Advances in Colloid and Interface Science 256 (2018) 242–255

Contents lists available at ScienceDirect

Advances in Colloid and Interface Science

journal homepage: www.elsevier.com/locate/cis

Historical perspective

Interactions between surfactants and the skin – Theory and practice

Artur Seweryn
Department of Chemistry, Kazimierz Pulaski University of Technology and Humanities, Chrobrego Street 27, Radom 26-600, Poland

a r t i c l e i n f o a b s t r a c t

Available online 13 April 2018 One of the primary causes of skin irritation is the use of body wash cosmetics and household chemicals, since they
are in direct contact with the skin, and they are widely available and frequently used. The main ingredients of
Keywords: products of this type are surfactants, which may have diverse effects on the skin. The skin irritation potential
Surfactants of surfactants is determined by their chemical and physical properties resulting from their structure, and specific
Skin irritation interactions with the skin. Surfactants are capable of interacting both with proteins and lipids in the stratum
Anti-irritants
corneum. By penetrating through this layer, surfactants are also able to affect living cells in deeper regions of
Cosmetics
Household products
the skin. Further skin penetration may result in damage to cell membranes and structural components of
keratinocytes, releasing proinflammatory mediators. By causing irreversible changes in cell structure, surfactants
can often lead to their death. The paper presents a critical review of literature on the effects of surfactants on the
skin. Aspects discussed in the paper include the skin irritation potential of surfactants, mechanisms underlying
interactions between compounds of this type and the skin which have been proposed over the years, and verified
methods of reducing the skin irritation potential of surfactant compounds. Basic research conducted in this field
over many years translate into practical applications of surfactants in the cosmetic and household chemical in-
dustries. This aspect is also emphasized in the present study.
© 2018 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 242
2. Physical and chemical characteristics of surfactants in their aqueous solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
2.1. Classification of surfactants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
2.2. Surfactant behavior in solution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
3. Interactions between surfactants and the skin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 245
3.1. Interactions with SC surface proteins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 245
3.2. Interactions with SC lipids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 247
3.3. Interactions with living skin cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 247
4. Methods to reduce the skin irritation potential . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 248
4.1. Use of surfactants with reduced skin irritation effect as primary washing agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . 248
4.2. Application of surfactant mixtures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 250
4.3. Addition of polymers and biopolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 251
4.4. Addition of refatting and hydrophobic substances . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 253
5. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 253
Declarations of interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 253
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 253
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 253

1. Introduction
Every day the skin is exposed to aggressive factors that can cause cu-
taneous irritation. In addition to chemical compounds affecting the skin
E-mail address: a.seweryn@uthrad.pl.
through direct contact, the condition of the skin also depends on phys-
ical, biological and environmental factors [1,2]. Some of them may act si-
multaneously, thus potentiating the effect produced by individual
factors. Examples include household chemicals containing abrasive in-
gredients or cosmetic scrubs. Abrasive substances used in both types
of formulations may cause abrasions and red patches on the skin
resulting from the mechanical impact of individual grains on the surface

https://doi.org/10.1016/j.cis.2018.04.002
0001-8686/© 2018 Elsevier B.V. All rights reserved.
 A. Seweryn / Advances in Colloid and Interface Science 256 (2018) 242–255
of the epidermis. Damage to the contact surface between the product
and the outer skin layer promotes an intensified activity of chemical fac-
tors which, in products of this type, are surfactants [1–5].
Surfactants have a wide range of applications in many industry
branches. They are used in the formulation of a vast number of commer-
cially available products such as cosmetics and household chemicals. On
account of their properties determined by the amphiphilic structure
(ability to reduce surface tension at the interface between phases:
liquid–liquid, liquid–solid and liquid–gas, fat emulsification capacity),
surfactants are a base for body wash cosmetics and a number of cleaning
agents (e.g. hand dishwashing liquids, liquid laundry detergents)
[5–12]. Consequently, surfactants belong to the substances most com-
monly having contact with the skin. A key role in understanding the
mechanisms which underpin the skin-irritating activity of surfactants
is attributed to the structure and physiochemical properties of their
aqueous solutions, an important factor being the form in which surfac-
tants occur in the solution [1–5,9,13–38].
Surfactants interact primarily with the outermost epidermal layer
called the stratum corneum (SC). The stratum corneum consists of
10–15 layers of corneocytes embedded in a lipid matrix (intercellular
cement). The SC is a barrier which prevents the entry of environmental
pollutants and pathogens into the body. Furthermore, it prevents exces-
sive water loss from deeper skin layers into the environment.
Corneocytes are formed in the process of disintegration of cells which
build up deeper layers of the epidermis (keratinocytes). Following the
loss of the cell nucleus and cytoplasm, keratinocytes are transformed
into dead structures with tough outer cellular shells [39].
The intercellular cement has a unique structure. It is composed of
alternating lipids, which are transported from dying cells in deeper
layers of the skin, and a thin layer of water saturated with considerable
amounts of various chemical compounds. The structure exhibits a
rhomboid and hexagonal pattern of the lamellar phase, which makes
it highly resistant to the effect of a range of chemical agents and repre-
sents the main factor inhibiting the migration of water from the dermis
to the epidermal surface [13,40]. The intercellular cement in well-
structured stratum corneum contains a number of compounds includ-
ing approximately 50% of ceramides, 25% of cholesterol, 15% of free
fatty acids and 10% of cholesterol esters [40–44].
Important constituents of the SC are substances present in
korneocytes forming the so-called natural moisturizing factor (NMF).
They are hygroscopic compounds resulting from enzymatic transforma-
tions of a specific protein called filaggrin. The NMF consists primarily of
free amino acids (about 40%), sodium salt of pyroglutamic acid (about
12%), lactic acid salts (about 12%), urea (about 7%), inorganic salts
(about 18.5%) and small amounts of ammonia, creatinine, uric acid,
citric acid salts, sugars and peptides [13,40,43,44].
A major function of the epidermis is the formation of the so-called
hydrolipidic film, a protective layer at the contact surface between the
SC and the environment. The system contains mainly sebum and seba-
ceous gland secretions, making the skin soft and forming antibacterial
and antifungal layers on the skin surface. It is a mixture of epithelial
lipids, free fatty acids (about 5%), glycerides (about 50%), waxes
(about 20%), squalene (about 10%), cholesterol esters (about 4%),
cholesterol (about 1%), sterols (about 1%) and other substances (about
9%). On the skin surface the mixture combines with a certain amount
of water and sweat constituents, creating a W/O type emulsion. The
formation of the emulsion is possible owing to the presence of sterols
which serve as W/O emulsifiers. The aqueous emulsion phase contains
dissolved substances which are secreted with sweat, most of which
have hygroscopic properties. They attract water from the environment
and hinder its evaporation from the stratum corneum [45].
An important role for preserving the structure and function of the
SC is played by an appropriate pH gradient. It is recognized that the
pH value on the skin surface should vary between 5.4 and 5.9. It is reg-
ulated among others by free fatty acids, metabolites of microorganisms
residing on the skin, products secreted by endocrine glands and NMF
243
components. Surfactants have an ability to alter the pH of the skin,
which results in abnormalities related to the synthesis of enzymes
that are responsible for the production of intercellular matrix lipids
and components of the NMF in the stratum corneum. Studies have re-
ported an increase in transepidermal water loss from the skin [46–48].
The literature widely describes possible interactions between sur-
factants and the skin which can result in dermal irritation. Surfactants
are analyzed in the aspect of their binding to the SC surface proteins.
The process can lead to protein denaturation, changes in the structure
of the intercellular cement through the incorporation of surfactants
into its liquid crystalline structure followed by the washing and solubi-
lization of lipids which lead to damage to the epidermal barrier and in-
teractions between surfactants and living cells due to their penetration
into deeper skin layers [1–5,9,13–40,46–49].
2. Physical and chemical characteristics of surfactants in their
aqueous solutions
Surfactants are chemical compounds which have an ability to accu-
mulate (become adsorbed) at the interface between phases and reduce
surface tension. The property is attributable primarily to their bipolar
structure. Surfactant molecules contain two distinct parts differing in
polarity. The hydrophilic part has affinity to water and polar solvents,
and forms the so-called head group of the surfactant molecule. It is com-
posed of (basic and acidic) groups that are capable of electrolytic disso-
ciation, and nonionic groups. The acidic groups are usually carboxylic,
sulphonic, sulphate and phosphate radicals. The hydrophilic group com-
posed of basic fragments includes, for example, primary, secondary and
tertiary pyridine groups and primary, secondary and tertiary amine
group. Hydroxide, sugar and thiol radicals represent nonionic groups.
The hydrophobic part which shows affinity to non-polar solvents and
oils typically consists of hydrocarbon chains. They can be fragments of
fatty acids or their derivatives, either branched or unbranched.
Also known are compounds in which the non-polar fragment is
composed of an aromatic carbohydrate with an attached long alkyl
chain [10,11,50–58].
2.1. Classification of surfactants
The most commonly recognized classification of surfactants is based
on their ability to dissociate in water. Surfactants which undergo elec-
trolytic dissociation in the aqueous environment are classified as ionic.
Where a negatively charged ion (anion) exhibits surface activity after
the process of dissociation, the compound is classified as an anionic sur-
factant. Where surface activity is demonstrated for a cation, the surfac-
tant is cationic in nature. There are also compounds which are capable of
dissociation in water, however the type of ion formed depends on
the pH of the environment in which they occur. The compounds are
classified as amphoteric surface-active agents. Accordingly, cations are
formed in the acidic and anions in the basic environment. The dominant
forms in solutions with a neutral pH are zwitterions, i.e. molecules con-
taining both a cation and an anion. Those surfactants which dissolve in
water thanks to the formation of hydrogen bonds between water mole-
cules and an atom having a free electron pair are categorized as nonionic
surfactants, as they fail to undergo electrolytic dissociation [11,50–58].
General classification of surfactants is shown in Table 1.
2.2. Surfactant behavior in solution
From the physicochemical viewpoint, most household chemicals
and body wash cosmetics can be regarded as aqueous solutions of sur-
factants enriched with various substances in order to achieve a desirable
fragrance or viscosity, skin conditioning effect or product preservation
[58–60]. In aqueous solutions surfactants undergo the process of self-
organization which is a consequence of their amphiphilic nature.
Owing to their bipolar structure and the presence of two fragments of
244 A. Seweryn / Advances in Colloid and Interface Science 256 (2018) 242–255

Table 1
General classification of surfactants.

Surfactant Example
type

Anionic Sulphates (alkyl sulphates, alkyl ether sulphates), sulphonates (alkylbenzene sulphonates, α-olefin sulphonates, paraffin sulphonates, sulphonated fatty acids,
sulphonated methyl esters, sulphosuccinates), carboxylate (soap, ether carboxylates, acyl sarcosinates, taurates, isethionates), phosphate esters, acylated
aminoacids (N-acyl L-glutamates, N-acyl glycinates)
Cationic Long-chain amines and their salts, acylated diamines and polyamines and their salts, quaternary ammonium salts, polyoxyethylenated long-chain amines,
quaternized POE long-chain amines
Amphoteric Amidoamines, amidobetaines, sulfobetaines, sultaines, N-alkylbetaines, imidazoline carboxylates
Non-ionic Fatty alcohol ethoxylates, alkyl phenol ethoxylates, polyoxethylene esters of fatty acids, methyl ester ethoxylates, polyalkylene oxide block co-polymers,
amine ethoxylates, fatty alkanolamides, amine oxides, glycol esters, glycerol esters, polyglycerol esters, polyoxyalkylene polyol esters, alkyl poly glucosides,
polyoxyethylenated silicones

