cosmetics

Review
Chitosan: A Promising Multifunctional Cosmetic Ingredient for
Skin and Hair Care
Eduardo Guzmán 1,2, * , Francisco Ortega 1,2 and Ramón G. Rubio 1

1 Departamento de Química Física, Facultad de Ciencias Químicas, Universidad Complutense de Madrid,

Ciudad Universitaria s/n, 28040 Madrid, Spain
2 Instituto Pluridisciplinar, Universidad Complutense de Madrid, Paseo Juan XXIII 1, 28040 Madrid, Spain
* Correspondence: [email protected]; Tel.: +34-913-944-107

Abstract: The cosmetic industry has an undeniable need to design and develop new ecosustainable
products to respond to the demands of consumers and international regulations. This requires substi-
tuting some traditional ingredients derived from petrochemical sources with new ones with more
ecofriendly profiles. However, this transition towards the use of green ingredients in the cosmetic
industry cannot compromise the effectiveness of the obtained products. Emerging ingredients in
this new direction of the cosmetic industry are chitosan and its derivatives, which combine many
interesting physicochemical and biological properties for the fabrication of cosmetic products. Thus,
the use of chitosan opens a promising future path to the design of cosmetic formulations. In particular,
chitosan’s ability for interacting electrostatically with negatively charged substrates (e.g., skin or
damaged hair), resulting in the formation of polymeric films which contribute to the conditioning
and moisturizing of cosmetic substrates, makes this polymer an excellent candidate for the design of
skin and hair care formulations. This review tries to provide an updated perspective on the potential
interest of chitosan and its derivatives as ingredients of cosmetics for skin and hair care.

Keywords: adsorption; antimicrobial; biopolymer; conditioning; chitosan; coating; layers; moisturizing;

Citation: Guzmán, E.; Ortega, F.;
polymers
Rubio, R.G. Chitosan: A Promising
Multifunctional Cosmetic Ingredient
for Skin and Hair Care. Cosmetics
2022, 9, 99. https://doi.org/10.3390/
1. Introduction
cosmetics9050099
The transition of the cosmetic industry towards “green cosmetics” imposed by the
Academic Editor: Carmen
current international regulations, which have banned the use of many chemicals as ingredi-
Garcia-Jares
ents in cosmetic products, and the demand of products with improved ecosustainability
Received: 19 August 2022 has led to extensive research aimed towards finding suitable ingredients for substituting
Accepted: 13 September 2022 traditional ones derived from petrochemical sources [1–7]. This is of paramount importance
Published: 27 September 2022 when the substitution of common polymers used in cosmetic formulations is considered.
In fact, polymers present a broad range of applications in cosmetics, e.g., rheological modi-
Publisher’s Note: MDPI stays neutral
with regard to jurisdictional claims in
fiers, emulsifiers, stimuli-responsive reagents, conditioners, film formers, fixations, foam
published maps and institutional affil-
stabilizers, skin-feel beneficial agents, or antimicrobial agents, which allows considering
iations.
these types of molecules as the most used ingredients in different families of cosmetic
products [8].
Currently, the cosmetic industry uses polymers belonging mainly to four different
families: (i) synthetic polymers; (ii) polysaccharide-based polymers; (iii) proteins, and
Copyright: © 2022 by the authors. (iv) silicones [9]. These polymers play very different roles in cosmetic formulations. How-
Licensee MDPI, Basel, Switzerland. ever, the substitution of synthetic polymers and silicones with new “green ingredients”
This article is an open access article is among the most important challenges for the modern cosmetic industry [10]. This
distributed under the terms and has stimulated the research on the use of polysaccharides to cover most of the roles of
conditions of the Creative Commons the rest of polymer families [11], opening new routes to design and develop ecofriendly
Attribution (CC BY) license (https:// and biodegradable formulations containing mainly ingredients from renewable natural
creativecommons.org/licenses/by/
sources [12,13].
4.0/).

Cosmetics 2022, 9, 99. https://doi.org/10.3390/cosmetics9050099 https://www.mdpi.com/journal/cosmetics

Cosmetics 2022, 9, 99 2 of 15

Polysaccharides are complex carbohydrate polymers containing many hydroxyl groups

along their backbone that have been exploited in the development of cosmetic and personal
care formulations for centuries [14]. This has been possible due to the multiple biological
and physicochemical properties of polysaccharides, including biodegradability, biocom-
patibility, nontoxicity, renewability, and availability [15]. Furthermore, polysaccharides
present a better safety profile than synthetic polymers, reducing the hazards and risks to
health and the environment associated with their use [16].
Among polysaccharides, it is possible to find a broad range of polymers with differ-
ent charges (cationic, nonionic, anionic, or amphoteric) and conformations (mainly loose
rigid helices or randomized coils) [17,18], which offers a broad variety of properties to
the formulators, pushing the use of polysaccharide to cover different cosmetic necessities,
including rheology modifiers, conditioners, healing and suspending agents, moisturizers,
hydrators, and emulsifiers [19,20]. Unfortunately, to date, there is no clear understanding
of the true role of polysaccharides in cosmetic products. Nevertheless, the use of these
long-lifespan, green, and raw materials has been rapidly extended in the cosmetic indus-
try [14]. In particular, the use of chitosan and its derivatives has received much attention
due to their low production costs and safety character [21]. Moreover, the environmental
aspects have been also considered as a main issue for the exploitation of this abundant
polysaccharide in cosmetics [22]. It should be noted that chitosan and chitosan derivatives
can be currently produced with a broad range of physicochemical and biological proper-
ties for their application in cosmetic, hygiene, and personal care products. In particular,
the cosmetic industry exploits different chitosan-based compounds, including chitosan
hydrochloride, chitosan acetate, chitosan lactate, carboxymethyl chitosan, quaternized
derivatives, oligosaccharides, and also chitin sulfate and carboxymethyl chitin [23–25].
Table 1 summarizes some examples of the potential uses of chitosan and its derivatives in
the cosmetic industry.

