Ring Hydroxylation Research Articles

Synthesis and Characterization of Cellulose Acetate—HBA/Poly Sulfone Blend for Water Treatment Applications

Cellulose acetate (CA) was chemically modified with p–hydrazinobenzoic acid (HBA) for the fabrication of a CA–HBA polymeric membrane. The CA–HBA was characterized using NMR, UV-Vis, and EDX/SEM techniques. CA–HBA exhibited high hydrophilicity, as it included carboxylic groups as well as the hydroxyl group of the CA glycosidic ring. The HBA moieties increased the hydrophilicity and the number of active sites inside the CA polymeric matrix, but they did not improve the thermal stability of the polymer, as shown by the thermogravimetry (TGA). Polysulfone (PSF) was blended with CA-HBA in various compositions to produce highly thermal and effective membranes for water treatment applications. The fabricated membranes (CA–HBA/PSF) (5:95) (10:90) (15:85) were found to exhibit high thermal stabilities. The CA–HBA/PSF 15:85 membrane exhibited the highest efficiency towards the removal of Cu (II) ions, while the 5:95 membrane exhibited the highest salt rejection (89%).

Hydrogen bonding in the crystal structure of molnupiravir Form I, C13H19N3O7

Molnupiravir Form I crystallizes in space group C2 (#5) with a = 6.48110(17), b = 8.71848(19), c = 27.0607(19) Å, β = 91.920(4)°, V = 1528.22(12) Å3, and Z = 4 at 295 K. The crystal structure consists of supramolecular double layers of molecules parallel to the ab-plane. The layer centers consist of hydrogen-bonded rings forming a 2D network and the outer surfaces of isopropyl groups, with van der Waals interactions between the layers. Each O atom acts as an acceptor in at least one hydrogen bond. A strong O–H⋯O hydrogen bond forms between the hydroxyl group of the oxolane ring and the carbonyl group of the oxopyrimidine ring. The other oxolane hydroxyl group forms bifurcated intra- and intermolecular hydrogen bonds. The hydroxylamino group forms an intramolecular O–H⋯N hydrogen bond with an N atom of the oxopyrimidine ring. The amino group forms an intermolecular N–H⋯N hydrogen bond to the same N atom of the ring. The powder pattern has been submitted to ICDD for inclusion in the Powder Diffraction File™ (PDF®).

N-Acyl Derivatives of 2-Amino-4,6-di-tERt-butylphenol — Potential Protectors Under Neutrophil-Induced Halogenating Stress

The effect of N-acyl derivatives of 2-amino-4,6-di-tert-butylphenolon the functions of neutrophils was studied. It has been established that these derivatives with a free hydroxyl group in the benzene ring, in contrast to O-methylated ones, modify the properties of cells, which is expressed in a decrease in hypochlorous acid generation during the “respiratory burst” formation. These compounds are scavengers of HOCl/OCl– generated by activated neutrophils and reduce the secretion of myeloperoxidase (MPO) from cells. N-(3,5-di-tert-butyl-2-hydroxyphenyl)acetamide has been shown to be the most effective hypochlorous acid scavenger. This substance significantly suppresses the secretory degranulation of neutrophils and has a cytoprotective effect under conditions of halogenating stress.

Co-metabolic Biotransformation of Bisphenol AF by a Bisphenol A-Growing Bacterial Enrichment Culture.

The fluorinated bisphenol A (2,2-bis[4-hydroxyphenyl]propane, BPA) substitute bisphenol AF (BPAF) could be more persistent and toxic than BPA, but little is known about its environmental fate. In this study, we established a co-metabolic BPAF-degrading bacterial enrichment culture with BPA as the growth substrate. BPAF degradation by the enrichment culture was dependent on BPA, and BPAF could be eliminated to below the detection limit with successive additions of BPA. BPAF was mainly degraded via phenolic ring hydroxylation and sequential ring cleavage, which are minor BPA transformation pathway. Conjugated BPAF products were also identified based on the characteristic CF3- fragment and were found to accumulate during BPAF degradation. Sphingopyxis was the key BPA and BPAF degrader in the aerobic enrichment cultures, which was the most abundant genera in only BPA-added and BPA and BPAF-added cultures and was proven to be able to degrade BPA and BPAF by isolation. The aerobic co-metabolic BPAF degrading community also contain non-BPA and BPAF degraders, such as Pandoraea, which may play a supporting role in the community.