different polarities in their molecules, surfactants exhibit surface activ-
ity. In water they migrate and become adsorbed at the interface be-
tween phases (e.g. water – air), where numerous active centres make
the adsorption of surface active agent molecules possible. As the surfac-
tant concentration in the solution increases, and all the active centres
become occupied, the concentration of compound molecules begins to
rise in the volume phase of the solution, where they are present in the
form of individual molecules called monomers. Surfactant monomers
present in solutions are in constant motion. There is an ongoing
exchange between monomers in the volume phase and monomers
adsorbed on the surface. The system tends to minimize interactions
which have an adverse effect on the system, occurring between water
molecules and hydrophobic groups of monomers present in the volume
phase. After a specific concentration, unique to each surfactant type and
referred to as the critical micelle concentration (CMC), is reached, ag-
gregates called micelles are formed in the solution [50–58]. Surfactant
behavior in solution is shown Fig. 1.
Micelle formation in the volume phase is determined by the so-
called hydrophobic effect which is associated with interactions taking
place between hydrophobic groups of surface active agents and water
molecules. Since the system strives to reduce the surface of contact be-
tween solvent molecules and surfactant hydrocarbon chains, micelles
develop in the solution [58,59]. Micellar aggregates consist of surfactant
molecules which are oriented with their hydrophilic parts towards
solvent molecules, protecting the hydrophobic aggregate core from
contact with water. The system thus achieved is thermodynamically
favourable. The quantity describing the mean number of surfactant mol-
ecules which can form a micelle is the so-called aggregation number.
Every surfactant type has its characteristic aggregation number, usually
ranging from 50 and approximately 200. Micelles are thermodynami-
cally unstable and, as a result, aggregates constantly disintegrate in
the solution and there is an ongoing exchange of individual molecules
from the solution with aggregate-forming monomers. After the CMC is
exceeded, a state of equilibrium is achieved in the solution between
molecules of surface active agents in the form of monomers and mole-
cules in micellar aggregates [50–58].
The shape and size of arising micelles are determined by the type,
structure and concentration of their constituent surfactants. The shape
of surfactant molecules is most commonly described by the packing fac-
tor V/l ∙ S, where l indicates molecular length, V denotes the volume of a
single surfactant molecule and S – the surface area occupied by a single
molecule on the micellar surface. If only the molecular geometry is
taken into account, the micellar shape in an aqueous solution can be
linked to the packing factor, as shown in Table 2 [6,58,63–65].
Micelles formed in aqueous surfactant solutions after the CMC is
exceeded are usually relatively small and spherical in shape or flattened.
A characteristic feature of ionic surfactants is that all micelles formed in
aqueous solutions are uniformly charged, which results in the develop-
ment of mutual electrostatic repulsion forces attributable to the so-
called zeta potential. The process prevents micellar aggregates from get-
ting together at close distances, and stops them from fusing into large
micelles. Repulsive forces exist not only between different micelles
but also between hydrophilic surfactant groups within a single aggre-
gate. The interaction prevents the entry of a large number of its mole-
cules into a single micelle (hence the value of the aggregation number
is constant) and is responsible for the continuous disintegration of
formed aggregates. The state of equilibrium enables only the exchange
of surfactant molecules between different micelles as well as micelles
and monomers present in the volume phase. As soon as a micelle disin-
tegrates, a new aggregate is formed immediately in its place. In nonionic
surfactants the repulsion of arising micelles is attributed to the spatial
barrier that prevents aggregates from moving close to each other and
is referred to as the steric effect [61]. Since household chemicals and
body wash cosmetics are systems comprising solutions of various sur-
factant types, mixed micelles are formed, larger in size and higher in sta-
bility [6,63–65]. The repulsion of such aggregates is attributed both to
the presence of the zeta potential and steric effects [7,8,49–58,62].
After the surfactant concentration in the solution rises above the
critical micelle concentration, the charges of individual aggregates grad-
ually change. Mutual repulsion forces between differently charged mi-
celles begin to disappear. Micelles can combine, which entails an
increase in the aggregation number and a marked enlargement in

Fig. 1. Surfactant behavior in solution. (a) Surfactant molecules in aqueous solution concentrate at the air–water interface with the hydrophobic part oriented towards the air side.
(b) When the concentration of surfactant increases, the interface saturates of surfactant molecules that penetrate into the solution. (c) To minimize their interaction with water, the
hydrophobic parts of the surfactants interact together and form micelles in solution.
 A. Seweryn / Advances in Colloid and Interface Science 256 (2018) 242–255 245

Table 2 of skin irritations is associated chiefly with the presence of individual

Relationship between micellar shape and packing factor. surfactant molecules (monomers) in the aqueous solution. Rhein et al.
V/ls Surfactant molecular structure Micellar shape have shown that the skin irritation potential depends mainly on the du-
b0–1/3 Simple surfactants with a single Spherical or oval micelle
ration of skin contact with the surfactant before the CMC is achieved,
chain and appropriately large and the surfactant type and concentration. In their studies, the authors
polar group have found that after the CMC is exceeded, the severity of the irritant ef-
fect is lower. They have also argued that monomers are the main factor
1/3–1/2 Simple surfactants with a smaller Cylindrical micelles
determining the influence of surfactants on the stratum corneum's ker-
polar group or ionic surfactants
in the presence of electrolyte atin protein [66,67].
Monomers adsorbed on the skin surface may interact with the SC
1/2–1.0 Double-chain surfactants with Vesicles, bimolecular structures keratin protein, causing denaturation of its α-helix structure. Damage
a large polar group and flexible
to the secondary and tertiary structure makes it possible to expose
chains
sites where water molecules can bind. Swelling of the stratum corneum
is observed. The degradation of the protein structure facilitates the
washing of proteins from the skin and their solubilization in the solu-
1.0 Double-chain surfactants with a Planar (flat) or stretched micelles tion. As a result, it becomes easier for amphiphilic compounds, other
small polar group and stiff chains chemical compounds and pathogens to penetrate to deeper SC layers.
Reaching more deeply situated living cells, they are a stimulus inducing
an immune response, which is manifested by the development of topi-
cal red patches on the skin or itching. What is more, swollen keratin pro-
N1.0 Double-chain surfactants with a Reverse micelles teins after the evaporation of excess water have a lesser water binding
small polar group and large
non-polar group
capacity. As a result, the skin moisture level is lower, and the skin be-
comes less flexible [13,36,66–69].
The impact on proteins is attributed primarily to ionic surfactants
which are able to bind to them via relatively strong electrostatic interac-
tions [17,70–78]. Research on the impact of surfactants on the skin is fo-
cused above all on anionic surface active agents, with sodium dodecyl
their size. Since the system strives to achieve the smallest possible area sulphate (SDS) being most commonly used as a model compound. In
of aggregates, at a high concentration of surfactants it undergoes self- nonionic surfactants interactions with proteins are based on the forma-
reorganization. Large spherical micelles are transformed into cylindrical tion of relatively weak hydrogen and van der Waals bonds, which is
micelles and, as the next stage, into lamellar phases which are character- why their ability to cause protein denaturation and trigger skin irrita-
ized by a smaller area than large spherical micelles. A similar effect can tion through this mechanism is limited [13–17,19,29,36,66–68,79–85].
be achieved by introducing a salt (e.g. NaCl), used as a viscosity modifier, In recent years, the effect of surfactants on the skin has been evalu-
into the system. The addition of sodium chloride, which is most com- ated, both in scientific studies and practical applications, using the
monly used for this purpose, not only lowers the CMC but also, by reduc- zein protein [29,30,86–89] and bovine serum albumin [31,32,73,90,91]
ing the zeta potential in ionic surfactants and causing dehydration of which are structurally similar to keratin, the epidermis-building
polyoxyethylene chains in nonionic surfactants, it contributes to a protein. Measurements of the zein number involve determining the
change in the shape of micelles forming in the solution (spherical quantity of the water-insoluble zein protein solubilized by surfactants
micelles N cylindrical micelles N lamellar phases) [52–62]. The phenom- in the aqueous solution and previously partially denatured as a conse-
enon is used in production processes in order to achieve an appropriate quence of contact with an amphiphilic compound. The result is
viscosity level in cosmetic formulations [63–65]. The formation of cylin- expressed as the mass of free nitrogen derived from protein in the solu-
drical micelles in the system leads to an increase in viscosity [53–58]. tion and presented as a measure of the irritant potential. The higher the
Viscosity changes in aqueous surfactant solutions resulting from test result, the higher the skin irritation potential of the test sample
changes in micellar shape and size is shown schematically in Fig. 2. [29,30,63–65]. The interaction between bovine serum albumin and
surfactants has found practical applications in the evaluation of the
3. Interactions between surfactants and the skin skin irritation potential of cosmetic materials, finished cosmetics and
household chemicals. In the bovine serum albumin test, the structure
3.1. Interactions with SC surface proteins of albumin changes as a result of denaturation of the protein caused
by exposure to surfactants, ultimately leading to changes in the pH of
Surfactants rank among the most important factors with a potential the solution. The introduction of anionic surfactants into the albumin
to cause skin irritation. The literature data indicate that the occurrence solution causes surfactant binding to the cationic groups of the albumin

