-
Nature Communications Feb 2022Artificial photosynthesis of HO using earth-abundant water and oxygen is a promising approach to achieve scalable and cost-effective solar fuel production. Recent...
Artificial photosynthesis of HO using earth-abundant water and oxygen is a promising approach to achieve scalable and cost-effective solar fuel production. Recent studies on this topic have made significant progress, yet are mainly focused on using organic polymers. This set of photocatalysts is susceptible to potent oxidants (e.g. hydroxyl radical) that are inevitably formed during HO generation. Here, we report an inorganic Mo-doped faceted BiVO (Mo:BiVO) system that is resistant to radical oxidation and exhibits a high overall HO photosynthesis efficiency among inorganic photocatalysts, with an apparent quantum yield of 1.2% and a solar-to-chemical conversion efficiency of 0.29% at full spectrum, as well as an apparent quantum yield of 5.8% at 420 nm. The surface-reaction kinetics and selectivity of Mo:BiVO were tuned by precisely loading CoO and Pd on {110} and {010} facets, respectively. Time-resolved spectroscopic investigations of photocarriers suggest that depositing select cocatalysts on distinct facet tailored the interfacial energetics between {110} and {010} facets and enhanced charge separation in Mo:BiVO, therefore overcoming a key challenge in developing efficient inorganic photocatalysts. The promising HO generation efficiency achieved by delicate design of catalyst spatial and electronic structures sheds light on applying robust inorganic particulate photocatalysts to artificial photosynthesis of HO.
Topics: Catalysis; Hydrogen Peroxide; Photosynthesis; Semiconductors; Water
PubMed: 35210427
DOI: 10.1038/s41467-022-28686-x -
Biomolecules Mar 2021Heavy metals (HMs) toxicity represents a global problem depending on the soil environment's geochemical forms. Biochar addition safely reduces HMs mobile forms, thus,...
Heavy metals (HMs) toxicity represents a global problem depending on the soil environment's geochemical forms. Biochar addition safely reduces HMs mobile forms, thus, reducing their toxicity to plants. While several studies have shown that biochar could significantly stabilize HMs in contaminated soils, the study of the relationship of soil properties to potential mechanisms still needs further clarification; hence the importance of assessing a naturally contaminated soil amended, in this case with Paulownia biochar (PB) and Bamboo biochar (BB) to fractionate Pb, Cd, Zn, and Cu using short sequential fractionation plans. The relationship of soil pH and organic matter and its effect on the redistribution of these metals were estimated. The results indicated that the acid-soluble metals decreased while the fraction bound to organic matter increased compared to untreated pots. The increase in the organic matter metal-bound was mostly at the expense of the decrease in the acid extractable and Fe/Mn bound ones. The highest application of PB increased the organically bound fraction of Pb, Cd, Zn, and Cu (62, 61, 34, and 61%, respectively), while the BB increased them (61, 49, 42, and 22%, respectively) over the control. Meanwhile, Fe/Mn oxides bound represents the large portion associated with zinc and copper. Concerning soil organic matter (SOM) and soil pH, as potential tools to reduce the risk of the target metals, a significant positive correlation was observed with acid-soluble extractable metal, while a negative correlation was obtained with organic matter-bound metal. The principal component analysis (PCA) shows that the total variance represents 89.7% for the TCPL-extractable and HMs forms and their relation to pH and SOM, which confirms the positive effect of the pH and SOM under PB and BB treatments on reducing the risk of the studied metals. The mobility and bioavailability of these metals and their geochemical forms widely varied according to pH, soil organic matter, biochar types, and application rates. As an environmentally friendly and economical material, biochar emphasizes its importance as a tool that makes the soil more suitable for safe cultivation in the short term and its long-term sustainability. This study proves that it reduces the mobility of HMs, their environmental risks and contributes to food safety. It also confirms that performing more controlled experiments, such as a pot, is a disciplined and effective way to assess the suitability of different types of biochar as soil modifications to restore HMs contaminated soil via controlling the mobilization of these minerals.
Topics: Cadmium; Charcoal; Chemical Fractionation; Copper; Environmental Pollution; Ferric Compounds; Hydrogen-Ion Concentration; Lamiales; Lead; Manganese Compounds; Metals, Heavy; Microscopy, Electron, Scanning; Organic Chemicals; Oxides; Principal Component Analysis; Sasa; Soil; Spectrometry, X-Ray Emission; Zinc
PubMed: 33802758
DOI: 10.3390/biom11030448 -
Scientific Reports Dec 2022Conventional nitrogen removal in wastewater treatment requires a high oxygen and energy input. Anaerobic ammonium oxidation (anammox), the single-step conversion of...
