CHAPTER NINE

Nutraceutical and
Pharmacological Implications
of Marine Carbohydrates
Ramjee Pallela1
Synthetic Biology and Biofuels Group, International Centre for Genetic Engineering and Biotechnology,
New Delhi, India
1
Corresponding author: e-mail address: rpallela@icgeb.res.in

Contents
1. Introduction 183
2. Marine Carbohydrate Sources 184
3. Marine Carbohydrates as Nutraceuticals 188
4. Marine Carbohydrates as Pharmaceuticals 189
5. Conclusion 191
References 191
Further Reading 195

Abstract
Current day's research has been focusing much on the potential pharmacological or
nutraceutical agents of selective health benefits with less toxicity. As a consequence
of increased demand of nutritional supplements of great medicinal values, develop-
ment of therapeutic agents from natural sources, in particular, marine environment
are being considered much important. A diverse array of marine natural products con-
taining medicinally useful nutritional substances, i.e., marine nutraceuticals have been
focused to the benefit of mankind. Carbohydrates, by being constituted in considerable
amount of many marine organisms display several nutraceutical and pharmaceutical
behavior to defend from various diseases. Moreover, the carbohydrates from algae
as well as from shellfish wastes, like chitosan and its derivatives, showed tremendous
applications in biology and biomedicine. In the current chapter, several of marine
carbohydrates from various marine flora and fauna have been covered with their appli-
cations and prospects in the development of nutraceuticals and pharmaceuticals.

1. INTRODUCTION
Carbohydrates along with protein and lipid molecules play a notice-
able contributory role in nutraceuticals and pharmaceutical development.

Advances in Food and Nutrition Research, Volume 73 # 2014 Elsevier Inc. 183
ISSN 1043-4526 All rights reserved.
http://dx.doi.org/10.1016/B978-0-12-800268-1.00009-3
184 Ramjee Pallela

Because of their possession of moderate barrier properties against diffusion of

oxygen and moisture, most of them exhibit enhanced stability of protein-
based emulsions (Colin et al., 2007). Although several carbohydrate mole-
cules are commercially been used as nutraceuticals, food supplements, or
pharmaceuticals to treat various diseases, natural sources of carbohydrates
like gum-arabic, derivatives from starch, cellulose derivatives, carrageenan,
alginate are gaining tremendous importance keeping in view of traditional
and ancient values of these sources. A great attention has been paid recently
by the consumers toward natural bioactive substances that act as functional
ingredients in the diets, which show several beneficial health effects (Zhang,
Li, & Kim, 2012). Moreover, marine-based medicinal foods like macroalgae
(seaweeds) are identified with several nutraceutically and pharmacologically
important carbohydrate molecules and moieties to combat several health
complications ( Jiménez-Escrig, Gómez-Ordóñez, & Rupérez, 2011).
Algae, by being a major constituent in the daily based diet in many of the
Asian countries, play significant role in better health of human beings. This
extensive use of algal foods augmented the interest of many researchers to
find out unique pharmacological and nutraceutical leads that work against
many health complications. The interest in marine nutraceuticals inspired
researchers to concentrate on several bioprocessed marine products as alter-
native sources for synthetic nutritional ingredients, as a part of nutraceuticals
and functional foods via the development of suitable technologies, one for an
example, the ultrafiltration membrane bioreactor system ( Jeon & Kim,
2000; Kim & Senevirathne, 2011). In addition, the polymeric macromole-
cules, e.g., chitosan and its derivatives, are mined from sea to their eventual
application in health and medicine via the extraction of these molecules
from shellfish wastes (Hayes, Carney, Slater, & Brück, 2008). Chitosan
and chitooligosaccharides (COS) and their derivatives have been proved
for their best implications as nutraceutical and pharmacological moieties
to play major role against some important health complications (Kim,
2010; Xia, Liu, Zhang, & Chen, 2011). The current chapter covers an over-
all nutraceutical and pharmacological potential of marine-based carbohy-
drates from various animals and plants to give a note on the perspectives
and prospects of using marine carbohydrates.