Fig. 2. Viscosity changes in aqueous surfactant solutions resulting from changes in micellar shape and size.
246 A. Seweryn / Advances in Colloid and Interface Science 256 (2018) 242–255
protein. In order to neutralize the negative protein charge resulting
from the predominance of anionic groups in its molecule, the adsorp-
tion of protons from the solvent takes place, causing a rise in the pH of
the solution. The greater the increase in the pH level of the solution,
the stronger the skin irritation potential associated with the solution
[31,32,91].
According to the commonly recognized model of interactions be-
tween surfactants and the SC proteins, only monomers – owing to
their small size – are capable of penetrating into the structure of the
outer skin layer and inducing structural changes in constituent proteins.
It was believed that as soon as the critical micelle concentration (CMC)
was achieved and micelles were formed, the severity of the irritant ef-
fect was reduced. The assumption was that micelles, being aggregates,
were too large to have an ability to deposit on or penetrate into the epi-
dermal surface. Furthermore, the potential to cause skin irritations was
also correlated with the value of the critical micelle concentration. In
surfactants with higher CMC values the concentration of free monomers
is higher, so the skin irritant effect increases as well [13–16,67–69,81].
The role of monomers as the only factor determining the skin irritant
effect of surfactants in solutions has been verified by Walters et al. [82].
The authors have found that the application of ready-made body wash
products in which the CMC is markedly exceeded also causes an in-
crease in skin irritation, and the irritation potential rises as a function
of surfactant concentration in the solution. Furthermore, they have
shown that both free monomers and micelles are capable of causing
protein denaturation. They claim that micelles, being unstable struc-
tures, may disintegrate after skin contact and affect its structure in the
form of monomers [82,83]. In contrast, Rehin and Simion [66,67] pro-
pose that an increase in skin irritation activity noted after the CMC is
achieved can be attributed to small-sized submicelles emerging in the
solution or monomers released during micelle breakdown. Similar find-
ings have been reported by Moore et al. [81]. Their studies examining
aqueous solutions of SDS at various concentrations have shown that
SDS is able to penetrate to the epidermis in monomeric and micellar
forms. The above findings have been confirmed by Cohen et al. [92] in
their most recent studies evaluating zein denaturation and solubiliza-
tion capacity of sodium alkyl benzene sulphonate solutions. Exploring
the correlation between zein and surfactant concentrations, the authors
have shown that the protein solubilization capacity increases over the
CMC. Based on their findings, they confirm that surfactants in micellar
forms are able to affect the epidermal protein structures.
Some studies have shown that a significantly higher skin irritation
potential is associated with those surfactants which form micelles of rel-
atively small size, with a correlation found between the study results
and the surfactant structure [13,14,19,33,66,81]. For example, the skin
irritant effect induced by sodium dodecyl sulphate (SDS) increases
quite considerably even after the CMC is exceeded. However, the in-
crease is much lower for ethoxylated sodium dodecyl sulphate. In the
case of SDS the increase in the skin irritation potential is due to the
small micelle size, since micelles are smaller than the orifices of hair fol-
licles. In the opinion of the authors, the latter represent another route
for the entry of SDS into the structures of the stratum corneum. In
other surfactants the size of micellar aggregates exceeds the diameter
of hair follicle orifices, making the process of penetration more difficult.
The findings thus show that the formation of micelles in the solution
does not aid in achieving total inhibition of the skin irritant effect
[13,14,66,67,81,93,94].
The skin irritation potential is significantly dependent on the chem-
ical structure of surfactants. Wilhelm et al. [68] have studied changes in
transepidermal water loss (TEWL) in 24-hour epidermal patch tests
performed on skin subjected to sodium alkyl sulphates with alkyl chains
of different lengths (C8, C10, C12, C14, C16). They have found that the
value of TEWL rises with increasing chain length, however only up to
C12, with the highest value recorded for SLS. Subsequent homologues
with longer lipophilic chains (C14 and C16) cause a smaller increase
in this parameter. Based on the findings, the authors have concluded
that an increase in the length of the sodium alkyl sulphate chain is ac-
companied by an increase in the lipophilic properties of the compound,
which may be initially desirable in interactions with the stratum
corneum. However, as soon as the chain reaches C12 in length, any fur-
ther elongation causes the optimum lipophilicity value in terms of affin-
ity to the stratum corneum to be exceeded. A further increase in
molecule size contributes to an increase in hydrophobicity and restricts
its penetration to protein structures. The observations have been cor-
roborated by studies conducted by Di Nardo et al. [95] to evaluate
changes in skin hydration, TEWL and skin colour in 24-hour epidermal
patch tests after the application of solutions of sodium alkyl sulphates
containing chains of different lengths (C8, C12 and C14) at a concentra-
tion of 0.2%. The highest increase in TEWL and the greatest decrease in
the skin moisture level and in the severity of skin erythema were ob-
served for SDS. The effect of the length of the lipophilic chain (C8, C10,
C12, C14, C16) on the ability to cause stratum corneum swelling has
been studied by Blake-Haskins et al. [33]. Their analysis of aqueous sur-
factant solutions showed the maximum intensity of swelling for the ho-
mologue with a chain length of C12. Similar findings have been reported
by Robbins and Fernee [96], demonstrating that among alkyl sulphates
the most severe adverse effect of surfactant homologues is associated
with the alkyl chain containing 12 carbon atoms. In addition to the
length of the CHO chain, the skin irritation potential of surfactants is
also linked to the size of the polar part of the molecule. Based on
oxyethylates of sodium lauryl sulphate, Rhein et al. [67] have evaluated
how the degree of ethoxylation (1, 2, 3, 6 or 12 mol of ethylene oxide)
influences the stratum corneum swelling capacity. In their studies,
they have found that the ability to induce SC swelling decreases in pro-
portion to increasing degrees of ethoxylation. The correlation, however,
disappears after the ethoxylation degree exceeds 6.
Similar studies have been conducted with Ammonium Laureth Sul-
phate (ALES) homologues ethoxylated with 0, 3, 6 and 9 mol of ethylene
oxide [33]. The least prominent swelling effect has been observed for
the analogue with the greatest degree of ethoxylation (9OE). The
highest skin irritation potential has been shown for ammonium lauryl
sulphate (ALS), and has been found to decrease in line with increasing
degrees of ethoxylation. Based on the studies presented above, it can
be concluded that an increase in the degree of ethoxylation is accompa-
nied by a decrease in the capacity of lauryl sulphates to induce SC swell-
ing and a reduction in their skin irritation potential. Such an effect can
be determined by a rise in the degree of ethoxylation which has an im-
pact on increasing the molecule size. Larger molecules exhibit a lower
ability to penetrate the skin's surface [33,67].
Studies have also been conducted to analyze solutions of different
lauryl sulphate salts (Na, Mg, TEA) with a focus on their ability to
cause stratum corneum swelling. The most pronounced swelling effect
has been shown for the sodium salt and the least pronounced for mag-
nesium alkyl sulphate [67]. Similar findings have been presented by
Cohen et al. [97], in their studies evaluating the effect of counterion in
alkyl sulphates on the skin irritation potential by determining the zein
number and correlating their results with measured CMC values and
the ionic radius size. The authors analyzed the effect of inorganic
metal ions including Li+, Na+, K+, Mg2+, and NH4+, and organic ions
including MEA+, DEA+ and TEA+. Among the compounds studied, the
lowest zein number values were shown for the magnesium salt. Other
salts with inorganic monovalent ions, however, exhibited no significant
differences in value. Organic salts were found to produce significantly
higher zein numbers than inorganic salts. According to the researchers,
the observation can be attributed to stronger binding of these ions in
micelles. Both the specific ability to cause the SC swelling and the zein
number results were linked by the authors to the CMC values and ion
size. The highest tolerability of magnesium salts by the skin may be
due to the fact that their aqueous solutions have lower CMC values
and, consequently, they are characterized by lower monomer concen-
trations in the system. According to another hypothesis, ion size is the
factor which determines the extent of interactions with the stratum
 A. Seweryn / Advances in Colloid and Interface Science 256 (2018) 242–255
corneum. In magnesium ions an excessive volume of ionic aggregates
(magnesium having the largest ionic radius of all studied) prevents
easy diffusion in the stratum corneum [67,97–99]. Similar results have
been obtained by Seweryn et al. [100] in applied studies evaluating
the skin irritation potential of hand dishwashing liquids in the coacer-
vate form obtained through the addition of various inorganic salts (of
mono- and divalent metals). The evaluation of the irritant potential
based on determining the zein number produced significantly lower
values of the parameter studied in the products obtained by adding
magnesium chloride and calcium chloride.
A specific class of amphiphilic substances comprises gemini surfac-
tants. Their chemical structure translates into a range of more beneficial
properties compared to their more conventional counterparts. Owing to
growing interest in surfactants of this type in the context of their prac-
tical applications in the cosmetic industry, a number of studies focusing
on their interactions with the skin have been published, demonstrating
that compounds of this type induce a negligible skin irritation effect
[101–112]. As Tsubone et al. [111] argue, since gemini surfactants
have markedly lower CMC values than conventional surfactants, it fol-
lows that they are also associated with a lower skin irritation potential.
In vivo tests performed for synthesized gemini-type anionic surfactants
have revealed low levels of skin irritation. In addition, the authors point
to a correlation found between their results and CMC values calculated
for the compounds studied. Diz et al. [112] have evaluated cationic
gemini-type surfactants in Draize tests, showing antibacterial activity
as well as the absence of any skin irritation effect at concentrations
below 0.5%.
The developments of biotechnology as a science and the search for
raw materials of natural origin have sparked a rapid expansion of
research into the development of surfactants of natural origin. One of
the most promising areas within this field of study relates to
biosurfactants. They are compounds of biological origin, usually pro-
duced by microorganisms such as bacteria, yeasts and moulds.
Biosurfactants are not only effective at reducing the surface or interfa-
cial tension, which is a characteristic feature of all surfactants, but they
are also non-toxic and highly biodegradable. Therefore, as opposed to
synthetic surfactants, they do not pose a threat to living organisms
[113,114]. The beneficial properties of biosurfactants, coupled with the
current development trends in cosmetics and household chemicals,
have brought about studies exploring the possibilities for using surfac-
tants of this type in production. An inherent element of this line of re-
search involves tests assessing the effect of biosurfactants on the skin.
Published research results show that biosurfactants are characterized
by limited skin irritation and toxicity, as compared to synthetic surfac-
tants [113–121]. In addition, some of them have antioxidant properties
and improve the bacterial microflora of the skin [113–115,122–127].
3.2. Interactions with SC lipids
Research investigating possible interactions between surfactants or
body wash products and the skin is largely focused on the evaluation
of skin irritations induced by interactions with proteins. Less attention
has been devoted to potential interactions with the liquid crystalline
lipid structure of the intercellular cement within the SC and its damage.
The first study in this area, by Imokawa et al., has investigated the im-
pact of surface active agents on the SC lipids in correlation with ob-
served skin dryness [128].
It was previously believed that the interactions between surfactants
and the SC lipids were limited exclusively to the processes of washing
lipids forming the epidermal hydrolipid film. They were related to
such aspects as daily hygiene, skin defatting, and elimination of sweat,
sebum and contaminants. It is currently proposed that surfactants,
being surface active agents, are capable of interacting with lipids
which form the SC intercellular cement [14–15,36,40,128,129].
The commonly recognized model of interactions takes into account
both possible effects produced by surfactants in the form of monomers
247
and micelles formed in the solution. A number of experimental studies
have shown that exposure to a surfactant solution in which the CMC
is exceeded leads to intemicellar solubilization of lipids and their
washing from the stratum corneum. Possible consequences include
