627

35
Application of Marine Algae Derived Nutraceuticals in the
Food Industry
Isuru Wijesekara and Se-Kwon Kim

35.1
Introduction

Marine organisms are rich sources of structurally diverse bioactive compounds

with valuable nutraceutical potential [15]. Among marine organisms, sea veg-
etables have been identied as an underexploited plant source and as a resource
of nutraceuticals and functional foods with health promoting eects [6, 7]. There
is a long history of sea vegetable consumption in Asia and the Pacics, versus a
low to zero expenditure in Europe and the American continent. Fresh and pro-
cessed sea vegetables have been used as food substances in the Asian countries
for centuries and are considered underexploited resources.
Marine algae are classied into three divisions such as Chlorophyta (green
algae), Phaeophyta (brown algae), and Rhodophyta (red algae) according to
their composition of pigments. Novel extraction and separation techniques,
such as enzyme-assisted extraction, supercritical CO2 extraction, pressurized
liquid extraction, ultrasonic-aided extraction, and membrane separation tech-
nology can be applied to develop bioactive nutraceuticals from marine algae
(Figure 35.1). Furthermore, sea vegetables have been utilized as raw materials
in the manufacture of many seaweed-incorporated food products, such as jam,
cheese, wine, tea, soup, and noodles, and in European countries, mainly as
a source of polysaccharides for the food, pharmaceutical, and cosmeceutical
industries [8]. Sea vegetable originated compounds exhibit various biological
activities [9, 10] and are used as raw or processed types. For example, Porphyra
spp. (Laver-English, Nori-Japanese, Kim-Korean, and Chi Choy-Chinese) are
a red (Rhodophyta), papery sea vegetable, and a popular delicacy thanks to its
rich content of protein, vitamins, minerals, and dietary bers [11]. In addition,
Porphyra spp. have also been reported to contain iodine, bioactive substances,
and antifungal compounds of therapeutic value [12, 13]. Another example is
the incorporation of a brown sea vegetable wakame (Undaria pinnatida,
Phaeophyceae) with pasta, which increases the value of the food product by
enhancing antioxidant activity and sensory qualities thanks to fucoxanthin and
fucosterol [14]. The bioprocessing of sea vegetables to improve the functional

Marine Algae Extracts: Processes, Products, and Applications, First Edition.

Edited by Se-Kwon Kim and Katarzyna Chojnacka.
2015 Wiley-VCH Verlag GmbH & Co. KGaA. Published 2015 by Wiley-VCH Verlag GmbH & Co. KGaA.
628 35 Application of Marine Algae Derived Nutraceuticals in the Food Industry

Marine
algae

- Enzyme assisted extraction

- Pressurized liquid extraction
- Supercritical CO2 extraction
- Ultrasonic-aided extraction
- Membrane separation technology

Phlorotannins
Sulfated polysaccharides
Astaxanthin/fucoxanthin
Lectins Health benefits
Microsporine-like amino acids
Fucosterol
Proteins and peptides

Figure 35.1 Development of nutraceuticals from marine algae.

characteristics of food ingredients could be the way to novel food products

to be used as functional foods and nutraceuticals. This contribution focuses
on chemistry and health benecial applications of seaweed-derived potential
nutraceuticals such as phlorotannins, sulfated polysaccharides (SPs), carotenoids,
fucosterols, bioactive peptides, and lectins.

35.2
Bioactive Components from Marine Algae as Nutraceuticals

35.2.1
Phlorotannins

Brown sea vegetables such as Ecklonia cava, Hizikia fusiformis, U. pinnati-

da, Sargassum thunbergii, Eisenia bicyclis, and so on accumulate a variety
of phloroglucinol-based polyphenols as phlorotannins of low, intermediate,
and high molecular weight containing both phenyl and phenoxy units. These
phlorotannins are highly hydrophilic components with a wide range of molecular
sizes ranging between 126 Da and 650 kDa [15]. The phlorotannins (Figure 35.2)
such as phloroglucinol, eckol, fucodiphloroethol G, phlorofucofuroeckol A,
7-phloroeckol, dieckol, diphlorethohydroxycarmalol, and 6,6 -bieckol consist
of phloroglucinol units linked to each other in various ways, and are of wide
occurrence among marine brown algae.
35.2.2
Sulfated Polysaccharides