Table 1. Potential uses of chitosan and its derivatives in cosmetic industry. Adapted by permission
from Springer-Nature from Morin-Crini et al. [23], Copyright (2019).

Type of Products Forms Applications

Toiletry Solution Functional additives
Hygiene Powder Moisturizers: maintain skin moisture, tone skin
Personal care Film Thickening agent
Skin care Hydrating and film-forming agent
Oral care Role in surfactant stability; stabilize emulsion
Dental care Antistatic effect
Hair care Bacteriostatic
Cosmeceuticals Encapsulating agent
Delivery systems
Products: shampoos, creams, skin creams, creams for acne treatment, lotions, bath
lotions, nail polish, fixtures, make-up powder, lacquers, nail lacquers, nail enamel,
varnishes, hair sprays, hair colorants, and wave agents
Cleaning products: cleansing milk, face peel, facial toner, soap, and bath agent
Hair care: elastic film on hair, increase its softness and mechanical strength, improve
suppleness of hair, remove oils and sebum from hairs, reduce static electricity in hair,
retain moisture, and maintain hair’s style
Oral care, dental care: toothpaste and chewing gum

This review aims to present an updated perspective on the use of chitosan as a potential
ingredient in cosmetic formulations for skin and hair care. This is important because the
introduction of chitosan in different cosmetic and cosmeceutical products is one of the most
active research areas of the cosmetic industry, and the understanding of their potential
activity in new products requires being comprehensively analyzed. It is important to
recall that chitosan is a naturally derived polymer, and, hence, before dealing with the
potential applications of chitosan in the cosmetic industry, it is necessary to discuss some
Cosmetics 2022, 9, x FOR PEER REVIEW 3 of 16

potential activity in new products requires being comprehensively analyzed. It is im-

Cosmetics 2022, 9, 99 3 of 15
portant to recall that chitosan is a naturally derived polymer, and, hence, before dealing
with the potential applications of chitosan in the cosmetic industry, it is necessary to dis-
cuss some of the most fundamental physicochemical and biological aspects of chitosan. It
of worth
is the most fundamental
mentioning that physicochemical
the introduction of and biological
chitosan aspects ofaschitosan.
in cosmetics a substitute It isfor
worth
tra-
mentioning
ditionally thatsynthetic
used the introduction
polymers ofprovides
chitosan important
in cosmetics as a substitute
benefits for traditionally
to the cosmetic industry.
used
In syntheticthe
particular, polymers
naturalprovides
origin ofimportant benefits tothe
chitosan promotes the fabrication
cosmetic industry.
of mostInsustainable
particular,
and safe products. Moreover, the use of chitosan can also contribute to reducingproducts.
the natural origin of chitosan promotes the fabrication of most sustainable and safe the pol-
Moreover,
lution of thethefabrication
use of chitosan can also
processes contribute to reducing the pollution of the fabrication
[26].
processes [26].
2. Chitosan: Physicochemical and Functional Properties
2. Chitosan: Physicochemical and Functional Properties
2.1. Physicochemical Properties
2.1. Physicochemical Properties
The study of chitosan cannot be understood without introducing some of the main
The study of chitosan cannot be understood without introducing some of the main
characteristics of its most common source: chitin. Chitin is a naturally occurring polysac-
characteristics of its most common source: chitin. Chitin is a naturally occurring polysac-
charide that can be found in a broad range of living organisms. In fact, chitin is the second
charide that can be found in a broad range of living organisms. In fact, chitin is the second
most
most abundant polysaccharide
abundant polysaccharide in in the
the world
world after
after cellulose,
cellulose, and
and is
is the
the main
main component
component of of
the
the exoskeleton
exoskeleton of of many
many invertebrates,
invertebrates, e.g.,
e.g., crustaceans,
crustaceans, mollusks,
mollusks, andand insects,
insects, butbut it
it also
also
plays aa vital
plays vital structural
structural role
role inin the
the cell
cell wall
wall ofofdifferent
different fungi
fungi and
andyeasts
yeasts[27,28].
[27,28].Chemically,
Chemically,
chitin is a crystalline polymer composed of N-acetyl-2-amino-2-deoxy-β-D-glucose
chitin is a crystalline polymer composed of N-acetyl-2-amino-2-deoxy-β-D-glucose units units
polymerized through (1,4)-links, presenting many structural analogies
polymerized through (1,4)-links, presenting many structural analogies with cellulose. In with cellulose. In
fact, the main chemical difference between chitin and cellulose appears
fact, the main chemical difference between chitin and cellulose appears at the C2 position, at the C2 position,
where the
where the hydroxyl
hydroxyl groups
groups of of cellulose
cellulose are
are replaced
replaced byby acetamide
acetamide groups
groups inin chitin.
chitin. More-
More-
over,
over, chitin also presents some 2-amino-2-deoxy-β-D-glucose residues (see Figure 1a for
chitin also presents some 2-amino-2-deoxy-β-D-glucose residues (see Figure 1a for
molecular
molecular structure
structure of of chitin).
chitin). Chitin
Chitin isis aa white,
white, hard,
hard, inelastic,
inelastic, and
and nitrogenous
nitrogenous polysac-
polysac-
charide, which presents
charide, which presentsaalimited
limitedchemical
chemicalreactivity
reactivity
and and
hashas
an an analogous
analogous rolerole to colla-
to collagens
gens in animals
in animals and cellulose
and cellulose in plants
in plants [28]. [28].

Figure 1. Chemical
Chemical structures
structures of chitin (a) and chitosan (b) Reprinted from Casadidio et al. [22], with
permission under
permission under Open
Open access
access CC
CC BY
BY 4.0
4.0 license,
license, https://creativecommons.org/licenses/by/4.0/
https://creativecommons.org/licenses/by/4.0/ (ac-
cessed on 22 July 2022).
(accessed on 22 July 2022).