delipidation of the stratum corneum, impairment of its barrier functions
and increase in the TEWL level. Some studies also postulate that mono-
mers, which are small-sized molecules, may become adsorbed and em-
bedded into the liquid crystalline structure of the stratum corneum,
disturbing its spatial structure and increasing permeability. In extreme
cases, following a prolonged contact between the SC and a surfactant so-
lution, the intercellular cement can become liquefied and the epidermal
lipids can be more prone to solubilization. As the permeability of the
epidermis increases, monomers are able to migrate into deeper-lying
regions of the stratum corneum. As a result, the skin irritation effect in-
tensifies. In addition, water molecules are able to migrate to the surface
of the epidermis, resulting in greater evaporation and dryness of the
stratum corneum. The skin becomes dry and loses its elasticity
[13–15,36,40,128,129].
Monomers present in the structure of the intercellular cement may
damage enzymes that produce lipids forming the matrix. Changes to
the composition and content of different lipids are observed. Fulmer
et al. [130] have studied the effect of SDS on the quantitative and qual-
itative composition of lipids in the stratum corneum, noting that SDS
contributes to a decrease in the content of long-chain free fatty acids
and cholesterol, without affecting the total content of ceramides and
non-polar lipids. Similar findings have been presented by Froebe et al.
[129] based on in vivo studies evaluating the correlation between the ef-
fect of sodium lauryl sulphate and sodium alkyl benzene sulphonate on
the SC proteins and lipids. The authors found that the lipids were
washed away only at or above the concentration at which micelles
formed in the system. Measurements of the SC composition after 20-
minute exposure to 2% surfactant solutions revealed a 7% decrease in
the total lipid content. An assessment of different lipid fractions demon-
strated the elimination of free fatty acids (8%), cholesterol (8–15%), and
cholesterol and squalene esters (under 1%), however ceramides were
not shown to be washed away. According to the researchers the lack
of interactions with the ceramide fraction is due to ceramides having
two carbohydrate chains, which reduces their potential for solubiliza-
tion in micelles. The authors point out that even though the elimination
of short-chain and unsaturated fatty acids is desirable in day-to-day hy-
gienic activities, the loss of stearic acid and other long-chain fatty acids
may adversely affect the barrier function of the stratum corneum
[36,40,129,130].
Based on the findings presented above, it may be concluded that
fatty acids are the most prone to potential interactions with surfactant
solutions. A precondition for the preservation of the bi-layer liquid
crystalline structure of the intercellular matrix in the SC is to ensure ap-
propriate preferential ratios between the ceramide, fatty acid and cho-
lesterol fractions. If one of the constituents is removed, the entire
system may become destabilized and defective. The removal of fatty
acids from the remaining components may adversely affect the preser-
vation of the desirable liquid structure, which may result in excessive
stiffness of the SC and reduced ability for normal tension relaxation pro-
cesses. Also, aside from an increase in TEWL, dry skin sensation, cracking
and, in extreme cases, erythema, normal epidermal desquamation may
become disturbed. The elimination of intercellular matrix lipids bound
covalently to corneocytes interferes with the perfect layered arrange-
ment of cells forming the epidermis. Corneocytes can get closer to one
another and migrate between layers, aggregating into larger cell clus-
ters. The process of desquamation involves non-uniform shedding of
skin scales [36,40,128–131].
3.3. Interactions with living skin cells
The denaturation of proteins building the stratum corneum, and
interactions between the intercellular substance and surfactants,
248 A. Seweryn / Advances in Colloid and Interface Science 256 (2018) 242–255
can cause damage to the skin's protective barrier. As a result of the pro-
cesses, the compounds are able to migrate more easily into deeper epi-
dermal layers, where keratinocytes, i.e. living epidermal cells, are
present. Surfactants are capable of binding to the keratinocytic cyto-
plasm and causing its impairment. They can also damage proteins
which build living cells. The processes may lead to permanent destruc-
tion of keratinocytes or even cell death. The capacity of surfactants to in-
duce permanent damage to living skin cells is referred to as skin toxicity
[132–137]. Furthermore, the presence of surfactants and their interac-
tions with proteins can cause damage to the structure of living epider-
mal cells, producing topical inflammatory reactions of the skin
[13–15,134,137,138]. This type of reaction to an irritant factor is re-
ferred to in the literature as irritant contact dermatitis (ICD), which be-
longs to the most common cutaneous diseases [134–142].
Depending on the type and concentration of surfactants, and the du-
ration of exposure to the irritating factor, the process involves
keratinocyte damage. It affects primarily the cellular cytoplasm, causing
the release of inflammatory mediators from cells, including various pro-
inflammatory cytokines such as interleukin 1 (IL-1), IL-6, IL-8 and tu-
mour necrosis factor (TNF). The presence of cytokines results in the
dilation of blood vessels and in the influx of immune cells which induce
the inflammatory process. They are mostly neutrophilic granulocytes,
and T and B lymphocytes. Concurrently, in order to reduce excessive in-
flammatory response, mechanisms are set in motion that involve
keratinocytes producing cytokines with antiinflammatory properties.
ICD-associated inflammatory processes occur exclusively within the
site of contact with the irritating substance. They result in topical skin
lesions presenting as red skin, desquamation and erythema. In some
cases patients develop only subjective sensations including severe pru-
ritus, pain, burning and feeling of discomfort. An important factor is that
ICD does not have immune aetiology, which means that the body pre-
serves no information about the skin-penetrating compound in the
form of antigens [138–143].
The literature reports suggest that irritant contact dermatitis is one of
the most common skin diseases. As Levin and Maibach [143] claim, aside
from the chemical structure of the triggering substance, the occurrence
of ICD is determined by a range of other factors such as age, sex, genetic
background, environmental conditions and coexistence of other cutane-
ous diseases such as atopic dermatitis. The disease must therefore be
recognized as multifactorial. A greater incidence of disease symptoms
has been found in people who are exposed to cosmetics and cleaning
agents on a prolonged basis, for example hairdressers and cleaners.
Another effect of interactions between surfactants and living
epidermal cells which, however, occurs very rarely, is allergic contact
dermatitis (ACD) [139,140,144,145]. As opposed to ICD, ACD is an
immunologically induced syndrome in which the immune system re-
sponds to a chemical substance referred to as an allergen. The mecha-
nism underlying contact allergy comprises two phases of body
response to a skin-penetrating substance (induction and release
phases) that involve complex physiological and biological processes.
In the first phase, the allergen is phagocytized by Langerhans cells, pre-
senting it to B lymphocytes, which are transformed into immunoglobu-
lin proteins (antibodies), which are specific and sensitive to particular
allergens. They are transported by the cardiovascular system all over
the body and presented to T lymphocytes – immune system cells
which retain information about the allergen. The process is symptom-
less and lasts from a few to about a dozen days. The phase of release in-
volves the recognition of T helper cells of the allergen by the immune
cells, accompanied by an increase in the production of histamines and
inflammatory cytokines. A severe inflammatory response develops not
only at the site of entry but also on the entire skin surface. The processes
lead to cutaneous eruptions in the form of bullae, red skin, oedema, and
the sensation of itching. Similarly to ICD, the development of ACD de-
pends on a number of factors such as age and sex, however the greatest
role is attributed to genetic predisposition related to the mutation of ap-
propriate genes [139,140,144,145].
Allergies resulting from skin contact with surfactants are noted rela-
tively rarely, however there are literature reports describing skin intol-
erance to a range of compounds including sodium lauryl sulphate
[19,138,146], cocamidopropyl betaine [147], alkyl polyglycosides
[148–150] or sarcosinates [151]. More common allergy-causing agents,
which occur both in cosmetics and household chemicals, are colourants,
preservatives, plant extracts and fragrances [152–154].
4. Methods to reduce the skin irritation potential
According to the literature, in order to reduce the irritation potential
of surfactants or products based on anionic surface active agents, at-
tempts should be made to lower the concentration of monomers, in-
crease the size of micelles and stabilize them in the solution having
contact with the skin. There are various methods comprising the steps
presented above which make it possible to reduce the negative impact
of surfactants on the skin in body wash products. For example, anionic
surfactants with a proven mild effect on the skin, mixtures of different
surfactant types, an addition of polymers or refatting and hydrophobic
substances can be used as the primary washing agent in the formula-
tions [1,13–16,155–159].
4.1. Use of surfactants with reduced skin irritation effect as primary
washing agents
A reduced skin irritation effect of cosmetic products can be achieved
by an appropriate selection of product components. A proper choice of
the type of primary surfactants seems to be a fundamental means to ob-
tain desired functional parameters and reduce the irritant effect on the
skin induced by products of this type. Both appropriate detergent and
foaming properties which are so sought-after in cosmetics, and a mild
effect on the skin produced by surfactants, are linked to their structure.
As mentioned, surfactants which interact strongly with proteins in
the stratum corneum, causing their denaturation and swelling, can
be regarded as compounds with a high skin irritation potential
[1,14,15,17]. It is possible to determine the tendency of surfactants to ir-
ritate human skin by analyzing a range of aspects which are widely de-
scribed in the literature, including a higher tendency of surfactants to
induce the swelling of keratin in the stratum corneum or model proteins
(keratin and collagen) [96,160], a specific effect of surfactants on the de-
naturation of the globular protein bovine serum albumin [31–35] or
their effectiveness in causing partial denaturation and solubilization of
the water-insoluble zein protein [29,30,87–92,100].
The molecular structure of surfactants is essentially the most impor-
tant factor for the problem of surfactant-associated skin irritation effect
which is discussed in the present paper. Generally, ionic surfactants
have a more pronounced irritant effect on the skin, which is attributable
to the nature of their interactions with proteins via electrostatic and hy-
drophobic bonds. However, unlike in the ionic type, the strength of in-
teractions in nonionic surfactants is low on account of the absence of
electrostatic forces (resulting from the lack of charge). The binding of
compounds of this type with proteins via hydrophobic interactions
and hydrogen bonds does not strongly affect the protein structure
[66–84]. Consequently, they are considered to be non-irritant on the
skin. In general terms, the tendency for protein interactions follows
this sequence:
anionic = cationic N amphoteric N nonionic surfactants.
Cationic surfactants are not used as primary washing agents in
washing products. On account of the fact that the surface of the skin
and hair is negatively charged, they may bind relatively strongly to
such surfaces. Positively charged hydrophilic heads of these surfactants
bind to keratin, whereas hydrophobic tails are oriented towards the
outside. Consequently, this surface has a more hydrophobic character.
As a result, the skin and hair conditioning effect is excessively increased,
but also the attraction of hydrophobic dirt is enhanced, making it more
difficult to remove such dirt and increasing the tendency for its
 A. Seweryn / Advances in Colloid and Interface Science 256 (2018) 242–255
redeposition on the surface [161]. There is a lot of contradictory infor-
mation about the irritant effect of cationic surfactants. Some claim that
they have a more severe irritant effect on the skin and hair than anionic
surfactants [136,162–165] whereas in zein solubilization tests, corre-
lated with the irritant effect, the protein solubilization capacity of cat-
ionic surfactants is almost twice as low as that of anionic surfactants
[1,13,14]. It seems evident that strong interactions of cationic surfac-
tants with proteins and their lack of effective detergent activity deter-
mine the application of surfactants of this type exclusively as auxiliary
conditioning agents in body wash cosmetics, lotions and hair condi-
tioners. Strong protein denaturation ability exhibited by some cationic
surfactants translates into their antibacterial activity.
Amphoteric surfactants are rarely used as the main ingredients of
cosmetic products, and they usually serve as auxiliary agents in such
formulations [10,11,21,58]. Depending on the pH level, they may be
positively or negatively charged, which affects the nature and strength
of interactions with proteins. Generally, compounds of this type have
