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.     

59Ni and 63Ni separation from boric acid concentrates produced at NPP

Procedure for direct separation of radionickel from boric acid concentrate was developed. Quantitative separation from 100 mL of real concentrate on the column filled with 3 mL of PAN-DMG composite material was achieved. PAN-DMG material (dimethylglyoxime in porous beads of polyacrylonitrile) was compared with Ni Resin and DMG-PAN material exhibited higher sorption capacity for nickel than Ni Resin.     

New redox titrants in non-aqueous or partially aqueous media--VI: potentiometric determinations using dibromamine-T and some further applications of dichloramine-T

A new redox titrant, Dibromamine-T (N,N'-dibromo-p-toluenesulphonamide) is introduced for use in acetic acid media. Potentiometric titrations of Sb(III), As(III), Tl(I), Fe(II), ferrocyanide, iodide, ascorbic acid, hydroquinone, hydrazine, aniline, phenol and oxine are described. Direct potentiometric titrations of oxinates of Mn, Fe, Co, Ni, Cu and Zn with Dibromamine-T as well as with Dichloramine-T are also described.     

Resin capsules: permeable containers for parallel/combinatorial solid-phase organic synthesis

A resin capsule is a permeable container for resin beads designed for multiple/combinatorial solid-phase organic synthesis. Resin capsules consist of a high density polyethylene ring sealed with peek mesh on both sides. The cylindrical shape of resin capsules enabled space-saving packing into plastic columnlike reaction vessels commonly used for solid-phase organic synthesis. Resin capsules have been evaluated for their use in combinatorial synthesis, and a set of model compounds with excellent purity was prepared.     

Nile blue and brilliant cresyl blue as redox indicators in iron(II) titrations

Nile Blue and Brilliant Cresyl Blue, two compounds related to diaminophenoxazine, have been studied as indicators in titrations of iron(II) with cerium(IV)(in hydrochloric, sulphuric and perchloric acid media), dichromate, vanadate and permanganate. They are particularly suited for titrations in a fairly concentrated sulphuric acid medium and for titrations with dilute solutions. A probable indicator mechanism is suggested.     

交流示波极谱滴定的研究(Ⅻ)——中和滴定

本文系统地报导了交流示波极谱滴定在中和滴定中的应用,解决了弱酸弱碱在水溶液中直接滴定等问题。同时提出了中和滴定的两大类指示剂的概念,并且总结了它们的性质。因此,示波极谱中和滴定将大大地丰富中和滴定的内容,扩大其应用范围。     

Removal of multi-metals from water using reusable pectin/cellulose microfibers composite beads

Pectin (Pec) and cellulose microfibers (CF) extracted from orange waste were combined to form composite beads with enhanced adsorption capacity. Such beads were extensively tested in the removal of multi-metal ions from water. A factorial design approach was conducted to establish the optimum conditions for adsorption of Cd(II), Cu(II), and Fe(II) on Pec-CF beads. Batch adsorption experiments revealed that removal efficiency of such metal ions falls in the range of 94–58% and it followed the order Fe(II) > Cu(II) > Cd(II). The maximum Cd(II), Cu(II) and Fe(II) adsorption capacities calculated from the Langmuir isotherm were 192.3, 88.5 and 98.0 mg/g, respectively. FTIR analysis suggests that the functional groups on Pec-CF beads (binding sites) favor the adsorption of such metal ions. Desorption and reuse experiments demonstrated the beads could be used for at least five consecutive adsorption/desorption cycles. Our finds suggest the Pec-CF beads can serve as an efficient adsorbent for the removal of multi-metal ions from wastewater.     

Hydrophobic indicators for two-phase titrations and their application to the determination of silver and pentachlorophenol

The hydrophobic dyes tetrabromophenolphthalein ethyl ester and 2,6-dichlorophenolindo-phenol are proposed as visual indicators for two-phase titrations. The aqueous phase is colourless throughout the titration and these indicators make it possible to detect the end-point of the titration by the colour of one or the other phase. The indicators allow the two-phase titration of the silver(I)-1,10-phenanthroline complex with tetraphenylborate and of pentachlorophenol with tetraphenylphosphonium chloride.     