The physicochemical
physicochemical and biological biological properties
properties of chitin and chitosan are extremely
dependent on onthetherawrawmaterial
material and thethe
and methodology
methodology used for their
used isolation.
for their In fact,Inchitin
isolation. fact,
is insoluble
chitin in aqueous
is insoluble solutions
in aqueous and most
solutions andcommon organicorganic
most common solvents. However,
solvents. it pre-
However,
it presents
sents good good solubility
solubility in otherin other solvents,
solvents, including
including hexafluoroacetone
hexafluoroacetone sesquihydrate,
sesquihydrate, hex-
hexafluoroisopropanol,
afluoroisopropanol, andand chloroalcohols.
chloroalcohols. Therefore,
Therefore, the utilization
the utilization of bare
of bare chitinchitin
as cos- as
cosmetic
metic ingredients
ingredients is very
is very limited
limited due
due tototheir
theirlow
lowsolubility
solubilityininaqueous
aqueous medium,
medium, which
makes its its handling
handlingvery verydifficult
difficult[21].
[21].Chitin
Chitin presents
presents much much
moremore applications
applications when when
it is
it is transformed
transformed to chitosan
to chitosan following
following a partial
a partial deacetylation
deacetylation processprocess
under under
alkalinealkaline
condi-
conditions
tions [29]. In[29]. Inthe
fact, fact,protonation
the protonation of theofamino
the amino groups
groups at the
at the C2 position
C2 position of chitin
of chitin leadsleads
to
to its deacetylation that allows obtaining chitosan, a cationic polysaccharide
its deacetylation that allows obtaining chitosan, a cationic polysaccharide with reasonably with reasonably
good solubility
good solubility in in acid
acid aqueous
aqueous solutions
solutions (lactic,
(lactic, acetic,
acetic, glutamic,
glutamic, and
and hydrochloric
hydrochloric acid acid
solutions) with
solutions) with aapH pHup uptoto6.5,
6.5,which
which is is
thethepKpK
a value of of
a value chitosan. Unfortunately,
chitosan. Unfortunately, when whenthe
pH
the of
pHthe of solutions
the solutionsis close to physiological
is close to physiological conditions, chitosan
conditions, becomes
chitosan insoluble
becomes insolubleand
undergoes
and undergoesprecipitation as a result
precipitation of amine
as a result deprotonation.
of amine Moreover,
deprotonation. the addition
Moreover, of inert
the addition
electrolytes to chitosan solutions or the increase in the polymer molecular
of inert electrolytes to chitosan solutions or the increase in the polymer molecular weight weight can also
worsen the polymer solubility [30].
can also worsen the polymer solubility [30].
On the contrary to that which happens when chitin is considered, chitosan is mainly
formed by 2-amino-2-deoxy-β-D-glucose units (see Figure 1b for the molecular structure of
chitosan) and a certain number of N-acetyl-2-amino-2-deoxy-β-D-glucose residues. The
amount of these residues within the polymer chains is accounted for by the deacetylation
Cosmetics 2022, 9, 99 4 of 15

degree (DD), which is defined as the percentage of deacetylated monomers in relation to

the total number of monomers in the polymer chain. The DD controls the solubility of the
polymer in acid aqueous solutions. In fact, the increase in chitin DD above a threshold
value of 50% makes the polymer soluble, changing its structure to that corresponding to
cationic chitosan [30]. The evaluation of the DD of chitosan is a very important issue, and
different methodologies have been developed for its determination, including different
spectroscopies (ultraviolet, infrared, Raman, and proton and carbon nuclear magnetic
resonance), gel permeation chromatography, circular dichroism, residual salicylaldehyde
analysis, titration methods, elemental analysis, high-performance liquid chromatography,
thermal analysis, or mass spectrometry [31,32].
Moreover, the molecular weight can impact the potential applications of polysaccha-
ride polymers. The molecular weight of chitin is generally in the range 400–2500 kDa and
depends on the source and the methodology used for its isolation [33,34]. On the other side,
the molecular weight of chitosan is lower than that of chitin due to the N-deacetylation
process, appearing commonly in the range of 100–500 kDa, and depends on the degree
of polymerization (DP). This parameter becomes very important because it influences the
chitosan’s solubility. In fact, when the DP ≤ 8, chitosan is soluble in water independently
of the deacetylation degree [35].

2.2. Functional Properties

Chitosan presents different functional properties that derive from their biological
activity, e.g., anticholesterolemic, wound-healing, anticancer, fungistatic, hemostatic, anal-
gesic, antiacid, antiulcer, or immunoadjuvant [36,37]. In the particular case of the cosmetic
industry, chitosan has been commonly used as an excipient and bioactive ingredient. This
is possible by exploiting several chitosan properties, including limited toxicity, biocompati-
bility, and biodegradability [22].

2.2.1. Antimicrobial Activity

Chitosan presents good antimicrobial activity against different microorganisms, includ-
ing bacteria, fungi, and yeast. However, the mechanism underlying chitosan antimicrobial
activity is far from clear and there are several hypotheses available trying to account for
this important role of chitosan. The first hypothesis suggests that the antimicrobial activity
of chitosan is associated with the ionic cross-linking occurring between the polycation and
the negatively charged cell surface. This leads to the formation of a very dense layer which
hinders the intake of nutrients into the microorganisms, causing their death. A second
hypothesis tries to explain the antimicrobial activity of chitosan on the basis of its chelating
properties and their influence on organism growth. The last hypothesis considers that
low-molecular-weight chitosan can penetrate through cell walls, which facilitates its inter-
actions with deoxyribonucleic acid (DNA), altering some important biological pathways,
including ribonucleic acid (RNA) and protein synthesis. It should be noted that the increase
in the chitosan charge, i.e., the increase in the DD, favors the antimicrobial role of chitosan,
improving its permeation and its electrostatic binding to the membrane [38,39]. Moreover,
the increase in the polymer molecular weight and the solution pH is also favorable for the
antimicrobial activity of chitosan [40]. In general, the antimicrobial effectiveness of chitosan
is higher against Gram-negative bacteria than against Gram-positive ones [41].

