CIS-01526; No of Pages 16

Advances in Colloid and Interface Science xxx (2015) xxxxxx

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Advances in Colloid and Interface Science

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

Historical Perspective

Co-assembly in chitosansurfactant mixtures: thermodynamics,

structures, interfacial properties and applications
Leonardo Chiappisi , Michael Gradzielski
Technische Universitt Berlin, Stranski Laboratorium fr Physikalische Chemie und Theoretische Chemie, Institut fr Chemie, Strae des 17. Juni 124, Sekr. TC7, D-10623 Berlin, Germany

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

Available online xxxx In this review, different aspects characterizing chitosansurfactant mixtures are summarized and compared.
Chitosan is a bioderived cationic polysaccharide that nds wide-ranged applications in various eld,
Keywords: e.g., medical or food industry, in which synergistic effects with surfactant can play a fundamental role. In partic-
Chitosansurfactant complexes ular, the behavior of chitosan interacting with strong and weak anionic, nonionic as well as cationic surfactants is
Phospholipids reviewed. We put a focus on oppositely charged systems, as they exhibit the most interesting features. In that
Fatty acids
context, we discuss the thermodynamic description of the interaction and in particular the structural changes
Interfacial properties
Applications
as they occur as a function of the mixed systems and external parameters. Moreover, peculiar properties of chi-
tosan coated phospholipid vesicles are summarized. Finally, their co-assembly at interfaces is briey reviewed.
Despite the behavior of the mentioned systems might strongly differ, resulting in a high variety of properties,
few general rules can be pointed out which improve the understanding of such complex systems.
2015 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0
1.1. Binding isotherms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0
1.2. Physico-chemical properties of chitosan in aqueous solution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0
1.3. Similarities with cellulose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0
2. Chitosansurfactant mixtures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0
2.1. Chitosanstrong anionic surfactant . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0
2.2. Chitosanweak anionic surfactant . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0
2.2.1. Chitosanfatty acid mixtures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0
2.2.2. Chitosanalkyl oligooxyethylene carboxylic acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0
2.3. Chitosanbile acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0
2.4. Chitosannonionic surfactant . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0
2.5. Chitosancationic surfactant . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0
3. Chitosan-coated liposomes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0
3.1. Binding process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0
3.2. Structural aspects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0
3.3. Membrane properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0
4. Co-assembly at interfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0
4.1. Co-assembly at the vaporliquid interface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0
4.2. Co-assembly at the liquidliquid interface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0
4.3. Co-assembly at the solidliquid interface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0
5. Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0
6. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0
Acknowledgment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0

Corresponding author.
Corresponding author. Tel.: +49 30 314 24934; fax: +49 30 314 79552.
E-mail addresses: leonardo.chiappisi@tu-berlin.de (L. Chiappisi), michael.gradzielski@tu-berlin.de (M. Gradzielski).

http://dx.doi.org/10.1016/j.cis.2015.03.003
0001-8686/ 2015 Elsevier B.V. All rights reserved.

Please cite this article as: Chiappisi L, Gradzielski M, Co-assembly in chitosansurfactant mixtures: thermodynamics, structures, interfacial
properties and applications, Adv Colloid Interface Sci (2015), http://dx.doi.org/10.1016/j.cis.2015.03.003
2 L. Chiappisi, M. Gradzielski / Advances in Colloid and Interface Science xxx (2015) xxxxxx

1. Introduction
Complexes of polyelectrolytes and surfactants are highly interesting
systems and accordingly have been studied in detail so far. However,
due to the large number of possible polyelectrolytes and surfactants
that can be combined, basically an endless number of mixtures can be
envisioned and a rich structural behavior has been observed in these
systems. Pronounced synergistic effects are found when surfactants
and polyelectrolytes are oppositely charged. These mixtures are used
both in the solid state, as they provide an easy route for the preparation
of highly structured materials [13] and in solution, due to the high
structural variety and the often present stimuli-responsiveness of such
supramolecular complexes [46].
For the interesting system of oppositely charged polyelectrolytes/
surfactants the driving force for their assembly is the entropic gain
due to release of the small counterions and water molecules. Typically
around charge equimolarity insolubility of the formed complexes is ob-
served [5,7]. Such complexes, due to their ability to modify rheological
properties and also their ability to incorporate active agents, are inter-
esting for many applications, for instance in the eld of cosmetics and
pharmaceutical formulations.
A particularly interesting class of polymers are biopolyelectrolytes,
which means that they are either directly biopolymers or ones that
are obtained from them by simple chemical modication. Within the
class of biopolyelectrolytes, charged polysaccharides, play a predomi-
nant role. These polymers are in general rather biocompatible, they de-
rive from renewable resources and most of them are available in large
quantities and at low cost, making them attractive for industrial pur-
poses [8]. For a general overview of the aspects characterizing ionic
polysaccharides and their mixtures with soft colloids we address the
reader to some recent reviews [6,912]. A general feature of
biopolyelectrolytes is that their backbone is based on carbohydrates,
e.g., cellulose based polyelectrolytes. This carbohydrate backbone is
substantially stiffer than that of synthetic polyelectrolytes that are typ-
ically based on vinyl building blocks.
The group of ionic polysaccharides is rather large and most of them are
negatively charged. In our review we will focus on chitosan, which is a
biopolycation in acidic conditions. The term chitosan is generally referred
to the random block copolymer of glucosamine (GlcN) and N-acetyl glu-
cosamine (GlcNAc), linked by -(14)-glycosidic bonds. The fraction of
N-acetyl glucosamine determines the degree of acetylation (DA). In
most cases, chitosan is obtained by alkaline or enzymatic deacetylation
of chitin, poly N-acetyl glucosamine (see Fig. 1). The density of chargeable
groups along the polymer backbone is determined by the degree of
deacetylation. Chitosan is rather well biodegradable and can easily be-
come chemically modied by reactions on its amino and hydroxylic side
groups [1315]. The ease of modication, in addition to its antibacterial,
antiinammatory and mucoadhesive properties are reasons why this bio-
polymer has found applications in a wide range of elds. For instance it is
interacting well with skin and hair and therefore is employed in different
types of cosmetic formulations or for food processing [16]. In the medical
eld chitosan has shown outstanding performance in the eld of wound
covering and healing [17]. The polyelectrolyte properties of chitosan itself
have for instance been employed for purposes of coagulation/occulation
processes, which is a relatively eco-friendly approach compared to
methods employed so far [1820]. Another environmentally relevant ap-
plication of chitosan is the removal of heavy metal ions [2123].
In this review we focus on complexes of positively charged chitosan.
Particular attention will be put on the thermodynamic driving forces
governing the co-assembly with surfactants and on the resulting struc-
tures. The main focus is on what structural control can be exerted in sur-
factant/chitosan mixtures and how by that control the properties of
such systems for applications can be tailored. By analyzing the behavior
of chitosan mixtures with cationic, anionic and nonionic surfactants as
well as with phospholipid vesicles, some aspects common to all system
will be pointed out.

Fig. 1. Chemical structure of, from top to bottom, chitin, chitosan and cellulose.

Please cite this article as: Chiappisi L, Gradzielski M, Co-assembly in chitosansurfactant mixtures: thermodynamics, structures, interfacial
properties and applications, Adv Colloid Interface Sci (2015), http://dx.doi.org/10.1016/j.cis.2015.03.003
 L. Chiappisi, M. Gradzielski / Advances in Colloid and Interface Science xxx (2015) xxxxxx 3

1.1. Binding isotherms

Admixing polyelectrolyte to surfactant solutions will render their

self-assembly behavior substantially more complex. While surfactants
as a function of concentration typically show just one critical micelle
concentration (cmc), above which micelles are formed, for surfactant/
polyelectrolyte mixtures several characteristic concentrations can be
discerned. Depending on the strength of interaction (which will be
most pronounced for oppositely charged surfactant and polyelectro-
lyte) additional effects will be seen at concentrations below the cmc.
Typically, different regions can be identied as a function of surfactant
concentration Cs:

i) at low Cs, surfactant molecules are in equilibrium between

monomerically soluble surfactants and non-cooperatively
bound surfactants. At this stage, solutions appear clear, with a
rather low solubilization capacity with respect to hydrophobic
molecules and with increasing Cs a decrease in surface tension
is observed.
ii) at intermediate Cs, provided that the local concentration of sur-
factant in the polymer surrounding is high enough, rst micellar
like aggregates, bound to the polyelectrolyte chain, are formed.
The total surfactant concentration, above which polymer-
induced micellization takes place, is dened as the critical aggre-
gation concentration (cac). Further addition of surfactant has lit- Fig. 2. Idealized, from top to bottom, typical trends of binding isotherm , surface tension
and binding enthalpy Hbinding as a function of total surfactant concentration, as found in
tle inuence on the surface tension, as most of the added oppositely charged surfactant/polyelectrolyte mixtures. See text for further details.
molecules are incorporated into the supramolecular complex.
Correspondingly, as the surfactant in the aggregate can be con-
sidered as a separate phase (as normally done for micellar aggre-
gates), its chemical potential remains constant. Typically, at this
point an increase in solubilization capacity (due to the presence with K, u and Cf being the binding constant, the cooperativity parameter
of hydrophobic domains) as well as an increase in turbidity, is and free surfactant concentration, respectively. The non-cooperative
observed. and cooperative free binding energies Gnc and Gc can be obtained as:
iii) a further increase in Cs results in a saturation of the polymer
chain, associated with an increase in free surfactant concentra- Gnc RT ln K 2
tion and another more or less strong decrease in surface tension
until the free surfactant concentration equals the cmc at the
given experimental conditions. The saturation of the polymer is Gc RT ln Ku 3
often associated with a macroscopic phase separation [5,7].
where R is the gas constant and T the temperature. In the SatakeYang
An idealized surface tension curve is reported in Fig. 2 (middle). Of model, the polymer chain is described as a linear array of binding sites.
course, every pair of surfactant and polyelectrolyte has its own charac- Three states are foreseen for each site: free, non-cooperatively occupied
teristic behavior, which may also substantially differ from the general and cooperatively occupied (when at the least two consecutive sites are
trends reported here. occupied). In a simplied but still realistic picture, the interactions
A quantitative description of the binding process is given by the between surfactant and polymer can be divided into vertical and
binding isotherm , i.e., a function describing the amount of surfactant horizontal forces: the former between surfactant and polymer, they
bound to the polyelectrolyte chain. In the last decades, several binding are mostly of electrostatic nature but also hydrophobic forces and hy-
isotherms have been derived with the aim of describing the binding of drogen bonding play a role; the latter consider the interaction among
small amphiphilic molecules to polyelectrolytes [2431]. From the the surfactant tails, mostly by hydrophobic and dispersion forces. For
binding isotherm not only the speciation of the system can be deduced, binding processes following the SatakeYang isotherm, which is often
i.e., the amount of free and bound surfactants as well as occupied poly- the case for semi-rigid polysaccharide/surfactant mixtures [3841], a
meric binding sites, but it provides binding constants and free energies. detailed calorimetric investigation can highlight the relevance of
Accordingly, several experimental methods were employed for the de- the different energetic contributions [42]. The outcome of a typical
termination of the binding isotherms in polyelectrolytesurfactant mix- isothermal calorimetric titration for oppositely charged surfactant/
tures, e.g., surfactant selective electrodes [3234], uorescence polyelectrolyte mixtures is reported in Fig. 2 (bottom).
experiments [35], or isothermal titration calorimetry [31,36]. A binding
isotherm as typically found in oppositely charged surfactant/polyelec- 1.2. Physico-chemical properties of chitosan in aqueous solution
trolyte mixtures is reported in Fig. 2 (top).
In general, the binding of surfactants to polyelectrolytes is a cooper- The behavior of cellulose based polyelectrolytes in aqueous solution
ative process and can be described with the SatakeYang binding iso- can vary quite largely depending on the detailed molecular architecture
therm [25,27], based on the ZimmBragg theory [37]: of the polymer and the extent of its hydrophobicity [43]. Accordingly
2 3 also the physico-chemical behavior of chitosan in solution and in mix-
tures with small amphiphilic compounds is unique and a closer look
16 KuC f 1 7
6 7
1 r 1 to its properties is of interest. In that context it might be noted that chi-
24  2 5
tosan is typically employed over a rather large range of molecular
1sKuC f 4KC f
weight Mw of 50 kDa to above 1 MDa and that parameter can play a

Please cite this article as: Chiappisi L, Gradzielski M, Co-assembly in chitosansurfactant mixtures: thermodynamics, structures, interfacial
properties and applications, Adv Colloid Interface Sci (2015), http://dx.doi.org/10.1016/j.cis.2015.03.003
4 L. Chiappisi, M. Gradzielski / Advances in Colloid and Interface Science xxx (2015) xxxxxx
signicant role in its comportment. In addition, chitosan is typically
quite polydisperse with polydispersity indices (PDIs) of 1.72.5 [44].
Charge density.
Compared to common synthetic polyelectrolytes, e.g., polystyrene
sulfonate or polyacrylates, chitosan carries at maximum one charge
every ~5 , considering full protonation and complete deacetylation
(DA = 0), i.e., a much lower charge density along the polymer back-
bone. Furthermore the charge density is given by the DA and pH,
and thereby easily changeable over a large range. The relation be-
tween degree of protonation , pH and DA is however rather complex,
as the pKa(, Da) varies to some extent with and DA [45]. A further
aspect playing an important role is the charge distribution along the
polymer chain. As mentioned before, chitosan is usually referred to
as a random copolymer of chargeable (glucosamine) and not charge-
able units (N-acetyl glucosamine). However, the primary sequence of
GlcN and GlcNAc depends on the deacetylation conditions [4648],
which means that they can differ even for chitosan of identical Mw
and DA. Accordingly, also the physico-chemical properties,
e.g., solubility, viscosity, crystallinity, depend on the deacetylation
procedure [46,48].
Differently from most other polyelectrolytes, cellulose based and syn-
thetic ones, chitosan carries its charges directly on the polymer back-
bone. This point, together with the high persistence length of the
polymer is expected to be one of the main structural directing forces
in the formation of supramolecular colloidal complexes and will be
mentioned later on in this review.
Hydrogen bonds and hydrophobic interactions.
The properties, e.g., conformation or solubility, of polysaccharides
strongly depend on the arrangement of the hydroxylic groups along
the polymer backbone as well as their molecular weight and the
type of glycosidic bonds. For instance, despite dextran and cellulose
have the same chemical sum formula their solubility in water strongly
differs.
Concerning chitosan, molecular simulations have shown that the
hydrogen bonding between HO(3) group and the O(5) of the next
glucosamine unit strongly reduces the exibility of chitosan [49].
Accordingly, the addition of urea as breaker of the water structure to
chitosan solutions affects its conformation in aqueous solution [50,
51]. Moreover, chitosan, like cellulose, presents hydrophobic pockets,
which play an important role for the interactions with amphiphilic
compounds, as discussed later in this review. The relatively low effect
of the ionic strength on the self-association of chitosan chains
highlights the importance of hydrophobic interactions and H-bonds
between the polymer units [52].
Stiffness.
Chitosan is considered a semi-rigid polymer with a persistence length
lp of 530 nm reported in literature [5355]. Simulations have shown
that the origin of chitosan rigidity has to be found in the high torsional
energy of the glycosidic bond [56,57] and in the presence of a number
of intrachain hydrogen bonds [49]. Accordingly, a number of factors
affect the exibility of chitosan chains in solution, e.g., degree of acet-
ylation, ionic strength, pH, and a clear correlation between the differ-
ent parameters and lp is everything but trivial. For instance,
contradicting results can be found in literature regarding the effect
of the DA on the persistence length: some authors report an increase
of stiffness with DA [56,58], others nd that lp remains unaffected by
the DA [53,54]. Schatz et al. reported that the effect of DA on the
physico-chemical behavior of chitosan can be divided into three
domains [54]:
(i) below DA = 0.2, where electrostatic interactions between the poly-
mer chains dominate, as here the Bjerrum length, i.e., the distance
at which electrostatic repulsion equals the thermal energy, is larger
than the average spacing between neighboring charged units.
ii) for 0.2 b DA b 0.5, where the polymer becomes increasingly hydro-
phobic and chain association starts to take place and
Please cite this article as: Chiappisi L, Gradzielski M, Co-assembly in chitosansurfactant mixtures: thermodynamics, structures, interfacial
properties and applications, Adv Colloid Interface Sci (2015), http://dx.doi.org/10.1016/j.cis.2015.03.003
(iii) for DA N 0.5, in which chitosan behaves as an increasingly
more hydrophobic polymer and stable multichain aggregates are
formed [54] for not too high DA. Finally, upon approaching
DA = 1.0 insoluble chitin is obtained. Another important factor
which adds further complexity to the effect of DA on the chain
conformation is the distribution of the GlcNAc units along the
backbone [56]. Monte Carlo simulations on chitosan oligosaccha-
rides have evidenced that the exibility is mostly given by the
number of GlcNGlcNAc sequences, while GlcNAcGlcNAc,
GlcNAcGlcN and GlcNGlcN sequences stabilize the extended
conformation via a number of interchain hydrogen bonds [56].
The importance of the primary sequence in determining the stiff-
ness of polymer might be a reason for the contradicting results
found in literature.
Similarly, pH and ionic strength affect the conformation of chito-
san in solution, as they directly affect the degree of ionization
(pKa,eff 6 6.5) and their screening, respectively. At low chito-
san concentration, an increase of ionic strength causes a decrease
of persistence length, radius of gyration and intrinsic viscosity, as
a consequence of charge screening and a more compact confor-
mation of the polymer chain [59].
Chitosan shows a high tendency to self-associate, whose origin can
be found in the intrinsically hydrophobic nature of the polymer back-
bone [52,59]. This intrinsic tendency can be further boosted if chitosan
becomes hydrophobically modied, e.g., by N-alkylation [60] as typical-
ly found also for other hydrophobically modied water-soluble poly-
mers [61,62]. As an example the N-alkylation with dodecyl chains lead
to an enhanced association and a substantial increase of viscosity al-
ready for 4 mol% modication [63]. The extent of aggregate formation
of such hydrophobically modied chitosan increases with increasing
content of hydrophobic groups, their length and upon increasing the
ionic strength of the solution [60,64].
1.3. Similarities with cellulose
Polysaccharides play a fundamental role in nature. This class of poly-
mers is present in all living organisms, covering very different functions:
from structural elements, to energy storage up to moisturizers, to men-
tion some important functions. In this section we shortly compare some
peculiar aspects of chitin and chitosan with those of cellulose, as this
helps to highlight the distinctive properties of chitosan and to better
understand its behavior in mixtures with surfactants.
Cellulose, poly -(14)-D-glucose, is the main structural element in
plants. Similarly, chitin, -(14)-N-acetyl glucosamine is the main
structural element of the exoskeleton of arthropods. Both polymers
are highly insoluble in water and contain crystalline and amorphous
regions. The low solubility in water of cellulose can be rationalized
considering the interplay of hydrogen bonding, dispersion forces, and
hydrophobic interactions [65,66]. According to Lindman et al., the
amphiphilic character of cellulose, arising from the arrangement of the
OH groups, plays a predominant role with respect to physico-chemical
behavior of cellulose in aqueous environment [65]. The same concepts
can be applied also to chitin, having the same arrangement of polar
and non-polar, hydrogen bond donating and accepting moieties
(see Fig. 1).
To increase the water-solubility of chitin and cellulose, chemical
modications are required. Chitosan is the most common water-
soluble (in acidic conditions) chitin derivative, whose solubility can be
ascribed to translational entropy of its counterions. In contrast, a large
spectrum of water-soluble ionic and non-ionic cellulose derivatives is
available. Systematic studies on the solubility of cellulose derivatives
are missing. However, it can be stated that the presence of sidegroups
avoids an efcient packing of the polymer chains and therefore
increases the solubility of the derivate.
 L. Chiappisi, M. Gradzielski / Advances in Colloid and Interface Science xxx (2015) xxxxxx 5

