Photoinduced Cross-Linking of Dynamic Poly(disulfide) Films via Thiol Oxidative Coupling.
Fiche publication
Date publication
janvier 2016
Journal
Macromolecular rapid communications
Auteurs
Membres identifiés du Cancéropôle Est :
Pr ALLONAS Xavier
Tous les auteurs :
Feillée N, Chemtob A, Ley C, Croutxé-Barghorn C, Allonas X, Ponche A, Le Nouen D, Majjad H, Jacomine L
Lien Pubmed
Résumé
Initially developed as an elastomer with an excellent record of barrier and chemical resistance properties, poly(disulfide) has experienced a revival linked to the dynamic nature of the S-S covalent bond. A novel photobase-catalyzed oxidative polymerization of multifunctional thiols to poly(disulfide) network is reported. Based solely on air oxidation, the single-step process is triggered by the photodecarboxylation of a xanthone acetic acid liberating a strong bicyclic guanidine base. Starting with a 1 μm thick film based on trithiol poly(ethylene oxide) oligomer, the UV-mediated oxidation of thiols to disulfides occurs in a matter of minutes both selectively, i.e., without overoxidation, and quantitatively as assessed by a range of spectroscopic techniques. Thiolate formation and film thickness determine the reaction rates and yield. Spatial control of the photopolymerization serves to generate robust micropatterns, while the reductive cleavage of S-S bridges allows the recycling of 40% of the initial thiol groups.
Mots clés
Catalysis, Disulfides, chemistry, Guanidines, chemistry, Light, Magnetic Resonance Spectroscopy, Oxidative Coupling, Photochemical Processes, Polyethylene Glycols, chemistry, Polymerization, Sulfhydryl Compounds, chemistry, Xanthones, chemistry
Référence
Macromol Rapid Commun. 2016 Jan;37(2):155-60