2.2.2. Antioxidant Activity

Chitosan presents scavenging ability against different radical species including oxygen,
e.g., alkyl, superoxide, hydroxyl, and DPPH (2,2-diphenyl-1-picrylhydrazyl). However, as
occurred for the antimicrobial activity of chitosan, to date, there is no clear description of
the mechanism driving the antioxidant activity of chitosan, which is commonly ascribed to
the ability of the hydroxyl and amino groups of chitosan to chelate free metal ions, leading
to the formation of stable species [22].
Cosmetics 2022, 9, 99 5 of 15

It should be stressed that the antioxidant properties of chitosan are governed by the
specific molecular properties of the chosen polymers. In fact, the increase in the DD and
the reduction in the molecular weight contribute to the enhancement of the antioxidant
properties of chitosan [42]. The role of the latter parameter can be understood considering
that the tendency of short chains to form intramolecular hydrogen bonds between their
hydroxyl groups is very limited, which results in an increase in the number of hydrophilic
groups available for radical scavenging [43].

2.2.3. Mucoadhesive Properties

The specific properties of chitosan, in particular its positive charge, favor its interaction
with the negative residues of the mucin. This interaction is enhanced for polysaccharides
of high DD and high molecular weight [44–46]. Moreover, the derivatization processes of
chitosan can also contribute to enhancing the mucoadhesive properties of the obtained
polymers in comparison to bare chitosan [44].

2.2.4. Penetration Enhancement

Chitosan can act as a penetration enhancer through a modification of the transepithe-
lial electric resistance occurring as a result of the opening and destruction of the epithelial
tight junctions. This is possible through the electrostatic binding of chitosan to the cell mem-
brane, which modifies the association of the proteins involved in the tight junctions [47,48].
For instance, Contri et al. [49] pointed out that the skin penetration of acrylic capsules
embedded into a chitosan gel can be enhanced in relation to the situation in which chitosan
is not in the medium. Thus, chitosan leads to a deeper skin penetration of the cosmetic
formulations mediated by the opening of the tight junctions of the stratum granulosum
upon its interaction with the positive charges of the polymer. The penetration of chitosan
into hair fibers was explored by Kojima et al. [50] by using time-of-flight secondary ion
mass spectrometry (TOF-SIMS), evidencing that the positive charge of chitosan controls its
penetration into hair fibers. This penetration depends strongly on the degradation degree
of hair. Thus, the formation of a cysteic acid group upon bleaching favors the deposition of
chitosan in comparison to the situation found for virgin hair.

3. Chitosan in Skin and Hair Care

Chitosan has been isolated for a long time, mainly from the skeletons of different crus-
taceans, including crab, shrimp, and lobster [51]. However, this chitosan is not suitable for
cosmetic applications due to the possible disease transmission (zoonosis), and different eth-
ical issues and concerns related to biodiversity and endangered-species protection [52,53].
This has stimulated the cosmetic application of chitosan derived from plants or biotechno-
logical processes. In particular, the isolation of chitosan through the fermentation of fungal
cell walls has been developed as a very interesting and economical approach for obtaining
this polymer with cosmetically acceptable properties [51].
The current cosmetic uses of chitosan are mainly related to the production of mascaras,
hair conditioners, hair foams, and body creams [23]. However, its many functional proper-
ties have expanded the research aimed towards the introduction of chitosan in cosmetic
and personal care formulations for skin, oral, nail, and hair care [21]. This section will be
focused on the discussion of the main aspects related to the use of chitosan for the design of
suitable formulations for skin and hair care. These take advantage of the specific properties
of chitosan, including its cationicity which favors the interaction with damaged hair fibers
and skin; bacteriostatic, fungistatic, and antistatic character; film-forming ability (essential
in the hair-conditioning process); moisture retaining (chitosan can retain moisture even
in low-humidity environments); and ability for the controlled release of bioactive agents.
Moreover, chitosan presents good compatibility with common ingredients of cosmetic
formulations, e.g., starch, glucose, saccharose, polyols, oils, fats, waxes, acids, nonionic
emulsifiers, and nonionic water-soluble gums [23]. This has led, recently, to the develop-
ment and commercialization of different cosmetic-grade ingredients based on chitosan
Cosmetics 2022, 9, 99 6 of 15

b [54]. Table 2 summarizes some of the currently available commercial cosmetic-grade

ingredients based on chitosan.

Table 2. Some examples of cosmetic-grade ingredients based on chitosan.

Commercial Name Manufacturer Application

Hydamer™ Chitinor AS (Tromsø, Norway) Film-forming and fixative agent, deodorizing
Ritachitosan® Rita Corporation (Crystal Lake, IL, USA) Film-forming agent
Chemisches Laboratorium Dr. Kurt Richter GmbH
Curasan™ Film-forming agent
(Berlin, Germany)
Film-forming agent, antimicrobial,
Zenvivo™ Clariant (Muttenz, Switzerland)
deodorizing, moisturizer
KIOsmetine® Kitozyme (Herstal, Belgium) Film-forming agent, moisturizer
Chitosonic® Acid Personal Care Products Council (Washington DC, USA) Antimicrobial, moisturizer
ChitoClearTM Primex Manufacturing Inc. (Langley, BC, Canada) Film-forming agent
Shining agent, antidandruff agent, hair
Everquat™ Q50H Sino Lion (Florham Park, NJ, USA)
growth promoter, anti-hair-loss agent
Vink Chemicals GmbH & Co. KG Film-forming and wetting agent,
Vinkocos p-6N
(Kakenstorf, Germany) thickener, stabilizer
Jeen-Chitosan Jeen International (Fairfield, NJ, USA) Film-forming agent, moisturizer
Triozan Ovensa Inc. (Aurora, ON, Canada) Penetration enhancer

Moreover, there are several brands including chitosan in their cosmetic products for
different applications [55]. Table 3 summarizes some currently commercialized cosmetic
products containing chitosan and their specific applications.

