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Seaweed Polysaccharides (Agar, Alginate Carrageenan)

Chapter · January 2018

DOI: 10.1016/B978-0-08-100596-5.21587-4

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 Seaweed Polysaccharides (Agar, Alginate Carrageenan)
Katerina Alba and Vassilis Kontogiorgos, University of Huddersfield, Huddersfield, United Kingdom
© 2018 Elsevier Inc. All rights reserved.

Introduction 1
Structure – Extraction 1
Carrageenan 1
Agar 2
Alginates 4
Physical Properties 5
Carrageenan 5
Agar 6
Alginates 7
Food Applications 8
Carrageenan 8
Agar 8
Alginates 9
Conclusions 9
References 10

Introduction

Red seaweeds or macro-algae (Rhodophyceae) are phylogenetically the oldest division of marine macrophytes. They contain sulph-
ated galactans, such as carrageenan and agar as the main structural materials of cell walls and intercellular matrices that are commer-
cially exploited across food industry. Carrageenan-containing seaweeds (carrageenophytes) are mainly collected from natural
sources around the globe (Table 1). Initially, the production of agar was limited only to several locations where Gelidium species
grow that produce agars with superior gelling properties. However, alkaline pre-treatment of alternative seaweed species (Gracilaria)
was introduced later and resulted in expansion of agar industry. Brown seaweeds (Phaeophyceae) are primarily used for production
of alginates that are also harvested in both northern and southern hemispheres (Table 1). The differences in compositional
characteristics and conformational arrangement in solution of carrageenan, agar and alginates produce a set of polysaccharides
with a wide spectrum of physical and chemical properties that are utilized in a large number of foods. The focus of the present
chapter is on the structure, extraction, physicochemical properties, and food applications of seaweed polysaccharides with major
industrial interest.

Structure – Extraction
Carrageenan
Carrageenan is a linear, sulphated galactan that is composed of alternating 3-linked b-D-galactopyranose and 4-linked a-D-galacto-
pyranose or 4-linked 3,6-anhydro-a-D-galactopyranose, thus forming their disaccharide repeating unit (Fig. 1) (Knutsen et al.,
1994). Besides galactose and sulphate groups, other carbohydrate residues (e.g., xylose, glucose, or uronic acids) and substituents
(e.g., methyl ethers, and pyruvate groups) may also be present (Van De Velde et al., 2002). These negatively charged polysaccharides
are typically classified into six basic forms, namely iota- (ι), kappa- (k), lambda- (l), mu- (m), nu- (n), and theta- (q) carrageenan based
on the number and position of sulphate groups, and the presence of 3,6-anhydro-bridge in galactose residues (Knutsen et al., 1994).
k-, ι-, and l-carrageenan have one, two, or three ester-sulphate groups per repeating disaccharide unit, respectively (Rochas et al.,
1986). The most industrially relevant types of carrageenan are kappa-, lambda-, and iota- whereas mu- and nu-are biological
precursors of k- and ι-carrageenan, respectively, and their food applications are limited. The chemical composition of carrageenan
varies between red seaweed species and depends on the extraction method. The k- and ι-carrageenan are predominantly extracted
from Kappaphycus alvarezii and Eucheuma denticulatum, whereas l-carrageenan is primarily sourced from Gigartina skottsbergi and
Sarcothalia crispata (Imeson et al., 2009).
Carrageenan is produced using two extraction methods resulting in isolation of semi-refined or refined powders (Rudolph et al.,
2000). During the isolation process of semi-refined carrageenan, hot KOH solution reacts with the sulphate esters of carrageenan
precursors (m- and n-) resulting in increase of 3,6-anhydrogalactose (3,6-AG) and production of k- or ι-carrageenan, respectively
(Fig. 2). In addition, potassium cations promote gel formation thus preventing carrageenan from dissolving in the hot alkaline
solution. At this stage, seaweed extract is in a gel form that is finally dried and milled into a powder (Fig. 2). This method is
only applicable for red seaweed species that contain mainly k- and ι-carrageenan because they form gels with potassium salts, as

1
2 Seaweed Polysaccharides (Agar, Alginate Carrageenan)

Table 1 Species and locations of industrially relevant hydrocolloid-producing seaweeds

