Ozonocatalytic decomposition of glyoxal and glyoxylic and formic acids in the presence of iron(III) ions

Rate constants of reactions of ozone with glyoxal, glyoxylic and formic acid in aqueous solutions at pH 1.5 were determined. It was shown that iron(III) in the form of ions accelerates oxidation of glyoxal and glyoxylic acid, but does not influence reaction between ozone and formic acid. It was established that the catalyst acts effectively if its concentration is comparable to the concentration of the oxidized substrate, the optimal stoichiometric ratio (Fe³⁺/substrate) being close to 1/3. The catalytic reaction mechanism was studied using a competitive chelate ligand, oxalic acid. We concluded that the catalytic activity of iron(III) in the investigated reaction was due to its ability to form chelate complexes in which the substrate was more easily oxidized by molecular ozone.     

Kinetics of metal ion exchange between citric acid and serum transferrin

The exchange of Fe(3+), Tb(3+), In(3+), Ga(3+), and Al(3+) between the C-terminal metal-binding site of the serum iron transport protein transferrin and the low-molecular-mass serum chelating agent citrate has been studied at pH 7.4 and 25 degrees C. The removal of Ga(3+), In(3+), and Al(3+) follows simple saturation kinetics with respect to the citrate concentration. In contrast, removal of both Fe(3+) and Tb(3+) shows a combination of saturation and first-order kinetic behavior with respect to the citrate concentration. The saturation component is consistent with a mechanism for metal release in which access to the bound metal is controlled by a rate-limiting conformational change in the protein. The first-order kinetic pathway is very rapid for Tb(3+), and this is attributed to a direct attack of the citrate on the Tb(3+) ion within the closed protein conformation. It is suggested that this pathway is more readily available for Tb(3+) because of the larger coordination number for this cation and the presence of an aquated coordination site in the Tb(3+)-CO(3)-Tf ternary complex. There is relatively little variation in the k(max) values for the saturation pathway for Tb(3+), Ga(3+), Al(3+), and In(3+), but the k(max) value for Fe(3+) is significantly smaller. It is suggested that protein interactions across the interdomain cleft of transferrin largely control the release of the first group of metal ions, while the breaking of stronger metal-protein bonds slows the rate of iron release. The rates of metal binding to apotransferrin are clearly controlled in large part by the hydrolytic tendencies of the free metal ions. For the more amphoteric metal ions Al(3+) and Ga(3+), there is rapid protein binding, and the addition of citrate actually retards this reaction. In contrast, the nonamphoteric In(3+) ion binds very slowly in the absence of citrate, presumably due to the rapid formation of polymeric In-hydroxo complexes upon addition of the unchelated metal ion to the pH 7.4 protein solution. The addition of citrate to the reaction accelerates the binding of In(3+) to apoTf, presumably by forming soluble, mononuclear In-citrate complexes.     

酒石酸脱除单铽转铁蛋白中铽（III）的荧光动力学研究

0.01 mol/L Hepes, pH7.4,室温条件下,以酒石酸为脱除剂,监测铽（III） 与脱铁蛋白结合的两种配合物C端单铽转铁蛋白和N端单铽转铁蛋白随酒石酸浓度变 化的脱除动力学,根据其动力学行为,我们推测存在两种平行的脱除途径：一次途 径和饱和途径,其中C端单铽转铁蛋白的铽（III）脱除呈现饱和与一次相结合途径 ,N端单铽转铁蛋白为简单的一次途径。NaCl的加入可促进两种单铽（III）的脱除 ,且C端铽转铁蛋白较N端单铽转铁蛋白更易受NaCl的影响。     

An iron reservoir model based on ferrichrome: iron(III)-binding and metal(III)-exchange properties of tripodal monotopic and ditopic hydroxamate ligands with an L-alanyl-L-alanyl-N-hydroxy-beta-alanyl sequence

