One-step novel synthesis of alginate-based SeNPs of cluster beans by reduction of Se(IV) by vitamin C in aqueous media.

Alginate powder was applied as stabilizer and capping agent surfactant in green synthesis of SeNPs of cluster shapes for the first time by reduction of Se (IV) with vitamin C. The naked eyes observations noticed a rapid change in color of Se (IV) solution from colorless to bright crimson aggregates as just the solution gets in contact with added mixture of vitamin C and alginate of powder natures then is rapidly turned to a reddish-pink aggregate. The formed aggregate was converted into violet crystals by aging or heating. In absence of vitamin C, addition of alginate powder to Se (IV) electrolyte whilst stirring the mixture leads to the formation of a precipitate of granule grains nature. The FTIR, XRD and SEM and TEM investigations indicated the formation of SeNPs of cluster beans for the crystals and alginate-based Se (IV) complex for the granule grains, respectively. The complex was invested for evaluation the alginate capacity for removal of Se (IV) ions from aqueous solutions and was found to be 63.66 mg/g at 25 °C. Some kinetic runs were performed to gain some information on growth rates of SeNPs formation in terms of electron-transfer pathway in the rate-determining step.

Innovative methodology for green synthesis of iridium nanoparticles of rod shapes by reduction of iridium (IV) using sustainable pectin with formation of keto-pectin derivatives.

A prospective novel technique has been developed for green synthesis of iridium nanoparticles of rod shapes for the first time with simultaneous formation of keto-derivative oxidation product with a yield of 98.3 %. This takes place by reduction of hexacholoroiridate (IV) by using sustainable pectin as a powerful reducing agent biomacromolecule in acidic media. The formation of nanoparticles (IrNPS) was identified by Fourier transform infrared (FTIR), Transmission electron microscope (TEM), X-ray diffraction (XRD), and Scanning electron microscope (SEM) investigations. The TEM morphology showed that the iridium nanoparticles were of crystalline rod shapes on contrary to the spherical shapes reported on all synthesized IrNPS earlier. The rates of nanoparticles growth were followed kinetically using a conventional spectrophotometer. The kinetic measurements revealed a unity order reaction in [IrCl6]2- as oxidant and fractional first-order in [PEC] as a reducing agent, respectively. A decrease in the reaction rates was noticed with increasing the acid concentration. Kinetic evidence reveals the creation of intermediate complex as transient species prior to the slow step. Such complex formation may be facilitated by the participation of one chloride ligand from [IrCl6]2- oxidant forming a bridge between the oxidant and reductant in such formed intermediate complex. Plausible reaction mechanisms for electron transfer pathway routes consistent with the kinetics observations were discussed.

Synthesis of keto-biomacromolecule derivatives by oxidation of carboxymethyl cellulose using alkaline hexacyanoferrate (III) for alternative applications in biotechnology.

The oxidation kinetics of polysaccharides involving carboxymethyl cellulose (CMC) by several oxidizing agent have been investigated in more detail with shedding some light on the synthesis of their respective keto-derivatives as oxidation precursor products. However, the literature survey indicated that no reports have appeared on the oxidation kinetics of CMC or the synthesis of keto-CMC using hexacyanoferrate (III) ion. Therefore, a lack of information on the transfer of electron process in the rate-determining stage as well as the nature of such keto-derivatives obtained as a result of polysaccharides oxidation using various oxidants in aqueous solutions. Accordingly, the present study presents synthesis of diketo CMC as a biomacromolecule derivative using potassium ferricyanide in alkaline media. The experimental results revealed the formation of either monoketo or diketo-derivatives of CMC based on initial molar ratio between the two reactants. The formation of such keto derivatives was confirmed by the reaction of the oxidation products with both 2,4-dinitrophenyl hydrazine and hydroxyl amine as well as FTIR spectra. The reaction kinetics of oxidation showed unity order in [Fe(CN)63-] and fractional first-orders with respect to both [CMC] and [OH-].The obedience of the reaction behavior to the Michael-Menten kinetics was indicative to the formation of 1:1 intermediate complex prior to the rate-determining step as a pathway route for oxidation.

Novel synthesis of natural cation exchange resin by crosslinking the sodium alginate as a natural polymer with 1,6-hexamethylene diisocyanate in inert solvents: Characteristics and applications.

Novel synthesis of natural polymeric cation exchanger from sodium alginate reagent as natural polymer (CAlg-Na)n has been developed. This procedure takes place by crosslinking the solid sodium alginate with 1,6-hexamethylene diisocyanate (HDI) in dryness benzene as inert solvent (DB). The experimental results for crosslinking the alginate using different degrees of crosslinking of HDI/DB (w/w) showed that the capacity of the synthesized resin for binding the polyvalent metal ions reached its maximum at 30% of (HDI/D) ratio. This work aims to present a novel synthesis of cation exchange resin from natural polymers as an alternative promising competitor of low-cost, high performance and non-toxicity for removal of the toxic heavy metal ions in wastewater remediation and radionuclide pollutants from environmental contaminated media. The results obtained from various applied techniques for determining the bounded metal ion concentrations with (CAlg-Na)n indicated that the resin capacity was followed the order U(VI) > Cu(II) > Sr(II) > Ca(II) at 25 °C, respectively. The factors influenced the alginate affinity for chelating the metal ions were explained in some correlation terms between the alginate capacity and some physicochemical properties of chelated metal ions and its respective formed complexes. Speculated geometrical configurations for chelation were suggested and discussed.