a relatively low irritant potential compared to cationic and anionic sur-
factants. In practical terms, in the context of interactions with the skin,
compounds of this type are used in products in combination with an-
ionic surfactants. By producing a synergistic effect, especially in mildly
acidic environments where a zwitterionic surfactant may have a cat-
ionic charge, they contribute to reducing the irritant effect of the formu-
lation [1,14,166,167].
In view of the absence of interactions with proteins, nonionic surfac-
tants are generally regarded as mild-acting [13–17,19,29,36,66–68,
79–84]. Based on that property, they are used in the formulation of
body wash products intended for babies and children [82]. On the
other hand, however, compounds of this type are good emulsifiers,
which may produce an adverse effect on the lipid components of the
skin's protective barrier and enhance the process of washing away in-
tercellular matrix lipids. Furthermore, alkyl polyglycosides, on account
of their high substantivity to the surface, when not completely removed
from the surface, may play a part in intensifying the process of emulsi-
fication of hydrophobic substances during the supply of consecutive
amounts of water during subsequent washing.
The most widely employed surfactants in body wash cosmetics
and selected types of household chemicals are anionic surfactants.
For this reason, their potential to interact with protein structures of
the skin and trigger skin irritations represents the most significant
problem.
The general model of interactions between ionic surfactants and
proteins can be based on a binding isotherm [86,168] (Fig. 3.) which
shows the average number of surfactant molecules bound per protein
molecule (ν) as a function of the logarithm of the free surface active
Fig. 3. The isotherm of the binding of ionic surfactants to proteins. Own study based on
[168].
249
agent concentration. Generally, binding isotherms have four character-
istic regions including: specific binding (a), non-cooperative binding
(b), cooperative binding (c) and saturation (d).
Specific binding is mainly electrostatic in nature [168]. Surfactant
headgroups bind to oppositely charged groups on the protein. A change
in pH entails a change in the net charge of the protein, leading to surfac-
tant binding to the protein. If the pH is lowered, the binding isotherm of
an anionic surfactant is shifted to lower surfactant concentrations [169].
In contrast, the binding isotherm for cationic surfactants is observed at a
higher concentration of the amphiphilic compound [170]. Specific bind-
ing (region a) of surfactants to proteins depends on the headgroup of
the ionic surfactant and may be selective in nature. In their study,
Reynolds et al. [171] report that the structure of bovine serum albumin
(BSA) comprises binding sites which do not bind alkyl carboxylates at
all or do so with a reduced affinity, whereas both alkyl sulphates and
sulphonates are strongly bound. However, for specific binding to
occur, the length of the hydrophobic part of the compound seems to
be an important factor. Jones and Manley [169] report that at low con-
centrations of n-dodecyl and n-decyl sulphates a specific binding to
the lysozyme is observed, however at higher concentrations of the com-
pounds the binding is cooperative (region b). In contrast, sodium octyl
sulphonate binds to protein exclusively via cooperative bonds. Similar
findings were noted for the binding of n-alkyl trimethylammonium bro-
mides to BSA [172]. For decyltrimethyl ammonium bromide, no transi-
tion from specific binding (region a) to cooperative binding was
observed, unlike in compounds with a longer alkyl chain – dodecyl
and tetradecyltrimethyl-ammonium bromide. On the other hand, how-
ever, in BSA specific binding is observed both for sodium dodecyl and
decyl sulphates, and sodium octyl sulphonates [173]. The number of
specific bonds with albumin (BSA) rises along with the increasing
length of the hydrocarbon chain for the homologous series of n-alkyl
sulphates and sulphonates [171]. In addition, binding is initiated at a
lower surfactant concentration along with an increase in chain length
[174].
Cooperative binding (region c) means an increased affinity for binding
to protein along with an increase in the concentration of free surfactant. A
sharp rise in the isotherm is noted within a narrow concentration range.
The formation of micelle-like structures of surfactants is observed on
the protein, representing a cooperative process. The protein may unfold
in a specified region. Takeda et al. [175] studied changes in the
structure of bovine serum albumin in solutions of sodium decyl sulphate
(SDeS), sodium dodecyl sulphate (SDS), decyltrimethylammonium
bromide (DeTAB), dodecyltrimethylammonium bromide (DTAB),
tetradecyltrimethylammonium bromide (TTAB) and hexadecyltrimethyl-
ammonium bromide (HTAB). All these surfactants caused changes in the
helical structure proportion in the protein from 66% to approximately
50%. However, the shorter the hydrocarbon chain in the structure of the
surface active agent, the higher concentration is required to cause an
equivalent decrease in the proportion of this structure. Study results
also indicate that the longer the hydrocarbon chain in a compound, the
greater the drop in the proportion of the helical structure. A mild increase
in the protein β-structure was observed for all surfactants except for
DeTAB.
A number of proteins (globular, fibrous, membrane proteins) bind
identical amounts of SDS at the saturation state (region d), with approx-
imately 1.4 g of SDS per 1 g of protein. The saturation with anionic sur-
factants is pH-independent and seems to be controlled by cooperative
hydrophobic bonds. For cationic surfactants, a reduced intensity of sat-
uration binding is noted in comparison with anionic surfactants [176].
Interactions taking place between ionic surfactants and proteins in-
volve primarily the effect of hydrophobic parts on hydrophobic protein
fragments and electrostatic binding of hydrophilic, charged surfactant
heads to some charged protein parts. It is, therefore, recognized that a
limited impact on the protein structures – and hence (in the case of
skin proteins) a reduced irritant effect on the skin – occurs in ionic sur-
factants with a lower hydrocarbon chain number and length and a
250 A. Seweryn / Advances in Colloid and Interface Science 256 (2018) 242–255
reduced charge density in the hydrophilic part, for example through the
incorporation of an additional hydrophilic part in the form of ethylene
oxide groups [33,67,86–99] Some research in this field indicates that
surfactants exhibiting higher self-assembling ability have a weaker irri-
tant activity [163,177,178]. Surfactant-induced protein denaturation
can be characterized through cooperative surfactant adsorption
[29,30,179]. If the functional group of the ionic surfactant is large in
size, interactions between the hydrophobic part of its molecule
and the hydrophobic protein fragment are limited, and no adsorption
on the protein is observed [86]. Furthermore, weak repulsion between
surfactants adsorbed on the protein induces minor changes in the
protein secondary structure, either diminishing or eliminating coopera-
tive adsorption [87]. The above findings are consistent with the obser-
vations made by Ozawa et al. [157] in their study of five anionic
surfactants: sodium polyoxyethylene lauryl ether carboxylate, sodium
polyoxyethylene alkyl ether sulphate, sodium dodecyl sulphate, potas-
sium laurate, and N-cocoyl-L-glutamic acid monosodium salt. The au-
thors correlated their findings obtained for epidermal swelling and
protein denaturation as determined by the zein test with the results
or surface tension and stratum corneum adsorption. The study showed
sodium polyoxyethylene lauryl ether carboxylate to have the lowest
skin irritation effect of all the surfactants studied. The finding was attrib-
uted to the size of the ionic functional group and the ability of the com-
pound to form specific aggregates with a vesicular structure in aqueous
solutions even below the CMC. Similar conclusions were presented by
Zhou et al. [163] who studied cyclodextrin/cationic trimeric surfactant
complexes. The authors point to the possibility of large aggregate sys-
tems of this type forming in aqueous solutions directly after the CAC is
achieved, and a decrease in the concentration of free monomers. Strong
self-assembly reinforces the repulsion of complexes from the zein
backbone. Furthermore, a reduced number of hydrophobic chains and
a decreased superficial charge density weaken the hydrophobic interac-
tion and electrostatic attraction of surfactants to the protein, which in
turn makes the compounds milder to the skin.
Generally, the literature describes a wide range of anionic surfac-
tants which are considered as mild-acting [1,9,14,15]. Such compounds
include sulphosuccinates [180], isethionates [35,36], sarcosinates [155],
acylated protein hydrolysates and their salts [181], alkyl ether carboxyl-
ates [157], glutamic acid derivatives [38] and certain salts of alkyl ether
sulphates (magnesium and zinc) [97,159].
4.2. Application of surfactant mixtures
Surfactant mixtures are widely used in body wash cosmetics and
household chemicals on account of the synergistic effect achieved by
different surfactants added to such mixtures [11,57–64]. For example,
nonionic surfactants used in combination with an anionic surfactant in
the solution improves the detergent properties of the system. The appli-
cation of an amphoteric compound enhances the stability of foam gen-
erated in the solution of anionic surfactants [6,57,58,63–65]. The
widespread use of mixtures of different surfactants has brought about
extensive studies investigating their skin irritation potential. As the lit-
erature demonstrates, the application of mixtures containing surfac-
tants of diverse types is one of the simplest methods to increase the
size of micelles in anionic surfactants and make them more stable.
Also, mixtures of different surfactants have an effect on lowering the
CMC, which decreases the concentration of monomers in the volume
phase. Research shows that the above effect triggers a reduction in the
skin irritation potential [1–5,13–15]. Fig. 4 shows a schematic represen-
tation of changes to the structure of micelles formed in the solution con-
taining mixtures of various surfactant types.
As shown in the figure, micelles formed in the solution by the same
surfactant (e.g. anionic) are relatively small in size (A), which can pro-
mote their penetration via the skin barrier and impact on the structural
elements of the epidermis. Strong electrostatic repulsion of hydrophilic
fragments in the micelle-forming molecules has an effect on reducing
micellar stability and leads to its relatively fast breakdown into mono-
mers. Following the addition of cationic surfactants (B) to a solution of
anionic surfactants, the former become embedded into the micelles
formed in the solution, giving rise to mixed micelles. Aggregates of
this type, containing both surfactant types, are much larger in size.
The forces of mutual repulsion are reduced, which has an additional sta-
bilizing effect on the micelles. After adding a nonionic compound (C) to
a solution of anionic surfactants, large-sized mixed micelles are formed,
as in the case of adding cationic surface active agents. Molecules of non-
ionic surfactants, which are relatively large, increase the distances be-
tween hydrophilic heads of ionic surfactants, at the same time
weakening the forces of electrostatic repulsion. As a consequence, mi-
celle stabilization occurs. A similar effect is attained by combining an an-
ionic surfactant solution with another anionic surfactant (D). On
account of a difference in the structure of the hydrophilic and hydro-
phobic segments, the distance between the hydrophilic parts grows,
which increases the stability of micelles. However, it needs to be
stressed that the level of stabilization thus achieved is markedly lower
than that noted after the addition of nonionic and cationic surfactants.
The stability of micelles in systems of this type is additionally affected
by the size difference of the hydrophobic part of anionic surfactants –
the greater the difference in the length of the hydrocarbon chain, the
higher the level of micellar stability. An addition of amphoteric surfac-
tants (E) induces an increase in micellar size, however the stability of
micelles depends on the pH of the system. In the acidic environment,
an amphoteric compound carries a positive charge and observed
changes are the same as after the addition of cationic surfactants (B).
In the basic environment, the effect is similar to that occurring after
the addition of an anionic surfactant (D) [14,52–60].
The theories outlined above are confirmed by a range of studies.
Hall-Manning et al. analyzed the irritant effect induced by a mixture
of SDS and alkyl polyglycosides in 4-hour epidermal patch tests. The au-
thors performed a visual assessment of the solution application sites
and correlated the results with the CMC values determined for the mix-
tures. Even a small amount of a nonionic surfactant added to an SDS so-
lution was found to decrease the irritant activity, compared to a 20%
solution of sodium lauryl sulphate. By comparing the results with the
CMC of the mixtures, the authors demonstrated a correlation between
the two parameters. A decrease in the micelle-forming concentration
ensures a reduction in the irritant activity of the surfactant solution
[182].
Similar reports have been published by Kawasaki et al. [183] and Lee
et al. [184] presenting results of visual assessments and TEWL measure-
ments after patch tests performed for mixtures of SDS and sodium
lauroyl glutamate (SLG). A fall in the concentration of SDS in the solu-