Sea vegetables are the most important source of nonanimal SPs, and the anionic
chemical structure of these polymers varies according to the algal species. The
 35.2 Bioactive Components from Marine Algae as Nutraceuticals 629

OH
HO OH

HO OH OH O
HO OH
O OH
(a)

O O
OH O HO OH OH
O OH

HO O OH O
O OH
OH

HO O
(b)
OH (c)

Figure 35.2 Some phlorotannins derived from marine algae (a) phloroglucinol, (b) bieckol,
and (c) dieckol.

amount of SPs in a particular seaweed is found to dier according to the three

major divisions of sea vegetables. The major SPs found in marine algae include
fucoidan and laminarans of brown algae, carrageenan of red algae, and ulvan of
green algae (Figure 35.3). In the past few years, various SPs isolated from sea
vegetables have been applied in the areas of nutritionals, cosmetics, and phar-
maceuticals. For example, carrageenans from red seaweeds are widely used as
food additives, such as emulsiers, stabilizers, or thickeners [16, 17]. In addition,
ulvan from green seaweeds displays several physiochemical and biological fea-
tures of potential interest for nutritional, pharmaceutical, agricultural, and chem-
ical applications [18]. Fucoidans are widely commercially available from various
cheap sources. Consequently, more and more fucoidans have been investigated to
develop nutraceuticals and functional foods [19].

35.2.3
Fucoxanthin and Astaxanthin

Seaweed-derived fucoxanthin and astaxanthin are carotenoids (Figure 35.4), a

family of pigmented compounds that are synthesized by plants, algae, fungi, and
microorganisms. These carotenoid pigments are thought to be responsible for
the benecial properties in preventing human diseases including cardiovascular
diseases, cancer, and other chronic diseases. Fucoxanthin can be found abun-
dantly in brown sea vegetables and contributes over 10% of the estimated total
production of carotenoids in nature [20].
 630 35 Application of Marine Algae Derived Nutraceuticals in the Food Industry

H3C
O
OH OH
O3SO OH
OSO3 H3C O
O O O OSO3
O

OSO3 O
OSO3 HO
(a) O (b)

O3SO

+
NaOOC
O H3C
O O
HO O

OH HO
OH
(c)

Figure 35.3 Monomeric units of some sulfated polysaccharides from marine algae
(a) fucoidan, (b) carrageenan, and (c) ulvan.

CH3
HO
CH3 CH3 CH3 CH3
O
O

CH3 CH3 CH3 H3C

OH
H3C
(a)
HO

CH3

H3C
O CH3 CH3 OR
H3C
H3C CH
3

O CH3 CH3 OH
H3C
(b)

Figure 35.4 Pigments derived from marine algae (a) astaxanthin and (b) fucoxanthin.
 35.2 Bioactive Components from Marine Algae as Nutraceuticals 631

35.2.4
Lectins

Lectins are carbohydrate binding proteins or glycoproteins that have a growing

commercial value in the biomedical industry. Further, lectins are a group of pro-
teins or glycoproteins present in a wide range of organisms. They are present from
bacteria to animals and have been considered to serve as recognition molecules
in cellcell interactions [21]. Studies have shown that sea vegetables can be good
sources of novel lectins [22, 23]. Moreover, algal lectins may be a new fascinating
group of lectins because many of them have some common features such as low
molecular weight, monomeric forms, thermo stability, and metal-independent
hemagglutination [24]. Phycolectins have low molecular masses with high speci-
city for complex oligosaccharides or glycoproteins. Therefore, some lectins from
sea vegetables can be developed as antibiotics against marine vibrios [25].

35.2.5
Fucosterol

All eukaryotes universally contain large amounts (2030%) of higher sterols in

their plasma membranes. Dierent eukaryotic kingdoms have dierent higher
sterols for their membrane reinforcement, in particular with cholesterol in
animals, ergosterol in fungi, and phytosterols in plants. Phytosterols (plant
sterols) are triterpenes and most of them contain 28 or 29 carbons and one or two
carboncarbon double bonds, typically one in the sterol nucleus and sometimes
a second in the alkyl side chain [26]. Fucosterols (Figure 35.5) have received much
attention in the past few years because of their cholesterol-lowering properties.

