Algins/Alginates

14
Chapter Outline

Sources and manufacture 293

Structures 294
Properties 296
Uses 298
Additional resources 301

Key information and skills that can be obtained from study of this chapter will enable
you to
1. Define or describe
M/G ratio
M block
G block
propylene glycol alginate (PGA)
egg-box model
2. Give the source of algins/alginates.
3. Explain the difference between alginic acid and an alginate.
4. (a) Describe the impact of the D-mannuronic acid-L-guluronic acid ratio on the gelling ability
and gel strength of alginates, and (b) give the molecular explanation for the phenomenon.
5. (a) Describe the effect of lowering the pH of sodium alginate solutions from 6.5 to 3.5, and
(b) give the molecular explanation for the phenomenon.
6. Explain the behavior of solutions of sodium alginate on addition of calcium ions. Explain
why this phenomenon occurs.
7. Describe the differences between diffusion setting, internal setting, and setting by cooling for
the preparation of calcium alginate gels.
8. Describe the preparation of propylene glycol alginates (PGAs).
9. Describe in molecular terms why PGA (a), in contrast to unmodified alginates, can be used in
low pH systems, (b) can be used in milk systems, and (c) has the ability to stabilize emulsions
and foams.

Sources and manufacture

Commercial algin is a salt, usually the sodium salt, of alginic acid, a linear
poly(glycuronic acid) that constitutes 18%e40% of the dry weight of brown
marine algae (brown seaweeds) (family Phaeophyceae). The major source of

Carbohydrate Chemistry for Food Scientists. https://doi.org/10.1016/B978-0-12-812069-9.00014-5

Copyright © 2019 AACCI. Published by Elsevier Inc. in cooperation with AACC International. All rights reserved.
294 Carbohydrate Chemistry for Food Scientists

algin/alginates in the United States has been the giant kelp, Macrocystis pyrifera,
growing in the Pacific Ocean, near the shore, from just north of San Diego
south into costal areas of Mexico. This seaweed, which attaches to the rocky sea-
floor, can reach a length of more than 40 m (125 ft). It has carbon dioxide-filled
bladders of about 2.5 cm (1 in.) in diameter along the strand, which float it in
an upright position so that it can receive sunlight. Under optimal conditions,
fronds1 will grow up to 60 cm (2 ft) per day and even under less than optimal
conditions will grow 30e35 cm (12e14 in.) per day. Harvesting is done by a
large ship that moves through the floating kelp cutting the plants about 1 m
below the surface and continuously lifting the cut kelp by means of a conveyor
into the ship. Macrocystis species also grow along the coasts of Chile, Peru,
and Argentina mixed with species of Lessonia, another brown algae containing
algin, and in cooler waters along the coasts of South Africa, Australia, New Zea-
land, and China, mixed with Eklonia species. Two other species of algin-
producing brown algae (namely Ascophyllum species and Laminaria species)
grow in cool water along the coasts of Northern Europe, the British Isles, and
Eastern North America. Seaweeds of the genus Ascophyllum are attached to rocks
near a shore. They grow to a length of 1-1.5 m (3-5 ft) and are harvested by hand
or by using a small mechanical harvester. Algins obtained from different species
of brown algae in different locations differ from each other in structures and
properties.
Harvested seaweed is first washed. Then, the alginate is extracted with a sodium
carbonate solution, which converts the polysaccharide into its soluble sodium salt
(sodium alginate). The polysaccharide is then precipitated from the extract by addition
of a solution of calcium chloride, which converts it into an insoluble calcium salt. The
precipitate is washed free of solubles. Addition of hydrochloric acid converts the prep-
aration into alginic acid, which is also insoluble. Finally, the alginic acid is neutralized
and converted into a monovalent ion saltdmost often into sodium alginate. Lesser
amounts of potassium and ammonium alginates are produced. Salts with monovalent
cations are soluble in water.

