Letters in Applied Microbiology ISSN 0266-8254
UNDER THE MICROSCOPE
Biosurfactants in cosmetics and biopharmaceuticals A. Varvaresou1 and K. Iakovou2 1 Laboratory of Cosmetology, Department of Aesthetics and Cosmetology, Technological Educational Institution of Athens, Athens, Greece 2 Department of Drugs, Ministry of Health, Athens, Greece
Keywords antimicrobials, biopharmaceuticals, biosurfactants, biotechnology, cosmetics. Correspondence Athanasia Varvaresou, Head of the Department of Aesthetics and Cosmetology, Technological Educational Institution of Athens, Ious 7, 14563 Kifissia, Athens, Greece. E-mail: [email protected] 2015/0077: received 13 January 2015, revised 23 April 2015 and accepted 25 April 2015
Abstract Biosurfactants are surface-active biomolecules that are produced by various micro-organisms. They show unique properties i.e. lower toxicity, higher biodegradability and environmental compatibility compared to their chemical counterparts. Glycolipids and lipopeptides have prompted application in biotechnology and cosmetics due to their multi-functional profile i.e. detergency, emulsifying, foaming and skin hydrating properties. Additionally, some of them can be served as antimicrobials. In this study the current status of research and development on rhamnolipids, sophorolipids, mannosyloerythritol lipids, trehalipids, xylolipids and lipopeptides particularly their commercial application in cosmetics and biopharmaceuticals, is described.
doi:10.1111/lam.12440
Introduction Surfactants are one of the most representative chemical products that are consumed in large quantities on a worldwide scale. They are amphiphilic compounds and contain hydrophobic and hydrophilic moieties which reduce surface tension. Food, pharmaceutical and cosmetic formulations make use of mixtures of surfactants with emulsifying, solubilizing, wetting, foaming and dispersing properties. Most of traditional commercial surfactants used in cosmetics are polyethylene glycol ethers. In particular, skin care formulations, i.e. dermocosmetic products must meet a whole series of demands. They must have a pleasing appearance and retain it during storage, give an agreeable feeling during application and provide long-term beneficial effects to the skin. On the other hand, it is known that surfactants can adversely affect the aquatic environment. The biodegrability and biocompatibility of surfactants have become almost as important as their functional performance to the consumer. There is a pressing need for discovery of efficient surfactants that are biodegradable and biocompatible. The term natural surfactant is not unambiguous. In the strictest sense, this means that natural surfactant is a surfactant taken directly from a natural renewable resource. The source may be a micro-organism, plant, invertebrate, or an animal and the product should be obtained by 214
some kind of separation such as extraction, precipitation or distillation. No organic synthesis should be involved, not even as an after-treatment. (Holmberg 2001). Among natural surfactants ones of microbial origin are especially classified into biological surfactants or biosurfactants (BS) (Makkar and Cameotra 1999). BS are a special promising class of natural surfactants that are produced by natural renewable resources by biotechnological means. The numerous advantages of BS have prompted applications not only in the food (Campos et al. 2013), cosmetic and pharmaceutical industries (Gharaei-Fathabad 2011) but also in environmental protection and energy-saving technology (Kitamoto et al. 2002). Our laboratory has reported a few studies on the research and development of cosmeceuticals (Varvaresou and Papageorgiou 2010; Papagianni et al. 2011; Varvaresou et al. 2011a) and cosmetics with natural ingredients (Papageorgiou et al. 2008, 2010; Varvaresou et al. 2009, 2011b; Kefala et al. 2011). In this study, we attempt to provide a comprehensive overview of BS that have been used in cosmetic industry and biopharmaceuticals. Biological surfactants or biosurfactants BS were first discovered as extracellular amphiphilic compounds in research into hydrocarbon fermentation, which
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started in the late 1960s. They can be produced when grown on water miscible or oily substrates and they either remain adherent to microbial cell surfaces or secreted in the culture broth. To date more than 225 patents are available describing these microbial amphiphilic molecules (Shete et al. 2006). BS are generally classified into glycolipids, lipopeptides, phospholipids, fatty acids and polymeric compounds (Mukherjee et al. 2006). The physiological role of BS is still unknown. One explanation is that BS facilitate the growth of microorganisms on water-immiscible substrates by reducing the interfacial tension. Another justification could be the increase of adhesion of cells to insoluble substrates (Neu 1996) and antibiotic activity. Additionally when pathogenic microorganisms infect plants or animals BS are considered to function as ‘dispersing agent’ for the microorganisms as well as a ‘wetting agent’ for the surface of the host cells (Kitamoto et al. 2002). It has also been discovered that some BS strongly complex metals suggesting its role in the interaction of microorganisms with metals in their environment (Mao et al. 2015). BS reduce the surface and interfacial tensions by the same mechanism as chemical surfactants. They are used as multifunctional ingredients in the formulation of cosmetics. BS have clear advantages to the chemically synthesized surfactants i.e. lower toxicity, higher biodegradability, lower critical micelle concentration (CMC), gradual adsorption and superior ability to form assembly and liquid crystal. Additionally, they possess antimicrobial and antitumor activities (Kitamoto et al. 2002; Marchant and Banat 2012). However, the use of BS is not extensive because of the high production costs (Desai and Banat 1997] and their limited structural variety. Most of them are produced biotechnologically i.e. by bacteria, yeasts and fungi during cultivation on various carbon sources. Many BS cannot easily be synthesized by chemical processes. Except for sophorolipids (SL) and mannosyloerythritol lipids (MEL), there has been no report on the production of BS in large quantities. In order the bioproduction to be profitable the yield of the product by the natural producer-microorganism must be high. The genetics of the producer organism is an important factor that influence the yield of the production of the biosurfactant (Roelants et al. 2014). Even if highyielding natural strains are available, the recombinant hyperproducers are always requested in order to economize further the process and to gain products with better properties. Additionally, the substrates for the production must be taken under consideration, also. Plant derived oils can be used as effective and cheap raw materials for biosurfactant production. However, the oils used to date for biosurfactant production are mostly edible oils and
