Journal of Carbohydrate Chemistry

ISSN: 0732-8303 (Print) 1532-2327 (Online) Journal homepage: https://www.tandfonline.com/loi/lcar20

The significance of complex polysaccharides in

personal care formulations

Haseeb Ahsan

To cite this article: Haseeb Ahsan (2019): The significance of complex

polysaccharides in personal care formulations, Journal of Carbohydrate Chemistry, DOI:
10.1080/07328303.2019.1615498

To link to this article: https://doi.org/10.1080/07328303.2019.1615498

Published online: 30 May 2019.

Submit your article to this journal

Article views: 8

View Crossmark data

Full Terms & Conditions of access and use can be found at

https://www.tandfonline.com/action/journalInformation?journalCode=lcar20
JOURNAL OF CARBOHYDRATE CHEMISTRY
https://doi.org/10.1080/07328303.2019.1615498

REVIEW

The significance of complex polysaccharides in personal

care formulations
Haseeb Ahsan
Department of Biochemistry, Faculty of Dentistry, Jamia Millia Islamia (A Central University),
New Delhi, India

ABSTRACT ARTICLE HISTORY

Complex polysaccharides have numerous pharmacological Received 13 January 2019
activities, such as antioxidant, antibacterial, antiviral, immuno- Accepted 2 May 2019
modulating, anticoagulant and anticancer effects. In personal
KEYWORDS
care products, these biopolymers are used as thickener and
Cosmetic products; complex
stabilizing agents or as moisturizing ingredients that could be polysaccharides; glycosami-
beneficial to the skin. Various polysaccharides, such as glyco- noglycans; hyaluronic acid;
saminoglycans (GAGs), hyaluronic acid (HA), carrageenan, chitin; chitosan;
fucose, fucoidan, chitin, chitosan, etc., have applications in carregeenan
cosmeceutical industries. GAGs and HA incorporated in
moisturizing creams strengthen the skin barrier by forming a
protective layer which prevents transdermal water loss.
Therefore, these polysaccharides have been formulated into
potential cosmeceuticals and biopharmaceuticals.

Introduction
Human beings have been using beauty care products for religious as well
as ornamental purposes for a long history and it is believed that earlier civ-
ilizations extracted such products from plants (flowers, fruits, seeds, vegeta-
bles, etc.) and soil (clay, ash, etc.). The cosmetics products have been used
to clean, perfume, change the appearance, protect from body odors, and
keep the skin surface, hair and teeth in good condition.[1] Cosmetics are
defined as “any substance or preparation intended to be used on the external
parts of the human body mainly for cleansing, perfuming, beautifying, odor-
ant, and promoting well-being without affecting body structure or function”.
The intention of using cosmetic products is to maintain the body in good
condition, protect it from the effects of the environment and aging proc-
esses, change the appearance, and make the body smell better.[1,2]
However, the added chemicals in the form of preservatives, emulsifiers,
emollients, antioxidants, humectants, polishes, dyes and fragrances may be

CONTACT Haseeb Ahsan [email protected], [email protected] Department of Biochemistry, Faculty of

Dentistry, Jamia Millia Islamia (A Central University), Jamia Nagar, New Delhi-110025, India
ß 2019 Taylor & Francis Group, LLC
2 H. AHSAN

hazardous and are sometimes prohibited due to various health risks.[1,2]

However, cosmetic preparations that are intended to prevent diseases by
influencing the function and structure of the human skin, such as
sunscreens or antidandruff shampoos, are considered as drugs.
The word “cosmeceutical” is derived from cosmetics and pharmaceuti-
cals, implying that the product contains ingredients which are intended for
therapeutic use. Albert Kligman, a dermatologist, introduced the term
“cosmeceutical” to products applied for personal care that have a dual sig-
nificance of being cosmetics and pharmaceuticals.[3] Cosmeceuticals contain
active ingredients in products such as creams, lotions and ointments and
ingestible beauty products in the form liquids, pills and functional foods.
In addition, ingestible beauty products or nutricosmetics and cosmeceuti-
cals can be obtained as liquids, pills or functional foods. These products
are formulated with ingredients or nutrients such as vitamins, minerals,
plant extracts and antioxidants and are believed to promote healthy skin,
hair, and nails.[1,4,5] Therefore, a huge interest has been shown by consum-
ers toward novel bioactive compounds formulated in cosmetics from nat-
ural resources because of their beneficial effects as compared to synthetic
ingredients. Marine resources have also been demonstrated as rich sources
of structurally diverse biologically active compounds with large cosmeceut-
ical potential. For example, marine algae have gained importance in cos-
metics due to the rich source of bioactive compounds extracted from them
for the development of cosmeceutical products.[1,6] They contain numerous
fatty acids, polysaccharides, minerals and vitamins, antioxidants, enzymes
and peptides.[4]
The beneficial effects promoted by the use of biomolecule-rich substances
into the formulations of some products are considered useful ingredients in
cosmetic and therapeutic applications. Polysaccharides are widely used in
food, cosmetic and pharmaceutical industries, because they provide essen-
tial nutrients, fibers, adhesives, hydrogels, etc. In personal care products,
these multipurpose biopolymers are used as thickener and stabilizing agents
or as moisturizing ingredients that could be beneficial to the skin. Various
polysaccharides, such as glycosaminoglycans (GAGs), hyaluronic acid (HA),
agar, fucose, chitosan, etc., have found applications in cosmeceutical indus-
tries. GAGs not only contribute to the improvement of skin hydration, but
also strengthen the skin barrier and increase the resilience of skin to exter-
nal factors. HA is incorporated in moisturizing creams to retain moisture
and form a protective layer against transdermal water loss. Therefore, this
review article attempts to differentiate and better understand the complex
carbohydrates and polysaccharides employed in cosmetic and personal care
products (Table 1).
 JOURNAL OF CARBOHYDRATE CHEMISTRY 3

