10/26/2009

FS630
Dr Nicolas Bordenave
Room 3151
nbordena@purdue.edu

Outline
Origin and sources
Physico-chemical properties
(Potential) Applications and uses
Food applications
Chitosan as dietary food additives
Original works and trends

10/26/2009

Origin and Sources

Crustacean shells, insect exoskeleton and some fungi =

mainly chitin.
Rouget (1859): chitin boiled in a concentrated potassium
hydroxide solution
CHITOSAN.

Origin and Sources

Annual production: 10,000 tons of chitin (2000)
Starch: 60 million tons in 2004.

Price: $ 10-30/lb
Starch: $ 0.10-0.15/lb

Chemical specialty
1300 million tons of chitin produced per year in marine
ecosystems
huge potential.

10/26/2009

Outline
Origin and sources
Physico-chemical properties
(Potential) Applications and uses
Food applications
Chitosan as dietary food additives
Original works and trends

Physico-chemical properties
Deacetylation
(boiling 40-50%
NaOH)

Chitin

Chitosan

- Decalcification (dilute HCl)

- Deproteination (dilute NaOH)
- Decolorization (0.5% KMnO4 and
oxalic acid)
Shrimp or custacean
shells

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Physico-chemical properties
(1
4) linked D-glucose units

(1
4) linked N-acetyl-D-glucos-2-amine units

(1
4) linked D-glucos-2-amine units
Degree of DeAcetylation > 60%

DDA

Physico-chemical properties
Slightly crystalline in native state.
Whitish / ivorish color.
Odorless / tasteless.
Soluble in water at acidic pH (
DDA).

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Physico-chemical properties
Molecular weight, degree of polymerization
Degree of DeAcetylation
Viscosity
Solubility
Antimicrobial properties
Reactivity
Complexation ability

Physico-chemical properties
Molecular weight ~ 105-106 Da
Determined by : GC / HPLC , Light scattering, Viscosimetry (
MarkHouwink law)

Film forming ability
Degree of DeAcetylation
Determined by : UV spectrophotometry, Dye adsorption, IR
spectroscopy, GC, Potentiometric titration
Viscosity affected by : DDA, Ionic strength, Mw, Concentration
Solubility affected by : DDA, Solvent mixing, Chemical modification

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Physico-chemical properties
Antimicrobial properties:
Mechanism still unknown
hypotheses:
binding to cell-wall phospholipids of Gram-negative
bacteria

modification of cell-wall permeability and loss of material
inhibition of certain enzymes and of mARN synthesis
Complexation ability
metal ions
anionic polymers
amino acids, proteins, DNA, cells
dyes
fats and cholesterol

Physico-chemical properties
Enzymatic or chemical
hydrolysis

Reactivity

10/26/2009

Physico-chemical properties
Reactivity
-OH: esterification, etherification, oxidation,
elimination
-NH2: amidation, reduction, mono-, di- and
trialkylation (electrophile subsitution)
Protection reactions
Elimination, oxidation

Modifications of solubility, antimicrobial activity,
complexation ability.
Kurita, K. Controlled functionalization of the polysaccharide chitin.
Progress in Polymer Science. 2001, 26(9), 1921-1971.

Outline
Origin and sources
Physico-chemical properties
(Potential) Applications and uses
Food applications
Chitosan as dietary food additives
Original works and trends

10/26/2009

(Potential) Applications and uses

Main properties used: antimicrobial , film forming, binding
capacity.
Application

Example

Water treatment

Removal of metal ions

Flocculant/coagulant (proteins, dyes, amino
acids)
Filtration

Pulp and paper

Surface treatment
Photographic paper
Carbonless copy paper

Medical

Bandages, sponges
Artificial blood vessels
Blood cholesterol control
Tumor inhibition
Skin burns, artificial skin
Eye humor fluid
Contact lenses
Controlled release of drugs

(Potential) Applications and uses

Application

Example

Cosmetics

Make-up powder
Nail polish
Mosturizers

Biotechnology

Enzyme/cell immobilization
Protein separation
Chromatography
Glucose electrode

Agriculture

Seed/leaf coating
Hydroponic/fertilizer
Controlled agrochemicals release

Food

Removal of dyes and acids

Preservative
Color stabilization
Animal feed additive

Membranes

Solvent separation
Permeability control

10/26/2009

Outline
Origin and sources
Physico-chemical properties
(Potential) Applications and uses
Food applications
Chitosan as dietary food additives
Original works and trends

Food Applications
 Chitosan as dietary food additives
As a dietary supplement, chitosan
doesnt need FDA approval.
BUT chitosan is NOT APPROVED as a
food additive in many countries.

10/26/2009

Food Applications
Applications as dietary supplement for hypocholesterolemic diets
Hypocholesterolemic potential of dietary fiber comes from:
nondigestibility in the upper gastrointestinal tract
high viscosity
polymeric nature (viscous)
high water binding properties
low water binding properties in the lower
gastrointestinal tract

Chitosan meets most of these criteria

Food Applications

Chitosan can bind anions (DDA): chitosan salts can be prepared with
bile acids and free fatty acids (oleic, linoleic, palmitic, stearic or
linolenic) or amidated with long alkyl chains

After ingestion, chitosan-fatty acid salts can bind additional lipids
because of hydrophobic interactions (cholesterol, triglycerides, sterols,
additional fatty acids)

A great portion of these bound lipids are excreted rather then
absorbed by the mammals
(HCl in stomach would not hydrolyze chitosan-fatty acid salts because
it would not be wet)

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10/26/2009

Food Applications
Alternative method:

Chitosan-citric acid salts can also be used: enhanced emulsification
with fats in the stomach, precipitation with pancreatic juice, excretion
of chitosan gelled matrices

80% of fat ingested not digested in rats

Other potential food application:

Binding of toxic peptides thought to be partly responsible for celiac
disease.

Outline
Origin and sources
Physico-chemical properties
(Potential) Applications and uses
Food applications
Chitosan as dietary food additives
Original works and trends

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10/26/2009

Original works and trends

Synthesis of a non pH-dependent antimicrobial agent from chitosan:

Water-soluble and antimicrobial

whatever the pH
Still with the characteristics of a biopolymer (biodegradable,
biocompatible, renewable resource,)

Original works and trends

Schiffs base
formation (with
formaldehyde)

Reduction of
Schiffs base

Here, R=H
Alkali catalyzed
alkylation

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10/26/2009

Original works and trends

Trends:
Nanoparticles for drug delivery (micelles, nanogels
with alginate, )
Scaffolds for tissue engineering (cell adhesion)
Biomaterials,

Summary
Crustacean shells

Chitin

Boiling in conc. alkali

Chitosan

Chemical properties: DDA, Mw, reactivity on hydroxyl and

amino groups

Physical properties: film forming ability, binding ability,

antimicrobial activity

Uses: mainly biomedical applications (antimicrobial

properties), food dietary supplement (binding properties)

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