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are not cheap. Several plant derived oils can act as effective and cheap raw materials for the production for example rapeseed oil (Trummler et al. 2003), Babassu oil (Vance-Harrop et al. 2003) and Turkish corn oil (Pekin et al. 2005). Another difficulty for their use is that the physicochemical properties of this kind of surfactants depend on the conditions of their biotechnological production. There are many factors that influence their production such as the kind of the microorganism (species or subspecies), the condition of the microorganism, pH of the cultivation, incubation temperature, inoculum size and the optimized ration of carbon and nitrogen. Recently the synthesis of BS has been developed using microbial enzymes. Using enzymes makes continuous production and recovery easy, and facilitates obtaining high region- and stereo-selectivity in the synthetic reactions. Though the enzyme method for glycolipid surfactants has several advantages compared to the fermentation method, there are still difficulties with the activity and stability of the enzyme, and the solubility of the substrate. The choice of the method for BS production depends on the aim of using BS. (Desai and Banat 1997). Glycolipids Chemically are carbohydrates in combination with longchain aliphatic acids or hydroxyl-aliphatic acids. Most known glycolipids is of bacterial origin and only few come from yeasts and fungi. Recently the synthesis of BS has been developed using microbial enzymes (Kitamoto et al. 2002). SL, rhamnolipids (RL) and mannosylerythritol lipids (MEL) are the most known glycolipids with application to cosmetics and pharmaceutical technology. Trehalipids (TL) and xylolipids offer possible therapeutic alternatives, as well. Sophorolipids They are consisted by a disaccharide sophorose moiety linked by a glycosidic bond to the hydroxyl group at the penultimate carbon of a 17-hydroxy-C18 saturated or monoenoic (cis-9) fatty acid. They are two conformations of the so called native sophorolipid during production (Fig. 1): Lactone form resulting from the esterification of the carboxylic acid group to the disaccharide ring and acidic form with two head groups of dimeric sugar sophorose and carboxylic acid, in which sophorose head is acetylated (Hommel et al. 1994). They are produced by cells of non-pathogenic yeast Candida bombicola when grown on carbohydrates, fatty acids, hydrocarbons or their mixtures. Some other strains have been enrolled for their production (Van Bogaert
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Razafindralambo, H., Paquot, M., Baniel, A., Popineau, Y., Hbid, C., Jacques, P. and Thonart, P. (1996) Foaming properties of surfactin, a lipopeptides biosurfactant from bacillus subtilis. J Am Oil Chem Soc 73, 149–151. Razafindralambo, H., Paquot, M., Baniel, A., Popineau, Y., Hbid, C. and Jacques, P. (1997) Foaming properties of a natural cyclic lipoheptapeptide belonging to a special class of amphiphilic molecules. Food Hydrocoll 11, 59–62. Renkin, M. (2003) Environmental profile of sophorolipid and rhamnolipid biosurfactants. Rivista Italiana delle Sostanze Grasse 80, 249–252. Rivardo, F., Turner, R.J., Allegrone, G., Ceri, H. and Martinotti, M.G. (2009) Anti-adhesion activity of two biosurfactants produced by Bacillus spp. prevents biofilm formation of human bacterial pathogens. Appl Microbiol Biotechnol 83, 541–553. Roelants, S.L.K.W., De Maeseneire, S.L., Ciesielska, K., Van Bogaert, I.N.A. and Soetaert, E. (2014) Biosurfactant gene clusters in eukaryotes: regulation and biotechnological potential. Appl Microbiol Biotecnol 98, 3449–3461. Saravanakumari, P. and Mani, K. (2010) Structural characterization of a novel xylolipid biosurfactant from Lactococcus lactis and analysis of antibacterial activity against multi-drug resistant pathogens. Bioresour Technol 101, 8851–8854. Schneider, J., Taraz, K., Budzikiewicz, H., Deleu, M., Thonart, P. and Jacques, P. (1999) The structure of two fengycins from Bacillus subtilis S499. Z Naturforsch C 54, 859–866. Shah, V., Doncel, G.F., Seyoum, T., Eaton, K.M., Zalenscaya, I., Hagver, R., Azim, A. and Gross, R. (2005) Sophorolipids, microbial glycolipids, with anti-human immunodeficiency virus and sperm-immobilizing activities. Antimicrob Agents Chemother 49, 4093–4100. Shete, A.M., Wadhawa, G., Banat, I.M. and Chopade, B.A. (2006) Mapping of patents on bioemulsifier and biosurfactant: a review. J Sci Ind Res 65, 91–115. Singh, K.S., Felse, A.P., Nunez, A., Foglia, T. and Gross, R.A. (2003) Regioselective enzyme-catalyzed synthesis of sophorolipid esters, amides and multifunctional monomers. J Org Chem 68, 5466–5477. Takahashi, T., Ohno, O., Ikeda, Y., Ryuishi, S., Homma, Y., Igarashi, M. and Umezawa, K. (2006) Inhibition of lipopolysaccharide activity by a bacterial cyclic lipopeptide surfactin. J Antibiot 59, 35–43. Takahashi, M., Morita, T., Fukuoka, T., Imura, T. and Kitamoto, D. (2012) Glycolipid biosurfactants, mannosylerythritol lipids, show antioxidant and protective effects against H2O2-induced oxidative stress in cultured human skin fibroblasts. J Oleo Sci 61, 457–464. Thanomsub, B., Pumeechockchai, W., Limtrakul, A., Arunrattiyakorn, P., Petscleelaha, W., Nitoda, T. and Kanzaki, H. (2007) Chemical structures and biological activities of rhamnolipids produced by Pseudomonas
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aeruginosa B189 isolated from milk factory waste. Bioresour Technol 98, 1149–1153. Trummler, K., Effenberger, F. and Syldatk, C. (2003) An intergrated microbial/enzymatic process for production of thamnolipids and l-(+)-rhamnose from rapeseed oil with Pseudomonas sp. DSM 2874. Eur J Lipid Sci Techol 105, 563–571. Tuleva, B., Christova, N., Cohen, R., Antonova, D. and Todorov, T.S.I. (2009) Isolation and characterization of trehalose tetraester biosurfactants from a soil strain Micrococcus luteus BN56. Process Biochem 44, 135–141. Ueno, Y., Hirashima, N., Inoh, Y., Furuno, T. and Nakanishi, M. (2007) Characterization of biosurfactant-containing liposomes and their efficiency for gene transfection. Biol Pharm Bull 30, 169–172. Van Bogaert, I.N.A., Zhang, J. and Soetaert, W. (2011) Microbial synthesis of sophorolipids. Process Biochem 46, 821–833. Vance-Harrop, M.H., De Gusm~ao, N.B. and De Campos Takaki, G.M. (2003) New bioemulsifiers produced by Candida lipolytica using D-Glycose and Babassu oil as carbon sources. Braz J Microbiol 34, 120–123. Varvaresou, A. and Papageorgiou, S. (2010) The development of self-preserving gels. Househ Personal Care Today 4, 18–21. Varvaresou, A., Papageorgiou, S., Tsirivas, E., Protopapa, E., Kintziou, H., Kefala, V. and Dementzos, C. (2009) Selfpreserving cosmetics. Int J Cosmet Sci 31, 163–175. Varvaresou, Α., Papageorgiou, S., Protopapa, E. and Katsarou, A. (2011a) Efficacy and tolerance study of an oligopeptide with potential anti-aging activity. JCDSA 1, 133–140. Varvaresou, A., Papageorgiou, S., Kintziou, E., Iakovou, K., Protopapa, E. and Kefala, V. (2011b) Clay minerals in cosmetology. Epitheor Clin Pharmacol Pharmacokinet 29, 215–221. € Vollenbroich, D., Ozel, M., Vater, J., Kamp, R.M. and Pauli, G. (1997) Mechanism of inactivation of enveloped viruses by the biosurfactant surfactin from Bacillus subtilis. Biologicals 25, 289–297. Yamamoto, S., Morita, T., Fukuoka, T., Imura, T., Yanagidani, S., Sogabe, A., Kitamoto, D. and Kitagawa, M. (2012) The moisturizing effects of glycolipid biosurfactants, mannosylerythritol lipids, on human skin. J Oleo Sci 61, 407–412. Yoneda, T. (2006) Cosmetic composition comprising A and A lipopeptide U.S. Patent 0222616. Zhang, L., Somasundaran, P., Singh, S.K., Felse, A.P. and Gross, R. (2004) Synthesis and interfacial properties of sophorolipid derivatives. Colloids Surf A Physicochem Eng Asp 240, 75–82. Zhao, X., Wakamatsu, Y., Shibahara, M., Nomura, N., Geltinger, C., Nakahara, T., Murata, T. and Yokoyama, K.K. (1999) Mannosylerythritol lipid is a potent inducer of apoptosis and differentiation of mouse melanoma cells in culture. Cancer Res 59, 482–486.