Cosmetic carbohydrates
In nature, carbohydrates are the most abundant organic compounds pro-
duced by photosynthetic organisms, which are used as source of energy
for heterotrophic organisms. Polysaccharides are complex carbohydrates
containing polyhydroxyl aldehydic and ketonic groups and interact
strongly with water due to their chemical composition. They are widely
used in food, cosmetics, and pharmaceutical industries as they are a
good source of essential nutrients, fibers, adhesives, colloidal gels, etc. In
personal care products, these polymeric compounds are used as thick-
ener and stabilizing agents (i.e., xanthan gum, cellulose) or moisturizing
ingredients that improve the condition of the skin (i.e., HA, guar deriva-
tives).[6–8] All polysaccharide-based formulations containing these sub-
stances are important for the function and protection of the
skin barrier.[9,10]

Table 1. The application and benefits of complex polysaccharides in cosmetic formulations

(Adapted and modified from Moore[9]; Elieh-Ali-Komi and Hamblin[45]).
Complex polysaccharides Potential Function
Alginate Emulsion and texture stabilizer, thickening agent
Carrageenan Viscosity modulating, thickening agent
Chitin Antiaging, Skin protection
Chitosan Moisturizer, Antimicrobial, Antioxidant, Emulsifying agent, Skin protection
Fucoidans Wound-healing
Hyaluronic acid Moisturizes and promotes tissue reorganization
Oligosaccharides Moisturizer

In recent times, a large amount of interest is shown by consumers in

bioactive compounds from natural marine sources instead of synthetic con-
stituents and ingredients. Marine organisms have been demonstrated as
rich sources of structurally diverse biologically active compounds with
cosmeceutical potential. The dermatology research suggests that marine
bioactive ingredients used in cosmeceuticals may also have other benefits
than their traditional moisturizing effects.[1] Among them, polysaccharides
represent some of the most abundant bioactive substances in marine organ-
isms (Figure 1). Since carbohydrates are ubiquitous and abundant and play
an important role in biogeochemical cycles they are also found in marine
water column and sediment-water interface.[4] The marine organisms are
good source of polysaccharides including chitin, chitosan, fucoidan, carra-
geenan and alginate which have pharmaceutical activities, such as antioxi-
dative, antibacterial, antiviral, immuno-stimulatory, anticoagulant and
anticancer effects.[11–23] Since these polysaccharides have beneficial effects
on humans, they have been developed into cosmeceuticals and nutraceuti-
cals.[4,5] The marine algal compounds, such as phlorotannins and sulfated
polysaccharides, are useful as cosmeceuticals. The seaweed extracts, such as
4 H. AHSAN

Figure 1. Marine polysaccharides useful in cosmeceutical applications (adapted and reproduced

from Ruocco et al.[5]).

phycocolloids alginate or carrageenan, are often found as ingredients in cos-

metics, particularly the face, hand and body creams or lotions. The fucoxan-
thin isolated from Laminaria japonica has been reported to suppress
melanogenesis in ultraviolet B (UV-B)-irradiated mice. Fucoxanthin signifi-
cantly suppressed skin mRNA suggesting that it downregulated melanogenesis
factor at the transcriptional level. The brown algae polyphenols, phlorotan-
nins, act as potential cancer chemopreventive agents against photocarcinogen-
esis and other adverse effects of UV-B exposure. The majority of
phlorotannins and sulfated polysaccharides reported are from the members of
species Ecklonia and Eisenia.[24] Moreover, a new trend in cosmetic formula-
tions is the use of polysaccharides from Klebsiella pneumonia (Gram negative
bacterium) and Myrtus communis (commonly known as true myrtle), which
are supposed to enhance cell renewal and improve skin hydration.

Glycosaminoglycans (GAGs)
GAGs are unbranched, linear polysaccharides such as HA, dermatan sul-
fate, heparan sulfate and chondroitin sulfate, etc. GAGs are composed of
repeated disaccharide units containing amino sugars or aminosaccharides
(galactosamine, glucosamine) and uronic acid (glucuronic, iduronic), linked
through a 1,3- or 1,4-b-glycosidic bond (Figure 2A, B). GAGs differ in the
composition of amino sugars, chain length, nature of bonding between
disaccharide and core protein units, amino acid composition and the distri-
bution in cells or tissues and their biological function.[24] The molecular
composition of GAGs is related to their role as the structural components
and functional biomolecules of cells and tissues in the human body. GAGs,
except for HA, contain sulfate groups and form complex with proteins to
generate proteoglycans (PGs). However, HA interacts non-covalently with
 JOURNAL OF CARBOHYDRATE CHEMISTRY 5

Figure 2 A. Different types of glycosaminoglycans (GAGs) (adapted and reproduced from

K€owitsch et al.[25]) copyright Wiley. 2B. The backbone structure of GAGs. CS or DS is composed
of alternating disaccharide units of GlcA or IdoA and GalNAc, respectively. Modification with
b-D-glucose has been found in squid CS. The presence of the a-L-fucose branch has been
reported in the CS preparations from sea cucumber and king crab. HS is composed of alternat-
ing disaccharide units of GlcA or IdoA and GlcN. HA is a linear polymer composed of GlcA and
GlcNAc (adapted and reprinted from Yamada et al.[26]) copyright Landes Bioscience.
6 H. AHSAN

Figure 3. The different application of glycosaminoglycans (adapted and reproduced from

