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Synthesis of new surfactants from renewable resources thanks to biocatalysts – Bioactive molecules with a high value added
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HIGHER EDUCATION INSTITUTE CONDORCET
PROVINCE OF HAINAUT (Be)
PhD Benoît Moreau Teacher-Researcher Benoit.moreau@condorcet.be
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, Belgium and Cuba
- First HE 09-2017 to 09-2019 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
Synthesis of new surfactants from renewable resources thanks to biocatalysts – Bioactive molecules with a high value added
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 – Bioactive molecules with a high value added
The surfactants are classified according to the nature of the polar head:
Synthesis of new surfactants from renewable resources thanks to biocatalysts – Bioactive molecules with a high value added
Surfactants are molecules which have different properties: wetting, solubilizing, detergent or emulsifying.
Synthesis of new surfactants from renewable resources thanks to biocatalysts – Bioactive molecules with a high value added
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 – Bioactive molecules with a high value added
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 – Bioactive molecules with a high value added
The surfactants are used mainly in:
- Detergents (dishwashing and maintenance products, detergents ...) - Cosmetics
Synthesis of new surfactants from renewable resources thanks to biocatalysts – Bioactive molecules with a high value added
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 – Bioactive molecules with a high value added
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 – Bioactive molecules with a high value added
How to integrate the synthesis of surfactants with the principles of the Green Chemistry? -
Synthesis of new surfactants from renewable resources thanks to biocatalysts – Bioactive molecules with a high value added
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 – Bioactive molecules with a high value added
- The economics of atoms - The use of catalytic processes such as biocatalytic process
Synthesis of new surfactants from renewable resources thanks to biocatalysts – Bioactive molecules with a high value added
- The design of products for final degradation under natural conditions
Synthesis of new surfactants from renewable resources thanks to biocatalysts – Bioactive molecules with a high value added
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 – Bioactive molecules with a high value added
Finally, oligopeptides and amino acids derived from wheat or corn gluten can be used.
Synthesis of new surfactants from renewable resources thanks to biocatalysts – Bioactive molecules with a high value added
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 – Bioactive molecules with a high value added
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 – Bioactive molecules with a high value added
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., 2005a,b).
Synthesis of new surfactants from renewable resources thanks to biocatalysts – Bioactive molecules with a high value added
Sugar Fatty Acid Esters
The challenge to synthesize sugar-fatty acid ester enzymatically is :
- to choose the right three-dimensional structure of the catalytic site of the lipase.
- to find good solvent(s) to solubilize the substrates that have different polarities, at the meantime, not deactivating enzymes.
- to optimize the synthesis of glucose esters with respect to substrate ratio and fatty acid types.
Synthesis of new surfactants from renewable resources thanks to biocatalysts – Bioactive molecules with a high value added
Sugar Fatty Acid Esters – three dimensional structure (Pleiss et al., 1998)
Synthesis of new surfactants from renewable resources thanks to biocatalysts – Bioactive molecules with a high value added
Sugar Fatty Acid Esters - solvent
A nonaqueous solvent is essential for lipase catalyzed synthesis of sugar fatty acid esters.
A suitable solvent must be able to dissolve sufficient amounts of both the substrates, i.e. the sugar and the fatty acid.
In addition, the solvent must not adversely affect the stability of the enzyme and its activity.
Synthesis of new surfactants from renewable resources thanks to biocatalysts – Bioactive molecules with a high value added
Sugar Fatty Acid Esters - solvent
Hazardous solvents such as pyridine, dimethyl formamide (DMF) and dimethylpyrolidone (DMP) were commonly used. Environmental and health risks of these solvents have driven the search for other suitable reaction solvents.
For example, Yan (1999) achieved reasonably good conversion yields in production of glucose caprylate in ethyl methyl ketone (66%) and acetone (90%).
During my thesis, I also achieved similar results using as solvent Tert-Butanol (68%).
Synthesis of new surfactants from renewable resources thanks to biocatalysts – Bioactive molecules with a high value added
Sugar Fatty Acid Esters - solvent
In summary, solvents with « high » log P values generally dedicate enzymes of highest activities and stabilities.
Synthesis of new surfactants from renewable resources thanks to biocatalysts – Bioactive molecules with a high value added
Sugar Fatty Acid Esters – Ratio Gluc/FA (Ren & Lamsal, 2016)
Palmitic acid Lauric acid
Synthesis of new surfactants from renewable resources thanks to biocatalysts – Bioactive molecules with a high value added
Sugar Fatty Acid Esters – Ration Gluc/FA (Moreau et al., 2005)
Synthesis of new surfactants from renewable resources thanks to biocatalysts – Bioactive molecules with a high value added
Sugar Fatty Acid Esters
To date, a considerable amount of researches have been reported about lipase synthesis for sugar esters of fatty acid.
