The Irish are given credit
for the discovery of the seaweeds and
their extracts. Some 600 years ago the
shore residents of county Carragheen on
the south Irish coast first used the weed
or Irish moss (Chondrus crispus) as they
are called, in food, medicine and as fertilizer
and also noted its milk reactivity. The
Irish settlers coming to America brought
with them a taste for Irish moss and it
was soon found to occur as a component
of natural flora of the coast of Massachusetts.
In the earlier literature the polysaccharide
extract of Irish moss was named as carrageen
and carrageenin but now these are dropped
on the recommendation of Polysaccharide
Nomenclature Committee and the name carrageenan
is adopted.
Carrageenans are water-soluble gums
which occur in certain species of red
seaweeds of Gigartinaceae, Solieriaceae,
Phyllophoraceae, Hypneaceae, Furcellariaceae,
Rhabdoniaceae, Rhodophyllidaceae and
some members of Rhodomelaceae, of which
five families occur on Indian coasts.
The important genera of carrageenophytes
occurring in India are Acanthophora,
Grateloupia, Halymenia, Hypnea, Laurencia,
Portieria, Sarconema, Sebdenia and Solieria.
Chemical Nature:
All carrageenans have the common structural
feature of being linear polysaccharides
built up of alternating 1,3 linked b
-D -galactopyranosyl and 1,4 linked
a -D- galactopyranosyl units. Carrageenans
are anionic polyelectrolytes. The charged
nature of the sugar units and their
structural arrangement within the macromolecules
render the carrageenans chemically highly
reactive and account for its gelling
property. Carrageenans have a wealth
of possibilities for substitution on
the basic co - polymer, admits the possibility
of a continuous spectrum of carrageenan
types. However, these exist as variants
and hybrids of a small number of ideal
or limit polysaccharides of definite
chemical nature.
In 1953 Smith and Cook separated from
Chondrus crispus (Irish moss) two fractions
of varying properties which they named
as kappa and lambda
carrageenans. Kappa was defined as that
fraction which was precipitated with
KCl, while lambda was the fraction,
which remained in solution. Chemical
studies of these fractions revealed
that nearly half of the sugar units
in kappa carrageenan were 3,6- anhydro
-D- galactose, while lambda carrageenan
contained little or none of this sugar
unit. Rees and his co-workers based
on their investigations have defined
carrageenans in terms of chemical structure
which for convenience are named by Greek-letter
prefixes as mu, kappa, nu, iota, lambda,
theta, and xi carrageenans.
In kappa-carrageenan, the 1,3- and
1,4-linked units are D-galactose-4-sulphate
and 3,6-anhydro-D-galactose respectively.
Mu- is considered to be the biological
precursor of kappa. Mu- differs from
kappa- in that the anhydride is replaced
by D-galactose-6-sulphate. In the seaweed,
the change from mu- to kappa- is catalysed
by the enzyme dikinkase. While kappa-
forms gel with water in the presence
of certain cations, notably potassium,
its precursor mud- is non-gelling.
Similarly nu- is believed to be the
precursor of iota. Chemically they differ
from their respective counterparts,
mu- and kappa- only in having a sulphate
group at C2 on the 1,4-linked units.
Again nu- is a non-gelling fraction
and iota is the gelling fraction
Lambda is a non-gelling carrageenan,
which differs from nu- in that about
70%
of the 1,3-linked units are sulphated
at C2 rather than C4, the remainder
being unsulphated. However, unlike either
iota- or kappa-, the alkali-modified
lambda-, which has been named theta-carrageenan,
is non-gelling. Theta carrageenan is
yet to be identified as occurring naturally.
Xi-carrageenan, which replaces lambda
in some Gigartina species (G. chamissoi,
and G. canaliculata) has not been completely
characterised, but seems to differ from
lambda- in that the 1,3-linked units
are completely sulphated at C2, while
at least some of the 1,4-linked units
are unsubstituted at C6.
