Carrageenan Modification

Sugar and Starch Technology

Advance Fisheries Processing
M Nur Ghoyatul Amin
 Concern area
• What is carrageenan modification ?
• Why carrageenan is modified?
• Assorted chemical modification of
carrageenan
• Future research on carrageenan modification
• A case study on enzymatically modified
carrageenan for ice cream making
Kappa-carrageenan (CR)
Source of CR : K.alvarezi
What is carrageenan modification?
• Modifying carrageenan through modifying the
free hydroxyl bound of carrageenan to
modulate its functionalities or even enhace its
functionalities
 Why?
• Modification is carried out to modulate its
physicochemical properties
• Native carrageenan can not meet
requirements in developing food product
• Meet industrial customer needs
• Worth
 Hydroxyalkyl carrageenan
• Production : Modified carrageenan avoiding
syneresis in gelled products
• Stimulate the wider industrial use
Syneresis
Syneresis
 Calcium cloride modification
• Production : The association of k-carrageenan
with CaCl2can change the swelling properties
of carrageenan gels, emphasizing the
commercial relevance of carrageenan
chemical modifications
Artificial Caviar can be made by using distictive
CaCl2 concentration
Polyacrylamide cross-linked carrageenan

• Production : this modified CR was made

through 2 steps
– Hydrogel product made by cross-linking
carrageenan- polyacrylamide
– Alkaline hydrolysis
• Carraggenan with high absorbance in high
saline solution
Gel formation process
 Grafted carrageenan
• Production : Grafting of k-carrageenan with
methyl methacrylate was carried out by
employing microwave irradiation
 Methyl methacrylate linked carrageenan

• Employed by using microwave irradiation

Stimuli response swelling hydrogel
 Carrageenan copolymerization
• Production : The copolymerization of k-
carrageenan with acrylic acid and 2-
acrylamido-2-methylpropanesulfonic acid led
to the development of biodegradable
hydrogels with potential use for novel drug
delivery systems
Hydrogel used for pharmaceutical purposes
Topical medication
 Copolymerizated carrageenan is used to
immobilize enzyme
• Increases of the storage and thermal stability
of the enzymes necessary for use in
continuous systems
 Nano composite carrageenan
• Production : Co-precipitation of calcium
phosphates into a k-carrageenan matrix
• Use : Modulate the porosity and morphology
carrageenan matrix for application in bone
tissue engineering
 Carrageenan-nano hydroxyapatite- collagen

• The association between carrageenan, Nano-

hydroxyapatite and collagen resulted in an
injectable bone substitute biomaterial,
suitable for bone reconstruction surgery
 Phosporilated carrageenan
1. Production through 3 steps
a. Sulphating was carried out using chlorosulphonic
acid (HClSO3)in N,N-dimethylform-amide (DMF)
b. Acetylation employed acetic anhydride (Ac2O)
and pyridine (Py) in DMF
c. Phosphorus oxychloride (POCl3)/Py in formamide
(FA) followed by hydrolysis
 The use of phosporylated carrageenan

• Enhance antioxydant activity

 K-Selenocarrageenan
• Low molecular weight CR for antitumor agent
 Acylated carrageenan
• Production : Depolymerized carrageenan was
acylated by carboxylic acid anhydrides using
DMF as solvent and 4-dimethyl-aminopyridine
(DMAP)/tributylamine (TBA) as catalysts
• Carried out in partial free hydroxyl group of k-
carrageenan
O-acylation of k-carrageenan
 The use of acylated carrageenan
• Anti-HIV
• Anticoagulant
 O-maleoyl k-carrageenan
• Production : Reaction of tetrabutylammonium
salt of the anionic polysaccharide fragments
with maleic anhydride,4 dimethylaminopyridine
and tributylamine under homogeneous
conditions in N,N-dimethylformamide
• It takes place at all free hydroxyl groups of k-
carrageenan, the maleoylate substitution
resulted in the formation of a monoester
derivative at the C2 of the G4S unit
Chemical reaction in O-maleoyl k-carrageen
syntesis
 The use of O-maleoyl k-carrageen
• Increase the density of the negative charge
and rigidity of the carrageenan molecule,
• Enhance the anti-HIV activity
 AZT (Azidothymidine) associated
carrageenan
• Production : A succinate diester spacer was
used to attach one molecule of AZT to a tirade
of k-carrageenan residues
 The use of AZT (Azidothymidine) associated
carrageenan
• Reduction of the individual doses, avoid-ing
AZT toxicity and preventing the emergence of
drug-resistant virus strains
 Why?
• Ice recrystalization in ice cream manufacturing
is unwanted because it can make grainy taste
and texture
• A piece of prior reserach revealed that k-
carrageenan could not well avoid
recrystalization
 Production of enzymatically modified
carrageenan
• Principles : decrease molecular weight of CR
• Using enzyme adhering to beta bond of CR
(beta glucosidase)
Native k-carrageenan
24h-hydrolized carrageenan with
beta-glucosidase
48h-hydrolized carrageenan with
beta-glucosidase
 How come ?
• The influence of k-carrageenan, guar gum and
LBG on the recrystallization rate in ice cream
and those substances influence re-deposition
of water molecules on ice crystals surfaces
 How come ?
• Oligosaccharides gained after k-carrageenan
acid hydrolysis, with lower molecular masses,
could selectively bind to certain faces of the
ice crystals and limit the crystal growth in
certain directions.
• This could lead to limitation of the possibility
of organization of water molecules in a crystal
lattice with large hexagonal ice crystals.
 Author’s recommendation
• Beta-galactosidase enzymatically hydrolized
carrageenan is not that good as acid hydrolysis
which was indicated by number of fractions
formed
 Future works
• Identifying more potent and specific
compounds with antitumor,
immunomodulatory, anti hyperlipidemic,
anticoagulant and antiviral activities
• Drug discovery and delivery by using modified
carrageenan
• Building prototype of products incorporated
by modified carrageenan
Thanks.