Species Location

Carrageenophytes
Kappaphycus alvarezii, Indonesia, Philippines
Eucheuma denticulatum
Gigartina skottsbergi, Central Chile, Argentina
Sarcothalia crispate
Agarophytes
Gelidium Spain, Portugal, Morocco, France, Japan, Republic of
Korea, Mexico, Sumatra, Indonesia, lower harvests in
Chile, China and South Africa
Gracilaria Chile, Indonesia, Argentina, Atlantic coast of Canada,
China, Vietnam, Namibia
Alginophytes
Ascophyllum nodosum Ireland, Scotland, Norway
Laminaria digitata France, Norway, Iceland
Laminaria hyperborea Ireland, Scotland, Norway
Macrocystis pyrifera USA, Mexico, Chile
Laminaria japonica China, Japan, Russia, France

-carrageenan -carrageenan -carrageenan

n n n

3,6-anhydro-α-D-galactopyranose -D-galactopyranose -D-galactopyranose

sulphate ester (O-SO3-) -(1 4) -(1 3)

Figure 1 Structural features of carrageenan. b-D-Galactopyranose residues in k- and i-carrageenan are sulphated at C-4, whereas in l-carrageenan
at C-2 position.

opposed to l-carrageenan-containing seaweeds that do not gel in the presence of potassium and would therefore be lost during the
alkali treatment. Extraction of refined carrageenan starts with seaweed heating in NaOH solution followed by precipitation with
alcohol or by inducement of gelation with potassium salts (e.g., KCl) (Fig. 2). Alcohol-precipitation method can be used for
any type of carrageenan, whereas the gel method is only applicable to k-carrageenan.

Agar
Agar is also a linear galactan with backbone comprised of b-D-galactopyranose and 3,6-anhydro-a-L-galactopyranose linked via
alternating a-(1/3) and b-(1/4) glycosidic linkages. The two alternating disaccharide units forming the backbone are agarobiose
and neoagarobiose (Fig. 3) (Duckworth and Yaphe, 1971). Agar is a heterogeneous complex mixture of related polysaccharides with
comparable backbone structure, but differences in the level of substitution of hydroxyl groups of sugar residues (e.g., ester sulphate,
methoxyl, etc.) (Duckworth and Yaphe, 1971; Lahaye and Rochas, 1991). Agar is composed of two major polysaccharide fractions,
namely agarose that is a neutral, low sulphate/methoxyl substituted fraction that exhibits high gelling capacity, and agaropectin that
is charged, heterogeneous, highly-substituted, and has low gelling capacity (Araki and Arai, 1967). The ratio of agarose to agaropec-
tin varies depending on the seaweed species and isolation conditions. In contrast to carrageenan, agar is only lightly sulphated
(<0.15%) (Armisén et al., 2009).
The major agar-producing red seaweeds (agarophytes) belong to genera Gelidium and Gracilaria. The extraction strategies of
food-grade agar generally include a washing step followed by pre-treatments and hot water extraction. The pre-treatment stage is
performed either with strong alkali (NaOH) for Gracilaria seaweed species or with acidified water for Gelidium species (Fig. 4).
The alkali pre-treatment is a critical step in agar production from Gracilaria seaweed species since it results in conversion of the
 Seaweed Polysaccharides (Agar, Alginate Carrageenan) 3

Cleaned and washed seaweed

Alkaline extraction

Washing Filtration

Colour removal Concentration

(Optional)

Gelation Precipitation
With KCl with alcohol
Sterilisation
(optional)
Gel pressing Precipitate pressing

Drying

Drying,
Milling blending

Semi-refined carrageenan Refined carrageenan

Figure 2 Generalized extraction strategy of semi-refined and refined carrageenan.

agarobiose

n n
neoagarobiose

3,6-anhydro- -L-galactopyranose -D-galactopyranose

-(1 4) -(1 3)

sulphate ester (O-SO3 -) methoxyl (O-CH3 )

Figure 3 Backbone structure of agarose. The repeating disaccharide units are called agarobiose and neoagarobiose. 3,6-anhydro-galactose residues
in agar are L-enantiomers, whereas in k- and i-carrageenan are D-enantiomers.

precursor porphyran (sulphated galactose) into the 3,6-anhydro-galactopyranose that is responsible for the gelling capacity and
mechanical properties of agar gels (Knutsen et al., 1994). In the hot-water extraction stage, seaweeds of Gelidium species are
typically extracted under pressure whereas seaweeds of Gracilaria species are treated with hot water and the mixture is filtered to
remove the residual seaweed (McHugh and Food and Agriculture Organization of the United Nations, 2003). Cooled filtrate forms
a gel that contains around 1%–2% of agar and which is later dehydrated using either a freeze-thaw process or by pressing water out
(“syneresis” method). The freeze-thaw method results in production of gels that contain 10%–12% of agar, whereas syneresis
method yields higher purity gels (
20%) (Armisén et al., 2009). After this treatment, isolated agar is dried in hot-air oven and
milled to the desired particle size.
4 Seaweed Polysaccharides (Agar, Alginate Carrageenan)

Washed and cleaned seaweed

Gelidium Gracilaria

Heating in acidified water Heating in strong alkali

Hot water extraction, filtration

Agar recovery

Freeze-thaw method Syneresis method

Drying and milling

Agar

Figure 4 Generalized extraction strategy for food-grade agar.