A new family of carrageenans with
1,3-linked units free of sulphates have
been reported as the polysaccharide
of Eucheuma gelatinae. This family consists
of beta carrageenan, analogous to kappa
carrageenan but lacking sulphate on
the C4 of the 1,3-linked units and its
precursor gamma carrageenan analogous
to mu-
Lambda- and kappa- carrageenans were
found to occur together in the carrageenan
extracted from Chondrus crispus and
some Gigartina species, although they
do not occur on the same plant. It has
been shown that kappa- occurs only on
the haploid gametophytes of Irish moss
and lambda- only on the diploid tetrasporic
forms. Since the various forms grow
together and harvested and used for
extraction yields contain a mixture
of two carrageenans. However, their
ratio varies and averages about 70%
kappa- and 30% of lambda-
Reactivity: The chemical reactivity
of carrageenans is primarily due to
half-ester sulphate groups that are
strongly anionic, being comparable to
sulphuric acid in this respect. The
free acid is unstable and commercial
carrageenans are available as stable
potassium and calcium salts or a mixture
of both. The associated cations together
with the conformation of the sugar units
in the polymer chain determine the physical
properties of the carrageenans.
Reactivity with proteins is exhibited
by both gelling and non-gelling carrageenans.
In most cases ion-ion interaction between
sulphate groups of the carrageenans
and the charged groups of the protein
are involved. The reaction depends on
protein/carrageenan net charge ratio
and thus is a function of isoelectric
point of protein, the pH of the system
and the weight ratio of carrageenan
to protein.
Carrageenan is an anionic polysaccharide
gum having hydrocolloidal properties.
The commercially important property
referred to as milk reactivity is rather
remarkable for carrageenan to stabilize
casein micelles. In natural milk this
is brought about by k-casein. On a weight
for weight basis, kappa carrageenan
is as effective a micelle-builder as
k-casein, while lambda- carrageenan
is less effective. Theta -carrageenan
is more effective than lambda- though
less effective than kappa-. The property
of micelle stabilization may account
for the effectiveness of carrageenan
as stabilizer for evaporated milk and
infant food formulae. Industrial importance
of carrageenan is greatly due to its
ability to cause agglomeration of protein
solutions, in particular the casein
particles in cow's milk. The carrageenan-protein
reaction is quite specific and is influenced
by the amount and location of O-sulphate
groups on the molecule and molecular
shape.
The less desirable property of carrageenan
is its susceptibility to depolymerization
through acid -catalysed hydrolysis.
This is shown to be related to 3,6-anhydride
content of carrageenans. Carrageenans
in gel state are more stable to acid
than those in sol state. The secondary
and tertiary structures developed on
gelation may exert a shielding effect
on the glycosidic bonds. This effect
permits the use of carrageenan in acid
system, if enough potassium salt is
present to develop a gel structure.
The carrageenans can be induced to form
thermally reversible gels in the presence
of specific cations. The rate of acid
catalysed degradation is proportional
to hydrogen ion activity with maximum
stability at a pH of about 9. The rate
of acid-catalysed degradation increases
with temperature. Carrageenans are relatively
resistant to alkaline degradation.
As in other naturally occurring polysaccharides,
carrageenans also do not have sharply
defined molecular weights, but rather
have average molecular weights representing
a distribution of molecular species
identical in structure but of varying
chain length. Commercial food grade
carrageenans typically have average
molecular weights in the region of 2,00,000
Daltons. The functionality of carrageenans
in most food and industrial application
depends on molecular weight and is largely
lost if it is below 1,00,000 Daltons.
PHYSICAL PROPERTIES:
Appearance: Commercial carrageenans
are cream-coloured to light brown powders.
Under low-power magnification, individual
particles are seen to be short -fibre
segments (alcohol-precipitated products),
or as thin flakes (roll-dried products).
Density: Particle density averages
about 1.7 gms. /cm3. Nominal bulk density
is about 0.6g. /cm3 (39 lb./ ft3 ) for
roll-dried products and 1g/cm3 (64 lb./ft3
) for alcohol-precipitated products.
Solubility: Hot water: Carrageenans
are soluble in hot (>75oC) water.
Only the viscosity of the solution limits
solubility. For commercial carrageenans,
solutions containing up to 10% carrageenan
can be prepared and handled with conventional
mixing equipment.
Cold water: Sodium salts of kappa-and
iota are soluble in cold water, while
salts of other cations such as potassium
and calcium do not dissolve completely
but exhibit swelling. Lambda- is fully
soluble in cold water, regardless of
the cations with which it is associated.
Hot milk: All carrageenans are soluble
in hot milk.
