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REVIEW ARTICLE

y Milica Lukic, Ivana Pantelic and Snezana Savic

An Overview of Novel Surfactants


for Formulation of Cosmetics with Certain
Emphasis on Acidic Active Substances

Novel surfactants which are nowadays available for incorpora- impact on the resulting colloidal structure and physico-
tion into various formulations of personal care and cosmetic chemical properties of the product, and its contribution or
products are numerous, implying a permanent need for their influence to the product’s overall efficacy.
classification. This overview provides essential information relat- This paper will encompass fundamental information re-
ing to synthesis, basic physicochemical characteristics, applica- lating to synthesis, basic characteristics, application and
tion and other relevant data on surfactants currently used in cos- other relevant data on surfactant use in cosmetic products.
metic products. In the second part of the paper an outline of In order to obtain more detailed information on certain sur-
acidic active substances with significant application in cosmetic factants, readers will be referred to a variety of references cit-
products is given, as well as the problems that arise during pre- ed throughout the paper.
paration/manufacture of the containing formulations, accompa- Although the very title of the paper mentions novel sur-
nied with the review of scientific publications and other avail- factants, the actual focus will be on the natural surfactants.
able reliable data dealing with the incorporation of these actives In order to clarify this discrepancy, the first part of the paper
in the cosmetic formulations stabilized with novel (mainly natur- will be dedicated to defining the green chemistry program,
al) surfactants. i. e. green or natural surfactants, followed by an overview of
the available surfactants, along with their classification and
Key words: green chemistry, biosurfactants, alkyl polygluco- application, and the review of the most interesting groups
sides, alpha-hydroxy acids of natural surfactants. The second part of the paper provides
an outline of acidic active substances with significant appli-
cation in cosmetic products, as well as the problems that
Eine Übersicht über neuartige Tenside in kosmetischen arise during preparation/manufacture of the containing for-
Formulierungen mit Schwerpunkt auf säureaktive Sub- mulations, accompanied with the results that stemmed
stanzen. Neuartige Tenside, die heutzutage verschiedenen For- from research encompassing both natural surfactants and
mulierungen von Körperpflegemitteln und Kosmetikprodukten these challenging actives.
beigemischt werden können, sind zahlreich, was einen ständigen
Bedarf an ihre Klassifikation einschließt. Dieser Übersichtsbeitrag 2 Green chemistry
liefert grundlegende Informationen in Bezug auf Synthese, physi-
ko-chemische Basischarakteristika, Anwendung und andere rele- Current development of the majority of novel substances/
vante Daten dieser Tenside, die gegenwärtig in kosmetischen chemicals, irrespective of their intended use, is based on
Produkten eingesetzt werden. Im zweiten Teil des Beitrags wird the Green Chemistry Program, established at the beginning
ein Aufriss über säureaktive Substanzen, die in kosmetischen of 1990s [15]. Since then, the development of many green
Produkten maßgeblich verwendet werden, gegeben, sowie über chemistry approaches and environment-friendly chemical
die Probleme, die während der Präparation/Produktion der sie syntheses have been driven by this program.
enthaltenen Formulierungen entstehen. Dies wird mit einem Re- Green chemistry is defined as the design of chemical pro-
view wissenschaftlicher Publikationen und weiterer zuverlässiger ducts and processes that reduce or eliminate the use or gen-
Daten, die die Einarbeitung solcher Aktivsubstanzen in die mit eration of hazardous substances, whereas a hazard is any-
den neuartigen (hauptsächlich natürlichen) Tensiden stabilisier- thing that could have a negative effect on human health
ten kosmetischen Formulierungen behandeln, belegt. and the environment [15]. Hence, a permanent priority for
both chemical industry and academic community became
Stichwörter: Grüne Chemie, Biotenside, Alkylpolyglucoside, Al- the development of greener or more environmentally benign
phahydroxysäuren processes and materials [16]. Similar to other fields, industry
needs are brought to the focus of academic work, which is
achieved through continual communication and collabora-
1 Introduction tion between industry and academia [17]. In this manner, re-
search areas are tailored according to the actual needs.
Original published papers which investigate surface proper- Personal care industry uses hundreds of chemicals in the
ties (solubility, emulsification, wetting, foaming and disper- formulation of consumer products. Among these ingredi-
sion) of different surfactant groups derived from nature, ents, surfactants perform a wide range of functions, thus
their synthesis and structure/properties relation, as well as being spent in enormous quantities every day worldwide.
review papers which summarize up-to-date publications are Consequently, their development and production is recog-
numerous [1 – 14]. On the other hand, there is only a hand- nized as an important research area and due to the vast con-
ful of original research articles investigating surfactants real- sumption and the resulting wide distribution in the environ-
time usage: focusing on their compatibility with different ac- ment, the green chemistry concept is especially outlined for
tives and other ingredients in the formulation, surfactants’ this group of chemicals.

Tenside Surf. Det. 53 (2016) 1 ª Carl Hanser Publisher, Munich 7


Milica Lukic et al.: An overview of novel surfactants for formulation of cosmetics with certain emphasis

