Oxidation Sites Research Articles

Layer symmetry and irradiation dominate the oxidation capability of birnessite on biogenic isoprene

The climate-active gas isoprene (C5H8) is one of the most abundant biogenic volatile organic compounds (VOCs). Soil is one of the significant sinks for isoprene, yet the role played by the naturally abundant birnessite in the soil surface layer during the oxidation of isoprene remains largely unknown. This study investigates the reactions of isoprene with triclinic and hexagonal birnessite on the Earth's surface environments. Hexagonal birnessite exhibits a superior oxidation capacity than triclinic birnessite, rapidly oxidizing isoprene. The transformation of birnessite from triclinic to hexagonal increases the number of interlayer Mn(III) octahedra, which creates numerous sites for isoprene oxidation. In-situ DRIFTS and DFT calculations indicate that abundant electrophilic active species on the surface of hexagonal birnessite, such as interlayer Mn(III) octahedra and 1O2, oxidize isoprene by attacking conjugated double bonds. Furthermore, birnessite exhibits excellent photoelectric response and photothermal effects, enabling sunlight irradiation under natural conditions to accelerate the oxidation of isoprene by birnessite. The findings of this study elucidates the critical role of birnessite in the oxidation of isoprene and shed light on the fate of isoprene in soil minerals.

Co-N-C catalyst with single atom active sites for base-free aerobic oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid under mild conditions

The production of 2,5-furandicarboxylic acid (FDCA), a promising biodegradable alternative to fossil-based terephthalic acid (PTA), from biomass-derived 5-hydroxymethylfurfural (HMF) is of significant importance. A major challenge is to develop an effective non-precious metal catalyst system that does not require a homogeneous base. In this study, we present a noble-metal-free Co-N-C catalyst, derived from the pyrolysis of cobalt-phenanthroline complexes on a carbon support. This catalyst demonstrates exceptional performance, achieving a FDCA yield of 99.9 % and maintaining reusability for up to five catalytic cycles in the base-free oxidation of HMF to FDCA under mild conditions. Through controlled experiments and comprehensive characterizations, we propose that the active sites in the Co-N-C catalyst are Co single atoms bonded to nitrogen within graphitic sheets. This approach provides valuable insights into the exact nature of the active sites in such noble-metal-free M-N-C catalysts designed for biomass conversion

Designing Artificial Laccase Catalysts by Introducing Substrate Oxidation Metals into Oxygen-Reducing Metal-Organic Frameworks: Cu-Doped ZIF-67.

Laccase, a multi-copper oxidase, is limited by its optimal temperature range and isolation costs. To overcome these challenges, we synthesized copper-doped zeolitic imidazolate framework-67 (Cu-doped ZIF-67) with 16 mol % Cu as an artificial laccase catalyst. The introduced Cu site acts as the phenol oxidation site, and Co-based ZIF-67 is the four-electron oxygen reduction site. Laccase also employs this division of oxidation and reduction sites. Cu-doped ZIF-67 demonstrated significant catalytic activity, superior to natural laccase, especially at elevated temperatures, and maintained stability across multiple reaction cycles. These findings suggest that Cu-doped ZIF-67 is a robust, reusable alternative for industrial applications requiring high thermal stability and efficient catalysis.

Engineering Topological and Chemical Disorder in Pd Sites for Record-Breaking Formic Acid Electrocatalytic Oxidation.