Cold milk: Lambda- carrageenan has the
greatest ability to disperse and thicken
milk without the need of solubilising
salts. Its insensitivity to calcium
and potassium ions, along with its high
ester sulphate content, may account
for this cold-milk reaction.
With regard to kappa- and iota- carrageenans,
the 3,6 -AG content, and the lower ester
sulphate content cause the greater insolubility
in cold milk. This is attributable in
part to the increased sensitivity of
these carrageenans to potassium and
calcium, which are the constituents
of the milk. However even kappa- and
iota types, which are practically insoluble
in cold milk, may be used effectively
for thickening and gelling if tetrasodiumpyrophosphate
(TSPP) is used.
Concentrated sugar and salt solutions:
Kappa- and lambda- carrageenans are
soluble in hot sucrose solutions with
concentrations as high as 65%. Iota-carrageenan,
however, is sparingly soluble under
these conditions. On the other hand,
iota- and lambda- solutions will tolerate
high concentrations of strong electrolytes
(20 to 25% of NaCl), while kappa- will
be salted out.
Water - miscible solvents: Alcohol,
propylene glycol, glycerin, dimethyl
sulphoxide and other such water-miscible
solvents may be incorporated into carrageenan
solutions. The concentration of the
solvent, which can be tolerated, depends
upon the molecular weight of carrageenan
and the type of carrageenan and cations
present, as well as the method of incorporation
of the solvent. Thus the higher the
ester sulphate contents of the carrageenan
and the lower its molecular weight,
the higher is the solvent tolerance.
Also, the lower the concentration of
salts present, the higher is the tolerance.
Organic solvents: All carrageenan products
are insoluble in organic solvents, even
the most polar ones.
Biological / Toxicological properties:
Carrageenan is listed as GRAS (Generally
Recognised As Safe) food product by
the FDA, of U.S.A. Intensive investigations
into carrageenan's safety carried out
by the FDA and other medical institutes
proved that no gastrointestinal ulceration
is caused by the carrageenans; carrageenan
is not teratogenic and it is not carcinogenic
either.
Rheological properties:
Viscosity: Carrageenans typically form
highly viscous solutions. This is due
to their unbranched, linear macromolecular
structure and polyelectrolyte nature.
Viscosity depends on concentration,
temperature, the presence of other solutes
and the type of carrageenan and its
molecular weight. The viscosity increases
nearly exponentially with concentration.
Salts lower the viscosity of carrageenan
solutions by reducing the electrostatic
repulsion among the sulphate groups.
The viscosity decreases with the increase
in temperature. Again the change is
exponential and also reversible under
specific conditions. The viscosity increases
with molecular weight. Commercial carrageenans
are generally available in viscosities
ranging from about 0.005 to 0.800 Pa.s
(5 to 800 cP) when measured at 1.5%
concentration at 75oC. Lambda- type
or the sodium salt of unmodified mixed
lambda- and kappa- carrageenans are
used for water thickening applications.
Here, high water viscosities are desirable
which is contributed by the high molecular
weight and the hydrophilicity of lambda-
carrageenan.
Gelation: Water gels: Kappa - and iota-
carrageenans have the ability to form
gels on cooling of a hot solution. These
gels are thermally reversible, i.e.
they melt on heating and gel again on
cooling. Kappa- and iota - carrageenans
will not gel in the sodium form but
will form gel with potassium, calcium
or ammonia. In the case of kappa- carrageenan,
potassium ions produce strongest gels
whereas iota carrageenan produces the
strongest gel with calcium. Pure potassium
kappa produces a gel that is clear and
compliant, and usually subjected to
syneresis. Iota- carrageenan by itself
yields compliant and transparent gels
that are not subject to syneresis. The
gelling temperature of a specific type
of carrageenan is relatively insensitive
to carrageenan concentration and is
primarily a function of the concentration
of gelling cations present. The melting
temperature of a carrageenan gel is
higher than its settling temperature.
The melting and gelling temperatures
of kappa- carrageenan are increased
by the presence of sucrose. Aqueous
kappa- gels do not normally exhibit
freeze-thaw stability. Considerable
change in gel structure, as well as
substantial water release, may take
place. The more hydrophilic iota- shows
better stability in the freeze-thaw
cycle.