2. Chitosansurfactant mixtures phospholipid mixtures will be discussed in detail. A list of interesting

Mixtures of chitosan and surfactants are highly interesting systems,
from a fundamental perspective and because they deserve particular at-
tention in the medical, food and detergency industry. The advantage of
such chitosan based systems is that chitosan possesses a high biocom-
patibility and by the admixture of suitable surfactants one may vary
the formulation properties or introduce desired functionality, like the
capacity to incorporate hydrophobic compounds (for instance for pur-
poses of drug delivery or to extract hydrophobic contaminants). Partic-
ularly interesting in that context are mixtures with oppositely charged
anionic surfactants since they yield strongly synergistic mixtures. A fur-
ther advantage of polycation/anionic surfactant mixtures, is that the lat-
ter are in general much less toxic than cationic surfactants. This is quite
an important point for any formulation from the elds of medical, bio-
logical, pharmaceutical, cosmetic, or agricultural applications.
Particular effort was put in studying mixtures of chitosan and sodi-
um dodecyl sulfate (SDS) [38,6770] with the latter being a well
known model anionic surfactant. Several studies also deal with chito-
san/fatty acids or ethoxylated fatty acids mixtures [7174]. In the fol-
lowing, we discuss the behavior of mixtures of chitosan with strong
anionic surfactants, i.e., surfactants whose ionic behavior is pH-
independent, weak anionic surfactants that show a pH-dependent be-
havior, non-ionic, and cationic surfactants. Afterwards, chitosan/
studies dealing with chitosan/surfactant mixtures is given in Table 1.
2.1. Chitosanstrong anionic surfactant
Chitosan strongly interacts with sulfated surfactants, forming water-
insoluble and structured complexes over a wide range of concentrations
and mixing ratios [67,69,76,101,102] (see Fig. 3). The interaction with so-
dium dodecyl sulfate was investigated in detail, as it represents a model
system for chitosan/anionic surfactants. Its binding is a cooperative pro-
cess, with the SatakeYang model (Eq. (1)) being a good approximation
of the adsorption process. Wei and Hudson systematically investigated
the effect of the degree of acetylation of chitosan (Mw = 190400 kDa,
DA = 0.080.24) on the interactions with SDS at pH = 4.2 [38]. From
the description of the binding isotherms with the SatakeYang model
(Eq. (1)) the authors concluded that an increase in DA decreases the
cooperativity of the binding process, as a consequence of the increased
spacing among the surfactant tails. The increase in DA does not affect
the non-cooperative binding constant, i.e., the vertical surfactant/
glucosammonium interaction. Furthermore, the authors found that an
increase in ionic strength decreases the binding constant K but not the
cooperativity of the process. This indicates the electrostatic nature of
the vertical interaction and the hydrophobic origin of the cooperativity.
The same results were conrmed by calorimetric and potentiometric

Table 1
Summary of relevant studies on chitosan/surfactant systems.

Molecular DA Surfactant Exp. techniques Topic Ref.

weight

Unkn. ca. 0.2 Sodium dodecyl sulfate ITC, SSE, Turbidity Effect of ionic strength and pH on the binding process [67]
Mw = 190400 0.080.24 Sodium dodecyl sulfate SSE Study of DA on binding isotherm [38]
kDa
Mw = 195 kDa 0.12 Sodium dodecyl sulfate Optical microscopy, SAXS Capsule formation and internal structure [75]
Mw = 120 kDa 0.15 Sodium lauryl ether sulfate Optical and electron Microcapsule formation and their Cu(II) uptake ability [76]
microscopy, UVVis
Unkn. 0.15 Sulfonated dyes UVVis Chitosandye interaction and effects on wool dyeing [77]
Mw = 296 kDa Unkn. 1-butyl-3-methylimidazolium Tensiometry, Study on the binding of [C4mim][C8OSO3] to chitosan [78]
octylsulfate conductimetry,
turbidimetry, DLS
Mw = 250 kDa ca. 0.2 Sodium taurocholate ITC Thermodynamics of binding [79]
Unkn. 0.25 Sodium taurodeoxycholate SAXS Structure formation at chitosansurfactant solution [80]
interfaces
Mw = 600 kDa Unkn. Sodium bis(2-ethylhexyl)sulfosuccinate Capsule formation Visual observation [81]
Mv = 0.61.1 MDa 0.00.2 Undecylenic acid UVvis, DLS, electron Behavior of chitosanundecylenic acid mixtures. [8284]
microscopy
Mw = 3.5270 kDa 0.160.22 Stearic acid Langmuir balance, AFM Chitosanstearic acid interactions at the airwater [71]
interphase.
Mw = 330 kDa 0.3 Unsaturated fatty acids Langmuir balance Chitosan interaction with different fatty acids at the [72]
airwater interphase.
Mw = 300 kDa 0.2 Ammonium phosphatidic fatty acids SEM, interfacial shear Formation of chitosan coated phosphatidic fatty acids [85]
rheology droplets and their decoration with polystyrene particles
Mw = 100 kDa 0.02 Linoleic and oleic acid DLS, uorescence, Characterization of chitosan fatty acids mixtures, their [86]
citotoxicity tests citotoxicity and their ability to solubilize a hydrophobic
model drug.
Mw = 100 kDa 0.15 Nonaoxyethylene oleylether DLS, SLS, SANS Strong pH-responsive and water soluble complexes [73,87]
carboxylate presented
Mw = 100 kDa 0.15 Oligooxyethylene alkyl ether SANS Structural characterization of bulk and solid complexes [74]
carboxylate
Mw = 400 Kda 0.14 Deoxycholic acid Release study Microparticle formation of drug and protein delivery [88,89]
Mw = 70 kDa Unkn. Octaethyleneglycol n-dodecyl ether Viscosimetry Time dependence of viscosity of chitosansurfactant [90]
mixtures
Mw = 70 kDa Unkn. Octaethyleneglycol n-dodecyl ether Viscosimetry Enhancement of dye adsorption on wool [91]
Mw = 160 kDa 0.12 octaethyleneglycol n-dodecyl ether Viscosimetry, DLS Relaxation of chitosanC12E8 mixtures [92]
Mw = 400 kDa 0.15 Sorbitan esters Microscopy, rheology [93,94]
Unkn. 0.075 Lauric arginate ethyl ester ITC & turbidity [95]
hydrochloride
Mw = 200 kDa 0.05 DOPC & DOPG Confocal microscopy & Interaction of chitosan with phospholipid vesicles, [96,97]
ITC & -potential & DLS thermodynamics and effect on bilayer bending.
31
Mw = 150 kDa 0.15 Phosphatidylcholine P NMR spectroscopy Effect of chitosan on headgroup mobility [98]
Mw ca. 150 kDa 0.15 DPPC Glucose quantication In vivo evaluation of chitosomes mucoadhesiveness and [99]
peptide release ability.
Mw = 370 kDa 0.15 Phosphatidylcholine Confocal microscopy Adsorption and release of chitosan-coated vesicles from [100]
electrodes