Alginates
Alginate is the term used for the salts of alginic acid, but it also refers to all derivatives of alginic acid and alginic acid itself. Alginates
are structural components of brown micro-algae (Phaeophyceae) cell walls that are present in the form of divalent salts of alginic acid
and form the intercellular gel matrix. Alginates are linear polysaccharides that are composed of b-D-mannuronic acid (M) and
a-L-guluronic acid (G) residues linked via 1/4 glycosidic linkages (Fig. 5). Accordingly, alginate backbone consists of sequences
of blocks of mannuronic acid (M-blocks) or guluronic acid (G-blocks), and regions of alternating sequences (e.g., MG, MMG, GGM)
(Grasdalen et al., 1979, 1981). The M-blocks are linked via b-1,4 linkages adopting 4C1 chair conformation that imparts flexibility to
the chain, whereas G-blocks are stiff structures of buckled shape due to the 1C4 conformation of guluronate residues linked via a-1,4
linkages (Atkins et al., 1970; Grasdalen et al., 1977; Penman and Sanderson, 1972). As a result, the stiffness of the blocks on the
backbone follows the order (from most to least stiff): GG > MM > MG (Smidsrød et al., 1973).
The main brown seaweed species used for commercial alginate production are Laminaria hyperborea, Macrocystis pyrifera,
Laminaria digitata, Ascophyllum nodosum and to a lesser extent from Laminaria japonica. The ratio of mannuronic to guluronic
acid, sequence of monomers, length of blocks, and molecular weight of the chains vary with the source and consequently impact
the physical properties of alginates (Penman and Sanderson, 1972; Smidsrod and Haug, 1972; Haug et al., 1967). Alginates isolated
from L. hyperborea typically have the highest guluronic acid content (M/G ratio
0.62), whereas those extracted from L. japonica
(M/G ratio: 2.34–3.18) and A. nodosum (M/G ratio: 1.29–1.85) are low in guluronic acid and therefore exhibit weak gelling
properties (Grasdalen et al., 1979; Penman and Sanderson, 1972; Draget et al., 2006; Haug and Larsen, 1962; Minghou et al., 1984).
Alginate extraction is based on conversion of all insoluble salts of alginic acid that are present within the cell wall of brown
seaweed to the soluble (Naþ) salt of alginic that is subsequently recovered as alginic acid or calcium alginate. Isolation of alginates
can be divided into three major stages that is pre-extraction, neutralization, and precipitation (Fig. 6). Initially, proton exchange
with a strong acid (e.g., HCl) converts salts of alginic acid into free alginic acid. In the next step, insoluble alginic acid is solubilized
by neutralization with alkali to form water-soluble sodium alginate, which is consequently recovered from the extraction solution
by precipitation with hydrochloric acid, calcium chloride, or alcohol, and finally dried and milled (Fig. 6). Sodium alginate is the

M - block G - block MG - block

-D-mannuronic acid (M) -L-guluronic acid (G)

-(1 4) -(1 4)
Figure 5 Idealized structure of alginates. Alginates are composed of b-D-mannuronic acid (M) and a-L-guluronic acid (G). Backbone consists of
sequences of blocks of mannuronic acid (M-blocks) or guluronic acid (G-blocks), and regions of alternating sequences (MG-block).
 Seaweed Polysaccharides (Agar, Alginate Carrageenan) 5

Salts of alginic acid of the

algal cell wall

Pre-extraction with
HCl

Alginic acid

Neutralisation with
Na2CO3 or NaOH

Sodium alginate

Precipitation with Precipitation with

CaCl2 HCl

Calcium alginate Alginic acid

Proton exchange Neutralisation with

with HCl and Na2CO3
neutralisation with
Na2CO3
Sodium alginate

Sodium alginate

Figure 6 Generalized extraction strategy of alginates.

major commercial form of alginate, however, there are other forms of soluble alginates such as alginic acid and its calcium,
ammonium, and potassium salts, or esters of alginic acid, such as the propylene glycol alginate (PGA).