Green surfactants present an important challenge for re- and antistatic agents. On the other hand, some of the cation-
searchers. The ideal green surfactant should have the least ic surfactants are used as bactericidal agents or emulsifiers.
possible impact on the environment and, therefore, as their This group comprises alkylamines, alkylimidazolines, qua-
first prerequisite, they should be produced from a sustain- ternary ammonium compounds, ethoxylated alkylamines
able source [16]. Most of the used surfactants are chemically and esterified quaternaries.
synthesized, petroleum-derived substances. As such, they
are non-biodegradable (remain toxic to the environment), 3.3 Amphoteric Surfactants
they can bioaccumulate and their production processes and
by-products can be hazardous to the environment [10]. Depending on the pH of the solution, amphoteric surfac-
Therefore, biodegradability and biocompatibility are addi- tants show either a positive or a negative charge, while
tional characteristics of surfactants important for \green showing a zwitterionic form at an isoelectric point (inter-
surfactant" classification. mediate pH). Their surfactant properties are therefore
It is not unusual that instead of \green" the term \natur- highly influenced by pH. For example, in acidic conditions
al" is used, since a natural surfactant is obtained from a nat- the cationic form prevails, providing surfactant substantivity.
ural, renewable source which may be a plant, a microorgan- They are generally used as foam stabilizers and thickening
ism, an invertebrate or an animal [18]. Further, a natural agents, but in the presence of acidic substances they tend
product should be obtained by some kind of separation pro- to lose those properties. Two groups of these surfactants that
cedure, without any organic synthesis, leading to the fact may find use in cosmetics are alkylamido alkyl amines and
that there are not many surfactants that fulfil such strict re- alkyl substituted amino acids [22].
quirements. Therefore, the term natural is usually used in
its broadest sense, while maintaining the basic prerequisite 3.4 Non-ionic surfactants
for a surfactant to be obtained from a natural source [19].
Consequently, the majority of novel surfactants is classi- The largest group of surfactants consists of non-ionics,
fied as natural. which do not dissociate in an aqueous solution. Their major
characteristic is good skin and eye compatibility, and de-
3 Surfactants pending on the type they are weak to moderate foaming
agents. Non-ionic surfactants may serve as cleansing agents
Surfactants, or surface-active agents, or tensides are an am- (mainly in the combination with anionic surfactants), but
phiphilic group of molecules, having both a hydrophilic and are generally used as emulsifiers, dominantly in cosmetic
a hydrophobic (or lipophilic) part. This unique class of products intended for sensitive skin, baby skin, as well as
chemicals has an ability to modify the properties of a surface for everyday skin care [21]. In Table 2, subgroups within the
and an interface. They can perform diverse functions includ- group of non-ionic surfactants are presented with their
ing: cleaning, wetting, emulsification, solubilization, disper- usual application and function [20 – 22].
sion, foaming and sometimes even penetration enhance-
ment and antimicrobial activity. Due to such an outstanding 3.5 Non-carbon speciality surfactants
functional diversity, surfactants may be applied in produc-
tion and processing of foods, agrochemicals, pharmaceuti- Specifically, these surfactants are alkoxylated polysiloxanes
cals, personal care and laundry products, petroleum, miner- and fluorosiloxans. The former group has a variety of differ-
al oils, lubricants, paints and many other [20]. The nature of ent applications in painting, foam control, phytosanitary
the hydrophilic moiety is commonly used to classify surfac- products, while in cosmetics they are found as emulsifiers
tants in four basic categories: anionic, cationic, amphoteric in personal care and hair products. The latter group does
and non-ionic. not have a significant application in the field of cosmetics.
In cosmetic products surfactants may serve as detergents
(cleansing agents), emulsifiers, wetting or foaming agents, 4 Natural Surfactants
opacifiers, thickening agents, foam depressors, hair condi-
tioners and antistatic agents. Hence, the selection of a sur- By a very strict definition a natural surfactant should be a
factant for a specific cosmetic product is a delicate task material from a natural source (plant or animal organ), ob-
which depends on numerous factors, starting from the in- tained by some kind of separation process (extraction, preci-
tended purpose of the product [21]. pitation or distillation), without any organic synthesis or
For better clarity, surfactant classification, their basic char- after-treatment. Although amphiphilic molecules are not
acteristics and main applications are presented in the follow- rare in plant and animal kingdom, there is a lack of truly
ing section. natural surfactants in the market. The small amount of
these products in the mentioned sources, together with the
3.1 Anionic Surfactants time consuming and sometimes expensive separation/isola-
tion procedure put real natural surfactants in an unfavour-
These molecules contain a polar head group which carries a able financial situation [12].
negative charge in slightly acidic, neutral or alkaline aque- Contemporary natural surfactants, as mentioned pre-
ous solutions. The most important functional groups are viously, in a much broader definition are surface-active sub-
carboxylate, sulfate, sulfonate or phosphate. For every sub- stances derived from natural raw materials. Moreover, only
group, typical representatives and their general characteris- one part of a natural surfactant, either hydrophobic or hy-
tics and application areas are given in Table 1 [20 – 22]. drophilic, may be from a renewable resource [8]. Therefore,
natural surfactants can be classified in three categories: am-
3.2 Cationic Surfactants phiphiles with a natural polar head group, amphiphiles with
a natural hydrophobic tail and amphiphiles of microbial ori-
Due to the positive charge they carry, cationic surfactants are gin (produced by yeast or bacteria). The last are also named
substantive to the keratin of hair which has determined biological surfactants or biosurfactants [8, 23]. In this section
their application in cosmetic industry as hair conditioners only groups of natural surfactants with a natural polar head

8 Tenside Surf. Det. 53 (2016) 1


Milica Lukic et al.: An overview of novel surfactants for formulation of cosmetics with certain emphasis

group and amphiphiles of microbial origin which are inter- eration, as a result of high production costs and their lim-
esting for application in cosmetic products will be covered. ited structural variety [25, 26]. Biological surfactants can be
classified according to different criteria: their molecular
4.1 Biosurfactants weight, ionic charge and secretion type. Nevertheless, the
main principle for classification remains their chemical
Biological surfactants or biosurfactants are specially classi- structure which allows them to be divided into the following
fied among natural surfactants, due to their microbial ori- classes: glycolipids, lipopeptides, particular surfactants, fatty
gin. Although they possess some crucial benefits compared acids, phospholipids, neutral lipids and polymeric surfac-
to the chemically synthesized surfactants (such as lower tants.
toxicity, higher biodegradability, greater environmental com-
patibility, lower critical micelle concentration (CMC), steady 4.1.1 Glycolipids
activity at pH or temperature extremes, diverse biological ac-
tivities like antimicrobial, antiviral and haemolytic activity Glycolipids are the most promising and the most widely used
[18, 24]), biosurfactants are used only after thorough consid- group of biosurfactants [10]. This is not only because of their

Group Subgroup Structure/Example Characteristics and Application


Carboxylates Carboxylated salts/ CH3(CH2)n COO–M+ Cleansing agents used as soap bars for fabric hand wash,
Soaps M = Na, K, NH4 skin cleansers (soap bars or liquids), shaving products,
deodorant sticks, w/o emulsifiers
Ester carboxylates Good foaming properties and substantivity on the hair
used in shampoos