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compressed cosmetic material (Kawano et al. 1981a,b). Amino acid sophorolipid conjugates is the new cationic, zwitterionic, or anionic form of SL with increased water solubility. They can also act as source for x and x-1 hydroxy fatty acids, since the chemical route for these acids is difficult. x and x-1 hydroxy fatty acids can be lactonized into macrocyclic esters, which find application in the perfume and fragrance industry (Inoue and Miyamoto 1980). Another interesting activity of SL that could be utilized in cosmetic and pharmaceutical industry is the enhancement of transdermal absorption of bovine lactoferrin through a model skin. Lactoferrin is multifunctional glycoprotein known to activate dermal fibroblasts leading to increase of cell proliferation and gene expression levels of collagen IV and hyaluronan synthases. A significant synergism between lactoferrin and sophorolipid has been observed (Ishii et al. 2012). SL are readily biodegradable surfactants according to the OECD 301F method (Renkin 2003; Hirata et al. 2009). Cytotoxicity was proven to be low by MTT assay with human epidermal keratinocytes (Hirata et al. 2009). SL may also be novel anti-inflammatory agents with therapeutic potential to cure diseases related with the alteration in the regulation of IgE (Hagler et al. 2007). Activity against cancerous cells in the pancreas by native SL produced by C. bombicola has been reported (Fu et al. 2008). Rhamnolipids The most frequently used are the mono-RL and di-RL shown in Fig. 2. They bear one or two rhamnose moieties which are bonded to up to three groups of hydroxyl fatty acids with a chain length from eight up to fourteen. They are produced by the cultivation of pathogen Pseudomonas aeruginosa on glycose, glycerol or triglycerides and this is
in contrast with the aforementioned SL, which are produced by nonpathogenic strains (Nitschke et al. 2005). Total synthesis has also been reported (Duynstee et al. 1998). The RL produced by Ps. aeruginosa strains are often a mixture of several homologues. They possess activity against fungi (Lang and Wullbrandt 1999; Abalos et al. 2001) and bacteria (Haba et al. 2014). RL have been used as anti-wrinkle agents. They have also been incorporated due to their antimicrobial action in several different cosmetic formulations such as deodorants, nail care products and toothpastes (Muhammad and Mahsa 2014). Additionally, RL show anti-adhesive and anti-biofilm activity (Nickzad and Deziel 2013). Biofilms are important in the pathogenesis of several bacterial infections. Adhesion of pathogens onto the host tissues is the initial requirement for most infectious diseases. RL generated 41–71% inhibition bacterial adherence on polystyrene surfaces as tested on Listeria monocytogenes (Araujo et al. 2011). Antiproliferative effects against human breast cancer cells at a concentration of 625 lg ml1 has also been reported for RL by microorganisms of the Ps. aeruginosa (Thanomsub et al. 2007). Anionic RL have also been used for the removal of heavy metals from contaminated water (Elouzi et al. 2012). Biocompatible lecithin–based microemulsions with RL and sophorolipid mixture have also been reported. The hexadecane detergency performance that mixture was higher than that of a commercial liquid detergent at the same surfactant active concentrations (Nguyen et al. 2010). Mannosyloerythritol lipids They contain 4-or 1-O-b-D-mannopyranosyl-meso-erythritol as the hydrophilic part and two fatty acids as hydrophobic moieties (Fukuoka et al. 2007a). Different types of MEL regarding the degree of acylation have been reported
OH OH O
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O O
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Figure 2 Rhamnolipids (RL): I=mono-RL, II=di-RL.
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(Fig. 3) mainly MEL-A (tri-acylated MEL), MEL-B (di-acylated MEL) and MEL-C (mono-acylated MEL). The fatty acid composition depends on both the microorganism as well as the carbon source (Fukuoka et al. 2007b). MEL are produced by yeast strains of the Pseudozyma antarctica, Pseudozyma aphidis, Pseudozyma rugulosa and Pseudozyma parantarctica (previously Candida) and are of the most promising BS. A great structural variety of this kind of lipids has been recently published. Pseudozyma parantarctica JCM 11752 was recently reported to produce mannosyl-mannitol lipid possessing mannitol (C6 sugar alcohol) as the hydrophilic part instead of erythritol (C4 sugar alcohol) using a medium containing olive oil and mannitol (Morita et al. 2009). Other new homologues possessing C5 sugar alcohol, mannosyl-arabitol lipids and mannosyl-ribitol lipids are also produced by Ps. parantarctica JCM 11752 (Morita et al. 2012). A novel MEL homologue having no acetyl groups, namely MEL-D, was synthesized by lipase-catalyzed hydrolysis of MEL-B (Fukuoka et al. 2011). Total synthesis has also been reported (Crich et al. 2002). MEL-A and MEL-B exhibit excellent surface and interface-lowering actions and low CMC. They are highly
hydrophobic and are used as emulsifiers, dispersants and detergents. MEL-A has a great potential for the formation for W/O microemulsion. MEL-B and MEL-C spontaneously form giant unilamellar vesicles of diameter larger than 10 lm in aqueous solution (Kitamoto et al. 2009). It is generally difficult to obtain giant vesicles from glycolipids, because the vesicle structure requires strictly balanced hydrophobic and hydrophilic groups. This indicates that both MEL-B and MEL-C have an excellent molecular orientation property and a superior hydrophilic-hydrophobic balance. They have been used as active ingredients in skin care smoothing products, as well. In a recent article the antioxidant properties of three different derivatives have been shown, one double esterified and two bearing one acyl-group each but at different positions, by using DPPH in vitro method and superoxide anion scavenging assay. In comparison with arbutin, a well-known antioxidant used in cosmetics as depigmenting agent, the in vitro activity of the MEL tested was lower (Morita et al. 2013). However, the antioxidant capacity of one mono-esterified derivative on human skin fibroblasts against superoxide –induced oxidative stress was higher than arbutin, and therefore MEL are proposed
CH3 O
m OH H2C
O H2C
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H
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CH3 OH n OH
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Figure 3 Mannosyloerythritol lipids (MEL): I=MeL-A, II=MEL-B and III=MEL-C. R1 = R2 = Ac; n = 4–16; m = 6–16.