Exploring protective mechanisms with triazine ring and hydroxyethyl groups: Experimental and theoretical insights

The current study investigates the protective mechanisms of a novel triazine-based compound, 2,2′,2''-((1,3,5-triazine-2,4,6-triyl)tris (azanediyl))triethanol (TATTE) (for carbon steel protection in 0.5 M sulfuric acid) were investigated. Potentiodynamic polarization and electrochemical impedance spectroscopy analyses unveiled that TATTE serves as a protective agent with a dual inhibitory mechanism, showcasing exceptional efficiency exceeding 96%. Scanning electron microscopy (SEM) observations demonstrated the formation of a protective layer by TATTE on the surface of carbon steel. Density functional theory (DFT) calculations offered valuable insights into the favorable adsorption of both the neutral and protonated forms of TATTE through interactions between their functional groups and the steel surface. Molecular dynamics simulations further substantiated this, revealing that the neutral molecule exhibits physical adsorption, while the protonated form engages in stronger chemical adsorption, as evidenced by binding energies and radial distribution functions. The superior protective mechanism performance observed in our experiments can be attributed to the synergistic adsorption of TATTE, facilitated by the presence of the triazine ring and multiple hydroxyl groups.

The presence of NSAIDs may affect the binding capacity of serum albumin to the natural products hymecromone and umbelliferone

The natural products 7-hydroxycoumarin (7HC) and 7-hydroxy-4-methylcoumarin (7H4MC), known as umbelliferone and hymecromone, respectively, are one of the simplest structural examples from coumarin's family, showing several biological activities. Bovine serum albumin (BSA) is the main model protein used in laboratory experiments to characterize the biophysical capacity of potential drugs to be carried until the target in the bloodstream. Thus, the interaction BSA:7HC and BSA:7H4MC was biophysically characterized by circular dichroism (CD), steady-state, and time-resolved fluorescence techniques combined with molecular docking calculations via cross-docking approach to better correlate with the biological medium. There is a ground-state association BSA:7HC/7H4MC, and the presence of the methyl group in the coumarin core did not change the binding affinity and trend to BSA significantly. However, comparing the obtained data with those reported to benzo-α-pyrone there is evidence that the incorporation of the hydroxyl group in the aromatic ring A of the coumarin core improves the binding affinity to albumin around 10-folds and changes the binding site from subdomain IIA to IIIA or IB. In addition, the presence of other drugs, e.g., naproxen or ketoprofen, might interfere with the binding capacity of 7HC and 7H4MC, resulting in perturbations on the residence time of some clinically used drugs in the bloodstream.

Peanut Hull lignin/ecamsule·2Na hollow nanoparticles (P/E LNPs): A natural light-coloured, broad-spectrum, highly antioxidant, and safe lignin-based sunscreen

Lignin represents a potentially significant natural sunscreen alternative due to its good UV-absorbing ability, but its poor UVA absorption and dark colour are still obstacles. Numerous methods have been developed to whiten the colour of lignin, mainly including aromatic ring interruption and hydroxyl group blocking. However, these complicated procedures would weaken the UV-blocking and radical scavenging abilities. Here, we develop a strategy for the valorization of lignin in sunscreen to overcome their drawbacks by the in situ self-assembly of the natural light-coloured peanut hull lignin with the commercially available UV-protectant Ecamsule·2Na to obtain peanut hull lignin/Ecamsule·2Na hollow nanoparticles (P/E LNPs). The results show that the sun protection factor (SPF) value increased from 20 to 27, and the antioxidant capacity increased exponentially with a scavenging rate of up to 82 % at the extremely low dosage up to 0.1 mg/L of P/E LNPs. In addition, their good biocompatibility and safety were further confirmed by in vitro cytotoxicity analysis. In summary, we have successfully prepared a safe, broad-spectrum, light-coloured, and highly antioxidant, peanut hull lignin-based sunscreen that avoids any complicated chemical modifications to meet the commercial sunscreen requirement and also provides a new solution for the valorization of lignin from the vast amount of waste fruit hulls.

Exploring the Correlation Between the Molecular Structure and Biological Activities of Metal-Phenolic Compound Complexes: Research and Description of the Role of Metal Ions in Improving the Antioxidant Activities of Phenolic Compounds.

