Ring-opened Compounds Research Articles

Seco-nortriterpenoids from Cirsium setosum and their anti-inflammatory activity

Five unusual seco-nortriterpenoids, 3β-hydroxy-20,21-seco-30-nortaraxastan-20,21-dioic acid (1), 3β-hydroxy-20,21-seco-30-nortaraxastan-20-oic-21-oate (2), 3β-hydroxy-20-oxo-21,22-seco-30-nortaraxastan-22-oic acid (3), 3β-hydroxy-19-oxo-20,21-seco-29,30-nortaraxastan-21-oic acid (4) and 3β-hydroxy-19-oxo-20,21-seco-19-norlupan-21-oic acid (5) were isolated and elucidated from the anti-inflammatory activity fraction of the ethanol extract of Cirsium setosum. The structures of these compounds were established through spectroscopic methods. Preliminary biological assays showed that compounds 1–5 had significant inhibitory effect on NO production on lipopolysaccharide-stimulated RAW 264.7 cells, and compound 1 showed the strongest anti-inflammatory activity. This type of ring-opening compound is the first seco-triterpenoid structure discovered from the genus of Cirsium.

Characterization of products formed from the oxidation of toluene and m-xylene with varying NOx and OH exposure

Aromatic volatile organic compounds (VOCs) are an important precursor of secondary organic aerosol (SOA) in the urban environment. SOA formed from the oxidation of anthropogenic VOCs can be substantially more abundant than biogenic SOA and has been shown to account for a significant fraction of fine particulate matter in urban areas. A potential aerosol mass (PAM) chamber was used to investigate the oxidised products from the photo-oxidation of m-xylene and toluene. The experiments were carried out with OH radical as oxidant in both high- and low-NOx conditions and the resultant aerosol samples were collected using quartz filters and analysed by GC × GC-TOFMS. Results show the oxidation products derived from both precursors included ring-retaining and -opening compounds (unsaturated aldehydes, unsaturated ketones and organic acids) with a high number of ring-opening compounds observed from toluene oxidation. Glyoxal and methyl glyoxal were the major ring-cleavage products from both oxidation systems, indicating that a bicyclic route plays an important role in their formation. SOA yields were higher for both precursors under high-NOx (toluene: 0.111; m-xylene: 0.124) than at low-NOx (toluene: 0.089; m-xylene: 0.052), likely linked to higher OH concentrations during low-NOx experiments which may lead to higher degree of fragmentation. DHOPA (2,3-dihydroxy-4-oxo-pentanoic acid), a known tracer of toluene oxidation, was observed in both oxidation systems. The mass fraction of DHOPA in SOA from toluene oxidation was about double the value reported previously, but it should not be regarded as a tracer solely for oxidation of toluene as m-xylene oxidation gave a similar relative yield.

Insights into ultrasound-promoted degradation of naphthenic acid compounds in oil sands process affected water. Part I: Accelerated H-abstraction and decarboxylation of aromatic and alicyclic compounds

Propelled by enormous increase in demand for fuel sources, Canadian oil sands are becoming increasingly important as a fuel source due to their abundance and upgrading capability. However, extraction of bitumen, a high acid crude (HAC) oil, requires 2–3 units of water per unit of oil resulting in naphthenic acid (NA)-rich oil sands process affected water (OSPW) collected in effluent ponds. This study illustrates the role of sonochemistry in the accelerated degradation through H-abstraction and subsequent decarboxylation of aromatic and alicyclic naphthenic acid model compounds. Benzoic acid and 3-methylcyclohexane carboxylic acid were selected as model NA compounds to investigate the mechanism of hydroxyl radical (OH•) initiated carboxylic acid degradation in 378 KHz sonochemical reactor. Established FTIR methods with low resolution LCMS spectroscopy confirmation were applied to determine the extent of carboxylic acid degradation and identify the formation of products. FTIR monitoring showed a non-linear degradation of carboxylic acids with formation of many intermediates highlighting the shift from cyclic carboxylic acids to cyclic alcohols during BA degradation. Subsequent decrease in carboxylic acid groups signifies scission of cyclic structures before complete mineralization. This is confirmed with the LCMS identification of products such as: 3-hydroxybenzoic acid and phenol. This study postulated new breakdown pathways for degradation of benzoic acid with complete mineralization at a sonochemical reaction time (SRT) of 4 h. A radical quenching process was also inferred through the formation of conglomerates during sonochemical degradation of BA. Extension of the study to 3-methylcyclohexane carboxylic acid (3mCHA) shows similar non-linearity with an increase in carboxylic acid groups indicating H-abstraction followed by ring-opened compounds. However, due to the complex nature of 3mCHA’s ring-opened compounds, complete mineralization is not achieved. The putative role of sonochemistry is a promising and sustainable degradation method for mitigating NAs in OSPW, but sonication periods need to be considered carefully to ensure adequate mineralization of their constituents and combinatorial methods with other advanced oxidation methods may be needed to enhance industrial application.In Part II, an in silico screening approach using first principles is reported to identify the breakdown of the organic compounds and determine molecular rates of reaction to confirm the mechanistic origins of the compounds formed.