Designing palladium-based formic acid oxidation reaction (FAOR) catalysts to achieve significant breakthroughs in catalytic activity, pathway selectivity, and toxicity resistance is both urgent and challenging. Here, these challenges are addressed by pioneering a novel catalyst design that incorporates both topological and chemical disorder, developing a new class of PdCuLaYMnW high-entropy amorphous alloys with a porous network (Net-Pd-HEAA) as a highly active, selective, and stable FAOR electrocatalyst. This novel Net-Pd-HEAA demonstrates record-breaking FAOR performance, achieving the mass and specific activities of 5.94 A mgPd -1 and 8.94mA cm-2, respectively, surpassing all previously reported Pd-based catalysts and showing strong competitiveness against advanced Pt-based catalysts. Simulataneously, Net-Pd-HEAA exhibits extraordinary stability in accelerated durability tests (ADT) and chronoamperometry (CA) tests. Advanced characterization and in situ, spectral analysis reveal that the extremely disordered atomic structure effectively regulates the geometric and electronic structure of the Pd sites, enhancing active intermediate coverage, facilitating dehydrogenation pathway, and inhibiting the production/adsorption of CO. Furthermore, when employed as the anode catalyst in proton exchange membrane water electrolysis (PEMWE), Net-Pd-HEAA only requires a potential of 1.28V to obtain a current density of 1 A cm-2, and operates stably in a highly corrosive electrolyte for over 100 h.

Metal Single Atom-Hydroxyl Incorporation in Poly(heptazine imide) to Create Active Sites for Photocatalytic Water Oxidation.

Poly(heptazine imide) (PHI) salts are extensively researched crystalline carbon nitride photocatalysts, but their photocatalytic water oxidation (PWO) performance is scarcely researched because of the difficulty in creating efficient active sites. Interference of metal ion (e.g., Na+ and K+) loss from the PHI salts in their PWO research has hardly been considered. Herein, metal single atom─OH (e.g., Co─OH) groups are incorporated into PHI to create efficient PWO active sites, via simple ion metathesis, hydrolysis, and deprotonation. The Co─OH modified PHI exhibits 9.3-fold higher PWO (oxygen evolution) activity than PHI, with an external quantum yield reaching 0.44% even at 600 nm. Excluding interference of the metal ion loss, the function of the Co─OH incorporation is evidenced mainly to facilitate the oxygen evolution reaction, as well as to promote photogenerated charge separation and raise visible light absorption, with the role of the OH especially revealed. Moreover, it is discovered that Na+ loss from sodium PHI will decrease its PWO activity, protonation of PHI has a detrimental effect on its PWO performance, and some other metal single atom─OH incorporation in PHI can also enhance its PWO activity. Overall, this work provides a general way to create PWO active sites in PHI.

Enhancing carbamazepine degradation in electrochemical systems: The interplay of sulfur vacancies and absorbed peroxydisulfate in molybdenite electrodes

Achieving high reaction efficiency with low energy input is crucial for electrochemical water remediation processes, yet remains a significant challenge. This study reported a practicable method, utilizing natural molybdenite as particle electrodes in an electro-activated peroxydisulfate (PDS) process (3D system) to develop a cost-efficient electrocatalytic oxidation system. Molybdenite’s unique ability to generate sulfur vacancies during electrocatalysis significantly enhances system efficiency. The 3D system enhanced the rate constant of carbamazepine (CBZ) abatement sixfold compared to the system without molybdenite. Additionally, a substantial decrease in electrical energy per order (EE/O) from 7.13 kWh/m3 to 0.326 kWh/m3 indicates a near 22-fold increase in energy efficiency. Characterizations involving electron microscopies, electrochemical experiments and density functional theory calculations confirm that hydroxyl radicals (•OH) and adsorbed PDS(PDS*) are the main active species. Molybdenite’s surface with plenty of edge-S, released S vacancy during electrocatalytic oxidation, providing adsorption and activation sites for PDS and H2O. This led to more active sites and facilitating the generation of PDS*, lowering the energy barrier for •OH formation and boosting the oxidation performance of the 3D system. The results underscore the constructed 3D system is a robust and energy-efficient method for practical water treatment.

