Résumé
p- Hydroxycinnamic acids, such as sinapic, ferulic, p -coumaric and caffeic acids, are among the most abundant phenolic compounds found in plant biomass and agro-industrial by-products (e.g. cereal brans, sugar-beet and coffee pulps, oilseed meals). These p- hydroxycinnamic acids, and their resulting decarboxylation products named vinylphenols (canolol, 4-vinylguaiacol, 4-vinylphenol, 4-vinylcatechol), are bioactive molecules with many properties including antioxidant, anti-inflammatory and antimicrobial activities, and potential applications in food, cosmetic or pharmaceutical industries. They were also shown to be suitable precursors of new sustainable polymers and biobased substitutes for fine chemicals such as bisphenol A diglycidyl ethers. Non-oxidative microbial decarboxylation of p -hydroxycinnamic acids into vinylphenols involves cofactor-free and metal-independent phenolic acid decarboxylases (EC 4.1.1 carboxyl lyase family). Historically purified from bacteria ( Bacillus, Lactobacillus , Pseudomonas , Enterobacter genera) and some yeasts (e.g. Brettanomyces or Candida ), these enzymes were described for the decarboxylation of ferulic and p -coumaric acids into 4-vinylguaiacol and 4-vinylphenol, respectively. The catalytic mechanism comprised a first step involving p -hydroxycinnamic acid conversion into a semi-quinone that then decarboxylated spontaneously into the corresponding vinyl compound, in a second step. Bioconversion processes for synthesizing 4-vinylguaiacol and 4-vinylphenol by microbial decarboxylation of ferulic and p -coumaric acids historically attracted the most research using bacterial recombinant phenolic acid decarboxylases (especially Bacillus enzymes) and the processes developed to date included mono- or biphasic systems, and the use of free- or immobilized cells. More recently, filamentous fungi of the Neolentinus lepideus species were shown to natively produce a more versatile phenolic acid decarboxylase with high activity on sinapic acid in addition to the others p-hydroxycinnamic acids, opening the way to the production of canolol by biotechnological processes applied to rapeseed meal. Few studies have described the further microbial/enzymatic bioconversion of these vinylphenols into valuable compounds: (i) synthesis of flavours such as vanillin, 4-ethylguaiacol and 4-ethylphenol from 4-vinylguaiacol and 4-vinylphenol, (ii) laccase-mediated polymer synthesis from canolol, 4-vinylguaiacol and 4-vinylphenol.