Milk gels: All carrageenan products
have the ability to form gels on cooling
a solution of the carrageenan in hot
milk. Even lambda-, which does not gel
in water, regardless of the cations
present, will form milk gels at levels
of 0.2% by weight of the milk. This
gelation is attributed to the formation
of carrageenan-protein bonds. The presence
of fat also influences the behaviour
of carrageenans in milk. Strongly gelling
kappa- carrageenan can be used in high
-fat systems. Kappa- produces gels in
milk, which have the same brittle nature
that they have in water. Moreover, they
are very prone to syneresis. These undesirable
properties can be ameliorated with the
addition of salts such as orthophosphates,
carbonates, citrates etc. Iota-carrageenan
does not produce the same syneresis
-free gels in milk that it does with
water. If TSPP is included, however,
syneresis is markedly reduced and the
gels become more compliant. In cold-milk
systems, soft gels can be produced by
lambda- or theta- when used at sufficient
concentration.
EXTRACTION OF CARRAGEENANS
Carrageenan is a complex process and
there are methods available. In this
manual two simple methods are described
in some detail. One describes extraction
with alkaline water and the other with
a solution of sodium bicarbonate.
A product similar to carrageenan in
all properties and feasible of application
in
All formulations in which carrageenan
is used, is obtained by cooking the
seaweed in a solution of potassium hydroxide.
This product is called semi-finished
carrageenan. Procedure preparation of
this product is also given below.
Before extraction, the seaweed is pulverized,
bleached and dried. For semi-finished
carrageenan, it may not be necessary
to pulverize the seaweed, but bleaching
is necessary.
Pulverizing the seaweed : This can
be achieved using a dry grinder and
sieving the powder through 40-mesh sieve.
If, however, the quantity of seaweed
is limited, mechanically grind with
mortar and pestle. Grinding is not necessary
for semi-finished carrageenan.
Bleaching : The seaweed powder or seaweed
thalli should be bleached by treating
first with 5 volumes of acetone with
stirring. Filter to get rid of the green
liquid. Treat the residue with boiling
80% alcohol for a few minutes and then
with absolute alcohol. A final treatment
with diethyl ether at room temperature
completes the bleaching process. The
seaweed powder is recovered by filtration
and is then dried in an oven at 60o
C.
The dry bleached seaweed is used in
the extraction process.
I. Extraction with alkaline water :
1. Soak 5 gms. of dried seaweed powder
in about 100 ml. of distilled water
made alkaline (pH 8) with 1N NaOH for
15 mints. Use 500 ml. Ehrlenmeyer flask.
2. Cover the flask with aluminium foil.
Make a small hole in the foil. Autoclave
for 11/2 hrs.
3. Filter the viscous solution while
it is hot, into a suitable beaker (500
ml.)
4. Cool the extracts to the room temperature.
5. Observe if the extract gels immediately
on cooling.
6. If the extract does not gel on cooling,
but remains highly viscous, the carrageenan
can be precipitated by adding 2.5 times
the volume of isopropanol
7. Remove carrageenan by filtration
and dry in an oven at 60o C overnight.
8. If gel is formed, place the gel in
a freezer. The following day, frozen
gel can be thawed and then dried.
9. Weigh the dry carrageenan obtained
and calculate the yield. Of carrageenan
from dry weight of seaweed used.
10. Save the product for further testing.
II. Extraction with sodium bicarbonate
1. Treat 5gms. of dried seaweed with
100 ml. of 0.5M sodium bicarbonate solution
(1:20 W/V)
2. Autoclave for 11/2 hrs.
3 to 10 - Repeat process as in I above
III. Semi-finished carrageenan:
1. Soak 5 gms of dry seaweed in 20 volumes
of distilled water for 20 minutes.
2. Place the soaked seaweed in a cloth
bag and secure the bag.
3. Immerse in 150 ml. of 1N solution
of potassium hydroxide and cook for
1 hr in a water bath.
4. Remove the bag containing cooked
seaweed and soak in fresh water for
1 hour to remove the residual alkali.
5. After soaking, take the bag out and
rinse thoroughly in running water.
6. Dry overnight in an oven at 60oC.
TESTS FOR CARRAGEENAN
KCl solubility:
1. Prepare 0.1% solution of the carrageenan
by dissolving 100mg.of dry powder in
100 ml. of distilled water at 70o C..