Gas- and Particle-Phase Products and Their Mechanisms of Formation from the Reaction of Δ-3-Carene with NO3 Radicals.

Monoterpenes are a major component of the large quantities of biogenic volatile organic compounds that are emitted to the atmosphere each year. They have a variety of structures, which influences their subsequent reactions with OH radicals, O3, or NO3 radicals and the tendency for these reactions to form secondary organic aerosol (SOA). Here we report the results of an environmental chamber study of the reaction of Δ-3-carene, an abundant unsaturated C10 bicyclic monoterpene, with NO3 radicals, a major nighttime oxidant. Gas- and particle-phase reaction products were analyzed in real time and offline by using mass spectrometry, gas and liquid chromatography, infrared spectroscopy, and derivatization-spectrophotometric methods. The results were used to identify and quantify functional groups and molecular products and to develop gas- and particle-phase reaction mechanisms to explain their formation. Identified gas-phase products were all first-generation ring-retaining and ring-opened compounds (ten C10 and one C9 monomers) with 2-4 functional groups and one C20 dinitrooxydialkyl peroxide dimer. Upon partitioning to the particle phase, the monomers reacted further to form oligomers consisting almost entirely of C20 acetal and hemiacetal dimers, with those formed from a hydroxynitrate and hydroxycarbonyl nitrate comprising more than 50% of the SOA mass. The SOA contained an average of 0.94, 0.71, 0.15, 0.11, 0.16, 0.13, and 7.80 nitrate, carbonyl, hydroxyl, carboxyl, ester, peroxide, and methylene groups per C10 monomer and was formed with a mass yield of 56%. These results have important similarities and differences to those obtained from a previous similar study of the reaction of β-pinene and yield new insights into the effects of monoterpene structure on gas- and particle-phase reactions that can lead to the formation of a large variety of multifunctional products and significant amounts of SOA.

The roles of oxygen and chloride in the degradation efficiency and mechanism of Basic Violet 16 by liquid glow discharge plasma

The degradation of Basic Violet 16 (BV16) dye in the aqueous solution by a novel Liquid Glow Discharge Plasma (LGDP) combined with KCl (supporting electrolyte) and oxygen (additive) was systematically investigated. Experimental results showed that the LGDP/Cl−/O2 system significantly facilitated the degradation of BV16 due to the involvement of UV irradiation and reactive species (e.g., HO⋅ and H2O2). The decolorization rate of BV16 reached up to 96.2% in 10 min with the TOC removal being 50.6% in 120 min. Meanwhile, reactive oxygen species (ROS) and reactive chlorine species (RCS) generated in the system were detected, and results show that oxygen injection was beneficial to accelerate the production of ROS. The transformation intermediates upon the degradation of BV16 by the LGDP process were monitored. Accordingly, the decay pathway of BV16 in the LGDP system was proposed, i.e., the cleavage of the C=C double bond of BV16 led to the formation of simple aromatic compounds, while further reaction gave rise to the ring opening compounds with the production of some low molecular weightacids (e.g., formic acid, acetic acid, lactate acid, and succinic acid), some of which could eventually be mineralized to CO2, H2O, and NH4+.

First insight on in vitro metabolism of three newly identified aryl organophosphate esters via a suspect coupled with nontarget screening approach