tion, coupled with a simultaneous increase in the SLG level, caused a de-
crease in TEWL and a drop in the visually assessed severity of the skin
irritation effect. According to the authors, a decrease in the CMC of the
SDS solution achieved by adding another type of anionic surfactant re-
duces the concentration of free monomers in the volume phase, which
limits interactions between the compounds and the proteins in the stra-
tum corneum. Another important aspect is the so-called effect of com-
petition for contact sites which occurs between both compounds.
Tadenuma et al. [185] assessed the impact of mixtures containing
SDS and ethoxylated lauryl alcohol on bovine serum albumin. Based
on their results, they argue that the addition of a nonionic surfactant
to an aqueous SDS solution markedly reduced the denaturation of the
protein – bovine serum albumin. The observed effect is stronger in pro-
portion to the concentration of ethoxylate in the system. The authors
explain the phenomenon by pointing out that the molecules of nonionic
surfactants are the first to become adsorbed on the protein chains,
which reduces the number of active centres available for SDS monomer
binding. Paye et al. [186] show that the denaturation of proteins is al-
ways more prominent in systems containing one type of surfactants
than in surfactant mixtures. The same conclusions have been presented
by Miyazawa et al. [187], showing that the application of surfactant
 A. Seweryn / Advances in Colloid and Interface Science 256 (2018) 242–255
Fig. 4. Structure of micelles in surfactant mixtures: A – mixture of the same anionic surfactant, B – mixture of anionic and cationic surfactants, C – mixture of anionic and nonionic
surfactants, D – mixture of two different anionic surfactants, E – mixture of anionic and amphoteric surfactants. Own study based on [14].
mixtures has an effect on reducing the number of monomers in the so-
lution. The author claims that monomers play main role in the develop-
ment of skin irritations. Blake [33] and Paye [164] in their studies
demonstrate that the incorporation of amphoteric surfactants into an
SDS solution markedly reduces the skin irritation potential by limiting
the possibilities for surfactant molecule binding to protein molecules.
Dominguez et al. [188] have studied SDS solutions with cocamidopropyl
betaine, concluding that a lower skin irritation potential is associated
with the use of two different types of surfactants forming mixed mi-
celles that are much larger in size and more stable than those present
in the SDS solution. Also, McFadden et al. [189] have conducted epider-
mal patch tests with mixtures of SDS and the cationic surfactant
benzalkonium chloride, noting that the addition of a cationic surfactant
to an anionic solution has an effect on changing the structures of aggre-
gates forming in the solution, which reduces its irritant activity com-
pared to pure SDS solutions.
Interesting findings have been reported by Ananthapadmanabhan
et al. [131] based on comparisons between the results of in vitro tests
of protein denaturation (zein test) and extraction of intercellular lipids
in the SC (stearic acid washing test) by aqueous solutions of ethoxylated
sodium lauryl sulphate and cocamidopropyl betaine. Even though, in
line with the authors' expectations, the zein number was found to de-
crease along with increasing amphoteric surfactant concentrations in
the solution, the second test demonstrated more intensive lipid wash-
ing. The authors thus conclude that adding amphoteric or nonionic sur-
factants to a solution of anionic surfactants does not guarantee the
attainment of systems that would be perfectly safe for the skin. The re-
searchers note that the evaluation of the skin irritant effect must be
comprehensive in scope, including interactions between surfactants
and proteins and lipids in the SC.
Recently, interesting study results were published by Chen et al.
[178] who investigated mixtures of anionic SDS with cationic Oleyl Bis
(2-hydroxyethyl)methyl Ammonium Bromide (OHAB) in contact with
the zein protein. Mixtures of these compounds were found to have
lower zein solubilization ability. The authors conclude that mixing op-
positely charged surfactants reduces the net charge of mixed aggre-
gates, which weakens the electrostatic attraction between the
aggregates and zein. In addition, the large size of the arising aggregates
may increase their steric repulsion in relation to the zein backbone. The
authors point out that it is possible to obtain a mixture with a low CMC
value and high surface activity by appropriately adjusting its quantita-
tive and qualitative composition. Moreover, since large-sized aggre-
gates formed in this manner are characterized by diminished zein
solubilization ability, their irritant effect is also reduced. The research
is highly promising from the practical perspective, in the context of for-
mulation of cosmetic detergent systems. In another study, the same au-
thor and co-workers [190] investigated mixtures of SLS with OHAB to
determine their ability to solubilize phospholipids and penetrate the
skin. Based on the study findings, they conclude that aggregates formed
in anionic/cationic surfactant mixtures have high lipid solubilization
ability and a reduced skin penetration potential. The results of the two
251
studies warrant the conclusion that the application of mixtures of oppo-
sitely charged surfactants may contribute to improving the mildness of
formulations (in the context of protein interactions) but, at the same
time, it may increase solubilization processes affecting epidermal lipids
which, as a consequence, may manifest as excessive skin dryness.
A number of researchers have described interactions between
surfactants in their mixtures resulting in a decrease of the skin irritation
potential in relation to the more irritant compound. Nearly all
authors point to a direct correlation between a decrease in the CMC of
surfactant mixtures and a reduction in the skin irritation potential
[13–16,160–167].
4.3. Addition of polymers and biopolymers
Unique interactions occurring between polymers and surfactants
may lead to a decrease in the skin irritation potential. Specific
polymer-surfactant complexes developing in mixtures result in the sys-
tem having different properties than in polymer-free surfactant solu-
tions [13–15,17,58,191]. Research in this scope shows that the effect is
characteristic both for synthetic polymers (polyvinylpyrrolidone [192],
polyethylene glycols [185], acrylic derivatives [193]) and biopolymers
(proteins and their hydrolyzed derivatives and rubbers [194,195–197]).
The mechanisms responsible for surfactant and polymer interactions
in an aqueous solution are complex processes which give such a system
different properties than in polymer-free systems [198–202]. An expla-
nation for this phenomenon can be found by analyzing the relationship
between surface tension as a function of surfactant concentration in
polymer-enriched and polymer-free systems. Within the identified re-
lationship, a few regions can be noted which reflect the nature of poly-
mer and surfactant interactions, and where the curve generated for the
relationship has a different shape compared to the additive-free aque-
ous surfactant solution [191,202]. An example of the relationship is
shown in Fig. 5.
At a low concentration of the surface active agent, monomers are
adsorbed at the interface between phases (e.g. water – air). Polymer
chains bound to the surfactant molecules are also adsorbed at the inter-
facial surface. In the volume phase of the solution, the surfactant con-
centration is low, and polymer chains occur in the form of the so-
called flocs. Such tangled chains represent an additional interface be-
tween phases, where molecules of the surface active agent are able to
be adsorbed (area I in the chart). As the surfactant concentration in
the solution rises, the monomers continue to settle at the interface be-
tween phases, while interactions with water result in gradual disentan-
glement of polymer chains. Monomers acquire an additional interface
where they are able to be adsorbed [58,191,198–202].
Further increases in the surfactant concentration result in the forma-
tion of micelles bound to polymer chains. The phenomenon takes place
at a specific concentration referred to as the critical aggregation concen-
tration (CAC). The correlations presented above demonstrate that the
addition of a polymer to a surfactant solution accelerates the process
of aggregation of surface active agents at a concentration lower than
252 A. Seweryn / Advances in Colloid and Interface Science 256 (2018) 242–255
Fig. 5. Schematic representation of interactions between polymers and surfactants in aqueous solutions. Own study based on [106,198–203].
the critical micelle concentration (CMC). Depending on the structure of
the polymer and the surfactant, a variety of interaction types can be
observed between them. As Nagarajan shows [203], electrostatic,
hydrophobic and dipole-dipole interactions are observed, as well as
hydrogen bonds between the macromolecule and the surfactants. The
formation of polymer-surfactant aggregates reduces the mobility of
hydrophilic groups in the micelle, which translates into an increase in
aggregate stability. In addition, polymer chains have an ability to pene-
trate partially into the structure of the micelle, increasing its size.
As the surfactant concentration continues to rise, the desorption of
polymer chains from the surface phase to the volume phase is observed
(area II). In addition, a growing number of micelles become attached to
polymer chains. Moreover, an increase in the surfactant concentration
and saturation of the interface cause the number of monomers in the
volume phase to grow. The saturation of the polymer – solution interfa-
cial surface by the micelles (resulting in the so-called “pearl-necklace”
structures, with the micelles wrapped by polymer chains) leads to an in-
crease in the number of monomers in the volume phase of the solution,
where free polymer-unbound micelles ultimately develop (area III) at a
characteristic surfactant solution. Their development, like in surfactant
solutions, is attributable to the hydrophobic effect [198,202,203]. The
concentration at which micelles begin to form in the volume phase in
the polymer-surfactant system is often referred to as the apparent crit-
ical micelle concentration (CMC*) [204].
Interactions between surfactants and polymers have been investi-
gated in multiple scientific studies for many years. Research in this
field plays an important role from the viewpoint of practical applica-
tions in food, pharmaceutical and cosmetic industries [205–210].
Depending on the molecular structures of the polymer and the
surface-active agent, and the nature of forces occurring between them,
various types of polymer-surfactant interactions can be distinguished
[203–210]. The main forces responsible for interactions taking place be-
tween the polymer and the surface active agent are electrostatic, dipole-
dipole and hydrophobic interactions, and hydrogen bonds between the
macromolecules of the polymer substance and surfactants. Bao et al.
[211] formulated a general principle pertaining to forces occurring be-
tween polymers and surfactants in electrolyte solutions. According to
the principle, ionic interactions present in such systems are stronger
than hydrophobic interactions, and hydrophobic interactions are supe-
rior in strength to ion-dipole interactions. Factors influencing these pro-
cesses are linked both to the surface active agent and the polymer. The
former include the structure of the hydrophobic and hydrophilic parts
of the surfactant and the concentration of the surface active agent,
while the latter comprise the chemical nature, charge density, hydro-
phobicity as well as conformation and flexibility of the polymer chain.
An important role can also be played by the solvent on account of its ca-
pacity to affect the degree of dissociation of ionizable groups [212–227].
Between the CAC and CMC* points, polymers and surfactants may
form a new phase called “coacervate”, in which aggregates may grow
in the process of self-association. However, it needs to be noted that a
strong electrostatic interaction in systems containing an oppositely
charged surfactant and polyelectrolyte may induce cooperative binding
of surfactant molecules to the polyelectrolyte even at concentrations
below the CAC point [228]. Similar observations were made by Purcell,
Lu and Thomas [229], who studied SDS solutions with polyvinylpyrrol-
idone. They found that below the critical aggregation concentration
(CAC) the adsorption of SDS is increased by the presence of PVP, thus
demonstrating that both components interact on the surface. Further-
more, the authors observed the formation of polymer-surfactant com-
plexes even below the CAC. Lange [230] concluded that the surface
tension of polymer-surfactant systems might be lower than the surface
tension of pure surfactant solutions, showing that the polymer or
polymer-surfactant complex has surface active properties. It should
also be noted that in systems containing a polyelectrolyte and a surface
active agent with opposite charges the relationship between surface
tension and surfactant concentration may demonstrate more than
three transition points referred to above [231].
There are a number of methods which can be used to investigate in-
teractions taking place between polymers and surfactants in solutions.
The most important of them include surface tension, viscosimetry,
calorimetry, nuclear magnetic resonance, conductometry, UV-VIS,
fluorescence and phosphorescence, potentiometry, vapour pressure
measurement, speed sound measurement, cyclic voltammetry and se-
lective electrodes for a given surfactant [232–243].
 A. Seweryn / Advances in Colloid and Interface Science 256 (2018) 242–255
As shown, the incorporation of a polymer into a surfactant solution