Physical Properties
Carrageenan
All forms of carrageenan are soluble in water and the type of carrageenan, temperature, pH, ionic strength of the medium and the
presence of cations are the factors that influence its aqueous solubility. Their hydrophilic character originates from sulphate and
hydroxyl groups whereas hydrophobicity from the 3,6-AG units resulting in differences of water solubility between different types
of carrageenan. For instance, l-carrageenan has three sulphate groups and no 3,6-AG content and, therefore, is easily soluble under
most conditions. Water solubility of carrageenan follows the order (from most to least soluble): l- > ι- > k-carrageenan. The
presence of cations in the solution induces aggregation between carrageenan helices resulting in alterations in solubility. For
instance, all salts of l- and sodium salts of k- and ι-carrageenan are soluble in cold water, whereas potassium salts of k- and ι-carra-
geenan are soluble only in hot water. The viscosity of carrageenan solutions decreases at pH values below 4.3 and in particular at
high temperatures (70–120  C) due to backbone depolymerisation (Imeson et al., 2009). Carrageenan solutions exhibit shear-
thinning flow behavior and gel at certain temperatures and cation concentrations. Gelation of k- and ι-carrageenan is comprised
of two consecutive steps: a coil-to-helix transition upon cooling and cation-induced aggregation of helices (Fig. 7). First, carra-
geenan dispersions are heated to about 80  C. At this stage, chains attain random coil conformation due to the electrostatic
repulsions between adjacent polymer chains. On cooling to approximately 40–60  C, carrageenan solutions demonstrate
pronounced increase in viscosity and undergo coil-to-double helix conformational transition. The final sol–gel transition occurs
in the presence of cations that leads to the helix–helix aggregation of the adjacent spiral chains that contain sulphate groups
and formation of a stable three-dimensional network (Piculell et al., 2006). l-Carrageenan does not gel, but forms polyelectrolyte
solutions and is utilized as a thickening agent in dairy products. k- and ι-carrageenan form thermo-reversible gels at concentrations
as low as 0.5% and cation concentrations between 0.2%–0.8%. The strength of carrageenan gels depends on the biopolymer
concentration, type of the salt (e.g., KCl, CaCl2, NaCl) and concentration of the gelling cation. For instance, k-carrageenan in the
presence of Kþ forms firm, brittle gels, whereas ι-carrageenan require Ca2þ and forms soft, and elastic gels (Kara et al., 2006).
k-Carrageenan has lower gelation temperature (35–65  C) as opposed to ι-carrageenan (40–70  C) at equivalent gelling conditions
6 Seaweed Polysaccharides (Agar, Alginate Carrageenan)

cation (e.g., K+, Na+, Ca2+)

Cooling Cooling

Heating Heating

Random coil Double helix Aggregated double helices

Figure 7 Gelation mechanism of carrageenan. Carrageenan dispersions are heated to about 80  C and chains attain random coil conformation. On
cooling to approximately 40–60  C, they undergo coil-to-double helix conformational transition. The final sol–gel transition occurs in the presence of
cations that leads to the helix–helix aggregation of the adjacent chains that contain sulphate groups. Gels are thermoreversible and melt on heating.

(Imeson et al., 2009; Nishinari et al., 1990). Typically, the higher the cation concentration, the greater the gelling temperature and
gel strength (Michel et al., 1997). The presence of co-solutes, such as sucrose also increases gelation and melting temperatures of
carrageenan solutions (Nishinari et al., 1990). Carrageenan gels are thermally reversible (melt at temperatures
5–20  C above
the gelling temperature and re-gel on cooling) and also exhibit hysteresis (difference between gelling and melting temperatures).
Textural properties and applications of k-carrageenan gels can be improved by addition of other hydrocolloids (e.g., galacto-
mannans or xanthan) (Williams et al., 1993). Hot solutions of k-carrageenan and galactomannans form strong and elastic gels
with low syneresis in contrast to brittle k-carrageenan gels. The synergistic effects between k-carrageenan–galactomannan systems
depend on the mannose/galactose ratio of the galactomannan backbone (Dea and Morrison, 1975). The mannose-free regions
of the galactomannans, particularly of locust bean gum, are able to associate with carrageenan helices resulting in gel formation
(Fernandes et al., 1991). Another notable synergistic interaction of carrageenan is with milk proteins, primarily with casein micelles
where carrageenan forms weak gels in the aqueous phase and adsorbs at the surface of casein micelles through interactions with
positively charged amino acids (Langendorff et al., 2000).