K€owitsch et al.[25]) copyright Wiley.

other biomolecules present in the extracellular space (ECM). GAGs and

PGs are specific and abundant components found in the ECM. The pri-
mary function of these macromolecules is to lubricate and join cells, tissues
and organs of the body.[24] Therefore, GAGs are widely used in implants,
components of tissue engineering scaffolds and hydrogels, diagnostic bio-
sensors and in controlled release applications (Figure 3).[25]
GAGs occur in the skin tissue in the form of PGs, bonded with struc-
tural proteins such as collagen and elastin. These compounds maintain
hydration, structure, osmotic pressure and turgor of the skin and regulate
transportation of raw materials and metabolites.[27] Cosmetic products make
use of their moisturizing ability, soothing and comforting effects and their
ability to stabilize and maintain the elasticity and firmness of skin cells. They
also significantly reduce the possibility of local irritation and allergies and
strengthen the skin resistance to the harmful effects of external factors.
Besides the use of GAGs in creams or lotions for skin care, they are also
used for hair care since they are naturally produced in the hair papilla sup-
plied with blood. The main role of GAGs is to control the proper transfer of
nutrients between the cell and the blood. They play an important role in the
proper nutrition of the matrix and the metabolism and growth of hair.
GAGs accumulate in the hair matrix in the growth phase, but are absent or
 JOURNAL OF CARBOHYDRATE CHEMISTRY 7

Figure 4. Representative structure of hyaluronic acid (A) HA disaccharide subunit, (B) the HA
polysaccharide chain (C) cross-linked HA used in cosmetic surgery (adapted and reproduced
from Maytin[28]) copyright Oxford University Press.

less abundant near dying hair. These compounds supply the hair matrix with
nutrients and having a positive effect on hair growth and appearance thereby
making them stronger, thicker and resistant.[27]

Hyaluronic acid (HA)

HA or hyaluronan is a GAG with unbranched polysaccharide chain con-
sisting of repeated disaccharide units linked by glycosidic bonds. However,
there are some exceptional properties of HA, which enable its distinction
from other GAGs. The sulfuric groups are absent in HA, and it is not able
to covalently bind with proteins, hence related PG are not formed. HA is a
polymer of disaccharides, composed of D-glucuronic acid and D-N-acetyl-
glucosamine, linked via alternating b-1,4 and b-1,3 glycosidic bonds
(Figure 4). It has a high molecular weight (about 100–800 kDa) with 10,000
or more repeating disaccharides units. Moreover, one HA molecule can
bind to approximately 250 water molecules (1 g of HA retains 6 L of water),
thus HA molecules expand in volume and form a network stabilized by
hydrogen bonds.[28] Therefore, it is a hygroscopic biopolymer giving its
polyanionic character at physiological pH and its fluidity depends on the
concentration and molecular weight (Figure 4).
HA as a large hydrophilic molecule confers a large volume of hydration
contributing to the rigidity and flexibility of healthy skin. Studies have found
that HA is produced by skin cells such as fibroblasts (cells of extracellular
matrix) and keratinocytes in the outer protective layer (epidermis). It plays a
regulatory role in these cells by modulating the cellular physiology through
interaction with the cell surface receptor, CD44. The interaction mediates
intracellular signaling with the cytoskeleton and epidermal growth factor
(EGF) and transforming growth factor-beta (TGF-b) receptors. Furthermore,
degradation of HA by specific hyaluronidase enzyme produces fragments
that regulate certain inflammatory processes.[29]
8 H. AHSAN

HA and its sodium and potassium salts are active ingredients of many
moisturizing, protective and anti-aging products. Este’e Lauder was the first
company to use animal HA in cosmetics but is now marketed by various
other biopharmaceutical companies such as Biomatrix (USA), Bio-
Technology General (Israel), Diagnostic Inc. (USA), Fermentech (UK),
Genzyme (USA), Pharmacia (Sweden), Shiseido Co. (Japan), etc. Moreover,
HA is present in creams and lotions produced by L’Oreal, Avon, Olay
Regenersit, etc.[28] It forms a biofilm on the surface of the skin and protects
the stratum corneum (SC). The HA biofilm hinders the transepidermal
water loss (TEWL) and also moisturizes the inner layer of the skin (epider-
mis). In cosmetic formulations, HA increases the water content of the skin
epidermis and prevents the cosmetic product from becoming dry (humec-
tant). L’Oreal adds proxylan which penetrates into skin to revive and
strengthen the production of HA. Since HA is nontoxic, nonirritating and
non-sensitizing and occurs naturally in the skin, it has become a popular
compound for intradermal injections to improve wrinkles and dermocos-
metic defects.[29]

Figure 5 A. Chemical structure of chitin and chitosan (reprinted and reproduced from Younes
and Rinaudo[30]). 5B: Chitin and chitosan chemical structure (adapted and reprinted from
Morganti et al.[31]).
 JOURNAL OF CARBOHYDRATE CHEMISTRY 9

Figure 6 A. Scanning electron micrograph of chitin nanofibrils (adapted and reprinted from
Morganti et al.[31]). 6B. The molecular structure of chitin scaffolds (adapted and reprinted from
Morganti et al.[31]).