The ubiquity of organophosphate esters (OPEs) in the environment has triggered research into metabolic pathways of OPEs. Using liquid chromatography coupled with a hybrid quadrupole Orbitrap high-resolution mass spectrometer, a suspect and characteristic fragment ion-based nontarget screening strategy for the identification of unknown OPE metabolites was developed and evaluated. Then, this integrated approach was successfully used for investigation of three newly identified organophosphate esters (NOPEs), namely 2-biphenylol diphenyl phosphate (BPDPP), tris(2-biphenyl) phosphate (TBPHP), and naphthalen-2-yl diphenyl phosphate (NDPHP), in human liver microsomes (HLMs). The results demonstrated that BPDPP, TBPHP, and NDPHP were effectively metabolized by HLMs, with zero-order kinetics (R2 = 0.48−0.94) within the time frame of the assay. The suspected approach identified a considerable number of dearylated phosphate (DP), and hydroxylated metabolites for each of NOPEs after incubation with HLMs for 2 h. In addition, the nontarget approach further identified 9 novel metabolites including 2 epoxide intermediates and 7 oxidative ring-opening compounds, which were first reported in the Phase I metabolism of OPEs. Collectively, this study provided a novel suspect coupled with nontarget screening approach and was successfully used to screen metabolites of three NOPEs. For the first time, we observed direct evidence that oxidative ring-opening might serve as another primary metabolic pathway regarding the metabolism of aryl OPEs.

Design, Synthesis, and Antifungal Evaluation of Cryptolepine Derivatives against Phytopathogenic Fungi.

Inspired by the widely antiphytopathogenic application of diversified derivatives from natural sources, cryptolepine and its derivatives were subsequently designed, synthesized, and evaluated for their antifungal activities against four agriculturally important fungi Rhizoctonia solani, Botrytis cinerea, Fusarium graminearum, and Sclerotinia sclerotiorum. The results obtained from in vitro assay indicated that compounds a1-a24 showed great fungicidal property against B. cinerea (EC50 < 4 μg/mL); especially, a3 presented significantly prominent inhibitory activity with an EC50 of 0.027 μg/mL. In the pursuit of further expanding the antifungal spectrum of cryptolepine, ring-opened compound f1 produced better activity with an EC50 of 3.632 μg/mL against R. solani and an EC50 of 5.599 μg/mL against F. graminearum. Furthermore, a3 was selected to be a candidate to investigate its preliminary antifungal mechanism to B. cinerea, revealing that not only spore germination was effectively inhibited and the normal physiological structure of mycelium was severely undermined but also detrimental reactive oxygen was obviously accumulated and the normal function of the nucleus was fairly disordered. Besides, in vivo curative experiment against B. cinerea found that the therapeutic action of a3 was comparable to that of the positive control azoxystrobin. These results suggested that compound a3 could be regarded as a novel and promising agent against B. cinerea for its valuable potency.

Efficient degradation of p-nitrophenol by Fe@pomelo peel-derived biochar composites and its mechanism of simultaneous reduction and oxidation process

In this study, waste pomelo peels (PP) mixed with iron salts was treated successively with hydrothermal and pyrolyzing carbonization processes to obtain Fe(0) containing biochar composites (Fe@PP-Hy-Py) and the catalytic degradation of p-nitrophenol (PNP) using these Fe@PP-Hy-Py composites was studied. The results showed that the hydrothermal pre-treatment of the mixture of iron salts and pomelo peels was favorable for the incorporation of iron precursor within biomass network, which enabled copolymerization during the following pyrolysis. Through the pyrolysis process, the iron precursor was reduced in situ to amorphous Fe(0) dopped into the carbonaceous matrix, which conversely decreased the defect and disorder degree of pseudo-graphitic carbons and catalyzed the formation of environmental persistent free radicals (EPFRs). Degradation tests showed that the composites obtained at 600 °C with the theoretical Fe mass loading of 10% exhibited the greatest PNP degradation efficiency. Over 90% of 10 mg/L PNP was removed in 2 min under both N2 and air conditions with 1.0 g/L of catalyst level. The degradation kinetics of PNP were all well fitted by the pseudo-first-order kinetics model with kobs of Fe@PP-Hy-Py600 being 0.953 min−1. HPLC-QTOF/MS analysis demonstrated that both oxidation and reduction of PNP occurred as indicated by the detection of 4-aminophenol and ring opening compounds. The Fe(0) on the Fe@PP-Hy-Py was responsible for the reduction of PNP, while oxidation was induced by EPFRs. This study highlights the feasibility of synthesizing active heterogeneous Fe(0)-biochar composites by hydrothermal-pyrolysis route and the associated mechanisms of pollutant degradation.

