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International Journal of Molecular... Aug 2023In the last few decades, reticular chemistry has grown significantly as a field of porous crystalline molecular materials. Scientists have attempted to create the ideal... (Review)
Review
In the last few decades, reticular chemistry has grown significantly as a field of porous crystalline molecular materials. Scientists have attempted to create the ideal platform for analyzing distinct anions based on optical sensing techniques (chromogenic and fluorogenic) by assembling different metal-containing units with suitable organic linking molecules and different organic molecules to produce crystalline porous materials. This study presents novel platforms for anion recognition based on reticular chemistry with high selectivity, sensitivity, electronic tunability, structural recognition, strong emission, and thermal and chemical stability. The key materials for reticular chemistry, Metal-Organic Frameworks (MOFs), Zeolitic Imidazolate Frameworks (ZIFs), and Covalent-Organic Frameworks (COFs), and the pre- and post-synthetic modification of the linkers and the metal oxide clusters for the selective detection of the anions, have been discussed. The mechanisms involved in sensing are also discussed.
Topics: Anions; Oxides; Electronics; Metal-Organic Frameworks; Porosity
PubMed: 37685850
DOI: 10.3390/ijms241713045 -
Water Research Apr 2024This publication summarizes my journey in the field of chemical oxidation processes for water treatment over the last 30+ years. Initially, the efficiency of the... (Review)
Review
This publication summarizes my journey in the field of chemical oxidation processes for water treatment over the last 30+ years. Initially, the efficiency of the application of chemical oxidants for micropollutant abatement was assessed by the abatement of the target compounds only. This is controlled by reaction kinetics and therefore, second-order rate constant for these reactions are the pre-requisite to assess the efficiency and feasibility of such processes. Due to the tremendous efforts in this area, we currently have a good experimental data base for second-order rate constants for many chemical oxidants, including radicals. Based on this, predictions can be made for compounds without experimental data with Quantitative Structure Activity Relationships with Hammet/Taft constants or energies of highest occupied molecular orbitals from quantum chemical computations. Chemical oxidation in water treatment has to be economically feasible and therefore, the extent of transformation of micropollutants is often limited and mineralization of target compounds cannot be achieved under realistic conditions. The formation of transformation products from the reactions of the target compounds with chemical oxidants is inherent to oxidation processes and the following questions have evolved over the years: Are the formed transformation products biologically less active than the target compounds? Is there a new toxicity associated with transformation products? Are transformation products more biodegradable than the corresponding target compounds? In addition to the positive effects on water quality related to abatement of micropollutants, chemical oxidants react mainly with water matrix components such as the dissolved organic matter (DOM), bromide and iodide. As a matter of fact, the fraction of oxidants consumed by the DOM is typically > 99%, which makes such processes inherently inefficient. The consequences are loss of oxidation capacity and the formation of organic and inorganic disinfection byproducts also involving bromide and iodide, which can be oxidized to reactive bromine and iodine with their ensuing reactions with DOM. Overall, it has turned out in the last three decades, that chemical oxidation processes are complex to understand and to manage. However, the tremendous research efforts have led to a good understanding of the underlying processes and allow a widespread and optimized application of such processes in water treatment practice such as drinking water, municipal and industrial wastewater and water reuse systems.
Topics: Bromides; Iodides; Water Pollutants, Chemical; Oxidation-Reduction; Oxidants; Water Purification
PubMed: 38387263
DOI: 10.1016/j.watres.2024.121148 -
Molecules (Basel, Switzerland) Jul 2023The chemistry of hypervalent iodine reagents has now become quite valuable due to the reactivity of these compounds under mild reaction conditions and their resemblance... (Review)
Review
The chemistry of hypervalent iodine reagents has now become quite valuable due to the reactivity of these compounds under mild reaction conditions and their resemblance in chemical properties to transition metals. The environmentally friendly nature of these reagents makes them suitable for Green Chemistry. Reagents with a dual nature, such as iodine(III) reagents, are capable electrophiles, while iodine(V) reagents are known for their strong oxidant behavior. Various iodine(V) reagents including IBX and DMP have been used as oxidants in organic synthesis either in stoichiometric or in catalytic amounts. In this review article, we describe various oxidation reactions induced by iodine(V) reagents reported in the past decade.
