Valorisation de l'écorce de Picea mariana par la production d'extraits naturels : les extraits aqueux et l'huile essentielle

L’épinette noire Picea mariana est une essence abondamment exploitée au Québec pour la qualité de son bois de charpente. Sa transformation par les scieries génère, en conséquence, d’énormes volumes d’écorces résiduelles. Dans un objectif de transformation de la ressource et de conception de produits et systèmes innovants, ce projet de doctorat a permis de développer un procédé de conversion de la biomasse forestière pour la valorisation complète de l’écorce de l’épinette noire, en utilisant des solvants respectueux de l’environnement. Ce procédé intègre deux types d’extractions différentes : l’hydrodistillation et l’extraction à l’eau chaude. Ainsi il produit simultanément trois extraits naturels, l’huile essentielle et l’hydrolat capturant la fragrance de l’épinette et l’extrait aqueux brut riche en polyphénols antioxydants. L’élucidation de la composition chimique de l’huile essentielle et de l’hydrolat d’écorce de l’épinette noire a mis en évidence plus de cinquante composés volatils et aromatiques appartenant à la famille des terpénoïdes. De plus, la fragrance de l’huile essentielle est très différente de celle produite industriellement à partir des aiguilles. Elle pourrait ainsi constituer un nouveau produit pour les secteurs de la parfumerie et des arômes. L’extrait brut aqueux, quant à lui, est riche en polyphénols antioxydants, en tanins et en sucres. Les composés phénoliques de faibles masses moléculaires appartiennent majoritairement à la famille des stilbènes dont les trans-isorhapontine, trans-resvératrol, trans-picéide et transastringine. Deux nouvelles molécules ont également été découvertes dans cet extrait : deux stéréoisomères de stilbènes, appelés picéasides O et P. Dans le but de récupérer ces molécules d’intérêt en plus grande quantité, une optimisation de l’extraction aqueuse a été réalisée pour établir les meilleurs paramètres d’extraction. La température 80 °C et le ratio écorce/eau 50 mg/mL ont été déterminés comme étant les paramètres les plus efficaces pour enrichir l’extrait aqueux en polyphénols d’intérêt, grâce à une approche statistique impliquant la chimiométrie. Ainsi, trois produits à haute valeur ajoutée sont disponibles à partir de l’écorce de l’épinette noire. Mais le plus pertinent au niveau industriel, c’est qu’ils peuvent être extraits simultanément via le procédé intégré dont le développement a permis de valider les rendements et les compositions chimiques tout en garantissant la disponibilité des écorces résiduelles pour la combustion. Ce projet de doctorat permet d’offrir une solution de gestion efficace des coproduits de transformation du bois par le biais d’un procédé vert produisant trois produits naturels à haute valeur ajoutée. Les extraits riches en polyphénols constitueraient de nouveaux ingrédients naturels potentiels pour les secteurs cosmétiques et de santé nutrition, en tant qu’actifs pour la peau ou compléments alimentaires antioxydants. De plus, les molécules d’intérêt thérapeutique comme le resvératrol et ses dérivés identifiés dans l’extrait aqueux seraient de bons candidats pour l’industrie pharmaceutique. Enfin, l’huile essentielle et l’hydrolat pourraient enrichir la palette du parfumeur ou être employés en tant qu’arômes.The transformation of black spruce Picea mariana, abundantly operated for the quality of its lumber in Quebec, generates huge volumes of residual bark in sawmills. With the objective of transforming the resource and designing innovative products and systems, this doctoral project has developed a process for converting forest biomass through the complete conversion of black spruce bark, using eco-friendly solvents. This process incorporating two different types of extractions (hydrodistillation and hot water extraction) simultaneously produces three natural extracts, the essential oil and hydrosol capturing the fragrance of black spruce and the hot water extract enriched with antioxidant polyphenols. The elucidation of the chemical composition of black spruce bark essential oil and hydrosol has revealed more than fifty volatile and aromatic compounds belonging to the terpenoid family. In addition, the fragrance of the essential oil is very different from the one produced industrially from the needles. It could thus constitute a new product for the perfume and aroma sectors. The aqueous crude extract, on the other hand, is rich in antioxidant polyphenols, tannins and sugars. Phenolic compounds of low molecular weight mainly belong to the stilbene family, including trans-isorhapontin, trans-resveratrol, trans-piceide and trans-astringin. Two new molecules have also been discovered in this extract: two stereoisomers of stilbene, called piceasides O and P. In order to optimally recover these molecules of interest, an optimization of the hot water extraction has made it possible to highlight the best extraction parameters. Thanks to a statistical approach involving chemometrics, the temperature 80 °C and the bark/water ratio 50 mg/mL were determined to be the most effective parameters for enriching the aqueous extract with polyphenols of interest. Thus, three high value-added products are extractable from the bark of black spruce. But the most interesting at an industrial level is that they can be extracted simultaneously via the integrated process whose development has validated the yields and chemical compositions while ensuring the availability of residual bark for combustion. This doctoral project offers a solution for an efficient management of co-products of wood processing through a green process, producing three natural products with high added value. The cosmetic and health nutrition sectors, constantly in search of new natural ingredients, may be interested in marketing these extracts as skin actives or as antioxidant dietary supplements. Molecules of therapeutic interest such as resveratrol and its derivatives identified in the aqueous extract could also be used by the pharmaceutical industry. Essential oil and hydrosol could enrich the perfumer's palette or be used as aromas