Sodium dilaureth-7 citrate


Ether carboxylates RO(CH2CH2O)nCH2COONa Emulsion stabilizers, good wetting and foam stability,
Alkyl polyglycol ether carboxylate, stable in the presence of alkali or acid
sodium salt
Sulfates Alkyl sulfates RCH2SO4–Na+ Properties depend on the chain length and the degree of
Sodium alkyl sulfate branching of the hydrocarbon chain, good foaming prop-
erties. Categorized as potential irritants but most useful
cleansing agents for cosmetics, shampoos, skin cleansers
Alkyl ether sulfates RCH2O(CH2CH2O)nSO3–Na Viscosity of surfactant solution is very sensitive to electro-
Sodium alkyl ether sulfate lytes; cleansing and foaming agents used in liquid soaps,
shower gels, foam baths, shampoos
Amide ether sulfates [RCONH(CH2CH2O)3SO3]2Mg Magnesium salts show excellent skin compatibility, good
Magnesium PEG-3 cocamide sulfate foaming agents; mild personal care cleaners
Alkyl glyceride sulfates RCOOCH2CH(OH)CH2OSO4Na Good foaming properties, foaming booster
Sodium alkyl monoglyceride sulfate
Sulfonates Alky sulfonates CH3(CH2)nCH2SO3Na Very water soluble, showing good foaming, wetting and
Primary sodium alkyl sulfonate emulsifying properties; household products (detergents);
acidic skin and hair cleansing compositions
Alkyl-aryl sulfonates Detergent for household products, fabric care, institutional
and industrial products. Low compatibility with skin, used
as hydrotropes and in some anti-seborrheic preparations

Sodium linear alkylbenzene sulfonate


Sulfosuccinates RCOOCH2CH(COOR)SO3Na The monoesters and their derivatives are used in personal
Sodium dialkyl sulfosuccinate care products, especially in shampoos, often in combina-
tion with anionic surfactants
Fatty acid isethionates RCOOCH2CH2SO3Na Good wetting, foaming, and emulsifying properties. Excel-
and taurides Fatty acid isethionate lent compatibility with the skin. Shampoos, bubble baths
and cleaning products
Phosphates Alkyl phosphates ROPO3H2 High electrolyte and low pH tolerance, used in acidic
Esters Alkyl ether phosphates Alkyl phosphoric ester household and industrial cleaning products
Acyl-Amino Acyl glutamates RCONHCH(COONa)CH2CH2COONa Mild for skin and eyes; poor foamers. Shampoos, mildly
Acids and Sodium acyl glutamate acidic skin cleansers
Salts
Acyl peptides RCO(NHC(X)HCO)nNHC(X)HCOONa Mild surfactants, substantivity for hair shampoos, mildly
Sodium acyl polypeptide (X = amino acid) acidic skin cleansers
Acyl sarcosides RCON(CH3)CH2COONa Mild to skin. Shampoos
Sodium acyl sarcoside

Table 1 Anionic surfactants [20 – 22]

Tenside Surf. Det. 53 (2016) 1 9


Milica Lukic et al.: An overview of novel surfactants for formulation of cosmetics with certain emphasis

Subgroup Function/Application
Fatty alcohols Co-emulsifiers, opacifiers, thickening agents, foam depressors
Alkoxylated (ethoxylated or Emulsifiers, wetting agents and solubilizers. Household, industrial and personal care products
propoxylated) fatty alcohols
Ethylene oxide/propylene Automatic dishwashing and laundry detergents, rinse aids. Good thickening and gelling properties makes them in-
oxide-block polymers teresting for cosmetic products, they are used as emulsifiers, solubilizing or fluidizing agents.
Alkylphenol ethoxylates Wetting and washing agents, emulsifiers and solubilizers. Due to ecotoxicological reasons their use is diminished
(alkylphenol polyglycol ethers)
Alkyl polygycosides (APGs) Emulsifiers, wetting and foaming agents. Detergents, personal care cleansers, skin care products. Chemically stable
in neutral, alkaline and acidic (pH < 5) conditions
Ethoxylated Oils and Fats Emulsifiers, mainly used in cosmetic industry
(lanolin and castor oil derivatives)
Straight alkanolamides Foamers, foam boosters and foam stabilizers. Household detergent products, shampoos and cleaners
Ethoxylated alkanolamides Thickening, foam stabilizing and dispersing agents. Personal care cleansers
Ethoxylated fatty acids Excellent emulsifiers for cosmetic, household and industrial use. Mild cleansers and viscosity agents. Domestic and
industrial detergents (degreasing composition)
Glycol and glycerol esters and Food industry, emulsifiers and stabilizers. In pharmaceutical and cosmetic industry they are used as emulsifying
ethoxylated derivatives agents, oily compounds, refatting agents, emollients and skin conditioners in creams, lotions, ointments, and gels
Sorbitan and sorbitol esters and Emulsifiers, components of oil phase, solubilizers and wetting agents in pharmaceutical, cosmetic and food indus-
ethoxylated derivatives try, similar to the previous group
Alkyl carbohydrate esters Food-grade ingredients used as food additives (emulsifiers and stabilizers). Mild surfactants which can be used as
(Sugar or Sucrose Esters) emulsifiers and cleansing agents with emollient properties.
Amine oxides Solubilizers and detergents, compatible with all other surfactants. Shampoos (viscosity agents, reduce eye irritancy,
enhance foam properties). Suitable in slightly acidic or neutral formulas. Domestic cleaners (used in association
with anionic surfactants). Industrial applications: liquid bleach products, textile industry, foam stabilizers and in anti-
corrosion formulations

