Synthesis of new surfactants from renewable …...Synthesis of new surfactants from renewable...

Synthesis of new surfactants from renewable resources thanks to biocatalysts

Sherbrooke 19 octobre 2017PhD Benoît Moreau

HIGHER EDUCATION INSTITUTECONDORCET

PROVINCE OF HAINAUT (Be)

PhD Benoît Moreau [email protected]

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

Geographical and administrative information

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

HEPH-Condorcet : key figures

7

7

50

9005

900

Agronomy (488)

Applied Arts (132)

Economy (1946)

Paramedical (3848)

Pedagogical (1435)

Social (509)

Technical (647)

(students in 2017)

Teaching categories

Geographic locations

Degrees

Students

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 ahigh 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 ». Internationalprojet with France (SupAgro Montpellier), Belgium (HELDB, HENALLUX etHEPH) and Cuba (ICIDCA et University of Havana)

- First HE 10-2017 to 10-2019 Synthesis, purification and characterization ofnew 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. MoreauCollaboration:- 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:


The main function of surfactants is to reduce surface andinterface tensions between hydrophobic substances (oil,hydrocarbons and sterols) and hydrophilic water molecules (Desaiand Banat, 1997).


Figure: The relationship between biosurfactant concentration, surface tension and formationof micelles (Pacwa- Plociniczak et al., 2011).


A theory of micellar structure, based upon the geometry of various micellarshapes and the space occupied by the hydrophilic and hydrophobic groups ofthe surfactant molecules, has been developed by Israelachvili, Mitchell, andNinham (1976, 1977) and Mitchell and Ninham (1981).


The surfactants are classified according to the nature of the polar head:


Surfactants are molecules which have different properties: wetting, solubilizing, detergent or emulsifying.


The surfactants can be classified according to their HLB(hydrophilic / lipophilic balance) as summarized in Table


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%.


The surfactants are used mainly in:

- Detergents (dishwashing and maintenance products, detergents ...)- Cosmetics


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).


However, the production of these surfactants is stillessentially dependent on the oil market (+/- 70%); since it iscarried out by chemical synthesis of the surfactants.

This chemical synthesis involves the use of acids, organicsolvents and the use of organic or inorganic catalysts which cangenerate serious toxicity for the people who produce them.

In addition, these reactions occur frequently at hightemperatures (Van Den Broek & Boeriu, 2013). In a worryingenvironmental context, these production criteria must findalternative solutions.


How to integrate the synthesis of surfactants with the principlesof the Green Chemistry?

-


How to integrate the synthesis of surfactants with the principlesof 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.


- The economics of atoms

- The use of catalytic processes such as biocatalytic process


- The design of products for final degradation under naturalconditions


The polar head of the surfactants consists of a carbohydrate or a protein.

It may be derived from co-products of the starch industry orfrom 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


Finally, oligopeptides and amino acids derived from wheat or corn gluten can be used.


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.


Sugar Fatty Acid Esters

Sugar fatty acid esters (SFAEs) are nonionic surfactants,which contain one or more saccharide rings, for examplesucrose, linked to one or multiple hydrophobic fatty acidchains.



• Sugar esters with low HLB values (HLB:3-6) are good water-in-oilemulsifier, with medium HLB values (7-9) are good wettingagent, and with high HLB values (10-16) are appropriateemulsifier 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 EstersMoreover, their tasteless, odorless, nontoxic, and

biodegradable features make them excellent biocompatible foodemulsifiers (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 generatedeodorant and eyelash, among other cosmetics (Khan & Rathod,2015).

Furthermore, the antimicrobial properties of SFAEs havedemonstrated their relevance for the pharmaceutical industry(Ferrer et al., 2005 a,b).


Sugar Fatty Acid EstersThe 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.


Sugar Fatty Acid Esters – three dimensional structure (Pleiss et al., 1998)


Sugar Fatty Acid Esters - solvent

A nonaqueous solvent is essential for lipase catalyzed synthesisof sugar fatty acid esters.

A suitable solvent must be able to dissolve sufficient amounts ofboth the substrates, i.e. the sugar and the fatty acid.

In addition, the solvent must not adversely affect the stability ofthe enzyme and its activity.


