Development of eco-participatory and new generation sun preparations : use of lignin as an SPF booster and production of a melanin substitute

Ce travail sur l’amélioration de la protection solaire suivant un concept éco-participatif propose 2 parties, (i) l’élaboration d’une formulation simple, (ii) la synthèse d’une mélanine de substitution. La formulation contient seulement 8 ingrédients, dont 2 filtres organiques sélectionnés sur leur photostabilité, caractéristiques physicochimiques, et l'absence d'impact (santé, écosystèmes), le BEMT et le DHHB. Une protection totale est atteinte par l’addition de lignine sulfatée (LiS), polymère largement disponible, non toxique, antiradicalaire et soluble dans l’eau. Des méthodologies expérimentales ont permis de minimiser les concentrations, débouchant sur 2 formules stables, SPF30 et SPF50, contenant respectivement 9 et 12% de filtres, et 5% de LiS chacune. De l'effet booster observé, des hypothèses sur les interactions LiS-filtres sont émises. La deuxième partie concerne la production de pyomélanine. Alors que les quantités produites par les microorganismes restent faibles, 3 procédés sont comparés: une autooxydation du HGA-Mn2+ (rendement 0,317 g/g de substrat), une culture induite d’Halomonas titanicae (0,55 g/L), et une polymérisation par une laccase (PyoENZ, 1,25 g/g). Les 3 structures ont été caractérisées par 13C RMN (CP-MAS) et FTIR, une réaction de décarboxylation biologique partielle conduit à la formation d'alcool gentisique et de gentisaldéhyde incorporés dans le polymère. PyoENZ est hyperthermostable, non (photo)cytotoxique, piège les ROS, réduit efficacement le Fe3+, et est proposée pour des applications.This work on the improvement of solar protection according to an eco-participatory concept proposes 2 parts, (i) the elaboration of a simple formulation, (ii) the synthesis of substitute melanin. The formulation contains only 8 ingredients, including 2 organic filters selected on their photostability, physicochemical characteristics, and absence of impact (health, ecosystems), BEMT and DHHB. Total protection is achieved by the addition of lignosulfonate (LiS), a widely available, non-toxic, anti-free radical, and a water-soluble polymer. Experimental design allowed to minimize the concentrations, resulting in 2 stable formula, SPF30 and SPF50, containing 9 and 12% filters respectively, and 5% LiS each. From the observed booster effect, hypotheses on LiS-filter interactions were proposed. The second part concerns the production of pyomelanin. While the quantities produced by the microorganisms remain low, 3 processes are compared: autooxidation of HGA-Mn2+ (yield 0.317 g/g substrate), an induced culture of Halomonas titanicae (0.55 g/L), and a method based on a laccase polymerization (PyoENZ, 1.25 g/g). The 3 structures had been characterized by 13C NMR (CP-MAS) and FTIR, a partial biological decarboxylation reaction was occurred and led to the formation of gentisic alcohol and gentisaldehyde which are incorporated in the polymer. PyoENZ is hyperthermostable, non-(photo)cytotoxic, traps ROS, effectively reduces Fe3+, and is proposed for applications

New insights and advances on pyomelanin production: from microbial synthesis to applications

International audiencePyomelanin is a brown-black phenolic polymer and results from the oxidation of homogentisic acid (HGA) in the L-tyrosine pathway. As part of the research for natural and active ingredients issued from realistic bioprocesses, this work re-evaluates the HGA pigment and makes an updated inventory of its syntheses, microbial pathways, and properties, with tracks and recent advances for its large-scale production. The mechanism of the HGA polymerization is also well documented. In alkaptonuria, pyomelanin formation leads to connective tissue damage and arthritis, most probably due to the ROS issued from HGA oxidation. While UV radiation on human melanin may generate degradation products, pyomelanin is not photodegradable, is hyperthermostable, and has other properties better than L-Dopa melanin. This review aims to raise awareness about the potential of this pigment for various applications, not only for skin coloring and protection but also for other cells, materials, and as a promising (semi)conductor for bioelectronics and energy

Production and properties of non-cytotoxic pyomelanin by laccase and comparison to bacterial and synthetic pigments

International audienceAbstract Pyomelanin is a polymer of homogentisic acid synthesized by microorganisms. This work aimed to develop a production process and evaluate the quality of the pigment. Three procedures have been elaborated and optimized, (1) an HGA-Mn 2+ chemical autoxidation (Pyo CHEM yield 0.317 g/g substrate), (2) an induced bacterial culture of Halomonas titanicae through the 4-hydroxyphenylacetic acid-1-hydroxylase route (Pyo BACT , 0.55 g/L), and (3) a process using a recombinant laccase extract with the highest level produced (Pyo ENZ , 1.25 g/g substrate) and all the criteria for a large-scale prototype. The chemical structures had been investigated by 13 C solid-state NMR (CP-MAS) and FTIR. C ar –C ar bindings predominated in the three polymers, C ar –O–C ar (ether) linkages being absent, proposing mainly C 3 -C 6 (α-bindings) and C 4 -C 6 (β-bindings) configurations. This work highlighted a biological decarboxylation by the laccase or bacterial oxidase(s), leading to the partly formation of gentisyl alcohol and gentisaldehyde that are integral parts of the polymer. By comparison, Pyo ENZ exhibited an M w of 5,400 Da, was hyperthermostable, non-cytotoxic even after irradiation, scavenged ROS induced by keratinocytes, and had a highly DPPH-antioxidant and Fe 3+ -reducing activity. As a representative pigment of living cells and an available standard, Pyo ENZ might also be useful for applications in extreme conditions and skin protection

AbstractSunscreen oil-in-water emulsions containing few ingredients and two EU-authorized organic filters had been developed in an eco-friendly approach. Based on their photostability, spectroscopic features, and the lack of data on toxicity, BEMT (UVA/B range; bis-ethylhexyloxyphenol methoxyphenyl triazine) and DHHB (UVA; diethylamino hydroxybenzoylhexyl benzoate) were selected and incorporated at minimal concentrations to reduce the risk of impact on human health and coastal marine ecosystems. Despite the inconclusive results previously reported, the use of the w-soluble and largely available Na-lignosulfonate (LiS) had been reconsidered with success. Since BEMT and DHHB alone or in combination were not able to higher the sun protection factor (SPF) value at 50, results showed that it becomes possible by supplementing with LiS at 5% (w/w), ensuring stability, antiradical property, and a non-toxicity of the sun emulsion. After defining the range doses for the three components, minimizing concentrations was achieved by experimental design studies using a response surface methodology in which SPF values before and after irradiation has been considered. Consequently, an SPF30 and SPF50 emulsions containing only 9 and 12% total filter respectively and 5% LiS each had been developed. This high boosting effect led to discussions on how LiS interacts, suggesting the involvement of J aggregation, the formation of LiS micelles that would partly encapsulate the o-soluble filters, and the mode of adsorption at the solid-liquid interface of the poly(methyl-methacrylate) plate or the skin.

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