Table 3. Some examples of currently commercialized cosmetic products containing chitosan and their
specific applications. Adapted from reference [55].

Product Manufacturer Application

Scalp Purifying Micellar Shampoo Kristin Ess Hair (Los Angeles, CA, USA) Shampoo
Brazilian Joia Strengthening + Smoothing Shampoo Sol de Janeiro, Inc. (New York, NY, USA) Shampoo
Extra Gentle Conditioner Kristin Ess Hair (Los Angeles, CA, USA) Hair conditioner
Herbal Essences Set Me Up Gel Procter and Gamble (Cincinnati, OH, USA) Hair-styling gel
Re Vamp Mid Length Repair Cream Vernom Francois (Los Angeles, CA, USA) Hair serum
Anti-Aging Moisture Lotion Murad LLC (El Segundo, CA, USA) Skin Care
Ultimate Miracle Worker Multi-Rejuvenating Cream Philosophy (New York, NY, USA) Skin Care
St. Yves Replenishing Mineral Therapy Body Lotion Unilever (London, UK) Skin moisturizer

3.1. Chitosan as Ingredient in Skin Care Products

The good antioxidant, cleansing, protecting, humectant, and antioxidant functions of
chitosan make it a suitable ingredient for skin care applications. In particular, chitosan has
been broadly exploited as an antiaging and moisturizing agent, in ultraviolet protection, in
skin cleansing, and as a boosting factor of different essential functions of the skin (protection,
absorption, thermal regulation, defense, reservation, and synthesis) [22]. One of the most
important aspects of chitosan in relation to its use in skin care products is related to its
minimal penetration through the skin, which limits its action mechanism in most of the
formulations to the skin/external environment interface [23,56].
Chitosan deposition on the skin surface can contribute to wound tissue healing by
creating a network structure and stimulate the synthesis of collagen, maintaining good
air permeation. Moreover, it presents good biocompatibility and biodegradability; an-
tibacterial, hemostatic, and anti-inflammatory properties; good absorption of exudate; and
promotion of tissue regeneration and skin collagen fiber growth. This favors its uses as an
ingredient of a broad range of skin care products [57]. Figure 2 shows a scheme highlighting
some of the most common uses of chitosan in skin care cosmetics.
 creating a network structure and stimulate the synthesis of collagen, maintaining good air
permeation. Moreover, it presents good biocompatibility and biodegradability; antibacte-
rial, hemostatic, and anti-inflammatory properties; good absorption of exudate; and pro-
motion of tissue regeneration and skin collagen fiber growth. This favors its uses as an
ingredient of a broad range of skin care products [57]. Figure 2 shows a scheme highlight-
Cosmetics 2022, 9, 99 ing some of the most common uses of chitosan in skin care cosmetics. 7 of 15

Figure 2. Potential
Figureuses of chitosan
2. Potential usesinofskin care cosmetics.
chitosan in skin careAdapted byAdapted
cosmetics. permission of Springer-Na-
by permission of Springer-Nature
ture from Rejinold et al. [56], Copyright (2021).
from Rejinold et al. [56], Copyright (2021).

3.1.1.
3.1.1. Chitosan Chitosan Applications
Applications as a Humectantas a and
Humectant and Moisturizing
Moisturizing Agent Agent
HumectantsHumectants
are cosmeticare cosmetic formulations
formulations or ingredients or that
ingredients thattocontribute
contribute the increaseto the increase
in the water content on the top layers of the skin, whereas moisturizers
in the water content on the top layers of the skin, whereas moisturizers increase the skin increase the skin
water content, contributing to improving skin softness and smoothness
water content, contributing to improving skin softness and smoothness [21]. Therefore, it [21]. Therefore, it
is possible to consider humectants as a moisturizer ingredient
is possible to consider humectants as a moisturizer ingredient used to replace the natural used to replace the natural
moisturizingmoisturizing factors
factors existing existing
in the keratininlayer
the keratin layer[58].
of the skin of the skin [58].
The role of chitosan as a humectant exploits
The role of chitosan as a humectant exploits its cationic character its cationic character
which allows which
its allows its
adsorption onadsorption on the
the negatively negatively
charged chargedInskin
skin surface. fact,surface.
chitosanIncanfact, chitosan
adsorb can
on the adsorb on the
neg-
negatively charged skin surface, improving the stratum corneum
atively charged skin surface, improving the stratum corneum water content and increas- water content and in-
creasing the fluidity of the cell membrane [59]. Moreover, the higher
ing the fluidity of the cell membrane [59]. Moreover, the higher the molecular weight, the the molecular weight,
the higher the moisture retention capacity of the chitosan. This can be understood by
higher the moisture retention capacity of the chitosan. This can be understood by consid-
considering the higher number of available monomers within the polymer chain, which
ering the higher number of available monomers within the polymer chain, which favors
favors the formation of intermolecular hydrogen bonds. These are responsible for the
the formation of intermolecular hydrogen bonds. These are responsible for the modula-
modulation of the moisture adsorption/retention by chitosan [60].
tion of the moisture adsorption/retention by chitosan [60].
Chaiwong et al. [61] showed that carboxymethyl chitosan may act as a suitable mois-
Chaiwong et al. [61] showed that carboxymethyl chitosan may act as a suitable mois-
turizing ingredient, and that moisturizing properties are enhanced with the increase in
turizing ingredient, and that moisturizing properties are enhanced with the increase in
the polymer molecular weight. This moisturizing effect can be explained considering the
ability of the polymer to form a hydrated chitosan layer on the skin surface, avoiding water
evaporation. On the other side, the moisturizing effect of chitosan also increases with the
deacetylation degree [59]. The use of carboxymethyl chitosans as suitable moisturizing
ingredients in cosmetics was further studied by Chaiwong et al. [61], who found that
this type of polymer may be applied successfully in deodorant creams for obtaining a
satisfactory water content in the skin upon application.
The chemical modification of chitosan by adding anionic moieties provides a suitable
strategy for enhancing the ability of chitosan for moisture adsorption, reaching a moistur-
izing effect even better than that provided by hyaluronic-acid-based products. Therefore,
anionic modified chitosans are emerging as promising ingredients for ensuring a good
adsorption and retention of moisture upon the application of cosmetic products [62].
Cosmetics 2022, 9, 99 8 of 15