leads to the “uptake” of surfactant monomers in the volume phase and
furthermore increases the size and stability of micelles [191,198–204].
The risk of skin irritation in such systems is minimized, as evidenced
by multiple studies [13,14,191–197].
4.4. Addition of refatting and hydrophobic substances
Refatting substances, which are also defined as components rebuild-
ing the skin barrier, are capable of reducing surfactant interactions with
the hydrolipidic coat and intercellular lipids of the SC. Their activity
comprises the formation of an occlusive film on the skin, thus limiting
monomer access to the skin surface [244,245]. This activity, however,
requires repeated application of a product containing substances of
this type. In addition, the decrease in the skin irritation potential in-
duced by a surfactant solution may result from interactions between
the compounds and micelles. By embedding into the aggregate struc-
ture, they increase its size and improve stability. Substances of this
type include esters of fatty acids and their ethoxylated derivatives
(e.g. PEG-7 Glyceryl Cocoate, Sucrose Cocoate), ethoxylated glycerides
and triglycerides (e.g. PEG-60 Maracuia Glycerides) as well as lanolin
derivatives (mainly PEG-75 Lanolin). Based on the TEWL and skin hy-
dration measurements, refatting additives have been shown to contrib-
ute to a substantial decrease in the loss of water from the epidermis,
which is associated with a lower degree of damage to the skin barrier.
They exhibit an ability to bind water in the skin themselves [13,14,65].
In recent years much attention has been paid to the application of
hydrophobic compounds in body wash products, where they serve as
additives preventing the development of skin irritation. Research in
this area focuses on the application of plant oils, hydrophobic plant ex-
tracts and fatty acids [245–249]. The most recent scientific develop-
ments suggest that the use of raw materials that are similar in
quantitative and qualitative composition to the ingredients naturally
occurring in the intercellular cement of the stratum corneum may com-
pensate losses of the components occurring in the washing process
[250–255]. Mukherjee et al. [255], studying polar sunflower oil and
completely non-polar mineral oil, have found that the addition of oil
markedly reduces skin irritation. The authors attribute the observed ef-
fect to the fact that different oils variously interact with the proteins
found in the stratum corneum. The same author has conducted a
study to determine the effect of stearic acid added to mild body wash
gels on the composition of the intercellular cement in the SC, comparing
the findings with results obtained for products containing soybean oil
and vaseline. The study has shown that molecules of stearic acid from
the product can become embedded into the structure of the intercellu-
lar cement within the SC, correcting its deficiency in the SC composition
due to the washing process [254]. Similar results have been reported by
Conti et al. [253] following an analysis of the effects of triglycerides of
fatty acids rich in linoleic acid radicals added to body wash products.
Based on their studies, the authors conclude that the application of
products containing esters of linoleic acid can correct changes in the
composition of the intercellular cement in the epidermis and signifi-
cantly improve the epidermal protective layer.
Wasilewski et al. [256,257] have analyzed how the concentration of
a hydrophobic extract obtained under supercritical CO2 conditions af-
fects the safety-in-use of hand dishwashing liquids, noting a decrease
in the irritant effect induced by these products. They also noted that
the additives reduced transepidermal water loss and epidermal dryness.
Based on the findings of their study, the authors propose a mechanism,
according to which hydrophobic plant extracts form aggregates in the
volume phase of the washing bath. The surface of the aggregates pro-
vides the adsorption area for surfactant monomers responsible for the
irritant effect. The researchers claim that the presence of the hydropho-
bic phase may lead to a decrease in the number of surfactant monomers.
In the case of low hydrophobic phase concentrations, intramicellar sol-
ubilization occurs, with micelles transforming into aggregates which
253
contain a hydrophobic substance, and an adsorptive surfactant layer
forming on their surface. An important factor is that the incorporation
of a hydrophobic phase into a surfactant solution results in the forma-
tion of an “additional” interface (between the hydrophobic and hydro-
philic phases), where monomers may be constituted. In this way, their
concentration in the system drops, resulting in the observed decrease
in the skin irritation potential. As the authors show, the extract used
in hand-dishwashing liquids can produce a positive skin effect not
only on account of its hydrophobicity but also the content of com-
pounds with a proven medicinal benefit.
5. Conclusions
As the discussion above reveals, the mechanism which underlies the
skin irritation potential of surfactants is complex, with an important role
being played by the form in which the compound occurs in the aqueous
solution. The severity of the irritant effect is conditional on a number of
factors such as the type, concentration and duration of skin exposure to
surfactants. Based on the literature review shown above, studies evalu-
ating methods of reducing the skin irritation potential of household
chemicals and body wash cosmetics should mainly take into account
ways to reduce the concentration of monomers in the solution and in-
crease the size and stability of emerging micellar aggregates. The choice
of an appropriate method of reducing the skin irritation potential, for
example by using mixtures of different surfactants, adding polymers
or refatting substances, should be based on a multifactorial analysis of
the irritant effect, including surfactant interactions with epidermal pro-
teins and the cement and lipid film in the stratum corneum.
Declarations of interest
None.
Acknowledgements
Funded with the assistance of the Ministry of Science and Higher
Education from subsidies for statutory activity. Project no. 3086/35/P
entitled “Development of formulations and technologies for the manu-
facture of innovative cosmetics, pharmacy supplies, household and in-
dustrial chemicals”.
References
[1] Paye M. In: Chew AL, Maibach HI, editors. Irritant dermatitis. Berlin Heidelberg:
Springer; 2006 [Chapter 45].
[2] Berardesca E, Distante F. Contact Dermatitis 1994;31:281–7.
[3] Wolf R, Wolf D, Tüzün B, Tüzün Y. Clin Dermatol 2001;19:502–15.
[4] Mehta SS, Reddy BS. Int J Dermatol 2003;42:533–42.
[5] Abbas S, Goldberg JW, Massaro M. Dermatol Ther 2004;17(s1):35–42.
[6] Karsa DR. Industrial applications of surfactants IV. Elsevier; 1999.
[7] Rosen MJ, Zhu ZH, Gao T. J Colloid Interface Sci 1993;157(1):254–9.
[8] Shiloach A, Blankschtein D. Langmuir 1998;14(7):1618–36.
[9] Mehling A, Kleber M, Hensen H. Food Chem Toxicol 2007;45(5):747–58.
[10] Adamson AW. Physical chemistry of surfaces. 5th ed. New York: Wiley; 1990.
[11] Piorr R. In: Falbe J, editor. Surfactants in consumer products: theory, technology
and application. Springer Science & Business Media; 2012 [Chapter 1].
[12] Sułek MW, Ogorzałek M, Wasilewski T, Klimaszewska E. J Surfactant Deterg 2013;
16(3):369–75.
[13] Polefka TG. In: Broze G, editor. Handbook of detergents. Part A: properties. Marcel
Dekker Inc.; 1999 [Chapter 11].
[14] Jackson CT, Paye M, Maibach HI. In: Barel A, Paye M, Maibach HI, editors. Handbook
of cosmetic science and technology fourth edition. CRC Press; 2014 [Chapter 32].
[15] Lips A, Ananthapadmanabhan KP, Vethamuthu M, Hua XY, Yang L, Vincent C, et al.
In: Rhein L, editor. Surfactants in personal care products and decorative cosmetics
third edition. CRC Press Taylor & Francis Group; 2007 [Chapter 9].
[16] Nielsen GD, Nielsen JB, Andersen KE, Grandjean P. Int J Occup Environ Health 2000;
6(2):138–42.
[17] Otzen D. Biochim Biophys Acta 2011;1814(5):562–91.
[18] Grammer NY, Fitzpatric JE, Jackson RL, Horton H, Damiano MA. J Am Acad Dermatol
1996;35:258–60.
[19] Lee CH, Howard IM. In: Chew A, Maibach HI, editors. Irritant dermatitis. Berlin:
Springer-Verlag; 2006 [Chapter 30].
[20] Goffin V, Paye M, Pierard GE. Contact Dermatitis 1995;33:38–41.
254 A. Seweryn / Advances in Colloid and Interface Science 256 (2018) 242–255
[21] Barel A, Paye M, Maibach HI. Handbook of cosmetic science and technology. Third
edition. CRC Press; 2009.
[22] Simion FA. In: Chew A, Maibach HI, editors. Irritant dermatitis. Berlin: Springer-
Verlag; 2006 [Chapter 53].
[23] Morrison Jr BM, Paye M. J Soc Cosmet Chem 1995;46:291–9.
[24] Zeidler U. J Soc Cosmet Chem Jpn 1986;20(1):17–26.
[25] Robinson MK, McFadden JP, Basketter DA. Contact Dermatitis 2001;45:1–12.
[26] Prottey C, Ferguson T. J Soc Cosmet Chem 1975;26(1):29–46.
[27] Frosch PJ, Kligman AM. J Am Acad Dermatol 1979;1(1):35–41.
[28] Hubbard AW, Moore LJ, Clothier RH, Sulley H, Rollin KA. Toxicol In Vitro 1994;8(4):
689–91.
[29] Pezron I, Galet L, Clausse DJ. Colloid Interface Sci 1996;180(1):285–9.
[30] Götte E. Skin compatibility of tensides measured by their capacity for dissolving
zein protein. IVth international congress on surface active substances, Brussels,
Belgium; 1964. p. 83.
[31] Imokawa G, Sumura K, Katsumi M. J Am Oil Chem Soc 1975;52:484–9.
[32] Tavss EA, Eigen E, Kligman AM. J Soc Cosmet Chem 1988;39:267–72.
[33] Blake-Haskins JC, Scala D, Rhein LD, Robbins CR. J Soc Cosmet Chem 1986;37:
199–210.
[34] Grubauer G, Elias PM, Feingold KR. J Lipid Res 1989;30(3):323–33.
[35] Ghosh S, Blankschtein D. Int J Cosmet Sci 2007;58(3):229–44.
[36] Ananthapadmanabhan KP, Moore DJ, Subramanyan K, Misra M, Meyer F. Dermatol
Ther 2004;17(1):16–25.
[37] Takagi Y, Shimizu M, Morokuma Y, Miyaki M, Kiba A, Matsuo K, et al. Int J Cosmet
Sci 2014;36(4):305–11.
[38] Corazza M, Lauriola MM, Bianchi A, Zappaterra M, Virgili A. Dermatitis 2010;21(5):
262–8.
[39] Wickett RR, Visscher MO. Am J Infect Control 2006;34(10):98-10.
[40] Ananthapadmanabhan KP, Mukherjee S, Chandar P. Int J Cosmet Sci 2013;35(4):
337–45.
[41] Rawlings AV, Scott IR, Harding CR, Bowser PA. J Invest Dermatol 1994;103(5):
731–40.
[42] Wertz PW, van der Bergh B. Chem Phys Lipids 1998;91:85–96.
[43] Elias PM. J Invest Dermatol 1983;80(suppl):44–9.
[44] Rawlings AV, Harding CR. Dermatol Ther 2004;17:43–8.
[45] Verdier-Sévrain S, Bonté F. J Cosmet Dermatol 2007;6:75–82.
[46] Braun-Falco O, Korting HC. Hautarzt 1986;37(3):126–9.
[47] Baranda L, González-Amaro R, Torres-Alvarez B, Alvarez CM, Ramírez V. Int J
Dermatol 2002;41(8):494–9.
[48] Korting HCh, Braun-Falco O. Clin Dermatol 1996;14:23–7.
[49] Lémery E, Briançon S, Chevalier Y, Bordes C, Oddos T, Gohier A, et al. Colloids Surf A
Physicochem Eng Asp 2015;469:166–79.
[50] Danov KD, Kralchevsky PA, Ananthapadmanabhan KP. Adv Colloid Interface Sci
2014;206:17–45.
[51] Kha A, Marques EF. Curr Opin Colloid Interface Sci 1999;4(6):402–10.
[52] Garcia MT, Ribosa I, Sanchez Leal J, Comelles F. J Am Oil Chem Soc 1992;69:25–9.
[53] Sein A, Engberta J. Langmuir 1995;11:455–65.
[54] Sein A, Engberta J, Linden E, Pas JC. Langmuir 1993;9:1714–20.
[55] Lasic D. Biochem J 1988;256(1):1–11.
[56] Hunter RJ. Zeta potential in colloid science: principles and applications. Academic
Press; 2013.
[57] Karsa DR, Farn RJ. Chemistry and technology of surfactants. John Wiley & Sons;
2008 [Chapter 1].
[58] Rosen MJ, Kunjappu JT. Surfactants and interfacial phenomena. 4th ed. John Wiley
& Sons; 2012.
[59] Maibaum L, Dinner AR, Chandler D. J Phys Chem B 2004;108(21):6778–81.
[60] Kronberg B. Curr Opin Colloid Interface Sci 2016;22:14–22.
[61] Penfold J, Tucker I, Thomas RK, Staples E, Schuermann R. J Phys Chem B 2005;109
(21):10760–70.
[62] Goloub TP, Pugh RJ, Zhmud BV. J Colloid Interface Sci 2000;229(1):72–81.
[63] Gambogi J, Arvanitidou ES, Lai KY. In: Lai KY, editor. Liquid detergents. Second edi-
tion. Taylor & Francis Group; 2006 [Chapter 1].
[64] Showell MS. Handbook of detergents. Part D: formulations. Taylor & Francis Group;
2006.
[65] Gallegos C, Franco JM. Curr Opin Colloid Interface Sci 1999;4(4):288–93.
[66] Rhein LD, Simion FA. Ser Surf Sci 1991;32:33–49.
[67] Rhein L, Robbins C, Fernee K, Cantore R. J Soc Cosmet Chem 1986;37:125–39.
[68] Wilhelm KP, Cua AB, Wolff HH, Maibach HI. J Invest Dermatol 1994;101:310–5.
[69] Wihelm KP. Curr Probl Dermatol 1995;22:72–9.
[70] Ciurleo A, Cinelli S, Guidi M, Bonincontro A, Onori G, LaMesa C. Biomacromolecules
2007;8(2):399–405.
[71] Stenstam A, Topgaard D, Wennerström H. J Phys Chem B 2003;107(32):7987–92.
[72] Goddard ED, Ananthapadmanabhan KP. Interactions of surfactants with polymers
and proteins. CRC Press; 1993.
[73] Moriyama Y, Takeda K. Langmuir 2005;21(12):5524–8.
[74] Giroux HJ, Britten M. Food Hydrocoll 2004;18(4):685–92.
[75] Ghosh S. Colloids Surf A Physicochem Eng Asp 2005;264(1):6–16.
[76] Ghosh S. Colloids Surf B Biointerfaces 2008;66(2):178–86.
[77] De Jongh CM, Verberk MM, Withagen CET, Jacobs JJL, Rustemeyer T, Kezic S. Con-
tact Dermatitis 2006;54:325–33.
[78] Mackie A, Wilde P. Adv Colloid Interface Sci 2005;117(1):3–13.
[79] Jones MN. Chem Soc Rev 1992;21(2):127–36.
[80] Fluhr JW, Akengin A, Bornkessel A, Fuchs S, Praessler J, et al. Br J Dermatol 2005;
143:125–31.
[81] Moore PN, Puvvada S, Blankschtein D. J Cosmet Sci 2003;54(1):29–46.
[82] Walters RM, Fevola MJ, Librizzi JJ, Martin K. Cosmet Toilet 2008;123(12):53–60.
[83] Walters RM, Mao G, Gunn ET, Hornby S. Dermatol Res Pract 2012;2012:1–9.
[84] Bromberg L, Liu X, Wang I, Smith S, Schwicker K, Eller Z, et al. Colloids Surf B
Biointerfaces 2017;157:366–72.
[85] Pinazo A. Colloids Surf B Biointerfaces 1996;8(1–2):63–72.
[86] Moore PN, Puvvada S, Blankschtein D. Langmuir 2003;19(4):1009–16.
[87] Deo N, Jockusch S, Turro NJ, Somasundaran P. Langmuir 2003;19(12):5083–8.