Topics: Iodine; Oxidants; Oxidation-Reduction; Indicators and Reagents; Catalysis
PubMed: 37446912
DOI: 10.3390/molecules28135250 -
Chemistry (Weinheim An Der Bergstrasse,... Aug 2023Steroids are highly prevalent structures in small-molecule therapeutics, with the level of oxidation being key to their biological activity and physicochemical... (Review)
Review
Steroids are highly prevalent structures in small-molecule therapeutics, with the level of oxidation being key to their biological activity and physicochemical properties. These C(sp )-rich tetracycles contain many stereocentres, which are important for creating specific vectors and protein binding orientations. Therefore, the ability to hydroxylate steroids with a high degree of regio-, chemo- and stereoselectivity is essential for researchers working in this field. This review will cover three main methods for the hydroxylation of steroidal C(sp )-H bonds: biocatalysis, metal-catalysed C-H hydroxylation and organic oxidants, such as dioxiranes and oxaziridines.
Topics: Hydroxylation; Oxidation-Reduction; Oxidants; Steroids; Biocatalysis
PubMed: 37235530
DOI: 10.1002/chem.202301066 -
International Journal of Biological... Jul 2023Zinc oxide nanoparticles (ZnO NPs) have gained significant attention in the textile industry for their ability to enhance the physicochemical properties of fabrics. In... (Review)
Review
Zinc oxide nanoparticles (ZnO NPs) have gained significant attention in the textile industry for their ability to enhance the physicochemical properties of fabrics. In recent years, there has been a growing focus on the development of ZnO-based nanomaterials and their applications for cotton and other fabrics. This review paper provides an overview of the synthesis and diverse applications of ZnO-based nanomaterials for textile fabrics, including protection against UV irradiation, bacteria, fungi, microwave, electromagnetic radiation, water, and fire. Furthermore, the study offers the potential of these materials in energy harvesting applications, such as wearable pressure sensors, piezoelectric nanogenerators, supercapacitors, and human energy harvesting. Additionally, we discuss the potential of ZnO-based nanomaterials for environmental cleaning, including water, oil, and solid cleaning. The current research in this area has focused on various materials used to prepare ZnO-based nanocomposites, such as metals/nonmetals, semiconductors, metal oxides, carbon materials, polymers, MXene, metal-organic frameworks, and layered double hydroxides. The findings of this review highlight the potential of ZnO-based nanomaterials to improve the performance of textile fabrics in a range of applications, and the importance of continued research in this field to further advance the development and use of ZnO-based nanomaterials in the textile industry.
Topics: Humans; Zinc Oxide; Textiles; Nanoparticles; Water
PubMed: 37276903
DOI: 10.1016/j.ijbiomac.2023.124916 -
Ecotoxicology and Environmental Safety Nov 2023The use of Advance Oxidation Process (AOPs) has been extensively examined in order to eradicate organic pollutants. This review assesses the efficacy of photolysis, O... (Review)
Review
The use of Advance Oxidation Process (AOPs) has been extensively examined in order to eradicate organic pollutants. This review assesses the efficacy of photolysis, O based (O/UV, O/HO, O/HO/UV, HO/UV, Fenton, Fenton-like, hetero-system) and sonochemical and electro-oxidative AOPs in this regard. The main purpose of this review and some suggestions for the advancement of AOPs is to facilitate the elimination of toxic organic pollutants. Initially proposed for the purification of drinking water in 1980, AOPs have since been employed for various wastewater treatments. AOPs technologies are essentially a process intensification through the use of hybrid methods for wastewater treatment, which generate large amounts of hydroxyl (•OH) and sulfate (SO4·-) radicals, the ultimate oxidants for the remediation of organic pollutants. This review covers the use of AOPs and ozone or UV treatment in combination to create a powerful method of wastewater treatment. This novel approach has been demonstrated to be highly effective, with the acceleration of the oxidation process through Fenton reaction and photocatalytic oxidation technologies. It is clear that Advance Oxidation Process are a helpful for the degradation of organic toxic compounds. Additionally, other processes such as •OH and SO4·- radical-based oxidation may also arise during AOPs treatment and contribute to the reduction of target organic pollutants. This review summarizes the current development of AOPs treatment of wastewater organic pollutants.