Conventional nitrogen removal in wastewater treatment requires a high oxygen and energy input. Anaerobic ammonium oxidation (anammox), the single-step conversion of ammonium and nitrite to nitrogen gas, is a more energy and cost effective alternative applied extensively to sidestream wastewater treatment. It would also be a mainstream treatment option if species diversity and physiology were better understood. Anammox bacteria were enriched up to 80%, 90% and 50% relative abundance, from a single inoculum, under standard enrichment conditions with either stepwise-nitrite and ammonia concentration increases (R1), nitric oxide supplementation (R2), or complex organic carbon from mainstream wastewater (R3), respectively. Candidatus Brocadia caroliniensis predominated in all reactors, but a shift towards Ca. Brocadia sinica occurred at ammonium and nitrite concentrations > 270 mg NH-N L and 340 mg NO-N L respectively. With NO present, heterotrophic growth was inhibited, and Ca. Jettenia coexisted with Ca. B. caroliniensis before diminishing as nitrite increased to 160 mg NO-N L. Organic carbon supplementation led to the emergence of heterotrophic communities that coevolved with Ca. B. caroliniensis. Ca. B. caroliniensis and Ca. Jettenia preferentially formed biofilms on surfaces, whereas Ca. Brocadia sinica formed granules in suspension. Our results indicate that multiple anammox bacteria species co-exist and occupy sub-niches in anammox reactors, and that the dominant population can be reversibly shifted by, for example, changing nitrogen load (i.e. high nitrite concentration favors Ca. Brocadia caroliniensis). Speciation has implications for wastewater process design, where the optimum cell immobilization strategy (i.e. carriers vs granules) depends on which species dominates.
Topics: Wastewater; Carbon; Nitrites; Anaerobic Ammonia Oxidation; Nitrogen Dioxide; Oxidation-Reduction; Ammonium Compounds; Nitrogen; Bacteria; Biotransformation; Biofilms; Bioreactors; Anaerobiosis
PubMed: 36522527
DOI: 10.1038/s41598-022-26069-2 -
International Journal of Molecular... Oct 2022Cu nanoparticles were produced by using solid-state dewetting (dry) of a 1.3 nm Cu layer or laser ablation of a Cu solid target (wet) in acetone and methanol. The...
Cu nanoparticles were produced by using solid-state dewetting (dry) of a 1.3 nm Cu layer or laser ablation of a Cu solid target (wet) in acetone and methanol. The morphology and chemical composition of the nanoparticles were investigated as a function of the synthesis methods and their key parameters of the annealing temperature (200-500 °C) and the liquid environment during the ablation. Cu nanoparticles were then embedded in transparent conductive oxide (TCO) films as aluminum-doped zinc oxide (AZO) or zirconium-doped indium oxide (IZrO); the TCO/Cu nanoparticle/TCO structures were synthesized with all combinations of AZO and IZrO as the top and bottom layers. The goal was to achieve a plasmonic and conductive structure for photovoltaic applications via a comparison of the involved methods and all fabricated structures. In particular, solid-state dewetting produced faceted or spherical (depending on the annealing temperature) nanoparticles with an average size below 150 nm while laser ablation produced spherical nanoparticles below 250 nm. Dry and wet plasmonic conductive structures as a function of the TCOs employed and the temperature of annealing could reach a sheet resistance of 86 Ω/sq. The energy band-gap E, absorbance, transmittance, and reflectance of the plasmonic conductive structures were investigated in the UV-vis-NIR range. They showed a dependence on the sequence of the top and bottom TCO, with best transmittances of 89.4% for the dry plasmonic conductive structure and 84.7% for the wet plasmonic conductive structure. The latter showed a higher diffused transmittance of between 10-20% in the visible range.
Topics: Acetone; Aluminum; Methanol; Nanoparticles; Organic Chemicals; Oxides; Zinc; Zinc Oxide; Zirconium
PubMed: 36233188
DOI: 10.3390/ijms231911886 -
Organic Letters May 2020For decades, oxidative dearomatization has been employed as a key step in the synthesis of complex molecules. Challenges in controlling the chemo- and site-selectivity...