3.1.2. Skin Aging

Skin aging is a very important problem associated with skin degradation as a result of
the combined effect of intrinsic aging occurring with time and different external factors,
including smoke, UV radiation, and pollution. This induces dryness, relaxation, roughness,
and laxity in the skin, which can originate skin hyperpigmentation and the appearance of
wrinkles, especially upon extensive exposure to UV radiation (photoaging) [63]. Chitosan
has been proven as a very promising ingredient to reduce the problem associated with
skin aging. In fact, the ability of chitosan, especially high-molecular-weight polymers, to
form films upon its application on the skin surface minimizes the cutaneous water loss
and enhances the skin’s mechanical properties (elasticity and smoothness), playing a very
important role as a moisturizing agent [64]. Kong et al. [65] demonstrated that the biological
activity of chitosan can be exploited for minimizing the undesirable changes associated
with extensive exposure to UV radiation. For instance, the application of chitosan can
contribute to reducing the macroscopic and histopathological damage occurring in skin
through the stimulation of the collagen production pathways. Moreover, chitosan can
also inhibit the production of postinflammatory cytokines and improve the activity of
different antioxidant enzymes and the moisture level of the skin. Therefore, chitosan can
be exploited to prevent UV-induced skin dryness, epidermal hyperplasia, and wrinkle
formation. This is possible because chitosan can increase the activity of certain enzymes
with an antioxidant role and suppress proinflammatory cytokine production, which in turn
inhibits the degradation of collagen fibers.
Libio et al. [66] pointed out that the ability of chitosan solubilized in citrate buffer to
form films on the skin surface can be exploited as a very interesting strategy for stratum
corneum exfoliation. This takes advantage of chitosan’s bioadhesive character for reducing
the cohesion of cells, and their subsequent detachment, which can contribute to prevent-
ing skin aging by inducing cell proliferation and the regeneration of the corneum layer.
Moreover, chitosan also presents an important role in increasing collagen density, reducing
lines and wrinkles. The main advantage of this strategy in comparison to wound-healing
processes is associated with the ability of chitosan to stimulate the interactions between
proteins and cells. This induces cell proliferation, the formation of a permeable barrier
(re-epithelialization), and angiogenesis.
Chen et al. [67] designed composites of quaternized carboxymethyl chitosan and or-
ganic montmorillonite as a novel antiaging ingredient for cosmetic creams. This ingredient
favors the adsorption and retention of moisture thanks to its layered structure and high
number of hydrophilic groups, providing very good protection against UV radiation.

3.1.3. UV Protection
Repeated exposure to UV radiation can induce oxidative stress and inflammatory
disequilibrium, leading to skin photoaging. This is characterized by the formation of
wrinkles, skin dryness, irregular pigmentation, and laxity. Moreover, the role of exposure
to UV radiation in the emergence of skin cancer cannot be neglected [21]. Therefore, skin
protection against the undesirable effects associated with UV exposure is essential for
ensuring the functional integrity of living organisms [56].
The UV-visible spectrum of chitosan presents absorption bands below 400 nm. This
makes possible the use of chitosan as a suitable ingredient for sunscreen cosmetics because
the UV rays associated with solar radiation presents wavelengths in the range 320–400 nm
and 290–320 nm in the case of UV-A and UV-B, respectively [21].
Chitosan’s power as sunscreen was proved by Verma et al. [68] who treated dyed
cotton fabric with chitosan, and found that the ultraviolet protection factor increased more
than 20% in relation to the value corresponding to the bare dyed cotton fabric. Moreover,
treatment with chitosan extended the durability of the photoprotection. It should be
noted that the UV-protection associated with the use of chitosan is strongly dependent on
the specific characteristic of the used polymer, including source, molecular weight, and
Cosmetics 2022, 9, 99 9 of 15

deacetylation degree [22]. Unfortunately, to date, there are no systematic studies dealing
with how the characteristics of chitosan can influence its performance as sunscreen.
Morsy et al. [69] fabricated sunscreen gels consisting of hydroxyapatite nanoparticles
homogeneously dispersed within a chitosan matrix. The deposition of a film of this hybrid
system on the skin surface was found to be a suitable strategy for minimizing the effects of
exposure to UV radiation.

3.1.4. Skin Cleansing

Skin-cleansing procedures aim to remove from the skin any substance that can be
deposited upon their exposure to ambient air or the application of cosmetic products. The
use of chitosan and some of its derivatives as skin cleansers is possible by exploiting their
cationic nature for designing carriers of active ingredients contributing to the cleansing
process. Thus, the interaction between the positive charges of the chitosan backbone and
the anionic charges of the skin surface can be exploited as a very promising tool for ensuring
the targeted release of cleaners [70]. Moreover, Theerawattanawit et al. [71] demonstrated
that chitosan gels may be exploited for reducing sebum levels without any side effects.
The ability of chitosan in the form of nanoparticles to control sebum levels was
studied by Tangkijngamvong et al. [72] who found a significant decrease in the sebum
levels after one week of the treatment with the cosmetic formulation containing chitosan
particles. Moreover, skin oiliness underwent a continuous decrease even after four weeks
of the formulation application. Sebum removal associated with chitosan is associated
with the ability of chitosan to form complexes with sebum, contributing to its removal.
Simultaneously, chitosan can form a film that prevents the deposition of sebum on the
skin surface.