Multifaceted Beneficial Effects of Erdosteine: More than a Mucolytic Agent

Erdosteine is a drug approved for the treatment of acute and chronic pulmonary diseases, originally developed as a mucolytic agent. It belongs to the thiol-based family of drugs that are known to also possess potentially important antioxidant and anti-inflammatory properties, and exhibit antibacterial activity against a variety of medically important bacterial species. Erdosteine is a prodrug that is metabolized to the ring-opening compound metabolite M1 (MET 1), which has mucolytic properties. Experimental studies have documented that erdosteine prevents or reduces lung tissue damage induced by oxidative stress and, in particular, that Met 1 also regulates reactive oxygen species production. The RESTORE study, which has been the only trial that investigated the effects of a thiol-based drug in chronic obstructive pulmonary disease (COPD) frequent exacerbators, documented that erdosteine significantly reduces the risk of acute exacerbations of COPD (AECOPDs), shortens their course, and also decreases the risk of hospitalization from COPD. The preventive action of erdosteine on AECOPDs was not affected by the presence or absence of inhaled corticosteroids (ICSs) or blood eosinophil count. These findings clearly contrast with the Global Initiative for Chronic Obstructive Lung Disease strategy’s approach to use erdosteine only in those COPD patients not treated simultaneously with an ICS. Furthermore, they support the possibility of using erdosteine in a step-down approach that in COPD is characterized by the withdrawal of the ICS.

Ring-opening and hydrodenitrogenation of indole under hydrothermal conditions over Ni, Pt, Ru, and Ni-Ru bimetallic catalysts

The activity and selectivity of activated-carbon-supported Ni, Pt, Ru, and Ni-Ru bimetallic catalysts was examined for hydrothermal denitrogenation of indole. The molar yield of pyrrole ring-opening compounds, without an added hydrogen source, are in the order: Ni < Pt < Ni90Ru10 < Ni75Ru25 < Ni50Ru50 ~ Ni25Ru75 ~ Ru. Ru-containing catalysts facilitated production of hydrocarbons (hydrodenitrogenation (HDN) products) when used with added formic acid (hydrogen source). We elucidated catalytic hydrothermal HDN pathways for indole based on the product distributions and the variation of their yields with time. Hydrogenation of indole to indoline is the primary pathway and ring-opening of indoline to form alkyl anilines is faster than forming HDN products (alkyl benzenes). DFT calculations confirmed experimental activity trends, showing Ru is more active than Ni for indole ring opening and for o-toluidine deamination. If no hydrogen source is present, directly breaking the N-C bond in the pyrrole ring is more favorable than breaking the C-N bond with an aromatic carbon. If a H source is provided, the pyrrole ring hydrogenates first, forming indoline, followed by cleavage of the C-N bond.

Boosted insights of novel accordion-like (2D/2D) hybrid photocatalyst for the removal of cationic dyes: Mechanistic and degradation pathways

In the present work, a novel (2D/2D) accordion like CS@g‒C3N4/MX hybrid composite was prepared through one-pot hydro-thermal synthesis method and utilized as a catalyst for the degradation of organic persistent dyes such as methylene blue (MB) and rhodamine B (RhB). Because the removal of such organic compounds is a major dispute in environmental aspects. In this study, the bio-assisted g‒C3N4/MX nanosheets was utilized for the removal of organic dyes from aqueous solution under visible light irradiation, respectively. The CS@g-C3N4/MX photocatalyst showed high catalytic activity based on ~99% and ~98.5% degradation of MB and RhB within 60 and 40 min using visible light irradiation. This outcome could have resulted in greater catalytic enactment towards the degradation of other persistent pollutants with enhanced light absorption property and it can efficiently suppress photo-generated charge recombination, thus improving the interfacial charge transfer rate. The OH radical was being effective oxidative species involved in the CS@g-C3N4/MX system for the degradation of organic contaminants. Furthermore, CS@g-C3N4/MX showed excellent photo-stability over five consecutive cycles for the degradation of organic dyes with negligible loss of photocatalytic activity. Finally, the purposed catalytic mechanisms and degradation pathways of MB and RhB were systematically discussed in detail based on experimental results. Thus, the organics which oxidized into ring-opened compounds such as ethoxyethane, butadiene etc., to non-toxic products like H2O, CO2 and some mineral salts.

Isolation of new streptimidone derivatives, glutarimide antibiotics from Streptomyces sp. W3002 using LC-MS-guided screening.