For decades, oxidative dearomatization has been employed as a key step in the synthesis of complex molecules. Challenges in controlling the chemo- and site-selectivity of this transformation have sparked the development of a variety of specialized oxidants; however, these result in stoichiometric amounts of organic byproducts. Herein, we describe a photocatalytic method for oxidative dearomatization using molecular oxygen as the stoichiometric oxidant. This provides environmentally benign entry to highly substituted -quinols, reactive intermediates which can be elaborated to a number of natural product families.
Topics: Benzaldehydes; Catalysis; Hydroquinones; Oxidants, Photochemical; Oxidation-Reduction; Photochemical Processes
PubMed: 32293185
DOI: 10.1021/acs.orglett.0c01207 -
Molecules (Basel, Switzerland) Sep 2020The demand for water is predicted to increase significantly over the coming decades; thus, there is a need to develop an inclusive wastewater decontaminator for the... (Review)
Review
The demand for water is predicted to increase significantly over the coming decades; thus, there is a need to develop an inclusive wastewater decontaminator for the effective management and conservation of water. Magnetic oxide nanocomposites have great potentials as global and novel remediators for wastewater treatment, with robust environmental and economic gains. Environment-responsive nanocomposites would offer wide flexibility to harvest and utilize massive untapped natural energy sources to drive a green economy in tandem with the United Nations Sustainable Development Goals. Recent attempts to engineer smart magnetic oxide nanocomposites for wastewater treatment has been reported by several researchers. However, the magnetic properties of superparamagnetic nanocomposite materials and their adsorption properties nexus as fundamental to the design of recyclable nanomaterials are desirable for industrial application. The potentials of facile magnetic recovery, ease of functionalization, reusability, solar responsiveness, biocompatibility and ergonomic design promote the application of magnetic oxide nanocomposites in wastewater treatment. The review makes a holistic attempt to explore magnetic oxide nanocomposites for wastewater treatment; futuristic smart magnetic oxides as an elixir to global water scarcity is expounded. Desirable adsorption parameters and properties of magnetic oxides nanocomposites are explored while considering their fate in biological and environmental media.
Topics: Graphite; Industry; Magnetics; Metal Nanoparticles; Nanocomposites; Nanotechnology; Organic Chemicals; Oxides; Wastewater; Water Pollutants, Chemical; Water Purification
PubMed: 32916776
DOI: 10.3390/molecules25184110 -
International Journal of Molecular... Jul 2021Metal oxide nanoparticles (MONPs) are inorganic materials that have become a valuable tool for many industrial sectors, especially in healthcare, due to their... (Review)
Review
Metal oxide nanoparticles (MONPs) are inorganic materials that have become a valuable tool for many industrial sectors, especially in healthcare, due to their versatility, unique intrinsic properties, and relatively inexpensive production cost. As a consequence of their wide applications, human exposure to MONPs has increased dramatically. More recently, their use has become somehow controversial. On one hand, MONPs can interact with cellular macromolecules, which makes them useful platforms for diagnostic and therapeutic interventions. On the other hand, research suggests that these MONPs can cross the blood-testis barrier and accumulate in the testis. Although it has been demonstrated that some MONPs have protective effects on male germ cells, contradictory reports suggest that these nanoparticles compromise male fertility by interfering with spermatogenesis. In fact, in vitro and in vivo studies indicate that exposure to MONPs could induce the overproduction of reactive oxygen species, resulting in oxidative stress, which is the main suggested molecular mechanism that leads to germ cells' toxicity. The latter results in subsequent damage to proteins, cell membranes, and DNA, which ultimately may lead to the impairment of the male reproductive system. The present manuscript overviews the therapeutic potential of MONPs and their biomedical applications, followed by a critical view of their potential risks in mammalian male fertility, as suggested by recent scientific literature.
Topics: Animals; Genitalia, Male; Humans; Male; Metal Nanoparticles; Organic Chemicals; Oxidative Stress; Oxides; Reactive Oxygen Species; Spermatogenesis
PubMed: 34360825
DOI: 10.3390/ijms22158061 -
Nature Communications Nov 2022Biogenic volatile organic compounds (BVOCs) affect climate via changes to aerosols, aerosol-cloud interactions (ACI), ozone and methane. BVOCs exhibit dependence on...