Prospective and comparative Novel technique for evaluation the affinity of alginate for binding the alkaline-earth metal ions during formation the coordination biopolymer hydrogel complexes.

A prospective novel technique has been developed for evaluation the capacity of alginate as a natural polymer absorbent for binding Ca (II), Sr (II) and Ba(II) as alkaline earth metal ions for formation of coordination biopolymer hydrogel complexes. This method was based on avoiding the non-chelated metal-ions which may present free into the interstitial spaces of the spongy network of the alginate matrix. Neglecting of non-chelated metal ions in the various techniques will lead to miscalculation in the definite concentration of the binding metal ions. Hence, some uncertainty and dissimilarity were observed in the reported data with respect to the alginate capacity for binding the metal ions. Therefore, a novel technique for more precise determination was achieved by synthesis of coordination metal alginate gels of granule nature which are free from such non-chelated metal ions. Here, the true binding metal ions were eluted by addition of dilute HClO4 and the concentration of the metal ions into the effluent was determined, conductometrically. The experimental results indicated that the capacity of alginate was decreased in the order Ba2+ > Sr2+ > Ca2+ ions in good accord with their thermal stability. The factors affected the affinity of alginate for binding the metal ions were interpreted and discussed.

Promising Biocompatible, Biodegradable, and Inert Polymers for Purification of Wastewater by Simultaneous Removal of Carcinogenic Cr(VI) and Present Toxic Heavy Metal Cations: Reduction of Chromium(VI) by Poly(ethylene glycol) in Aqueous Perchlorate Solutions.

A spectrophotometric technique has been applied for studying the reduction of chromium(VI) by poly(ethylene glycol) (PEG) as water-soluble and nontoxic synthetic polymer at a constant ionic strength of 4.0 mol dm-3 in the absence and presence of the ruthenium(III) catalyst. In the absence of the catalyst, the reaction orders in [Cr(VI)] and [PEG] were found to be unity and fractional first orders, respectively. The oxidation process was found to be acid-catalyzed with fractional second order in [H+]. The addition of Ru(III) was found to catalyze the oxidation rates with observation of zero-order reaction in [CrO4 2-] and fractional orders in both [PEG] and [Ru(III)], respectively. The PEG reduces the soluble toxic hexavalent Cr(VI) as a model pollutant to the insoluble nontoxic Cr(III) complex, which is known to be eco-friendly and more safer from the environmental points of view. The acid derivative of PEG was found to possess high affinity for the removal of poisonous heavy metal ions from contaminant matters by chelation. Formation of the 1:1 intermediate complex has been kinetically revealed. A consistent reaction mechanism of oxidation was postulated and discussed.

Oxidation of Some Sustainable Sulfated Natural Polymers: Kinetics and Mechanism of Oxidation of Water-Soluble Chondroitin-4-Sulfate Polysaccharide by Hexachloroiridate(IV) in Aqueous Solutions.

The kinetics and mechanism of hexachloroiridate(IV) oxidation of chondroitin-4-sulfate as a sustainable coordination biopolymer macromolecule (CS) in aqueous acidic solutions at a constant ionic strength of 0.1 mol dm-3 has been investigated spectrophotometrically. Pseudo first-order plots gave sigmoidal curves of S-shape nature, indicating that the kinetics is complex. Two distinct stages have been observed. The first stage was relatively fast corresponding to the autoacceleration period, followed by a slow stage which became linear at a longer time period called the induction period. First-order dependence with respect to the [OX] and fractional first order in [CS] was observed for both stages. Kinetic evidence for formation of the 1:1 intermediate complex within the two stages has been revealed. The influence of [H+] on the rate constants indicated that the oxidation was of acid inhibition nature. The kinetic parameters have been evaluated, and a suitable reaction mechanism is suggested and discussed in terms of the nature of the electron-transfer process.

Kinetics of corrosion inhibition of aluminum in acidic media by water-soluble natural polymeric chondroitin-4-sulfate as anionic polyelectrolyte inhibitor.

Corrosion inhibition of aluminum (Al) in hydrochloric acid by anionic polyelectrolyte chondroitin-4-sulfate (CS) polysaccharide has been studied using both gasometrical and weight-loss techniques. The results drawn from these two techniques are comparable and exhibit negligible differences. The inhibition efficiency was found to increase with increasing the inhibitor concentration and decreased with increasing temperature. The inhibition action of CS on Al metal surface was found to obey both of Langmuir and Freundlich isotherms. The factors affecting the corrosion rates such as the concentration and geometrical structure of the inhibitor, concentration of the corrosive medium, and the temperature were examined. The kinetic parameters were evaluated and a suitable corrosion mechanism consistent with the results obtained is discussed.