2. MARINE CARBOHYDRATE SOURCES

Over the last few decades, medical and pharmacological industries as
well as academic research institutions have gained increased interest in
Marine Carbohydrates as Nutraceuticals and Pharmaceuticals 185

marine-based carbohydrates. This is because of the wide potentiality of

marine carbohydrates and their application in several biological, biomedical,
and nutritional fields. The molecular weights, structural parameters, and
physiological characteristics of marine carbohydrates are diverse in the sense;
therefore, they behave accordingly to result in specific bioactivities such as
antiproliferative, antitumor, antiviral, anticoagulant, antioxidant, anti-
inflammatory effects, etc.
Majority of marine organisms with potential carbohydrates are macro-
algae or seaweeds that produce vast number of carbohydrates, localized
within the intercellular spaces (Kraan, 2012). The three types of marine algae
viz., green algae (Chlorophyta), red algae (Rhodophyta), and brown algae
(Phaeophyta) contain sulfated polysaccharides (SPs), sulfated galactans,
xylans, alginic acid, fucoidan (sulfated fucose), laminarin (β-1, 3 glucan)
and sargassan, agar, carrageenans, xylans, floridean starch (amylopectin-like
glucan), water-soluble sulfated galactan, as well as porphyran as mucopoly-
saccharides. Algal species that produce these important carbohydrates along
with other polysaccharide sugars like rhamnose, arabinose, glucose, galac-
tose, fucose, etc., have been covered in other sections of this book to specify
their biomedicinal properties. However, some important species of algae,
Ecklonia cava, Ecklonia kurome, Laminaria japonica, Laminaria digitata, Lessonia
vadosa, Porphyra haitanensis, Ascophyllum nodosum, Nothogenia fastigiata, Sargas-
sum horneri, Gigartina skottsbergii, Schizymenia binderi, Grateloupia indica, Mon-
ostroma latissimum, Codium fragile, Undaria pinnatifida, Codium pugniformis,
Caulerpa racemosa, Ulva conglobata, Ulva pertusua, Ulva lactuca, Gayralia oxy-
sperma, Cryptonemia crenulata, Nemalion helminthoides are to be exemplified
for their medicinal as well as nutritional interest (Wijesekara,
Pangestuti, & Kim, 2011). Most of these species are with higher biomass
and the possible edibility of them is an attracting characteristic feature to
use them in medicinal foods by direct consumption through diet and indi-
rect consumption through the extracted nutraceutical and functional food
molecules. Polysaccharides, especially from marine red and brown algae,
have been isolated and characterized for their anticoagulant activity.
Macroalgal polysaccharides such as carrageenans (Chondrus, Eucheuma,
and Kappaphycus), alginates (Ascophyllum and Laminaria), algal polysaccha-
rides (Macrocystis), and agars (Gelidium and Gracilaria) are of much industrial
application purpose, which are having much economic potential. Sulfated
galactans and sulfated fucans from Ulva fasciata exhibit high anticoagulant
activity, which may address their use in functional foods and nutraceuticals.
Despite of the much anticoagulant activity from the polysaccharides of
186 Ramjee Pallela

brown and red algae, however, there are very few reports of anticoag-
ulant polysaccharides green algae (Govindan, Thomas, Pratheesh, &
Muraleedhara, 2012). Similarly, polysaccharides are isolated and character-
ized from marine green algae (Ulva) of Kerala coast of India based on the
bioactive and bioeconomic importance of Ulva species (Govindan, 2012).
Despite of the generally available SPs, several other carbohydrate species like
furcellaran, funoran, ascophyllan and sargassan, uronic acid, rhamnose,
xylose, glucose, mannose, mannitol, and galactose as monosaccharide
components were also found in macroalgae. Another combinatorial polysac-
charide, termed phycocolloid, is used to refer to three main products
viz., alginate, carrageenan, and agar, which are extracted from brown and
red seaweeds, respectively.
Even microalgal species of marine environment can be produced at high
biomass to produce highly potential bioactive molecules from lipid, protein,
and carbohydrate molecules. Microalgal biomass, moreover, is not only rich
in lipids but also in carbohydrates and proteins where the lipid-extracted
microalgal debris consists of mainly proteins and carbohydrates used directly
for animal feed. These leftover materials can further be redirected to process
them for the extraction of required carbohydrate molecules of nutraceutical
interest (Pleissner & Lin, 2013). Phytoplanktons, on the other hand, possess
valuable carbohydrates of medicinal value, e.g., chrysolaminaran an abun-
dant type of storage carbohydrate present in marine phytoplanktons like
Phaeocystis and diatoms (Kurita, 2006). The cycling of carbohydrates is
one of the most important processes in the marine carbon cycle to determine
the carbohydrate composition of the biomass of phytoplankton. It is
reported that Phaeocystis is a cosmopolitan in nature and known to produce
copious amounts of carbohydrates majorly, the extracellular mucopolysac-
charides in the colony matrix and storage glucans, of which chrysolaminaran
is the main constituent.
Moreover, the marine microbial carbohydrates have been screened
structurally and functionally for their potential applications in pharmaceuti-
cals, adhesives, and textile industries (Kim, 2013).
Marine animals although contribute in diversified medical and health
applications through the production of various macro- and micromolecules
like proteins, lipids, and carbohydrates, the application of marine polysac-
charides limited majorly to the chitin, chitosan, and its derivatives produced
from shellfish. Properties of chitosan solutions are similar to those of cellu-
lose ethers and thus one may imply the established cellulose applications
to chitosan for its effective conversion to further derivatives like COS
Marine Carbohydrates as Nutraceuticals and Pharmaceuticals 187