[88] Ruso JM, Deo N, Somasundaran. Langmuir 2004;20(21):8988–91.
[89] Mehta SK, Bhasin KK, Kumar A. Colloids Surf A Physicochem Eng Asp 2009;346(1):
195–201.
[90] Mehta SK, Bhasin KK, Kumar A. J Colloid Interface Sci 2008;323(2):426–34.
[91] Kelley D, McClements DJ. Food Hydrocoll 2003;17(1):73–85.
[92] Cohen L, Sanchez E, Martin M, Soto F, Trujillo F. J Surfactant Deterg 2016;19(5):
1089–92.
[93] Faucher JA, Goddard ED. J Soc Cosmet Chem 1978;29:323–37.
[94] Putterman GJ, Wolejsza NF, Wolfram MA, Laden K. J Soc Cosmet Chem 1977;28:
521–32.
[95] Di Nardo A, Conti A, Martini M, Seidenari S. Skin Res Technol 1998;4:192–5.
[96] Robbins CR, Fernee K. J Soc Cosmet Chem 1983;34:21–34.
[97] Cohen L, Martin M, Soto F, Trujillo F, Sanchez E. J Surfactant Deterg 2016;19(1):
219–22.
[98] Cohen L, Moreno A, Berna JL. J Surface Sci Technol 1997;13:59–71.
[99] Cohen L, Moreno A, Berna JL. Tenside Surfactant Deterg 1998;35:265–9.
[100] Seweryn A, Wasilewski T, Bujak T. Ind Eng Chem Res 2016;55(4):1134–41.
[101] Menger FM, Littau CA. J Am Chem Soc 1993;115(22):10083–90.
[102] Menger FM, Littau CA. J Am Chem Soc 1991;113(4):1451–2.
[103] Song LD, Rosen MJ. Langmuir 1996;12(5):1149–53.
[104] Acharya DP, Kunieda H, Shiba Y, Aratani KI. J Phys Chem B 2004;108(5):1790–7.
[105] Shukla D, Tyagi VK. J Oleo Sci 2006;55(5):215–26.
[106] Rosen MJ, Tracy DJ. J Surfactant Deterg 1998;1(4):547–54.
[107] Zana R. Adv Colloid Interface Sci 2002;97(1):205–53.
[108] Kamal MS. J Surfactant Deterg 2016;19(2):223–36.
[109] Kumar N, Tyagi R. Cosmetics 2013;1(1):3–13.
[110] Kumar N, Tyagi R. J Dispers Sci Technol 2014;35(2):205–14.
[111] Tsubone K, Ogawa T, Mimura K. J Surfactant Deterg 2003;6(1):39.
[112] Diz M, Manresa A, Pinazo A, Erra P, Infante M. J Chem Soc Perkin Trans 1994;2(8):
1871–6.
[113] Mulligan CN. Environ Pollut 2005;133(2):183–98.
[114] Banat IM. Bioresour Technol 1995;51(1):1–12.
[115] Allemann IB, Baumann L. Skin Therapy Lett 2008;13(7):5–9.
[116] Bai L, McClements DJ. J Colloid Interface Sci 2016;479:71–9.
[117] Vecino X, Cruz JM, Moldes AB, Rodrigues LR. Crit Rev Biotechnol 2017;37(7):
911–23.
[118] Ferreira A, Vecino X, Ferreira D, Cruz JM, Moldes AB, Rodrigues LR. Colloids Surf B
Biointerfaces 2017;155:522–9.
[119] Lee S, Lee J, Yu H, Lim J. Colloids Surf A Physicochem Eng Asp 2018;536:224–33.
[120] Burgos-Díaz C, Martín-Venegas R, Martínez V, Storniolo CE, et al. Int J Pharm 2013;
453(2):433–40.
[121] Kim HS, Jeon JW, Kim SB, Oh HM, Kwon TJ, Yoon BD. Biotechnol Lett 2002;24(19):
1637–41.
[122] Alonso C, Lucas R, Barba C, Marti M, Rubio L, et al. J Pharm Pharmacol 2015;67(7):
900–8.
[123] Takahashi M, Morita T, Fukuoka T, Imura T, Kitamoto D. J Oleo Sci 2012;61(8):
457–64.
[124] Luna JM, Rufino RD, Sarubbo LA, Rodrigues LR, Teixeira JA, de Campos-Takaki GM.
Curr Microbiol 2011;62(5):1527–34.
[125] Gudina EJ, Teixeira JA, Rodrigues LR. Colloids Surf B Biointerfaces 2010;76(1):
298–304.
[126] Madhu AN, Prapulla SG. Appl Biochem Biotechnol 2014;172(4):1777–89.
[127] Gudiña EJ, Fernandes EC, Teixeira JA, Rodrigues LR. RSC Adv 2015;5(110):90960–8.
[128] Imokawa G, Akasaki S, Minematsu Y, Kawai M. Arch Dermatol Res 1989;281:
45–51.
[129] Froebe CL, Simion FA, Rhein LD, Cagan RH, Kligman A. Dermatology 1990;181:
277–83.
[130] Fulmer AW, Kramer GJ. J Invest Dermatol 1986;5:598–602.
[131] Ananthapadmanabhan KP, Yang L, Vincent C, et al. Quadrant 2009;22(6):
307–16.
[132] Lémery E, Briançon S, Chevalier Y, Bordes C, Oddos T, Gohier A, et al. Colloids Surf A
Physicochem Eng Asp 2015;469:166–79.
[133] Som I, Bhatia K, Yasir M. Status of surfactants as penetration enhancers in transder-
mal drug delivery. J Pharm Bioallied Sci 2012;4(1):2–9.
[134] Astner S, Gonzalez E, Cheung AC, Rius-Diaz F, Doukas AG, et al. J Invest Dermatol
2005;124:351–9.
[135] Lee JK, Kim DB, Kim JI, Kim PY. Toxicol In Vitro 2000;14(4):345–9.
[136] Effend I, Maibach HI. Contact Dermatitis 1995;33(4):217–25.
[137] Corazza M, Lauriola MM, Zappaterra M, Bianchi A, Virgili A. J Eur Acad Dermatol
Venereol 2010;24(1):1–6.
[138] Nosbaum A, Vocanson M, Rozieres A, Hennino A, Nicolas JF. Eur J Dermatol 2009;19
(4):325–32.
[139] Slodownik D, Lee A, Nixon R. Aust J Dermatol 2008;49:1–11.
[140] Frosch PJ, John SM. In: Johansen JD, Frosch PJ, Lepoittevin JP, editors. Contact
dermatitis. Berlin Heidelberg: Springer; 2011 [Chapter 15].
[141] Berardesca E, Distante F. Contact Dermatitis 1994;31(5):281–7.
[142] Yokota M, Maibach HI. Contact Dermatitis 2006;55(2):65–72.
[143] Levin CY, Maibach HI. Int J Immunopharmacol 2002;2:183–9.
[144] Van Der Valk PG, Nater JP, Bleumink E. J Invest Dermatol 1984;82(3):291–3.
[145] Zhai H, Maibach HI. Contact Dermatitis 2001;44(4):201.
 A. Seweryn / Advances in Colloid and Interface Science 256 (2018) 242–255
[146] Belsito DV, Fransway AF, Fowler JF, Sherertz EF, Maibach HI, Mark JG, et al. J Am
Acad Dermatol 2002;46(2):200–6.
[147] Groot AC, Walle HB, Weyland JW. Contact Dermatitis 1995;33(6):419–22.
[148] Blondeel A. Contact Dermatitis 2003;49(6):304–5.
[149] Gijbels D, Timmermans A, Serrano P, Verreycken E, Goossens A. Contact Dermatitis
2014;70(3):175–82.
[150] Andrade P, Gonçalo M, Figueiredo A. Contact Dermatitis 2010;62(2):119–20.
[151] Malanin KEN. Contact Dermatitis 2002;47(1):50.
[152] Biebl KA, Warshaw EM. Dermatol Clin 2006;24(2):215–32.
[153] Wolf R, Wolf D, Tüzün B, Tüzün Y. Dermatol Ther 2001;14:181–7.
[154] Thomson KF, Wilkinson SM. Br J Dermatol 2000;142:84–8.
[155] Ray GB, Ghosh S, Moulik SP. J Surfactant Deterg 2009;12(2):131–43.
[156] Takagi Y, Shimizu M, Morokuma Y, Miyaki M, et al. Int J Cosmet Sci 2014;36(4):
305–11.
[157] Ozawa T, Endo K, Masui T, Miyaki M, Matsuo K, Yamada S. J Surfactant Deterg 2016;
19(4):785–94.
[158] Corazza M, Lauriola MM, Bianchi A, Zappaterra M, Virgili A. Dermatitis 2010;21(5):
262–8.
[159] Bigotti C, Guaio F, Merlo E, Gazzanig G, Villa G. J Appl Cosmet 2005;23:139–47.
[160] Blake-Haskins J, Scala D, Rhein L, Robbins C. J Soc Cosmet Chem 1985;36:379.
[161] Rhein L. In: Johansson I, Somasundaran P, editors. Handbook for cleaning/decon-
tamination of surfaces. Elsevier; 2007 [Chapter C3].
[162] Basketter DA, Marriott M, Gilmour NJ, White IR. Contact Dermatitis 2004;50(4):
213–7.
[163] Zhou C, Wang D, Cao M, Chen Y, Liu Z, Wu C, et al. ACS Appl Mater Interfaces 2016;
8(45):30811–23.
[164] Li Y, Wang X, Wang Y. J Phys Chem B 2006;110(16):8499-05.
[165] Bakshi MS, Singh J, Kaur G. Chem Phys Lipids 2005;138(1–2):81–92.
[166] Blagojević SN, Blagojević SM, Pejić ND. J Surfactant Deterg 2016;19(2):363–72.
[167] Blagojević SM, Pejić ND, Blagojević SN, Russ J. Phys Chem A 2017;91(13):2690–5.
[168] Jones MN. Biochem J 1975;151(1):109–14.
[169] Jones MN, Manley P. J Chem Soc Faraday Trans I 1979;75:1736–44.
[170] Subramanian M, Sheshadri BS, Venkatappa MP. J Biosci 1986;10:359–71.
[171] Reynolds J, Herbert S, Steinhardt J. Biochemistry 1968;7:1357–61.
[172] Kaneshina S, Tanaka M, Kondo T, Mizuno T, Aoki K. Bull Chem Soc Jpn 1973;46:
2735–8.
[173] Reynolds JA, Gallagher JP, Steinhardt J. Biochemistry 1970;9:1232–8.
[174] Sarmiento F, Ruso JM, Prieto G, Mosquera V. Langmuir 1998;14:5725–9.
[175] Takeda K, Sasa K, Kawamoto K, Wada A, Aoki K. J Colloid Interface Sci 1988;124:
284–9.
[176] Reynolds JA, Tanford C. Proc Natl Acad Sci 1970;66:1002–7.
[177] James-Smith MA, Hellner B, Annunziato N, Mitragotri S. Ann Biomed Eng 2011;39:
1215–23.
[178] Chen Y, Ji X, Han Y, Wang YL. Langmuir 2016;32:8212–21.
[179] Ananthapadmanabhan KP, Yu KK, Meyers CL, Aronson MP. J Soc Cosmet Chem
1996;47:185–200.
[180] Tyagi VK. J Oleo Sci 2006;55(9):429–39.
[181] Secchi G. Clin Dermatol 2008;26(4):321–5.
[182] Hall-Manning TJ, Holland GH, Rennie G, Revell P, Hines J, Barrat MD, et al. Food
Chem Toxicol 1998;36:233–8.
[183] Kawasaki Y, Quan D, Sakamoto K, Cooke R, Maibach HI. Skin Res Technol 1999;5
(2):96–101.
[184] Lee CH, Kawasaki Y, Maibach HI. Contact Dermatitis 1994;30:205–9.
[185] Tadenuma H, Yamada K, Tamura T. Jpn Oil Chem Soc 1999;48:207–13.
[186] Paye M, Block C, Hamaide N, Hüttman GE, Kirkwood S, et al. Tenside Surfactant
Deterg 2006;43(6):290–4.
[187] Miyazawa K, Ogawa M, Mitsui T. Int J Cosmet Sci 1984;6:33–46.
[188] Dominguez JG, Balaguer F, Parra JL, Pelejero CM. Int J Cosmet Sci 1981;3:
57–68.
[189] McFadden JP, Holloway DB, Whittle EG, Basketter DA. Contact Dermatitis 2000;43
(5):264–6.
[190] Chen Y, Qiao F, Fan Y, Han Y, Wang Y. Langmuir 2017;33(11):2760–9.
[191] Holmberg K, Jonsson B, Kronberg B, Lindman B. Surfactants and polymer in aque-
ous solution. John Wiley & Sons; 2002.
[192] Bujak T, Wasilewski T, Nizioł-Łukaszewska Z. Colloids Surf B Biointerfaces 2015;
135:497–503.
[193] Draelos Z, Hornby S, Walters RM, Appa Y. J Cosmet Dermatol 2013;12(4):314–21.
[194] Goddard ED, Leung PS. Cosmet Toilet 1982;97:55–69.
[195] Pugliese P, Hines G, Wielenga W. Cosmet Toilet 1990;105:105–11.
[196] Teglia A, Secchi G. Int J Cosmet Sci 1994;16:235–46.
[197] Teglia A, Mazzola G, Secchi G. Cosmet Toilet 1993;108(11):56–65.
[198] Goddard ED. Colloids Surf 1986;19(2–3):255–300.
[199] Hansson P, Lindman B. Curr Opin Colloid Interface Sci 1996;1(5):604–13.
[200] Loyen K, Iliopoulos I, Audebert R, Olsson U. Langmuir 1995;11(4):1053–6.
[201] Persson K, Bales BL. J Chem Soc Faraday Trans 1995;91(17):2863–70.
[202] Goddard ED, Hannan RB. J Am Oil Chem Soc 1977;54(12):561–6.
255
[203] Nagarajan R. Polymer–surfactant interactions. New horizons: detergents for the
new millennium conference invited papers. FortMyers, Florida: American Oil
Chemists Society and Consumer Specialty Products Association; 2001.
[204] Jones MN. J Colloid Interface Sci 1967;23(1):36–42.
[205] Goddard ED, Phillips TS, Hannan RB. J Soc Cosmet Chem 1975;26:461–75.
[206] Goddard ED, Ananthapadmanabhan KP, editors. Interactions of surfactants with
polymers and proteins. Boca Raton, FL: CRC Press; 1993.
[207] Goddard ED, Ananthapadmanabhan KP, editors. Applications of polymer–
surfactant systems. Surfactant science seriesMarcel Dekker; 1998.
[208] Taylor DJF, Thomas RK, Penfold J. Adv Colloid Interface Sci 2007;132(2):69–110.
[209] Nylander T, Samoshina Y, Lindman B. Adv Colloid Interface Sci 2006;123:105–23.
[210] JCT Kwak, editor. Polymer-surfactant systems. Surfactant science seriesNew York:
Marcel Dekker; 1998.
[211] Bao H, Li L, Gan LH, Zhang H. Macromolecules 2008;41:9406–12.
[212] Vinceković M, Bujan M, Šmit I, Filipović-Vinceković N. Colloids Surf A Physicochem
Eng Asp 2005;255:181–91.
[213] Bakshi MS, Kaur I. Colloids Surf A Physicochem Eng Asp 2003;224:185–97.
[214] Thalberg K, Lindman B, Karlstrom G. J Phys Chem 1991;95:3370–6.
[215] Taylor DJF, Thomas RK, Hines JD, Humphreys K, Penfold J. Langmuir 2002;18:
9783–91.
[216] Hayakawa K, Kwak JCT. J Phys Chem 1983;87:506–9.
[217] Hayakawa K, Santerre JP, Kwak JCT. Macromolecules 1983;16:1642–5.
[218] Hayakawa K, Kwak JCT. J Phys Chem 1982;86:3866–70.
[219] Bai G, Wang Y, Yan H, Thomas RK, Kwak JCT. J Phys Chem B 2002;106:2153–9.
[220] Thalberg K, Lindman B, Karlström G. J Phys Chem 1990;94:4289–95.
[221] Thalberg K, Lindman B. J Phys Chem 1989;93:1478–83.
[222] Cardenas M, Nylander T, Joensson B, Lindman B. J Colloid Interface Sci 2005;286:
166–75.
[223] Cooke DJ, Dong CC, Lu JR, Thomas RK, Simister EA, Penfold J. J Phys Chem B 1998;
102:4912–7.
[224] Alves L, Lindman B, Klotz B, Böttcher A, Haake HM, Antunes FE. J Colloid Interface
Sci 2018;513:489–96.
[225] Thomas RK, Penfold J. Curr Opin Colloid Interface Sci 1996;1(1):23–33.
[226] Penfold J, Thomas RK, Taylor DJF. Curr Opin Colloid Interface Sci 2006;11:337–44.
[227] Persson B, Hugerth A, Caram-Lelham N, Sundelof LO. Langmuir 2000;16:313–7.
[228] Babak VG, Vikhoreva GA, Lukina IG. Colloids Surf A Physicochem Eng Asp 1997;
128:75–89.
[229] Purcell IP, Lu JR, Thomas RK, Howe AM, Penfold J. Langmuir 1998;14(7):1637–45.
[230] Lange H. Kolloid Z Z Polym 1971;243:101–9.
[231] Bahramian A, Thomas RK, Penfold J. J Phys Chem B 2014;118:2769–83.
[232] Sehgal P, Mizuki T, Doe H, Wimmer R, Larsen KL, Otzen DE. Colloid Polym Sci 2009;
287:1243–52.
[233] Guo R, Zhu XJ, Guo X. Colloid Polym Sci 2003;281:876–81.
[234] Okubo T, Kitano H, Ise N. J Phys Chem 1976;80:2661–4.
[235] Zhou Y, Yu H, Zhang L, Sun J, Wu L, Lu Q, et al. J Incl Phenom Macrocycl Chem 2008;
61:259–64.
[236] Valente AJM, Dinis CJS, Pereira RFP, Ribeiro ACF, Lobo VMM. Port Electrochem Acta
2006;24:129–36.
[237] Rafati AA, Safatian F. Phys Chem Liq 2008;46:587–98.
[238] Li J, Zhao C, Chao J. J Incl Phenom Macrocycl Chem 2008;62:325–31.
[239] Fonasaki N, Ishikawa S, Hirota S. Anal Chim Acta 2006;555:278–85.
[240] Tang B, Wang X, Wang G, Yu Ch, Chen Zh. Talanta 2006;69:113–20.
[241] Mwakibete H, Cristantino R, Bloor DM, Wyn-Jones E, Holzwarth JF. Langmuir 1995;
11:57–60.
[242] Dharmawardana UR, Christian SD, Tucker EE, Taylor RW, Scamehorm JF. Langmuir
1993;9:2258–63.
[243] Wilson LD, Verrall RE. J Phys Chem B 1998;102:480–8.
[244] Elder R. L. J Am Acad Dermatol 1984;11(6):1168–74.
[245] Parente ME, Solana G. Int J Cosmet Sci 2005;27(6):354.
[246] Lodén M, Am J. Clin Dermatol 2003;4(11):771–88.
[247] Levi K, Kwan A, Rhines AS, Gorcea M, Moore DJ, Dauskardt RH. Br J Dermatol 2010;
163:695–703.
[248] Lodén M, Buraczewska I, Edlund F. Br J Dermatol 2004;150(6):1142–7.
[249] Yang B, Bonfigli A, Pagani V, Isohanni T, von Knorring A, Jutila A, et al. J Appl Cosmet
2009;27(1):1–13.
[250] Förster T, Issberner U, Hensen H. J Surfactant Deterg 2000;3(3):345.
[251] Takagi Y, Nakagawa H, Higuchi K, Imokawa G. Dermatology 2005;211:128–34.
[252] Lee YB, Park HJ, Kwon MJ, Jeong SK, Cho SH. Eur J Dermatol 2011;21:710–6.
[253] Conti A, Rogers J, Verdejo P, Harding CR, Rawlings AV. Int J Cosmet Sci 1996;18:
1–12.
[254] Mukherjee S, Edmunds M, Lei X, Ottaviani MF, Ananthapadmanabhan KP, Turro NJ.
J Cosmet Dermatol 2010;9:202–10.
[255] Mukherjee S, Yang L, Vincent C, Lei X, Ottaviani MF, Ananthapadmanabhan KP. Int J
Cosmet Sci 2015;37(4):371–8.
[256] Wasilewski T, Seweryn A, Krajewski M. J Surfactant Deterg 2016;19(6):1315–26.
[257] Wasilewski T, Seweryn A, Bujak T. Green Chem Lett Rev 2016;9(2):114–21.