Sugar Fatty Acid Esters - solventHazardous solvents such as pyridine, dimethyl formamide

(DMF) and dimethylpyrolidone (DMP) were commonly used.Environmental and health risks of these solvents have driven thesearch for other suitable reaction solvents.

For example, Yan (1999) achieved reasonably good conversionyields in production of glucose caprylate in ethyl methyl ketone(66%) and acetone (90%).

During my thesis, I also achieved similar results using as solventTert-Butanol (68%).


Sugar Fatty Acid Esters - solvent

In summary, solvents with « high » log P values generally dedicate enzymes of highest activities and stabilities.


Sugar Fatty Acid Esters – Ratio FA/Sugar (Ren & Lamsal, 2016)

Palmitic acid Lauric acid


Sugar Fatty Acid Esters – Ration Gluc/FA (Moreau et al., 2005)



To date, a considerable amount of researches have beenreported about lipase synthesis for sugar esters of fatty acid.

Among these products, fructose esters exhibit interestingsurface properties and higher interfacial tension values comparedto commercial sugar esters.


Sugar Fatty Acid Esters (Li et al., 2014)



Most researches focused on total ester yield and acylation of thespecific hydroxyl site of sugar, but only limited data are availablewith regard to DE, in particular, influences of solvent medium andenzyme characteristics on this point.

The study of Li et al. (2014) demonstrated that the conformationof CALB binding mono-ester was affected by organic solventsessentially determined DE.



More, fructose esters or sucrose esters exhibit antibacterialproperties lead to the potential use in food additives (Ferrer et al.,2005).

The study of Zhao et al. (2015) also showed that sucrosemonocaprate significantly inhibit the growth of tested bacteria.The permeability of the cell membrane and intracellular proteinswere both changed by sucrose monocaprate according to cellconstituents’ leakage.


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 andcosmetics.

Sugar esters are nonionic type emulsifiers, mono sucrose is used for thestabilization of O / W emulsion (dairy products).

Some sugar esters exhibit antimicrobial properties, bacteriostatic.


Sugar Fatty Acid EstersAnother 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 theresearch lab (DGO6).



Niosomes are vesicular systems composed of surfactantmolecules, claimed to be used as drug delivery carriers thanks totheir physico-chemical and biological properties.

The aim was to synthetisized a niosomes obtained with asurfactant synthesized from glucuronic acid (Tavano et al., 2014).


Sugar Fatty Acid EstersValorization 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 underdevelopment - 2018)

Figure from Alonsoet al; 2015


Amino-acid-based surfactants constitute a novel class of surfactantsproduced from renewable raw materials and can be seen as an alternative toconventional surfactants (Perinelli et al., 2016; Pinazo et al., 2010). Thisresearch project of synthesis (Path 1 & 3) using lipases was deposited inSeptember 2017 in collaboration with the UCL and the CRA of Gembloux


Lipoamino acids are premium candidates for use as multifunctionaladditives in pharmaceutical, food, personal care and cosmeticformulations in view of their excellent emulsifying and potentantimicrobial activities (Bordes & Holmberg, 2015; Perez et al., 2008; Soo etal., 2002).

The current challenge is not to start from pure reagents but fromrenewable sources.


Work package:

- Enzymes screening at different temperatures.

- Effect of solvent.

- Effect of substrate molar ratio.

- Effect of enzyme amount.


Nowadays, synthetic cationic amino acid-based surfactants are beingexplored as promising alternatives to conventional antimicrobial agents asshown in the studies of Pinazo et al. (2016) and Perez et al. (2009) where thefamily of lysine surfactants exhibited a wide spectrum of antimicrobialactivity against Gram-positive and Gram-negative bacteria.


Future of surfactants:

The surfactants, which are renewable, enjoy a verygood image (low toxicity and ecotoxicity), A higher biodegradability than petrochemical

surfactants, and less aggressiveness on the skin. . .),which suggests that their penetration rate shouldincrease in future years. They are now positioned on niche applications and

have high added value.


Future of surfactants:

new sources of original synthons through thedevelopment of new crops (eg cuphea oil with shortchain fatty acids, erucian rapeseed, algae).


Thank you for your attention and I am available now to answer your question

@ : [email protected]

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