Agar
Agar is insoluble in cold water and for dissolution requires heating at temperatures of above
85  C. The viscosity of agar solutions
at 45  C is not affected by ionic strength or pH in the pH-range between 4.5–9.0 (Stanley et al., 2006) and it depends on history, as
when they are cooled and reheated back to initial temperature, they exhibit higher viscosity (Armisén et al., 2009). Agar is potent
gelling agent, as it forms networks at concentrations as low as 0.1%–0.2% w/v in the absence of any cross-linking ions in contrast to
carrageenan. Their gelling capacity arises from the agarose fraction and is stabilized exclusively by hydrogen bonding between the
3,6-anhydro-a-L-galactopyranose residues of the chains. The gelation of agar commences with a heating step (
85–95  C) where
chains adopt random coil conformation. Cooling the system to gelling temperature (
33–45  C) results in the sol–gel transition
that proceeds in two steps (Armisén et al., 2009; Normand et al., 2000). Initially, randomly distributed, single agarose coils join to
form a double helical association via intra-molecular hydrogen bonding. This is followed by aggregation of double helices via
inter-molecular hydrogen bonding into a three-dimensional gelled network (Fig. 8).
Agar forms thermo-reversible gels, that melt by heating and gel again upon cooling showing considerable hysteresis (melting

85–95  C and gelling
33–45  C). Agar gels have the most pronounced hysteresis values among gelling polysaccharides that
are typically in the range of 40–60 depending on the source of seaweed. For instance, hysteresis values of k-carrageenan are in
the range of 15–27 , whereas the lowest values are reported for ι-carrageenan (2–5 ) (Rees et al., 1969). The gelation temperatures
of agar increase with the degree of methoxylation (Guiseley, 1970; Falshaw et al., 1998). Agar gels are susceptible to “syneresis” that
is separation of water from the system during ageing. This is attributed to the contraction of the network by slow further aggregation
of double helices that reduces the interstitial space available for water. The rate of syneresis is lower for agar gels that contain high
ester sulphate content (Lahaye, 2001).
Agar typically forms transparent, stiff gels; however, their rheological properties can be modified by addition of sugars
(e.g., sucrose, glucose, trehalose) or incorporation of other polysaccharides (e.g., locust bean gum, xanthan, alginates). The addition
of sugars to the agar solutions promotes formation of helices and results in increased gel strength and higher gelation temperatures
(Rees et al., 1969; Watase et al., 1990; Vilgis, 2015). This is attributed to the “exchange” of free water by sugar molecules that leads to
increased hydrocolloid concentration and decreased distance between polymer chains thus favouring intermolecular polymer–
polymer interactions. Agar–locust bean gum mixtures show the most notable synergistic interaction that results in formation of
 Seaweed Polysaccharides (Agar, Alginate Carrageenan) 7

Cooling Cooling Cooling

Heating Heating Heating

Random coil Double helix Aggregated double helices 3D network

Figure 8 Gelation mechanism of agar. The gelation of agar commences with a heating step (
85–95  C) where chains adopt random coil
conformation. Cooling the system to gelling temperature (
33–45  C) results in the sol–gel transition and formation of double helical associations.
This is followed by aggregation of double helices into a three-dimensional network. Double helices of agar are more compact than carrageenan due
to the smaller amount of sulphate groups.

stronger gels and improved mouthfeel making the texture of agar gel similar to gelatin, a property that is widely utilized in food
formulations (Armisén et al., 2009; Stanley et al., 2006; Sousa and Gonçalves, 2015). Multicomponent gel systems of agar, xanthan
and alginate are also formulated and typically aim to expand the range of textures and mouth-feel of agar gels (Russ et al., 2013).