Chitin and chitosan

Chitin, poly(b-(1!4)-N-acetyl-D-glucosamine), is a natural polysaccharide
and is the most abundant natural polymers after cellulose. It is synthesized
by animals. It is a linear nitrogen-containing polymer made up of b-(1,4)-
linked N-acetyl-D-glucosamine (NAG) units and is an important constitu-
ent of exoskeleton and shell of crustaceans and fungal cell walls (Figure 5A,
B). Chitin is found in the exoskeleton of crustaceans (crab and shrimp)
forming a crystalline structure to protect them from predators, and the
exopolysaccharides (EPS) secreted by marine bacteria.[5] In natural form,
chitin occurs as ordered crystalline microfibrils forming structural compo-
nents in the exoskeleton of arthropods or the cell wall of fungi and
yeast.[30] Microfibril is a complex structure made up of minerals and pro-
teins in a scaffold which is important for its physicochemical properties.
10 H. AHSAN

The characteristic properties of chitin, such as biodegradability, structural

integrity, nontoxicity to cells and biocompatibility, make it an ideal candi-
date to produce polymeric tissues.[31] Chitin nanofibrils and nanocrystals
maintain cutaneous homeostasis and are a natural carrier for the transcuta-
neous penetration of active compounds (Figure 6A, B). Chitin can be
modified to form chitin nanofibrils as biomaterials which are biocompatible
with human skin cells and nontoxic and biodegradable. These nanofibrils
are also capable of forming complexes with other compounds such as vita-
mins, carotenoids and collagen, facilitating their transcutaneous penetration
(Figure 6A, B).[5]
Chitosan, a linear polymer obtained by the partial deacetylation of
chitin, is composed of glucasamine and N-acetylglucosamine units with
free amino groups and is a partially deacetylated derivative of a natural
polysaccharide chitin. Therefore, chitosan is a linear copolymer of b-(1-
4)-linked 2-acetamido-2-deoxy-b-D-glucopyranose and 2-amino-2-deoxy-
b-D-glycopyranose subunits (Figure 5A, B).[5] Chitosan is a cationic pH-
sensitive polymer, which can be molded into beads, hydrogels, nanofib-
ers and nanoparticles. At relatively acidic pH (pH 6.0), chitosans are
positively charged (–NH3þ) and tend to be soluble in dilute aqueous sol-
utions, but at higher alkaline pH, they tend to lose their charge and
precipitate from solution due to the deprotonation of amino groups.[5]
As a hydrogel, chitosan has superior water absorbing property making it
valuable as a moisturizer. Another important function of chitosan is its
antimicrobial activity which helps to protect from environmental factors
and facilitate their delivery into the skin. Thus, chitosan has been identi-
fied as a novel ingredient in cosmeceutical formulations.[5] Moreover,
chitosans have many useful characteristics such as biorenewability, bio-
degradability, biocompatibility, bioadhesivity and nontoxicity, making
them commercially important. By chemically modifying the amino and
hydroxyl groups, carboxymethyl chitosan can be synthesized by carboxy-
methylation reaction. Carboxymethyl chitosan is a chitosan derivative
and found to be more water soluble than the parent compound.
Carboxymethyl chitosans have been investigated for their cosmetic appli-
cations due to their moisture absorption and retention, anti-microbial
and antioxidant properties, delivery systems and emulsion stabilization.
Therefore, the high water solubility of chitosan derivatives makes them
an ideal candidate for use in cosmetics products.[32]

Fucose and fucoidan

Fucoidan is a group of fucose-containing sulfated polysaccharides (FCSPs),
made up of (1!3)-linked a-L-fucopyranosyl or (1!3) and (1!4)-linked
 JOURNAL OF CARBOHYDRATE CHEMISTRY 11

Figure 7. Fucoidan are sulfated fucose-rich polysaccharides, built of a backbone of L-fucose

units, and characteristically found in brown seaweeds. (Adapted and reproduced from Ale
and Meyer[33]).

a-L-fucopyranosyl residues, sulfated galactofucan consisting of of (1!6)-

b-D-galacto- and/or (1!2)-b-D-mannopyranosyl units with fucose and/or
glucuronic acid, xylose or glucose monomers.[33] Therefore, fucoidans are a
family of sulfated fucose-rich polysaccharides, particularly found in brown
seaweeds (Figure 7).[34] These polysaccharides have a fucose backbone and
are highly branched in algae, whereas echinoderm fucoidans contain linear
structure and are both sulfated and acetylated. Fucoidans are sometimes
considered to be plant homologs of the mammalian heparin and exhibit an
effect on the coagulation cascade and growth factor activity.[35] The fucoi-
dans combine bioactivity, protective properties and are a natural organic
source. The fucoidan-rich macroalgal extracts have a growing role to play
in the nutraceutical market and a strong potential for commercial cosmet-
ics.[35] The cell wall of marine algae are rich in various bioactive polysac-
charides e.g., fucoidans in brown algae, carrageenans in red algae and
ulvans in green algae.[5] Seaweeds, or marine macroalgae, notably brown
seaweeds (class Phaeophyceae), contain fucoidans. Fucoidan from brown
seaweed (Saccharina japonica, Fucus vesiculosus, Undaria pinnatifida and
Hizikia fusiformis) and marine invertebrates, such as sea cucumber, repre-
sent the most abundant and commercially available polysaccharides.[5]
There has been a growing research interest on bioactive fucoidans as a
potential cosmeceutical ingredient. When fucoidans are used in cosmetic
12 H. AHSAN

Figure 8. Mechanism of action of fucoidan: The macrophage activation by FCSPs mediated

through specific membrane receptor activation-TLR4, CD14, CR3, SR which activates intracellular
signaling through mitogen-activated protein kinases (MAPKs) (adapted and reproduced from
Ale et al.[35]).