(Xia et al., 2011). Shellfish comprise crustaceans (shrimps, lobsters, and crabs)
and molluscs (such as scallops, cockles, mussels, clams, and oysters). Shellfish
wastes from scallops (Chlamys hastate), cockles (Cerastoderma edule, Clinocardium
nuttalli), whelks (Buccinum undatum), clams and mussels (Mercenaria mercenaria,
Mytilus galloprovincialis, Mytilus edulis), oysters (Crassostrea gryphoides, Crassostrea
gigas), and crustaceans (crab—Cancer pagurus; lobster—Nephrops norvegicus
Homarus americanus; shrimp—Crangon crangon) have been redirected toward
the developments of various biopolymers of importance that can be used as
nutritional substances, animal feed, biomedical materials, etc. As the emerging
interest of using animal foods especially of marine origin, the consumption
rate of several shellfish species has been increasing annually. However, the
processing of these shellfish wastes is costly and only a few regions in the world
would be able to produce required quantities of chitin, chitosan, and their
derivatives toward their implication in biological and biomedical fields
(Archer, Watson, Garret, & Large, 2005). In addition, the use and application
of these derivatives in medical and pharmacological sectors is very limited as
shellfish waste is classed as a “Category 3 animal by-product,” which has to be
handled and approved properly by the suitable legislation authorities
(Mangi & Catchpole, 2012).
According to the simplest process described by Dutta et al. (2004),
obtaining chitosan from marine animals involved four important steps
for producing chitosan from chitin, for instance, from crustacean shells
viz., (i) deproteination, (ii) demineralization, (iii) decoloration, and
(iv) deacetylation; and further the development of COS is possible from
the membrane bioreactor system via enzyme hydrolysis (chtiosanase treat-
ment) method ( Dutta, Dutta, & Tripati, 2004; Jeon & Kim, 2000). Several
stages of this whole processing were demonstrated as a simple flow diagram
in Scheme 9.1.
Further the COSs, which are the degraded products of chitosan or chitin,
have been produced by several methods, such as enzymatic and acidic

Crustacean shells Size reduction Deproteination (NaOH) Washing

Demineralization (HCl) Washing  Dehydration Decoloration Chitin
Deacetylation (NaOH) Washing  Dehydration Chitosan Enzymatic hydrolysis
(chitosanase) in membrane reactor system or Chemical hydrolysis (acids)
Chitooligosaccharides (COS)
Scheme 9.1 A stepwise process of producing chitosan and chitooligosaccharides from
shellfish wastes.
188 Ramjee Pallela

hydrolysis, to use these derivatives in multiple biological applications (Xia

et al., 2011). Comprehensive studies on the properties and new modification
reactions of chitin, chitosan, COS, and their derivatives are being conducted
to apply these macromolecules in the promising fields of medicine, phar-
macy, cosmetics, toiletries, food processing, agriculture, etc. (Kim, 2010;
Kurita, 2006).
Similarly, clandosan is also a kind of polymeric carbohydrate molecule
from crustacean chitin has been used in fertilizing applications because of
its insecticidal or nematocidal behavior (Spiegel, Chet, Cohn, Galper &
Sharon, 1988). However, the nutritional or pharmacological applications
of clandosan are not well studied.

