Chemical Oxidation Research Articles

Mechanical properties of poly(ethylene succinate) thin films incorporated with chemical synthesis copper oxide nanoparticles

This study investigates the synthesis and characterization of poly(ethylene succinate) (PES) thin films and their composites with copper oxide (CuO) nanoparticles. CuO nanoparticles were synthesized using a chemical synthesis method, achieving an average size of 20 nm. PES/CuO composites were prepared by incorporating CuO at various concentrations of 0, 1, 3, and 5 wt%. The thin films were produced through solution polymerization followed by casting. Mechanical testing revealed that the tensile strength of pure PES was 25 MPa, while incorporating 1 wt% CuO increased the tensile strength to 30 MPa. At 3 wt%, the tensile strength reached 35 MPa, and at 5 wt%, it peaked at 40 MPa, demonstrating a significant enhancement in mechanical properties. The elongation at break also improved, increasing from 200% for pure PES to 250% for the 5 wt% CuO composite. Characterization of the materials was performed using Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and scanning electron microscopy (SEM) to analyze structural and morphological properties. The results confirm that the PES/CuO composites exhibit enhanced mechanical properties, indicating their potential for diverse applications in sustainable materials and biomedical fields.

Formylation facilitates the reduction of oxidized initiator methionines

Within a cell, protein-bound methionines can be chemically or enzymatically oxidized, and subsequently reduced by methionine sulfoxide reductases (Msrs). Methionine oxidation can result in structural damage or be the basis of functional regulation of enzymes. In addition to participating in redox reactions, methionines play an important role as the initiator residue of translated proteins where they are commonly modified at their α-amine group by formylation or acetylation. Here, we investigated how formylation and acetylation of initiator methionines impact their propensity for oxidation and reduction. We show that in vitro, N-terminal methionine residues are particularly prone to chemical oxidation and that their modification by formylation or acetylation greatly enhances their subsequent enzymatic reduction by MsrA and MsrB. Concordantly, in vivo ablation of methionyl-tRNA formyltransferase (MTF) in Escherichia coli increases the prevalence of oxidized methionines within synthesized proteins. We show that oxidation of formylated initiator methionines is detrimental in part because it obstructs their ensuing deformylation by peptide deformylase (PDF) and hydrolysis by methionyl aminopeptidase (MAP). Thus, by facilitating their reduction, formylation mitigates the misprocessing of oxidized initiator methionines.

Kinetic analysis on low‐temperature oxidation of wood pellets by isothermal microcalorimetry

AbstractLow‐temperature chemical oxidation is the major driver of self‐heating during storage of wood pellets and its kinetics is essential to describe the heat evolution. In the present work, isothermal microcalorimetry was used to characterize heat generation behavior of three types of wood pellets (pine, fir, and redwood pellets) at 30–70°C. The obtained data were employed to derive the kinetics of low‐temperature oxidation by the peak power, iso‐conversional method, and non‐steady analysis. The consistency and applicability of the kinetics derived by the three methods were evaluated. Kinetic parameters determined by the peak power method were observed to match those from the iso‐conversional method at lower conversions of the oxidation for heat generation. The kinetics derived by the iso‐conversional method indicated the oxidation reactivity generally decreasing and activation energy increasing with the conversion because of O2 consumption and reaction mechanism changing. With the impact of O2 consumption considered separately, the kinetics from the non‐steady analysis is capable of describing the evolution of heat power with the conversion and also consistent with that from the peak power method in describing intrinsic reactivity of pellet materials. The kinetics from the peak power and iso‐conversional methods lump the impact of O2 concentration with the reaction reactivity, suggesting their applications requiring additional models for connecting with O2 consumption.

Selective Oxidation of Alcohols to Carbonyls Under Decatungstate-Mediated Photoelectrochemical Conditions.

The oxidation of alcohols to the corresponding carbonyl derivatives has been realized under photoelectrochemical conditions in the presence of tetrabutylammonium decatungstate (TBADT) as the homogeneous photocatalyst. The protocol can be applied to both primary and secondary, benzylic and aliphatic alcohols. The desired products are obtained selectively, skipping the need for purposely added chemical oxidants. An in-depth study of photoelectrochemical conditions revealed that the protocol works best under amperostatic conditions in an undivided electrochemical cell irradiated with a 390 nm LED lamp. The comparison with analogous electrochemical and chemical oxidant-promoted photocatalytic transformations demonstrates the superior efficiency and selectivity of the hereby reported photoelectrochemical conditions.