products, they are topically applied to the skin, due to their property of forming
a protective layer on the surface of the skin enhancing skin hydration. Since
the brown edible algae are rich in fucoidan, and a dietary foodstuff, their con-
sumption could be beneficial in reducing the inflammatory conditions involv-
ing extracellular matrix degradation by metalloproteinases (MMPs).[5] The
MMPs are the enzymes responsible for the degradation of collagen and other
proteins in the extracellular matrix (ECM). Furthermore, fucoidan treatment
increases type I procollagen expression suggesting that it may prevent UV-B-
induced matrix metalloproteinase-1 (MMP-1) expression and inhibit downre-
gulation of type I procollagen synthesis. The UV-B reduces type I procollagen
and increased MMP-1 levels in human skin and plays a major role in photoag-
ing process (Figure 8). Hence, fucoidan has been suggested to have wide appli-
cation as a potential agent to prevent and treat skin photoaging. Fucoidans
were also shown to exhibit an immunomodulatory effect on various bio-
markers affecting the inflammatory and immune response.[35] Fucoidans is
considered to be a dietary fiber and are nontoxic in cell cultures. There were no
toxicological changes observed in rats that orally administered (300 mg/kg
body weight) fucoidan from Laminoria japonica. The anticoagulant effects
 JOURNAL OF CARBOHYDRATE CHEMISTRY 13

Figure 9 A. Red seaweed agaro-oligosaccharide (AOS) and carrageenan-oligosaccharide (COS)

(adapted and reproduced from Cheong et al.[36]). 9B. AOS, COS (adapted and reproduced from
Cheong et al. [36]).

were observed at even higher doses (900–2,500 mg/kg body weight) with no
evident sign of toxicity.[35]
Fucoidans are important nutraceutical ingredients with significant potential
for topical cosmetic formulations. The purified fractions can be easily incor-
porated into creams and lotions, providing anti-aging benefits such as inhib-
ition of matrix enzymes, anti-inflammatory activity, and increasing the
numbers of dermal fibroblasts and collagen firmness. The key focus has been
14 H. AHSAN

Figure 10. The chemical structure of carrageenan subunits (adapted and reproduced from
Anbuchezhian et al.[24]) copyright Springer and Capital Publishing Company.

on the inhibitory effects of topically applied fucoidan on aging and ultraviolet

radiation induced- skin damage. Fucoidan is an effective inhibitor of C-X-C
Motif Chemokine Receptor (CXCR4) and inhibits the accumulation of eosi-
nophils in models of allergic skin infammation. As nutraceutical ingredients
they offer unique opportunities in immunomodulation and rejuvenation. The
topical application of heparin is useful in the treatment of burns and CXCR4
interaction may result in better hea1ing. Hence, fucoidans have the potential
as a topical and oral anti-inflammatory agent for sunburns, soothing product
on allergic skin and a postsurgical agent to inhibit eosinophilia.[34]

Carrageenan and alginate

Carrageenan is a linear sulfated polysaccharide composed of D-galactose
units (Figure 9), derived from marine red algae and is one of the most
 JOURNAL OF CARBOHYDRATE CHEMISTRY 15

commonly used polysaccharides in cosmeceuticals.[5,11] Carrageenan can be

classified into three types based on their structure and chemical properties,
viz., kappa carrageenan, iota-carrageenan and lambda-carrageenan which
have one, two and three sulfate groups per disaccharide, respectively
(Figure 10). They are composed of a linear galactose backbone having
varying degree of sulfatation (15–40%). The carrageenans vary in compos-
ition and conformation resulting in a wide range of functional proper-
ties.[24] Marine organisms are rich in carbohydrates mostly in the form of
sulfated and non-sulfated polysaccharides representing a good source of
nutrients. The carbohydrates extracted from marine algae have attracted
the attention due to their applications in the food, pharmaceutical and
cosmetic industries. Seaweeds containing sulfated polysaccharides have the
potential due to its antiviral, antioxidant, anticancer, immunomodulating,
antilipidepic properties. Sulfated polysaccharides are an important product
in cosmetics for its antiaging, antioxidant, and anticarcinogenic activity.
The gelling ability of carrageenan from marine algae is useful in produc-
ing a thicker texture with good consistency in many products such as
skin lotions, toothpaste binders and shaving foams.[5,11]
Alginates (algin) are linear polyuronic acid polysaccharide glycuronans of
commercial importance obtained from marine brown seaweeds. The cell
walls of brown algae contain alginates providing mechanical strength and
flexibility to the algae. Alginates are made of two units of guluronic and
mannuronic acids consisting of (1!4) linked b-D-mannuronic acid (M)
and a-L-guluronic acid (G) residues (Figure 11).[24] The alginates have a
wide range of applications in the cosmeceuticals due to their stability, and
as a thickening and gelling agent and antioxidant activity. It has applica-
tions in plastic surgery and wound healing due to hydrogel formation and
degradability.[5]

Figure 11. The repeating units of alginate: mannuronate (M) and guluronate (G) (adapted and
reproduced from Anbuchezhian et al.[24]) copyright Springer and Capital Publishing Company.
16 H. AHSAN