A LC-MS-guided screening led to the isolation of two new streptimidone derivatives (2 and 3) containing a glutarimide ring and two glutarimide ring-opened compounds (4 and 5) along with a known glutarimide-containing polyketide, streptimidone (1) from Streptomyces sp. W3002 strain. Their structures were elucidated by MS and NMR spectroscopic analyses and by comparison with data from the literature. Compound 2 is a non-hydroxylated analog at the C-5 position of streptimidone. The structure of 3 was determined as a streptimidone derivative possessing the α, β-unsaturated ketone moiety at positions C-5 and C-6. Compound 4 had similar chemical shifts and splitting patterns with 3, but the glutarimide ring is opened. Compound 5 closely resembles that of 4 with the only difference being the existence of an additional methoxy group instead of an amide group. Streptimidone (1) and 3 showed weak cytotoxic activity against three human cancer cell lines, respectively.

Multiple C-H Bond Activations and Ring-Opening C-S Bond Cleavage of Thiophene by Dirhenium Carbonyl Complexes.

The reaction of Re2(CO)8(μ-C6H5)(μ-H) (1) with thiophene in CH2Cl2 at 40 °C yielded the new compound Re2(CO)8(μ-η2-SC4H3)(μ-H) (2), which contains a bridging σ-π-coordinated thienyl ligand formed by the activation of the C-H bond at the 2 position of the thiophene. Compound 2 exhibits dynamical activity on the NMR time scale involving rearrangements of the bridging thienyl ligand. The reaction of compound 2 with a second 1 equiv of 1 at 45 °C yielded the doubly metalated product [Re2(CO)8(μ-H)]2(μ-η2-2,3-μ-η2-4,5-C4H2S) (3), formed by the activation of the C-H bond at the 5 position of the thienyl ligand in 2. Heating 3 in a hexane solvent to reflux transformed it into the ring-opened compound Re(CO)4[μ-η5-η2-SCC(H)C(H)C(H)][Re(CO)3][Re2(CO)8(μ-H)] (4) by the loss of one CO ligand. Compound 4 contains a doubly metalated 1-thiapentadienyl ligand formed by the cleavage of one of the C-S bonds. When heated to reflux (125 °C) in an octane solvent in the presence of H2O, the new compound Re(CO)4[η5-μ-η2-SC(H)C(H)C(H)C(H)]Re(CO)3 (5) was obtained by cleavage of the Re2(CO)8(μ-H) group from 4 with formation of the known coproduct [Re(CO)3(μ3-OH)]4. All new products were characterized by single-crystal X-ray diffraction analyses.

Flexible Analogues of Azaindole DYRK1A Inhibitors Elicit Cytotoxicity in Glioblastoma Cells

DYRK1A is a novel target for epidermal growth factor receptor (EGFR)-dependent glioblastoma and it represents a promising strategy for cancer therapy. DYRK1A inhibition has been found to promote EGFR degradation in glioblastoma cells by triggering endocytosis and lysosomal degradation, thus reducing the self-renewal ability of tumorigenic cells. Using a deconstruction approach of a DYRK1A lead molecule DANDY (1a), a set of novel ring-opened compounds was prepared. Despite showing no activity towards DYRK1A, a reduction in the viability of glioblastoma cells was observed with some of the compounds. This suggests other mechanistic pathways are leading to the apoptosis of glioblastoma cells.

The antiproliferative and proapoptotic effects of cladosporols A and B are related to their different binding mode as PPARγ ligands

Cladosporols are secondary metabolites from Cladosporium tenuissimum characterized for their ability to control cell proliferation. We previously showed that cladosporol A inhibits proliferation of human colon cancer cells through a PPARγ-mediated modulation of gene expression. In this work, we investigated cladosporol B, an oxidate form of cladosporol A, and demonstrate that it is more efficient in inhibiting HT-29 cell proliferation due to a robust G0/G1-phase arrest and p21waf1/cip1 overexpression. Cladosporol B acts as a PPARγ partial agonist with lower affinity and reduced transactivation potential in transient transfections as compared to the full agonists cladosporol A and rosiglitazone. Site-specific PPARγ mutants and surface plasmon resonance (SPR) experiments confirm these conclusions. Cladosporol B in addition displays a sustained proapoptotic activity also validated by p21waf1/cip1 expression analysis in the presence of the selective PPARγ inhibitor GW9662. In the DMSO/H2O system, cladosporols A and B are unstable and convert to the ring-opened compounds 2A and 2B. Finally, docking experiments provide the structural basis for full and partial PPARγ agonism of 2A and 2B, respectively. In summary, we report here, for the first time, the structural characteristics of the binding of cladosporols, two natural molecules, to PPARγ. The binding of compound 2B is endowed with a lower transactivation potential, higher antiproliferative and proapoptotic activity than the two full agonists as compound 2A and rosiglitazone (RGZ).