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as anti-ageing skin care products. The attention of the antioxidant properties of MEL, is focused on the unsaturated fatty acids components of the molecules (Takahashi et al. 2012). Additionally, MEL have shown moisturizing properties towards human skin cells, comparable to the moisturizing activities of a natural ceramide (Kitamoto et al. 2009; Yamamoto et al. 2012). Furthermore, the repairing effect on damaged hair has been investigated. On electron microscopic observation the recovery of artificially damaged hair was impressive with the application of MEL-A and MEL-B. The tensile strength was remarkably increased, whereas the average friction coefficient was decreased. Therefore MEL are proposed not only for recovery of damaged hair but also for providing smoothness and flexibility (Morita et al. 2010a). Moreover, 0001 lg ml1 of MEL-A activates dramatically (150% of cell viability) the papilla cells –a key factor for follicle formation and new hair growth. Thus, MEL-A would have great potential as a new hair growth agent stimulating the papilla cells (Morita et al. 2010b). Another interesting application of MEL in cosmetic science is their coating properties of metal oxide particles such as titanium dioxide and iron oxides in development of foundations. The usual coting materials have been synthetic chemicals such as silicones, thus the conventional foundations are difficult to provide moisturizing properties towards the skin. The metal oxide particles coated with MEL have enhanced dispersibility and water resistance as well as hydrophilicity, offering excellent moisture retention property to the skin (Morita et al. 2013). MEL have antiinflammatory action inhibiting the secretion of inflammatory mediators from mast cells (Morita et al. 2011). Additionally, MEL inhibit cell-differentiation with respect to human leukaemia (Isoda et al. 1997) and mouse melanoma cells (Zhao et al. 1999). MEL can also induce the activity of tyrosinases and increase the production of melanins (Zhao et al. 1999). MEL-A and MEL-B have shown antimicrobial activity against Gram-positive bacteria (Morita et al. 2013). MEL-A especially increased the efficiency of gene transfection mediated with cationic liposomes. The introduction of exogenous nucleotides into mammalian cells is critical for gene therapy (Ueno et al. 2007). Trehalipids They contain a trehalose disaccharide moiety bound to the carbon 6 and 60 of the hydroxylated fatty acids in a and b configurations. They are produced by Micrococcus luteus and Rhodococcus erythropolis (Tuleva et al. 2009). TL-1 possess antifungal activity by inhibiting the germination of conidia from Glomerella cingulate (Kitamoto et al. 2002). Succinyl TL show antifungal and antiviral activity. They inhibit herpes simplex and influenza viruses at
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concentrations from 11 to 33 mg l1 (Desai and Banat 1997; Lang and Philp 1998). Xylolipids As hydrophilic moiety xylose or methyl-2-O-methyl b-Dxylopyranoside is bound to hydrophobic fractions of the octadecanoic acid. They are produced by probiotic bacteria such as Lactococcus lactis using paraffin as carbon source and are active against pathogens Escherichia coli and Staph. aureus resistant to methicillin. They can be used as alternatives antimicrobials for oral and dermal administration, or as preservatives for food industry (Saravanakumari and Mani 2010). Lipopeptides They are amphiphilic cyclic peptides composed of ten or seven amino acids which are bonded with b-hydroxyacids. Fengycin has ten aminoacids, iturin and surfactin seven aminoacids respectively (Schneider et al. 1999; Bonmantin et al. 2003). Surfactin–A has L-leucine, surfactin-B has L-valine and surfactin-C has L-isoleucine at the amino acid position involved in lactone ring formation with the C14-15 b-hydroxy fatty acid (Takahashi et al. 2006). The length of the fatty acid chains vary from C13 to C16 for surfactins, from C14 to C17 for iturins and from C14 to C18 for fengycins, giving different homologous compounds and isomers (n, iso, anteiso) for each lipopeptide. Bacillus subtilis was first reported to produce surfactin a lipopeptide, which has been used for pharmaceutical purposes and in food applications, as well (Arima et al. 1968). Lipopeptides are produced also from Pseudomonas sp. and Arthrobacter sp. (Cameotra and Makkar 2004). However, B. subtilis is the most appropriate economic source for the production of lipopeptides from starchy substrates. Potato process effluents (wastes from potato processing industries) were used to produce the lipopeptide surfactin by B. subtilis (Noah et al. 2002). Cassava wastewater, another carbohydrate rich residue, which is created in large amounts during the preparation of cassava flour, has also been used for the production of surfactin (Nitschke and Pastore 2006). Surfactin lowers the surface tension of water from 72 to 279 mN m1. It has been reported that surfactin lowered the surface tension to a range of 267–544 mN m1 with an interfacial tension of 036–34 mN m1 at the cmc of 1– 240 lmol l1 and are compared with those of sodium lauryl sulfate (Kanlayavattanakul and Lourith 2010). The surface properties depend on the hydrophobic character of the alkyl chain incorporated in the aminoacids. Surfactin possesses excellent foaming properties compare with sodium dodecyl sulfate (Razafindralambo et al. 1996, 1997).
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Lipopeptides have been used in anti-wrinkle cosmetics (Guglielmo and Montanari 2003; Montanari and Guglielmo 2008). They also have been incorporated for their deterging (Mukherjee 2007) and emulsifying activity (Gallot and Douy1986; Lang and Philp 1998; Meena and Kanwar 2015) into cosmetic cleansing products (Bockm€ uhl 2012). Cleansing cosmetics containing lipopeptides show excellent washability and low skin irritation (Yoneda 2006). Some lipopeptides have been used to deliver an amelanocyte-stimulating hormone including an application in whitening cosmetics (Ogawa et al. 1999). An interaction of surfactin with lipopolysaccharide and the subsequent suppression of the transportation of lipids has been also reported. Thus, the incorporation of surfactin into anti-cellulite products it could be useful (Takahashi et al. 2006). Lipopeptides possess antibacterial and antifungal activity (Mandal et al. 2013a) and therefore have been used for the treatment and prevention of microbial infections and for products preservation, as well (Deleu et al. 2004; Mandal et al. 2013b). Additionally, inhibition of the adhesion of pathogenic organisms has been reported. Two lipopeptides BS produced by B. subtilis and Bacillus licheniformis inhibited the biofilm adhesion of the pathogenic bacteria E. coli and Staph. aureus by using Minimal Biofilm Eradication Concentration device (Rivardo et al. 2009). Surfactin inhibits biofilm formation of wild-type s Salmonella enterica grown in urethral catheters (Mireles et al. 2001). The activity of surfactin against herpes viruses and retroviruses has also been reported (Vollenbroich et al. 1997). Discussion Over the past two decade the development of BS has been promoted due to their significant interfacial and biochemical properties. Some of them have been established as multi-functional cosmetic materials due to their low toxicity, biocompatibility and dermo-cosmetic i.e. detergency, emulsifying, foaming and skin hydrating and hair repairing properties. Additionally BS become a viable alternative in the pharmaceutical industry mainly due to their antimicrobial and anti-adhesive properties. A lot of research has been performed on the optimization of their production. In contrast to the traditional surfactants inexpensive bio-resources i.e. vegetable oils can be used, thus the improving of the fermentation process is needed. Glycolipid BS are the most promising, due to relatively higher productivity from renewable resources. Genetic engineering could open up perspectives for better yield and further modification of the mixture produced and therefore the improvement of their activities. Considering the current social and technological backgrounds, the use of BS, which are environmentally friendly and highly 220
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Biosurfactants in cosmetics and biopharmaceuticals A. Varvaresou1 and K. Iakovou2 1 Laboratory of Cosmetology, Department of Aesthetics and Cosmetology, Technological Educational Institution of Athens, Athens, Greece 2 Department of Drugs, Ministry of Health, Athens, Greece
Keywords antimicrobials, biopharmaceuticals, biosurfactants, biotechnology, cosmetics. Correspondence Athanasia Varvaresou, Head of the Department of Aesthetics and Cosmetology, Technological Educational Institution of Athens, Ious 7, 14563 Kifissia, Athens, Greece. E-mail: [email protected] 2015/0077: received 13 January 2015, revised 23 April 2015 and accepted 25 April 2015
Abstract Biosurfactants are surface-active biomolecules that are produced by various micro-organisms. They show unique properties i.e. lower toxicity, higher biodegradability and environmental compatibility compared to their chemical counterparts. Glycolipids and lipopeptides have prompted application in biotechnology and cosmetics due to their multi-functional profile i.e. detergency, emulsifying, foaming and skin hydrating properties. Additionally, some of them can be served as antimicrobials. In this study the current status of research and development on rhamnolipids, sophorolipids, mannosyloerythritol lipids, trehalipids, xylolipids and lipopeptides particularly their commercial application in cosmetics and biopharmaceuticals, is described.