Immunopharmacology of polysaccharide cosmeceuticals

Cosmeceuticals refer to cosmetic products that have medicinal benefits and
topical biopharmaceutical products intended to enhance the health and
beauty of skin. Many of the cosmeceuticals available in the market seem
very exciting but care should be taken to choose the best products. Hence,
there is an increasing requirement to regulate the manufacture and use of
cosmeceuticals.[37,38] As technology advances and cosmeceuticals continue
to become more sophisticated and widely used, the physicians must con-
tinue to take an active role in familiarizing themselves with these products
and in educating patients about the benefits and risks of cosmeceuticals.[39]
The understanding of the phenomena behind skin damage and aging and
the utilization of natural products against such damages highlight the
importance of cosmetics as skin-protective agents rather than being mere
ornamental. The direct exposure of skin to the environment makes it sensi-
tive and vulnerable to damage from UV radiation and can result in aging,
pigmentation, and wrinkle formation. The UV radiation is a primary regu-
lator of melanin and it can be utilized for preventing skin-pigmentation,
freckling, and age-spot appearance. The marine seaweed oligosaccharides
have been found to be useful in vitro studies as potential cosmetics for
skin-whitening since they suppress melanin production. Moreover, they
have been successfully tested in vitro, suggesting their potential use as skin
moisturizers.[36]
Allergic reactions on the skin produce side effects including sensitivity,
dermatitis, asthma and migraine.[40] Cosmetic products contain potential
contact allergens or precursors that require metabolic conversion or oxida-
tion to generate contact allergens. The contact allergens are fragrances and
preservatives which pose a health hazard to humans due to their ability to
activate T cells causing allergic contact dermatitis (ACD).[41,42] Allergic
contact dermatitis is an inflammatory skin disease characterized by erythema
which may develop into a chronic condition with scaling and painful fissures
on the skin.[43] It may sometimes spread to other areas of the body not in
direct contact with the allergen and is comparable to a systemic exposure (the
allergen may reach the skin through circulation and produce systemic con-
tact-type dermatitis).[41] Atopic dermatitis (AD) or eczema is an inflammatory
skin condition which affects nearly 15–30% of children and 2–10% adults.
The clinical strategy to manage AD involves prescribing anti-inflammatory
medications and dermocosmetic products. A moisturizing cream or emollient
which restores the skin barrier with ingredients able to revive natural cutane-
ous defenses by providing nutritional supplements to regulate the cutaneous
microbiota offers the best option for management of AD.[44] Therefore, cos-
metics such as epidermal creams for anti-aging and moisturizing lotions with
 JOURNAL OF CARBOHYDRATE CHEMISTRY 17

Figure 12. The application and target of cosmetic products on the outer layers of skin: 1. The
stratum corneum (SC), the outermost layer of the skin consisting of mostly dead skin cells is a
major barrier to harmful substances; 2. The epidermis, the major outer thin layer of skin. The
figure show the probable routes of transport of therapeutic products through them: (A) intercel-
lular through lipid bilayers, (B) transcellular through keratinocytes (C) Shunt through hair fol-
licles and sweat glands (Adapted and reprinted from Zakrewsky et al.[44]) copyright Elsevier.

complex polysaccharides can be designed for the regeneration of epidermal

layer of the skin by influencing the local immune system (Figure 12).

Polysaccharide as delivery vehicles and stabilizers for cosmetics

Chitin is the most abundant aminopolysaccharide polymer occurring in
nature and is the building material that gives strength to the exoskeletons
of crustaceans and insects and cell wall of fungi. The shrimp and crab
shells, a natural source of chitin, are an abundant byproduct of the food-
processing industry providing a large quantity of the biopolymer for use in
biomedical applications. Due to unique properties, chitin and chitosan,
have found many promising biomedical applications. Nanotechnology has
also increasingly applied chitin and chitosan-based materials recently such
as fabrication of polymer scaffolds. Moreover, the use of chitosan to pro-
duce designed-nanocarriers and to enable microencapsulation techniques is
under increasing investigation for the delivery of drugs, bioactives and vac-
cines. Chitosan can be successfully used in solution, as hydrogels and/or
nano/microparticles, and an endless array of derivatives with customized
biochemical properties can be prepared. Therefore, chitin and chitosan are
being increasingly considered for tissue engineering, wound dressings, anti-
microbial agents, antiaging cosmetics, and vaccine adjuvants.[45]

Conclusion
Carbohydrates are the most abundant biomolecules and essential compo-
nents which have attracted the attention of researchers because of their
18 H. AHSAN

numerous health benefits. Among carbohydrates, the complex polysacchar-

ides, such as chitin, chitosan, fucoidan, carrageenan and alginate, have
numerous biopharmaceutical activities, such as antioxidant, antibacterial,
antiviral, immunomodulating, anticoagulant and anticancer effects.
Therefore, these polysaccharides have been developed into potential cosme-
ceuticals and nutraceuticals. However, technological advancements of bio-
markers in biomedical sciences are essential for identification and
understanding of ingredients in cosmetic preparations.

Acknowledgments
This review article is dedicated to the memory of my late beloved father. He was the great-
est father and husband, an extraordinary and remarkable gentleman and above all the finest
human being. We all miss him so much that life will never be the same again without him.
The author wishes to thank Dr. Fahim H. Khan, Aligarh for his insight and suggestions.
HA also wishes to that thank those authors from whose work the various data/tables/fig-
ures have been adapted and reprinted. The figures have been reprinted and reproduced
with permission from authors, publishers or from open access articles with due acknow-
ledgment and citations. The various cosmetic companies such as L’Oreal, Avon, Olay
Regenersit, Este’e Lauder, Biomatrix, Bio-Technology General, Diagnostic Inc., Fermentech,
Genzyme, Pharmacia, Shiseido Co., etc. are the license holders and copyright owners of the
products mentioned in the review article and have also been acknowledged wherever pos-
sible whose products are available in the market.