To gain knowledge about biological iron mobilization, tripodal monotopic and ditopic hydroxamate ligands (1 and 2) are prepared, and their iron-chelating properties are investigated. Ligands 1 and 2 contain three Ala-Ala-beta-(HO)Ala units and three [Ala-Ala-beta-(HO)Ala](2) units connected with tris(alanylaminoethyl)amine, respectively, and form six-coordinate octahedral complexes with iron(III) in aqueous solution. Ligand 1 and 1 equiv of iron give Fe-1, and ligand 2 and 1 or 2 equiv of iron produce Fe(1)-2, or Fe(2)-2. These complexes exhibit absorptions at lambda(max) 425 nm of epsilon 2800-3000/Fe, characteristic of tris(hydroxamato)iron(III) complexes, and preferentially assume the Delta-cis configuration. Loading of Fe(III) on 1, 2, and M(III)-loaded ligands (M-1 and M(1)-2, M = Al, Ga, In) with ammonium ferric oxalate at pH 5.4 is performed, and the second-order rate constants of loading with respect to Fe(III) and the ligand or M(III)-loaded ligands are determined. The rates of loading of Fe(III) on M-1 increase in the order Al-1 < Ga-1 < In-1, and those on M(1)-2 in the order Al(1)-2 < Ga(1)-2 < Fe(1)-2 < In(1)-2, indicating that the dissociation tendency of M(III) ions from the hydroxamate ligand is an important factor. The iron complexes formed with 2 are subjected to an iron removal reaction with excess EDTA in aqueous pH 5.4 solution at 25.0 degrees C, and the collected data are analyzed by curve-fitting using appropriate first-order kinetic equations, providing the rate constants for the upper site and the lower site of 2. Similar analysis for FeM-2 affords removal rate constants for Fe(up)-2, M(up)-2, and Fe(low)-2, and the iron residence probability at each site. The protonation constants of the hydroxamate groups for 1 and 2 (pK(1,) pK(2), pK(3), and pK(1,) pK(2)., pK(6)) are determined, and the proton-independent stability constants for Fe-1, the upper site of Fe(2)-2, and the lower site of Fe(1)-2 are 10(28), 10(29), and 10(28.5), respectively.     

Modeling manganese removal in chelating polymer-assisted membrane separation systems for water treatment

The removal of manganese from groundwater, using water-soluble chelating polymers such as polyacrylic acid (PAA) in combination with ultrafiltration (UF), was investigated. The effects of the solution pH and polymer dosages on the manganese removal were evaluated, and the removal efficiency was modeled considering the relevant chemical equilibria. In the absence of polymer, manganese removal with UF membranes alone was negligible at acidic pH values, but the removal increased substantially when polyacrylic acid (PAA) was added to the feed solution. The increase can be attributed to the formation of Mn²⁺–PAA chelates which are rejected by the membranes. A mathematical model was developed to explain this phenomenon based on chemical equilibria, including complex formation and precipitation. The chelation number (i.e., the number of carboxyl groups in the PAA binding to a single metal ion) and the equilibrium constants for metal–PAA chelation reactions were obtained by fitting experimental data at acidic pH in single-divalent metal systems. The model was able to predict Mn removal in chelation/UF systems at various pH levels and polymer dosages, and to account for the competitive interactions of PAA with the target (Mn²⁺) and background species (Ca²⁺, Mg²⁺) in multi-component systems. The predicted Mn removal efficiency was most sensitive to the chelation number.     

Properties of TiO2-polyacrylic acid dispersions with potential for molecular recognition

Titanium dioxide (TiO₂)/polyacrylic acid (PAA) (TiO₂/PAA) particles were formed by mixing PAA and an acidic solution of TiO₂ nanoparticles in dimethylformamide (DMF) followed by heat treatment. TEM and particle analysis showed that the resulting particles had a narrow size distribution. The colloid was very stable and aggregation was not observed over a wide pH range (3–9) or at high salt concentration. The residual carboxylic acid of PAA could be modified via EDC/NHS activation to form an amide bond with a protein. An antibody was attached to the hybrid nanoparticle and specific binding to antigen was monitored by surface plasmon resonance. The results suggest that TiO₂/PAA nanoparticles are candidates as the base component of a photocatalytic system with potential for substrate selectivity.     

