Chlorpromazine hydrochloride as a new redox indicator in vanadametry

Chlorpromazine hydrochloride is proposed as an indicator in the vanadametric titration of iron(II) and molybdenum(V). It gives a sharp, reversible colour change from green to violet at the equivalence point. It has advantages over the diphenylamine class of indicators. Its redox and transition potentials are reported.     

Tin(II) sulphate as a new reductimetric titrant--direct titration of thallium(III) with use of ion-pair and redox indicators

The use of tin(II) sulphate as a direct reductimetric titrant for thallium(III) has been investigated, with potentiometric and visual detection of the end-point. Some azure dyes are used as redox indicators and Methylene Blue is used as both a redox and an ion-pair indicator.     

Test determination of reducing agents using noncovalently immobilized quinonimine indicators

The noncovalent immobilization of indophenols (2,6-dichloroindophenol and 2,6-dibromoin-doguaiacol) and indamines (Variamine Blue and Bindshendler’s Green) on reversed-phase silica gels and ion exchangers was studied. It was shown that the properties of indicator powders can be improved by the double modification of reversed-phase silica gels with cetyltrimethylammonium chloride and 2,6-dichloroindophenol or with dodecyl sodium sulfate and Bindshlender’s Green. Ionization constants and formal redox potentials of the noncovalently immobilized quinonimine compounds were determined by solid-phase spectrophotometry. Indicator tubes and indicator powders were proposed for the test determination of 0.3–1000 mg/L ascorbic acid and 0.02–3.0 mg/L iron(II)     

Argentometric determination of iodide and cyanide using a depolarisation end-point

It has been shown that the depotarisation end-point technique, based on the phenomenon of a sudden out-of-balance current, produced by the establishment of a new redox potential at the indicator electrode in a pre-balanced circuit, can also be applied to precipitation titrations. The use of a platinum indicator electrode instead of one made of silver, and determination in very dilute solution, yield better results than those obtained using the classical potentiometric method.     

Xerogels doped with phosphomolybdic heteropoly compounds: Indicator tubes and indicator powders for determining hydrazines and tin(II) in solution

Xerogels were prepared on the basis of silicon dioxide and doped with phosphomolybdic heteropoly acid, its ammonium salt, and the Vavele reagent. Reactions of modified xerogels with hydrazines, ascorbic acid, hydroquinone, iodide ion, and iron(II) and tin(II) ions were studied by solid-phase spectrophotometry. It was found that the oxidizing properties of heteropoly compounds enhance when they are included into xerogels. It was found that the formal redox potential of phosphomolybdic acid in xerogel is +0.751 V at pH 3.6. Indicator tubes were proposed for the test determination of 10–80 mg/g tin(II) in reagents used in the synthesis of radiopharmaceutical preparations. Indicator powders and indicator tubes were proposed for the test determination of hydrazines in solution (analytical ranges 0.08-6 mg/L and 0.02-1 mg/L, respectively). Deceased.     

Potential response in the uncatalyzed bromate oscillatory system

The potential response of the platinum indicator electrode in the uncatalyzed bromate oscillator (UBO) with three different substrates, namely gallic acid (GA), pyrogallol (PG) and veratraldehyde (VA) has been analyzed. The large amplitude oscillations obtained with a Pt electrode are due to the sequential response of the indicator electrode to the varying concentration ratios of the redox couples present in the reaction mixture.     

Colorimetric assay for sulfate using positively-charged gold nanoparticles and its application for real-time monitoring of redox process

A flexible nanoparticle-based sulfate assay is demonstrated in which the positively-charged gold nanoparticles (cysteamine-AuNPs) act as indicator. The aggregation of cysteamine-AuNPs is selectively induced by sulfate, which allows the rapid colorimetric sensing of sulfate without any precipitant, sample preparation and specific instruments. In this work, the cysteamine-AuNPs probe has been successfully applied to the colorimetric detection of sulfate and demonstrates superior sensitivity with a detection limit of sulfate of ~50 ppb. A surprise finding is that the proposed probe can achieve the goal of real-time monitoring and translating a redox process into an appreciable color change via the aggregation of nanoparticles. This is a novel application of a positively-charged AuNPs-based nanoprobe for sulfate detection, kinetic study of the redox process, and opens up new opportunities for design of more novel colorimetric strategies and expansion of AuNPs-based application in different fields.     