doi:10.1111/lam.12440
Introduction Surfactants are one of the most representative chemical products that are consumed in large quantities on a worldwide scale. They are amphiphilic compounds and contain hydrophobic and hydrophilic moieties which reduce surface tension. Food, pharmaceutical and cosmetic formulations make use of mixtures of surfactants with emulsifying, solubilizing, wetting, foaming and dispersing properties. Most of traditional commercial surfactants used in cosmetics are polyethylene glycol ethers. In particular, skin care formulations, i.e. dermocosmetic products must meet a whole series of demands. They must have a pleasing appearance and retain it during storage, give an agreeable feeling during application and provide long-term beneficial effects to the skin. On the other hand, it is known that surfactants can adversely affect the aquatic environment. The biodegrability and biocompatibility of surfactants have become almost as important as their functional performance to the consumer. There is a pressing need for discovery of efficient surfactants that are biodegradable and biocompatible. The term natural surfactant is not unambiguous. In the strictest sense, this means that natural surfactant is a surfactant taken directly from a natural renewable resource. The source may be a micro-organism, plant, invertebrate, or an animal and the product should be obtained by 214
some kind of separation such as extraction, precipitation or distillation. No organic synthesis should be involved, not even as an after-treatment. (Holmberg 2001). Among natural surfactants ones of microbial origin are especially classified into biological surfactants or biosurfactants (BS) (Makkar and Cameotra 1999). BS are a special promising class of natural surfactants that are produced by natural renewable resources by biotechnological means. The numerous advantages of BS have prompted applications not only in the food (Campos et al. 2013), cosmetic and pharmaceutical industries (Gharaei-Fathabad 2011) but also in environmental protection and energy-saving technology (Kitamoto et al. 2002). Our laboratory has reported a few studies on the research and development of cosmeceuticals (Varvaresou and Papageorgiou 2010; Papagianni et al. 2011; Varvaresou et al. 2011a) and cosmetics with natural ingredients (Papageorgiou et al. 2008, 2010; Varvaresou et al. 2009, 2011b; Kefala et al. 2011). In this study, we attempt to provide a comprehensive overview of BS that have been used in cosmetic industry and biopharmaceuticals. Biological surfactants or biosurfactants BS were first discovered as extracellular amphiphilic compounds in research into hydrocarbon fermentation, which
Letters in Applied Microbiology 61, 214--223 © 2015 The Society for Applied Microbiology
A. Varvaresou and K. Iakovou
started in the late 1960s. They can be produced when grown on water miscible or oily substrates and they either remain adherent to microbial cell surfaces or secreted in the culture broth. To date more than 225 patents are available describing these microbial amphiphilic molecules (Shete et al. 2006). BS are generally classified into glycolipids, lipopeptides, phospholipids, fatty acids and polymeric compounds (Mukherjee et al. 2006). The physiological role of BS is still unknown. One explanation is that BS facilitate the growth of microorganisms on water-immiscible substrates by reducing the interfacial tension. Another justification could be the increase of adhesion of cells to insoluble substrates (Neu 1996) and antibiotic activity. Additionally when pathogenic microorganisms infect plants or animals BS are considered to function as ‘dispersing agent’ for the microorganisms as well as a ‘wetting agent’ for the surface of the host cells (Kitamoto et al. 2002). It has also been discovered that some BS strongly complex metals suggesting its role in the interaction of microorganisms with metals in their environment (Mao et al. 2015). BS reduce the surface and interfacial tensions by the same mechanism as chemical surfactants. They are used as multifunctional ingredients in the formulation of cosmetics. BS have clear advantages to the chemically synthesized surfactants i.e. lower toxicity, higher biodegradability, lower critical micelle concentration (CMC), gradual adsorption and superior ability to form assembly and liquid crystal. Additionally, they possess antimicrobial and antitumor activities (Kitamoto et al. 2002; Marchant and Banat 2012). However, the use of BS is not extensive because of the high production costs (Desai and Banat 1997] and their limited structural variety. Most of them are produced biotechnologically i.e. by bacteria, yeasts and fungi during cultivation on various carbon sources. Many BS cannot easily be synthesized by chemical processes. Except for sophorolipids (SL) and mannosyloerythritol lipids (MEL), there has been no report on the production of BS in large quantities. In order the bioproduction to be profitable the yield of the product by the natural producer-microorganism must be high. The genetics of the producer organism is an important factor that influence the yield of the production of the biosurfactant (Roelants et al. 2014). Even if highyielding natural strains are available, the recombinant hyperproducers are always requested in order to economize further the process and to gain products with better properties. Additionally, the substrates for the production must be taken under consideration, also. Plant derived oils can be used as effective and cheap raw materials for biosurfactant production. However, the oils used to date for biosurfactant production are mostly edible oils and
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are not cheap. Several plant derived oils can act as effective and cheap raw materials for the production for example rapeseed oil (Trummler et al. 2003), Babassu oil (Vance-Harrop et al. 2003) and Turkish corn oil (Pekin et al. 2005). Another difficulty for their use is that the physicochemical properties of this kind of surfactants depend on the conditions of their biotechnological production. There are many factors that influence their production such as the kind of the microorganism (species or subspecies), the condition of the microorganism, pH of the cultivation, incubation temperature, inoculum size and the optimized ration of carbon and nitrogen. Recently the synthesis of BS has been developed using microbial enzymes. Using enzymes makes continuous production and recovery easy, and facilitates obtaining high region- and stereo-selectivity in the synthetic reactions. Though the enzyme method for glycolipid surfactants has several advantages compared to the fermentation method, there are still difficulties with the activity and stability of the enzyme, and the solubility of the substrate. The choice of the method for BS production