3. MARINE CARBOHYDRATES AS NUTRACEUTICALS

Most of the Asian countries use macroalgae as food for human con-
sumption, which are the primary source of hydrocolloids such as agar, car-
rageenan, and alginate that possess profuse industrial applications, for
example, gelling, stabilizing, or binding agents. Like other plants, marine
algae contain nutritional elements like proteins, lipids, carbohydrates, vita-
mins, and minerals; the content of these elements varies depending on season
and the area of production (Holdt & Kraan, 2011). Marine algae contain
large amounts of polysaccharides, remarkably the cell wall structural poly-
saccharides, but also the mucopolysaccharides and other storage polysaccha-
rides (Kraan, 2012). The dietary fibers of seaweeds contain valuable
nutritional substances, hence the use of seaweeds as marine medicinal foods
brings much attention to use them in meal, functional foods, and
nutraceuticals for human consumption, because the polysaccharides show
tremendous biological activities like antitumor, antihepatitic, antimicrobial,
as well as antiviral activities (Ghosh et al., 2009; McHugh, 1987). SPs, one of
the best examples of the seaweed polysaccharides, are nontoxic and possess
tremendous antioxidative capacity. These antioxidant principles of marine
algal polysaccharides are an indicative of developing them as potential func-
tional foods or nutraceuticals as well (Wijesekara et al., 2011). In addition,
fucose rich SPs, fucoidans of brown seaweeds have tremendous significance
of their use as nutraceuticals despite of other biological and biomedical
applications (Wijesinghe & Jeon, 2012). It is interesting to note that the
fucoidan-based products are taken up to the level of commercialization,
e.g., Marinova Pty Ltd. supplies commercial volumes of fucoidan extract
and their derivatives, further formulated to the purity levels of up to 95%
Marine Carbohydrates as Nutraceuticals and Pharmaceuticals 189

(Kraan, 2012). Further, it is noted that several species like Undaria sp.,
Lessonia sp., Macrocystis sp., Cladosiphon sp., Durvillea sp., Laminaria sp.,
Ecklonia sp., Fucus sp., Sargassum sp., Ascophyllum sp., and Alaria sp. are con-
sidered to be Halal and Kosher certified.
Animal carbohydrates like chitosan, COS, and their further derivatives
are also gaining some importance of using as nutraceuticals (Barrow &
Shahidi, 2007; Fernandes et al., 2012). According to the reports of
Fernandes et al. (2012), the modeling studies of COS should also be impor-
tant to evaluate the efficacy in modern therapeutic strategies, as it is in the use
of nutraceuticals. COS has gained much importance by nutritional and func-
tional food experts to use them in daily supplements because of the high sol-
ubility and biological compatibility of COS. Although application of
chitosan as some dietary supplement is biomedically significant to decrease
body weight and serum lipids through gastrointestinal fat binding, its efficacy
remains in dispute (Mhurchu et al., 2004). Hence, possible use of COS is
well advised because of its easy solubility and miscibility in the biological
systems to act at the targeted areas. However, high costing situations and
severe environmental concerns on the disposal and discarding of marine
processing wastes have led the researchers to show an amplified interest in
the identification and extraction and the development of low cost but high
value by-products from shellfish wastes via sustainable technologies (Hayes
et al., 2008).

4. MARINE CARBOHYDRATES AS PHARMACEUTICALS

SPs in the cell walls of marine algae, e.g., fucoidans in brown algae,
carrageenans in red algae, and ulvans in green algae contribute major appli-
cation in the development of nutraceuticals, pharmaceuticals, and cos-
meceuticals (Wijesekara et al., 2011). The antioxidant capabilities of the
SPs are a gained advantage for the researchers to apply them in pharmaceu-
tical industries as well as nutraceutical industries.
Among the animal-derived marine carbohydrates, majorly, chitosan
and its derivatives have been involved in several pharmacological applica-
tions as these carbohydrate macromolecules have unique properties of acting
as excipients to deal with various health complications (Dodane & Vilivalam,
1998; Illum, 1998) (Table 9.1). Moreover, chitin and chitosan-based
nanofibers are contributed in the development of conventional and novel
pharmaceutical products, because of their favorable biological properties
such as nontoxicity, biocompatibility, biodegradability, and antibacterial
190 Ramjee Pallela