3.1.5. Antibacterial Role

The most accepted mechanism explaining the antibacterial activity of chitosan upon
application on the skin can be explained considering that positively charged chitosan can
interact with the negatively charged bacterial cell wall, which leads to its weakening as a
result of a shrinkage process. This results in the inactivation of the bacterial cell, which is
strongly dependent on the molecular weight and charge density of the chitosan chains. In
fact, the higher the chitosan molecular weight, the stronger the antimicrobial power [56].
This antibacterial role was proved by Verma et al. [68] who found a reduction in the bacterial
proliferation upon chitosan treatment higher than 90%.
Chi et al. [73] showed that the use of formulations containing chitosan microneedles for
skin treatment reduces the inflammatory response associated with bacterial proliferation,
accelerating collagen deposition, angiogenesis, and granulation tissue formation. Moreover,
the formation of a chitosan hydrogel-like layer provides a significant protective effect,
acting as a barrier to prevent future bacterial infections.
Burkatovskaya et al. [74] showed that chitosan acetate presents higher antimicrobial
effectiveness against Pseudomonas aeruginosa and Proteus mirabilis than alginate and silver
sulfadiazine. This high activity against Gram-negative bacteria is explained by their fast
action mechanism mediated by the destabilization of the lipopolysaccharide bacterial cell
membrane and its subsequent permeabilization, leading to the leakage of cellular content
and avoiding a further proliferation of bacteria.

3.2. Chitosan as an Ingredient in Hair Care Products

Chitosan is not only a very good ingredient for skin care products, providing also
many benefits to the hair, improving hair hydration, helping to rebuild damaged hair, and
providing a healthy shine. This has stimulated the use of chitosan in a broad range of hair
care products, including shampoos, rinses, permanent wave agents, hair colorants, styling
lotions, hair sprays, and hair tonics [75,76]. This intensive use of chitosan is mainly associ-
ated with chitosan’s ability to improve the rheological properties of cosmetic formulations
or enhance the adhesion of specific components to the hair [21].
Cosmetics 2022, 9, 99 10 of 15

One of the most common hair care aspects in which cationic polymers, such as chitosan,
are involved is the conditioning process. In fact, the proteinic structure of damaged hair is
characterized by a denaturalized structure with negative charges which cannot be repaired
by biological processes, and, hence, it is necessary to use physicochemical methods for its
temporal reparation. This is possible by taking advantage of the ability of cationic polymers
to form a film on the surface of negatively charged surfaces [3,77–79]. In particular, the
interaction of chitosan and its cationic derivatives with the negatively charged keratin
surface of damaged hair fibers leads to the formation of transparent elastic films, which
increase hair softness and strength, minimizing the hair damage induced by mechanical,
thermal, or environmental stresses [80].
Hernández-Rivas et al. [5] explored the ability of chitosan to form conditioning films
on the surface of negatively charged surfaces mimicking the hair fibers, and found that
even though chitosan presents a good ability to deposit on negatively charged surfaces, its
performance as a conditioner is, in general, worse than that found for traditional condi-
tioning polymers such as poly(diallyl-dimethyl-ammonium chloride), polyquaternium-6,
and JR400, polyquaternium-10. However, a correct choice of the molecular weight and the
deacetylation degree of the used chitosan is of paramount importance in improving its
conditioning effects, and allows exploiting the full potential of chitosan in hair cosmetics.
Sionkowska et al. [81] contributed to the understanding of the role of chitosan in
conditioning formulations. They explored the effect of ternary blends including chitosan,
collagen, and hyaluronic acid, which appear as very promising formulations for hair-
conditioning purposes, and found that chitosan can contribute to improving the mechanical
properties, surface free energy, and stability in aqueous conditions on the conditioning
deposits, contributing to an improvement in the appearance of hair fibers. Moreover,
the combination of collagen, hyaluronic acid, and chitosan as a conditioning formulation
increases the elasticity and resistance of hair fibers against damage. In fact, the use of the
ternary mixture increases the Young’s modulus and the maximum elongation before the
breaking of fibers [82].

4. Chitosan as Delivery Systems

Chitosan-based delivery systems have gained interest in the cosmetic industry due to
their capacity to release active ingredients at specific targets in a controlled way [28]. In
particular, the use of chitosan nanoparticles emerges as a very promising alternative because
this type of material can interact with the skin lipid layers [83], which has stimulated their
use for the topical and transdermal delivery of different active compounds [84].
Panonnummal et al. [83] demonstrated that the use of formulations based on chitosan
nanogel particles loaded with an antipsoriatic active ingredient (clobetasol) favors the
transdermal flux of the drug in comparison to a conventional formulation, ensuring a
higher retention of the active ingredient within the deep layers of the skin. This provides
evidence of the potential benefits of nanogel for the delivery of active ingredients in
skin care applications. Ta et al. [58] designed chitosan gel particles which present high
moisture adsorption ability and low moisture retention capacity. This allows their use for
the encapsulation of hydrophilic cosmetic ingredients, and the subsequent release of the
encapsulated molecules within a hydrophobic environment such as the skin. Moreover, this
type of particle presents good capacities for penetrating through the skin and gathering in
the dermis layer, offering suitable properties for the dermal delivery of active ingredients.
Abd-Allah et al. [85] fabricated chitosan particles loaded with nicotinamide, and
tested their use against acne. These particles exhibited very strong adhesion to the skin,
providing a high deposition of nicotinamide in the different layers of the skin, which led to
an important reduction in the inflammatory acne lesions.
Chitosan particles have been exploited in hair care applications. In particular, Matos
et al. [86] produced chitosan particles loaded with minoxidil to face alopecia problems
(topical treatment). These particles presented high accumulation in the hair follicles and
Cosmetics 2022, 9, 99 11 of 15

contributed to a good drug release profile, ensuring a relevant therapeutic concentration

for more than 12 h.
Chitosan particles loaded with eugenol and carvacrol have shown good properties for
ensuring the preservation of cosmetic formulations against microbial contamination [87].
Similar preservation of cosmetic formulations can be obtained by loading other preserva-
tives such as thymoquinone [88]. Therefore, the encapsulation ability and release profile of
chitosan particles present are of paramount importance in the design of natural preserva-
tives of cosmetic products.