We discussed and summarized the latest data from the global literature on the action of polyphenolic antioxidants and their metal complexes. The review also includes a summary of the outcomes of theoretical computations and our many years of experimental experience. We employed various methods, including spectroscopy (FT-IR, FT-Raman, NMR, UV/Vis), X-ray diffraction, thermal analysis, quantum calculations, and biological assays (DPPH, ABTS, FRAP, cytotoxicity, and genotoxicity tests). According to our research, the number and position of hydroxyl groups in aromatic rings, as well as the delocalization of electron charge and conjugated double bonds, have a major impact on the antioxidant effectiveness of the studied compounds. Another important factor is metal complexation, whereby high ionic potential metals (e.g., Fe(III), Cr(III), Cu(II)) enhance antioxidant properties by stabilizing electron charge, while the low ionic potential metals (e.g., Ag(I), Hg(II), Pb(II)) reduce efficacy by disrupting electron distribution. However, we observed no simple correlation between ionic potential and antioxidant capacity. This paper gives insights that will aid in identifying new, effective antioxidants, which are vital for nutrition and the prevention of neurodegenerative illnesses. Our results outline the connections between biological activity and molecular structure, offering a foundation for the methodical design of antioxidants. Our review also shows in detail how we use various complementary methods to assess the impact of metals on the electronic systems of ligands. This approach moves beyond the traditional "trial and error" method, allowing for the more efficient and rational development of future antioxidants.

A comprehensive review of structure-activity relationships and effect mechanisms of polyphenols on heterocyclic aromatic amines formation in thermal-processed food.

Heterocyclic aromatic amines (HAAs) are potent carcinogenic substances mainly generated in thermal-processed food. Natural polyphenols have been widely used for inhibiting the formation of HAAs, whereas the effect of natural polyphenols on HAAs formation is complex and the mechanisms are far from being clearly elucidated. In order to clarify the comprehensive effect of polyphenols on HAAs, this review focused on the structure-activity relationships and effect mechanisms of polyphenols on the formation of HAAs. In addition, the effects of polyphenols on HAAs toxicity were also first reviewed from cell, gene, protein, and animal aspects. An overview of the effect of polyphenol structures such as parent ring and exocyclic group on the mitigation of HAAs was emphasized, aiming to provide some valuable information for understanding their effect mechanism. The HAAs formation is inhibited by natural polyphenols in a dose-dependent manner largely through eliminating free radicals and binding precursors and intermediates. The inhibitory effect was probably affected by the quantity and position of hydroxyl groups in the aromatic rings, and polyphenols with m-hydroxyl group in the aromatic ring had the stronger inhibitory effect. However, the presence of other substituents and excessive hydroxyl groups in natural polyphenols might mitigate the inhibitory effect and even promote the formation of HAAs. This review can provide theoretical reference for effectively controlling the formation of HAAs in thermal-processed food by natural polyphenols and reducing their harm to human health.

Target Discovery of Dhilirane-Type Meroterpenoids by Biosynthesis Guidance and Tailoring Enzyme Catalysis.

Dhilirane-type meroterpenoids (DMs) featuring a 6/6/6/5/5 ring system represent a rare group of fungal meroterpenoids. To date, merely 11 DMs have been isolated or derived, leaving their chemical diversity predominantly unexplored. Herein, we leverage an understanding of biosynthesis to develop a workflow for discovery of DMs by genome mining, metabolite analysis, and tailoring enzyme catalysis. Twenty-three new DMs, including seven unprecedented scaffolds, were consequently identified. An α-ketoglutarate (α-KG)-dependent oxygenase DhiD was found to catalyze the stereodivergent ring contraction of dhilirolide D to form the dhilirane skeleton; while the cytochrome P450 DhiH reshaped the structural diversity by establishing diverse C-C bonds and oxidation. Crystallographic and mutagenesis experiments provide a molecular basis for the DhiD reaction and its stereodivergent products. Notably, DhiD exhibits substrate-controlled catalytic versatility in the chemical expansion of DMs through ring contraction, hydroxylation, dehydrogenation, epoxidation, isomerization, epimerization, and α-ketol cleavage. Bioassay results demonstrated that the obtained meroterpenoids exhibited anti-inflammatory and insecticidal activities. Our work provides insight into nature's arsenal for DM biosynthesis and the functional versatility of α-KG-dependent oxygenase and P450, which can be applied for target discovery and diversification of DM-type natural products.