Table 2 Non-ionic surfactants and their respective application [20 – 22]

aforementioned advantages and interesting properties (i. e. range [39, 40]. However, they show considerable instability
physicochemical properties, biological activity, biocompatibil- at pH values higher than 7.0 – 7.5 when they are prone to hy-
ity and biodegradability), but also due to their high productiv- drolysis. As for their solubility, at pH 5 or lower sophoroli-
ity from renewable resources [27 – 36]. Among the biosurfac- pids are dispersed rather than dissolved in water [38].
tants, glycolipids may be more frequently found in the com- Based on the general surfactants’ classification, sophoroli-
position of cosmetics and personal care products, serving as pids are nonionic surfactants. They have various functions
multifunctional ingredients in their formulations [37]. and may serve as emulsifiers, wetting and foaming agents,
Structurally, they are long-chain aliphatic acids or hydro- solubilizers, detergents, irrespective of their biological activ-
xyaliphatic acids in combination with a carbohydrate moiety. ity [18]. Hence, they are used as multifunctional cosmetic in-
Based on the nature of the carbohydrate moiety, glycolipids gredients which have good skin compatibility and their ap-
can be sub-divided into rhamnose lipids, trehalose lipids, so- plication is mainly presented trough a number of patents
phorose lipids, cellobiose lipids, mannosylerythritol lipids, [37]. Due to their bactericidal activity, they may be found in
lipomannosyl-mannitols, lipomannans and lipoarabinoman- cosmetics intended for acne, dandruff and body odours
nanes, diglycosyl diglycerides, monoacylglycerol and galacto- treatment [41]. Sophorolipids have shown additional activ-
syl-diglyceride [27]. Within this group, rhamnose lipids, so- ities which make them interesting as possible active cos-
phorose lipids, and mannosylerythritol lipids are the most metic ingredients such as: (i) desquamating and depigment-
investigated surfactants, and are envisioned for prospective ing agents, due to the removal of stratum corneum surface
application in the production of cosmetics [37]. layers, (i) agents for cellulite treatment since they stimulate
leptin synthesis in adipocytes, and (iii) anti-age actives as
Sophorolipids both stimulators of fibroblast metabolism and collagen neo-
synthesis and inhibitors of free radicals [37]. They are also
Sophorolipids are produced by nonpathogenic yeast strains used in decorative cosmetics: pencil-shaped lip rouge, lip
such as Candida sp, especially Candida bombicola. Although cream, eye shadow and compressed powder [41].
some other strains such as Wickerhamiella domercqiae, Pichia Although sophorolipids find various uses in cosmetic in-
anomala, Rhodotorula bogoriensis serve this purpose as well, dustry due to their poor solubility at pH values lower then 5,
C. bombicola is the only strain used for their commercial they are by no means good candidates for formulations with
production to this day [38]. The hydrophilic part of a so- acidic active substances [38].
phorolipid consists of disaccharide sophorose (2-O-b-D-glu-
copyranosyl-D-glucopyranose) while the hydrophobic part Rhamnolipids
comprises a terminal or subterminal hydroxylated fatty acid,
linked via a b-glycosidic bond to the sophorose molecule Although sophorolipids were the first microbiological bio-
(Fig. 1). Sophorolipids preserve their function and activity surfactants on the market, rhamnolipids are the most inves-
in high salt concentrations and across a wide temperature tigated ones [42]. Rhamnolipids consist of one or two mole-

10 Tenside Surf. Det. 53 (2016) 1


Milica Lukic et al.: An overview of novel surfactants for formulation of cosmetics with certain emphasis

cules of l-(+)-rhamnose and one or two molecules of b-hy- For rhamnolipids it was shown that their tension activity
droxyalkanoic acid (Fig. 2). Even though investigation and remained unaltered over a broad pH range from 5 to 10
optimization of rhamnolipid production as well as product [57 – 60]. Although none of the consulted literature describes
portfolio expansion represent an emerging research field, cosmetic formulations with both acidic active substances
the most important strain for rhamnolipids’ commercial and rhamnolipids, it could be assumed that these biosurfac-
production remains Pseudomonas aeruginosa [43 – 46]. tants may be appropriate for formulations with lower pH.
Rhamnolipids have an anionic character and Nguyen et
al. showed that they are hydrophilic surfactants [47, 48], Mannosylerythritol lipids
while their hydrophilicity–hydrophobicity balance (HLB)
has been reported to be 22 – 24 by Xie et al [49]. They have Mannosylerythritol lipids (MELs) or ustilipids present a very
shown an excellent emulsifying potential with different interesting sub-class of glycolipids which are currently con-
compounds [50, 51], and their antimicrobial activity against sidered the most promising group of biosurfactants [61].
both fungi and bacteria has been confirmed [52, 53]. They consist of 4-O-b-D-mannopyranosyl-meso-erythriol as
Rhamnolipids have been used in health care products not hydrophilic moiety, and fatty acids of different hydrocarbon
only due to their high surface activity and emulsifying prop- chains, as the hydrophobic portion as presented in Fig. 3
erties, but also because of their biological activity. Some of [41]. They are further subdivided to MEL-A (di-acetylated),
the products mentioned in Lourith and Kanlayavattanakul MEL-B (mono-acetylated at C-4’), MEL-C (mono-acetylated
and Muhammad and Mahsa papers are insect repellents, at C-6’) and a new non-acetylated group MEL-D. MELs are
acne pads, antacids, anti-dandruff products, contact lens so- produced by fungal strains Pseudozyma sp. and Ustilago sp.
lutions, deodorants, nail care products and toothpastes [37, in relatively high and low quantities, respectively [62]. MEL-
54]. Additionally, among the available patents there are cer- A and MEL-B are highly hydrophobic and show an excellent
tain anti-ageing cosmetic products which contain rhamnoli- surface activity with low CMC; hence, it is appropriate to use
pids as active agents [55, 56]. them as emulsifiers, dispersants and detergents [63].