Exploring Pt-Cu synergistic effects on porous SiO2 support with different Pt loadings for low-temperature oxidation of CO and C3H6

To address the high cost of noble metals, this study aims to optimize Pt loading and the synergistic effect of Cu on porous SiO2 support for low-temperature oxidation of CO and C3H6. A simulated test bench system was used to evaluate the performance of PtxCu1/SiO2 (where x= 0.3, 0.5, 0.7, and 1 wt%), Cu1/SiO2 and Ptx/SiO2 (where x= 0.5 and 1 wt%) catalysts with varying Pt loadings. Comprehensive characterization, including BET, XRD, SEM, TEM, and XPS was conducted to assess particle size, structure, and surface morphology. The effects of Pt incorporation on reduction and oxidation properties were further examined using H2-TPR and CO-TPD techniques. Results demonstrated a significant enhancement in catalytic activity with the addition of Cu confirming a synergistic interaction between Pt and Cu. This synergy was particularly pronounced in lower Pt loadings, where PtxCu1/SiO2 composites outperformed Ptx/SiO2 in catalytic activity. Pt addition reduced the particle size, which resulted in the creation of PtCu alloy, with 1 and 0.7 % wt Pt loading exhibiting comparable effects in CO conversion and 0.7 % Pt loading exhibiting better activity at higher temperatures in C3H6 oxidation indicating that catalytic activity was maintained even with a reduced Pt loading. Additionally, minimal difference in activity for C3H6 oxidation was observed among PtxCu1/SiO2 catalysts with 0.7, 0.5, and 0.3 wt% Pt loadings as indicated by T50 and T80 values. Reducing Pt loading from 0.7 wt% had minimal impact on catalytic efficiency for C3H6 oxidation with catalysts maintaining high activity. 0.7 wt% Pt loadings provide sufficient active sites for effective CO and HC oxidation. The enhanced catalytic activity and stability of bimetallic catalysts over monometallic Cu/SiO2 and Pt/SiO2 result from the simultaneous presence of active sites created by the synergetic effect of PtCu alloy formation with optimal ratio and well-optimized surface. These findings demonstrate the potential to optimize Pt usage without compromising catalytic performance, offering a cost-effective approach to catalyst design.

Synergistic effect of Co-MOF/epoxy modified tannic acid/ammonium polyphosphate on flame retardancy, anti-melt dripping and mechanical properties of polylactic acid

Achieving flame retardancy and anti-dripping properties in polylactic acid (PLA) while preserving its mechanical integrity remains a significant challenge. In this study, a novel organic ligand rich in phosphorus (P) and nitrogen (N) was synthesized and coordinated with Co2+ions to form a cobalt-based metal–organic framework (Co-MOF) with a multilayer mesoporous structure, acting as an effective carbonization agent. This Co-MOF was then compounded with epoxy-modified tannic acid (eTA) and ammonium polyphosphate (APP) to create a synergistic flame-retardant system for PLA (PLA/MAT). The Co-MOF provides numerous active sites for catalytic oxidation, promoting the formation of a uniform, hill-like expanded carbon layer. During pyrolysis, the Co-MOF and APP yield cobalt oxides and polyphosphates, which catalyze the dehydration of PLA and eTA, facilitating carbonization and forming a continuous, dense protective layer. Consequently, the PLA/MAT system exhibits both robust mechanical properties and excellent flame retardancy, as demonstrated by a limiting oxygen index (LOI) of 27.0 % and a UL-94 V-0 rating, with no melt dripping observed during combustion tests. This work offers a novel approach for enhancing the flame retardancy and anti-dripping performance of PLA, with potential applications in engineering, electronics, and the automotive industry.

Morphological characteristics of low-asphalt RAP and influence of its reaction product during combustion heating on regenerated asphalt