Characterization and evaluation of the recovery process of saturated reverse osmosis membranes by chemical oxidation

Characterization and evaluation of the recovery process of saturated reverse osmosis membranes by chemical oxidation

Does short-span chemical oxidation induce more weathering than prolonged thermal aging on polypropylene microplastics? Its consequence during the interaction with cadmium

Does short-span chemical oxidation induce more weathering than prolonged thermal aging on polypropylene microplastics? Its consequence during the interaction with cadmium

Catalytic membrane with dual-layer structure for ultrafast degradation of emerging contaminants in surface water treatment

The catalytic membrane-based oxidation-filtration process integrates physical separation and chemical oxidation, offering a highly efficient water purification strategy. However, the oxidation-filtration process is limited in practical applications due to the short residence time of milliseconds within the catalytic layer and the interference of coexisting organic pollutants in real water. Herein, a dual-layer membrane containing a top selective layer and a bottom catalytic layer was fabricated using an in situ co-casting method with a double-blade knife. Experimental results demonstrated that the selective layer rejected macromolecular organic pollutants, thereby alleviating their interference with bisphenol A (BPA) degradation. Concurrently, the catalytic layer activated peracetic acid oxidant and achieved a high BPA degradation exceeding 90 % in milliseconds with reactive oxygen species (especially •OH). The finite-element analysis confirmed a high-concentration reaction field occupying the pore cavity of the catalytic layer, enhancing collision probability between reactive oxygen species and BPA, i.e., the nano-confinement effect. Additionally, the dual-layer membrane achieved a long-term stable performance for emerging contaminant degradation in surface water treatment. This work underscores a novel catalytic membrane structure design for high-performance oxidation-filtration processes and elucidates its mechanisms underlying ultrafast degradation.

Selective Photocatalytic C-H Oxidation of 5-Methylcytosine in DNA.

Selective C-H activation on complex biological macromolecules is a key goal in the field of organic chemistry. It requires thermodynamically challenging chemical transformations to be delivered under mild, aqueous conditions. 5-Methylcytosine (5mC) is a fundamentally important epigenetic modification in DNA that has major implications for biology and has emerged as a vital biomarker. Selective functionalisation of 5mC would enable new chemical approaches to tag, detect and map DNA methylation to enhance the study and exploitation of this epigenetic feature. We demonstrate the first example of direct and selective chemical oxidation of 5mC to 5-formylcytosine (5fC) in DNA, employing a photocatalytic system. This transformation was used to selectively tag 5mC. We also provide proof-of-concept for deploying this chemistry for single-base resolution sequencing of 5mC and genetic bases adenine (A), cytosine (C), guanine (G), thymine (T) in DNA on a next-generation sequencing system. This work exemplifies how photocatalysis has the potential to transform the analysis of DNA.

Heavier Diferrocenylpnictogenium Ions.

The synthesis, characterization and reactivity of the diferrocenylphosphenium ion [Fc2P]+ was extended to the heavier diferrocenylpnictogenium ions, [Fc2E]+ (E = As, Sb, Bi). The lighter diferrocenylnitrenium ion, [Fc2N]+, was detected by mass spectrometry, but could not be isolated. The molecular structures of [Fc2E]+ (E = P, As, Sb, Bi) reveal intramolecular coordination of the iron atoms, which counterbalance the electron deficiency of the pnictogens without affecting the strong Lewis acidities, which were determined according to the method of Gutmann and Beckett. The (electro-)chemical oxidation and reduction afforded the dications [Fc2E]2+ (E = P (unstable), As) and the neutral dipnictogens Fc2EEFc2 (E = P, As).