Figure 1 Sophorolipids

Figure 2 Rhamnolipids

Tenside Surf. Det. 53 (2016) 1 11


Milica Lukic et al.: An overview of novel surfactants for formulation of cosmetics with certain emphasis

MELs have attracted considerable attention as new cos- [85]. For that reason, lipopeptides are not regarded as pro-
metic ingredients owing to their ability to form liquid-crys- spective candidates for the stabilization of acidic formula-
tals, their moisturizing and antioxidant properties, as well tions.
as their hair repair effect [18, 64]. Since MELs easily form
lyotropic liquid crystals, it was expected that they would be 4.2 Surfactants based on a natural polar head group
effective in moisture retention and maintenance at the skin’s
intercellular level. Additionally, similarity in the structure of 4.2.1 Sugar as polar headgroup
MELs and ceramides directed some researchers to investi-
gate the moisturizing capacity of MELs. The subsequently Three classes of these sugar-based surfactants were gaining
conducted studies have proved their excellent moisturizing tremendous interest over past few decades: alkyl poly-
characteristics, equivalent to those of natural ceramides [61, glucosides (APGs), alkyl glucamides and sugar esters [12].
65]. Regarding the use of MELs in damaged hair treatment Also, sorbitan esters and their ethoxylated derivatives have
Morito et al. demonstrated the efficiency of MELs in recovery their place in this group, and they are commonly referred
of damaged hair, improving the hair smoothness and flex- to by their original registered trade names Span and Tween,
ibility [66]. The same research group confirmed the antioxi- respectively [86]. In spite of the fact that they have been used
dant properties of MELs which make them interesting as po- for many years, with large and relatively stable market share,
tential anti-aging skin care ingredients [67]. these surfactants are, generally, no longer in the focus of re-
searchers [87].
4.1.2 Lipopeptides
Alkyl polyglucosides
Lipopeptides or acylpeptides are composed of a fatty acid
linked to a short linear or cyclic peptide chain. They are a APGs have been the most intensively explored sugar surfac-
family of structural homologues differing in type, number tants. Work done on this topic in the last few decades and
(7 to 25) and configuration of the amino acids in the peptide numerous results which concern APGs have been the focus
moiety, the length (13 to 17 carbons) and the composition of of several thorough overviews summarized in articles and
the fatty acid chain, as well as the link between the two parts books [8, 87 – 92].
[68 – 73]. Lipopeptides are produced by various microorgan- APGs are synthesised through a glucosidation reaction,
isms, including fungi and numerous bacterial genera [74]. by a direct reaction of glucose and fatty alcohol or, alterna-
For this group of biosurfactants, it has been reported that tively, by transacetalization of a short chain alkyl glucoside
their functions are dependant not only on the biosurfactant with a long chain alcohol [12]. In Fig. 4 a schematic repre-
properties, but also on the applied bacterial strain [75]. The sentation of APGs is given. Once the optimal reaction condi-
most important producers of lipopeptides are Bacillus sp, tions for their synthesis (temperature, pressure, reaction
Paenibacillus sp. and Pseudomonas sp. [74, 76, 77]. Structural time and ratio of glucose to fatty alcohol) were established,
diversity of lipopeptides contributes to their numerous func- commercial manufacturing of high quality APG products,
tional properties; they can be used as emulsifiers, disper- under safe and economically acceptable conditions has be-
sing, foaming, viscosity, solubilizing and mobilizing agents, gun [87].
foaming depressors. Surfactin, iturin, fengycin, and licheny- Physicochemical properties such as surface and interfacial
sin are the most documented lipopeptide families [75]. They tension, CMC, behaviour in solution (phase behaviour) for
are found in different application fields including cosmetics, APGs are meticulously investigated and described [8, 87,
almost as much as glycolipids [28, 72]. Lipopeptides have 93]. Subsequently, this class of surfactants has found use in
been used in diverse cosmetic products, so far encompass- various applications, mainly in cosmetic products, manual
ing: cleansing products as detergents and emulsifying dishwashing, detergent application, but agricultural applica-
agents, anti-ageing products as anti-wrinkle agents, whiten- tion as well. With respect to their favourable environmental
ing cosmetics as whitening agents, and finally, due to their profile and excellent dermatological properties (mildness, in
broad spectrum of antimicrobial activity they could also en- terms of skin irritation potential), APGs attract considerable
sure product preservation [78 – 83]. Many of the mentioned interest in personal care industry [94]. In the field of perso-
applications are presented as patents [84]. nal care products they are, mainly, used as emulsifiers and
For lipopeptides an important parameter for their charac- cleansing agents (Table 2). Regarding their use in cleansing
terization is the isoelectric point. Fçrester et al. investigated products, APGs foam considerably better than fatty alcohol
a group of lipopeptides and found that their isoelectric point ethoxylates, improving the foam properties of the final pro-
lies in the acidic pH range between 2.7 and 4.5 (assessed in duct (better foam height and stability), while their high
soft water), while their molecules bear a negative charge in cleaning performance level is not affected by changes in the
aqueous dispersion at pH 6.5, necessary for stabilization of pH level [8]. Therefore, a majority of personal care cleansing
oil droplets against coalescence (emulsion stabilizing effect) products (face, body and hair cleaning) in the market around
the world contains APGs in the ingredients list.

Figure 3 Mannosylerythritol lipids Figure 4 Alkyl polyglucosides

12 Tenside Surf. Det. 53 (2016) 1


Milica Lukic et al.: An overview of novel surfactants for formulation of cosmetics with certain emphasis