To provide reference for regeneration of the finely separated low-asphalt reclaimed asphalt pavement (RAP), the macroscopic and microscopic laboratory testing and quantum chemical simulation were combined. The morphological characteristics of the basalt and limestone low-asphalt RAP were analyzed. The low-asphalt RAP needs to be dried before regeneration, so the reaction mechanism and product of the asphalt film on its surface during drying were clarified. The product influence on the temperature resistance and fatigue performance of the virgin asphalt was studied, so as to consider their mixing during the subsequent regeneration process. Result shows that the gradation of limestone low-asphalt RAP is coarser and particles are slenderer than basalt with the same particle size grade. The 5–10 mm low-asphalt RAP particles are slenderer than those in the 10–20 mm grade. In the drying cylinder, asphalt basically generate no new functional groups below 200℃, while the asphalt film on the low-asphalt RAP surface undergoes pyrolysis to produce carbon black with the particle size around 100μm in the combustion heating area. The most easily oxidation or pyrolysis site in asphalt molecule is the carbon atom connected to the benzene ring. The pyrolysis of asphalt molecules to generate free radicals in the local oxygen deficient environment is the prerequisite for the carbon black formation, and pyrolysis requires higher temperature than oxidation because of its higher energy barrier. As the carbon black content increases, the penetration and ductility of asphalt decrease, the softening point increases, the high-temperature performance is enhanced, the low-temperature performance is weakened, and the fatigue performance is not significantly affected. As the particle size of carbon black increases, the decrease range in penetration, ductility and low-temperature performance of asphalt declines, the increase or improvement range of softening point and high-temperature performance enhanced, while the fatigue performance still shows no significant and regular change.

Mutations of methionine 444 interacting with T1Cu-coordinating amino acids affect the structure and function of multicopper oxidase CopA.

Manganese is an essential trace element for humans, animals, and plants, but excessive amounts of manganese can cause serious harm to organisms. The biological manganese oxidation process mainly oxidizes Mn(II) through the secretion of unique manganese oxidase by manganese-oxidizing bacteria. The T1 Cu site of multicopper oxidase is the main site for substrate oxidation, and its role is to transfer electrons to TNC, where dioxygen reduction occurs. In this study, methionine (Met) No. 444 interacting with the T1Cu-coordinating amino acid in the multicopper oxidase CopA from Brevibacillus panacihumi MK-8 was mutated to phenylalanine (Phe) and leucine (Leu) by the enzyme. Based on the analysis of enzymatic properties and the structural model, the mutant protein M444F with 4.58 times the catalytic efficiency of the original protein CopA and the mutant protein M444L with 1.67 times the catalytic efficiency of the original protein CopA were obtained. The study showed that the manganese removal rate of the manganese-oxidizing engineered bacterium Rosetta-pET-copAM444L cultured for 7 days was 88.87%, which was 10.77% higher than that of the original engineered bacterium. Overall, this study provides a possibility for the application of genetic engineering in the field of biological manganese removal.

Assessment of Quality of Life of Caregivers of Patient with Alcoholic Liberty Disease

Alcoholic liver disease (ALD) is a progressive condition resulting from chronic and excessive alcohol consumption, leading to liver cell damage. Although the liver is the primary site for alcohol oxidation, a small amount is also metabolized in the stomach. Ethanol metabolism primarily produces acetaldehyde, a toxic byproduct responsible for symptoms such as facial flushing, headaches, nausea, and increased heart rate, all of which contribute to the development of ALD. The risk of developing ALD varies among individuals, but it generally increases with alcohol intake beyond certain thresholds: more than two standard drinks per day for men and more than one standard drink per day for women. Alcoholic liver disease (ALD) can progress to fibrosis and cirrhosis, potentially leading to liver infection. The prevalence of ALD fluctuates over time and varies by region due to factors such as alcohol consumption patterns, healthcare accessibility, and public health initiatives. ALD poses a significant global health challenge, highlighting the need for increased awareness about the dangers of excessive alcohol consumption and the promotion of responsible drinking practices. Medical guidance and support are essential in educating individuals about the risks of overconsumption. According to the latest surveillance report from the National Institute on Alcohol Abuse and Alcoholism, liver cirrhosis ranked as the 12th leading cause of death in the United States in 2007, with 29,925 deaths, nearly 48% of which were alcohol-related.