Among these products, fructose esters exhibit interesting surface properties and higher interfacial tension values compared to commercial sugar esters.
Synthesis of new surfactants from renewable resources thanks to biocatalysts – Bioactive molecules with a high value added
Sugar Fatty Acid Esters (Li et al., 2014)
Synthesis of new surfactants from renewable resources thanks to biocatalysts – Bioactive molecules with a high value added
Sugar Fatty Acid Esters
Most researches focused on total ester yield and acylation of the specific hydroxyl site of sugar, but only limited data are available with regard to DE, in particular, influences of solvent medium and enzyme characteristics on this point.
The study of Li et al. (2014) demonstrated that the conformation of CALB binding mono-ester was affected by organic solvents essentially determined DE.
Synthesis of new surfactants from renewable resources thanks to biocatalysts – Bioactive molecules with a high value added
Sugar Fatty Acid Esters More, fructose esters or sucrose esters exhibit antibacterial properties lead to the potential use in food additives (Ferrer et al., 2005). The study of Zhao et al. (2015) also showed that sucrose monocaprate significantly inhibit the growth of tested bacteria. The permeability of the cell membrane and intracellular proteins were both changed by sucrose monocaprate according to cell constituents’ leakage.
Synthesis of new surfactants from renewable resources thanks to biocatalysts – Bioactive molecules with a high value added
Sugar Fatty Acid Esters
Synthesis of new surfactants from renewable resources thanks to biocatalysts – Bioactive molecules with a high value added
Sugar Fatty Acid Esters
Another alternative is the synthesis of fatty alcohol glucuronate which is still undeveloped (Moreau et al., 2005; Bleker et al., 2008).
This synthesis is currently the subject of a research program within the research lab (DGO6).
Synthesis of new surfactants from renewable resources thanks to biocatalysts – Bioactive molecules with a high value added
Sugar Fatty Acid Esters Valorisation of cheese whey into gluconic acids by fermentation and these acids will be the synthon molecules for the synthesis of new set of surfactants (Wagralim Project under development)
Figure from Alonso
et al; 2015
Synthesis of new surfactants from renewable resources thanks to biocatalysts – Bioactive molecules with a high value added
The sugar esters are produced by esterification with a sugar (sucrose, glucose) and a fatty acid.
Sugar-free and color-free, sugar esters are used in the field of food and cosmetics.
Sugar esters are nonionic type emulsifiers, mono sucrose is used for the stabilization of O / W emulsion (dairy products).
Some sugar esters exhibit antimicrobial properties, bacteriostatic.
Synthesis of new surfactants from renewable resources thanks to biocatalysts – Bioactive molecules with a high value added
Synthesis of new surfactants from renewable resources thanks to biocatalysts – Bioactive molecules with a high value added
Amino-acid-based surfactants constitute a novel class of surfactants produced from renewable raw materials and can be seen as an alternative to conventional surfactants (Perinelli et al., 2016; Pinazo et al., 2010). This research project of synthesis (Path 1 & 3) using lipases was deposited in September 2017 in collaboration with the UCL and the CRA of Gembloux
Synthesis of new surfactants from renewable resources thanks to biocatalysts – Bioactive molecules with a high value added
Nowadays, synthetic cationic amino acid-based surfactants are being explored as promising alternatives to conventional antimicrobial agents as shown in the studies of Pinazo et al. (2016) and Perez et al. (2009) where the family of lysine surfactants exhibited a wide spectrum of antimicrobial activity against Gram-positive and Gram-negative bacteria.
Synthesis of new surfactants from renewable resources thanks to biocatalysts – Bioactive molecules with a high value added
Future of surfactants:
The surfactants, which are renewable, enjoy a very good image (low toxicity and ecotoxicity),
A higher biodegradability than petrochemical surfactants, and less aggressiveness on the skin. . .), which suggests that their penetration rate should increase in future years.
They are now positioned on niche applications and have high added value.
Synthesis of new surfactants from renewable resources thanks to biocatalysts – Bioactive molecules with a high value added
Future of surfactants:
new sources of original synthons through the development of new crops (eg cuphea oil with short chain fatty acids, erucian rapeseed, algae).
Synthesis of new surfactants from renewable resources thanks to biocatalysts – Bioactive molecules with a high value added
Thank you for your attention and I am available now to answer your question
@ : benoit.moreau@condorcet.be
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