Alginates
Alginates have a wide range of molecular weight distribution and are charged polysaccharides with electrostatic forces originating
from the carboxylic groups within the biopolymer backbone. Therefore, its solubility depends strongly on the pH and ionic strength
of the solvent, and the presence of ions in the solution (Mackie et al., 1980). Alginates are soluble in aqueous solutions at pH above
its dissociation constant (pKa). The pKa of mannuronic and guluronic acids are 3.38 and 3.65, whereas the pKa of the global alginate
structure varies within this range (Haug et al., 1967). An abrupt decrease of pH results in protonation of carboxyl groups leading to
precipitation of alginate, whereas a slow and controlled release of protons results in formation of alginic acid gel. The pH range at
which precipitation of alginates occurs is controlled by chemical composition, molecular weight and sequence of M, G-, and
MG-blocks of the backbone. For instance, alginates that contain more MG-blocks will precipitate at lower pH values as opposed
to those that contain homogeneous M and G-blocks. Change in the ionic strength of alginate solution has considerable impact
on alginate solubility and viscosity due to the decrease of electrostatic interactions between the biopolymer chains. Monovalent
metal ions (e.g., Naþ) form soluble salts with alginate whereas divalent or multivalent cations form gels. Alginates form highly
viscous solutions due to the highly extended conformation of the chains and large hydrodynamic volume. The viscosity of alginate
solutions depends the length of M and G blocks on the backbone, and on external factors such as pH and ionic strength of the
solution.
The most prominent physical property of alginates is the selective binding of divalent and multivalent cations that determines
their ability to form gels. Cations have different affinity for alginates, although the extent of cross-linking may be also influenced by
the chemical composition (M/G ratio). For instance, alginates with high content of G-blocks form tightly held junction zones in the
presence of divalent cations (e.g., Ca2þ) and form gels of considerably higher strength compared to alginates rich in M or M-G-
blocks that exhibit lower affinity towards divalent cations (Morris et al., 1978; Wang et al., 1993). In contrast, trivalent cations
(e.g., La3þ and Pr3þ) bind to both M- and G-blocks of alginate backbone (Deramos et al., 1997). The affinity of alginates towards
divalent ions decreases in the following order: Pb > Cu > Ba > Sr > Ca > Zn > Mn, however, Ca2þ is the most commonly utilized to
induce gelation. Gelation of alginates is described by the “egg-box” model, according to which alginate chain–chain interactions are
induced by the presence of cross-linking divalent cations (Stokke et al., 2000; Donati et al., 2005). Alginate blocks show different
mechanisms of interactions with cross-linking cations. For instance, G-blocks integrate cations into pocket-like structures formed
between adjacent chains of guluronate residues, whereas M-blocks bind cations externally near the carboxylate groups. In MG
blocks, cations are preferentially located in a concave structure formed by MG pairs (Emmerichs et al., 2004). The strongest
interactions between junction zones occur in guluronic acid residues, as the buckled chain conformation enables strong gel forma-
tion (Donati et al., 2005; Grant et al., 1973). Ionotropic gelation of alginates can be performed by two ion-dependent methods:
“diffusion” (sometimes referred as “dialysis”) and “internal setting” method. In the “diffusion” method, alginate solution is dripped
into the solution of cross-linking ion (e.g., soluble calcium salts, CaCl2). Calcium ions diffuse into the alginate solution and alginate
beads are formed (Fig. 9).
8 Seaweed Polysaccharides (Agar, Alginate Carrageenan)

cation (e.g., Ca 2+) G-block M- and MG-blocks

+ Ca2+ + Ca2+

Random coil -
Figure 9 Gelation mechanism of alginates. G-blocks integrate divalent cations into pocket-like structures formed between adjacent chains of
guluronate residues leading to formation of a network. This is known as the “egg box” model.

This method is characterized by fast gelation kinetics, heterogeneous distribution of alginate and widely utilized in the produc-
tion of restructured food products and encapsulation of bioactive compounds. In “internal setting” method, inactive form of
cross-linking ion (e.g., insoluble calcium salts, CaCO3, CaSO4) is mixed with alginate solution. Then, a slowly hydrolyzing agent
(e.g., D-glucono-d-lactone, GDL) is added to the mixture of alginate and inactive cross-linker. The hydrolysis of GDL to gluconic acid
results in gradual decrease of the pH of the system and production of protons that convert inactive cross-linker (e.g., CaCO3) into its
active form (e.g., Ca2þ). Slow release of cross-linker in the alginate solution leads to the formation of homogeneous gels. Alginates
also gel following cation-independent gelation mechanism. In this method, pH of alginate solutions is gradually lowered below the
pKa of the uronate residues leading to the reduction of electrical repulsion between biopolymer chains and consequently formation
of alginic acid gels though intermolecular hydrogen bonding. Alginic acid gels are typically produced either by addition of a hydro-
lyzing lactone (e.g., GDL) or by conversion of ionically cross-linked (pre-formed) gel to the acid gel by addition of mineral acids.
The M/G ratio and length of those blocks in the alginate backbone have a considerable impact on the mechanical properties of the
resulting gels. Alginates with low M/G ratios produce strong and brittle gels with good heat stability but with pronounced syneresis
after freeze-thaw processing, whereas alginates with high M/G ratios produce more elastic gels with good freeze-thaw stability
(Grant et al., 1973; Braccini and Pérez, 2001). The strength of alginate gel increases when the average length of guluronate blocks
changes from 5 to 15 leading to a formation of mechanically strong, stable, and porous gel. However, gel strength is relatively unaf-
fected by molecular weight values greater than 200 103 gmol1.