Biogenic volatile organic compounds (BVOCs) affect climate via changes to aerosols, aerosol-cloud interactions (ACI), ozone and methane. BVOCs exhibit dependence on climate (causing a feedback) and land use but there remains uncertainty in their net climatic impact. One factor is the description of BVOC chemistry. Here, using the earth-system model UKESM1, we quantify chemistry's influence by comparing the response to doubling BVOC emissions in the pre-industrial with standard and state-of-science chemistry. The net forcing (feedback) is positive: ozone and methane increases and ACI changes outweigh enhanced aerosol scattering. Contrary to prior studies, the ACI response is driven by cloud droplet number concentration (CDNC) reductions from suppression of gas-phase SO oxidation. With state-of-science chemistry the feedback is 43% smaller as lower oxidant depletion yields smaller methane increases and CDNC decreases. This illustrates chemistry's significant influence on BVOC's climatic impact and the more complex pathways by which BVOCs influence climate than currently recognised.
Topics: Ozone; Earth, Planet; Industry; Methane; Oxidants; Volatile Organic Compounds
PubMed: 36418337
DOI: 10.1038/s41467-022-34944-9 -
Environmental Science & Technology Feb 2024Ozonolysis of alkenes is known to produce reactive intermediates─stabilized Criegee intermediates (SCIs), and their subsequent bimolecular reactions with various...
Ozonolysis of alkenes is known to produce reactive intermediates─stabilized Criegee intermediates (SCIs), and their subsequent bimolecular reactions with various carboxylic acids can form α-acyloxyalkyl hydroperoxides (AAHPs), which is considered a major class of organic peroxides in secondary organic aerosol (SOA). Despite their atmospheric and health importance, the molecular-level identification of organic peroxides in atmospheric aerosols is highly challenging, preventing further assessment of their environmental fate. Here, we synthesize 20 atmospherically relevant AAHPs through liquid-phase ozonolysis, in which two types of monoterpene-derived SCIs from either α-pinene or 3-carene are scavenged by 10 different carboxylic acids to form AAHPs with diverse structures. These AAHPs are identified individually by liquid chromatography coupled with high-resolution mass spectrometry. AAHPs were previously thought to decompose quickly in an aqueous environment such as cloud droplets, but we demonstrate here that AAHPs hydrolysis rates are highly compound-dependent with rate constants differing by 2 orders of magnitude. In contrast, the aqueous-phase formation rate constants between SCI and various carboxylic acids vary only within a factor of 2-3. Finally, we identified two of the 20 synthesized AAHPs in α-pinene SOA and two in 3-carene SOA, contributing ∼0.3% to the total SOA mass. Our results improve the current molecular-level understanding of organic peroxides and are useful for a more accurate assessment of their environmental fate and health impact.
Topics: Monoterpenes; Peroxides; Air Pollutants; Hydrogen Peroxide; Carboxylic Acids; Ozone; Aerosols; Bicyclic Monoterpenes
PubMed: 38324703
DOI: 10.1021/acs.est.3c07048 -
International Journal of Molecular... Dec 2023Dinitrosyl iron complexes (DNICs) are important physiological derivatives of nitric oxide. These complexes have a wide range of biological activities, with antioxidant...
Dinitrosyl iron complexes (DNICs) are important physiological derivatives of nitric oxide. These complexes have a wide range of biological activities, with antioxidant and antiradical ones being of particular interest and importance. We studied the interaction between DNICs associated with the dipeptide L-carnosine or serum albumin and prooxidants under conditions mimicking oxidative stress. The ligands of these DNICs were histidine residues of carnosine or His39 and Cys34 in bovine serum albumin. Carnosine-bound DNICs reduced the level of piperazine free radicals in the reaction system containing -butyl hydroperoxide (-BOOH), bivalent iron ions, a nitroxyl anion donor (Angeli's salt), and HEPES buffer. The ability of carnosine DNICs to intercept organic free radicals produced from -BOOH decay could lead to this effect. In addition, carnosine DNICs reacted with the superoxide anion radical (O) formed in the xanthine/xanthine oxidase enzymatic system. They also reduced the oxoferryl form of the heme group formed in the reaction of myoglobin with -BOOH. DNICs associated with serum albumin were found to be rapidly destroyed in a model system containing metmyoglobin and t-BOOH. At the same time, these protein DNICs inhibited the -BOOH-induced oxidative degradation of coenzymes Q and Q in rat myocardial homogenate. The possible mechanisms of the antioxidant and antiradical action of the DNICs studied and their role in the metabolism of reactive oxygen and nitrogen species are discussed.
Topics: Rats; Animals; Antioxidants; Histidine; Carnosine; Nitrogen Oxides; Iron; Nitric Oxide; Free Radicals; Superoxides; Oxygen; Serum Albumin
PubMed: 38139065
DOI: 10.3390/ijms242417236