Stability and removal of selected avobenzone's chlorination products

Wang, Cheng; Kralj, Mojca Bavcon; Košmrlj, Berta; Yao, Jun; Košenina, Suzana; Polyakova, O. V.; Artaev, Viatcheslav B.; Lebedev, A. T.; Trebše, Polonca

doi:10.1016/j.chemosphere.2017.04.125

Cited by 17 publications

(6 citation statements)

References 21 publications

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“…The DK tautomer absorbs at higher UV energies (λ max = 265 nm) and has been shown to be responsible for formation of a reactive triplet. Indeed, the instability of the diketo form is well established. ,− Wang et al, for example, demonstrated that AB photodegrades (in the UVA) more quickly as a function of chlorine substitution at the α-carbon (C2) since this promotes the diketo form …”

Section: Introductionmentioning

confidence: 99%

“…32,34−36 Wang et al, for example, demonstrated that AB photodegrades (in the UVA) more quickly as a function of chlorine substitution at the α-carbon (C2) since this promotes the diketo form. 37 A considerable number of studies have been performed to explore how AB tautomerization, and hence photostability, is affected by the solvent. 38−40 These studies prompt questions of whether other local environmental factors can influence the extent of tautomerization.…”

Section: Introductionmentioning

confidence: 99%

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Unravelling the Keto–Enol Tautomer Dependent Photochemistry and Degradation Pathways of the Protonated UVA Filter Avobenzone

et al. 2020

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Avobenzone (AB) is a widely used UVA filter known to undergo irreversible photodegradation. Here, we investigate the detailed pathways by which AB photodegrades by applying UV laser-interfaced mass spectrometry to protonated AB ions. Gas-phase infrared multiple-photon dissociation (IRMPD) spectra obtained with the free electron laser for infrared experiments, FELIX, (600−1800 cm −1 ) are also presented to confirm the geometric structures. The UV gas-phase absorption spectrum (2.5−5 eV) of protonated AB contains bands that correspond to selective excitation of either the enol or diketo forms, allowing us to probe the resulting, tautomer-dependent photochemistry. Numerous photofragments (i.e., photodegradants) are directly identified for the first time, with m/z 135 and 161 dominating, and m/z 146 and 177 also appearing prominently. Analysis of the production spectra of these photofragments reveals that that strong enol to keto photoisomerism is occurring, and that protonation significantly disrupts the stability of the enol (UVA active) tautomer. Close comparison of fragment ion yields with the TD-DFT-calculated absorption spectra give detailed information on the location and identity of the dissociative excited state surfaces, and thus provide new insight into the photodegradation pathways of avobenzone, and photoisomerization of the wider class of β-diketone containing molecules.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Unravelling the Keto–Enol Tautomer Dependent Photochemistry and Degradation Pathways of the Protonated UVA Filter Avobenzone

et al. 2020

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“…For example, common drugs including metformin, diclofenac, and tamoxifen entering freshwater sources are subject to direct chlorination causing drinking water contamination associated with largely unexplored implications for human health (126)(127)(128)(129). Likewise, chlorination of PPCPs including sunscreen ingredients such as the common UVAsunscreen avobenzone are associated with formation of a dichloro-species, and cosmetics are equally subject to chlorination with unexplored effects on human health (16,(130)(131)(132)(133)(134)(135).…”

Section: Molecular Mediators Signaling Pathways and Human Target Orga...mentioning

confidence: 99%

Hypochlorous Acid: From Innate Immune Factor and Environmental Toxicant to Chemopreventive Agent Targeting Solar UV-Induced Skin Cancer

2022

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A multitude of extrinsic environmental factors (referred to in their entirety as the ‘skin exposome’) impact structure and function of skin and its corresponding cellular components. The complex (i.e. additive, antagonistic, or synergistic) interactions between multiple extrinsic (exposome) and intrinsic (biological) factors are important determinants of skin health outcomes. Here, we review the role of hypochlorous acid (HOCl) as an emerging component of the skin exposome serving molecular functions as an innate immune factor, environmental toxicant, and topical chemopreventive agent targeting solar UV-induced skin cancer. HOCl [and its corresponding anion (OCl-; hypochlorite)], a weak halogen-based acid and powerful oxidant, serves two seemingly unrelated molecular roles: (i) as an innate immune factor [acting as a myeloperoxidase (MPO)-derived microbicidal factor] and (ii) as a chemical disinfectant used in freshwater processing on a global scale, both in the context of drinking water safety and recreational freshwater use. Physicochemical properties (including redox potential and photon absorptivity) determine chemical reactivity of HOCl towards select biochemical targets [i.e. proteins (e.g. IKK, GRP78, HSA, Keap1/NRF2), lipids, and nucleic acids], essential to its role in innate immunity, antimicrobial disinfection, and therapeutic anti-inflammatory use. Recent studies have explored the interaction between solar UV and HOCl-related environmental co-exposures identifying a heretofore unrecognized photo-chemopreventive activity of topical HOCl and chlorination stress that blocks tumorigenic inflammatory progression in UV-induced high-risk SKH-1 mouse skin, a finding with potential implications for the prevention of human nonmelanoma skin photocarcinogenesis.

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“…Consequently, the aqueous chlorination reaction proceeded at the double bond of the enol form of avobenzone rather than at the activated benzene ring. The primary products 1-( tert -butyl)-2-chloro-3-(4-methoxyphenyl) -1,3-dione and 1-( tert -butyl)-2,2-dichloro-3-(4-methoxyphenyl)propan-1,3-dione were synthesized, and their spectra and retention times coincided with those observed upon the aqueous chlorination of avobenzone [ 96 ].…”

Section: Transformation Of Olefins and Compounds With C=c Bondsmentioning

confidence: 99%

Transformation of Organic Compounds during Water Chlorination/Bromination: Formation Pathways for Disinfection By-Products (A Review)

Mazur

Lebedev

2022

J Anal Chem

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The purity of drinking water is an important issue of the human life quality. Water disinfection has saved millions people from the diseases spread with water. However, that procedure has a certain drawback due to formation of toxic organic disinfection products. Establishing the structures of these products and the mechanisms of their formation and diminishing their levels in drinking water represent an important task for chemistry and medicine, while mass spectrometry is the most efficient tool for the corresponding studies. The current review throws light upon natural and anthropogenic sources of the formation of disinfection by-products (DBPs) and the mechanisms of their formation related to the structural peculiarities and the presence of functional groups. In addition to chlorination, bromination is discussed since it is used quite often as an alternative method of disinfection, particularly, for the purification of swimming pool water. The benefits of the contemporary GC/MS and LC/MS methods for the elucidation of DBP structures and study of the mechanisms of their formation are discussed. The reactions characteristic for various functional groups and directions of transformation of certain classes of organic compounds in conditions of aqueous chlorination/bromination are also covered in the review.

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Stability and removal of selected avobenzone's chlorination products

Cited by 17 publications

References 21 publications

Unravelling the Keto–Enol Tautomer Dependent Photochemistry and Degradation Pathways of the Protonated UVA Filter Avobenzone

Unravelling the Keto–Enol Tautomer Dependent Photochemistry and Degradation Pathways of the Protonated UVA Filter Avobenzone

Hypochlorous Acid: From Innate Immune Factor and Environmental Toxicant to Chemopreventive Agent Targeting Solar UV-Induced Skin Cancer

Transformation of Organic Compounds during Water Chlorination/Bromination: Formation Pathways for Disinfection By-Products (A Review)

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