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Natural Surfactants Towards a More Sustainable Fluorine Chemistry", Green Chem., 2018, 20, 13–27

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Natural Surfactants Towards a More Sustainable Fluorine Chemistry Natural surfactants towards a more sustainable fluorine chemistry V. Dichiarante, *a R. Milani b and P. Metrangolo *a,b,c Fluorinated materials play an essential role in modern industry and technology, and their importance is expected to grow even more in the near future. Unfortunately, their practical application often requires dispersion by means of fluorinated surfactants, which raised huge environmental and toxicity concerns due to their long-lasting persistence in the environment and high tendency to accumulate in animals and humans. A greener and more sustainable strategy towards the replacement of synthetic fluorosurfactants is offered by the use of amphiphiles of biological origin. Among them, phospholipids have been the most widely exploited as emulsifiers of fluorous compounds. Some interesting examples were also reported using amphiphilic proteins, in particular fungal hydrophobins, as biosurfactants and coating agents for fluorinated substrates. This perspective offers an overview of the main natural surfactants currently used in fluorine chemistry, focusing in particular on two main application areas: (i) fluorous oil-in-water emulsions and gas microbubbles for biomedical imaging and drug delivery, and (ii) coating and functionalization of solid fluorinated surfaces. aLaboratory of Supramolecular and Bio-Nanomaterials (SupraBioNanoLab), Department of Chemistry, Materials, and Chemical Engineering “Giulio Natta”, Politecnico di Milano, 20131 Milan, Italy. E-mail: [email protected], [email protected]; http://www.suprabionano.eu; Fax: (+39) 02 2399 3180; Tel: (+39) 02 2399 3041 bVTT Technical Research Centre of Finland Ltd, 02150 Espoo, Finland cUNITWIN Network GREENOMIcS, Aalto University, 02150 Espoo, Finland This is the accepted version of V. Dichiarante, R. Milani, P. Metrangolo, "Natural surfactants towards a more sustainable fluorine chemistry", Green Chem., 2018, 20, 13–27. The final publication is available at: https://doi.org/10.1039/C7GC03081A 1. Introduction Fluorine chemistry has become essential for many aspects of modern day life, so that related industry and technology are expected to further increase in the next years with an esti-mated Chart 1 Chemical structures of perfluorooctanoic acid (PFOA) and annual growth rate comprised between 2 and 4% for different perfluorooctanesulfonic acid (PFOS). specialties.1 Indeed, several fluorocompounds –including – polymers, surfactants and surface coating agents are widely exploited to enhance the functionality and dura- taining more than six CFn units (like PFOA and PFOS) may bility of aircrafts, automobiles, buildings and electronics, induce serious toxic and endocrine disrupting effects.6 Due to thanks to their unmatched thermal and chemical stabilities, their long-lasting persistence, worldwide distribution, high 2 unique dielectric properties, and water and oil repellency. tendency to bioaccumulate, and suspected toxicity, PFOS and Fluoropolymers, for example, find widespread use in automo- its salts were thus listed as persistent organic pollutants under tive applications thanks to their exceptional resistance to fuels, the Stockholm Convention.7 Furthermore, in 2006 the US lubricants, high temperatures and aggressive chemicals, as Environmental Protection Agency (EPA), in collaboration with ffi well as to their low coe cients of friction and non-wetting sur- the eight major companies in the fluorochemical industry, 3 faces. Furthermore, these polymers can greatly enhance the launched a Stewardship Program to commit to working properties of coatings used in modern industrial, household, towards the elimination of PFOA and its derivatives from emis- and construction products, particularly in terms of chemical, sions and products by 2015.8 Given the increasing need for UV, moisture, and dirt resistance. Fluorinated coatings find fluorinated products in everyday life and industry on the one applications also in electronics, optics, polishes, inks, textiles, hand, and their potential for danger for the environment and 1 and adhesives. One of the most common classes of fluoro- animal species on the other, a key target is thus to reach a chemicals is that of fluorinated surfactants (F-surfactants), compromise between these two crucial issues, establishing a amphiphilic molecules containing both a hydrophilic and a route towards a more sustainable fluorine chemistry.9 Several 4 fluorophilic moiety. These surface-active compounds allow world-leading companies (e.g., Daikin, DuPont, 3M/Dyneon the stabilization of various colloidal systems, including and Solvay Solexis) have met the EPA program’s intermediate ff di erent types of emulsions and