Table 9.1 Pharmaceutical applications of chitosan, chitooligosaccharides, and their

derivatives.
Route of
administration Delivery system References
Oral Microparticulate Lorenzo-Lamosa, Remuñán-López, Vila-Jato,
and Alonso (1998)
Liposomes Takeuchi, Yamamoto, Niwa, Hino, and
Kawashima (1996)
Buccal disk Remuñán-López, Portero, Vila-Jato, and
Alonso (1998)
Solution Lueßen et al. (1996)
Vesicle Uchegbu et al. (1998)
Film coating Remuñán-López and Bodmeier (1997)
Tablets Acartürk (1989), Sabnis, Rege, and Block,
(1997), Yomota, Miyazaki, and Okada (1994)
Spray-dried Kulvanich, Prugmahachaikul, and Kraisintu
particles (1997)
Capsules Odoriba et al. (1997), Tozaki et al. (1997)
Parenteral Microspheres Jameela, Misra, and Jayakrishnan (1995),
Patashnk, Rabinovich, and Golomb (1997),
Thanoo, Sunny, and Jayakrishnan (1992),
Vasishtha, Barlow, Brashear, and Rastellini
(1997)
Solution Kamiyama, Onishi, and Machida (1996)
Nasal Solution Aspden, Illum, and Skaugrud (1997), Aspden,
Mason, et al. (1997), Illum, Farraj, and Davis
(1994), Tengamnuay, Sahamethapat, Sailasuta,
and Mitra (2000), Sinswat, & Tengamnuay
(2003)
Ocular Suspension Calvo, Vila-Jato, and Alonso (1997), Genta et al.
(1997)
Gene therapy Borchard and Bivas-Benita (2005), Mao et al.
(2001), Mao, Roy, Truong-Le, and Leong
(1997), Murata, Ohya, and Ouchi (1996, 1997)
Other Gel systems Filar and Wirick (1978), Hoffman, Matsura, Wu,
and Gombotz (1997)
Modified from Dodane and Vilivalam (1998)
Marine Carbohydrates as Nutraceuticals and Pharmaceuticals 191

activity. These nanofibers are further considered as promising material for

the enhancement of absorption of drugs, enzyme immobilization, cell pro-
liferation, and wound healing ( Jayakumar, Prabaharan, Nair & Tamura,
2010). In addition to chitin nanofibers, chitin and chitosan derivatives are
used as excipients and drug carriers in the pharmaceutical field, where
chitosan is used as an excipient in oral dosage form and chitosan tablet
can exhibit a sustained drug release compared to existing commercial prod-
ucts. Films prepared using chitin or chitosan have been developed as wound
dressings, oral mucoadhesive, and water-resisting adhesive by virtue of their
release characteristics and adhesion (Kato, Onishi & Machida, 2003).
Recent efforts by Zhang et al. (2010) focused on the chemical and bio-
logical modification of chitosan in order to increase the solubility of chitosan
in aqueous solutions and absorbability in the in vivo system, thereby better
use of chitosan is possible in the pharmaceutics and medicine (Zhang
et al., 2010).

5. CONCLUSION
There is growing interest in the use of functional foods and
nutraceuticals based on marine-derived carbohydrates. These medical food
sources of traditional value lead the researchers to develop some
nutraceuticals as well as pharmaceuticals from marine flora and fauna to
combat several health complications. Although several carbohydrate mole-
cules of marine origin are researched for their chemicobiological impor-
tance, several gaps have to be filled to bring out efficient nutraceuticals
and pharmaceuticals from these molecules. Since most of the applications
of marine carbohydrates are restricted to the laboratory level, supplementary
studies are very important to confirm the clinical level applications, and fur-
ther commercialization of these macromolecules. The present chapter is a
cumulative review content on various sources of marine carbohydrates
and their possible applications in nutraceutical and pharmaceutical
development.

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FURTHER READING
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