Please cite this article as: Chiappisi L, Gradzielski M, Co-assembly in chitosansurfactant mixtures: thermodynamics, structures, interfacial
properties and applications, Adv Colloid Interface Sci (2015), http://dx.doi.org/10.1016/j.cis.2015.03.003
6 L. Chiappisi, M. Gradzielski / Advances in Colloid and Interface Science xxx (2015) xxxxxx
Fig. 3. Phase boundaries found in chitosan/sulfated surfactant mixtures as a function of the
molar concentration of glucosamine units and surfactant. Dotted line represents equimo-
lar mixtures. Data points marked with and are for mixtures of chitosan (600 kDa, DA
not given) and sodium dodecyl sulfate in acetic acid at 1 and 2.5 wt.%, respectively, from
Ref. 81; Data points marked with are for mixtures of chitosan (120 kDa, DA = 0.15)
and sodium lauryl ether sulfate in 0.5 wt.% acetic acid, from Ref. 76.
titrations that yield the corresponding adsorption isotherms [67]. SDS
binds to chitosan (Mw not given, DA = 0.150.25) forming a stoichio-
metric insoluble complex and, despite the strength of the interactions
depends on the ionic strength, the amount of SDS in the complex does
not [67].
All these studies show that the hydrophobic horizontal interactions
among the surfactant alkyl chains are mainly responsible for the
cooperativity of the process and that strong electrostatic vertical inter-
actions are present between the glucosammonium units and the sulfated
and sulfonated headgroups. This picture is further conrmed by the bind-
ing process of a short-chain surfactant, 1-butyl-3-methylimidazolium
octylsulfate ([C4mim][C8OSO3]) to chitosan (Mw = 300 kDa, DA not
given), which shows a weaker cooperativity of the binding process, as ev-
idenced by only a small reduction in cmc upon complexation [78].
The low solubility of chitosan/sulfated surfactant complexes limits
the use of these mixtures. However, they can be exploited for the prep-
aration of microcapsules [75,76,102]. When chitosan is dropwise added
to the surfactant solution, or viceversa, a capsule of the size of the drop-
let is formed by local ionic cross-linking of the polymer chains by the
surfactant micelles. Small-angle X-ray scattering (SAXS) experiments
have revealed a higher degree of ordering within the capsule wall, aris-
ing from a dense packing of surfactant micelles [75,102]. The size of the
capsules is given by the preparation method: smaller droplets will pro-
duce smaller capsules and basically the size of the added droplets is
retained. Accordingly, authors reported the formation of m sized drop-
lets by emulsication of the chitosan solution in decane before admixing
[102]. Even smaller capsules (radius of 200250 nm) were obtained by
spraying a surfactant solution under high pressure (up to 5 MPa) into a
chitosan solution [76]. The initial increase in wall thickness of the drop-
lets follows a t0.5 power law [102], i. e., is diffusion controlled. An ap-
parent diffusion coefcient D = 1013 1012m2s1 (corresponding
to a hydrodynamic radius of 0.252.5 m) for chitosan can be estimated
p
from the relation t 2Dt [102]. The capsules were shown to be sta-
ble over long periods of time [76] and they can be used for a controlled
release of enzymes [102], for the separation of metal ions [76] or organic
pollutants [103].
The complexation of chitosan (Mw = 300 kDa, DA = 0.2) with
phosphatidic fatty acids can be exploited for the formation of oil-in-
water and water-in-oil capsules [85]. Monodisperse capsules (diameter
Please cite this article as: Chiappisi L, Gradzielski M, Co-assembly in chitosansurfactant mixtures: thermodynamics, structures, interfacial
properties and applications, Adv Colloid Interface Sci (2015), http://dx.doi.org/10.1016/j.cis.2015.03.003
of 260 m) can be prepared using microuidic devices. Differently,
batch production consisting in mixing the aqueous chitosan and the
oily surfactant solutions under gentle stirring leads to the formation of
polydisperse capsules with sizes of typically 30800 m. Also in this
case, the capsule wall formation is a diffusion limited process, as
found in chitosanSDS mixtures. In both cases, the same elastic modulus
of the chitosan/surfactant membrane of ca. 104105 Pa is found
[85,102].
Microcapsules can be formed also in chitosan/sodium bis(2-
ethylhexyl) sulfosuccinate (AOT) mixtures [81,104]. Shape and size of
the microparticles can be controlled by varying the mixing proce-
dure [104]. A comparison of chitosan (Mw = 600 KDa, DA not
given) AOT capsules with chitosan SDS capsules reveals that the
AOT capsules are formed in a narrower composition range. This is ex-
plained by the retention of the bilayer structure of the AOT aggregates
also in the complex, which is more difcult to cross-link compared to
the small globular micelles formed by SDS [81].
Similar complexes can also be formed with chitosan (Mw not given,
DA = 0.15)sulfated surfactant-like dyes [77]. These complexes are sol-
uble in chitosan excess but a stoichiometric precipitate is formed in the
dye-excess region of the phase diagram. The formation of stoichiometric
complexes can be exploited for an enhanced adsorption of anionic dyes
on wool [77]. Moreover, chitosansulfated surfactant complexes have
been employed for the preparation of membranes for pervaporation
separation of methanol [105,106]. In general, such chitosan complexes
possess a promising potential for binding and retaining anionic organic
compounds with the aim of subsequent controlled delivery or for pur-
poses of decontamination.
2.2. Chitosanweak anionic surfactant
2.2.1. Chitosanfatty acid mixtures
The study of chitosanfatty acid mixtures was motivated by the use
of chitosan as a dietary supplement for weight reduction purposes
[107109]. This initiated several in vitro and in vivo studies. However,
contradicting results are found in literature and a signicant effect of
chitosan in body weight reduction in human beings has not been veri-
ed [107,108,110]. However, the interaction of fatty acids and chitosan
is also relevant in other elds, e.g., medicine [86], food packaging
[111113] and preservation [114116] as two fully biocompatible
components are combined. This then allows the formulation of variable
systems for a multitude of applications in the elds of life science,
pharmacy, nutrition etc.
Chitosanfatty acids mixtures are highly complex systems, as the
degree of ionization of both components is pH dependent. Three main
regions can be identied:
i) at low-pH, chitosan is charged and soluble in aqueous solution
and the fatty acids are in their neutral form, being mostly insolu-
ble in water;
ii) at intermediate pH both components are at least partially
charged and soluble in water;
iii) at high pH, chitosan is uncharged and unsoluble whereas the
ionic form of the fatty acids prevails. These different cases have
to be considered, for instance, when the fat-binding activity of
chitosan is examined, where the mixtures go from pH 2 of the
stomach to pH 78 in the intestine. In general, pH can be expect-
ed to be a powerful control parameter with respect to the struc-
tures formed.
Even more complexity arises from the interplay of different forces
acting in the co-assembly of chitosan and fatty acids. In addition to elec-
trostatics, also hydrogen bonds and hydrophobic interactions were
shown to strongly affect the behavior of fatty acids lms at the air
water interface [72]. These results are discussed in detail in Section 4
of this review.
 L. Chiappisi, M. Gradzielski / Advances in Colloid and Interface Science xxx (2015) xxxxxx
A major parameter in chitosanfatty acids mixtures is the length of
the acid alkyl chain, as it determines the solubility of the complex salt.
For instance, soluble salts are formed in mixtures of chitosan with
short chain carboxylic acids, i.e., formic, acetic, butyric and valeric
[117]. Interestingly, the maximum amount of short chain carboxylic
acids (n(C 5)) bound to chitosan (Mw = 200 kDa, DA = 0.2) de-
creases with increasing chain length [118], indicating the predominant-
ly electrostatic origin of the interaction. Moreover, investigation of the
speciation in chitosan (Mw = 310 kDa; DA not given) mono-, di-,
tri-, and tetra-carboxylic acids showed that the binding constant in-
creases with increasing number of carboxylic groups [119].
Differently, dispersion and hydrophobic interactions are mainly
driving the formation of chitosan-stabilized emulsions in mixtures
with long-chain fatty acids (C16, C18:0, C18:1, C18:2) [86,120,121], At low
pH, the binding of chitosan with fatty acids is driven by hydrophobic in-
teractions, the non-ionic form of the acid being predominant [71,72].
Accordingly, the amount of oil which can be bound by chitosan in-
creases with increasing degree of acetlyation, i.e., with increasing hy-
drophobicity of the polymer [121]. However, the pH seems to have a
remarkably low effect on chitosanoleic acid mixtures (except for
pH N 7, where the solubility of chitosan is drastically reduced) [86].
Chitosan-stabilized emulsions have a high solubilization capacity with
respect to hydrophobic molecules, e.g., the solubility of clarithromycin
is increased by a factor of 20 by chitosanoleic acid complexes [86].
An intermediate case, in terms of alkyl chain length, is given by chi-
tosan (Mw = 0.61.1 MDa, DA = 0.00.2)sodium 10-undecenoate
mixtures [8284]. 10-undecenoate forms micellar aggregates [122],
and, depending on the chitosanfatty acid mixing ratio, different aggre-
gation types have been identied. At low chitosan content large ocs are
formed which can be resolubilized into 200500 nm large colloidally
stable complexes if the chitosan content is increased [83]. The
redissolution concentration depends on the concentration of glucos-
amine only, and being therefore only indirectly inuenced by the DA
of chitosan [82].
Summarizing, the behavior of chitosanalkyl carboxylic acid mix-
tures strongly depends on both pH and hydrophobicity of the fatty
acid. It is generally true that chitosan acts as a supramolecular glue,
providing an extended network for the assembly of the surfactant ag-
gregates. In detail, no supramolecular ordering is observed when chito-
san is mixed with short-chain carboxylic acids (n(C) 5), as the needed
hydrophobic cooperative interactions among the aliphatic chains is
missing. Differently, in the case of long-chain fatty acids (n(C) 16),
which form self-emulsied droplets also in their unprotonated form,
stable -meter sized emulsions are formed. Well-dened supramolecu-
lar aggregates are formed when chitosan is mixed with intermediate-
chain fatty acids, which form nanometer sized micelles in acidic medi-
um. A corresponding structural phase diagram is given in Fig. 4. In
Fig. 4. Schematic phase behavior and structures of chitosancarboxylic acid mixtures,
depending on the solution pH and hydrophobicity of the organic acid.
Please cite this article as: Chiappisi L, Gradzielski M, Co-assembly in chitosansurfactant mixtures: thermodynamics, structures, interfacial
properties and applications, Adv Colloid Interface Sci (2015), http://dx.doi.org/10.1016/j.cis.2015.03.003
7
general, these mixtures are poorly soluble and complex, stable aggre-