Synergistic Effects of Polydopamine/Medical Stone Bio-Adsorbents for Enhanced Interfacial Adsorption and Dynamic Filtration of Bacteria

Polymer-based wastewater disinfection, which is typically performed using chemical oxidation or irradiation, can result in various toxic byproducts and corrosion under harsh environments. This study introduces a robust bio-adsorbent prepared from naturally abundant polydopamine-modified medical stone (MS@PDA) for the high-efficiency removal of bacteria from water. The PDA nanocoating can be easily applied through an in situ self-polymerization process, resulting in a considerably high bacterial adsorption capacity of 6.6 k pcs mm−2 for Staphylococcus aureus. A cyclic flow-through dynamic filtration and a disinfection system was implemented using an MS@PDA porous filter with an average pore size of 21.8 ± 1.4 µm and porosity of ~83%, achieving a 5.2–6.0-fold enhancement in the cumulative removal efficiency for MS@PDA2. The underlying mechanisms were elucidated through the synergistic effects of interfacial bio-adsorption and size-dependent interception. Notably, the bacteria captured on the surface could be killed using the enhanced photothermal effects of the PDA nanocoating and the inherent antimicrobial properties of the mineral stone. Thus, this study not only provides a new type of advanced bio-adsorbent but also provides new perspectives on an efficient and cost-effective approach for sustainable wastewater treatment.

Solar Selectivity of Silver Nanoparticles Modified Copper Oxide Nanocomposite Thin Films Prepared by Facile Chemical Oxidation Method

AbstractSilver nanoparticles modified copper oxide nanocomposite thin films (Ag‐CuO NC TFs) and pristine CuO TF were successfully synthesized on copper substrates using a chemical oxidation route. X‐ray diffractometry (XRD) characterization of Ag‐CuO NC TFs revealed the formation of monoclinic crystal structured CuO. Scanning electron microscopy (SEM) images showed a star‐like grain morphology of the Ag‐CuO NC TFs. Energy dispersive X‐ray spectroscopy (EDX) analysis ascertained the presence of anticipated elements without impurities. Fourier transform infrared spectroscopy (FTIR) investigation confirmed the presence of Ag NPs on CuO in the Ag‐CuO NC TFs. Raman spectroscopy examination indicated the presence of a spinel structure with vibrational and tetrahedral sites. UV‐Vis‐NIR reflectance analysis demonstrated that Ag‐CuO NC TFs with 2.0 wt.% Ag NPs exhibited solar absorptance of 72.39 %, thermal emittance of 4.3 %, and a highest solar selectivity of 16.83 among the prepared thin films. These results suggest that the Ag‐CuO NC TFs could be promising candidates for use as solar selective absorbers in solar thermal energy conversion devices.

Reevaluation of XPS Pt 4f peak fitting: Ti 3s plasmon peak interference and Pt metallic peak asymmetry in Pt@TiO2 system

The structural, electronic, and electrochemical properties of noble metals supported on transition metal oxides, such as Pt nanoparticles (NPs) supported on TiO2 (Pt@TiO2), have been extensively studied for their relevance to energy technologies, including photocatalysis, electrocatalysis, and electrochemical energy conversion. As the need to lower the amount of Pt and other noble metals used in energy conversion systems becomes urgent, it is essential to accurately quantify the loading of these metals and electronic density redistribution between them and their supports. X-ray photoelectron spectroscopy (XPS) is widely used for the identification and quantification of chemical species. In particular, fitting of the Pt 4f spectra for Pt@TiO2 is frequently performed to determine the chemical environment and oxidation state of Pt, which strongly affect the physical behavior and catalytic performance of this system. Here, we show that neglecting contributions due to the Pt surroundings and the asymmetry of the Pt metal peak in the line shape fitting can lead to severe mischaracterization of the oxidation state of Pt. We quantify the effects of background contributions that stem from the TiO2 support and discuss how factoring in the strong asymmetry of Pt 4f doublets, which stems from the shake-up type processes, affects the interpretation of Pt 4f XPS line shape.

Heterogeneous visible-light photoredox catalysis with NiCl2@g-C3N4 for induced C(sp2)-H/N[sbnd]H cross-dehydrogenative coupling

A novel photoactive NiCl2@g-C3N4 catalyst system, which effectively drives C(sp2)-H/NH bond formation between quinolin-2(1H)-ones, primary and secondary aliphatic amines under blue light irradiation. The NiCl2@g-C3N4 composite with a NiCl2 loading of 0.7wt% had the highest photoactivity, and the calculated band gap energy value is 2.56 eV The nickel ion could act as an electron acceptor enhancing carrier separation and transfer efficiency, greatly enhanced the photoreaction efficiency of g-C3N4. Preliminary mechanistic studies indicate upon visible light irradiation, the photo-generated electrons and holes act as oxidants, thereby generating amine radicals in the absence of external chemical oxidants. This provides a straightforward and efficient approach for directly 3-aminating quinoxalines-2(1H)-ones. Moreover, the heterogeneous catalyst can be recycled at least six times without significant activity loss.