Complexation reactions of pyridinols

Complexation of iron(III) with several pyridinols has been studied and used in selective detection and determination (spectrophotometric and chelatometric) of the metal. Iron(III)-pyridinol complexes are also used as indicators in acid-base titrations. A thiol group vicinal to a phenol group in a pyridine molecule provides a reagent that is a suitable ligand for palladium(II) determination. Stability constants of bivalent metal complexes with pyridinols have been determined potentiometrically.     

New extraction chromatographic material for rhenium separation

AbstractThree types of the extraction chromatographic materials, composed from Aliquat® 336 deposited in the polyacrylonitrile (PAN) beads and prepared by different procedures, were compared for extraction of rhenium. The best properties were exhibited when the solid extractant was prepared by impregnation of the ready-made PAN beads. Solid extractant prepared by direct coagulation of the beads from the suspension of Aliquat® 336 in solution of PAN in nitric acid differs only by lower capacity in dynamic conditions. Material prepared from the PAN solution in dimethylsulfoxide was the worst because Aliquat® 336 was washed out from the beads during coagulation of the polymer and the extraction capacity was low. As it is shown, the first two solid extractants are fully comparable with the commercial TEVA Resin.     

Quantitative study of the reaction between quinones and iron(II) in phosphoric acid medium

A simple method is described for the determination of some quinones with ammonium iron(II) sulphate, by titration potentiometrically or with cacotheline, Methylene Blue, Methylene Green, thionine, Toluidine Blue, Azure A, Azure C or Azure-2-eosin as redox indicators. The reverse titrations can be used for estimation of iron(II). Alternatively, excess of iron (II) can be added and the iron(III) produced determined colorimetrically with thiocyanate.     

Adsorption indicators in the titrations of hexacyanoferrate(II) and oxalate with thorium ions

Alizarin Red S, Pyrocatechol Violet and Xylenol Orange are shown to be effective adsorption indicators for the titrations of hexacyanoferrate(II) and oxalate with Thorium(IV) solution. The action of the indicators can be explained by the theory of surface compound formation.     

Potentiometric and visual titrations with bromamine-B

Bromamine-B is proposed as an oxidimetric titrant for potentiometric and visual end-point titrations of arsenic(II), hexacyanoferrate(II), antimony(III), hydroquinone, semicarbazide hydrochloride, isonicotinic acid hydrazide, hydrazine sulphate, ascorbic acid, phenylhydrazine hydrochloride and metol. Quinoline Yellow, naphthidine, dimethylnaphthidinedisulphonic acid, o-dianisidine, diphenylbenzidine, Variamine Blue, alpha-naphthoflavone, Amaranth, Methyl Orange and Methyl Red are proposed as indicators in macro and micro titrations of the reductants with bromamine-B. The transition potentials of Quinoline Yellow, naphthidine, dimethylnaphthidinedisulphonic acid, and o-dianisidine in the titration of ascorbic acid are reported. Arsenic(III) and hexacyanoferrate(II) are suggested for the standardization of bromamine-B solutions.     

Cooperation of solid granule and solvent as porogenic agents. Novel porogenic mode of biporous media for protein chromatography

A novel porogenic mode, cooperation of solid granule and solvent, has been introduced to prepare a biporous medium for protein chromatography. The matrix, a ternary copolymer of glycidyl methacrylate, triallylisocyanurate and divinylbenzene, was produced by a simple in situ polymerization with granules of sodium sulfate and cyclohexanol and dodecanol as porogenic agents. Functionalized with diethylamine, the resin (denoted as Resin C) was used as an anion exchanger. The pore structure, specific surface area and chromatographic properties of Resin C were determined and compared with those of the resin with only the solvents as porogen (Resin A) and the resin with only the salt granules as porogen (Resin B). The results indicated that Resin C contained regions of micropores with a maximum at approximately 55 nm and regions of macropores with a distinct maximum near 340 nm, which swelled to about 1 microm in aqueous solution. Compared with Resins A and B, the biporous medium Resin C simultaneously possessed a high specific surface area of 37.2 m2/g and a low back-pressure at mobile phase flow velocity up to 720 cm/h. The result of dynamic porosity showed that mobile phase was able to convectively flow through the macropores in Resin C. The dynamic adsorption capacity of Resin C for bovine serum albumin was as high as 57.0 mg/ml column volume (95.0 mg/g wet resin), basically identical to its static capacity, while that of Resin A was only 1.95 mg/ml column volume (3.12 mg/g wet resin), about 3% that of its static capacity. In addition, the column efficiency of Resin C was comparable to that of Resin B, but much higher than that of Resin A, indicating that the mass transfer behavior of proteins in the column was greatly improved by convective flow through the macropores.     