The use of APGs as emulsifying agents has been inten- lease may be obtained in this manner. Additionally, the posi-
sively studied. A complete physicochemical characterization tive effect on the skin barrier is very important for formula-
of surfactants is based on the knowledge of their interfacial tions which contain actives with possible adverse effects on
properties and phase behaviour, and both are discussed in the skin and this will be discussed in more detail in one of
detail in the aforementioned reviews. Particularly important the following sections.
for APGs’ emulsion stabilizing properties is their phase be-
haviour. Temperature has only a slight influence on their Alkyl glucamides
phase behaviour, and that gives them a significant advantage
over ethoxylated non-ionic surfactants, which show the Alkyl or fatty acid glucamides are composed of only one sin-
phase inversion temperature (PIT) phenomenon. APGs gle carbohydrate molecule attached to the fatty acid chain.
form, in their pure state, both thermotropic and lyotropic Their synthesis involves the reaction of glucose with methyl-
liquid crystalline phases on heating, or on addition of a sol- amine under reductive conditions in order to avoid signifi-
vent, respectively. Generally, their behaviour is influenced by cant amounts of unreacted N-methyl glucamine (potential
APGs’ structure, especially the alkyl chain length, where the precursor for nitrosamines). Due to some of the manufac-
increase in chain length results in a greater thermal stability turing difficulties this class of compounds failed to enter
of both phases. the market until certain improvements have been made
When a fatty alcohol is added as a third component to the [111].
binary APG/water mixtures different lamellar phases appear These surfactants are biologically active and therefore con-
over the entire concentration range. Therefore, medium- sidered as good prospects for future chemical preparation of
and long-chain APG mixtures with long-chain fatty alcohols compounds useful as antibiotics and even anticancer agents
are especially interesting as emulsifiers for delivery systems [112]. On the other hand, they are commercially important
that are, hence, stabilized with lamellar liquid crystalline products for the detergent sector, mainly used in powdered
phases [8, 95, 96]. APG mixed emulsifiers have been exten- and liquid detergents and liquid dishwashing agents [12,
sively investigated in previous years, regarding their usage 87].
in cosmetic and pharmaceutical emulsion systems [97 – 107].
Savic et al. [98] showed that C16 – C18 mixed APG emulsi- Sugar esters
fier, despite its low HLB value (around 6), enables the stabi-
lisation of oil in water (o/w) systems by a synergistic effect From the market perspective, sugar surfactants are a rela-
of hydrophilic and lipophilic gel network, as well as by la- tively new class of surfactants, although they have received
mellar liquid crystalline bilayers surrounding the oil dro- the attention of scientific community for the last 50 years.
plets. Subsequent investigations of APG mixed emulsifiers Their hydrophilic part is a carbohydrate, usually mono- or
with shorter (C12 – C14), and longer chain length (C20 – C22) oligosaccharide and the hydrophobic tail, which is usually
confirmed the presence of similar patterns [105, 107], show- derived from a fatty acid, is esterified onto the carbohydrate
ing that APGs stabilize emulsion systems via the formation [113]. Although some may be found in nature, most of them
of various liquid crystalline structures. These three-dimen- are synthesized from renewable sources, either chemically
sional anisotropic structures, although cannot be considered or enzymatically [114 – 119]. The selective acylation of sugars
as a new phenomenon, have gained considerable attention is difficult due to the similar reactivity of the hydroxyl
as a part of cosmetic or pharmaceutical delivery systems, be- groups; consequently the chemical synthesis requires mul-
cause they are not only able to provide a satisfactory stability, ti-step protection and de-protection to avoid di- and tri-esters
but they induce interesting water distribution within the sys- formation as by-products which affect quality of the final
tem as well [108]. Regarding the fact that other excipients in product [120 – 121]. Contrary to the conventional chemical
the formulation may have considerable impact on the self- catalysis, enzyme catalysis can be performed under milder
assemble process that occurs prior to the liquid crystalline and simpler process conditions, and with higher selectivity.
phase formation, those excipients, primarily oil compo- Despite the fact that the majority of technical difficulties in
nents, may also become a part of a lamellar phase and influ- their large-scale production have already been overcome,
ence the liquid crystalline phase’s overall characteristics there is still a great interest in improvement of sugar surfac-
[109]. Depending on the chosen surfactant/oil combination, tant synthesis [122 – 127].
the obtained colloidal structure may possess variable frac- Sugar esters are non-ionic biodegradable surfactants with
tions of water: (i) free (or bulk) water, (ii) water bound within attractive properties, available in a wide range of HLB values
the lipophilic gel phase (secondary water), (iii) interlamellar related to different sugar and fatty acid combinations used
water fixed between the gel crystalline lipid bilayers and (iv) in the synthesis [128]. Depending on their HLB values, they
interlamellar water fixed between lipid bilayers in the liquid are suitable for a range of applications varying from emulsi-
crystalline state [99, 107, 110]. Lukic et al. have explored the fiers, solubilizing and foaming agents, antibacterial agents
hydration potential of simple APG based emulsions in real- to lubricants [129]. The most promising group of sugar sur-
time conditions and showed that the prolonged moisturiz- factants are sucrose esters [87]. They are tasteless, odourless,
ing effect of the investigated emulsions could be explained non-toxic and have good functional properties (emulsifica-
by the gradual liberation of the interlamellar water [107]. It tion, emulsion stabilization, foaming, etc), thus making
was later confirmed that the specific colloidal structure of them an interesting option for the food industry [113]. Re-
APG based emulsion systems contributes to their high garding their dermatological properties, they are described
moisturizing potential, while due to the similarity of the liq- as very mild which places them among raw materials favour-
uid crystalline phase and the stratum corneum organisation, able for personal care products and cosmetic application
these emulsion systems increase the skin barrier integrity [87]. Although these surfactants have been known since
and can contribute to the recovery of damaged skin [110]. 1960s, they are relatively new materials in the field of phar-
Advantages provided by the APG based vehicles find prac- maceutical technology [129]. Their use in the advanced deliv-
tical usage in cosmetic formulation. Gradual liberation of ery systems such as microemulsions and nano-carriers is
water leads to a prolonged moisturizing effect. Also if the being assessed. Thevenin et al. demonstrated that a sucrose
active substance is water soluble, its prolonged/modified re- ester could be adopted to form water in oil (w/o) microemul-

Tenside Surf. Det. 53 (2016) 1 13


Milica Lukic et al.: An overview of novel surfactants for formulation of cosmetics with certain emphasis

