Value-Added

Chemicals and Polymers

from
Locally Available Resources

Biotechnology

Material Science

38

Search for Value-Added Chemicals and Polymers From Locally

Available Resources
The exploitation of indigenous land and
marine resources can help Mauritius position
itself as an important provider of a welldesigned selection of high-value chemicals
and products (Scheme 15). This part focuses
on oriented-type research aiming at
promoting the Green Bio-Refinery concept.
A bio-refinery is a facility that integrates

- fuels (e.g. ethanol, acetone, butanol,

esters)
- food / feed (e.g. amino acids, protein
products, peptides)
- fiber products (e.g. fiberboards, biocomposites, insulation material)
- fine chemicals (e.g. flavors, chlorophyll,
pigments, aromas, pigments), and

biomass
conversion
processes
and
equipment to produce fuels, power, and
chemicals from biomass. The bio-refinery
concept is analogous to today's petroleum
refineries, which produce multiple fuels and
products from petroleum. Instead of refining
petroleum to make hydrocarbon derivatives,
the technology refines biomass mainly into

- biogas (=> electricity + heat).

sugars, fibers, fuel, and energy. The sugars

are raw materials that can be used for
making many further products. Products
generated in a green bio-refinery may
include:
- bulk chemicals (e.g. organic acids like
lactic acid and solvents like ethyl lactate)

We have focused on sugar-cane as a

renewable raw material and our efforts
have been geared towards developing multidisciplinary expertise in the area of
advanced biotechnological fermentation of
sugar syrup/molasses to more value-added
chemicals.
Mauritius possesses a huge Exclusive
Economic Zone and the exploitation of
marine resources remains mostly untapped.
We have directed our research towards the
extraction of high value-added marine
polysaccharides from algae and seaweeds.

Renewable Resources

Land resources

Marine resources

Sugar-cane
Seaweeds and Algae

Saccharides and derivatives

glucose, sucrose
lactic acid and polylactic
amino acids and polypeptides
Natural polysaccharides:
cellulose, amylose etc.

Biopolymers, agar,
carrageenans, ulvans

Scheme 15. Value-added products from land and marine renewable resources

39

I Biofermentation of sugar-cane juice

The Sugar Industry has for long been the

One such niche product is lactic acid that can

backbone of the Mauritian economy with an

annual sugar-cane production of 5.2 Mtons,
yielding approximately 520,000 tons sugar,
150,000 tons molasses and 1.7 Mtons bagasse.
This industry is presently faced with major
challenges on account of the liberalization of
the world market and abolition of established
sugar protocols resulting in a 36% cut in the

be commercialized as such or after conversion

into other products. Present global demand
of lactic acid as a raw material for the
chemical industry is estimated at 90,000 MT
p.a. Various studies point to a major boost in
demand of lactic acid and related products
such as polylactic acid (bioplastics) and
lactate esters (300,000 MT by 2010). In

price of sugar.
The new price will be
readjusted
from
527
Euros/ton
to
approximately 340 Euros/ton by 2008. To be
prepared against future unforeseeable
fluctuations in the market, such as removal of
quota and further drop in price, the Sugar
Industry in Mauritius will have to diversify in
the medium and longer terms. Given this

industry, the most commonly used producer

strains come from the genus Lactobacillus, of
which the most widely used strain for
producing lactic acid is Lactobacillus
delbrueckii NCIB 8130.

perspective, sugar may no longer be the end

product but rather be considered as a raw
material for the local manufacture of valueadded chemicals and products. This also
assures the continued development of sugarcane in Mauritius. A list of possible end
products is given in Scheme 16.

ethanol (higher energy density, less volatile,

less corrosive). In support of our strategy, we
consider production of ethanol as a zero-order
solution for Mauritius, that is, it may prove
helpful in the short term only. However,
world
overproduction
and/or
strong
competition will push down the prices at least
at a mid-term perspective.

sucrose

Another interesting product is butanol, which

is considered as a biofuel more efficient than

chemical
conversion

furfural, furans, esters

sorbitol, manitol

fermentation
ethanol
glycerol
glycols
butanol
butanediol
isopropanol

lactic acid
citric acid
adipic acid
fumaric acid
acetic acid
acetaldehyde

propionic acid
butyric acid
succinic acid
itaconic acid
cyclodextrins
biopolymers

Scheme 16. Value-added products from sugar

39

Our contribution
We have performed the fermentation of
sugar-cane juice and syrup from Mauritius into
L-lactic acid using Lactobacillus delbrueckii
subsp delbrueckii (NCIM 2365) (Fig. 29). We
have demonstrated the feasibility of the
process in reasonably good yield. We have
also developed a reliable method to
quantitatively assess the amount of L-lactic
acid produced during fermentation using 1H
NMR. The conditions required for accurate
determination of lactic acid have been
determined through model studies using
mandelic acid as internal standard.
The
relaxation delay (RD) used for each NMR pulse
was found to be determinant in the
correlation between experimental and
theoretical ratios.