A Ru(II) complex with 2-(4-(methylsulfonyl)phenyl)-1H-imidazo[4,5-f][1,10]phenanthroline: synthesis, characterization, and acid-base and DNA-binding properties

A new Ru(II) complex of [Ru(bpy)2(Hmspip)]Cl2 {in which bpy=2,2'-bipyridine, Hmspip=2-(4-(methylsulfonyl)phenyl)-1H-imidazo[4,5-f][1,10]phenanthroline} have been synthesized and characterized. The ground- and excited-state acid-base properties of [Ru(bpy)2(Hmspip)]Cl2 and its parent complex of [Ru(bpy)2(Hpip)]Cl2 {Hpip=2-phenyl-1H-imidazo[4,5-f][1,10]phenanthroline} have been studied by UV-visible (UV-vis) and emission spectrophotometric pH titrations. [Ru(bpy)2(Hmspip)]Cl2 acts as a calf thymus DNA intercalators with a binding constant of 4.0×10(5) M(-1) in buffered 50 mM NaCl, as evidenced by UV-vis and luminescence titrations, steady-state emission quenching by [Fe(CN)6]4-, DNA competitive binding with ethidium bromide, reverse salt titrations and viscosity measurements.     

Theory of photoelectric complex formation titrations using metal indicators

The general principles of photoelectric complex formation titrations using metal indicators are given and the mathematical equations necessary for the exact determination of the equivalence point are derived for titrations with one-colour and two-colour indicators.A method for preparing a comparison solution of exactly the right composition is suggested.The influence of various factors on the titrations is discussed and it is shown that the theoretically attainable precision and accuracy are extremely high.Some titrations of copper and magnesium with EDTA are described which illustrate the accuracy attainable.     

The dynamic behaviour of the silver-silver hexacyanoferrate(II) electrode: coulometric production of hexacyanoferrate(II)

The electrochemical behaviour of the silver-silver hexacyanoferrate(II) elec-trode was studied. The reaction Ag₄[Fe(CN)₆] + 4e^- → 4Ag + [Fe(CN)₆]^4- was shown to be useful for the coulometric production of hexacyanoferrate(II) ions in titrations of zinc(II). Coulometric titrations of organometallic compounds such as R₂Sn(ClO₄)₂, with electrically generated hexacyanoferrate(II) are also reported.     

VI. Direct titrimetric microdetermination of L-serine and L-lysine VII. Simultaneous stepwise microdetermination of combinations of amino acids without separating

-Serine and -lysine have been quantitatively determined in microamounts separately and in presence of each by direct titrations against mercuric and zinc chlorides, respectively. The two amino acids form complexes with mercuric and zinc ions in the ratio of 1:2. Maximum error for -serine and -lysine is 0.5 and 0.9%, respectively. These two amino acids in double and triple combinations with -histidine and -arginine have been titrated successfully in one solution without separation. In separate titrations, and in other combinations, congo red and xylenol orange solutions have been used only as indicators. Titrations are accurate, quick, and reproducible.     

Electrometric titrations of Cr(VI), Mn(IV), V(V), Co(III) and U(VI) with a standard iron(II) solution in alkaline media containing hexitols

Direct and indirect potentiometric, bipotentiometric and biamperometric titrations with a standard iron(II) solution are described for some inorganic compounds in alkaline media containing hexitols (mannitol, dulcitol and sorbitol). The optimal conditions for titrations based on the Cr(VI) → Cr(III), Mn(IV) → Mn(III) → Mn(II), V(V) → V(IV), Co(III) → Co(II) and U(VI) → U(IV) systems are discussed. Of the hexitols studied, sorbitol has the greatest effect on the value of the redox potential of the Fe(III)/Fe(II) system; the E_f° value is about —1.10 V vs. SCE.     

A comparative study of some hydroxyanthraquinones as acid-base indicators

Alizarin, Alizarin S, quinizarin and quinalizarin have been compared as acid-base indicators with Bromocresol Green and Methyl Orange as reference indicators. The chromaticity co-ordinates, complementary chromaticity co-ordinates, pK(a) values, transition pH-range, pH of maximum colour change, optimum concentration for titrations and the quality of colour change were determined. The results show all four to be good indicators with a colour change quality similar to that of Bromocresol Green.