Kinetics of Corrosion Inhibition of Aluminum in Acidic Media by Water-Soluble Natural Polymeric Pectates as Anionic Polyelectrolyte Inhibitors.

Corrosion inhibition of aluminum (Al) in hydrochloric acid by anionic polyeletrolyte pectates (PEC) as a water-soluble natural polymer polysaccharide has been studied using both gasometric and weight loss techniques. The results drawn from these two techniques are comparable and exhibit negligible differences. The inhibition efficiency was found to increase with increasing inhibitor concentration and decrease with increasing temperature. The inhibition action of PEC on Al metal surface was found to obey the Freundlich isotherm. Factors such as the concentration and geometrical structure of the inhibitor, concentration of the corrosive medium, and temperature affecting the corrosion rates were examined. The kinetic parameters were evaluated and a suitable corrosion mechanism consistent with the kinetic results is discussed in the paper.

A mechanistic approach to the kinetics of oxidation of uranium(IV) by hexachloroplatinate(IV) in aqueous perchlorate solutions. Evidence of the formation of a binuclear intermediate complex.

The kinetics of hexachloroplatinate(IV) oxidation of uranium(IV) ion in aqueous perchloric acid solutions at a constant ionic strength of 1.0 mol dm(-3) has been investigated using the stopped-flow and conventional spectrophotometric techniques. The oxidation reaction was found to proceed through two distinct stages. The initial stage was found to be relatively fast corresponding to the formation of [(H(2)O)(n)U(IV)·Cl(6)Pt(IV)](2+) binuclear intermediate complex (with the rate constant k(1) = 1.75 × 10(4) dm(3) mol(-1)s(-1), k(-1) = 6.8 s(-1), and the formation constant K = 2.6 × 10(3) dm(3) mol(-1) at [H(+)] = 1.0 mol dm(-3) and 25 °C for binuclear formation). This stage was followed by a much slower stage corresponding to the transfer of two electrons from U(IV) to Pt(IV) in the rate-determining step (with the rate constant k = 5.32 × 10(-5) s(-1) at [H(+)] = 1.0 mol dm(-3) and 25 °C). The reaction stoichiometry was found to depend on the molar ratio of the reactants concentration. The experimental results indicated the decrease of the observed first-order rate constants with increasing the [H(+)] for the decomposition of the binuclear intermediate complex through the slow-second stage, whereas no change was observed with respect to the rate of formation of the binuclear complex at the initial rapid part. A tentative reaction mechanism consistent with the kinetic results is discussed.

Kinetics and mechanism of permanganate oxidation of iota- and lambda-carrageenan polysaccharides as sulfated carbohydrates in acid perchlorate solutions.

The kinetics of oxidation of iota- and lambda-carrageenan as sulfated carbohydrates by permanganate ion in aqueous perchlorate solutions at a constant ionic strength of 2.0 mol dm(-3) have been investigated spectrophotometrically. The pseudo-first-order plots were found to be of inverted S-shape throughout the entire courses of reactions. The initial rates were found to be relatively slow in the early stages, followed by an increase in the oxidation rates over longer time periods. The experimental observations showed first-order dependences in permanganate and fractional first-order kinetics with respect to both carrageenans concentration for both the induction and autoacceleration periods. The results obtained at various hydrogen ion concentrations showed that the oxidation processes in these redox systems are acid-catalyzed throughout the two stages of oxidation reactions. The added salts lead to the prediction that Mn(III) is the reactive species throughout the autoacceleration periods. Kinetic evidence for the formation of 1:1 intermediate complexes was revealed. The kinetic parameters have been evaluated and tentative reaction mechanisms in good agreement with the kinetic results are discussed.

Further evidence for detection of short-lived transient hypomanganate(V) and manganate(VI) intermediates during oxidation of some sulfated polysaccharides by alkaline permanganate using conventional spectrophotometric techniques.

Spectrophotometric evidence for the formation of hypomanganate(V), [CAR-Mn(V)O43-], and manganate(VI), [CAR-Mn(VI)O42-], intermediate complexes has been confirmed during the oxidation of iota- and lambda-carrageenan-sulfated polysaccharides (CAR) by alkaline permanganate at pHs 12 using a conventional spectrophotometer. These short-lived intermediate complexes were identified and characterized. A reaction mechanism in good consistence with the experimental results is suggested.

Spectrophotometric evidence for the formation of short-lived hypomanganate(V) and manganate(VI) transient species during the oxidation of K-carrageenan by alkaline permanganate.

Spectrophotometric detection of the formation of short-lived hypomanganate(V), [KCAR-Mn(V)O43-], and manganate(VI), [KCAR-Mn(VI)O42-], intermediates has been confirmed through the oxidation of K-carrageenan (KCAR) by potassium permanganate in alkaline solutions of pH's >or= 12 using a conventional spectrophotometer. The short-lived transient species were characterized and a mechanism consistent with experimental observations is suggested.