Food Applications
Carrageenan
Carrageenan is utilized mainly as gelling agent, thickener, and stabilizer at concentrations between 0.005% and 2.0% w/w. Carra-
geenan is weaker gelling agent than agar, however, their ability to produce gels with a wide variety of textures is highly valued. Food
applications of carrageenan depend on whether they are added to dairy or aqueous systems (e.g., water-based dessert gels) (Table 2).
All forms of carrageenan are utilized at concentrations <0.3% in dairy formulations (Anderson et al., 2002; Langendorff et al.,
1999). Carrageenan interacts with milk proteins and forms a network that prevents whey separation and aggregation, and stabilizes
particles such as cocoa suspensions in chocolate milk. Water-based desserts are the typical non-dairy carrageenan applications, in
which k-carrageenan or k-/ι-carrageenan blends are used at concentrations >0.3%. The synergistic interactions of carrageenan with
galactomannans are also widely utilized in the production of fruit sorbets, poultry and meat products. The thixotropic nature of
ι-carrageenan gels is applied in salad dressings formulations to stabilize suspended herbs and vegetable particles. In drink industry,
they are used at low concentrations (
0.2%) to stabilize suspensions (e.g., fruit juices) and colloidal systems (e.g., soft drinks) or
increase the viscosity and add palatability to liquid food products (Piculell et al., 2006). Recently, carrageenan is also explored in
bread making industry with particular interest in improvement of dough proofing characteristics and formulation of gluten-free
breads (Rosell et al., 2001; Sciarini et al., 2010).

Agar
Food applications of agar rest on its high gelling capacity, high hysteresis, and perfect gel reversibility. Agar is largely utilized in the
baking industry due to the ability to withstand high temperatures as opposed to carrageenan, and is effective in retarding staling of
 Seaweed Polysaccharides (Agar, Alginate Carrageenan) 9

Table 2 Food applications of seaweed polysaccharides (Stanley et al., 2006; Hambleton et al., 2009; Fabra et al., 2012)

Applications Functionality Seaweed polysaccharide

Desserts (e.g., dessert jellies, low-energy jellies,
non-dairy puddings, sorbets)
Seasonings (e.g., relishes, sauces, vinaigrette
salad dressings)
Meat (e.g., low fat meats, cooked hams, meat
preserves, canned meat, restructured meat
and fish products, pet food)
Beverages
(e.g., fruit drinks, beer, wine)
Bakery (e.g., gluten-free breads, pastry fillings,
pie fillings, icings and glazes)
Milk gels (e.g., custard, pudding) and whipped
dairy products
Milks (pasteurized, sterilized)
Frozen desserts (e.g., ice cream, ice milk)
Processed cheeses (e.g., cheese slices, cream
cheese)
Food films and coatings
Foods with encapsulation technology
Gelation, emulsion stabilization, emulsification k- and i-carrageenan, k- carrageenan with
galactomannans, alginates, agar
Gelation k- and i-carrageenan, alginates
Gelation, thickening, k-Carrageenan and galactomannans,
fat stabilization and reduction i-carrageenan and konjac gum, alginates, agar
Emulsion stabilization, k- and i-carrageenan, Na-alginates, agar
foam stabilization, flocculating agent
Improve loaf volume, k-Carrageenan, alginates, agar
gel formers/binders, moisture barrier,
antistaling agent
Gelation, syneresis control, thickening, All forms of carrageenan and their mixtures
emulsion stabilization
Suspension, mouthfeel, emulsion stabilization Combinations of k-, i- and l-carrageenan
Prevents whey separation, prevents formation k-Carrageenan, alginates, agar
of ice crystals
Gelation, moisture binding, improve slicing, k-Carrageenan with locust bean gum, agar
texture improver
Extended shelf-life Alginates, all forms of carrageenan
Aroma encapsulation, controlled release of i-Carrageenan, alginates
aroma compounds

cakes and bread. In confectionary products (e.g., cakes or doughnuts), agar is primarily utilized (0.2%–1.0% w/v) to prevent the
dehydration of the product and maintain the integrity of the icing during storage. Agar is also important in fruit jelly confections,
due to its ability to gel without high sugar concentrations. In meat industry, agar is used at levels of 0.5% to 2.0% in gelled canned
meat products, fish, poultry and boiled sausages as a structuring and fat reducing agent (Stanley et al., 2006).