sion system in the presence of a short chain alcohol as co- data, these surfactants could present an interesting alterna-
emulsifier, while Khiew et al. found that sucrose ester-based tive to diglycerides and lecithins in the formulations that
microemulsions provide a suitable microenvironment for need antimicrobial properties.
the preparation of nanomaterials [130, 131].
Although they are commercially available and commonly 5 Formulations with acidic pH
employed surfactants in the food and personal care industry,
sucrose esters’ behaviour in multiphase systems, unlike At the beginning of any product formulation there are a
APGs, has not been thoroughly investigated. Recent work variety of factors that have to be considered, such as essen-
of Klang et al. evaluated the influence of processing tem- tial ingredients, critical ingredients and formulation stability
perature, type and amount of sucrose esters and the incor- [139]. Therefore, it is not unusual that formulations with
porated oil on the physical properties of the produced emul- acidic active substances present a challenge for formulators,
sions [132]. They have confirmed that the investigated since the essential ingredients within these products are also
sucrose esters are excellent surfactants for the formulation critical ingredients as well, which have negative effect on the
of skin-friendly semi-solid emulsions. Once again their work formulation stability.
pointed out that in order to understand emulsions’ colloidal Although the majority of these active substances can be
structure, to optimize formulation properties as well as to classified based on their chemical structure as acids, the fact
investigate the appropriate formulation for commercial ap- that a substance is an acid is underlined only when the
plication, a detailed characterization of the system has to be acidic pH of the formulation is necessary for chemical or
conducted. biological stability or/and performance of the cosmetic pro-
duct [140]. The most exploited actives with a pH-dependant
4.2.2 Amino acid as polar headgroup stability are the group of alpha-hydroxy acids, antiperspirant
actives, self-tanning active dihydroxy-acetone and some ac-
Hydrophilic moiety of these surfactants comprises amino tives like ascorbic acid and polyphenols which are more
acids or short peptides. The long aliphatic chain can be stable at the acidic pH.
bound to the amino acid by acyl, ester, alkyl or amide lin- In order to identify promising, novel surfactants which
kages and their synthesis is based on organic or enzymatic can be used as stabilizers of vehicles for acidic active sub-
processes [133]. Amino acid-based surfactants are classified stances, we have reviewed scientific publications and other
based on three main structures: linear or a single chain, di- available reliable data dealing with the incorporation of
meric or gemini and glycerolipid-like structures; depending these actives in the cosmetic formulations stabilized with
on the choice of amino acid and the synthesis procedure, novel (mainly natural) surfactants. In the following section
either anionic, cationic, non-ionic or amphoteric surfactants a more detailed description of potential problems regarding
can be prepared [14]. Generally, a research of amino acid- the chosen acidic active substances is given, together with
based surfactants is mainly addressing their synthesis, prop- the achievements accomplished in this field.
erties and biological activity, and for more detailed reading
on these topics the following references are recommended 5.1 Alpha-hydroxy acids
[14, 133 – 135]. Due to the large variety of amino acid/pep-
tide structures, together with variations in the fatty acid The alpha-hydroxy acids (AHAs) have been utilized in count-
chain structure, length and number, this group shows a less cosmetic formulations due to their well-established ben-
wide structural diversity, as well as different physico-chem- efits for both normal and diseased skin. AHAs are effective
ical and biological properties [14]. Although some amino exfoliants, moisturizers and anti-aging agents [141, 142].
acid-based surfactants are established on the market, their A problem related to AHA use is that they often cause ir-
share is still relatively small [134]. ritation to the skin, usually manifested as redness, burning
For the synthesis of a single chain amino acid/peptide and itching [143]. This irritation is mainly due to the non-io-
surfactant, any of the 20 standard amino acids can be used, nized AHA itself, which rapidly penetrates the skin and the
but the most common are arginin-based surfactants [12]. For inevitably low pH of these formulations. A formulation’s pH
the investigated surfactants within this group, it was demon- value has to be set near the AHA’s pKa value in order to re-
strated that: (i) Their surface activity is comparable to that of tain a higher percentage of the non-ionized, free acid form,
conventional long chain quaternary ammonium salts. (ii) since only this form is immediately bioavailable for penetra-
They show complex and unusual phase behaviour and (iii) tion through the skin. In order to diminish adverse effects
some of them have very valuable antimicrobial properties but maintain efficacy, two approaches have been the most
[14]. Lipoamino acid vehicles were investigated as potential intensively investigated. First approach involves certain con-
drug carriers and for the preparation of functional lipo- trolled-release mechanisms and includes the use of ampho-
somes with lipopeptide ligands where they showed good en- teric amino-acids and molecular complexing agents [144,
capsulation efficiencies for the selected solutes [136, 137]. 145]. For the purpose of this review, another approach based
Gemini surfactants are amphipathic compounds formed on the investigation of a proper vehicle which could contri-
by two hydrophilic and two hydrophobic groups per mole- bute to the overall efficacy of actives and the reduction of po-
cule linked by a spacer at the level of the head groups [14]. tential adverse effects is much more interesting.
Due to their dimeric structure gemini surfactants usually In order to optimize delivery and efficacy of the product,
show a lower CMC, higher efficiency in surface tension re- AHA formulations have to be developed in a low pH range,
duction and a better solubilizing capacity when compared to typically around 4. Consequently, this rules out the use of
the conventional single chain products [138]. some of the more traditional cosmetic ingredients. Namely,
Amino acid glyceride conjugates consist of one or two ali- the small chain esters (emollients or fragrances) hydrolyse
phatic chains and one amino acid, linked through an ester under acidic conditions, while thickeners which have to be
bond in the glycerol backbone and they can be synthetized neutralized via an alkaline base are not able to function in
using chemical and enzymatic methodologies [14]. They are an acidic formulation. The use of ingredients that perform
a new group of compounds and their properties have not well in a low pH range and have a good electrolyte tolerance
been extensively explored. Based on some of the published is recommended for AHA formulation. Therefore, a suitable

14 Tenside Surf. Det. 53 (2016) 1


Milica Lukic et al.: An overview of novel surfactants for formulation of cosmetics with certain emphasis