Structures
Alginic acid is composed of b-D-mannopyranosyluronic acid (M) and a-L-gulo-
pyranosyluronic acid (G) units. The relative amount of each monomer unit is
expressed as the M/G ratio of the preparation. M/G ratios vary from less than
0.5 to almost 2 in commercial sources of alginates. The two monomeric units
occur in homogeneous regions composed of only one of the two units and in re-
gions containing both units. Segments containing only D-mannuronopyranosyl
units are referred to as M blocks and those containing only L-guluronopyranosyl
units as G blocks. MG blocks contain both units in a mixed arrangement.

1
Fronds are the leaflike branches.
Algins/Alginates 295

D-Mannuronopyranosyl units are in the 4C1 conformation (Chapter 1), whereas L-

guluronopyranosyl units are in the 1C4 conformation, which gives the different
blocks quite different chain configurations (Figs. 14.1e14.3). Different percent-
ages of the different block segments cause alginates from different species of
brown algae to have different properties.
At least seven different brown seaweed species from different parts of the
world are used to obtain alginates. The more commonly used ones vary in
L-guluronic acid content from about 40 to about 70% and in G block
content from about 18 to about 60%. Alginates with high G block contents
produce gels of high strength with calcium ions. Blending of alginates from
different species is done to create preparations with desired properties. Average
degrees of polymerization from 80 to 1000 (MW 16,000e2,00,000) have been
reported.

CO2-
O O
CO2-
OH HO OH HO
O O

O OH
CO2- OH
O -O C
O HO
2

HO
O

βManpA unit αLGulpA unit

Figure 14.1 Ionized units of b-D-mannopyranosyluronic acid (bManpA) in both the Haworth
projection and the 4C1 conformation and of a-L-gulopyranosyluronic acid (aLGulpA) in both the
Haworth projection and the 1C4 conformation.

CO2- O HO
O OH
O OH
HO O
CO2-
DP/2

Figure 14.2 A segment of an M-block region in the ionized form. Note the similarity of this
structure to that of cellulose (Chapter 8) and of the mannan backbone of the galactomannans
(Fig. 14.1) and the flat ribbon-like structure formed by the equatorial/equatorial glycosidic
bonds.
296 Carbohydrate Chemistry for Food Scientists

OH CO2- OH CO2-
O O
O O
O H O H
H O H O
O O
O O
CO2- OH CO2- OH

-O
OH -O 2C
2C OH
O O
O O
O H O H
O O
O O
H O H O
CO2- OH -O C
2
OH

Figure 14.3 Segments of G-block regions. Note the pleated conformations of the chains formed
by the axial/axial glycosidic bonds and the “holes” that complex calcium ions. Compare
with Fig. 15.3.

Propylene glycol alginates (PGAs) are made by reacting moist alginic acid with
propylene oxide until 50%e90% of the carboxyl groups are esterified. PGA products
can vary in degree of esterification and molecular weight.
O O O
R C O- + CH2 CH CH3 R C O CH2 CHOH CH3

Where R–COO- = a unit of D-mannopyranosyluronic acid or

L-guluronopyranosyluronic acid

Properties
Alginate solutions are slightly pseudoplastic (Chapter 5). Addition of very small
amounts of calcium ions will increase viscosity. Slightly more will make alginate so-
lutions thixotropic (Chapter 5). And even more will convert alginate solutions into per-
manent gels.2
Sodium alginate solutions gel on addition of calcium ions which coordinate with
hydroxyl and carboxylate groups on adjacent chains (Fig. 14.4) and partially fill the
cavities formed between parallel G-block chain regions. These cavities contain two
carboxylate and two hydroxyl groups, one each from each chain (Fig. 14.5). In fact,
calcium ions connect four poly(L-glucuronic acid) chains and four water molecules
in an octahedral coordination. The result is a junction zone that has been called an

2
Presented is the classic explanation for gelation of alginates. It has been concluded from the results of
several research projects that this model (the egg-box model) is not exactly correct. However, the egg-box
model effectively explains the behaviors of alginates from different sources.
Algins/Alginates 297

COO- OH

Ca2+

HO -OOC

Figure 14.4 The coordination of a calcium ion with hydroxyl and carboxylate groups on
adjacent G-block chains.