Design and investigation of novel iridoid-based peptide conjugates for targeting EGFR and its mutants L858R and T790M/L858R/C797S: an in silico study.

In this work, we designed novel peptide conjugates with plant-based iridoid and lichen-derived depside derivatives to target the wild-type EGFR (WT) and its mutants, L858R and T790M/L858R/C797S triple mutant. These mutations are often expressed in multiple cancers, particularly lung cancer. Specifically, the iridoids included 7-deoxyloganetic acid (7-DGA) and loganic acid (LG), while the depside derivative was sekikaic acid (SK). These compounds are known for their innate anticancer properties and were conjugated with two separate peptide sequences KLPGWSG (K) and YSIPKSS (Y). These sequences have been shown to target EGFR in previous phage display library screening, although the mechanism is unknown. Thus, we created the di-conjugates for dual targeting and investigated their interactions of the di-conjugates and that of the neat peptides with the kinase domain of EGFR (WT) and the two mutants using molecular docking, molecular dynamics (MD) simulations, and MM-GBSA analysis. Docking studies revealed that the (7-DGA)2-K showed the highest binding affinity at - 9.3kcal/mol with the L858R mutant, while (LG)2-Y displayed the highest binding affinity at - 9.0kcal/mol for the triple mutant receptor. Our results indicated that several of the conjugates interacted with crucial residues of the kinase domain, including ASP855 and THR854 (activation loop), MET793 and PRO794 (hinge region), ARG841 (catalytic loop), and LYS728 and LEU718 of the glycine-rich P-loop. Interestingly, strong hydrophobic interactions were also observed with the C-terminal tail residues, such as PHE997 and ALA1000 as well as with ARG999 for the YSIPKSS peptide and most of the conjugates. The hydroxyl group of the cyclopentane ring and the oxygen of the pyran ring of the (7-DGA)2-peptide conjugates contributed to binding particularly in the hinge region, while the peptide components formed an extended structure that bound well into the C-lobe. The (SK)2-Y di-conjugate and KLPGWSG peptide formed hydrogen bonds with the SER797 residue of the triple mutant. Overall, our results show that the (7-DGA)2-K, di-conjugate, the (7-DGA)2-Y di-conjugate, and the neat YSIPKSS demonstrated strong and stable binding with the L858R mutant and the highly resistant triple mutant EGFR, respectively. The novel designed conjugates demonstrate potential for further optimization for laboratory studies aimed at developing new therapeutics for targeting specific EGFR mutant expressing cells.

Refinement of the Drude Polarizable Force Field for Hexose Monosaccharides: Capturing Ring Conformational Dynamics with Enhanced Accuracy.

We present a revised version of the Drude polarizable carbohydrate force field (FF), focusing on refining the ring and exocyclic torsional parameters for hexopyranose monosaccharides. This refinement addresses the previously observed discrepancies between calculated and experimental NMR 3J coupling values, particularly in describing ring dynamics and exocyclic rotamer populations within major hexose monosaccharides and their anomers. Specifically, α-MAN, β-MAN, α-GLC, β-GLC, α-GAL, β-GAL, α-ALT, β-ALT, α-IDO, and β-IDO were targeted for optimization. The optimization process involved potential energy scans (PES) of the ring and exocyclic dihedral angles computed using quantum mechanical (QM) methods. The target data for the reoptimization included PES of the inner ring dihedrals (C1-C2-C3-C4, C2-C3-C4-C5, C5-O5-C1-C2, C4-C5-O5-C1, O5-C1-C2-C3, C3-C4-C5-O5) and the exocyclic torsions, other than the pseudo ring dihedrals (O1-C1-O5-C5, O2-C2-C1-O5, and O4-C4-C5-O5) and hydroxyl torsions used in the previous parametrization efforts. These parameters, in conjunction with previously developed Drude parameters for hexopyranose monosaccharides, were validated against experimental observations, including NMR data and conformational energetics, in aqueous environments. The resulting polarizable model is shown to be in good agreement with a range of QM data, experimental NMR data, and conformational energetics of monosaccharides in aqueous solutions. This offers a significant improvement of the Drude carbohydrate force field, wherein the refinement enhances the accuracy of accessing the conformational dynamics of carbohydrates in biomolecular simulations.