Regioselective Ring Opening of Styrene Oxide Catalyzed by MoO2(acac)2

The ring-opening reaction of styrene oxide with various nitrogen, oxygen, and carbon nucleophiles catalyzed by MoO2(acac)2 was described. The corresponding ring-opening compounds with nearly 100% regioselectivities were obtained under mild conditions in moderate to good yields. MoO2(acac)2 is a highly efficient catalyst for the ring opening of styrene oxide. The reaction serves as a simple and efficient method for the synthesis of 1,2-bifunctional compounds.

Mechanism and kinetic properties for the OH-initiated atmospheric oxidation degradation of 9,10-Dichlorophenanthrene

Chlorinated polycyclic aromatic hydrocarbons (ClPAHs) have become a serious environmental concern due to their widespread occurrence and dioxin-like toxicities. In this work, the mechanism of the OH-initiated atmospheric oxidation degradation of 9,10-dichlorophenanthrene (9,10-Cl2Phe) was investigated by using high-accuracy quantum chemistry calculations. The rate constants of the crucial elementary reactions were determined by the Rice–Ramsperger–Kassel–Marcus (RRKM) theory. The theoretical results were compared with the available experimental data. The main oxidation products are a group of ring-retaining and ring-opening compounds including chlorophenanthrols, 9,10-dichlorophenanthrene-3,4-dione, dialdehydes, chlorophenanthrenequinones, nitro-9,10-Cl2Phe and epoxides et al. The overall rate constant of the OH addition reaction is 2.35×10−12cm3 molecule−1s−1 at 298K and 1atm. The atmospheric lifetime of 9,10-Cl2Phe determined by OH radicals is about 5.05days. This study provides a comprehensive investigation of the OH-initiated oxidation degradation of 9,10-Cl2Phe and should contribute to clarifying its atmospheric fate.

Synthesis of steroidal and nonsteroidal vicinal heterocyclic alcohols, N-(1-cycloalkenyl)heterocycles and their antibacterial studies

A solvent free steroidal and nonsteroidal epoxide ring opening reaction by nitrogen containing heterocycles under microwave irradiation is described. Some of the epoxide ring opening compounds were converted to their corresponding N-(1-cycloalkenyl)heterocycles via an acid catalyzed dehydration reaction. The antimicrobial activities of the epoxide ring opening compounds and N-(1-cycloalkenyl)heterocyclic compounds were tested by agar diffusion assay. Compounds 6, 9–12, 24 and 27 showed moderate inhibition against the growth of pathogenic bacteria Escherichia coli, Pseudomonas syringae, Bacillus subtilis, Proteus vulgaris and Staphylococcus aureus.

ChemInform Abstract: The Synthesis of Rigid Polycyclic Structures for the Study of Diatropic or Steric Effects of a Phenyl Ring on CF Bond.

Polycyclic compounds 1a-c were synthesized to study the diatropic effects of a flanking phenyl ring on nearby CH and CF bonds. (19)F NMR spectra of 1b and 1c were strongly deshielded compared with those of the ring-opened compounds 3b, 7b, and 7c. DMol3 calculations on 1a-c provided quantitative bond lengths and torsional angles to support the conclusion that the downfield shifts in the (19)F NMR spectra are mainly due to steric interactions between the CF bonds and the π clouds of the phenyl ring(s).

Assessing the photochemical transformation pathways of acetaminophen relevant to surface waters: Transformation kinetics, intermediates, and modelling

This work shows that the main photochemical pathways of acetaminophen (APAP) transformation in surface waters would be direct photolysis (with quantum yield of (4.57 ± 0.17)⋅10−2), reaction with CO3−· (most significant at pH > 7, with second-order rate constant of (3.8 ± 1.1)⋅108 M−1 s−1) and possibly, for dissolved organic carbon higher than 5 mg C L−1, reaction with the triplet states of chromophoric dissolved organic matter (3CDOM*). The modelled photochemical half-life time of APAP in environmental waters would range from days to few weeks in summertime, which suggests that the importance of phototransformation might be comparable to biodegradation. APAP transformation by the main photochemical pathways yields hydroxylated derivatives, ring-opening compounds as well as dimers and trimers (at elevated concentration levels). In the case of 3CDOM* (for which the triplet state of anthraquinone-2-sulphonate was used as proxy), ring rearrangement is also hypothesised. Photochemistry would produce different transformation products (TPs) of APAP than microbial biodegradation or human metabolism, thus the relevant TPs might be used as markers of APAP photochemical reaction pathways in environmental waters.