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Abstract Background The field of enzymology has been profoundly transformed by the discovery of lytic polysaccharide monooxygenases (LPMOs). LPMOs hold a unique role in the natural breakdown of recalcitrant polymers like cellulose and chitin. They are characterized by a “histidine brace” in their active site, known to operate via an O2/H2O2 mechanism and require an electron source for catalytic activity. Although significant research has been conducted in the field, the relationship between these enzymes, their electron donors, and H2O2 production remains complex and multifaceted. Results This study examines TthLPMO9G activity, focusing on its interactions with various electron donors, H2O2, and cellulose substrate interactions. Moreover, the introduction of catalase effectively eliminates H2O2 interference, enabling an accurate evaluation of each donor’s efficacy based on electron delivery to the LPMO active site. The introduction of catalase enhances TthLPMO9G’s catalytic efficiency, leading to increased cellulose oxidation. The current study provides deeper insights into specific point mutations, illuminating the crucial role of the second coordination sphere histidine at position 140. Significantly, the H140A mutation not only impacted the enzyme’s ability to oxidize cellulose, but also altered its interaction with H2O2. This change was manifested in the observed decrease in both oxidase and peroxidase activities. Furthermore, the S28A substitution, selected for potential engagement within the His1–electron donor–cellulose interaction triad, displayed electron donor-dependent alterations in cellulose product patterns. Conclusion The interaction of an LPMO with H2O2, electron donors, and cellulose substrate, alongside the impact of catalase, offers deep insights into the intricate interactions occurring at the molecular level within the enzyme. Through rational alterations and substitutions that affect both the first and second coordination spheres of the active site, this study illuminates the enzyme’s function. These insights enhance our understanding of the enzyme’s mechanisms, providing valuable guidance for future research and potential applications in enzymology and biochemistry.

Sn–Ni alloy matrix coatings co-deposited with TiO2 nanoparticles (Evonik P25) were produced utilizing direct (DC) and pulse electrodeposition (PC) from a tin–nickel chloride-fluoride electrolyte with a loading of TiO2 nanoparticles equal to 20 g/L. The structural and morphological characteristics of the resultant composite coatings were correlated with the compositional modifications that occurred within the alloy matrix and expressed via a) TiO2 co-deposition rate and b) composition of the matrix; this was due to the application of different current types (DC or PC electrodeposition), and different current density values. The results demonstrated that under DC electrodeposition, the current density exhibited a more significant impact on the composition of the alloy matrix than on the incorporation rate of the TiO2 nanoparticles. Additionally, PC electrodeposition favored the incorporation rate of TiO2 nanoparticles only when applying a low peak current density (Jp = 1 Adm−2). All of the composite coatings exhibited the characteristic cauliflower-like structure, and were characterized as nano-crystalline. The composites’ surface roughness demonstrated a significant influence from the TiO2 incorporation rate. However, in terms of microhardness, higher co-deposition rates of embedded TiO2 nanoparticles within the alloy matrix were associated with decreased microhardness values. The best wear performance was achieved for the composite produced utilizing DC electrodeposition at J = 1 Adm−2, which also demonstrated the best photocatalytic behavior under UV irradiation. The corrosion study of the composite coatings revealed that they exhibit passivation, even at elevated anodic potentials.

Abstract Background Lytic polysaccharide monooxygenases (LPMOs) are copper-dependent enzymes that oxidatively cleave recalcitrant lignocellulose in the presence of oxygen or hydrogen peroxide as co-substrate and a reducing agent as electron donor. One of the possible systems that provide electrons to the LPMOs active site and promote the polysaccharide degradation involves the mediation of phenolic agents, such as lignin, low-molecular-weight lignin-derived compounds and other plant phenols. In the present work, the interaction of the bulk insoluble lignin fraction extracted from pretreated biomass with LPMOs and the ability to provide electrons to the active site of the enzymes is studied. Results The catalytic efficiency of three LPMOs, namely MtLPMO9 with C1/C4 regioselectivity, PcLPMO9D which is a C1 active LPMO and NcLPMO9C which is a C4 LPMO, was evaluated in the presence of different lignins. It was correlated with the physicochemical and structural properties of lignins, such as the molecular weight and the composition of aromatic and aliphatic hydroxyl groups. Moreover, the redox potential of lignins was determined with the use of large amplitude Fourier Transform alternating current cyclic voltammetry method and compared to the formal potential of the Cu (II) center in the active site of the LPMOs, providing more information about the lignin-LPMO interaction. The results demonstrated the existence of low-molecular weight lignin-derived compounds that are diffused in the reaction medium, which are able to reduce the enzyme active site and subsequently utilize additional electrons from the insoluble lignin fraction to promote the LPMO oxidative activity. Regarding the bulk lignin fractions, those isolated from the organosolv pretreated materials served as the best candidates in supplying electrons to the soluble compounds and, finally, to the enzymes. This difference, based on biomass pretreatment, was also demonstrated by the activity of LPMOs on natural substrates in the presence and absence of ascorbic acid as additional reducing agent. Conclusions Lignins can support the action of LPMOs and serve indirectly as electron donors through low-molecular-weight soluble compounds. This ability depends on their physicochemical and structural properties and is related to the biomass source and pretreatment method.

Lytic polysaccharide monooxygenases (LPMOs) consist of a class of enzymes that boost the release of oxidised products from plant biomass, in an approach that is more eco-friendly than the traditional ones, employing harsh chemicals. Since LPMOs are redox enzymes, they could possibly be exploited by immobilisation on electrode surfaces. Such an approach requires knowledge of kinetic and thermodynamic information for the interaction of the enzyme with the electrode surface. In this work, a novel methodology is applied for the determination of such parameters for an LPMO from the filamentous fungus Thermothelomyces thermophila, MtLPMO9H.

The use of organic solvents in an electrolytic system for neodymium electrorecovery by electrolysis at low temperatures is studied in the current work. More specifically, an alternative route, that of the system of DMSO (Dimethyl sulfoxide) with dissolved NdCl3 has been researched and has given promising results. The study of this electrolytic system has been divided into two stages. Firstly, the characteristics of the electrolyte, the dissolution of NdCl3 in DMSO, the conductivity and the viscosity of NdCl3 solutions in DMSO at various temperatures, and the Nd complexation in the solution were studied and secondly, the electrolysis parameters and their impact on the Nd electrodeposition process were evaluated. Finally, the deposits were submitted to SEM-EDS (Scanning Electron Microscopy-Energy Dispersive X-Ray Spectroscopy) analysis and metallic Nd was confirmed to be electrodeposited by X-ray Photoelectron Spectroscopy (XPS) spectroscopy.

The scope of the current research was to assess the feasibility of encapsulating three commercial antifouling compounds, Irgarol 1051, Econea and Zinc pyrithione, in biodegradable poly(lactic acid) (PLA) nanoparticles. The emulsification–solvent evaporation technique was herein utilized to manufacture nanoparticles with a biocide:polymer ratio of 40%. The loaded nanoparticles were analyzed for their size and size distribution, zeta potential, encapsulation efficiency and thermal properties, while the relevant physicochemical characteristics were correlated to biocide–polymer system. In addition, the encapsulation process was scaled up and the prepared nanoparticles were dispersed in a water-based antifouling paint in order to examine the viability of incorporating nanoparticles in such coatings. Metallic specimens were coated with the nanoparticles-containing paint and examined regarding surface morphology.