gates are formed in a narrow pH and alkyl chain length range.
2.2.2. Chitosanalkyl oligooxyethylene carboxylic acids
Alkyl oligooxyethylene carboxylates show the same pH dependent
behavior as normal alkyl carboxylates but possess an increased solubil-
ity to the presence of the hydrophilic oligooxyethylene group. Corre-
spondingly, mixtures of chitosan (Mw = 100 kDa, DA = 0.15) and
alkyl oligooxyethylene carboxylic acids have recently been shown to
form soluble, versatile and strongly pH-responsive complexes [73,74,
87,123] with much less precipitation tendency then their normal alkyl
carboxylic acid counterparts. Alkyl oligooxyethylene carboxylic acids
are by themselves highly interesting surfactants: depending on pH,
they present typical properties of ionic and non-ionic surfactants
[124126]. Moreover, the structures formed in aqueous solutions do
not depend on pH and temperature only, but also on the chemical archi-
tecture of the surfactant, i.e., the relative length of the hydrophobic and
hydrophilic part of the molecule [127].
In Fig. 5 the structures observed in mixtures of chitosan (Mw =
100 kDa, DA = 0.15) and oleyl nonaoxyethylene carboxylic acid
(C18:1E9Ac) are shown as a function of pH, where here mostly the degree
of ionization of the surfactant is affected, and mixing ratio Z, dened as
the ratio of surfactant molecules and GlcN units. Depending on Z and on
the degree of ionization of the micelle, different structures are found, as
a result of two main forces acting in the system: (i) the binding energy
of the surfactant micelles to the chitosan network, (ii) the bending of
the semi-rigid polymer chains. At low-pH and low surfactant content,
the micelles simply decorate the chitosan network. At intermediate
pH and Z, within the complex domains of linearly ordered micelles are
found. Their SANS scattering pattern can be described using a model
of N aligned micelles in a homogeneous cylinder [128], where the driv-
ing force for the formation of rodlike aggregates is the intrinsic stiffness
of the polymer. Usually, two to ve micelles per cylinder are found in
these mixed assemblies [73,74]. Similar structures have also been
found in mixtures of chitosan (Mw = 300 kDa; DA = 0.13) with silica
nanoparticles of 10 nm radius [129,130]. At high pH and surfactant con-
centration, these domains collapse into a core-corona superstructure,
with a core formed by ca. 104105 densely packed micelles surrounded
by a stabilizing chitosan corona. The formation of such core-corona
suprastructures can be ascribed to the length and stiffness of the
Fig. 5. Structural phase diagram obtained for chitosanoleyl nona ethoxy carboxylic acid,
at different pH and mixing ratio Z and constant chitosan concentration of 0.3 wt.%.
Adapted with permission from Ref. 73 Copyright 2014, American Chemical Society.
8 L. Chiappisi, M. Gradzielski / Advances in Colloid and Interface Science xxx (2015) xxxxxx
chitosan chains [73]. Accordingly, such suprastructures are found in
other long chain polysaccharide/surfactant complexes [131133]. In a
similar fashion, microphase separation in double hydrophilic block-
copolymer/surfactant mixtures leads to comparable coassembled
structures [134136].
The high pH-responsiveness of chitosan/C18:1E9Ac mixtures can be
elegantly exploited for the selective and controlled release of drug mol-
ecules or removal of pollutants [87] and thereby constitutes an interest-
ing approach to constructing biocompatible delivery systems.
The same structural progression is found in mixtures with other
alkyl oligoethylenoxide carboxylic acids (C8E5Ac and C12E10Ac) with
the tendency to form globular micelles [74]. In contrast, when chitosan
(Mw = 100 kDa, DA = 0.15) is mixed with an alkyl oligoethoxy carbox-
ylic acid (C12E4.5Ac) forming bilayered vesicles [127], self-assembly into
well ordered multilayered vesicles is observed [74]. This shows that the
structural integrity of the surfactant aggregate is retained and that the
admixture of chitosan only directs the supramolecular assembly; in
this case the formatiation of multilamellar vesicles. A high control over
the number of lamellae forming the vesicle wall and, consequently,
the vesicle wall thickness, allows for the formulation of delivery systems
with programmable release times.
Summarizing, the supramolecular structures formed in mixtures of
alkyl oligoethylenoxide acids and chitosan depend on mixing ratio, pH
and on the packing parameter, that controls the surfactant aggregate
shape. Moreover, they show a rather high solubility when compared
to analogue alkyl sulfates or carboxylic acids. Interestingly one nds
that the local organization of the surfactant is largely given by its natural
tendency for self-assembly (packing parameter) and the type of
aggregate formed in the pure surfactant solution (spherical micelle, ves-
icle, etc.) is retained within the more complex structure of the
supraaggregate.
2.3. Chitosanbile acid
A further aspect which makes chitosan particularly relevant as a di-
etary supplement is its ability to bind bile salts, and in consequence its
effect on the reduction of cholesterol blood levels. With this purpose,
chitosanbile salts mixtures have intensively been studied, both
in vitro [137,138] and in vivo [109,139].
From a physico-chemical perspective it is useful to discuss the inter-
actions of chitosan with carboxylic bile acids and sulfated bile acids,
i.e., taurocholic acid and its derivatives.
Sodium taurocholate and chitosan (Mw = 250 kDa, DA ca. 0.2 &
Mw = 150 kDa, DA = 0.13) were shown to form near-stoichiometric
insoluble complexes [79,138]. Isothermal titration experiments re-
vealed that the interactions are driven by both electrostatic interactions
among the sulfated headgroup and the charged ammonium ion and by
hydrophobic interactions between the apolar steroidal backbones [79].
The complexes formed are capable of adsorbing large quantities of
hydrophobic lipids, i.e., 22 g of olive oil or butter per gram of freeze-
dried complex [138]. However, the adsorption is unselective with
respect to the different components of the olive or butter oil. Tangso
et al. investigated in detail the structures formed at chitosansodium
taurodeoxycholate solution interface, showing the presence of hexago-
nal and lamellar phases, depending on the distance from the interface
[80]. The complexes were also shown to be able to release a model
drug upon increase of temperature and salt concentration.
Moreover, drug and protein delivery system were prepared based on
chitosan (Mw = 400 kDa, DA = 0.14)deoxycholic acid microparticles
(size of 1080 m) with the aim of using this microencapsulation
method for mucosal delivery [88,89].
2.4. Chitosannonionic surfactant
The interaction of chitosan with non-ionic surfactants is generally
weak although present [9092]. Accordingly no precipitate formation
Please cite this article as: Chiappisi L, Gradzielski M, Co-assembly in chitosansurfactant mixtures: thermodynamics, structures, interfacial
properties and applications, Adv Colloid Interface Sci (2015), http://dx.doi.org/10.1016/j.cis.2015.03.003
is expected provided that the pH remains low enough to guarantee sol-
ubility of chitosan. Despite chitosan (Mw = 70 kDa, DA not given) and
the non-ionic surfactant octaethyleneoxide n-dodecyl ether (C12E8) do
not self-assemble into large supramolecular aggregates, their interac-
tion has a strong effect on the viscosity time-dependence [90], with a
systematic viscosity drop over time. The authors explained this effect,
observed only at concentrations above the cmc of the surfactant
(which is not affected by the presence of the polymer), with a change
in polymer conformation in the presence of surfactant micelles [90,91].
Mixtures of chitosan and non-ionic sorbitan esters were investigat-
ed, due to their potential in food industry and cosmetics as emulsion
stabilizers [93,94]. In particular, mixtures of chitosan (Mw = 400 kDa,
DA = 0.15) and sorbitan monooleate, sorbitan monolaurate, and
sorbitan trioleate were investigated. In all cases m sized emulsions
are formed with the size of the droplets increasing with increasing hy-
drophobicity of the surfactant. Confocal microscopy evidenced the for-
mation of a coreshell structure, with a chitosan-rich shell and a
chitosan-poor core. This nding further evidences the amphiphilic char-
acter of chitosan and its tendency to interact with the interface of vari-
ous colloids, being them small micelles, large vesicles or emulsion
droplots [87,93,140].
Similarly, also chitosan (low molecular weight, DA not given.)
polyoxyethylene (20) sorbitan monoleate mixtures were shown to af-
fect the colloidal stability of slightly acidic (pH 6) tuna oil emulsions
[141]. In particular, the addition of chitosan causes a charge inversion
of the emulsied droplets. Accordingly, a stability gap is observed at in-
termediate chitosan concentrations. However, the size of the single
emulsion droplets is not affected by the presence of chitosan. Further-
more, given the low interaction of non-ionic surfactants and chitosan,
monoalkylated sorbitan polyoxyethylene esters are used as additives
allowing an efcient spreading of chitosan solutions [142146], which
generally show a high surface tension. This allows for the preparation
of effective coatings for, e.g., fruits or vegetables increasing their shelf
life.
2.5. Chitosancationic surfactant
Due to electrostatic repulsions, there is no evidence for signicant
complex formation between chitosan and cationic surfactants. For in-
stance, the addition of chitosan to a cetyl trimethyl ammonium bromide
(CTAB) solution did not affect its solubilization power [147]. Moreover,
repulsive interactions between chitosan (Mw not given, DA b 0.15) and
the cationic lauric arginate ethyl ester hydrochloride lead to a decrease
in cmc of the surfactant, despite no supramolecular aggregates are
formed [95]. The decrease in cmc was explained by excluded volume ef-
fect, arising from the electrostatic repulsion between chitosan and
surfactant.
W/O emulsions of chitosan (Mw = 230 kDa, DA = 0.02) cetyl
trimethylammonium bromide (CTAB) cyclohexane showed marked
shear-thinning properties, as a results of breaking the chitosan bridges
between the aqueous droplets [148]. As in general no stronger synergis-
tic interactions between cationic surfactant and chitosan are expected
such systems have also been little investigated so far.
3. Chitosan-coated liposomes
Chitosan-coated liposomes, often referred to as chitosomes, are
promising drug, gene or peptide delivery vectors [140,149151], as
they are fully biocompatible. With respect to conventional liposomes,
chitosomes show an increased stability upon pH, temperature or salt
stresses [152158] and possess higher mucoadhesive properties [99,
140]. Accordingly, a number of articles describe the potential of
chitosan-coated vesicles for drug delivery purposes [159162]. In addi-
tion to the abovementioned properties, chitosan-coated vesicles can be
selectively adsorbed on and released from electrodes, depending on the
applied potential [100].
 L. Chiappisi, M. Gradzielski / Advances in Colloid and Interface Science xxx (2015) xxxxxx 9

