Dataset Information

Photogeneration of singlet oxygen catalyzed by hexafluoroisopropanol for selective degradation of dyes.

ABSTRACT: Singlet oxygen (¹O₂) shows great potential for selective degradation of dyes in environmental remediation of wastewater. In this study, we showcased that ¹O₂ can be effectively generated from an anion complex composed of deprotonated hexafluoroisopropanol anion ([HFIP_-H]^‒) with hydroperoxyl radical (⋅HO₂) via ultraviolet (UV) photodetachment. Electronic structure calculations and cryogenic negative ion photoelectron spectroscopy unveil critical proton transfer upon complex formation and electron ejection, effectively photoconverting prevalent triplet ground state ³O₂ to long-lived excited ¹O₂, stabilized by nearby HFIP. Inspired by this spectroscopic study, a novel "photogeneration" strategy is proposed to produce ¹O₂ with the incorporation of atmospheric O₂ and HFIP, acting as a catalyst. Conceptually, the designed catalytic cycle upon UV irradiation and electron injection is able to achieve different degradations of dye molecules in a controllable fashion from decolorization to complete mineralization, shedding new light on potential water purification.

SUBMITTER: Han J

PROVIDER: S-EPMC10374460 | biostudies-literature | 2023 Aug

REPOSITORIES: biostudies-literature

ACCESS DATA

Publications

Photogeneration of singlet oxygen catalyzed by hexafluoroisopropanol for selective degradation of dyes.

Han Jia J Wang Lei L Cao Wenjin W Yuan Qinqin Q Zhou Xiaoguo X Liu Shilin S Wang Xue-Bin XB

iScience 20230710 8

Singlet oxygen (1O2) shows great potential for selective degradation of dyes in environmental remediation of wastewater. In this study, we showcased that 1O2 can be effectively generated from an anion complex composed of deprotonated hexafluoroisopropanol anion ([HFIP-H]‒) with hydroperoxyl radical (⋅HO2) via ultraviolet (UV) photodetachment. Electronic structure calculations and cryogenic negative ion photoelectron spe ...[more]

PMID: 37520730

Similar Datasets

Project description:Cholesterol (Ch) is an important lipidic building block and a target for oxidative degradation, which can be induced via free radicals or singlet oxygen ((1)O2). Suprofen (SP) is a nonsteroidal anti-inflammatory drug that contains the 2-benzoylthiophene (BZT) chromophore and has a π,π* lowest triplet excited state. In the present work, dyads (S)- and (R)-SP-α-Ch (1 and 2), as well as (S)-SP-β-Ch (3) have been prepared from β- or α-Ch and SP to investigate the possible competition between photogeneration of biradicals and (1)O2, the key mechanistic steps in Ch photooxidation. Steady-state irradiation of 1 and 2 was performed in dichloromethane, under nitrogen, through Pyrex, using a 400 W medium pressure mercury lamp. The spectral analysis of the separated fractions revealed formation of two photoproducts 4 and 5, respectively. By contrast, under the same conditions, 3 did not give rise to any isolable Ch-derived product. These results point to an intramolecular hydrogen abstraction in 1 and 2 from the C7 position of Ch and subsequent C-C coupling of the generated biradicals. Interestingly, 2 was significantly more photoreactive than 1 indicating a clear stereodifferentiation in the photochemical behavior. Transient absorption spectra obtained for 1-3 were very similar and matched that described for the SP triplet excited state (typical bands with maxima at ca. 350 nm and 600 nm). Direct kinetic analysis of the decay traces at 620 nm led to determination of triplet lifetimes that were ca. 4.1 μs for 1 and 2 and 5.8 μs for 3. From these data, the intramolecular quenching rate constants in 1 and 2 were determined as 0.78 × 10(5) s(-1). The capability of dyads 1-3 to photosensitize the production of singlet oxygen was assessed by time-resolved near infrared emission studies in dichloromethane using perinaphthenone as standard. The quantum yields (ΦΔ) were 0.52 for 1 and 2 and 0.56 for 3. In conclusion, SP-α-Ch dyads are unique in the sense that they can be used to photogenerate both biradicals and singlet oxygen, thus being able to initiate Ch oxidation from their triplet excited states following either of the two competing mechanistic pathways.

Dataset Information

Photogeneration of singlet oxygen catalyzed by hexafluoroisopropanol for selective degradation of dyes.

Publications

Photogeneration of singlet oxygen catalyzed by hexafluoroisopropanol for selective degradation of dyes.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets