Unraveling Multiple Pathways of Electron Donation from Phenolic Moieties in Natural Organic Matter.

Natural organic matter (NOM) exhibits a distinctive electron-donating capacity (EDC) that serves a pivotal role in the redox reactions of contaminants and minerals through the transformation of electron-donating phenolic moieties. However, the ambiguity of the molecular transformation pathways (MTPs) that engender the EDC during NOM oxidation remains a significant issue. Here, MTPs that contribute to EDC were investigated by identifying the oxidized products of phenolic model compounds and NOM samples in direct or mediated electrochemical oxidation (DEO or MEO, respectively) using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). It was found that the oxidation of newly formed phenolic-OH (ArOH) and the oxidative coupling reaction of the phenoxy radical are the main MTPs that directly contribute to EDC, in addition to the transformation of hydroquinones to quinones. Notably, the oxidative coupling reaction of ArOH contributed at least 22-42% to the EDC. Ferulic acid-like structures can also directly contribute to EDC by incorporating H2O into their acrylic substituents. Furthermore, the opening of C rings can indirectly attenuate the EDC through structural alterations in the electron-donating process of NOM. Decarboxylation can either weaken or enhance the EDC depending on the structure of the phenolic moieties in NOM. These findings suggest that the EDC of NOM is a comprehensive result of multiple NOM MTPs, involving not only ArOH oxidation but also the addition of H2O to olefinic bonds and bond-breaking reactions. Our work provides molecular evidence that aids in the comprehension of the multiple EDC-associated transformation pathways of NOM.

Formation of Larger Molecular Weight Disinfection Byproducts from Acetaminophen in Chlorine Disinfection.

Acetaminophen is widely used to treat mild to moderate pain and to reduce fever. Under the worldwide COVID-19 pandemic, this over-the-counter pain reliever and fever reducer has been drastically consumed, which makes it even more abundant than ever in municipal wastewater and drinking water sources. Chlorine is the most widely used oxidant in drinking water disinfection, and chlorination generally causes the degradation of organic compounds, including acetaminophen. In this study, a new reaction pathway in the chlorination of acetaminophen, i.e., oxidative coupling reactions via acetaminophen radicals, was investigated both experimentally and computationally. Using an ultraperformance liquid chromatograph coupled to an electrospray ionization-triple quadrupole mass spectrometer, we detected over 20 polymeric products in chlorinated acetaminophen samples, some of which have structures similar to the legacy pollutants "polychlorinated biphenyls". Both C-C and C-O bonding products were found, and the corresponding bonding processes and kinetics were revealed by quantum chemical calculations. Based on the product confirmation and intrinsic reaction coordinate computations, a pathway for the formation of the polymeric products in the chlorination of acetaminophen was proposed. This study suggests that chlorination may cause not only degradation but also upgradation of a phenolic compound or contaminant.

Identification of the first diphenyl ether gene cluster for pestheic acid biosynthesis in plant endophyte Pestalotiopsis fici.

The diphenyl ether pestheic acid was isolated from the endophytic fungus Pestalotiopsis fici, which is proposed to be the biosynthetic precursor of the unique chloropupukeananes. The pestheic acid biosynthetic gene (pta) cluster was identified in the fungus through genome scanning. Sequence analysis revealed that this gene cluster encodes a nonreducing polyketide synthase, a number of modification enzymes, and three regulators. Gene disruption and intermediate analysis demonstrated that the biosynthesis proceeded through formation of the polyketide backbone, cyclization of a polyketo acid to a benzophenone, chlorination, and formation of the diphenyl ether skeleton through oxidation and hydrolyzation. A dihydrogeodin oxidase gene, ptaE, was essential for diphenyl ether formation, and ptaM encoded a flavin-dependent halogenase catalyzing chlorination in the biosynthesis. Identification of the pta cluster laid the foundation to decipher the genetic and biochemical mechanisms involved in the pathway.

Deciphering the effect of amine versus imine ligands of copper(II) complexes in 2-aminophenol oxidation.