3.1. Binding process
Chitosan was shown to adsorb with a at conformation on various
phospholipid vesicles [9698,153,155,156,163165], presumably
aided by its rather pronounced stiffness. This process was shown to be
independent from the molecular weight of chitosan [155] and the ad-
sorption takes places on negative, neutral as well as positive vesicles
[140,164]. The adsorption of chitosan on negatively charged vesicles
causes a charge inversion of its -potential, reaching a maximum of ca.
+4060 mV [153155,163,166,167]. Despite phase separation usually
occurs near charge neutrality [154,164], the decorated vesicles usually
show an increased kinetic stability with respect to uncoated vesicles
[154]. A summary of these results is given in Fig. 6.
Mertins and Dimova reported an isothermal titration calorimetric
study on chitosan (Mw = 200 kDa, DA = 0.05) binding to 1,2-
dioleoyl-sn-glycero-3-phosphocholine (DOPC)/1,2-dioleoyl-sn-glycero-
3-phosphate (DOPG) vesicles in which the net negative charge of the
vesicles was systematically varied (27 mV b -potential b 80 mV)
[163]. Regardless of the charge of the vesicles the binding is an exother-
mic process and little affected by the vesicle composition. Interestingly,
the process is less favored, i.e., shows an increasing free binding energy
with increasing charge of the vesicle. Accordingly, also the entropic
gain is reduced with increasing DOPG content (see Fig. 7). These obser-
vations can be explained with an unfavorable packing arising from the
relatively large chitosan unit as compared to the headgroup spacing be-
tween the charged DOPG molecules. The increasing -potential corre-
sponds to a decreasing spacing between the phospholipid charges,
which makes it more difcult to accomodate the chitosan charges. The
authors investigated also the effect of the charge density of chitosan
(Mw = 200 kDa, DA = 0.05) on the thermodynamics of binding to
DOPC/DOPG vesicles [97]. In this work, the binding enthalpy becomes
more exothermic with increasing pH, i.e., with decreasing charge density
on the polymer. The increasing binding enthalpy can be explained by the
decreasing solubility of chitosan in water with increasing pH, therefore
increasing the relative stability of chitosan on the liposome surface and
enhancing the hydrophobic interaction with the surfactant.