2. Add 10 ml. of 3M KCl solution.
3. Observe if a precipitate is formed
and record your observation. (The solution
can be subsequently filtered and reprecipitated
with 2.5 volumes of isopropanol)
Methylene blue test:
1. Prepare 1% solution of carrageenan
in distilled water.
2. To 10 ml of the sample solution add
4-5 drops of 1% aqueous solution of
methylene blue.
3. Observe the interface part of the
solution for fibrous agglomeration.
Milk reactivity:
1. Prepare 10 ml. of 0.154% solution
of carrageenan.
2. Add this to 10 ml. of hot homogenised
milk.
3. Look for flocculation of milk casein.
Gel formation
1. Dissolve 1 gm. of carrageenans in
100 ml. of 1% KCl solution at 70oC.
2. Transfer part of the solution to
a 50ml. beaker and allow it to cool
down to room temperature.
3. Observe if gel is formed.
Viscosity measurements using Ostwald's
viscometer
The apparatus : Ostwald's viscometer
makes use of the rate of flow of a fluid
through a capillary tube of a given
length. The figure below gives the details
of construction of the apparatus.
The determination of the viscosity of
carrageenan solution with this viscometer
involves the following steps :
1. Determination of viscometer constant
2. Determination of density of solvent
3. Determination of the absolute viscosity
of the solvent
4. Preparation of carrageenan solutions
5. Determination of density of carrageenan
solutions
6. Determination of rate of flow of
carrageenan solutions and
7. Calculation of viscosity
1. Determination of viscometer constant
: Take one litre of filtered and deaerated
distilled water in a suitable vessel.
Immerse the viscometer in the water
upto about 2 cms. above the upper graduation
mark. The viscometer should be clamped
vertically. Using a serological pipette
with a long tip, add 3 ml. of distilled
water to the wider arm of the viscometer
(if its capacity is 5 ml.) carefully,
avoiding air bubbles. Allow to equilibrate
for 5 mints. With a soft rubber bulb,
gently draw the liquid up the capillary
arm to a level just above the upper
graduation mark. Using a stop-watch,
time the flow of water from the upper
graduation mark to the lower mark, to
the nearest 0.1 sec. Repeat the process
five times and average the five recorded
times.
Calculate the viscometer constant k
using the formula k = h / td , where
h is the absolute viscosity of water
= 0.8937 cps at 25 oC t is the time
in seconds and d is the density of water
= 0.9978 ml -1 at 25oC.
Repeat these proceedings for each viscometer.
2. Determining density of solvent
Carrageenan solution is prepared only
by using 0.1M sodium chloride as solvent.
Therefore, density of the solvent has
to be determined.
Use a clean volumetric flask of 10 ml.
capacity. Accurately determine its tare.
Fill the flask upto the graduation mark
with deaerated distilled water. Determine
the weight. Determine the exact volume
of the flask from the formula V = M
/D where V is volume in millilitres,
M is weight in grams and D is the density
of water = 0.9978 ml -1 at 25oC.
Using this calibrated flask, determine
the density of 0.1 M NaCl using the
formula Do = M /V where Do is the density
of the solvent, M is the weight of the
solvent and V is the volume of the flask,
as determined above.
3. Determining the absolute viscosity
of the solvent
Prepare 500 ml. of 0.1 M NaCl solution
using deaeratd distilled water and filter
through a membrane. Determine the absolute
viscosity of this solution using an
Ostwald viscometer, following the procedure
given in (1) above.
4. Preparation of carrageenan solutions
Use 0.1 M NaCl solution as solvent.
Accurately weigh out 75 mg. of carrageenan
into a volumetric flask. Add approximately
40 ml. of the solvent and stir vigorously
for 30 to 45 mts. at room temperature,
until all the carrageenan is dissolved.
(A magnetic stirring bar can be used.
In that case, after dissolution, the
magnetic bar should be retrieved and
rinsed with a small amount of the solvent
into the flask.) Allow to remain for
10 mts. to equilibrate and then make
up the volume with the solvent. The
stock solution will have 0.15% concentration.
Prepare three dilutions in the following
proportions between stock and the solvent.
(i) 15 ml. stock - 25 ml. solvent
(ii) 15 ml. stock - 50 ml. solvent
(iii) 3.0 ml. stock - 25 ml. solvent
The final concentrations of the solutions
will be
Stock - 0.15%
Dilution (i) - 0.09%
Dilution (ii) - 0.045%
Dilution (iii) - 0.018%
The above dilutions will serve well
for k-carrageenan; if lambda- carrageenan
is used, use only half the above concentrations.