vesicles, and improvement of goal of a 95% reduction in global emissions and product the solubility of poorly water-soluble materials thanks to their content by 2010, and are actively searching for more sustain- excellent performance as emulsifying, dispersing, foaming, able F-surfactants. wetting, cleansing, and phase separating agents. For these It would be highly desirable, for example, to design environ- reasons, fluorosurfactants find several applications in mentally sustainable fluoropolymers that are able to form poly- polymer, food, cosmetic and pharmaceutical industries. meric films or coatings from an aqueous phase without the Among them, perfluorooctanoic acid (PFOA) and perfluoro- need for fluorinated dispersing agents. Unfortunately, their octanesulfonic acid (PFOS) have been for years the most exten- very low water solubility and surface tension require the use of sively produced and used (Chart 1). surfactants or other forms of surface modification. The use of Unfortunately, a series of environmental and toxicity F-surfactants to stabilize colloidal dispersions is still wide- studies raised huge concern about their use, since both PFOA spread, in spite of the related significant environmental con- and PFOS were shown to degrade slowly under environmental cerns. The first, more immediate, approach adopted to face 5 conditions. Due to their persistence in the environment, concerns over the environmental impact of long-chain per- these man-made perfluorinated derivatives tend to accumulate fluoroalkyl acids (PFAAs) was their substitution with alterna- in cells and were found in animal and human tissues almost tive, but structurally similar, fluorinated substances. The main everywhere. A series of toxicity studies performed on animals companies active in the fields of the fluoropolymer industry suggested that long-chain linear perfluoroalkyl derivatives con- and textile treatment developed several alternative compounds having shorter perfluorinated groups (typically shifting from C8 to C4 perfluorinated chains) or “weak” degradable points, like methylene or ether groups. Unfortunately, such fluori- nated alternatives, particularly short-chain PFAAs and perfluoro- ether-carboxylic and sulfonic acids, are less performing from a technical point of view, possess high environmental stability and mobility, and may still have a contamination potential.5 Global Warming Potential (GWP) values relative to CO2 for C3 and C4 perfluoroalkanes, for example, are quite similar to those of longer-chain PFCs, reaching values higher than 10 000 on a 500-year time horizon.10 In addition to that, some of these fluorinated alternatives were identified as possibly toxic for animals and humans, although a deep knowledge hydrophobins rapidly reduce the interface tension by typically − about the real risks posed by them is currently lacking.11 15–20 mN m 1. This feature, together with the peculiar ability A greener, effective, and long-term more sustainable strategy of HFBs to form strong interfacial films, makes them poten- towards the elimination of chemically synthesized tially more advantageous than other biosurfactants for solubil- F-surfactants is their replacement with natural amphiphilic izing fluorous phases in aqueous environments. compounds produced by a variety of microorganisms, such as Here we will present an overview of the natural surfactants bacteria, yeasts, and fungi.12,13 Surfactants of biological origin most commonly used for filming or dispersing fluorinated show unique properties in terms of low toxicity, specific substrates. Papers reported in the literature will be classified activity even under extreme conditions, and biodegradability. into two main areas, according to the type of pursued appli- They include low molecular weight compounds (like lipopep- cation. First, we will focus on the stabilization of fluorous oil- tides or glycolipids) and high molecular weight polymers in-water (o/w) emulsions and gas microbubbles for biomedical (e.g., proteins). Up to now, phospholipids have been the most purposes and drug delivery. In the following section, we will extensively studied biosurfactants for applications in fluorine highlight examples of coating, modification, and functionali- chemistry. Many research efforts focused in particular on the zation of solid fluorinated surfaces by means of biosurfactants use of egg yolk phospholipids (EYP), a natural mixture of phos- and their derivatives. pholipids derived from chicken hen’s eggs composed mainly of phosphatidylcholine and phosphatidylethanolamine plus a significant percentage of unsaturated acyl chain species. 2. Biomedical imaging and drug Several naturally occurring proteins are already used as delivery applications foaming agents and surfactants in food processing, cosmetics and pharmaceuticals. In the biomedical field, biocompatible Fluorocarbon-based
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