ORCID
Haseeb Ahsan http://orcid.org/0000-0002-5313-5959

References
[1] Ahsan, H. The Biomolecules of Beauty: biochemical Pharmacology and
Immunotoxicology of Cosmeceuticals. J. Immunoassay Immunochem. 2019, 40,
91–108. doi:10.1080/15321819.2018.1555766.
[2] Siti Zulaikha, R.; Sharifah Norkhadijah, S. I.; Praveena, S. M. Hazardous Ingredients
in Cosmetics and Personal Care Products and Health Concern: A Review. Public
Health Res. 2015, 5, 7–15.
[3] Kligman, A. M. Cosmetics. A dermatologist looks to the future: promises and prob-
lems. Dermatol. Clin. 2000, 18, 699–709.
[4] Kim, S. K. Marine Cosmeceuticals. J. Cosmet. Dermatol. 2014, 13, 56–67. doi:
10.1111/jocd.12057.
[5] Ruocco, N.; Costantini, S.; Guariniello, S.; Costantini, M. Polysaccharides from the
Marine Environment with Pharmacological, Cosmeceutical and Nutraceutical
Potential. Molecules 2016, 21, pii:551. doi:10.3390/molecules21050551.
[6] Thomas, N. V.; Kim, S. K. Beneficial Effects of Marine Algal Compounds in cosme-
ceuticals. Mar. Drugs. 2013, 11, 146–164. doi:10.3390/md11010146.
 JOURNAL OF CARBOHYDRATE CHEMISTRY 19

[7] Semenzato, A.; Costantini, A.; Baratto, G. Green Polymers in Personal Care
Products: Rheological Properties of Tamarind Seed Polysaccharide. Cosmetics 2014,
2, 1–10. doi:10.3390/cosmetics2010001.
[8] Brode, G. L. Polysaccharides: “Naturals” for Cosmetics ad Pharmaceuticals. In
Cosmetic and Pharmaceutical Applications of Polymers; Gebelein, C.G., Cheng, T.C.,
Yang V.C., Eds. Springer: Boston, MA, 1991.
[9] Moore, A. The the Biochemistry of Beauty the Science and Pseudo-Science of
Beautiful Skin. EMBO Rep. 2002, 3, 714–717. doi:10.1093/embo-reports/kvf169.
[10] de Camargo Junior, F. B.; Gaspar, L. R.; Campos, P. Immediate and Long-Term
Effects of Polysaccharides-Based Formulations on Human Skin. Braz. J. Pharm. Sci.
2012, 48, 547–555. doi:10.1590/S1984-82502012000300022.
[11] Ahmed, A. B.; Adel, M.; Karimi, P.; Peidayesh, M. Pharmaceutical, Cosmeceutical,
and Traditional Applications of Marine Carbohydrates. Adv. Food Nutr. Res. 2014,
73, 197–220.
[12] Colliec-Jouault, S.; Bavington, C.; Delbarre-Ladrat, C. Heparin-Like Entities from
Marine Organisms. Handb. Exp. Pharmacol. 2012, 207, 423–449.
[13] Jimenez-Escrig, A.; Gomez-Ord ~ez, E.; Ruperez, P. Seaweed as a Source of Novel
on
Nutraceuticals: sulfated Polysaccharides and Peptides. Adv. Food Nutr. Res. 2011, 64,
325–337.
[14] Pomin, V. H. Review: An Overview about the Structure-Function Relationship of
Marine Sulfated Homopolysaccharides with Regular Chemical Structures.
Biopolymers 2009, 91, 601–609. doi:10.1002/bip.21200.
[15] Mycroft-West, C. J.; Yates, E. A.; Skidmore, M. A. Marine Glycosaminoglycan-like
Carbohydrates as Potential Drug Candidates for Infectious Disease. Biochm. Soc.
Trans. 2018, 46, 919–929. doi:10.1042/BST20170404.
[16] Xu, S. Y.; Huang, X.; Cheong, K. L. Recent Advances in Marine Algae
Polysaccharides: isolation, Structure, and Activities. Mar. Drugs 2017, 15, pii:388.
doi:10.3390/md15120388.
[17] Shi, Q.; Wang, A.; Lu, Z.; Qin, C.; Hu, J.; Yin, J. Overview on the Antiviral
Activities and Mechanisms of Marine Polysaccharides from Seaweeds. Carbohydr.
Res. 2017, 453-454, 1–9. doi:10.1016/j.carres.2017.10.020.
[18] Lee, Y. E.; Kim, H.; Seo, C.; Park, T.; Lee, K. B.; Yoo, S. Y.; Hong, S. C.; Kim, J. T.;
Lee, J. Marine Polysaccharides: Therapeutic Efficacy and Biomedical Applications.
Arch. Pharm. Res. 2017, 40, 1006–1020. doi:10.1007/s12272-017-0958-2.
[19] Cunha, L.; Grenha, A. Sulfated Seaweed Polysaccharides as Multifunctional
Materials in Drug Delivery Applications. Mar. Drugs 2016, 14, pii:42. doi:10.3390/
md14030042.
[20] Ahmadi, A.; Zorofchian Moghadamtousi, S.; Abubakar, S.; Zandi, K. Antiviral
Potential of Algae Polysaccharides Isolated from Marine Sources: A Review. Biomed.
Res. Int. 2015, 2015, 1. doi:10.1155/2015/825203.
[21] Jiao, H.; Shang, X.; Dong, Q.; Wang, S.; Liu, X.; Zheng, H.; Lu, X. Polysaccharide
Constituents of Three Types of Sea Urchin Shells and Their Anti-Inflammatory
Activities. Mar. Drugs 2015, 13, 5882–5900. doi:10.3390/md13095882.
[22] Vo, T. S.; Ngo, D. H.; Kang, K. H.; Jung, W. K.; Kim, S. K. The Beneficial
Properties of Marine Polysaccharides in Alleviation of Allergic Responses. Mol.
Nutr. Food Res. 2015, 59, 129–138. doi:10.1002/mnfr.201400412.
[23] Vo, T. S.; Kim, S. K. Marine-Derived Polysaccharides for Regulation of Allergic
Responses. Adv. Food Nutr. Res. 2014, 73, 1–13. doi:10.1016/B978-0-12-800268-
1.00001-9.
20 H. AHSAN