5. Determination of densities of carrageenan
solutions
Follow procedure given in (2) above,
but with the carrageenan solutions (all
dilutions) prepared.
6. Determination of flow of carrageenan
solutions
Follow procedure given for water in
(1)
7. Calculation of viscosity
i. Calculate the absolute viscosity
h for each solution from the formula
h = ktd, where k is viscometer constant,
t is the time of flow in seconds and
d is the density of the solution
ii. Calculate the specific viscosity
using the formula h sp = (h - ho ) /
h0 where ho is absolute viscosity of
the solvent.
iii. Calculate the reduced specific
viscosity h sp / C where C is the percentage
concentration of the solution
iv. Plot h sp / C against C in a linear
graph and draw a straight line through
the data using a least squares fit.
Infrared spectroscopic analysis can
be done for the samples if extracts
and can be compared with Authentic samples
of kappa-, lambda- and iota carrageenan
CHEMICAL ANALYSES OF CARRAGEENAN
I. Estimation of galactose (Total carbohydrate)
Phenol-sulphuric acid method
Reagents:
5% phenol: 5 gms. of phenol crystals
dissolved in 100 ml. of glass distilled
water.
Sulphuric acid (analytical reagent -
96%)
Procedure:
1. Take 1 ml of the carrageenan solution
provided.
2. Add 1 ml. of 5% phenol and 5 ml.
of sulphuric acid and mix thoroughly
by shaking (or using a cyclomixer)
3. Allow the solution to stand for 10
mints.
4. Read optical density at 490 nm.
5. Compare with standard graphs prepared
with different concentrations of D-
galactose ranging from 10 to 100mg/ml.
6. Express the result as mg. of galactose
per mg. of carrageenan.
Estimation of 3, 6 anhydrogalactose:
Acetol -resorcinol method (Yaphe and
Arsenault, 1965)
Reagents
I. Preparation of acetol :
1. Place 50gms. of anhydrous calcium
chloride and 260 gms. (323 ml.) of 95%
ethyl alcohol in a 1 litre narrow necked
bottle and cool the mixture below 8oC.
2. Introduce 120 gms. of fresh acetaldehyde
(Boiling point 20-25oC) slowly down
the sides of the bottle to form a layer
of alcoholic solution.
3. Stopper the bottle and mix by shaking
for 3-4 mins.
4. Allow the bottle to stand for 20-30
hrs.,with intermittent shaking.
5. After final shaking, leave undisturbed
for 1-2 hrs. till the mixture separates
into two layers.
6. Separate the upper layer.
7. Wash three times with 80 ml. distilled
water.
8. Dry for several hours over 6gms.
Anhydrous potassium carbonate and fractionate.
The fraction collected is pure acetol,
boiling point 101-104oC. Specific gravity
ml = 850 mg. Yield - 200 gms.
Stock solutions:
A. Take 0.1 ml of acetol and make up
to 10.3 ml. with glass-distilled water.
B. Take 0.1 ml. of stock A and make
up to 2.5 ml. with glass distilled water
II. Resorcinol:
Dissolve 150 mgs. of resorcinol in 100
ml. of glass distilled water. Keep in
refrigerator until required.
Procedure:
a. To 1 ml. of carrageenan solution
taken in ice-bath, add 5 ml. of cold
acetol-resorcinol reagent and mix thoroughly
by shaking.
ii. Transfer the sample to an oven maintained
at 80oC for 30 mins. until a permanent
light violet colour appears and then
transfer back to the ice- bath for three
mins. Read O.D. at 555 nm. in a spectrophotometer.
Compare with standard graphs prepared
with different concentrations of D-fructose
( 10 - 100 mg / ml.)
Estimation of sulphate content in carrageenan:
Reagents:
1N HCl 6M HCl.
70% solution of sorbitol Barium chloride
Procedure
a. Take 10 ml. of the carrageenan solution
and add 1 ml. 6M HCl and 5 ml. of 70%
sorbitol followed by 1 gm. Of barium
chloride, shake in a rotor and then
read absorbance at 470 nm.
b. Compare with standard graphs made
with different concentrations of potassium
sulphate (10 to50mm / ml)
ECONOMIC IMPORTANCE
Carrageenan is employed in food application
primarily to gel, thicken or stabilize.
