3-Aminoperylene and ascorbate in aqueous SDS, one green laser flash ... and action! Sustainably detoxifying a recalcitrant chloro-organic

Autoren

Tim Kohlmann
Robert Naumann
Christoph Kerzig
Martin Goez

DOI

10.1039/c7pp00311k

eISSN

1474-9092

ISSN

1474-905X

Ausgabe der Veröffentlichung

11

Zeitschrift

Photochemical & Photobiological Sciences

Sprache

en

Online publication date

2020

Paginierung

1613 - 1622

Datum der Veröffentlichung

2017

Status

Published

Herausgeber

Springer Science and Business Media LLC

Herausgeber URL

http://dx.doi.org/10.1039/c7pp00311k

Datum der Datenerfassung

2022

Titel

3-Aminoperylene and ascorbate in aqueous SDS, one green laser flash … and action! Sustainably detoxifying a recalcitrant chloro-organic

Ausgabe der Zeitschrift

16

Datenquelle: Crossref

Abstract

The hydrated electron represents a "super-reductant" in water, providing 2.9 eV of reductive power, which suffices to decompose nonactivated aliphatic halides. We show that 3-amino-perylene in SDS micelles, when combined with the bioavailable ascorbate as an extramicellar sacrificial donor, sustainably produces hydrated electrons through photoredox catalysis with green light, from a metal-free system, and at near-physiological pH. Photoionization of the amine with a 532 nm laser yields an extremely long-lived radical cation as the by-product, and a subsequent reaction of the latter with the sacrificial donor across the micelle/water interface regenerates the catalyst. The regeneration step involves parallel reactions between differently protonated forms, causing a bell-shaped pH dependence in basic medium. We have separated these processes kinetically. Employing this catalytic cycle for the laboratory-scale decomposition of chloroacetate, an accepted model compound for toxic and persistent halo-organic waste, gave turnover numbers of about 170. Even though both the substrate and the sacrificial donor compete for the hydrated electron, their consumption ratio is practically independent of the initial concentration ratio because the formal radical anion of the ascorbate undergoes secondary scavenging by the chloroacetate. In the course of the reaction, the initial hydrophobic catalyst is converted into a secondary species that is hydrophilic and still exhibits catalytic activity.

Addresses

Martin-Luther-Universität Halle-Wittenberg, Institut für Chemie, Kurt-Mothes-Str. 2, D-06120 Halle (Saale), Germany. martin.goez@chemie.uni-halle.de.

Autoren

Tim Kohlmann
Robert Naumann
Christoph Kerzig
Martin Goez

DOI

10.1039/c7pp00311k

eISSN

1474-9092

Externe Identifier

PubMed Identifier: 28926067

Open access

false

ISSN

1474-905X

Ausgabe der Veröffentlichung

11

Zeitschrift

Photochemical & photobiological sciences : Official journal of the European Photochemistry Association and the European Society for Photobiology

Sprache

eng

Medium

Print

Paginierung

1613 - 1622

Datum der Veröffentlichung

2017

Status

Published

Datum der Datenerfassung

2017

Titel

3-Aminoperylene and ascorbate in aqueous SDS, one green laser flash … and action! Sustainably detoxifying a recalcitrant chloro-organic.

Sub types

Journal Article

Ausgabe der Zeitschrift

16

Datenquelle: Europe PubMed Central

Abstract

The hydrated electron represents a "super-reductant" in water, providing 2.9 eV of reductive power, which suffices to decompose nonactivated aliphatic halides. We show that 3-amino-perylene in SDS micelles, when combined with the bioavailable ascorbate as an extramicellar sacrificial donor, sustainably produces hydrated electrons through photoredox catalysis with green light, from a metal-free system, and at near-physiological pH. Photoionization of the amine with a 532 nm laser yields an extremely long-lived radical cation as the by-product, and a subsequent reaction of the latter with the sacrificial donor across the micelle/water interface regenerates the catalyst. The regeneration step involves parallel reactions between differently protonated forms, causing a bell-shaped pH dependence in basic medium. We have separated these processes kinetically. Employing this catalytic cycle for the laboratory-scale decomposition of chloroacetate, an accepted model compound for toxic and persistent halo-organic waste, gave turnover numbers of about 170. Even though both the substrate and the sacrificial donor compete for the hydrated electron, their consumption ratio is practically independent of the initial concentration ratio because the formal radical anion of the ascorbate undergoes secondary scavenging by the chloroacetate. In the course of the reaction, the initial hydrophobic catalyst is converted into a secondary species that is hydrophilic and still exhibits catalytic activity.

Autoren

Tim Kohlmann
Robert Naumann
Christoph Kerzig
Martin Goez

Autoren-URL

https://www.ncbi.nlm.nih.gov/pubmed/28926067

DOI

10.1039/c7pp00311k

eISSN

1474-9092

Ausgabe der Veröffentlichung

11

Zeitschrift

Photochem Photobiol Sci

Sprache

eng

Country

England

Paginierung

1613 - 1622

Datum der Veröffentlichung

2017

Status

Published

Datum, an dem der Datensatz öffentlich gemacht wurde

2018

Titel

3-Aminoperylene and ascorbate in aqueous SDS, one green laser flash … and action! Sustainably detoxifying a recalcitrant chloro-organic.

Sub types

Journal Article

Ausgabe der Zeitschrift

16

Datenquelle: PubMed

3-Aminoperylene and ascorbate in aqueous SDS, one green laser flash ... and action! Sustainably detoxifying a recalcitrant chloro-organic

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