Advances in Exploring Mechanisms of Oxidative Phenolic Coupling Reactions

AbstractBiphenolic compounds serve as important scaffolds for the development of biologically active molecules. Among the methods for the synthesis of biarenols, oxidative coupling, which directly forms a C−C bond, has been extensively explored in various metal‐catalyzed (V, Cr, Co, Fe, Cu, etc.) reactions, electrochemical reactions, and photochemical reactions over the decades. While the exact mechanisms remain elusive in many cases, numerous mechanistic studies have provided valuable insights. This review focuses on the mechanistic details of the oxidative coupling of phenols or naphthols, involving at least one radical intermediate. Additionally, the factors governing chemoselectivity (homo‐ and cross‐coupling), regioselectivity (ortho‐, meta‐ and para−), and enantioselectivity (R and S configuration) are discussed, with a particular emphasis on intermediates and transition states, encompassing various oxidation sites for phenols and potential coupling sites.

Modulating the chemical environment of Ni2+ for the oxidative dehydrogenation of ethane: The formation of LAS(Al3+/Ga3+)-Ni-OH site

The oxidative dehydrogenation of ethane to ethylene (ODHE) usually suffers from the issues of ethane conversion-ethylene selectivity seesaw. Herein, a series of alumina-supported Ni and Ga catalysts with different molar ratios of Ni to Ga were synthesized by facile impregnation method constructing the Lewis acid site (LAS) strategy to obtain great ethylene selectivity (97 %). The variation of Ni:Ga ratio adjusted the ionic substitution ability, redox ability and acidity, thus regulate the chemical environment of Ni2+ to the formation of LAS(Al3+/Ga3+)-Ni-OH structure, which was proposed to be the active site for selective oxidation of ethane to ethylene, as proved by H2-TPR, ToF-SIMS, quasi in-situ XPS and in-situ FTIR. Moreover, the probable mechanism of ODHE reaction was proposed that C2H6 molecules were mainly adsorbed on LAS sites and activated on Ni-OH site of the catalyst. The pulse test further suggested that O- was mainly associated with the generation of CO2 and Ni(2-n)+ was connected with the production of CH4. It is highlighted that adjusting the Ni-related species and oxygen species on the catalyst surface are crucial to further improve the ethylene selectivity.

Strain-Controlled Galvanic Synthesis of Platinum Icosahedral Nanoframes and Their Enhanced Catalytic Activity toward Oxygen Reduction.

The unique strain distribution on the surface of a Pd icosahedral nanocrystal is leveraged to control the sites for oxidation and reduction involved in the galvanic replacement reaction. Specifically, Pd is oxidized and dissolved from the center of each {111} facet due to its tensile strain, while the Pt(II) precursor adsorbs onto the vertices and edges featuring a compressive strain, followed by surface reduction and conformal deposition of the Pt atoms. Once the galvanic reaction is initiated, the {111} facets become more vulnerable to oxidation and dissolution, as the vertices and edges are protected by the deposited Pt atoms. The site-selected galvanic reaction naturally results in the formation of Pt icosahedral nanoframes covered by compressively strained {111} facets, which show enhanced catalytic activity and durability toward oxygen reduction relative to commercial Pt/C.

Designing flexible TiO2/SrTiO3/BiOBr recyclable fiber membrane with spatial dual oxidation sites for photocatalytic uranium extraction under visible light

The utilization of nuclear energy generates a substantial volume of wastewater containing uranium, posing a significant threat to both aquatic ecosystems and human health. The current photocatalytic materials utilized for uranium extraction commonly exhibit insufficient redox capabilities, inefficient separation of photogenerated carriers, and challenging recovery. Therefore, recyclable TiO2/SrTiO3/BiOBr (TSB) dual Z-scheme heterojunction fiber membrane materials with dual oxidation sites were successfully synthesized, with advantages of rapid carrier separation and transfer and a broad photo-response range of the dual Z-scheme heterojunctions. Due to the presence of dual oxidation sites, TSB exhibited an exceptional uranium extraction performance, achieving a remarkable 98.9 % extraction rate without the need for sacrificial agents, which was 2.48, 1.79, and 3.34 times of those of ordinary TiO2, SrTiO3, and BiOBr, respectively. The extraction rate of uranium from TSB was 85 % after five cycles. Optical and photoelectric tests revealed that TSB reduced the bandgap width by 0.25 eV compared to that of TiO2, enhanced the fluorescence lifetime by 1.3 ns, lowered the electrical resistance, and higher optical current density, confirming the effective charge transport at the catalyst interfaces. The charge transfer routes in the TSB dual Z-scheme were confirmed by X-ray photoelectron spectroscopy and density functional theory. The potent oxidizing ·OH generated by TSB played a crucial role in facilitating the conversion of U(VI) into insoluble (UO2)O2·2H2O. In conclusion, this work provides a novel strategy for the design of dual Z-scheme heterojunctions and offers a new method for practical and recoverable uranium extraction.

Cyanide Linkage Isomerization Induced by Cobalt Oxidation-State Changes at a Co-Fe Prussian-Blue Analogue/ZnO Interface.

Understanding the interfacial composition in heterostructures is crucial for tailoring heterogenous electrochemical and photoelectrochemical processes. This work aims to elucidate the structure of a series of Co-Fe Prussian blue analogue modified ZnO (PBA/ZnO) electrodes with interface-sensitive vibrational sum frequency generation (VSFG) spectroscopy. Our measurements revealed, for the first time, a cyanide linkage isomerism at the PBA/ZnO interface, when the composite is fabricated at elevated temperatures. In situ VSFG spectro-electrochemistry measurements correlate the CoII→CoIII oxidation with the flip of the bridging CN ligand from Co-NC-Fe coordination mode to a Co-CN-Fe one. Photoluminescence measurements and X-ray photoelectron spectroscopy reveal that this unprecedented linkage isomerism originates from surface defects, which act as oxidation sites for the PBA. The presence of such surface defects is correlated with the fabrication temperature for PBA/ZnO. Thus, this contribution identifies the interplay between the surface states of the ZnO substrates and the chemical composition of PBA at the ZnO surface, suggesting an easily accessible approach to control the chemical composition of the interface.

Triggering Asymmetric Layer Displacement Polarization and Redox Dual-Sites Activation by Inside-Out Anion Substitution for Efficient CO2 Photoreduction.

Sluggish bulk charge transfer and barren catalytic sites severely hinder the CO2 photoreduction process. Seeking strategies for accelerating charge dynamics and activating reduction and oxidation sites synchronously presents a huge challenge. Herein, an inside-out chlorine (Cl) ions substitution strategy on the layered polar Bi4O5Br2 is proposed for achieving layer structure-dependent polarization effect and redox dual-sites activation. Cl ions in the bulk phase shrink the halogen layer interspace by 8‰, triggering asymmetric [Bi4O5]2+ layer displacement polarization, prolonging the average photocharge lifetime to 201.8ps. Meanwhile, surface substituted Cl ions enhance the electron-donating capability of neighboring Bi atoms, activating the intrinsic Bi reduction sites, and increasing H2O molecule adsorption on nearby intrinsic O oxidation site (cal. by 0.105eV), also self-donating as an alien oxidation site. Besides, Cl upshifts the p-band center closer to the Fermi level, facilitating the reactant adsorption. Therefore, the energy barrier for CO2 activation and rate-limiting *COOH intermediate formation steps are significantly decreased. Without cocatalysts and sacrificial reagents, inside-out Cl-substituted Bi4O5Br2 delivers a remarkable CO2-to-CO photoreduction rate of 50.18µmol g-1 h-1, being one of the state-of-the-art catalysts. This finding offers insights into exploiting polarization at the molecular-level and enhances understanding of catalytic site activation.