35.2.6
Mycosporine-Like Amino Acids

Mycosporine-like amino acids (MAAs) are a family of intracellular compounds

involved in the protection of aquatic organisms against solar UV radiation.
Moreover, some MAAs can act as antioxidants. The oxocarbonyl-MAAs such

H H

HO

Figure 35.5 Fucosterol derived from marine brown algae.

632 35 Application of Marine Algae Derived Nutraceuticals in the Food Industry

as mycosporine-glycine [2729] and mycosporine-taurine [30] are capable of

protecting against the cellular damage caused by high levels of reactive oxygen
species (ROS) such as superoxide anion, hydroxyl radicals, and H2 O2 induced in
organisms under dierent stresses [31].

35.2.7
Proteins and Peptides

The protein content of seaweeds diers between species. Generally, the protein
fraction of brown seaweeds is low (315% of the dry weight) compared with that
of green or red seaweeds (1047% of the dry weight). Fleurence et al. [32] reported
about the nutritional value of algal proteins and described the promising poten-
tial applications and commercialization trends. With respect to their high protein
content and amino acid composition, red seaweeds appear to be an interesting
potential source of food proteins in the development of nutraceuticals. Enzymatic
hydrolysis of sea vegetable-derived proteins is the tool for the isolation of bioactive
peptides. The physicochemical conditions of the reaction media, such as tempera-
ture and pH of the protein solution, must then be adjusted in order to optimize the
activity of the proteolytic enzyme used. Nowadays, there is a growing demand for
the isolation of novel bioactive peptides from sea vegetables with biological prop-
erties such as antioxidant, antihypertensive, and anticoagulant activities [33, 34].

35.3
Health Benecial Eects of Nutraceuticals from Marine Algae

35.3.1
Anticancer Eect

A phlorotannin, from the brown sea vegetable E. cava, namely, dioxinode-

hydroeckol can reduce the growth of human breast cancer cells (MCF-7) via
induction of apoptosis [35]. Moreover, phlorotannins such as fucodiphloroethol
G, dieckol, eckol, and phlorofucofurofuroeckol from E. cava have been shown to
provoke potential cytotoxic eects on human cancer cell lines such as cervical
cancer (HeLa), brosarcoma (HT1080), lung cancer (A549), and colon cancer
(HT-29) cells. However, cytotoxicity to human normal lung broblast (MRC-5)
cells has been shown to be less successful [36]. Anticancer activity of SPs from
sea vegetables has been reported to be closely related to their sulfate content
and molecular weight. Several studies have shown that SPs from sea vegetables
show potential antiproliferative activity in various cancer cell lines in vitro, as
well as inhibitory activity of tumor growth in mice [37, 38]. In addition, they
demonstrate antimetastatic activity by blocking the interactions between cancer
cells and the basement membrane [39], but so far their exact mechanisms
of action are not yet completely understood. Porphyran, the SPs of a red sea
vegetable Porphyra yezoensis, can induce cancer cell death via apoptosis in a
 35.3 Health Benecial Eects of Nutraceuticals from Marine Algae 633

dose-dependent manner in vitro without aecting the growth of normal cells

[40]. The SPs puried from E. cava stimulate the induction of apoptosis in vitro
[41] and have potential antiproliferative eect on human leukemic monocyte
lymphoma cell line (U-937). Similarly, the antiproliferative activity of dietary
fucoidan was reported to associate with the induction of apoptosis and with
autophagy in human gastric cancer (AGS) cells [42].
The carotenoid, fucoxanthin, could be useful in chemoprevention against hep-
atic cancer. Fucoxanthin showed to reduce the viability of HepG2 (human hep-
atocellular carcinoma) cells accompanied with the induction of cell cycle arrest
during the G0 /G1 phase at 25 M [43]. Moreover, fucoxanthin induces apoptosis
in human leukemia HL-60 cells [44].

