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.

Cu-Doped 1D Hydroxyapatite as a Highly Active Catalyst for the Removal of 4-Nitrophenol and Dyes from Water.

Metallic copper nanoparticle (Cu NP)-doped 1D hydroxyapatite was synthesized using a simple chemical reduction method. To describe the structure and composition of the Cu/HAP nanocomposites, physicochemical techniques such as X-ray diffraction, Fourier transform infrared spectroscopy, inductively coupled plasma, N2 adsorption-desorption, X-ray photoelectron spectroscopy, and high-resolution transmission electron microscopy were used. The TEM scan of the Cu/HAP nanocomposite revealed a rod-like shape with 308 nm length and 117 nm width on average. The catalytic activity of Cu/HAP nanocomposites for the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) in the presence of NaBH4 has been thoroughly investigated. The 0.7% Cu/HAP nanocomposite was shown to have superior catalytic activity than the other nanocomposites, converting 4-NP to 4-AP in ∼1 min with good recyclability. Moreover, this nanocomposite showed excellent catalytic performance in the organic dye reduction such as Congo red and acriflavine hydrochloride dyes. The high dispersion of Cu NPs on HAP support, the high specific surface area, and the small Cu particles contributed to its remarkable catalytic performance.

A comparative study of Cu-anchored 0D and 1D ZnO nanostructures for the reduction of organic pollutants in water.

In this work, Cu NPs were loaded at a fixed percentage (5 wt%) on 1D, (1D + 0D) and 0D ZnO nanostructures to investigate the effect of the support morphology on the reduction of organic pollutants in water. The synthesized materials were characterized by high-resolution transmission electron microscopy (HR-TEM), ultraviolet-visible spectroscopy (UV-Vis), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), N2 adsorption-desorption and X-ray photoelectron spectroscopy (XPS). The results reveal that the loading of Cu NPs decreases the optical band gap, and a slight change in the crystallite sizes increases the specific surface area value of the nanocomposites. The TEM images reveal that 1D ZnO has an average width of 44.7 nm and an average length of 211 nm, while 0D ZnO has an average diameter of 54.5 nm. The HR-TEM and XPS data confirm the loading of metallic Cu NPs on the surface of the ZnO nanostructures. The pure ZnO and nanocomposites were tested for 4-nitrophenol (4-NP) reduction in the presence of NaBH4 at room temperature. The obtained results show that pure ZnO nanostructures have no catalytic performance, while the nanocomposites showed good catalytic activities. The catalytic reduction efficiency of 4-NP was found to follow the order of Cu/0DZnO > Cu/(1D + 0D)ZnO > Cu/1DZnO. The complete reduction of 4-NP has been observed to be achievable within 60 s using the Cu/0DZnO nanocomposite, with a k app value of 8.42 min-1 and good recyclability of up to five cycles. This nanocomposite was then applied in the reduction of organic dyes in water; it was found that the reduction rate constants for the methylene blue, Congo red, and acriflavine hydrochloride dyes were 1.4 min-1, 1.2 min-1, and 3.81 min-1, respectively. The high catalytic performance of this nanocomposite may be due to the small particle size, high specific surface area, and the high dispersion of Cu NPs on the surface of ZnO.

Kinetics and Mechanism Studies of Oxidation of Dibromothymolsulfonphthalein Toxic Dye by Potassium Permanganate in Neutral Media with the Synthesis of 2-Bromo-6-isopropyl-3-methyl-cyclohexa-2,5-dienone.

The oxidation of 3',3″-dibromothymolsulfonphthalein (DBTS) in neutral medium by potassium permanganate multi-equivalent oxidant has been studied spectrophotometrically. Pseudo-first-order plots showed inverted S-shape throughout the entire course of the reaction. The initial rates were found to be relatively fast in the early stages, followed by a decrease in the oxidation rates over longer time periods in the slow stage. Under pseudo-first-order conditions where [DBTS] ≫ 10 [MnO4 -], the experimental results showed a first-order dependence in [MnO4 -] and fractional-first-order kinetics in the [DBTS] concentration. The formation of 1:1 coordination intermediate complex prior to the rate-determining step was revealed kinetically. In addition, the intermediate species involving complexes of Mn(V) coordination has been detected. The oxidation product of DBTS was identified by Fourier transform infrared spectroscopy, ultraviolet-visible spectrophotometry, and gas chromatography-mass analysis. The obtained results indicated the formation of 2-bromo-6-isopropyl-3-methyl-cyclohexa-2,5-dienone as a derivative oxidation of DBTS.

Novel synthesis of antibacterial pyrone derivatives using kinetics and mechanism of oxidation of azithromycin by alkaline permanganate.

Dimethylamino-2H-5-dihydropyrane-6-methyl-4-one (DADHP) is a novel antibacterial pyrones derivatives and potential pharmaceutical that was quantitatively synthesized by oxidizing azithromycin (AZ) antibiotic with potassium permanganate in an alkaline medium (pH > 12). The oxidation reaction was kinetically studied using spectrophotometric technique at ionic strength equal to 0.02 mol dm-3. The redox reaction was discovered to have two separate stages that could be measured. The first stage was relatively fast and corresponding to the formation of coordination intermediate complexes involving blue hypomanganate (V) and/or green manganate (VI) transient species. Variable parameters like as the concentration of permanganate ion and AZ substrate, as well as pH and ionic strength, have been studied to see how they affect oxidation rates. The experimental results showed a first-order dependency in [MnO4-] and fractional first-order kinetics in each of [AZ] and alkali concentration under pseudo-first-order reaction conditions of [AZ] ≫ 10 [MnO4-]. The oxidation process was base-catalyzed, and the oxidation rates increased as the alkali concentration increased. The product was confirmed by Fourier Transform Infrared spectroscopy (FTIR), elemental analysis, condensation tests with 2,4-dinitrophenyl haydrazine and hydroxyl amine, and GC-Mass. The oxidation product obtained can be employed as interesting class of organic compounds with diverse chemical and pharmacological applications.

Early Diagnosis of Classic Homocystinuria in Kuwait through Newborn Screening: A 6-Year Experience.

Kuwait is a small Arabian Gulf country with a high rate of consanguinity and where a national newborn screening program was expanded in October 2014 to include a wide range of endocrine and metabolic disorders. A retrospective study conducted between January 2015 and December 2020 revealed a total of 304,086 newborns have been screened in Kuwait. Six newborns were diagnosed with classic homocystinuria with an incidence of 1:50,000, which is not as high as in Qatar but higher than the global incidence. Molecular testing for five of them has revealed three previously reported pathogenic variants in the CBS gene, c.969G>A, p.(Trp323Ter); c.982G>A, p.(Asp328Asn); and the Qatari founder variant c.1006C>T, p.(Arg336Cys). This is the first study to review the screening of newborns in Kuwait for classic homocystinuria, starting with the detection of elevated blood methionine and providing a follow-up strategy for positive results, including plasma total homocysteine and amino acid analyses. Further, we have demonstrated an increase in the specificity of the current newborn screening test for classic homocystinuria by including the methionine to phenylalanine ratio along with the elevated methionine blood levels in first-tier testing. Here, we provide evidence that the newborn screening in Kuwait has led to the early detection of classic homocystinuria cases and enabled the affected individuals to lead active and productive lives.

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.