Secondary advantage includes improved
palatability and appearance. It is used
in both milk and water systems.
Food applications:
Carrageenans are valuable gelling agents
as well as viscosity improvers in foods
and they are effective at relatively
low concentrations, which can offset
their somewhat high cost. They are used
in dry mixes such as cooked puddings
and pie fillings, cooked flans and custards.
In chocolate milk, chocolate syrup,
ice creams and sherbets, canned milk,
infant food formulations, whipped cream
etc. All these are milk-based applications.
As for as water applications are concerned
they are used in fruit drinks, jellies,
relishes, pizza, fish gels, pet foods
etc. While using carrageenan in most
cases locust bean gum is used which
alters the structure of the carrageenan
gel and gives a smoother texture.
Medical and pharmaceutical uses:
A discovery by Elsner, Broser and Burger,
which is important from the medical
point of view is that carrageenan even
in very great dilution acts as an anti-coagulant
of blood. Among the carrageenans lambda
type was found to be most potently anticoagulant
at low concentrations. In France and
Great Britain carrageenan is used in
control of stomach ulcers.
Lambda carrageenan at concentrations
of 0.1 to 1.0 may be used as hand lotions
and creams to provide slip and improved
rub-out. It is interesting to know that
it is frequently noted that fishermen
who collect Irish moss have surprisingly
soft skin on their hands.
In toothpaste carrageenans function
as a "binder" to impart the
desired rheological properties to the
paste and to provide the cosmetic "sheen".
Carrageenan suffers severe competition
with sodium carboxymethyl cellulose,
a much cheaper gum. Despite this, carrageenan
has maintained a strong position in
this application due to its superior
quality and its immunity to degradation
by enzymes, which attack cellulose gums.
Apart from toothpaste, carrageenan is
also used in the production of shaving
soaps, hair creams etc. The extractive
plus potassium salts are used for tablet
binding in pharmaceuticals.
Other applications:
Air freshener gels: Mixture of kappa-
carrageenan, other gums and a gelling
salt such as potassium chloride are
used to prepare air freshener gels.
Volatile odour-absorbing compounds and
fragrant oils incorporated in the gel
are released uniformly from the gel
surface as the gel dries down.
In textile industry carrageenan is extensively
used at a concentration of about 5%
as a stiffening and binding material.
It produces a soft finish and a surface
to which the printing will adhere.
For beverage clarification, for metal
fabrication, to thicken latex emulsion
paints, as abrasive suspensions, for
ceramic glazing etc also carrageenans
are used.
A new important use is in connection
with antibiotic ice used in fishing
boats in order to preserve the fish.
The antibiotic is far better distributed
through the ice in the presence of carrageenan.
Carrageenan and locust bean gum provided
the greatest range of condition at which
recrystallisation rate of ice is inhibited.
TRY OUT THESE RECIPES
Desserts : Water Gel
Ingredients :
Carrageenan 6gms
Sugar 80gms
Trisodium citrate 0.8gm
Adipic acid 3gms
Flavour and colour 0.3 gm
The ingredients are mixed well and dissolved
completely in one (8 oz.) of boiling
water. Then one cup of cold water is
added. The solution is frozen in a zero
degree constant temperature for 24 hrs.
The gel is removed and thawed at room
temperature for 4 hrs. and then served.
Milk pudding :
Ingredients :
Lambda carrageenan 270 mesh 4gms
Non-fat milk solids 20gms
Sugar 47gms
Colour and flavour as desired
Blend dry ingredients and place in small
electric mixer bowl. Mix in one cup
(237 ml. ) of cold milk at low speed.
Whip at high speed for 3 mns. Fold in
one cup of cold milk at low speed for
1 min. Pour into mold; refrigerate.
Unmold after one hour. Pudding may be
consumed after 5 to 10 minutes.
Cooked custard:
Ingredients :
Iota - carrageenan 1.4 g.
Mixed kappa- and lambda- carrageenan
0.3 g.
Tetrasodium pyrophosphate 0.8 g.
Salt 0.3 g.
Sugar 54.2 g.
Colour and flavour as desired
Blend the dry ingredients, add one pint
of milk, and stir thoroughly in a saucepan
until completely dispersed. Bring to
a full boil over medium heat, stirring
constantly to prevent sticking. Remove
from heat, pour into molds, and refrigerate.