thickener is often one of the natural polysaccharides such as 1947, aluminium chlorhydrate was introduced which is con-
xanthan gum and cellulose ethers. As for the emulsifier, a sidered less irritant but also less effective, while in the late
mixture of non-ionic emulsifiers and fatty alcohols is the 1960s the first aluminium-zirconium salts were placed on
most common combination for emulsion stabilization. The the market. Therefore, it is obvious that the formulators
majority of products on the market contain some of the non- had to deal with similar challenging actives for almost a cen-
ionic emulsifiers which include mixtures of fatty acids and/ tury. Antiperspirants are applied underarm and, unlike the
or alcohols of about 12 to 24 carbon atoms in length and actives in these products, the way that they are applied has
emulsifying waxes prepared from cetostearyl alcohol con- changed intensely over time. First antiperspirants were liq-
taining a polyethylene glycol (PEG) derivative of a fatty ester uid formulations applied to the armpit with cotton balls,
of sorbitan [146 – 149]. Some studies have shown that tradi- which were slow to dry. With the introduction of roll-on,
tionally used acid-stable PEG emulsifiers could induce er- sticks and aerosols began the era of aesthetically appealing
ythema in healthy skin [150]. For the last two decades, enor- and easy to apply antiperspirants which are today on the
mous interest in the field of natural surfactants with sugar market. The biggest innovation in this field was the intro-
polar headgroup has introduced APG surfactants and su- duction of cyclomethicone, a quick-dry solvent which evapo-
crose esters in the formulations with low pH values [151 – rates quickly, leaving the active ingredient behind without
153]. Although the market of cosmetics is overflowed with any greasiness or stickiness. However, these compounds
the formulations containing these surfactants, there are only are nowadays submitted through regulatory enquiries in
few studies dealing with the influence of an acidic active on Europe because of some concerns that they may bioaccumu-
the vehicles’ physicochemical characteristics and overall per- late in the environment [162, 163]. Outcome of these safety
formance of such products. Majority of scientific work was considerations and environmental issues could drastically
done with the most investigated APG surfactants, as it was jeopardise current trends in antiperspirant formulations
already mentioned. and potentially provoke certain changes and maybe even in-
Tasic-Kostov et al. have demonstrated in several very de- troduce natural surfactants to these products.
tailed studies that commercially available APG-mixed emul- As for the generally used emulsifiers within emulsion
sifiers (investigated emulsifiers and co-emulsifier: (i) cetearyl antiperspirant products, traditionally used acid-stable emul-
alcohol and coco glucoside, (ii) cetearyl alcohol and cetearyl sifiers are commonly listed as ingredients in these formula-
glucoside and (iii) myristyl alcohol and myristyl glucoside) tions [164]. To the best of our knowledge, there are no find-
can be used as stabilizers for emulsions intended to be ap- ings among the scientific literature referring to antiperspir-
propriate carriers for acidic active substances: alpha- and ant formulations with novel surfactants. Based on the data
polymeric, glycolic and lactobionic acid, respectively [154 – reviewed in this paper we could presume that biosurfac-
156]. Their findings have shown that lactobionic acid, as a tants, due to their biological, i. e. antimicrobial activity, espe-
highly hygroscopic substance, strongly influenced the colloi- cially rhamnolipids which are claimed to be used in deodor-
dal structure of the emulsion based on APGs and even pro- ant products, could be the most interesting for this special
moted the formation of lamellar structures thus influencing personal care field.
the mode of water distribution within the cream [154]. The
investigation of glycolic acid efficacy confirmed that, when 5.3 Dihydroxyacetone
incorporated in an APG-based emulsion, this active shows
less irritation [156]. Also, significantly improved skin mois- Dihydroxyacetone (DHA) is the active substance in sunless
turization and lack of skin irritation and damage, which are tanning cosmetic products which has been commercially
demonstrated in this study, are explained with the effect of available for nearly half a century [165]. Browning of the
APG-based vehicle itself. In the study which was focused skin after DHA application is caused by the Maillard reac-
on the investigation of the systems’ sensory characteristics, tion, which is a non-enzymatic glycation of the amino
Lukic et al. have shown that long-chain APG emulsifier com- groups of amino acids, peptides and proteins from the
prising arachidyl alcohol, behenyl alcohol and arachidyl glu- upper layer of the stratum corneum by the carbonyl groups
coside, could also successfully serve as the stabilizer for sys- of sugars, resulting in the formation of advanced glycation
tems containing glycolic and salicylic acid [157]. end products [166]. DHA is by far the most common active
in sunless tanning products, and when about to formulate
5.2 Antiperspirants DHA-based preparations one factor has to be especially con-
sidered. Although stable as a crystalline powder, when dis-
Antiperspirants are sweating-inhibiting agents, and antiper- solved in water DHA gradually tautomerizes to glyceralde-
spirant preparations are mainly intended to reduce the hyde and this process escalates along with the pH and
amount of sweating [158]. The most important representa- temperature increase [167]. Therefore, it is generally ac-
tives of this group of actives are aluminium and zirconium cepted that stable sunless tanning products should have pH
salts which reduce sweat by causing mechanical obstruction values between 3 and 4 [140].
to the eccrine sweat duct at the acrosyringium level. These Sunless tanning formulas have become increasingly pop-
active ingredients are mainly complexes which differ only ular in recent years, since they provide desirable tan without
in the relative amounts of aluminium, chloride, and zirco- the dangers of developing skin cancer [168]. Nevertheless,
nium [159]. Aluminium-based compounds in antiperspir- there is an absence in the scientific interest towards the
ants are characterized by an acidic pH value, thus being re- problem of DHA’s stability in some of the novel delivery sys-
sponsible for the acidity of the entire formulation (pH tems or systems based on novel surfactants. A possible ex-
ranging from 3.5 to 4.5) [160]. The first antiperspirant intro- planation lies in the fact that the existing cosmetic formula-
duced to the market at the beginning of the last century, in tions are already favoured with generally satisfying stability
1916, was aluminium chloride hexahydrate [161]. Due to its and efficacy. For these actives, stabilization is accomplished
high acidity, skin irritation and clothing damage this com- with the same, traditional, acid-stable emulsifiers, as already
pound is not used in personal care/cosmetic products any- mentioned for AHAs [148, 149, 169 – 173]. Among the re-
more. However, it is still frequently used as a prescription lated patents, an APG surfactant was used as the emulsifier
antiperspirant for the treatment of hyperhidrosis [158]. In in self tanning products containing DHA [174].

Tenside Surf. Det. 53 (2016) 1 15


Milica Lukic et al.: An overview of novel surfactants for formulation of cosmetics with certain emphasis

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personal care products: Prerequisite for human and environmental exposure Milica Lukic works as research and teaching assistant at the Department of Pharma-
assessment. Environment International 62 (2014) 86 – 94. ceutical Technology and Cosmetology of the University of Belgrade – Faculty of
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ants, skin care products and hair care products. Chemosphere 93 (2013) macy, where she works as a research and teaching assistant at the Department of
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166. Finot, P. A.: Nonenzymatic browning products: physiologic effects and meta- search interest encompasses both the field oh Pharmaceutical Technology and Cos-
bolic transit in relation to chemical structure. A review. Diabetes 31 (1982) metology, especially focused on skin delivery systems of emulsion type and novel
22 – 28. DOI:10.2337/diab.31.3.S22 surfactants characterization.

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