Revealing OH species in situ generated on low-valence Cu sites for selective carbonyl oxidation

Catalytic oxidation through the transfer of lattice oxygen from metal oxides to reactants, namely the Mars-van Krevelen mechanism, has been widely reported. In this study, we evidence the overlooked oxidation route that features the in situ formation of surface OH species on Cu catalysts and its selective addition to the reactant carbonyl group. We observed that glucose oxidation to gluconic acid in air (21% O2) was favored on low-valence Cu sites according to X-ray spectroscopic analyses. Molecular O2 was activated in situ on Cu0/Cu+ forming localized, adsorbed hydroxyl radicals (*OH) which played the primary reactive oxygen species as confirmed by the kinetic isotope effect (KIE) study in D2O and in situ Raman experiments. Combined with DFT calculations, we proposed a mechanism of O2-to-*OH activation through the *OOH intermediate. The localized *OH exhibited higher selectivity toward glucose oxidation at C1HO to form gluconic acid (up to 91% selectivity), in comparison with free radicals in bulk environment that emerged from thermal, noncatalytic hydrogen peroxide decomposition (40% selectivity). The KIE measurements revealed a lower glucose oxidation rate in D2O than in H2O, highlighting the role of water (H2O/D2O) or its derivatives (e.g., *OH/*OD) in the rate-determining step. After proving the C1-H activation step kinetically irrelevant, we proposed the oxidation mechanism that was characterized by the rate-limiting addition of *OH to C1=O in glucose. Our findings advocate that by maneuvering the coverage and activity of surface *OH, high-performance oxidation of carbonyl compounds beyond biomass molecules can be achieved in water and air using nonprecious metal catalysts.

Methionine-rich domains emerge as facilitators of copper recruitment in detoxification systems

Copper homeostasis mechanisms are critical for bacterial resistance to copper-induced stress. The Escherichia coli multicopper oxidase copper efflux oxidase (CueO) is part of the copper detoxification system in aerobic conditions. CueO contains a methionine-rich (Met-rich) domain believed to interact with copper, but its exact function and the importance of related copper-binding sites remain unclear. This study investigates these open questions by employing a multimodal and multiscale approach. Through the design of various E. coli CueO (EcCueO) variants with altered copper-coordinating residues and domain deletions, we employ biological, biochemical, and physico-chemical approaches to unravel in vitro CueO catalytic properties and in vivo copper resistance. Strong correlation between the different methods enables evaluation of EcCueO variants' activity as a function of Cu+ availability. Our findings demonstrate the Met-rich domain is not essential for cuprous oxidation, but it facilitates Cu+ recruitment from strongly chelated forms, acting as transient copper binding domain thanks to multiple methionines. They also indicate that the Cu6/7 copper-binding sites previously observed within the Met-rich domain play a negligible role. Meanwhile, Cu5, located at the interface with the Met-rich domain, emerges as the primary and sole substrate-binding active site for cuprous oxidation. The Cu5 coordination sphere strongly affects the enzyme activity and the in vivo copper resistance. This study provides insights into the nuanced role of CueO Met-rich domain, enabling the functions of copper-binding sites and the entire domain itself to be decoupled. This paves the way for a deeper understanding of Met-rich domains in the context of bacterial copper homeostasis.

Oxidation is a potentially significant methane sink in land-terminating glacial runoff

Globally, aquatic ecosystems are one of the largest but most uncertain sources of methane, a potent greenhouse gas. It is unclear how climate change will affect methane emissions, but recent work suggests that glacial systems, which are melting faster with climate change, may be an important source of methane to the atmosphere. Currently, studies quantifying glacial emissions are limited in number, and the role of methanotrophy, or microbial methane oxidizers, in reducing atmospheric emissions from source and receiving waters is not well known. Here we discuss three potential sites for methane oxidation that could mitigate emissions from glaciers into the atmosphere: under ice oxidation, oxidation within proglacial lakes, and oxidation within melt rivers. The research presented here increases the number of glacial sites with methane concentration data and is one of only a few studies to quantify the net microbial activity of methane production and oxidation in two types of land-terminating glacial runoff (lake and river). We find that oxidation in a glacial river may reduce atmospheric methane emissions from glacial melt by as much as 53%. Incorporating methane oxidation in estimates of glacial methane emissions may significantly reduce the estimated magnitude of this source in budgeting exercises.