Kinetic demonstration of the intramolecular nature of the rearrangement of aromatic N-nitroso-amines (Fischer-Hepp)

Rate equations have been deduced for two possible mechanisms for the reactions of N-methyl-N-nitrosoaniline in acid solution, namely, (1) for the generally accepted intermolecular mechanism which involves denitrosation followed by C-nitrosation and (2) a mechanism involving intramolecular rearrangement which takes place concurrently with denitrosation. The observed rate constants obtained under various experimental conditions are consistent only with mechanism (2). In particular the question of halide ion catalysis differentiates clearly between the two mechanisms. Mechanism (1) predicts a first-order dependence upon chloride (or other halide) ion under all conditions, whereas (2) allows a first-order chloride ion dependence only in the presence of a large excess of a “nitrite trap” such as sulphamic acid, urea, hydrazoic acid, hydroxylamine, etc., whereas at the other limit of high concentration of added N-methylaniline, the rate constants should be independent of the halide ion concentration. The predictions based on mechanism (2) are all borne out by experiment.     

The Electrochemical Measurement of Rate Constants for the Catalyzed Oxidation and Reduction of Water in microheterogeneous systems

The appearent first-order rate constants for the oxidation of water by iron tris (bipyridyl) (Fe (bpy)³⁺₃), and reduction of water by methylviologen (MV⁺) catalyzed by a stabilized RuO₂ or Pt-sol, respectively, were measured. Rate constants for water oxidation at pH 7 of 0.4 s^?1 and water reduction at pH 4.7 and pH 1 of up to 460 s^?1 for different sols were found.     

Kinetics of two-electron oxidations by the compound I derivative of chloroperoxidase, a model for cytochrome P450 oxidants

[structure: see text] Rate constants for two-electron oxidation reactions of Compound I from chloroperoxidase (CPO) with a variety of substrates were measured by stopped-flow kinetic techniques. The thiolate ligand of CPO Compound I activates the iron-oxo species with the result that oxidation reactions are 2 to 3 orders of magnitude faster than oxidations by model iron(IV)-oxo porphyrin radical cations containing weaker binding counterions.     

Modeling the mechanism involved during the sorption of methylene blue onto fly ash

Batch sorption experiments were carried out to remove methylene blue from its aqueous solutions using fly ash as an adsorbent. Operating variables studied were initial dye concentration, fly ash mass, pH, and contact time. Maximum color removal was observed at a basic pH of 8. Equilibrium data were represented well by a Langmuir isotherm equation with a monolayer sorption capacity of 5.718 mg/g. Sorption data were fitted to both Lagergren first-order and pseudo-second-order kinetic models and the data were found to follow pseudo-second-order kinetics. Rate constants at different initial concentrations were estimated. The process mechanism was found to be complex, consisting of both surface adsorption and pore diffusion. The effective diffusion parameter D(i) values were estimated at different initial concentrations and the average value was determined to be 2.063 x 10(-9)cm2/s. Analysis of sorption data using a Boyd plot confirms the particle diffusion as the rate-limiting step for the dye concentration ranges studied in the present investigation (20 to 60 mg/L).     

Kinetic study of non-reactive iron removal from iron-gall inks

The removal of non-reactive iron for different combinations of Fe²⁺ and tannic acid in irongall inks, via calcium phytate solutions, was studied. In parallel, the non-reactive iron removal kinetics was investigated using the pseudo first-order and second-order kinetic models. The results showed that the use of a dilute solution of calcium phytate to wash the impregnated paper strips removed the non-reactive iron from iron-gall inks in approximately 15 min in stoichiometric and non-stoichiometric combinations of iron and tannic acid. A second washing of the paper strips after an accelerated ageing, showed a distinct kinetic behaviour, with iron removal taking place simultaneously but apparently via a different mechanism. The use of a reference calcium phytate solution exhibited the same behaviour, suggesting that the use of dilute solutions as iron removal agents would represent less damage to historical documents. The results of kinetic modelling showed that all the combinations of Fe²⁺ and tannic acid used fitted the pseudo first-order kinetic model, when dilute and reference phytate solutions were tested as iron-desorbing agents.     