depends on the aim of using BS. (Desai and Banat 1997). Glycolipids Chemically are carbohydrates in combination with longchain aliphatic acids or hydroxyl-aliphatic acids. Most known glycolipids is of bacterial origin and only few come from yeasts and fungi. Recently the synthesis of BS has been developed using microbial enzymes (Kitamoto et al. 2002). SL, rhamnolipids (RL) and mannosylerythritol lipids (MEL) are the most known glycolipids with application to cosmetics and pharmaceutical technology. Trehalipids (TL) and xylolipids offer possible therapeutic alternatives, as well. Sophorolipids They are consisted by a disaccharide sophorose moiety linked by a glycosidic bond to the hydroxyl group at the penultimate carbon of a 17-hydroxy-C18 saturated or monoenoic (cis-9) fatty acid. They are two conformations of the so called native sophorolipid during production (Fig. 1): Lactone form resulting from the esterification of the carboxylic acid group to the disaccharide ring and acidic form with two head groups of dimeric sugar sophorose and carboxylic acid, in which sophorose head is acetylated (Hommel et al. 1994). They are produced by cells of non-pathogenic yeast Candida bombicola when grown on carbohydrates, fatty acids, hydrocarbons or their mixtures. Some other strains have been enrolled for their production (Van Bogaert
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Razafindralambo, H., Paquot, M., Baniel, A., Popineau, Y., Hbid, C., Jacques, P. and Thonart, P. (1996) Foaming properties of surfactin, a lipopeptides biosurfactant from bacillus subtilis. J Am Oil Chem Soc 73, 149–151. Razafindralambo, H., Paquot, M., Baniel, A., Popineau, Y., Hbid, C. and Jacques, P. (1997) Foaming properties of a natural cyclic lipoheptapeptide belonging to a special class of amphiphilic molecules. Food Hydrocoll 11, 59–62. Renkin, M. (2003) Environmental profile of sophorolipid and rhamnolipid biosurfactants. Rivista Italiana delle Sostanze Grasse 80, 249–252. Rivardo, F., Turner, R.J., Allegrone, G., Ceri, H. and Martinotti, M.G. (2009) Anti-adhesion activity of two biosurfactants produced by Bacillus spp. prevents biofilm formation of human bacterial pathogens. Appl Microbiol Biotechnol 83, 541–553. Roelants, S.L.K.W., De Maeseneire, S.L., Ciesielska, K., Van Bogaert, I.N.A. and Soetaert, E. (2014) Biosurfactant gene clusters in eukaryotes: regulation and biotechnological potential. Appl Microbiol Biotecnol 98, 3449–3461. Saravanakumari, P. and Mani, K. (2010) Structural characterization of a novel xylolipid biosurfactant from Lactococcus lactis and analysis of antibacterial activity against multi-drug resistant pathogens. Bioresour Technol 101, 8851–8854. Schneider, J., Taraz, K., Budzikiewicz, H., Deleu, M., Thonart, P. and Jacques, P. (1999) The structure of two fengycins from Bacillus subtilis S499. Z Naturforsch C 54, 859–866. Shah, V., Doncel, G.F., Seyoum, T., Eaton, K.M., Zalenscaya, I., Hagver, R., Azim, A. and Gross, R. (2005) Sophorolipids, microbial glycolipids, with anti-human immunodeficiency virus and sperm-immobilizing activities. Antimicrob Agents Chemother 49, 4093–4100. Shete, A.M., Wadhawa, G., Banat, I.M. and Chopade, B.A. (2006) Mapping of patents on bioemulsifier and biosurfactant: a review. J Sci Ind Res 65, 91–115. Singh, K.S., Felse, A.P., Nunez, A., Foglia, T. and Gross, R.A. (2003) Regioselective enzyme-catalyzed synthesis of sophorolipid esters, amides and multifunctional monomers. J Org Chem 68, 5466–5477. Takahashi, T., Ohno, O., Ikeda, Y., Ryuishi, S., Homma, Y., Igarashi, M. and Umezawa, K. (2006) Inhibition of lipopolysaccharide activity by a bacterial cyclic lipopeptide surfactin. J Antibiot 59, 35–43. Takahashi, M., Morita, T., Fukuoka, T., Imura, T. and Kitamoto, D. (2012) Glycolipid biosurfactants, mannosylerythritol lipids, show antioxidant and protective effects against H2O2-induced oxidative stress in cultured human skin fibroblasts. J Oleo Sci 61, 457–464. Thanomsub, B., Pumeechockchai, W., Limtrakul, A., Arunrattiyakorn, P., Petscleelaha, W., Nitoda, T. and Kanzaki, H. (2007) Chemical structures and biological activities of rhamnolipids produced by Pseudomonas
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aeruginosa B189 isolated from milk factory waste. Bioresour Technol 98, 1149–1153. Trummler, K., Effenberger, F. and Syldatk, C. (2003) An intergrated microbial/enzymatic process for production of thamnolipids and l-(+)-rhamnose from rapeseed oil with Pseudomonas sp. DSM 2874. Eur J Lipid Sci Techol 105, 563–571. Tuleva, B., Christova, N., Cohen, R., Antonova, D. and Todorov, T.S.I. (2009) Isolation and characterization of trehalose tetraester biosurfactants from a soil strain Micrococcus luteus BN56. Process Biochem 44, 135–141. Ueno, Y., Hirashima, N., Inoh, Y., Furuno, T. and Nakanishi, M. (2007) Characterization of biosurfactant-containing liposomes and their efficiency for gene transfection. Biol Pharm Bull 30, 169–172. Van Bogaert, I.N.A., Zhang, J. and Soetaert, W. (2011) Microbial synthesis of sophorolipids. Process Biochem 46, 821–833. Vance-Harrop, M.H., De Gusm~ao, N.B. and De Campos Takaki, G.M. (2003) New bioemulsifiers produced by Candida lipolytica using D-Glycose and Babassu oil as carbon sources. Braz J Microbiol 34, 120–123. Varvaresou, A. and Papageorgiou, S. (2010) The development of self-preserving gels. Househ Personal Care Today 4, 18–21. Varvaresou, A., Papageorgiou, S., Tsirivas, E., Protopapa, E., Kintziou, H., Kefala, V. and Dementzos, C. (2009) Selfpreserving cosmetics. Int J Cosmet Sci 31, 163–175. Varvaresou, Α., Papageorgiou, S., Protopapa, E. and Katsarou, A. (2011a) Efficacy and tolerance study of an oligopeptide with potential anti-aging activity. JCDSA 1, 133–140. Varvaresou, A., Papageorgiou, S., Kintziou, E., Iakovou, K., Protopapa, E. and Kefala, V. (2011b) Clay minerals in cosmetology. Epitheor Clin Pharmacol Pharmacokinet 29, 215–221. € Vollenbroich, D., Ozel, M., Vater, J., Kamp, R.M. and Pauli, G. (1997) Mechanism of inactivation of enveloped viruses by the biosurfactant surfactin from Bacillus subtilis. Biologicals 25, 289–297. Yamamoto, S., Morita, T., Fukuoka, T., Imura, T., Yanagidani, S., Sogabe, A., Kitamoto, D. and Kitagawa, M. (2012) The moisturizing effects of glycolipid biosurfactants, mannosylerythritol lipids, on human skin. J Oleo Sci 61, 407–412. Yoneda, T. (2006) Cosmetic composition comprising A and A lipopeptide U.S. Patent 0222616. Zhang, L., Somasundaran, P., Singh, S.K., Felse, A.P. and Gross, R. (2004) Synthesis and interfacial properties of sophorolipid derivatives. Colloids Surf A Physicochem Eng Asp 240, 75–82. Zhao, X., Wakamatsu, Y., Shibahara, M., Nomura, N., Geltinger, C., Nakahara, T., Murata, T. and Yokoyama, K.K. (1999) Mannosylerythritol lipid is a potent inducer of apoptosis and differentiation of mouse melanoma cells in culture. Cancer Res 59, 482–486.