5. Toxicity Aspects of Chitosan

Chitosan is commonly considered as a nontoxic, biocompatible polymer [89], and
has been approved for regulatory agents for different uses. However, chitosan cannot be
included as a generally recognized as safe (GRAS) material. This is because the specific
characteristics of the used chitosan as well as its chemical modifications can influence the
safety profile of the specific polymer. Therefore, the safety of the use of chitosan in cosmetics
should be assessed case by case, even though in most cases, chitosan can be considered
safe for cosmetic applications [90]. The inclusion of chitosan in cosmetic products may
modify the biodistribution profiles of the different compounds in the formulation. For
instance, the interactions with cells may be altered due to the presence of charged particles
in chitosan. Therefore, the number of positive charges contained in the chitosan molecules,
which depends on the molecular weight and deacetylation degree of the polymer and the
pH of the medium, may modify chitosan interactions with cells and the microenvironment,
and, hence, the control of the above parameter is essential for modulating the potential
toxicity of formulations containing chitosan. Moreover, the nature of the products and the
application mode can also influence the potential toxicity of chitosan in cosmetics [90].

6. Prospects and Challenges of Chitosan as Cosmetic Ingredients

The above discussion has pointed out that chitosan is an emerging ingredient for
fulfilling some of the main requirements of the “green cosmetic” industry. This is reflected
in the rapid growth in the chitosan market for cosmetic applications. In fact, in recent
years, it has been possible to find many papers and patents dealing with the use of chitosan
in the cosmetic industry. Unfortunately, there is a limited number of commercialized
products containing chitosan, and when it is used as a cosmetic ingredient, in most cases,
its bioactivity and physicochemical properties are not completely exploited. This is in part
because it is extremely difficult to access chitosan with enough purity and reliability of its
sources. Moreover, the natural origin of chitosan makes it very difficult to obtain, at the
industrial level, raw materials with the same characteristics, and when it is possible, the
production costs become very elevated (higher than that of petroleum-derived polymers),
which is a very important drawback to the introduction of chitosan as an ingredient in
the cosmetic industry [23]. Therefore, it is mandatory to seek ecological and economical
sustainable alternatives for producing chitosan with suitable characteristics for use in
the cosmetic industry. This can pass through the design of synthetic routes providing
chitosan, or its derivatives, with enough purity and properties to be considered as a
suitable ingredient for cosmetic products. Moreover, it is essential to obtain extensive
knowledge of the structural and physicochemical aspects of chitosan, which is not always
easy due to the above-mentioned heterogeneity of isolated chitosan [91]. In fact, one of
the most important questions that emerges in front of cosmetic formulators is related to
the suitability of a specific chitosan sample for a fixed application. Therefore, a detailed
characterization of the samples before their application in cosmetic products is needed [21].
In addition to the aspects related to the quality of the chitosan as a cosmetically
acceptable ingredient, it is mandatory to perform in vivo tests, which can provide evidence
of the effectiveness of chitosan as an active ingredient for cosmetics, giving also information
about the possible harmful effect of this ingredient [21,23].
Cosmetics 2022, 9, 99 12 of 15

7. Concluding Remarks
The undeniable need for cosmetic products with a more ecosustainable profile and
higher safety has pushed the cosmetic industry towards a progressive substitution of many
ingredients derived from petrochemical sources. This is only possible by introducing
natural-derived polymers in cosmetics, which may contribute to reducing the environmen-
tal impact of the cosmetic industry and the negative effects on human health of specific
ingredients. The use of natural-derived polymers in cosmetics exploits their physicochem-
ical and biological properties for a broad range of applications, including skin and hair
care and make-up, but also, they can be exploited as stabilizers and modifiers, resulting in
the fabrication of highly marketable products which can fulfil consumer demands and the
current international regulations.
Among natural polymers, chitosan and its derivates are receiving particular and
increasing attention, contributing to the change in the traditional paradigm of the cosmetic
industry. This has been possible because chitosan presents suitable properties to be used in
several types of cosmetics, including skin and hair care products, nail lacquers and lotions,
or moisturizers for lips and skins. Moreover, chitosan presents suitable properties for
providing sunscreen with water resistance. On the other side, the antimicrobial properties
of chitosan allow its use in the fabrication of different deodorants or products for acne
treatments. This multifunctionality of chitosan in cosmetic applications is strongly related
to the specific physicochemical and biological properties of this polymer and its derivates.
Despite the broad range of potential uses of chitosan in the cosmetic industry, there are
several unclear issues that require additional research for ensuring the optimal utilization
of this biopolymer and its derivates. The main challenge is associated with the optimization
and scaling of the isolation and purification processes of chitosan from its sources. Moreover,
the development of suitable strategies for the characterization of the raw material from
a physicochemical and biological perspective will be essential for chitosan exploitation.
On the other side, one of the main limitations towards the use of chitosan in cosmetics
derives from the absence of in vitro and in vivo tests of the new formulations, which limits
the evaluation of their efficacy. In this review, we have attempted to provide an updated
perspective of the current trends in the use of chitosan for skin and hair care cosmetics. It is
expected that this can be useful for cosmetic formulators to optimize the use of chitosan
and its derivatives in new cosmetic products that can be marketed and fulfill the demands
of the cosmetic green challenge.

Funding: This work was funded by MICIN under grant PID2019-106557GB-C21, and by the E.U.
on the framework of the European Innovative Training Network-Marie Sklodowska-Curie Action
NanoPaInt (grant agreement 955612).
Conflicts of Interest: The authors declare no conflict of interest. The funders had no role in the design
of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript; or
in the decision to publish the results.

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