Topics: Hydroxyl Radical; Hydrogen Peroxide; Wastewater; Oxidation-Reduction; Environmental Pollutants
PubMed: 37890248
DOI: 10.1016/j.ecoenv.2023.115564 -
International Journal of Molecular... Oct 2023Graphitic carbon nitride (g-CN), a metal-free polymer semiconductor, has been recognized as an attractive photocatalytic material for environmental remediation because... (Review)
Review
Graphitic carbon nitride (g-CN), a metal-free polymer semiconductor, has been recognized as an attractive photocatalytic material for environmental remediation because of its low band gap, high thermal and photostability, chemical inertness, non-toxicity, low cost, biocompatibility, and optical and electrical efficiency. However, g-CN has been reported to suffer from many difficulties in photocatalytic applications, such as a low specific surface area, inadequate visible-light utilization, and a high charge recombination rate. To overcome these difficulties, the formation of g-CN heterojunctions by coupling with metal oxides has triggered tremendous interest in recent years. In this regard, zinc oxide (ZnO) is being largely explored as a self-driven semiconductor photocatalyst to form heterojunctions with g-CN, as ZnO possesses unique and fascinating properties, including high quantum efficiency, high electron mobility, cost-effectiveness, environmental friendliness, and a simple synthetic procedure. The synergistic effect of its properties, such as adsorption and photogenerated charge separation, was found to enhance the photocatalytic activity of heterojunctions. Hence, this review aims to compile the strategies for fabricating g-CN/ZnO-based Z-scheme and S-scheme heterojunction photocatalytic systems with enhanced performance and overall stability for the photodegradation of organic pollutants. Furthermore, with reference to the reported system, the photocatalytic mechanism of g-CN/ZnO-based heterojunction photocatalysts and their charge-transfer pathways on the interface surface are highlighted.
Topics: Zinc Oxide; Photolysis; Oxides; Environmental Pollutants
PubMed: 37834469
DOI: 10.3390/ijms241915021 -
Chemosphere Aug 2023In this work, comparative study of paddy and upland soils were carried out to unravel mechanisms of enhanced soil organic carbon (SOC) sequestration in paddy soils using...
In this work, comparative study of paddy and upland soils were carried out to unravel mechanisms of enhanced soil organic carbon (SOC) sequestration in paddy soils using fractionation methods, C NMR and Nano-SIMS analysis, as well as organic layer thickness calculations (Core-Shell model). The results showed that although there is a strong increase in particulate SOC in paddy soils compared to that in the upland soils, the increase in mineral-associated SOC is more important, explaining 60-75% of SOC increase in the paddy soils. In the wet and dry alternate cycles of paddy soil, iron (hydr)oxides adsorb relatively small and soluble organic molecules (fulvic acid-like), promote catalytic oxidation and polymerization, thus accelerating formation of larger organic molecules. Upon reductive iron dissolution, these molecules are released and incorporated into existing less soluble organic compounds (humic acid or humin-like), which are coagulated and associated with clay minerals, becoming part of the mineral-associated SOC. The functioning of this "iron wheel" process stimulates accumulation of relatively young SOC into mineral-associated organic carbon pool, and reduces the difference in chemical structure between oxides-bound and clay-bound SOC. Further, the faster turnover of oxides and soil aggregates in paddy soil also facilities interaction between SOC and minerals. The formation of mineral-associated SOC may delay degradation of organic matter during both wet and dry period in the paddy field, therefore enhancing carbon sequestration in paddy soils.