Chocolate milk
Ingredients :
Fine sugar 32.3 g
Cocoa 6.9 g
Mixed kappa- and lambda- carrageenan
0.15 g
Vanillin 0.08 g
Blend the above ingredients and disperse
in one pint of 2% butterfat milk with
agitation. Heat the milk to 71oC. Maintain
this temperature for several minutes
under agitation, then cool the mixture
rapidly with constant agitation as over
a surface cooler
FOR FURTHER READING
1. Anderson , N.S., T.C.S. Dolan, A.
Penman, D.A. Rees, G.P. Mueller, D.J.Stancioff
and N.F.Stanley. 1968 Carrageenans Part
IV. Variations in the structure and
gel properties of carrageenan, and the
characterization of sulphate esters
by infrared spectroscopy. J.Chem. Soc.
(C) : 602 - 06
2. Chapman, V.J., and D.J. 1980 Seaweeds
and their uses (Third Ed.) Chapman and
Hall, New York pp. 334
3. Craigie J.S., and C.Leigh 1978. Carrageenans
and agars. In : J.A. Hellebust and J.S.
Craigie, (eds.) Handbook of Phycological
methods : Physiological and Biochemical
Methods. Cambridge University Press,
Cambridge. Pp. 109 - 131.
4. Doshi, Y.A., R.G.Parekh, V.D.Chauhan
and M.M.Taqui Khan. 1984. Polysaccharides
fro Indian seaweeds. Proc. Industrial
carbohydrates conference. ATIRA, Ahemadabad
pp. 286 - 302
5. Guisley,K.B., N.F. Stanley and P.A.
Whitehouse. 1980 Carrageenan. In: R.L.
Davidson, (ed.) Handbook of Water-soluble
Gums and Resins. McGraw - Hill, New
York, pp. 5.1 to 5.30.
6. Guist, G.G. 1990. Application for
seaweed hydrocolloids in prepared foods.
In : I.Akatsuka, (ed.) Introduction
to Applied Phycology. SPB Academic Publishing.
The Netherlands. Pp. 391 - 400
7. Guven K.C., B. Guvener and E. Guller.
1990 Pharmacological activities of marine
algae. In : I.Akatsuka, (ed.) Introduction
to Applied Phycology. SPB Academic Publishing.
The Netherlands. Pp. 67 - 72
8. .Lewis, J.G., N.F.Stanley and G.G.Guist.
1988 Commercial production and application
of algal hydrocolloids. In : Carole
A.Lembi and J. Robert Walland, (eds.)
Algae and Human affairs. Cambridge University
Press, Cambridge pp. 205 - 236.
9. McLachlan, J.1985.Macroalgae (Seaweeds):
Industrial resources and their Utilization.Plant
and Soil 89 : 137 - 157.
10. Moirano, A.L. 1977.Sulphated seaweed
polysaccharides. In : Graham , H.D.
(ed.) Food Colloids. Avi.Publ. Co.,
Connect.347-381
11. Parekh.R,G.,Y.A. Doshi and V.D.
Chauhan. 1992. Indian Carrageenanophytes:
Economic potential and prospects. Seaweed
Rews. and Utiln. 15 (1&2) : 197
- 204.
12. Rees, D.A 1963 The carrageenan system
of polysaccharides I. The relation between
the K- and l- components. J.Chem. Soc.
1821 - 32
13. Smith , D.B. and W.H.Cook 1953 Fractionation
of carrageenin. Arch. Biochem.Biophys.
45 : 232 -3
14. Smith, D.B., W.H.Cook and J.L.Neal.
1954. Physical studies on carrageenin
and carrageenin fractions. Arch. Biochem.
Biophys. 53 : 192 - 204
15. Stancioff, D.J. and N.F.Stanley.
1969. Infrared and chemical studies
on algal polysaccharides. Proc. Int.
Seaweed Symp. 6 : 595 - 609
16. Stanford, E.C.C.1862 On the economic
applications of seaweed J. Soc. Arts.
10: 185 - 195
17. Yaphe, W. and G.P.Arsenault 1965
Improved resorcinol reagent for the
determination of fructose and 3,6-anhydrogalactose
in polysaccharides Anal. Biochem. 13
: 143 - 148