Chitosan–poly(acrylic acid) nanofiber networks prepared by the doping induction of succinic acid and its ammonia‐response studies

Chitosan–poly(acrylic acid) (CS–PAA) composite membrane with a 3D network nano‐structure was prepared using an electrostatic interaction process by adding succinic acid as a branch promoter. Variations of the final solution pH values, concentration of CS, and PAA/CS volume ratio were examined systematically for their effects on average fiber diameter size, intensity of surface charge, and tendency of network formation. It was found that nanofiber size was affected by the mixing ratio of PAA and CS, the concentration of CS, and the final pH of the CS–PAA solution. The smallest diameter size distribution of the scaffold can be obtained when the PAA/CS ratio is in the range of 2:1–1:2 in a pH 3 environment. Negative charge nanofibers prepared using PAA and CS in a ratio of 2:1 in pH 3 environments had an average diameter of 215 nm. The formation of the interconnecting 3D self‐organized network structure can be built up with limited parasitic branching by crystallized succinic acid. The gas response to ammonia, including sensitivity and response time, was evaluated using impedance spectroscopy at room temperature. The results of sensing experiments indicate that the sensitivity of nanofibrous membrane (NM)‐coated sensors was eight times higher than that of continuous film‐coated sensors. NM‐coated sensors exhibited high sensitivity towards a low concentration of ammonia, as low as 50 ppm at a relative humidity of 45%. Copyright © 2008 John Wiley & Sons, Ltd.     

Initial state and transition state contributions to solvent effects on rate constants for racemisation and dissociation of the [Fe(phen)3]2+ cation in DMSO-water mixtures

Summary Rate constants for racemisation and dissociation of the tris(1,10-phenanthroline)iron(II) cation, and solubilities of its picrate, are reported for dimethyl sulphoxide-water mixtures (0 to 40% by vol DMSO) at 298.2 K. The observed solvent effects on reactivity are analysed in terms of initial state and transition state contributions, and the pattern established compared with patterns for methanol- and acetone-water mixtures. In all cases the hydrophobic periphery of the ligand is dominant. Rate constants are also reported for racemisation and dissociation of the analogous complex [Fe(sb)₃]²⁺, where sb = the Schiff base from 2-benzoylpyridine andp-toluidine, in aqueous methanol.     

Rates of ligand substitution by bromide,thiocyanate, and azide lons at iron (III) ion in dimethyl sulfoxide as solvent

Rate constants for ligand substitution by bromide, thiocyanate and azide ions at iron(III) ion in dimethyl sulfoxide as solvent, determined by stopped-flow spectrophotometry, are similar and are consistent with a dissociative mechanism. In addition, azide ion gives a second much slower, reaction, attributed to formation of a binuclear complex. Results of similar measurements with thiocyanate ion in acetonitrile were more complicated, attributed to a marked influence of residual water on the reactivity of iron (III) ion.     

Fabrication of Fe3O4/SiO2 core/shell nanoparticles attached to graphene oxide and its use as an adsorbent

Thermoresponsive gelling behavior of concentrated alumina suspensions with poly(acrylic acid) (PAA) and triblock copolymer (PEO(101)-PPO(56)-PEO(101), Pluronic F127) was investigated as a function of PAA concentration (0.4-1.2 mass%) for ceramic solid free forming. The copolymer species assemble into micelles at temperatures above 15°C, yielding aqueous physical gel. In this study, the concentrated alumina aqueous suspensions (φ=35 vol%) were first prepared using the anionic dispersant of PAA, and then the copolymer species (10 mass%) were dissolved at a cooled temperature at 10°C. The addition of the copolymer species had a negligible influence on the adsorption state of PAA onto the alumina surfaces. The PAA concentration needed for the saturation adsorption on the alumina surfaces was ~0.6 mass%. When the PAA concentration was this value or slightly less, the suspension became gel state at 30°C from low viscous state at 10°C. The thermally induced alumina gel had excellent viscoelastic properties, and thereby the three dimensional periodic ceramic structures were successfully fabricated by a direct colloidal printing method that using the gels as "solid" inks at the room temperature. On the other hand, when it exceeded the saturation adsorption limit, the gelling behavior was not observed, indicating that the non-adsorbing PAA species may partly suppress the micellization of the copolymer on the heating.     