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compressed cosmetic material (Kawano et al. 1981a,b). Amino acid sophorolipid conjugates is the new cationic, zwitterionic, or anionic form of SL with increased water solubility. They can also act as source for x and x-1 hydroxy fatty acids, since the chemical route for these acids is difficult. x and x-1 hydroxy fatty acids can be lactonized into macrocyclic esters, which find application in the perfume and fragrance industry (Inoue and Miyamoto 1980). Another interesting activity of SL that could be utilized in cosmetic and pharmaceutical industry is the enhancement of transdermal absorption of bovine lactoferrin through a model skin. Lactoferrin is multifunctional glycoprotein known to activate dermal fibroblasts leading to increase of cell proliferation and gene expression levels of collagen IV and hyaluronan synthases. A significant synergism between lactoferrin and sophorolipid has been observed (Ishii et al. 2012). SL are readily biodegradable surfactants according to the OECD 301F method (Renkin 2003; Hirata et al. 2009). Cytotoxicity was proven to be low by MTT assay with human epidermal keratinocytes (Hirata et al. 2009). SL may also be novel anti-inflammatory agents with therapeutic potential to cure diseases related with the alteration in the regulation of IgE (Hagler et al. 2007). Activity against cancerous cells in the pancreas by native SL produced by C. bombicola has been reported (Fu et al. 2008). Rhamnolipids The most frequently used are the mono-RL and di-RL shown in Fig. 2. They bear one or two rhamnose moieties which are bonded to up to three groups of hydroxyl fatty acids with a chain length from eight up to fourteen. They are produced by the cultivation of pathogen Pseudomonas aeruginosa on glycose, glycerol or triglycerides and this is
in contrast with the aforementioned SL, which are produced by nonpathogenic strains (Nitschke et al. 2005). Total synthesis has also been reported (Duynstee et al. 1998). The RL produced by Ps. aeruginosa strains are often a mixture of several homologues. They possess activity against fungi (Lang and Wullbrandt 1999; Abalos et al. 2001) and bacteria (Haba et al. 2014). RL have been used as anti-wrinkle agents. They have also been incorporated due to their antimicrobial action in several different cosmetic formulations such as deodorants, nail care products and toothpastes (Muhammad and Mahsa 2014). Additionally, RL show anti-adhesive and anti-biofilm activity (Nickzad and Deziel 2013). Biofilms are important in the pathogenesis of several bacterial infections. Adhesion of pathogens onto the host tissues is the initial requirement for most infectious diseases. RL generated 41–71% inhibition bacterial adherence on polystyrene surfaces as tested on Listeria monocytogenes (Araujo et al. 2011). Antiproliferative effects against human breast cancer cells at a concentration of 625 lg ml1 has also been reported for RL by microorganisms of the Ps. aeruginosa (Thanomsub et al. 2007). Anionic RL have also been used for the removal of heavy metals from contaminated water (Elouzi et al. 2012). Biocompatible lecithin–based microemulsions with RL and sophorolipid mixture have also been reported. The hexadecane detergency performance that mixture was higher than that of a commercial liquid detergent at the same surfactant active concentrations (Nguyen et al. 2010). Mannosyloerythritol lipids They contain 4-or 1-O-b-D-mannopyranosyl-meso-erythritol as the hydrophilic part and two fatty acids as hydrophobic moieties (Fukuoka et al. 2007a). Different types of MEL regarding the degree of acylation have been reported
OH OH O
OH
O
O
CH3
OH
O
O O
OH
O
O
CH3
OH
O
O
O
OH
OH
O
CH3
OH
OH I
II
Figure 2 Rhamnolipids (RL): I=mono-RL, II=di-RL.
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(Fig. 3) mainly MEL-A (tri-acylated MEL), MEL-B (di-acylated MEL) and MEL-C (mono-acylated MEL). The fatty acid composition depends on both the microorganism as well as the carbon source (Fukuoka et al. 2007b). MEL are produced by yeast strains of the Pseudozyma antarctica, Pseudozyma aphidis, Pseudozyma rugulosa and Pseudozyma parantarctica (previously Candida) and are of the most promising BS. A great structural variety of this kind of lipids has been recently published. Pseudozyma parantarctica JCM 11752 was recently reported to produce mannosyl-mannitol lipid possessing mannitol (C6 sugar alcohol) as the hydrophilic part instead of erythritol (C4 sugar alcohol) using a medium containing olive oil and mannitol (Morita et al. 2009). Other new homologues possessing C5 sugar alcohol, mannosyl-arabitol lipids and mannosyl-ribitol lipids are also produced by Ps. parantarctica JCM 11752 (Morita et al. 2012). A novel MEL homologue having no acetyl groups, namely MEL-D, was synthesized by lipase-catalyzed hydrolysis of MEL-B (Fukuoka et al. 2011). Total synthesis has also been reported (Crich et al. 2002). MEL-A and MEL-B exhibit excellent surface and interface-lowering actions and low CMC. They are highly
hydrophobic and are used as emulsifiers, dispersants and detergents. MEL-A has a great potential for the formation for W/O microemulsion. MEL-B and MEL-C spontaneously form giant unilamellar vesicles of diameter larger than 10 lm in aqueous solution (Kitamoto et al. 2009). It is generally difficult to obtain giant vesicles from glycolipids, because the vesicle structure requires strictly balanced hydrophobic and hydrophilic groups. This indicates that both MEL-B and MEL-C have an excellent molecular orientation property and a superior hydrophilic-hydrophobic balance. They have been used as active ingredients in skin care smoothing products, as well. In a recent article the antioxidant properties of three different derivatives have been shown, one double esterified and two bearing one acyl-group each but at different positions, by using DPPH in vitro method and superoxide anion scavenging assay. In comparison with arbutin, a well-known antioxidant used in cosmetics as depigmenting agent, the in vitro activity of the MEL tested was lower (Morita et al. 2013). However, the antioxidant capacity of one mono-esterified derivative on human skin fibroblasts against superoxide –induced oxidative stress was higher than arbutin, and therefore MEL are proposed
CH3 O
m OH H2C
O H2C
CH3
CH3 H CH3
C
CH3
OH
n
OR1
O
n
OR1
O
n H
C
OH
O
O
OH
H
C
OH
O CH2
HO CH2
R2O
C
O
O
O
H n
O
O
O
O I
II
OH H2C
H
C
OH
H
C
OH
CH3 OH n OH
O
O CH2
R2O
O
O III
Figure 3 Mannosyloerythritol lipids (MEL): I=MeL-A, II=MEL-B and III=MEL-C. R1 = R2 = Ac; n = 4–16; m = 6–16.
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as anti-ageing skin care products. The attention of the antioxidant properties of MEL, is focused on the unsaturated fatty acids components of the molecules (Takahashi et al. 2012). Additionally, MEL have shown moisturizing properties towards human skin cells, comparable to the moisturizing activities of a natural ceramide (Kitamoto et al. 2009; Yamamoto et al. 2012). Furthermore, the repairing effect on damaged hair has been investigated. On electron microscopic observation the recovery of artificially damaged hair was impressive with the application of MEL-A and MEL-B. The tensile strength was remarkably increased, whereas the average friction coefficient was decreased. Therefore MEL are proposed not only for recovery of damaged hair but also for providing smoothness and flexibility (Morita et al. 2010a). Moreover, 0001 lg ml1 of MEL-A activates dramatically (150% of cell viability) the papilla cells –a key factor for follicle formation and new hair growth. Thus, MEL-A would have great potential as a new hair growth agent stimulating the papilla cells (Morita et al. 2010b). Another interesting application of MEL in cosmetic science is their coating properties of metal oxide particles such as titanium dioxide and iron oxides in development of foundations. The usual coting materials have been synthetic chemicals such as silicones, thus the conventional foundations are difficult to provide moisturizing properties towards the skin. The metal oxide particles coated with MEL have enhanced dispersibility and water resistance as well as hydrophilicity, offering excellent moisture retention property to the skin (Morita et al. 2013). MEL have antiinflammatory action inhibiting the secretion of inflammatory mediators from mast cells (Morita et al. 2011). Additionally, MEL inhibit cell-differentiation with respect to human leukaemia (Isoda et al. 1997) and mouse melanoma cells (Zhao et al. 1999). MEL can also induce the activity of tyrosinases and increase the production of melanins (Zhao et al. 1999). MEL-A and MEL-B have shown antimicrobial activity against Gram-positive bacteria (Morita et al. 2013). MEL-A especially increased the efficiency of gene transfection mediated with cationic liposomes. The introduction of exogenous nucleotides into mammalian cells is critical for gene therapy (Ueno et al. 2007). Trehalipids They contain a trehalose disaccharide moiety bound to the carbon 6 and 60 of the hydroxylated fatty acids in a and b configurations. They are produced by Micrococcus luteus and Rhodococcus erythropolis (Tuleva et al. 2009). TL-1 possess antifungal activity by inhibiting the germination of conidia from Glomerella cingulate (Kitamoto et al. 2002). Succinyl TL show antifungal and antiviral activity. They inhibit herpes simplex and influenza viruses at