Chemical Composition of Essential Oil and Hydrosol from Picea mariana Bark Residue

For the first time, the essential oil of Black spruce (Picea mariana) bark residue was obtained using two types of hydrodistillations: steam distillation (SD) and water distillation (WD). Both gave similar yields and compositions as analyzed using gas chromatography and mass spectrometry. The essential oil composition is turpentine-like with the predominance of α-pinene (40.6% SD; 40.5% WD) and β-pinene (33.9% SD; 25.9% WD), followed by hydrocarbon monoterpenes β-phellandrene (4.8% SD; 3.6% WD), 3-carene (4.1% SD; 3.1% WD), and limonene (4.0% SD; 3.7% WD). Hydrosol’s composition is rich in oxygenated compounds with α-terpineol (29.3% SD; 33.5% WD), trans-pinocarveol (5.2% SD; 3.7% WD), terpinen-4-ol (5.0% SD; 5.8% WD), verbenone (4.9% SD; 5.4% WD), borneol (4.9% SD; 3.9% WD), and pinocarvone (4.6% SD; 4.3% WD). These black spruce bark essential oils differ in composition from those from needles, which are commercially available and rich in bornyl acetate

Optimization of Bioactive Polyphenols Extraction from Picea Mariana Bark

Reported for its antioxidant, anti-inflammatory and non-toxicity properties, the hot water extract of Picea mariana bark was demonstrated to contain highly valuable bioactive polyphenols. In order to improve the recovery of these molecules, an optimization of the extraction was performed using water. Several extraction parameters were tested and extracts obtained analyzed both in terms of relative amounts of different phytochemical families and of individual molecules concentrations. As a result, low temperature (80 °C) and low ratio of bark/water (50 mg/mL) were determined to be the best parameters for an efficient polyphenol extraction and that especially for low molecular mass polyphenols. These were identified as stilbene monomers and derivatives, mainly stilbene glucoside isorhapontin (up to 12.0% of the dry extract), astringin (up to 4.6%), resveratrol (up to 0.3%), isorhapontigenin (up to 3.7%) and resveratrol glucoside piceid (up to 3.1%) which is here reported for the first time for Picea mariana. New stilbene derivatives, piceasides O and P were also characterized herein as new isorhapontin dimers. This study provides novel information about the optimal extraction of polyphenols from black spruce bark, especially for highly bioactive stilbenes including the trans-resveratrol

Structure elucidation of the new citharoxazole from the Mediterranean deep-sea sponge Latrunculia (Biannulata) citharistae

Citharoxazole (1), a new batzelline derivative featuring a benzoxazole moiety, was isolated from the Mediterranean deep-sea sponge Latrunculia (Biannulata) citharistae Vacelet, 1969, together with the known batzelline C (2). This is the first chemical study of a Mediterranean Latrunculia species and the benzoxazole moiety is unprecedented for this family of marine natural products. The structure was mainly elucidated by the interpretation of NMR spectra and especially HMBC correlations

The Polysaccharidic Nature of the Skeleton of Marennine as Determined by NMR Spectroscopy

The water-soluble blue–green pigment marennine, produced and partly excreted by the diatom Haslea ostrearia, and known for a long time for its role in the greening of oysters, was isolated from the culture medium, purified, and analyzed by Nuclear Magnetic Resonance (NMR) in order to gain insight into its chemical structure. The spectra show mainly carbohydrates of a complex composition, apparently highly branched, and with a mass in the order of 10 kDa. There are, in addition, some signals of aliphatic and, much weaker, aromatic groups that present aglycons. The latter might be responsible for the color. These carbohydrates are always associated with the blue–green color and cannot be separated from it by most treatments; they are interpreted as constituting the frame of the pigment. NMR after hydrolysis identifies the most abundant monosaccharides in marennine as galactose, xylose, mannose, rhamnose, and fucose

What Was Old Is New Again: The Pennate Diatom Haslea ostrearia (Gaillon) Simonsen in the Multi-Omic Age

The marine pennate diatom Haslea ostrearia has long been known for its characteristic blue pigment marennine, which is responsible for the greening of invertebrate gills, a natural phenomenon of great importance for the oyster industry. For two centuries, this taxon was considered unique; however, the recent description of a new blue Haslea species revealed unsuspected biodiversity. Marennine-like pigments are natural blue dyes that display various biological activities—e.g., an-tibacterial, antioxidant and antiproliferative—with a great potential for applications in the food, feed, cosmetic and health industries. Regarding fundamental prospects, researchers use model organisms as standards to study cellular and physiological processes in other organisms, and there is a growing and crucial need for more, new and unconventional model organisms to better correspond to the diversity of the tree of life. The present work, thus, advocates for establishing H. ostrearia as a new model organism by presenting its pros and cons—i.e., the interesting aspects of this peculiar diatom (representative of benthic-epiphytic phytoplankton, with original behavior and chemodiversity, controlled sexual reproduction, fundamental and applied-oriented importance, reference genome, and transcriptome will soon be available); it will also present the difficulties encountered before this becomes a reality as it is for other diatom models (the genetics of the species in its infancy, the transformation feasibility to be explored, the routine methods needed to cryopreserve strains of interest). © 2022 by the authors. Licensee MDPI, Basel, Switzerland