Evaluation of immobilized redox indicators as reversible, in situ redox sensors for determining Fe(III)-reducing conditions in environmental samples

An in situ methodology based on immobilized redox indicators has been developed to determine when Fe(III)-reducing conditions exist in environmental systems. The redox indicators thionine (Thi, formal potential at pH 7 (E(7)(0')) equals 66 mV), toluidine blue O (TB, E(7)(0')=31 mV), and cresyl violet (CV, E(7)(0')=-75 mV) have been immobilized to 40-60 mum agarose beads via an amine-aldehyde coupling reaction. These beads were packed into a flow cell to allow spectrophotometric monitoring of the redox state of simple solutions and wastewater slurries pumped from in a bioreactor. Fe(II), a product of microbial activity, at levels observed in real systems reduces both the free (non-immobilized) and immobilized redox indicator to different degrees for samples with pH 6.5 or higher. At pH 7, immobilized Thi and TB are significantly reduced at Fe(II) concentrations greater than 0.1 and 0.3 mM, respectively. CV, with the lowest formal potential, requires Fe(II) levels in excess of 10 mM. The degree of reduction of the indicators (i.e. the fraction of indicator oxidized) observed during titrations can be qualitatively modeled with a simple equilibrium model based on ferrihydrite or lepidocrocite as the Fe(III)-solid phase. The reversibility of Fe(II)-indicator reactions was also demonstrated by showing that the reduced indicator becomes re-oxidized when Fe(II) levels decrease.     

Titrimetric determination of vanadium(IV) with cerium (IV)sulphate at room temperature using ferroin as indicator

A procedure has been developed for the visual titrimetric determination of vanadium(IV) with cerium(IV) sulphate, using ferroin is redox indicator. The method has been extended to the determination of iron(II) and vanadium(IV) in mixtures.     

A Calculation Method Based on Amperometric Titration with Two Indicator Electrodes

A new calculation method was proposed for determining substances by amperometric titration with two indicator electrodes. The model is based on the modified Dalahay equation for reversible redox systems and electrodes of different surface areas.     

VINYL RADICAL POLYMERIZATION INITIATED WITH CERIC ION AND ETHYL N, N-DIETHYLDITHIOCARBAMYL ACETATE SYSTEM

Acrylamide polymerization initiated with a redox initiation system consisting of cericion and ethyl N, N-diethyldithiocarbamyl acetate (EDCA) has been studied. It was foundthat the polymerization rate equation is in good agrement with that of a redox initiatedpolymerization, and the overall activation energy of the polymerization was determinedto be 25.2kJ·mol~(-1). Accordingly, the system belongs to a redox initiator. The initiationmechanism was proposed based on the end group analysis using FT-IR, UV spectroscopies.Analysis results revealed that the N, N-diethyldithiocarbamyl radical produced from theredox reaction of EDCA with ceric ion can initiate acrylonitrile (AN) polymerization andform the end group on PAN. The resulting PAN was photopolymerized with butyl acrylate(BA) to form PAN-b-PBA block copolymer.     

Total systematic error in redox titrations with visual indicators--I: basic principles

The following factors contribute to the total error in redox titrations with visual indicators: the end-point error (DeltaV(T)), which arises from the difference between the potential of the equivalence point and that of the actual end-point determined by a given indicator ; the indicator consumption error (DeltaV(T)), which arises from the amount of indicator oxidized (or reduced) by the titrant; the irreversibility error, which is in fact a part of the indicator consumption error, arising from the generally uncontrolled processes connected with the irreversibility of the redox processes, decomposition of the reaction products, etc. The first two factors can be evaluated on the basis of the physicochemical characteristics of all the systems involved. They contribute to the total systematic error. The third, being not strictly controlled, in general increases the positive indicator consumption error, depending on such parameters as rate of titrant addition, stirring, effect of decomposition products on the potential, etc.     

Role of Frontier Molecular Orbital Symmetry of Reagents in Redox Catalytic Indicator Reactions

Some hypotheses are discussed for the nature of “inhibited” or “kinetically hindered” redox reactions, which are employed as indicator reactions in kinetic analytical methods. Some reactions are considered as examples to demonstrate that redox reactions are kinetically hindered because the key frontier orbitals of the reagents differ in their symmetry types. It is suggested that the redox reactions of this type be considered forbidden by inconsistency between the symmetry types of the key frontier orbitals.     

Properties of α-Ferrocenylcarbenium and Ferricinium Salts by Nonaqueous Potentiometric Titration

Potentiometric titration of -ferrocenylcarbenium and ferricinium salts in anhydrous acetonitrile with sodium ethylate involves redox reaction between the titrate and titrant, which, once equimolar amount of the latter has been added, produces a potential jump of 300-400 mV (platinum indicator electrode). The oxida- tion potentials of the -ferrocenylcarbenium and ferricinium salts in anhydrous acetonitrile were estimated at 410-500 mV. The experimental data gave evidence for intramolecular redox processes (redox tautomerism) in the compounds studied.     