Topics: Soil; Carbon; Clay; Carbon Sequestration; Oryza; Minerals; Iron; Oxides
PubMed: 37187382
DOI: 10.1016/j.chemosphere.2023.138927 -
Environmental Science. Processes &... Oct 2023Air-discharged waste from commonly used trenchless technologies of sewer pipe repairs is an emerging and poorly characterized source of urban pollution. This study...
Air-discharged waste from commonly used trenchless technologies of sewer pipe repairs is an emerging and poorly characterized source of urban pollution. This study reports on the molecular-level characterization of the atmospherically discharged aqueous-phase waste condensate samples collected at four field sites of the sewer pipe repairs. The molecular composition of organic species in these samples was investigated using reversed-phase liquid chromatography coupled with a photodiode array detector and a high-resolution mass spectrometer equipped with interchangeable atmospheric pressure photoionization and electrospray ionization sources. The waste condensate components comprise a complex mixture of organic species that can partition between gas-, aqueous-, and solid-phases when water evaporates from the air-discharged waste. Identified organic species have broad variability in molecular weight, molecular structures, and carbon oxidation state, which also varied between the waste samples. All condensates contained complex mixtures of oxidized organics, N- and S-containing organics, condensed aromatics, and their functionalized derivatives that are directly released to the atmospheric environment during installations. Furthermore, semi-volatile, low volatility, and extremely low volatility organic compounds comprise 75-85% of the total compounds identified in the waste condensates. Estimates of the component-specific viscosities suggest that upon evaporation of water waste material would form the semi-solid and solid phases. The low volatilities and high viscosities of chemical components in these waste condensates will contribute to the formation of atmospheric secondary organic aerosols and atmospheric solid nanoplastic particles. Lastly, selected components expected in the condensates were quantified and found to be present at high concentrations (1-20 mg L) that may exceed regulatory limits.
Topics: Volatile Organic Compounds; Mass Spectrometry; Water; Aerosols
PubMed: 37682218
DOI: 10.1039/d3em00084b -
Environmental Research Aug 2023Graphitic carbon nitride (g-CN)-based materials are attracting attention for their unique properties, such as low-cost, chemical stability, facile synthesis, adjustable... (Review)
Review
Graphitic carbon nitride (g-CN)-based materials are attracting attention for their unique properties, such as low-cost, chemical stability, facile synthesis, adjustable electronic structure, and optical properties. These facilitate the use of g-CN to design better photocatalytic and sensing materials. Environmental pollution by hazardous gases and volatile organic compounds (VOCs) can be monitored and controlled using eco-friendly g-CN- photocatalysts. Firstly, this review introduces the structure, optical and electronic properties of CN and CN assisted materials, followed by various synthesis strategies. In continuation, binary and ternary nanocomposites of CN with metal oxides, sulfides, noble metals, and graphene are elaborated. g-CN/metal oxide composites exhibited better charge separation that leads to enhancement in photocatalytic properties. g-CN/noble metal composites possess higher photocatalytic activities due to the surface plasmon effects of metals. Ternary composites by the presence of dual heterojunctions improve properties of g-CN for enhanced photocatalytic application. In the later part, we have summarised the application of g-CN and its assisted materials for sensing toxic gases and VOCs and decontaminating NOx and VOCs by photocatalysis. Composites of g-CN with metal and metal oxide give comparatively better results. This review is expected to bring a new sketch for developing g-CN-based photocatalysts and sensors with practical applications.
Topics: Graphite; Volatile Organic Compounds; Gases; Oxides
PubMed: 37209982
DOI: 10.1016/j.envres.2023.116149