Coexistence of diverse metabolic pathways promotes p-cresol biodegradation by Bacillus subtilis ZW

The aromatic compound p-cresol is a notorious industrial pollutant characterized by its high toxicity, persistence and bioaccumulation within higher organisms. A thorough understanding of the microbial metabolic pathways involved in p-cresol degradation is critical for the design and optimization of microbial wastewater treatment systems. Despite numerous studies on the degradation pathways of p-cresol by various microbial species, the metabolic diversity within a single strain remains largely unexplored. This study investigated the metabolic mechanism of p-cresol in Bacillus subtilis ZW, a bacterium capable of degrading p-cresol. Through LC-MS analysis, we identified twelve distinct metabolic intermediates in the culture of strain ZW, leading to the proposal of three plausible degradation pathways. These include methyl hydroxylation, direct aromatic ring hydroxylation, and phosphorylation of the hydroxyl group, and all of which may concurrently contribute to p-cresol biodegradation by strain ZW. Further study showed that the genome of strain ZW harbored 47 coding genes associated with the degradation of p-cresol and its structural analogs, underscoring the metabolic versatility of this strain and its potential for xenobiotic biodegradation. These findings contribute valuable insights into the biodegradation mechanisms of pollutants. Under optimal degradation conditions of 35 °C and pH 7.0, strain ZW demonstrated the capacity to metabolize 27.5 % of p-cresol (10 mg/L) in minimal salt media within a week, and was capable of completely degrading 10 mg/L p-cresol in wastewater within five days. The potential utility of strain ZW in the bioremediation of p-cresol and other aromatic compounds is thus evident.

Synthesis, Physicochemical Characterization, and Antimicrobial Evaluation of Halogen-Substituted Non-Metal Pyridine Schiff Bases

Four synthetic Schiff bases (PSB1 [(E)-2-(((4-aminopyridin-3-yl)imino)methyl)-4,6-dibromophenol], PSB2 [(E)-2-(((4-aminopyridin-3-yl)imino)methyl)-4,6-diiodophenol], PSB3 [(E)-2-(((4-aminopyridin-3-yl)imino)methyl)-4-iodophenol], and PSB4 [(E)-2-(((4-aminopyridin-3-yl)imino)methyl)-4-chloro-6-iodophenol]) were fully characterized. These compounds exhibit an intramolecular hydrogen bond between the hydroxyl group of the phenolic ring and the nitrogen of the azomethine group, contributing to their stability. Their antimicrobial activity was evaluated against various Gram-negative and Gram-positive bacteria, and it was found that the synthetic pyridine Schiff bases, as well as their precursors, showed no discernible antimicrobial effect on Gram-negative bacteria, including Salmonella Typhi (and mutant derivatives), Salmonella Typhimurium, Escherichia coli, and Morganella morganii. In contrast, a more pronounced biocidal effect against Gram-positive bacteria was found, including Bacillus subtilis, Streptococcus agalactiae, Streptococcus pyogenes, Enterococcus faecalis, Staphylococcus aureus, and Staphylococcus haemolyticus. Among the tested compounds, PSB1 and PSB2 were identified as the most effective against Gram-positive bacteria, with PSB2 showing the most potent biocidal effects. Although the presence of reactive oxygen species (ROS) was noted after treatment with PSB2, the primary mode of action for PSB2 does not appear to involve ROS generation. This conclusion is supported by the observation that antioxidant treatment with vitamin C only partially mitigated bacterial inhibition, indicating an alternative biocidal mechanism.

Benzoylation of Tetrols: A Comparison of Regioselectivity Patterns for O- and S-Glycosides of d-Galactose.