35.3.2
Antioxidant Eect

Phlorotannins derived from brown sea vegetables are known for their strong
antioxidant activities on free radicals [45]. This antioxidant activity can be the
result of a metal chelating ability or of the specic scavenging of radicals formed
during peroxidation or even submitted by an oxygen-containing compound.
According to the signicant results of total antioxidant activity compared to
tocopherol as positive control in the linoleic acid model system, the phlorotannins
present an interesting potential against 1,1-diphenyl 1,2-picrylhydrazyl (DPPH),
hydroxyl, superoxide, and peroxyl radicals in vitro, using the electron spin
resonance (ESR) technique [46]. Furthermore, several phlorotannins, puried
from brown sea vegetables such as E. cava, Ecklonia kurome, E. bicyclis, and
H. fusiformis are responsible for antioxidant activities and they have proven to
exhibit protective eects against hydrogen peroxide-induced cell damage [47].
The benecial eects of fucoxanthin is through its role as antioxidant, which
is based on its singlet oxygen quenching properties and its ability to trap free
radicals, which depends mainly on the number of conjugated double bonds of
the molecule. Fucoxanthin can eectively inhibit intracellular ROS formation,
DNA damage, and apoptosis induced by H2 O2 . Noticeably, fucoxanthin also
exhibited a strong enhancement of cell viability against H2 O2 induced oxidative
damage [48]. Fucosterol, obtained from the n-hexane fraction of Pelvetia siliquosa
(Phaeophyceae), is eective against free radical and CCl4 induced hepatotoxicity
in vivo [49]. Moreover, fucosterol elevates the activities of free radical scavenging
enzymes such as superoxide dismutase, catalase, and glutathione peroxidase.
Recently, some research works reported the potential antioxidant and free radical
scavenging eect of sea vegetable-derived peptides by enzymatic hydrolysis.

35.3.3
Anticoagulant Eect

The anticoagulant activity of bioactives from marine algae has been determined by
the prolongation of activated partial thromboplastin time (APTT), prothrombin
634 35 Application of Marine Algae Derived Nutraceuticals in the Food Industry

time (PT), and thrombin time (TT) assays. SPs derived from seaweeds are alterna-
tive sources for the manufacturing of novel anticoagulant nutraceuticals [5053].
Two types of SPs are identied with high anticoagulant activity including sulfated
galactans also known as carrageenan from red sea vegetables [54] and sulfated
fucoidans from brown seaweeds [55, 56]. Sea vegetables derived SPs have been
described to possess anticoagulant activity similar to or higher than heparin [57].
Phlorotannins from S. thunbergii were analyzed for their potential anticoagulant
activity and it has been suggested that phlorotannins are potential anticoagulants
in vitro and in vivo. In addition, phlorotannins from S. thunbergii had a signicant
eect on the prolongation of APTT, PT, and TT, especially at the concentration of
1 mg/ml. For example, phloroglucinol can be developed as a novel anticoagulant
in the pharmaceutical industry [58].

35.3.4
Anti-HIV and Antimicrobial Eects

Marine brown sea vegetables are a valuable source for the isolation of novel anti-
HIV compounds. For the rst time, Ahn et al. [59] reported that the phlorotannins
8,8 -bieckol and 8,4 -dieckol show an inhibitory eect on HIV-1 reverse tran-
scriptase and protease in vitro. Moreover, 6,6 -bieckol from E. cava demonstrates
to selectively inhibit the activity of HIV-1 reverse transcriptase enzyme with an
IC50 (inhibitory concentration) of 1.07 M and prevents also the entry of HIV-
1. Furthermore, it exhibits no cytotoxicity at the concentration, where it almost
completely inhibited HIV-1 replication [60].
Fucoidans from brown sea vegetables show the antiviral activity against infec-
tious diseases, such as HIV, herpes simplex virus types (HSV-1 and HSV-2) and
cytomegalovirus [61]. In addition, SPs such as carrageenans and sulfated rhamno-
galactans have inhibitory eects on the entry of enveloped viruses including her-
pes and HIV into cells. Saringosterol, a derivative of fucosterol, which can be found
in several brown sea vegetables such as Lessonia nigrescens and Sargassum ring-
goldianum, has been shown to inhibit the growth of Mycobacterium tuberculosis,
the pathogenic bacteria that causes tuberculosis [62]. Moreover, phlorotannins
are eective against some pathogenic food-borne bacteria. For example, dieckol
and 8,8 -bieckol from E. kurome have successfully reduced the growth of Campy-
lobacter jejuni and Vibrio parahaemolyticus [63].

35.4
Concluding Remarks

The awareness of consumers regarding the link between diet and health has
raised the demand for novel nutraceutical products. Recent evidences suggest
that sea vegetables derived nutraceuticals play a vital role in human health and
nutrition. Collectively, the wide range of health benecial activities associated

with nutraceuticals derived from sea vegetables have potential to expand their
health benecial value in the food and pharmaceutical industries.
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