Fig. 6. a) -potential (squares) and particle diameter (triangles) as a function of the chitosan/accessible DOPC ratio. Open and lled symbols refer to experiments carried out at pH = 3.5
and 6.0, respectively. b) Schematic representation of aggregation/stabilization process observed at pH 6.0. In c) the corresponding microscopy images are shown.
Reproduced from Ref. 164 with permission of The Royal Society of Chemistry.

Please cite this article as: Chiappisi L, Gradzielski M, Co-assembly in chitosansurfactant mixtures: thermodynamics, structures, interfacial
properties and applications, Adv Colloid Interface Sci (2015), http://dx.doi.org/10.1016/j.cis.2015.03.003
10 L. Chiappisi, M. Gradzielski / Advances in Colloid and Interface Science xxx (2015) xxxxxx
Fig. 7. Gibbs free binding energy and binding entropy of chitosan on DOPG/DOPC vesicles
as a function of DOPG content. Straight lines are best t to the experimental data and are
only a guide for the eyes.
Data are taken from Ref. 163.
3.2. Structural aspects
For an efcient formulation of chitosan/phospholipid mixtures an
understanding of the morphological modication upon complexation
is needed. For unilamellar vesicles, usually a simple decoration of lipo-
some is observed [96] but eventually chitosan (Mw = 200 kDa, DA =
0.05) acts as a glue with the consequent formation of aggregates of
unilamellar vesicles [97]. In some cases, the chitosan-induced formation
of a small fraction of multilamellar vesicles with bilayer multiplicity ~3
has been reported [168,169]. Differently, a large fraction of multi-
lamellar vesicles with bilayer multiplicity N N 7 is found in mixtures of
chitosan (Mv = 100 kDa, DA = 0.15) and dodecyl oligoethyleneoxide
carboxylate [74]. Bilayered vesicles with a larger spacing between the
lamellae were also found in a mixture of hydrophobically modied chi-
tosan and cetyl trimethylammonium tosylate/sodium dodecyl benzene
sulfonate vesicles [170]. The process of formation of multiwalled vesi-
cles is depicted in Fig. 8.
Chitosan (Mw = 11300 kDa, DA = 0.010.56) can also interact
with multilamellar vesicles, being incorporated between the lamellae
[158]. SAXS experiments have revealed that the interplanar spacing
increases with increasing degree of acetylation of chitosan, irrespective
of its Mw [158]. The addition of chitosan (Mw = 160 kDa, DA = 0.17) to
phosphatidylcholine multilammelar vesicles increased the thermal
stability of the lamellar phase [152].
The addition of chitosan (Mw = 1.85 MDa, DA = 0.08) to a concen-
trated lecithin solution (25 wt.%) promotes the transition from planar
lamellar to closed vesicular systems upon shearing [171].
Fig. 8. Schematic representation of bilayer vesicle formation in chitosan/phospholipid mixtures prepared in the phospholipid excess regime. Sketch is not to scale.
Please cite this article as: Chiappisi L, Gradzielski M, Co-assembly in chitosansurfactant mixtures: thermodynamics, structures, interfacial
properties and applications, Adv Colloid Interface Sci (2015), http://dx.doi.org/10.1016/j.cis.2015.03.003
3.3. Membrane properties
Chitosan was shown to strongly affect liposomal membranes. Upon
complexation, the membrane becomes stiffer [96,149,152,172175],
the mobility of the single components is reduced [98], the melting en-
thalpy decreases [176,177], and a chain expansion in the monolayer ar
the airwater interface is observed [172,178,179]. All these parameters
have to be considered when using chitosan-coated vesicles for drug de-
livery purposes. In detail, different authors have shown that the mem-
brane stiffness increases upon adsorption of chitosan [96,149,152,
172175]. Chitosan (Mw = 200 kDa, DA = 0.05) was shown to increase
threefold the bending modulus 0 of DOPC vesicles by its attachment to
the membrane [96]. Similar values are found also in chitosan/alkyl eth-
ylene oxide carboxylic acid mixtures previously described [74]. Of
course, this stiffening effect is observed only above the melting temper-
ature of the bilayer [173], as otherwise the rigidity is determined by the
membrane in its L state. Moreover, the presence of chitosan (Mw =
150 kDa, DA = 0.15) reduces the motional freedom of the phosphate
group of phosphatidylcholine liposomes, as shown by 31P-NMR spec-
troscopy [98].
The interaction of chitosan (Mw 110 and 210 kDa, DA ca. 0.13)
strongly reduces the melting enthalpy of DPPC membranes, despite
having little effect on the melting temperature [176,177]. Differently,
Mertins et al. reported that the addition of chitosan (Mw = 160 kDa,
DA = 0.17) shifted the phase transition temperature of phosphatidyl-
choline from 57 C to 64 C [152].
4. Co-assembly at interfaces
In the previous sections, we have described the behavior of chitosan
at surfactant interfaces, i.e., phospholipid vesicles or fatty acid emul-
sions. A high afnity towards surfaces with low curvature could be evi-
denced, arising from the rather small conformational entropic loss
observed upon adsorption of this rather stiff polymer. However, the be-
havior of chitosansurfactant mixtures at liquidliquid, liquidsoluid or
liquidvapor interfaces represents an interesting topic as well, especial-
ly for the agricultural and food industries [180,181]. For the behavior at
the interfaces of hydrophobically modied chitosan we address the
reader to some recent reviews [182184].
4.1. Co-assembly at the vaporliquid interface
The behavior of chitosanstrong anionic surfactant mixtures was in-
vestigated at the airwater interface [184186], with focus on the inter-
facial properties, e.g., surface tension or viscoelasticity of the adsorbed
layers. Chitosan itself shows no airwater surface activity, however, its
addition to SDS solutions causes a remarkable decrease in surface ten-
sion below the cmc (see also Fig. 2, middle), as hydrophobic, surface ac-
tive complexes are formed, which explains this pronounced synergistic
behavior [185187]. However, at high surfactant concentration, the
 L. Chiappisi, M. Gradzielski / Advances in Colloid and Interface Science xxx (2015) xxxxxx 11

surface tension is higher in the presence of chitosan, indicating an unfa-
vorable packing with respect to the pure surfactant solution [185,187].
The same effects are found also for other strong anionic surfactant mix-
tures [184,188]. The reduction of surface tension is even stronger, when
hydrophobically modied chitosan is used, which can be explained by a
higher afnity of the hydrophobically modied chitosan to the air
water interface [68]. From a thermodynamic perspective, the surface
tension is an index of the chemical potential of the adsorbed surfactant
molecules. The increase of surface tension at higher surfactant concen-
tration upon addition of polyelectrolyte can then be simply explained
by a reduction of the chemical potential of the surfactant as a direct con-
sequence of the adsorption process, i.e., the concentration of the free
surfactant is reduced. Moreover, in a more extended view, surfactant
molecules adsorbed at the interface are in dynamic equilibrium with
the free molecules in solution, with those incorporated into the supra-
molecular complex and with eventually free micelles present in solu-
tion. See schematic representation in Fig. 9. Of course, the same
applies also to the polyelectrolyte chains, with the chemical potential
of free chitosan, chitosan chains involved in the complex and adsorbed
at the interface having the same chemical potential.
In addition to the surface tension reduction, an increase in the elastic
modulus of the surface lm is observed [184]. It has to be remarked, that
to reach the equilibrium at the interface very long times are required,
given the high molecular weight of the polymer and the corresponding-
ly low molecular concentration of the complexes.
The interaction of chitosan with lipids at the airwater interface was
thoroughly investigated by means of the LangmuirBlodgett technique
[72,71,172,178,179,189192,192,193]. Wydro et al. showed that chito-
san (Mw = 330 kDa; DA = 0.3) affects the packing of stearic, oleic,
linoleic and -linoleic acid monolayers at the air water interphase
[72]. This series of acids allowed the systematic investigation on the
interaction of chitosan with lipid lms of decreasing compactness. The
addition of chitosan to the subphase (pH = 4.0) reduces the maximal
compression modulus of the unsaturated stearic acids while slightly
increasing that of its saturated analogues. Moreover, the presence of
chitosan increases the limiting molecular areas of the fatty acids, the
effect being more pronounced the more unsaturated the surfactant
which should simply reduce the area requirements. These ndings can-
not be explained solely with electrostatic interactions, and an insertion
of chitosan within the hydrophobic aliphatic tails has been inferred. It
has to be pointed out that the chitosan used in this study had a relatively
high DA (DA = 0.3), therefore having a rather pronounced hydrophobic
character. Differently, the effect of the molecular weight seems to be of
minor importance, as similar results are found in chitosanstearic acid
mixtures with chitosans of DA of ~ 0.17 and Mw = 100 and 270 kDa
[71].
Similar results are found for chitosan interacting with DPPG mono-
layers at the airwater interface [189,190,193]. Chitosan (Mw =
1.2 MDa; DA = 0.17) does not interact with the monolayer only super-
cially via electrostatic interactions, but inserts also into the lm [193].
This is further conrmed by its effect on the zwitterionic DPPC and non-
ionic cholesterol monolayers, which are also affected by chitosan
(Mw = 1.2 MDa; DA = 0.17), though to a smaller extent than the
anionic DPPG or distearoylphosphatidylglycerol (DSPG) monolayers
[189,190,192].
4.2. Co-assembly at the liquidliquid interface
Co-assembly of chitosan and surfactants at the liquidliquid inter-
face is particularly relevant for emulsion stabilization, where the inter-
face between two immiscible liquids, mostly oil and water, has to be
stabilized and made impermeable [188,192,194200].
Two main mechanisms are responsible for emulsion destabilization,
Ostwald ripening and coalescence. For instance, SDS-stabilized tetra-
decane emulsions were shown to grow via an Ostwald ripening mech-
anism [195]. The addition of chitosan (Mw = 190310 kDa; DA =
0.150.25) strongly reduces their growth, as an impermeable SDSchi-
tosan lm is formed at the oilwater interface [194]. Furthermore, elec-
trostatic repulsion and higher elasticity of the emulsion membrane
increase the stability towards coalescence [199]. The two modes of ac-
tion are schematically represented in Fig. 10. However, the addition of
high molecular weight chitosan can destabilize the system by bringing
the single emulsion droplets or by depletion forces [196,194]. In sum-
mary, the addition of chitosan to surfactant-stabilized emulsion drop-
lets can either enhance or reduce their stability, depending on the
polymer molecular weight and the total concentration of the system.
The permeability of the chitosan-surfactant lm at the emulsion
droplet interface is an important parameter when it comes to stabilize
the emulsied oil towards, e.g., oxidation processes. Literature results
are however contradicting with this regard and a unique pattern could
not be identied. Tikekar et al. could not detect an effective reduction
of the diffusion of oxygen through the SDSchitosan (low Mw; DA =

Fig. 9. Schematic representation of the different equilibria involving the surfactant molecules taking place in a polymersurfactant solution: a) free surfactant molecule in solutionsur-
factant adsorbed at the airwater interface; b) free surfactant molecule in solutionsurfactant in free micelle; c) free surfactant molecule in solutionsurfactant in the polymer complex;
d) surfactant in free micellesurfactant in the polymer complex; e) surfactant in free micellesurfactant adsorbed at the airwater interface; f) surfactant in the polymer complex
surfactant adsorbed at the airwater interface.