Electrochemical N‐Centered Radical‐Triggered Intramolecular N−N Coupling for the Cyclization of o‐Aminyl Azobenzenes

AbstractAn electrochemical radical cyclization of o‐aminyl azobenzenes via N‐centered radical generation has been developed for the synthesis of benzotriazoles. The cyclization of o‐aminyl azobenzenes bearing a sulfonyl protection on amine readily proceeds in the absence of any external transition metal catalyst or chemical oxidant, and exhibits good tolerance towards functional groups.

A Critical Review of Deep Oxidation of Gaseous Volatile Organic Compounds via Aqueous Advanced Oxidation Processes.

Volatile organic compounds (VOCs) are considered to be the most recalcitrant gaseous pollutants due to their high toxicity, diversity, complexity, and stability. Gas-solid catalytic oxidation methods have been intensively studied for VOC treatment while being greatly hampered by energy consumption, catalyst deactivation, and byproduct formation. Recently, aqueous advanced oxidation processes (AOPs) have attracted increasing interest for the deep oxidation of VOCs at room temperature, owing to the generation of abundant reactive oxygen species (ROS). However, current reviews mainly focus on VOC degradation performance and have not clarified the specific reaction process, degradation products, and paths of VOCs in different AOPs. This study systematically reviews recent advances in the application of aqueous AOPs for gaseous VOC removal. First, the VOC gas-liquid mass transfer and chemical oxidation processes are presented. Second, the latest research progress of VOC removal by various ROS is reviewed to study their degradation performances, pathways, and mechanisms. Finally, the current challenges and future strategies are discussed from the perspectives of synergistic oxidation of VOC mixtures, accurate oxidation, and resource utilization of target VOCs via aqueous AOPs. This perspective provides the latest information and research inspiration for the future industrial application of aqueous AOPs for VOC waste gas treatment.

Chromium speciation from tannery wastewater using spectroscopic techniques

The toxicity and reactivity of chromium (Cr) depend on its chemical form or oxidation state which directs the significance of chromium speciation. Cr(VI) is a ‘Class A’ carcinogen whereas Cr(III)) is considered as essential for metabolism. In this work, concentrations of Cr species in different sampling sites of a tannery effluent have been spectroscopically determined. Cr(VI) was determined by UV-visible spectrophotometer through azo dye formation. Total Cr was determined by FAAS while Cr(III) was through subtraction. The Cr(IV) concentration before and after treatment was found in close proximity since the wastewater treatment process was evidently not effective at reducing the level of Cr(IV) in the waste stream (i.e., 3.34 mg/ L versus 3.15 mg/L). The Cr(VI) concentration after treatment (3.15 mg/L) is more than 31 times higher than the permissible limit of WHO (0.1 mg/L). Furthermore, the concentration of Cr(VI) in the downstream of the receiving river (0.59 mg/L) is more than 12 times higher than the upstream (0.046 mg/L) while Cr(III) in the downstream (25.73 mg/L) is more than 50 times higher than the upstream concentration (0.51 mg/L), confirming that the pollution of the river is from the tannery effluent.

The Feasibility of Using Electrostatic Interactions for Immobilizing Ru-bda Catalysts in Covalent Organic Framework: A Proof-of-concept.

Heterogenetization of molecular catalysts effectively resolves the separation issues of homogeneous catalysts and expands their application scenarios. In recent years, more and more studies have been using non-covalent interactions to achieve the heterogenization of molecular catalysts. Herein, electrostatic attraction was used to immobilize molecular catalysts, Ru-bda small molecular catalysts in COF materials, where the charged Ru-bda catalysts were immobilized in the oppositely charged COF with a high [Ru] loading content of ~0.2 mmol [Ru] g-1 COF. The leakage experiment verified that the immobilization of Ru-bda catalysts in COF by electrostatic interactions is stable in 0.1 M HClO4 and less than 5% of molecular Ru-bda catalysts were leached into the solution in 2 hours. The chemical water oxidation experiment was conducted as a model catalysis reaction to verify the feasibility of using electrostatic interactions for immobilizing Ru-bda catalysts in COFs. The prepared Ru(bda)@COFs demonstrate a high catalytic activity of 268 μmol L-1 s-1 O2 for chemical water oxidation, illustrating the electrostatic attractions between COF and small molecules that can be used to immobilize homogeneous catalysts in heterogeneous materials. However, the robustness of COF material itself under catalytic conditions should be considered in practical applications.