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concentrations from 11 to 33 mg l1 (Desai and Banat 1997; Lang and Philp 1998). Xylolipids As hydrophilic moiety xylose or methyl-2-O-methyl b-Dxylopyranoside is bound to hydrophobic fractions of the octadecanoic acid. They are produced by probiotic bacteria such as Lactococcus lactis using paraffin as carbon source and are active against pathogens Escherichia coli and Staph. aureus resistant to methicillin. They can be used as alternatives antimicrobials for oral and dermal administration, or as preservatives for food industry (Saravanakumari and Mani 2010). Lipopeptides They are amphiphilic cyclic peptides composed of ten or seven amino acids which are bonded with b-hydroxyacids. Fengycin has ten aminoacids, iturin and surfactin seven aminoacids respectively (Schneider et al. 1999; Bonmantin et al. 2003). Surfactin–A has L-leucine, surfactin-B has L-valine and surfactin-C has L-isoleucine at the amino acid position involved in lactone ring formation with the C14-15 b-hydroxy fatty acid (Takahashi et al. 2006). The length of the fatty acid chains vary from C13 to C16 for surfactins, from C14 to C17 for iturins and from C14 to C18 for fengycins, giving different homologous compounds and isomers (n, iso, anteiso) for each lipopeptide. Bacillus subtilis was first reported to produce surfactin a lipopeptide, which has been used for pharmaceutical purposes and in food applications, as well (Arima et al. 1968). Lipopeptides are produced also from Pseudomonas sp. and Arthrobacter sp. (Cameotra and Makkar 2004). However, B. subtilis is the most appropriate economic source for the production of lipopeptides from starchy substrates. Potato process effluents (wastes from potato processing industries) were used to produce the lipopeptide surfactin by B. subtilis (Noah et al. 2002). Cassava wastewater, another carbohydrate rich residue, which is created in large amounts during the preparation of cassava flour, has also been used for the production of surfactin (Nitschke and Pastore 2006). Surfactin lowers the surface tension of water from 72 to 279 mN m1. It has been reported that surfactin lowered the surface tension to a range of 267–544 mN m1 with an interfacial tension of 036–34 mN m1 at the cmc of 1– 240 lmol l1 and are compared with those of sodium lauryl sulfate (Kanlayavattanakul and Lourith 2010). The surface properties depend on the hydrophobic character of the alkyl chain incorporated in the aminoacids. Surfactin possesses excellent foaming properties compare with sodium dodecyl sulfate (Razafindralambo et al. 1996, 1997).
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Lipopeptides have been used in anti-wrinkle cosmetics (Guglielmo and Montanari 2003; Montanari and Guglielmo 2008). They also have been incorporated for their deterging (Mukherjee 2007) and emulsifying activity (Gallot and Douy1986; Lang and Philp 1998; Meena and Kanwar 2015) into cosmetic cleansing products (Bockm€ uhl 2012). Cleansing cosmetics containing lipopeptides show excellent washability and low skin irritation (Yoneda 2006). Some lipopeptides have been used to deliver an amelanocyte-stimulating hormone including an application in whitening cosmetics (Ogawa et al. 1999). An interaction of surfactin with lipopolysaccharide and the subsequent suppression of the transportation of lipids has been also reported. Thus, the incorporation of surfactin into anti-cellulite products it could be useful (Takahashi et al. 2006). Lipopeptides possess antibacterial and antifungal activity (Mandal et al. 2013a) and therefore have been used for the treatment and prevention of microbial infections and for products preservation, as well (Deleu et al. 2004; Mandal et al. 2013b). Additionally, inhibition of the adhesion of pathogenic organisms has been reported. Two lipopeptides BS produced by B. subtilis and Bacillus licheniformis inhibited the biofilm adhesion of the pathogenic bacteria E. coli and Staph. aureus by using Minimal Biofilm Eradication Concentration device (Rivardo et al. 2009). Surfactin inhibits biofilm formation of wild-type s Salmonella enterica grown in urethral catheters (Mireles et al. 2001). The activity of surfactin against herpes viruses and retroviruses has also been reported (Vollenbroich et al. 1997). Discussion Over the past two decade the development of BS has been promoted due to their significant interfacial and biochemical properties. Some of them have been established as multi-functional cosmetic materials due to their low toxicity, biocompatibility and dermo-cosmetic i.e. detergency, emulsifying, foaming and skin hydrating and hair repairing properties. Additionally BS become a viable alternative in the pharmaceutical industry mainly due to their antimicrobial and anti-adhesive properties. A lot of research has been performed on the optimization of their production. In contrast to the traditional surfactants inexpensive bio-resources i.e. vegetable oils can be used, thus the improving of the fermentation process is needed. Glycolipid BS are the most promising, due to relatively higher productivity from renewable resources. Genetic engineering could open up perspectives for better yield and further modification of the mixture produced and therefore the improvement of their activities. Considering the current social and technological backgrounds, the use of BS, which are environmentally friendly and highly 220
functional alternatives is in favourable situation in cosmetic and biopharmaceuticals industry. Conflict of Interest None declared. References Abalos, A., Pinazo, A., Infante, M.R., Casals, M., Garcıa, F. and Manresa, A. (2001) Physicochemical and antimicrobial properties of new rhamnolipids produced by Pseudomonas aeruginosa AT10 from soy bean oil refinery wastes. Langmuir 17, 1367–1371. Araujo, L.V., Abreu, F., Lins, U., Anna, L.M.D.M.S., Nitschke, M. and Freire, D.M.G. (2011) Rhamnolipid and surfactin inhibit Listeria monocytogenes adhesion. Food Res Int 44, 481–488. Arima, K., Kakinuma, A. and Tamura, G. (1968) Surfactin, a crystalline peptide lipid surfactant produced by Bacillus subtilis: isolation, characterization and its inhibition of fibrin clot formation. Biochem Biophys Res Commun 31, 488–494. Bhangale, A.P., Wadekar, S.D., Kale, S.B. and Pratap, A.P. (2014) Sophorolipids synthesized using non-traditional oils with glycerol and studies on their surfactant properties with synthetic surfactant. Tenside, Surfactants, Deterg 51, 387–396. Bischt, K.S., Gross, R.A. and Kaplan, D.L. (1999) Enzymemediated regioselective acylations of sophorolipids. J Org Chem 64, 780–789. Bisht, K.S., Gao, W. and Gross, R.A. (2000) Glycolipid from Candida bombicola. Macromolecules 33, 6208–6210. Bockm€ uhl, D. (2012) Biosurfactants as antimicrobial ingredients for cleaning products and cosmetics. Tenside, Surfactants, Deterg 49, 196–198. Bonmantin, J.-M., Laprevote, O. and Peyroux, F. (2003) Diversity among microbial cyclic lipopeptides: iturins and surfactins. Activity-structure relationships to design new bioactive agents. Comb Chem High Throughput Screen 6, 541–556. Cameotra, S.S. and Makkar, B.S. (2004) Recent applications of biosurfactants as biological and immunological molecules. Curr Opin Microbiol 7, 262–266. Campos, J.M., Montenegro Stamford, T.L., Sarubbo, L.A., de Luna, J.M., Rufino, R.D. and Banat, I.M. (2013) Microbial biosurfactants as additives for food industries. Biotechnol Progress 29, 1097–1108. Crich, D., de la Mora, M.A. and Cruz, R. (2002) Synthesis of the mannosyleryrthiritol lipid MEL A; a confirmation of the configuration of the meso-erythritol moiety. Tetrahedron 58, 35–44. Deleu, M., Brasseur, R., Paquo, M., Legros, H.R., Dufour, S., Jacques, P., Destain, J., Thonart, P. et al. (2004) Novel use of lipopeptide preparations. World Patent 002510.
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