Please cite this article as: Chiappisi L, Gradzielski M, Co-assembly in chitosansurfactant mixtures: thermodynamics, structures, interfacial
properties and applications, Adv Colloid Interface Sci (2015), http://dx.doi.org/10.1016/j.cis.2015.03.003
12 L. Chiappisi, M. Gradzielski / Advances in Colloid and Interface Science xxx (2015) xxxxxx
Fig. 10. Schematic representation of the two modes of action of chitosan towards the sta-
bilization of emulsions. See text for further details.
0.2) at the canola oilwater interface [200]. Moreover, this membrane
effectively reduces the oxidation rate of limonene and citral [196].
4.3. Co-assembly at the solidliquid interface
The co-assembly of chitosan (Mw = 150 kDa; DA = 0.16) and SDS
was investigated also at solidliquid interfaces, like mica [201] or silica
[187]. The authors showed that pure chitosan adsorbs on both surfaces.
At pH 4.0 the amount is however much larger on the more densely
charged mica surface than on the silica one. At low SDS concentration,
the surfactant is incorporated into the chitosan layer, inducing a signif-
icant collapse of it. However, at higher surfactant concentrations the
redissolution of the chitosan layer is observed, given that the complexes
in the bulk phase are more stable than at the solidliquid interface
[187]. The decreased stability of the complexes at the interface can be
explained when the negatively charged silica is regarded as a competi-
tor of the surfactant molecules [187].
5. Applications
As mentioned throughout the manuscript chitosan possesses several
advantages, e.g., biodegradability, anti-inammatory, high muco-
adhesiveness, etc., which makes it attractive in a number of elds and
therefore it has been the object of several review articles [202208].
The range of uses can be further widened when chemically modied
chitosan derivatives are employed [209213], mainly as biomaterials
in the medical eld. In this section, we focus on particular applications
arising from a synergistic use of chitosan and surfactants. Different ap-
plications are summarized in Table 2.
As discussed thoroughly in the text, anionic surfactants strongly
bind to chitosan. In a rst instance this causes a rather limited solubility
of the mixtures which can be exploited for the preparation of capsules
[75,76,80,81,102,104,214216]. These capsules were shown to be able
to efciently adsorb metal ions such as Cu(II) [76] as well as organic
dyes [215,216] but they can also be employed as drug carrier systems
[80,214]. For instance, chitosanSDS complexes were shown to ef-
ciently protect insulin in the gastric tract from digestive enzymes
[214]. However, further work is necessary to improve the successive
availability of insulin.
A further use of anionic surfactantschitosan mixtures consists in
their application as emulsion stabilizers [194197]. Their combination
provides not only an electrostatic stabilization to the emulsied drop-
lets, but increases also the long-term chemical stability of, e.g., natural
avors towards oxidative processes [196]. This nding can be explained
by the low permeability of oxygen through the chitosanSDS layer at
the emulsionwater interface [200]. The stability of chitosanSDS emul-
sion droplets towards environmental stresses (temperature, pH or salt)
can be largely enhanced when the particles are covered with an addi-
tional layer of negatively charged biopolymers, such as pectin [198,199].
The strong interactions of chitosan with sulfated dyes, which chem-
ically resemble common sulfated surfactants, can be employed for an
improved adsorption of coloring dyes on textiles [77]. More relevantly,
Please cite this article as: Chiappisi L, Gradzielski M, Co-assembly in chitosansurfactant mixtures: thermodynamics, structures, interfacial
properties and applications, Adv Colloid Interface Sci (2015), http://dx.doi.org/10.1016/j.cis.2015.03.003
Table 2
Summary of actual and possible applications of chitosan/surfactant mixtures.
Surfactant Application Ref.
Sulfonated dyes Textile dyeing systems [77]
Sulfonated dyes Wastewater treatment [220228]
Sodium Responsive release system [80]
taurodeoxycholate
Sodium dodecyl Emulsion stabilizer [188,192,194200]
sulfate
Sulfated surfactants Microcapsules for pollutant recovery [76,215,216]
Anionic surfactants Methanol selective pervaporation [105,106]
membranes
Fatty acids Food packaging [111,113,229,230]
Phospholipids Drug delivery [162,232235]
Non-ionic surfactants Spreading agent in food industry [142146]
chitosan represents one of the most important low-cost adsorbents for
the decolorization of wastewater [217219]. Accordingly, a large num-
ber of examples of chitosan used for the removal of anionic dyes from
wastewater can be found in literature [220228].
Also in mixtures with fatty acids with longer chain length insoluble
complexes are formed, which can be exploited for the formulation of
lms [111,113,115,229,230], In particular, chitosanfatty acids lms
play a relevant role in food packaging [111,113,229,230], as the antimi-
crobial properties of chitosan are combined with the low permeability
arising from the fatty acids [231].
In Section 3 the behavior of chitosan-coated liposomes is presented.
These systems result particularly interesting in the medical industry for
the delivery of hydrophilic cargos solubilized within the chitosome
lumen [140,149151]. In particular, their potential as topical delivery
system was demonstrated by several studies [162,232235], in particu-
lar dealing with ocular, nasal, and pulmonary delivery arising from the
high adherence of chitosan towards these tissues [205,236]. A different
approach for the use of chitosan and phospholipids for drug delivery
purposes consists in the adsorption of chitosan-modied gold nanopar-
ticles the outer surface of loaded liposomes [237]. Such liposomes were
shown to be stable in acidic medium, while they exhibit a pronounced
tendency to fuse with bacterial membrane upon increase of pH, there-
fore effectively releasing their content.
Chitosan solutions show a high surface tension, and accordingly are
difcult to spread on hydrophobic surfaces. However, a successful
spreading is necessary for an efcient coating, e.g., for increasing the
shelf life of food products. With this respect, several authors investigat-
ed the effect of the addition of non-ionic surfactants to chitosan solution
on its spreading behavior [142146]. In the presented studies,
polyoxyethylene sorbitan fatty acid esters were used, as these surfac-
tants are edible, surface active and show little interaction with chitosan.
In all cases, their addition increases the spreading efciency and there-
fore the quality of the chitosan coating.
6. Conclusions
Chitosan is an interesting biopolymer which has a rather stiff poly-
mer backbone and whose charge density can be controlled over a larger
range by the degree of acetylation (DA) and pH. With increasing DA it
becomes an increasingly amphiphilic polymer with hydrophobic re-
gions where the hydrophobic parts of surfactants can attach. In most
cases, chitosan can be regarded as a supramolecular glue, providing
a large supramolecular network for soft and hard colloids. The forma-
tion of linearly ordered complexes is often observed, e.g., in mixtures
with globular micelles [73,74] or silica nanoparticles [129,130]. Similar-
ly, complexes with a one-dimensional symmetry are found also in mix-
tures of ionically modied cellulose and surfactants [238,239]. This
similarity can be related to the structural analogy of cellulose and chitin
discussed in Section 1.3.
In mixtures of chitosan with oppositely charged surfactant strongly
synergistic interactions are observed. With strong anionic surfactants
 L. Chiappisi, M. Gradzielski / Advances in Colloid and Interface Science xxx (2015) xxxxxx
this then leads to the formation of stoichiometric complexes and precip-
itation over a large range of the phase diagram. Such precipitation can for
instance be used for the formation of well-dened capsules, with a rather
robust and elastic complex shell, which are very variable in size (con-
trolled by the formation process) and are mainly composed of the
biofriendly chitosan. In order to form water-soluble complexes one has
to employ more hydrophilic surfactants that after ionic complexation
still retain sufcient hydrophilicity. This is for instance given for the
class of alkyl oligooxyethylene carboxylates. These mixtures are particu-
larly interesting due to their strong pH-responsiveness and the variabil-
ity of different self-assembled structures obtained by simply varying the
length of hydrophilic and hydrophobic blocks of the surfactant.
Similarly, the length of the alkyl chains of fatty acids mainly deter-
mines the behavior of complexes with chitosan. Accordingly, one can
distinguish between short carboxylic acids which do not self-assemble
in aqueous solution, long chain fatty acids which are not soluble in
water and form stable emulsions when admixed to chitosan. In between
complexes with a well dened mesoscale order are found, when chito-
san is mixed with fatty acids able to self-assemble into water soluble mi-
cellar aggregates.
Finally, the adsorption of chitosan chains on phospholipid vesicles
was reviewed, with a particular focus on the driving forces governing
the adsorption process, on structural changes taking place upon adsorp-
tion as well as on the liposome membrane properties. The binding of the
chitosan is an exothermic process, becoming more exothermic with
increasing pH, i.e., when the chitosan becomes more hydrophobic.
Moreover, the membranes become stiffer upon adsorption of chitosan.
All these aspects have to be considered when chitosan-coated phospho-
lipid are employed, e.g., for drug delivery purposes.
In summary, one nds that complexes formed by chitosan and sur-
factants can be very exible with respect to their structural organiza-
tion, where this applies in particular to the case of oppositely charged
systems. The local structure of the surfactant assemblies is largely con-
trolled by their intrinsic packing preference (as characterized by the
packing parameter) but the superstructure of the chitosan/surfactant
complex varies substantially by the mixing ratio and the charge condi-
tions, which can be controlled by the pH. Accordingly, the structure of
such complexes can be modied easily especially by pH and this respon-
siveness of the complexes can then be exploited for purposes of delivery
and sequestration. Due to the fact that these systems are largely bio-
compatible they can be expected to play an increasingly prominent
role in future water based applications and formulations.
Acknowledgment
LC thanks the Technische Universitt Berlin for funding this research.
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