Methyl orange as a redox indicator in titrations with ceric ammonium nitrate in perchloric acid

Summary Conditions for the use of methyl orange as a redox indicator for the titration of iron(II), hydroquinone and oxalate with cerio ammonium nitrate dissolved in perchloric acid, have been established. It is found that methyl orange behaves as a reversible indicator with a transition potential of 955±10 mV. Nitric acid as a medium of titration is not satisfactory.

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Zusammenfassung Methylorange kann als Redoxindicator bei der Titration von Eisen(II), Hydrochinon und Oxalat mit Cer(IV)-ammoniumnitrat in perchlorsaurer Lösung verwendet werden. Der Indicator hat ein Umschlagspotential von 955±10 mV. In salptersaurem Medium erhält man keine befriedigenden Werte.

     

New insights into iron release from ferritin: direct observation of the neurotoxin 6-hydroxydopamine entering ferritin and reaching redox equilibrium with the iron core

Iron release from the iron storage protein ferritin has been studied extensively because of its important role in oxidative stress and its possible role in the progression of Parkinson's disease. For many years external indicators, notably strong iron(II) chelators, have been used to investigate this reaction. Such chelators can, however, drastically affect the electrochemical and thermodynamic properties of iron. The present study is unique in that it has been possible to follow a reaction taking place within the ferritin shell. This was made possible by our serendipitous discovery that, at physiological pHs, the oxidation product of 6-hydroxydopamine (a deprotonated quinone) acts as its own indicator (G. N. L. Jameson and W. Linert, J. Chem. Soc., Perkin Trans. 2, 2001, 563-568). The redox equilibrium data and the kinetics of the formation of this red-coloured species can only be explained on the basis that reduction of the iron(III) takes place within the ferritin shell. This is, in fact, the first time that a reaction actually taking place inside the ferritin shell has been followed. It has also been established that, at least in vitro, all eight hydrophilic channels are capable of being simultaneously involved in the reaction. It has also been possible to calculate the rate of oxidation of the 6-hydroxydopamine within the ferritin and it is demonstrated that a redox equilibrium is established within the protein. Finally, evidence is provided confirming that chelators are in fact intrinsically linked to iron removal from ferritin.     

Total systematic error in redox titrations with visual indicators--II. Experimental verification

The equations for calculating the transition potential of a redox indicator and the total titration error have been verified experimentally. Good agreement has been obtained for reversible indicators such as Variamine Blue, 4-methyl-4'-aminodiphenylamine and ferroin. In the latter case it was shown that at the usual concentrations the indicator acts as a one-colour indicator, whereas for higher concentrations its behaviour is typical of a two-colour indicator. In the case of a pseudoreversible indicator--diphenylaminosulphonic acid--the calculated values give only the minimum error. In real conditions the error is always more positive.     

脱氧核糖核酸在硬脂酸铝离子膜上固定杂交及BAR基因片段检测

将石墨粉、固体石蜡和硬脂酸按一定比例混合制得表面富含羧基的碳糊电极,然后在电极表面组装荷正电的铝离子膜。在硬脂酸铝离子膜上进行DNA探针的固定和与目标基因的杂交。以亚甲蓝为杂交指示剂,用循环伏安法优化了DNA的固定和杂交条件。应用该电化学生物传感器以微分脉冲伏安法对转基因玉米外源BAR基因片段进行了检测,结果令人满意。     

基于PAMAM/聚2,6-吡啶二甲酸膜DNA电化学生物传感器的制备及对禽病毒基因检测的研究

以铂电极上聚合的2,6-吡啶二甲酸(PDC)膜组装G5.0树状高分子(PAMAM)固定ssDNA探针, 制备了一种新型的DNA电化学生物传感器. 用[Fe(CN)6]3－/4－作氧化还原指示剂, 以电化学交流阻抗和循环伏安技术对探针ssDNA的固定和杂交进行了表征. 实验表明, 当ssDNA在复合膜上固定及与其互补序列杂交后, 电极表面的传递电阻(Ret)依次增大. 因此, 可以利用Ret的明显差异, 以此固定探针的修饰电极, 对互补序列DNA进行无标记交流阻抗检测. 基于该生物传感器结合交流阻抗技术对禽病毒基因进行检测, 在优化实验条件下, 靶基因ssDNA-2在2.0×10－11～1.0×10－8 mol•L－1线性范围内, 其浓度与电极表面的电子传递电阻(Ret)之间呈良好的线性关系, 检测限为3.6×10－12 mol•L－1. 表明该方法为病毒灵敏地检测提供了一个有益的传感平台.