Alginates
Alginates are used as thickeners, gelling agents, and stabilizers of aqueous mixtures, dispersions, and emulsions. Alginates are
polyelectrolytes and therefore can interact electrostatically with proteins in mixed systems resulting in increase in viscosity. These
types of interactions can be utilized to stabilize and enhance the mechanical properties of gelled networks in some restructured food
products. The process of food restructuring is based on binding together sectioned, chunked or milled food components (e.g. meat
cuts with high connective tissue content, or homogenized fruits and vegetables) to make them resemble the original or formulate
novel food products (Draget et al., 2006). Gelation of alginates is independent of temperature and therefore can be used in the
restructuring of foods that may become damaged or oxidized at high temperatures (e.g. meat products, fruits and vegetables).
Common restructured foods produced using alginates are reconstituted onion rings, pimento olive fillings, and cocktail berries
(Draget et al., 2006; Mancini and McHugh, 2000; Manjunatha and Gupta, 2006). Synergistic interactions between G-rich alginates
and pectins with high degree of esterification result in formation of thermo-reversible gels that are commonly utilized in the produc-
tion of jams (Walkenström et al., 2003; Toft et al., 1986). The advantage of alginate-pectin gels is that they are independent of sugar
content and therefore can be utilized in low-calorie food products. PGA is the most common alginate derivative used in food formu-
lations acting simultaneously as surface-active and gelling agent and finds applications in foams (e.g., desserts, beer froth) and
emulsions (Nilsen-Nygaard et al., 2016; Jackson et al., 1980). PGA has also high tolerance to Ca2þ and low pH and is suitable
for applications in fermented milk-based products and salad dressings. In food industry, alginates matrices (e.g., alginate, alginate
with xanthan gum, chitosan, or pectin) may also be used for encapsulation and delivery of live cells (probiotics) to the large intes-
tine and colon and in immobilization of reactive or volatile molecules (e.g., enzymes, flavours, etc.) (Cook et al., 2012; Desai and
Park, 2005). Alginates have been also used as edible coatings in meat products and a number of fresh fruits and vegetables where the
coating maintains texture, reduces the rate of browning, inhibits the growth of yeast and molds, decreases weight loss, and provides
color and moisture retention (Rojas-Graü et al., 2007; Azarakhsh et al., 2014; Jiang et al., 2013; Sipahi et al., 2013; Robles-Sánchez
et al., 2013).

Conclusions

Seaweed polysaccharides are widely utilized in the food industry and are of particular technological importance due to their broad
spectrum of functionality. The physical properties (e.g., gelling, viscosity enhancement etc.) are tunable by controlling molecular
10 Seaweed Polysaccharides (Agar, Alginate Carrageenan)

properties of the chains and the environmental conditions (e.g., pH, ionic strength, etc.). This results in hydrocolloid systems with
remarkably wide spectrum of physical properties that find applications across food industry. The most industrially relevant types of
carrageenan are kappa-, lambda-, and iota-that are sulphated anionic galactans. Agar is also a linear galactan with backbone of two
alternating disaccharides, agarobiose and neoagarobiose consisting of two major polysaccharide fractions, namely agarose and
agaropectin. k- and ι-types of carrageenan are able to form gels (l-does not form gels) assisted by the presence of cations most
commonly potassium. In contrast to carrageenan, agar forms networks in the absence of any cross-linking ions and is more potent
gelling agent. Gelling capacity of agar arises from the agarose fraction as agaropectin does not play central role in the process.
Alginates are linear polysaccharides that are composed of mannuronic acid (M) and guluronic acid (G) residues. Accordingly,
alginate backbone consists of sequences of M or G-blocks, and regions of alternating sequences (e.g., MG, MMG, GGM).
Consequently, the length of sequence of M and G blocks in the alginate backbone controls its physical properties. The most
prominent physical property of alginates is the selective binding of divalent cations and in food industry gels are usually formed
in the presence of calcium. Use of seaweed polysaccharides in foods is well established and future technologies should focus on
their potential applications beyond food industry (e.g., biomedical, pharmaceutical, or drug industries) with the overall aim to
create advanced formulations with tailored functionality (e.g., for nutrient and drug delivery, or wound healing).

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