Ca2+ Ca2+ Ca2+ Ca2+

Ca2+ Ca2+ Ca2+ Ca2+ Ca2+

Figure 14.5 A representation of the proposed formation of a junction between two alginate
molecules promoted by calcium ions.

egg-box arrangement with the calcium ions being likened to eggs in the pockets of an
egg carton. Strength of the gel depends on the content and size of the G blocks in the
alginate used and the concentration of calcium ions. Because of the effect of cross-
linking of alginate molecules by polyvalent ions, such as calcium ions, the hardness
of the water used to dissolve algin has an important effect on solution viscosity.
Because alginate molecules are salts of weak carboxylic acids with pKa values of 3.38
(ManA) and 3.65 (LGulA), the extent of carboxyl group ionization decreases as the pH
is decreased and is greatly reduced at pH values of 3 or less. As the pH approaches and
drops below the pKa values of the carboxylate groups (-COO-), more and more of them
are converted into uncharged carboxylic acid (-COOH) groups. This loss of ionization at
low pH values means that the alginate chains lose their negative charges, giving the mol-
ecules more and more of the characteristics of long neutral molecules as the pH drops,
which allows intermolecular associations to develop. As intermolecular associations in-
crease, the viscosity of the solution increases. Finally, when the pH is low enough,
alginic acid precipitates from solution because of extensive intermolecular associations.
Solutions of propylene glycol alginate (PGA) are thixotropic (Chapter 5) and much
more tolerant of low pH values and polyvalent cations, including calcium ions and pro-
teins, than are solutions of nonesterified alginates because esterified carboxyl groups
298 Carbohydrate Chemistry for Food Scientists

cannot ionize. Hence, propylene glycol alginates have much less negative charge than
do alginate salts. The propylene glycol group also introduces a bulge on the chain that
blocks interchain associations, giving stability to PGA solutions. Because propylene
glycol alginates can tolerate calcium ions, they can be used in dairy products. The hy-
drophobic propylene glycol groups also give the molecules interfacial activity (that is,
emulsifying, emulsion-stabilizing, and foaming properties). For example, PGA will
stabilize beer foam and, as described in Chapter 11, it is often used in combination
with xanthan in oil-in-water, pourable salad dressings.
Physical properties that can vary between specific commercial preparations are
powder particle size (a characteristic of all hydrocolloids), particle form (granular
vs. fibrous), color, odor, load of microorganisms (a characteristic of most hydrocol-
loids), and texture profiles (stressestrain relationships) of solutions and gels. Molec-
ular characteristics that can vary are M/G ratio, G and M block contents, molecular
weight (viscosity type), salt type (cation present), calcium content, and degree of ester-
ification (of PGA). The presence or absence of other substances, such as sequestrants3
of calcium ions, is another variable. Sequestrants that may be added to tie up calcium
ions are sodium hexametaphosphate, sodium tripolyphosphate, sodium hydrogen py-
rophosphate, and sodium citrate.

Uses
Alginates can be used to provide viscosity at low concentrations. Higher viscosity
(under low shear conditions) can be achieved by adding small amounts of calcium
ions to the alginate solution. Thickening action, and particularly thixotropic behavior
brought about by low concentrations of calcium ions, tends to hold insoluble particles
in suspension.
When PGA is used, the calcium ion cross-linking of chains that occurs through the
remaining carboxylate groups produces thickening without producing a weak gel.
Propylene glycol alginates with less than 60% esterification produce thixotropic
solutions. Their ability to produce thixotropic solutions decreases with increasing
esterification. The mild interfacial activity of PGA, which is imparted by the somewhat
hydrophobic ester groups, stabilizes oil-in-water emulsions.
The most extensive use of alginates is to produce gels. Calcium alginate gels are
obtained by diffusion setting, by internal setting, and by setting by cooling. All three
processes are used to prepare structured foods. In diffusion setting, calcium ions first
contact the surface of a system containing sodium alginate and diffuse from the
outside in. Two examples of products of diffusion setting are structured pimento
strips and structured onion rings. In the production of pimento strips for stuffing green
olives, pimento puree is mixed with water containing a small amount of guar gum
(Chapter 9), which thickens the diluted puree and reduces shrinkage of the final strip.
Then, sodium alginate is added. The mixture is applied to a conveyor belt as a sheet.