A series of amine (1-6) and imine (5',6') based copper(II) complexes with tridentate (NNO) ligand donors were synthesized and characterized using modern analytical techniques. All the complexes were subjected to 2-aminophenol (OAP) oxidation to form 2-aminophenoxazin-3-one, as a functional analogue of an enzyme, phenoxazinone synthase. In addition, a critical comparison of the reactivity using the amine-based complexes with their respective imine counterparts was achieved in both experimental as well as theoretical studies. For instance, the kinetic measurement revealed that the imine-based copper(II) complexes (kcat, 2.4 × 105-6.2 × 106 h-1) are better than amine-based (kcat, 6.3 × 104-3.9 × 105 h-1) complexes. The complex-substrate adducts [Cu(L3)(OAP)] (7) and [Cu(L3')(OAP)] (7') were characterized for both systems by mass spectrometry. Further, the DFT study was performed with amine- (3) and imine- (3') based copper(II) complexes, to compare their efficacy in the oxidation of OAP. The mechanistic investigations reveal that the key elementary step to determine the reactivity of 3 and 3' is the proton-coupled electron transfer (PCET) step occurring from the intermediates 7/7'. Further, the computed HOMO-LUMO energy gap of 7' was smaller than 7 by 0.8 eV, which indicates the facile PCET compared to that of 7. Moreover, the coupling of the OAP moiety using imine-complexes (ΔGR.E = -5.8 kcal/mol) was found to be thermodynamically more favorable than amine complexes (ΔGR.E = +3.3 kcal/mol). Overall, the theoretical findings are in good agreement with the experimental results.

Cellulose-Supported Sulfonated Magnetic Nanoparticles: Utilized for One-pot Synthesis of α-Iminonitrile Derivatives.

ntroduction: An instrumental strategy for α-iminonitrile derivatives preparation by Fe3O4@cellulose-OSO3H (MCSA) as an eco-friendly nanocatalyst and oxidative agent in aerobic condition, is presented. MATERIALS AND METHODS: Through this method, a one-pot three-component condensation reaction of various aldehydes, primary amines and trimethylsilylcyanide (TMSCN) were applied to synthesize the desired products. It was performed in absolute ethanol and under a mild condition by using the presented nanocatalyst. High reaction yields were obtained through using the presented magnetic agent, as well. Moreover, the threecomponent reactions were executed using accessible and economical precursors. The convenient separation and recyclability of the used nanocatalyst were also precisely investigated. RESULTS AND DISCUSSION: In this research, we identified novel α-iminonitrile derivatives using 1H NMR, 13C NMR, CHN, and FT-IR analyses, as well. In order to determine the well-known derivatives, we used FT-IR method as well as comparing their melting points with those of reported. CONCLUSION: In summary, an extremely efficient method was used for the environmentally-friendly synthesis of α-iminonitrile derivatives that are important bioactive substances. The catalytic oxidative coupling reaction afforded the products via a one-pot three-component condensation reaction of various aldehydes, primary amines and TMSCN with great reaction yields, in ethanol under mild conditions.

Transformation of triclosan by laccase catalyzed oxidation: The influence of humic acid-metal binding process.

Laccase is a widely present extracellular phenoloxidase excreted by fungi, bacteria, and high plants. It is able to catalyze one-electron oxidation of phenolic compounds into radical intermediates that can subsequently couple to each other via covalent bonds. These reactions are believed to play an important role in humification process and the transformation of contaminants containing phenolic functionalities in the environment. In this study, we investigated the kinetics of triclosan transformation catalyzed by laccase. It was found that the rate of triclosan oxidation was first order to the concentrations of both substrate and enzyme. Humic acid (HA) could inhibit the reaction by quenching the radical intermediate of triclosan generated by laccase oxidation. Such inhibition was more significant in the presence of divalent metal cations. This is because that binding to metal ions neutralized the negative charge of HA molecules, thus making them more accessible to laccase molecule that is also negatively charged. Therefore, it has greater chance to quench the radical intermediate that is very unstable and can only diffuse a limited distance after being released from the enzyme catalytic center. Based on these understandings, a reaction model was developed by integration of metal-HA binding equilibriums and kinetic equations. This model precisely predicted the transformation rate of triclosan in the presence of HA and divalent metal ions including Ca2+, Mg2+, Cd2+, Co2+, Mn2+, Ba2+, and Zn2+. Overall, this work reveals important insights into laccase catalyzed oxidative coupling process.