work is an investigation into the utility of bismuth-film electrodes (BiFEs) for the determination of indium in the presence of cadmium and lead by square wave anodic stripping voltammetry (SWASV). The purpose of this study was to demonstrate that, after judicious choice of the associated chemical and instrumental conditions, it is possible to achieve satisfactory separation of the relevant stripping peak and, thus, to determine simultaneously trace concentrations of cadmium, lead and indium. It was conclusively demonstrated that a BiFE performed better than the equivalent mercury-film electrode (MFE) in this particular application. 相似文献
9.
The [4+2] cyclodimerization of cyclohexa-2,4-dienone derivatives of the orthoquinone monoketal and orthoquinol types has been the topic of numerous investigations over the last 50 years in the aim of rationalizing the extraordinary level of regio-, site-, and stereoselectivities observed in these processes. In particular, the double diastereo-π-facial differentiation expressed in cyclodimerizations of chiral orthoquinols (i.e., 6-alkyl-6-hydroxycyclohexa-2,4-dienones) is an important aspect of these transformations, for they relate to the construction of several natural products. The experimental and theoretical results that are described in this article offer a comprehensive understanding of the factors controlling these site-specific regio- and diastereoselectivities. Our interpretation of these results relies on a combination of Woodward-Hoffmann and Salem-Houk secondary orbital interactions and Cieplak-type hyperconjugative effects in bispericyclic C2-symmetric transition states. 相似文献
10.
《Electroanalysis》2005,17(20):1861-1864
Electrochemical study of barley grain lipid‐transfer protein (LTP) revealed that it may belong to the metal‐binding protein class. Using differential pulse polarography the presence of Cu(II) and Zn(II) ions in the native LTP structure was proved, as well as its affinity for binding Ni(II) ion. Application of a more sensitive electroanalytical technique, such as anodic stripping voltammetry with analyte preconcentration, revealed the presence of Pb(II) and Cd(II) ions and also enabled the following Hg(II) ion binding. Possible biological role of LTP in plant stress response and its contribution to barley phytoextraction potential are discussed. 相似文献