3
Syneresis is the expulsion/separation of liquid from a gel caused by shrinking of the gel.
Algins/Alginates 299

Spraying the sheet with calcium chloride solution sets the surface. The moving belt is
then passed through a calcium chloride setting bath, where more calcium ions diffuse
into the sheet, gelling it even more. The final sheet is tough, flexible, and resilient.
Equilibration for several days in a solution of sodium and calcium chlorides allows
the alginate gel to undergo syneresis4 and shrink to an acceptable level of consistency.
The sheet is then cut into strips, which are bent double and stuffed into pitted green
olives by a machine.
Structured, frozen onion rings are made in much the same way from minced onions
or rehydrated onion flakes, sodium alginate, salt, and flavor. The resulting paste is
formed into rings and gelled by immersion in a setting bath of 3%e5% calcium chlo-
ride. After setting, the rings are battered and fried.
Products made by diffusion setting may have liquid centers. Whether or not they do
is controlled by the time they are in the calcium chloride bath because the calcium
chloride solution will diffuse relatively slowly through the outer gel layer that is
formed on initial contact with calcium ions. Liquid centers are useful in such products
as structured blueberries.
Internal setting is used to produce structured fruit (such as apple, peach, and pear)
pieces. Internal setting involves slow release of calcium ions within the mixture. In the
preparation of fruit pieces, a two-mix system is employed. One mix contains sodium
alginate and an insoluble calcium ion source such as dicalcium phosphate or calcium
sulfate dihydrate. (No calcium alginate is formed because the calcium salt is insoluble.)
The second mixture contains minced fruit, sequestrant,3 and acid. The two mixtures are
then mixed and allowed to stand under shear-free conditions in their final container or
shaped form on a conveyer belt. Setting occurs due to the controlled release of calcium
ions by the acid, resulting in partial cross-linking of alginate chains. The purpose of the
sequestrant is to tie up the calcium ion released by the acid so that the product does not
set too fast (that is, it delays setting until the mixture is transferred to the mold). Use of
dicalcium phosphate results in a faster release of calcium ions and more rapid gel
development, which may be undesirable. Slow release of acid, for example, via use
of D-glucono-d-lactone (GDL; Chapter 2), is also effective. The specific ingredients
to be used are a function of the product being made and the equipment used.
Setting by cooling involves dissolving a calcium salt, a slightly soluble acid (such
as adipic acid), and a sequestrant in hot water and allowing the mixture to set on cool-
ing. The calcium salt may be calcium citrate, calcium gluconate, calcium lactate, or
dicalcium phosphate. Which one is used is often a function of the pH of the mixture.
It may also be a matter of regulation. GDL may be used in place of a slowly dissolving
acid to slowly lower the pH. In this process, calcium ions are released at a moderate
rate when the mixture is heated, bringing about a low degree of cross-linking. Suffi-
cient thermal energy is provided by the hot water that the alginate chains form only
weak, temporary junction zones. Gelation does not occur until cooling slows polymer

4
Sequestrants are substances that form chelate complexes with divalent or trivalent cations. In this context,
sequestrants are substances that chelate with calcium(II) ions and prevent them from combining with an
alginate, which would otherwise form a gel in the presence of the calcium ions.
300 Carbohydrate Chemistry for Food Scientists

chain movement. Gels produced in this way exhibit little or no syneresis,4 allowing the
process to be used to make structured fruit pieces. The gels are also heat stable, so
those containing fruit can be used for pie fillings that remain stable through pasteuri-
zation and cooking.
Unlike gelatin gels, alginate gels are not thermoreversible and can be used as dessert
gels in warm climates, but also unlike gelatin gels, they do not melt in the mouth. In
fact, no polysaccharide gels have this property.
An alginate solution whose pH has been lowered so that some of the carboxylate
groups (-COO-) are converted into carboxylic acid (-COOH) groups, with or without
addition of some calcium ions, is employed in the preparation of soft, thixotropic, non-
melting gels.
Strong complexes and precipitates are often formed when the pH of a mixture con-
taining proteins and alginate is lowered from 7 to 5. Interaction between protein and
alginate molecules occurs at pH values below the protein’s isoelectric pH value (pI)
where the protein molecules have a net positive charge. (Alginate molecules remain