Efficient protecting group strategies are important for glycan synthesis and represent a unique synthetic challenge in differentiating sugar ring hydroxyl groups. Direct methods to enable regioselective protecting group installation are thus desirable. Herein, we explore a one-step regioselective benzoylation to deliver 2,3,6-protected d-galactose building blocks from tetrols across a variety of α- and β-, O- and S-glycoside substrates. We focus on benzoyl chloride as the esterifying reagent and a reaction temperature of -40 °C to screen the regioselectivity outcome for twenty-two different glycosides, based on isolated yields. Using this methodology, we demonstrate the capability for α-linked aryl and alkyl glycosides (O- and S- d-galactosides, d-galactosamines, and l-fucose), delivering consistent isolated yields (>65%) for 2,3,6-benzoylated products. We extend to explore β-linked systems, where the observed regioselectivity is not paralleled. We posit that both steric and electronic factors from the anomeric substituent contribute to modulating the reactivity competition between 2-OH and 4-OH, enabling the formation of regioisomeric mixtures. However, a certain balance of these factors within the aglycon can deliver 2,3,6-regioselectivity, notably for β-O-Et and β-O-CH2CF3 glycosides. The methodology contributes toward understanding the peculiarities of regioselective carbohydrate-protecting group installation, exploring the importance of the anomeric substituent upon ring hydroxyl group reactivity.

Effects of hydrothermal pretreatment on sulfadiazine degradation during two-stage anaerobic digestion of pig manure

Antibiotics in animal manure pose significant risks to the environment and health. While anaerobic digestion (AD) is commonly used for pig manure treatment, its efficiency in antibiotic removal has been considerably limited. This study investigated the impact of hydrothermal pretreatment (HTP) on sulfadiazine (SDZ) removal in a two-stage AD system. Results indicated that the HTP process reduced SDZ concentration by 40.61%. Furthermore, the SDZ removal efficiency of the AD system coupling HTP increased from 50.90% to 65.04% compared to the untreated system. Biogas yield was also improved by 26.17% while maintaining system stability. Changes induced by HTP in the microbial communities revealed that Firmicutes, Bacteroidetes, Caldatribacteriota, and Proteobacteria emerged as the primary bacterial phyla. Following HTP, the relative abundance of Prevotella, which exhibited a strong negative correlation with SDZ concentration, increased significantly by 25-fold in the acidogenic stage. Proteiniphilum, Syntrophomonas and Sedimentibacter showed notable increases in the methanogenic stage after HTP. The N-heterocyclic metabolism carried out by Prevotella might have been the predominant SDZ degradation pathway in the acidogenic stage, while the benzene ring metabolism and hydroxylation by the Proteiniphilum emerged as the primary degradation pathways in the methanogenic stages. Furthermore, biodegradation intermediates were proven to be less toxic than SDZ itself, indicating that the HTP-enhanced two-stage AD process could be a viable way to lower the environmental risks associated with SDZ. The findings from this study provide valuable insights for removing SDZ from the environment via two-stage AD.

Halogenation of Anilines: Formation of Haloacetonitriles and Large-Molecule Disinfection Byproducts.

Aniline-related structures are common in anthropogenic chemicals, such as pharmaceuticals and pesticides. Compared with the widely studied phenolic compounds, anilines have received far less assessment of their disinfection byproduct (DBP) formation potential, even though anilines and phenols likely exhibit similar reactivities on their respective aromatic rings. In this study, a suite of 19 aniline compounds with varying N- and ring-substitutions were evaluated for their formation potentials of haloacetonitriles and trihalomethanes under free chlorination and free bromination conditions. Eight of the aniline compounds formed dichloroacetonitrile at yields above 0.50%; the highest yields were observed for 4-nitroaniline, 3-chloroaniline, and 4-(methylsulfonyl)aniline (1.6-2.3%). Free bromination generally resulted in greater haloacetonitrile yields with the highest yield observed for 2-ethylaniline (6.5%). The trihalomethane yields of anilines correlated with their haloacetonitrile yields. Product analysis of aniline chlorination by liquid chromatography-high-resolution mass spectrometry revealed several large-molecule DBPs, including chloroanilines, (chloro)hydroxyanilines, (chloro)benzoquinone imines, and ring-cleavage products. The product time profiles suggested that the reaction pathways include initial ring chlorination and hydroxylation, followed by the formation of benzoquinone imines that eventually led to ring cleavage. This work revealed the potential of aniline-related moieties in micropollutants as potent precursors to haloacetonitriles and other emerging large-molecule DBPs with the expected toxicity.

