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Synthesis of new surfactants from renewable resources thanks to biocatalysts Sherbrooke 19 octobre 2017 PhD Benoît Moreau HIGHER EDUCATION INSTITUTE CONDORCET PROVINCE OF HAINAUT (Be) PhD Benoît Moreau Teacher-Researcher [email protected] Geographical and administrative information Map of the 5 Provinces in the Walloon Region - Hainaut (Ath) - Walloon Brabant - Namur - Liège - Luxembourg Hainaut Province : - 3.786 km² - 1,3 million inhabitants EDUCATION CENTER IN HAINAUT HEPH-Condorcet is part of a network of 37 educational institutions spread all over the Hainaut Province This educational network (Pole Hainuyer) consists of : • Universities, • Higher Education Institutes, • Higher schools of Arts, • Social Advancement Courses (second-chance education) The specificity of Higher Education Institutes is to be dispersed in the territory (proximity to population) and in contact with companies and applied laboratories (work experience for students) COURSES AT HEPH- Condorcet HEPH- Condorcet offers courses for more than 8.000 students every year in fields of : - paramedical, - agronomy, - pedagogy, - technical, - economics, - social, - applied arts Over 50 different certificates (Bachelors, Masters, Specialisations) HEPH-Condorcet (Provincial High School of the Hainaut Province) A HIGHER EDUCATION INSTITUTE Agronomy (488) HEPH-Condorcet : key figures Applied Arts (132) Economy (1946) Paramedical (3848) 7 Teaching categories Pedagogical (1435) Social (509) 7 Geographic locations Technical (647) (students in 2017) 50 Degrees 9005 Students 900 Staff members Researches inside the HEPH_Condorcet and Connections with Research Centres : • Between 10 - 20 TEACHER-RESEARCHERS 1 Department of Agronomy grouping the Units of: - « Green Chemistry and Biobased Products » PhD B. Moreau - « Applied Vegetable Ecophysiology » PhD M. Gosselin - « In Vitro Culture and Synthetic Biology » PhD N. Desoignies - « Biotechnology – Molecular Biology » PhD D. Lanterbeck Researches inside the HEPH_Condorcet : The Research unit of « Green Chemistry and Biobased Products » PhD B. Moreau and Ig D. Depauw This unit of research is mainly focused on the production of molecules with a high added value from either food waste or industrial co-products. Ongoing projects: - ARES 2017-2022: « Production and Immobization of recombinant Dextransucrases using Residual of Sugarcane AgroIndustry ». International projet with France (SupAgro Montpellier), Belgium (HELDB, HENALLUX et HEPH) and Cuba (ICIDCA et University of Havana) - First HE 10-2017 to 10-2019 Synthesis, purification and characterization of new set of glucuronate esters using biocatalysts (industrial partner: TensioFix) Researches inside the HEPH_Condorcet The Research unit of « Green Chemistry and Biobased Products » PhD B. Moreau Collaboration: - Belgium: Institut Meurice R&D, Henallux, UCL, Gembloux Agro BioTech (Ulg). : TensioFix, Brasserie des Carrières, REALCO, Galactic… - France: Université de Bourgogne (Dijon), SupAgro (Montpellier), AgroParisTech - Cuba: ICIDCA, University of Havana - Brésil: Senai, INT, UFRJ - Canada: Synthesis of new surfactants from renewable resources thanks to biocatalysts The main function of surfactants is to reduce surface and interface tensions between hydrophobic substances (oil, hydrocarbons and sterols) and hydrophilic water molecules (Desai and Banat, 1997). Synthesis of new surfactants from renewable resources thanks to biocatalysts Figure: The relationship between biosurfactant concentration, surface tension and formation of micelles (Pacwa- Plociniczak et al., 2011). Synthesis of new surfactants from renewable resources thanks to biocatalysts A theory of micellar structure, based upon the geometry of various micellar shapes and the space occupied by the hydrophilic and hydrophobic groups of the surfactant molecules, has been developed by Israelachvili, Mitchell, and Ninham (1976, 1977) and Mitchell and Ninham (1981). Synthesis of new surfactants from renewable resources thanks to biocatalysts The surfactants are classified according to the nature of the polar head: Synthesis of new surfactants from renewable resources thanks to biocatalysts Surfactants are molecules which have different properties: wetting, solubilizing, detergent or emulsifying. Synthesis of new surfactants from renewable resources thanks to biocatalysts The surfactants can be classified according to their HLB (hydrophilic / lipophilic balance) as summarized in Table Synthesis of new surfactants from renewable resources thanks to biocatalysts The current market for surfactants affects many industrial sectors such as detergents, food, agronomy, cosmetology and pharmacy. According to Professor Marchant (Functional Foods Conference at Kalamata (Gr) July 2016), the