Box 14.1 Typical Products Containing Algins

Sodium alginatea Propylene glycol alginate (PGA)
Alfredo sauce Buttered pancake syrups
Barbecue sauce Cheesecake
Breakfast bars Cheese spreads
Caramels Chocolate milk mixes
Dry soup mixes Cocktail mixes
Frozen gravy Frozen desserts and novelties
Frozen guacamole Fruit punch
Fruit purees Fruit syrups
Macaroni and cheese Icings and frostings
Nonrefrigerated dessert gels Instant cocoa mix
Pimento pieces for Spanish olives Low pH syrups
Sauce mixes Milk shakes
Structured bacon substitute pieces Pourable salad dressings (regular and
and structured fruit pieces reduced-calorie)
Structured nut pieces Sandwich spreads
Structured onion rings Seasonings
Vegetable patties Tarter sauce
Whipped toppings
Sodium alginate D acid
Fruit-containing, filled breakfast cereal products and cereal bars
Jelly-type bakery fillings
Nonrefrigerated dessert gels
Tomato aspic
a
Many of these applications require natural or added calcium ions.
Algins/Alginates 301

negatively charged at pH 5.) Alginate-minced fish, alginate-comminuted meat, and

alginateewhey complexes are formed in this way.
Ingredient labels for products containing an algin may read algin, alginic acid, so-
dium alginate, potassium alginate, or ammonium alginate depending on the product
used.
Propylene glycol alginate (PGA) is used when stability to acid, nonreactivity with
calcium ions (for example, in milk products), or its surface-active property is desired
(Box 14.1). It is a common ingredient in salad dressings, including low-calorie salad
dressings. In both regular and low-calorie pourable dressings, it is often used together
with xanthan (Chapter 11). The PGA plus xanthan combination produces more uni-
form flow than does xanthan alone. PGA is also used as a thickener for fruit syrups.
Propylene glycol alginate and algin derivative are acceptable label designations.
Alginic acid, although insoluble, swells in water and is used commercially as a
tablet disintegrant. It is sensitive to heat, a property that is characteristic of all polysac-
charides with free carboxylic acid groups, except xanthan (Chapter 11).

Additional resources
Donati, I., Holtan, S., Mørch, Y.A., Borgogna, M., Dentini, M., Skjåk-Bræk, G., 2005. New
hypothesis on the role of alternating sequences in calcium-alginate gels. Bio-
macromolecules 6, 1031e1040.
Draget, K.I., Smidsrød, O., Skjåk-Braek, G., 2002. Alginates from algae. In: Vandamme, E.J.,
De Baets, S., Steinb€uchel, A. (Eds.), Biopolymers, Polysaccharides II, Polysaccharides
from Eukaryotes, Vol. 6. Wiley-VCH, Weinheim, pp. 215e224.
Draget, K.L., 2009. Alginates. In: Phillips, G.O., Williams, P.A. (Eds.), Handbook of Hydro-
colloids, second ed. CRC Press, Boca Raton, pp. 807e828.
Helgerud, T., Gåserød, O., Fjæreide, T., Anderson, P.O., Larsen, C.K., 2009. Alginates. In:
Imeson, A. (Ed.), Food Stabilisers, Thickeners and Gelling Agents. Wiley-Blackwell,
Oxford, pp. 50e72.
Siew, C.K., Williams, P.A., Young, N.W.G., 2005. New insights into the mechanism of gelation
of alginate and pectin: charge annihilation and reversal mechanism. Biomacromolecules 6,
963e969.