Biodegradation of 3-methylpyridine by an isolated strain, Gordonia rubripertincta ZJJ

Methylpyridines are a class of highly toxic pyridine derivatives. In this study, a novel degrading bacterium was isolated for 3-methylpyridine (3-MP) degradation (Gordonia rubripertincta ZJJ, GenBank accession NO. OP430847.1; CCTCC M 2022975). The maximum specific degradation rate, half-saturation constant and inhibition constant were fitted to be 0.48 h−1, 88.3 mg L−1 and 924.0 mg L−1, respectively. During 3-MP biodegradation, the lost total organic carbon was transformed into CO2 (67.4 %) and biomass (32.6 %), and ammonia nitrogen was almost the sole inorganic species with a conversion rate of 36.3 %. Three metabolic pathways were possibly involved in 3-MP degradation: I) methyl oxidation followed by ring hydroxylation and hydrogenation; II) rupture of C=C and C–N bonds after ring reduction; III) initial ring hydroxylation. The study not only provides a novel strain for the high-efficient degradation of 3-MP, but also contributes to an in-depth understanding of 3-MP biotransformation.

Pulsed corona discharge: an advanced treatment method for antibiotic-contaminated water

Water pollution is one of the most significant problems of the current century. With the increase in medicine availability and use, pharmaceutical pollutants such as antibiotics become more prevalent in natural environments with potentially negative impact. In this study, a pulsed corona discharge was investigated as a possible treatment method of water contaminated with amoxicillin (AMX). Two system configurations were used: plasma and plasma-ozonation. In order to better grasp the effect of system and water matrix on degradation, different pulse widths, solutions pH and conductivity values, as well as the nature of the dissolved salts were investigated. Decreasing the pulse width from 300 ns to 106 ns (full width at half maximum) led to almost a two-fold increase in energy yield at 50% pollutant removal, and the addition of the ozonation reactor resulted six times enhancement in efficiency. While the water matrix had little impact on AMX degradation, the buffering capacity of carbonates has proven beneficial by preventing pH decrease during treatment. Under optimum conditions, the energy yield was 57 g kWh−1 at 93% removal of AMX in tap water. A number of 26 potential degradation products have been identified, resulting from hydroxylation of the benzene ring, oxidation of the thioester and amine groups, hydrolysis, and cleavage of the benzene, β-lactam and thiazole rings, along with fragmentation of the resulting compounds. All but seven degradation intermediates are completely removed by extending treatment duration to 60 min and the persistent ones are less toxic than the parent compound.

Biochemical insights into the biodegradation mechanism of typical sulfonylureas herbicides and association with active enzymes and physiological response of fungal microbes: A multi-omics approach

The extensive use of sulfonylurea herbicides has raised major concerns regarding their long-term soil residues and agroecological risks despite their role in agricultural protection. Microbial degradation is an important approach to remove sulfonylureas, whereas understanding the associated biodegradation mechanisms, enzymes, and physiological responses remains incomplete. Based on the rapid biodegradation of nicosulfuron by typical fungal isolate Talaromyces flavus LZM1, the dependency on cellular accumulation and environmental conditions, e.g. pH and nutrient supplies, was shown in the study. The biodegradation of nicosulfuron occurred intracellularly and followed the cascade of reactions including hydrolysis, Smile contraction rearrangement, hydroxylation, and opening of the pyrimidine ring. Besides 2-amino-4,6-dimethoxypyrimidine (ADMP) and 2-aminosulfonyl-N,N-dimethylnicotinamide (ASDM), numerous products and intermediates were newly identified and the structural forms of methoxypyrimidine and sulfonylurea bridge contraction rearrangement are predicted to be more toxic than nicosulfuron. The biodegradation should be enzymatically regulated by glycosylphosphatidylinositol transaminase (GPI-T) and P450s, which were manifested with the significant upregulation in proteomics. It is the first time that the hydrolysis of nicosulfuron into ADMP and ASDM have been associated with GPI-T. The integrated pathways of biodegradation were further elucidated through the involvement of various active enzymes. Except for the enzymatic catalysis, the physiological responses verified by metabolo-proteomics were critical not only to regulate material synthesis, uptake, utilization, and energy transfer but also to maintain antioxidant homeostasis, biodegradability, and tolerance of nicosulfuron by the differentially expressed metabolites, such as acetolactate synthase and 3-isopropylmalate dehydratase. The obtained results would help understand the biodegradation mechanism of sulfonylurea from chemicobiology and enzymology and promote the use of fungal biodegradation in pollution rehabilitation.