Impact of Harvest Method on Development of European Sea Bass Skin Microbiome during Chilled Storage

European sea bass (Dicentrarchus labrax) is one of the most significant species farmed in the Mediterranean, yet a very perishable product. Its quality deteriorates rapidly as a result of three mechanisms: microbial activity, chemical oxidation, and enzymatic degradation. Microbial spoilage is the mechanism that contributes most to the quality deterioration of fresh and non-processed fish. To this end, our study aims to identify for the first time the combined effect of aquatic environment and harvest method on the composition and trajectory at storage at 0 °C of the European sea bass skin microbiome. Sampling was performed in two commercial fish farms in Western (WG) and Central Greece (CG) where fish were harvested using different methods: direct immersion in ice water or a mixture of slurry ice; application of electro-stunning prior to immersion in ice water. Samples were collected on harvest day and one week post-harvest. To profile the bacterial communities in the fish skin, 16S ribosomal RNA gene sequencing was used. The results and the following analyses indicated that the aquatic environment shaped the original composition of the skin microbiome, with 815 ASVs identified in the WG farm as opposed to 362 ASVs in the CG farm. Moreover, Pseudomonas and Pseudoalteromonas dominated the skin microbiome in the WG farm, unlike the CG farm where Shewanella and Psychrobacter were the dominant genera. All these genera contain species such as Shewanella putrefaciens, Pseudomonas aeruginosa, Pseudoalteromonas spp., and Psychrobacter sp., all of which have been implicated in the deterioration and spoilage of the final product. The different harvest methods drove variations in the microbiome already shaped by the aquatic environment, with electro-stunning favoring more diversity in the skin microbiome. The aquatic environment in combination with the harvest method appeared to determine the skin microbiome trajectory at storage at 0 °C. Although Shewanella had dominated the skin microbiome in all samples one week post-harvest, the diversity and the relative abundance of genera were strongly influenced by the aquatic environment and the harvest method. This study sheds light on the hierarchy of the factors shaping the fish skin microbiome and their importance for controlling post-harvest quality of fresh fish.

Evaluation of Conductive Porous Biobased Composites with Tunable Mechanical Properties for Potential Biological Applications.

In this work, starch-based porous cryogels with controlled mechanical and electrical properties were prepared for tissue engineering applications. The starch cryogels were formulated using κ-carrageenan, poly(vinyl alcohol) (PVA), and styrylpyridinium-substituted PVA (SbQ) into the composite. A conductive cryogel was polymerized by chemical oxidation of 3,4-ethylenedioxythiophene (EDOT) using iron(III) p-toluenesulfonate as a strategy to control the electrical properties. The physical, thermal, and mechanical properties were evaluated for the obtained composites. Macro- and nanoscale results confirmed the capability of tuning the mechanical properties of the material by the addition of biopolymers in different contents. The presence of κ-carrageenan significantly increased the storage modulus and decreased the damping effect in the formulations. The presence of PVA showed a plasticizing effect in the formulations, confirmed by the buffering effect and an increase in storage modulus. PVA-SBQ improved the mechanical properties by cross-linking. The addition of PEDOT increased the mechanical and electrical properties of the obtained materials.

Implementation of 2,2'-azobispyridine radical mono- and dianions in dinuclear rare earth metal complexes.

The seminal isolation of a dinuclear rare earth metal complex comprising a bridging 2,2'-azobispyridyl radical anion, [(Cptet2Y)2(μ-abpy˙)](BPh4), is presented, which was obtained from a one-electron chemical oxidation of [(Cptet2Y)2(μ-abpy)]. The unprecedented compounds were characterized by crystallography, spectroscopy and DFT computations. The radical character was proven by EPR spectroscopy.