market for surfactants in 2015 was 13 million tonnes worldwide, including 2.5 million tonnes in Europe. According to various sources (Global Market Insights, 2016, Grand View Research, 2016, Surfactant Market, 2015), the growth of this surfactant market at the dawn of 2020 would be more than 4%. Synthesis of new surfactants from renewable resources thanks to biocatalysts The surfactants are used mainly in: - Detergents (dishwashing and maintenance products, detergents ...) - Cosmetics Synthesis of new surfactants from renewable resources thanks to biocatalysts But also in the: - the treatment of leather (preparation of the skin with tanning), - synthesis and formulation of plastics, cleaning and degreasing of materials, - the formulation of the paints (stabilization of the formulations, wetting of the pigments, etc.) - Operations in the petroleum industry, - the formulation of phytosanitary products and fertilizers (granulation, suspension of phytosanitary agents), - textile processing (sizing, fiber lubrication, washing and dyeing). Synthesis of new surfactants from renewable resources thanks to biocatalysts However, the production of these surfactants is still essentially dependent on the oil market (+/- 70%); since it is carried out by chemical synthesis of the surfactants. This chemical synthesis involves the use of acids, organic solvents and the use of organic or inorganic catalysts which can generate serious toxicity for the people who produce them. In addition, these reactions occur frequently at high temperatures (Van Den Broek & Boeriu, 2013). In a worrying environmental context, these production criteria must find alternative solutions. Synthesis of new surfactants from renewable resources thanks to biocatalysts How to integrate the synthesis of surfactants with the principles of the Green Chemistry? - Synthesis of new surfactants from renewable resources thanks to biocatalysts How to integrate the synthesis of surfactants with the principles of the Green Chemistry? - The use of renewable feedstocks instead of fossil products. So it's time to find other sources of carbon. In particular, renewable carbon from agricultural sources is believed, whether it is agricultural raw materials or their by- products. Synthesis of new surfactants from renewable resources thanks to biocatalysts - The economics of atoms - The use of catalytic processes such as biocatalytic process Synthesis of new surfactants from renewable resources thanks to biocatalysts - The design of products for final degradation under natural conditions Synthesis of new surfactants from renewable resources thanks to biocatalysts The polar head of the surfactants consists of a carbohydrate or a protein. It may be derived from co-products of the starch industry or from sugars: glucose, fructose, galactose, sucrose. It may also be lactose, polyols (sorbitol and xylitol), pentoses (xylose and arabinose), glycerol. It may also be organic acid such as lactic acid Synthesis of new surfactants from renewable resources thanks to biocatalysts Finally, oligopeptides and amino acids derived from wheat or corn gluten can be used. Synthesis of new surfactants from renewable resources thanks to biocatalysts The lipophilic chain of the surfactants is essentially derived from vegetable oils obtained by trituration of the seeds of oleaginous plants: coconut oil, palm oil. The major fatty acids are lauric (C12), myristic (C14), palmitic (C16), stearic (C18), oleic (C18: 1), linoleic (C18: 2) and linolenic (C18: 3) acids. Synthesis of new surfactants from renewable resources thanks to biocatalysts Sugar Fatty Acid Esters Sugar fatty acid esters (SFAEs) are nonionic surfactants, which contain one or more saccharide rings, for example sucrose, linked to one or multiple hydrophobic fatty acid chains. Synthesis of new surfactants from renewable resources thanks to biocatalysts Sugar Fatty Acid Esters • Sugar esters with low HLB values (HLB:3-6) are good water-in-oil emulsifier, with medium HLB values (7-9) are good wetting agent, and with high HLB values (10-16) are appropriate emulsifier for oil-in-water emulsion. Synthesis of new surfactants from renewable resources thanks to biocatalysts – Bioactive molecules with a high value added Sugar Fatty Acid Esters Moreover, their tasteless, odorless, nontoxic, and biodegradable features make them excellent biocompatible food emulsifiers (Ducret et al.,1995). In addition, since they are not irritating to the skin or eyes, SFAEs are extensively used in skin-care products to generate deodorant and eyelash, among other cosmetics (Khan & Rathod, 2015). Furthermore, the antimicrobial properties of SFAEs have demonstrated their relevance for the pharmaceutical industry (Ferrer et al., 2005 a,b). Synthesis of new surfactants from renewable resources