Article Dans Une Revue European Polymer Journal Année : 2025

Polyoxometalate-derived porphyrins as promising visible light photo-initiating systems for antibacterial applications

Anne Dolbecq
Olivier Oms

Résumé

Two hybrid photosensitizers composed of a porphyrin unit covalently linked to one (POM1) or two (POM2) [Mo6O19]2− polyoxometalates (POMs) have been synthesized. These compounds exhibit strong absorption in the visible range and were fully characterized via NMR, ESI-MS and UV–vis spectroscopy, fluorescence, electrochemistry, and DFT calculations. Their efficiency as photosensitizers for the free-radical polymerization (FRP) of acrylated soybean oil (SOA) was evaluated in combination with co-initiators (iodonium salt (Iod) and/or N-methyldiethanolamine (MDEA)). Despite the low fluorescence and triplet quantum yields of POM1 and POM2 (Φfluo (POM1) = 0.007, Φfluo (POM2) = 0.004, ΦT (POM1) = 0.23, ΦT (POM2) = 0.19), we demonstrate that photopolymerization occurs via photoinduced electron transfer reaction and H-abstraction process. Kinetic studies by RT-FTIR confirmed excellent reactivity under LED@405 and 455 nm irradiations, with final acrylate conversions (FCs) reaching up to 98 % in laminate. Notably, FCs of SOA with the three-components systems POM1/Iod/MDEA and POM2/Iod/MDEA reach 93 % and 98 % respectively under LED@405 nm, and 85 % and 86 % under LED@455 nm. EPR spin trapping and laser flash photolysis experiments revealed the formation of phenyl and aminoalkyl radicals, supporting a photo-oxidative initiation mechanism. The resulting materials displayed improved mechanical performance and thermal stability. Also, and due to efficient singlet oxygen (1O2) production under visible light, both POM-based materials highlighted full photobactericidal activity against Staphylococcus aureus, demonstrating thus their potential in light-activated antibacterial coatings.

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Dates et versions

hal-05344134 , version 1 (03-11-2025)

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Hassan Hayek, Mouhieddinne Guergueb, Fares Mouhoubi, Sonia Lajnef, Fabienne Peyrot, et al.. Polyoxometalate-derived porphyrins as promising visible light photo-initiating systems for antibacterial applications. European Polymer Journal, 2025, 240, pp.114316. ⟨10.1016/j.eurpolymj.2025.114316⟩. ⟨hal-05344134⟩
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