Phosphate triester hydrolysis promoted by an N2S(thiolate)Zn complex: mechanistic implications for the metal-dependent reactivity of peptide deformylase

The zinc(II) complex (PATH)ZnOH, where PATH is an N2S(thiolate) ligand, has been investigated for its ability to promote the hydrolysis of the phosphate triester tris(4-nitrophenyl) phosphate (TNP). The hydrolysis of TNP was examined as a function of PATH-zinc(II) complex concentration, substrate concentration, and pH in a water/ethanol mixture (66:33 v/v) at 25 degrees C. The reaction is first order in both zinc(II) complex and substrate, and the second-order rate constants were derived from linear plots of the observed pseudo-first-order rate constants versus zinc complex concentration at different pH values. A pH-rate profile yielded a kinetic pK(a) of 8.52(5) for the zinc-bound water molecule and a pH-independent rate constant of 16.1(7) M(-1) s(-1). Temperature-dependent studies showed linear Eyring behavior, yielding the activation parameters DeltaH++ = 36.9(1) kJ mol(-1) and DeltaS++ = -106.7(4) J mol(-1) K(-1). Interpretation of the kinetic data leads to the conclusion that hydrolysis of TNP takes place through a hybrid mechanism, in which the metal center plays a dual role of providing a nucleophilic hydroxide and activating the substrate through a Lewis acid effect. The synthesis and structural characterization of the related nickel(II) and iron(II) complexes [(PATH)2Ni2]Br2 (2) and (PATH)2Fe2Cl2 (3) are also described. Taken together, these data suggest a possible explanation for the low reactivity of the zinc(II) form of peptide deformylase as compared to the iron(II) form.     

A unified analytical treatment of the acid-dissociation equilibria of weakly acidic linear polyelectrolytes and the conjugate acids of weakly basic linear polyelectrolytes

 The influence of added sodium chloride concentration levels on the acid-dissociation equilibria of a weakly acidic linear polyelectrolyte and a conjugate acid of weakly basic linear polyelectrolyte has been investigated potentiometrically by use of polyacrylic acid (PAA) and poly(N-vinylimidazole) (PVIm) as examples of polyelectrolytes. Both equilibria are strongly influenced by the degree of dissociation of the polyacids as well as the concentration levels of sodium chloride due to an electrostatic effect originating from the negatively or positively charged polymer surfaces. These have been analyzed in a unified manner by taking accounts of two-phase properties of the charged linear polyions. Distribution of counterions and coions between a polyelectrolyte phase formed around the polymer skeleton and a bulk solution phase has been rationalized by a Donnan’s relation. Introduction of a volume term for the polyelectrolyte phase permits definition of averaged concentrations of mobile ions in the vicinity of the polyion molecules, which enables us to define hypothetical intrinsic acid-dissociation constants in the polyion domain. The intrinsic constants estimated by extrapolation of apparent acid-dissociation constants at zero-charge state are in good agreement with the acid-dissociation constants of the monomer analogs of the polymers, i.e., acetic acid for PAA and imidazole for PVIm, respectively. The difference between the apparent and intrinsic acid-dissociation constants for PVIm was much higher than that for PAA at defined degree of dissociation of the polyacids, even though the separations of the functionalities fixed on the linear polymers are approximately equal to each other. Received: 4 February 1997 Accepted: 26 May 1997     

Bioinspired crystallization of CaCO3 coatings on electrospun cellulose acetate fiber scaffolds and corresponding CaCO3 microtube networks

This article describes the mineralization behavior of CaCO(3) crystals on electrospun cellulose acetate (CA) fibers by using poly(acrylic acid) (PAA) as a crystal growth modifier and further templating synthesis of CaCO(3) microtubes. Calcite film coatings composed of nanoneedles can form on the surfaces of CA fibers while maintaining the fibrous and macroporous structures if the concentration of PAA is in a suitable range. In the presence of a suitable concentration of PAA, the acidic PAA molecules will first adsorb onto the surface of CA fibers by the interaction between the OH moieties of CA and the carboxylic groups of PAA, and then the redundant carboxylic groups of PAA can ionically bind Ca(2+) ions on the surfaces of CA fibers, resulting in the local supersaturation of Ca(2+) ions on and near the fiber surface, which can induce the nucleation of CaCO(3) on the CA fibers instead of in bulk solution. Calcite microtube networks on the macroscale can be prepared by the removal of CA fibers after the CA@CaCO(3) composite is treated with acetone. When the CA fiber scaffold is immersed in CaCl(2) solution with an extended incubation time, the first deposited calcite coatings can act as secondary substrate, leading to the formation of smaller calcite mesocrystal fibers. The present work proves that inorganic crystal growth can occur even at an organic interface without the need for commensurability between the lattices of the organic and inorganic counterparts.     

Pb(II) removal from aqueous solution by polyacrylic acid stabilized zero-valent iron nanoparticles: process optimization using response surface methodology

Optimization and modeling of Pb(II) removal using polyacrylic acid stabilized zero-valent iron nanoparticles (PAA-ZVINs) from aqueous solution was performed. Central composite design (CCD) as the most applicable method in response surface methodology (RSM) was employed for optimization of Pb(II) removal. ZVINs were synthesized using the borohydride reduction method in the presence of PAA as a stabilizer and characterized via scanning electron microscopy (SEM) and X-ray diffraction (XRD). The independent variables for CCD optimization of Pb(II) removal were initial solution pH, ZVINs concentration (g/L), and initial concentration of Pb(II) (mg/L). Results showed a significant correlation between predicted values obtained from second-order polynomial model and experimental values (R ² = 93.19 and adj-R ² = 87.07). Maximum removal of Pb(II) (90.09 %) was observed at the optimal conditions of ZVINs concentration of 3 g/L, initial Pb(II) concentration of 10 mg/L, and initial solution pH of 5.     

Inorganic asymmetric synthesis: diastereoselective syntheses of mono- and dinuclear complexes containing octahedral, two-bladed propeller, bis(pyridine-2-aldehyde 2'-pyridylhydrazone)iron(II) stereocenters

A C2 hexadentate diester derived from (5-hydroxymethyl)pyridine-2-aldehyde 2'-pyridylhydrazone (5-HOCH2PAPHY) and an enantiomerically pure (aS)-spirane dicarboxylic acid diastereoselectively reacts with iron(II) benzenesulfonate in methanol to furnish a 20% diastereomeric excess (de) of a two-bladed propeller, octahedral iron complex in which the P configuration of the newly created (+/-)-[Fe(PAPHY)2](2+) stereocenter predominates; when the reaction mixture is heated under reflux for 12 h, however, the excess of the diastereomer having the P configuration at iron increases to 80%, as determined by (1)H NMR spectroscopy. The configuration at iron in the major diastereomer of the complex was determined by comparison of the circular dichroism spectrum of the deprotonated complex with that of a related complex of known configuration. Repositioning of the hydroxymethyl group of the pyridine-2-aldehyde from the 5- to the 6-position produced a C2-spirane ligand that generates a double-stranded diiron(II) helicate in >99% de. Single crystal X-ray structure determinations of the racemates of the protonated and deprotonated helicates revealed that the complexes crystallize diastereoselectively, that is, two ligand strands of a S configuration generate two octahedral iron(II) stereocenters of P configuration to give a dinuclear metal helicate of P configuration and vice versa for the ligand of a R configuration.