[24] Anbuchezhian, R.; Karuppiah, V.; Li, Z. Chapter 9. Prospect of marine algae for
production of industrially important chemicals. Debabrata Das (Editor) Algal
Biorefinery: An integrated approach, Co-published by Springer International
Publishing, Cham, Switzerland, with Capital Publishing Company, New Delhi, India.
Springer Cham Heidelberg New York Dordrecht London # Capital Publishing
Company 2015, pp. 195–217.
[25] K€owitsch, A.; Zhou, G.; Groth, T. Medical Application of Glycosaminoglycans: A
Review. J. Tissue Eng. Regen. Med. 2018, 12, e23–e41. doi:10.1002/term.2398.
[26] Yamada, S.; Sugahara, K.; Ozbek, S. Evolution of Glycosaminoglycans: Comparative
Biochemical Study. Commun. Integr. Biol. 2011, 4, 150–158. doi:10.4161/cib.4.2.14547.
[27] Kroma, A.; Feliczak-Guzik, A.; Nowak, I. The Use of Glycosaminoglycans in
Cosmetic Products. Chemik 2012, 66, 136–139.
[28] Olejnik, A.; Goscianska, J.; Nowak, I. Significance of Hyaluronic Acid in Cosmetic
Industry and Aesthetic Medicine. Chemik 2012, 66, 129–135.
[29] Maytin, E. V. Hyaluronan: More than Just a Wrinkle Filler. Glycobiology 2016, 26,
553–559. doi:10.1093/glycob/cww033.
[30] Younes, I.; Rinaudo, M. Chitin and Chitosan Preparation from Marine Sources.
Structure, Properties and Applications. Mar. Drugs 2015, 13, 1133–1174. doi:
10.3390/md13031133.
[31] Morganti, P.; Danti, S.; Coltelli, M. B. Chitin and Lignin to Produce Biocompatible
Tissues. Res. Clin. Dermatol. 2018, 1, 5–11.
[32] Jimtaisong, A.; Saewan, N. Utilization of Carboxymethyl Chitosan in Cosmetics. Int.
J. Cosmet. Sci. 2014, 36, 12–21. doi:10.1111/ics.12102.
[33] Ale, M. T.; Mikkelsen, J. D.; Meyer, A. S. Important Determinants for Fucoidan
Bioactivity: A Critical Review of Structure-Function Relations and Extraction
Methods for Fucose-Containing Sulfated Polysaccharides from Brown Seaweeds.
Mar. Drugs 2011, 9, 2106–2130. doi:10.3390/md9102106.
[34] Ale, M. T.; Meyer, A. S. Fucoidans from Brown Seaweeds: An Update on Structures,
Extraction Techniques and Use of Enzymes as Tools for Structural Elucidation. RSC
Adv. 2013, 3, 8131–8141. doi:10.1039/C3RA23373A.
[35] Fitton, J. H.; Irhimeh, M.; Falk, N. Macroalgal Fucoidan Extracts: A New
Opportunity for Marine Cosmetics. Cosmet. Toiletries Mag. 2007, 122, 55–64.
[36] Cheong, K. L.; Qiu, H. M.; Du, H.; Liu, Y.; Khan, B. M. Oligosaccharides Derived
from Red Seaweed: Production, Properties, and Potential Health and Cosmetic
Applications. Molecules 2018, 23, pii:2451. doi:10.3390/molecules23102451.
[37] Vermeer, B. J.; Gilchrest, B. A. Cosmeceuticals. A Proposal for Rational Definition,
Evaluation, and Regulation. Arch. Dermatol. 1996, 132, 337–340.
[38] Ligade, V. S.; Sreedhar, D.; Manthan, J.; Udupa, N. Cosmeceuticals: Are They Truly
Worth the Cost? Indian J. Dermatol. Venereol. Leprol. 2009, 75, 89.
[39] Martin, K. I.; Glaser, D. A. Cosmeceuticals: The New Medicine of Beauty. Mo. Med.
2011, 108, 60–63.
[40] Goossens, A. Contact-Allergic Reactions to Cosmetics. J. Allergy (Cairo) 2011, 2011,
467071. doi:10.1155/2011/467071.
[41] Martin, S. F. Mechanistic Understanding of Contact Allergy. Cosmetics 2016, 3, 8.
doi:10.3390/cosmetics3010008.
[42] Beri, K. Skin Microbiome & Host Immunity: Applications in Regenerative
Cosmetics & Transdermal Drug Delivery. Future Sci. OA 2018, 4, FSO302. doi:
10.4155/fsoa-2017-0117.
 JOURNAL OF CARBOHYDRATE CHEMISTRY 21

[43] Seite, S.; Bieber, T. Barrier Function and Microbiotic Dysbiosis in Atopic
Dermatitis. Clin. Cosmet. Investig. Dermatol. 2015, 8, 479–483.
[44] Zakrewsky, M.; Kumar, S.; Mitragotri, S. Nucleic Acid Delivery into Skin for the
Treatment of Skin Disease: Proofs-of-Concept, Potential Impact, and Remaining
Challenges. J. Control Release 2015, 219, 445–456. doi:10.1016/j.jconrel.2015.09.017.
[45] Elieh-Ali-Komi, D.; Hamblin, M. R. Chitin and Chitosan: Production and
Application of Versatile Biomedical Nanomaterials. Int. J. Adv. Res. (Indore). 2016,
4, 411–427.