NMR spectra of solutions containing mixtures

of lactic acid, mandelic acid, and a fixed
concentration of sucrose were analyzed under
conditions preliminarily established and the
corresponding calibration curve plotted (Fig.
30). The accuracy of the determination was
found to be excellent for ratios of lactic acid
to mandelic acid between 0 and 2 but
deviations occurred as the concentration of
lactic acid compared to mandelic acid
increased.
The amount of lactic acid formed during
fermentation was calculated using the 1H NMR
spectra (Fig. 31) and equation 1. This
analytical method offers various advantages
over existing ones and can be extended to online monitoring of fermentation of sugars into
lactic acid in industry.

Molar percentage composition

90
80
70
60
Lactic acid
Unfermented saccharide

50
40
30
20
10
0
0

50

100

150

200

Time (h)

Fig. 29. Molar percentage composition of lactic acid and unfermented saccharides after 24 h,
48 h, 72 h, 96 h and 144 h as determined by 1H NMR.

40

Experimental molar ratio of lactic acid

to mandelic acid

5.00
4.50
4.00
3.50
3.00
2.50
y = 1.1118x - 0.0731
2.00
R2 = 0.9939
1.50
1.00
0.50
0.00
0.00
1.00
2.00
3.00
4.00
Theoretical molar ratio of lactic acid
to mandelic acid

Fig. 30. Calibration plot for mixture of lactic acid, mandelic acid, and sucrose.

HOD

OH

OH

C
c

b
COOH

C 6 H5
d

H
COOH
H3C

unfermented
saccharides
d

Fig. 31. 1H NMR spectrum of fermentation medium

41

Equation 1
a
I CH 3
mLA =
d
I
C 6 H 5
aI

CH 3

dI

C6 H 5

m MA

V soln

m 1000
x1.67 MA 90

152 V soln

= intensity of methyl protons of lactic acid

= intensity of phenyl protons of mandelic acid
= mass of mandelic acid
= volume of solution analysed

Publication
Ramanjooloo A, Bhaw-Luximon A, Jhurry D, Cadet F
1
H NMR quantitative assessment of lactic acid produced by biofermentation of cane sugar juice
Spectroscopy Letters, in press (2008)

42

II Extraction and Characterization of Biopolymers from Mauritian

marine environment
Seaweeds are classified into three major
groups: green algae (Chlorophyta), brown
algae
(Phaeophyta)
and
red
algae
(Rhodophyta) according to their pigments and
coloration.
Phycocolloids,
that
is,
polysaccharides of high molar masses can be
obtained from red algae. Carrageenophytes

Seaweeds and algae are abundantly available

on the Mauritian beaches, particularly on the
eastern coast. This proliferation constitutes a
major environmental problem and causes a
lot of inconveniences to the public and hotels
in that region. At present, the seaweeds are
treated as waste and disposed off by

and agarophytes produce two phycocolloids

namely: carrageenans and agar. These two
polysaccharides find numerous commercial
applications in the food, cosmetics and
pharmaceutical
industries.
The
carrageenophytes and agarophytes are found
in either tropical and warm waters, e.g.
Eucheuma and Hypnea or in colder waters,

incineration, which involves additional costs.

Prior studies in this area have been limited to
a taxonomic survey of algae and seaweeds
found around our coastal regions.
Red algae and seaweeds (Fig. 32) are major
sources of biopolymers such as carrageenans
and agarose, which find numerous specialty or
high added-value applications in food

e.g. Chrondus and Furcellaria species. In the

year 2001, the carrageenan production from
different regions via different precipitating
methods amounted to approximately 43,000
tons and the total market has a value of
about US$ 300 million.

industry, pharmaceuticals and cosmetics

formulations. From an economical point of
view, the exploitation of these naturally
occurring resources via extraction of their
biopolymers can prove to be most beneficial
to Mauritius rather than being considered as
trash.

Fig. 32. (a) Hypnea (b) Eucheuma (c) Gracilaria (d) Ulva species

43

Our contribution

I Extraction and characterization

biopolymers from seaweeds/algae

of

We have extracted biopolymers from red

seaweed and algae species, namely Hypnea,
Eucheuma and Gracilaria collected around
the coastal regions of Mauritius.
Various extraction conditions were used and
their effects on yield and structure of the
corresponding
biopolymers
were
investigated. The extracted polysaccharides
were characterized by a combination of IR,
NMR (Fig. 33, 34), SEC (Table 15),
viscometry and elemental analyses. These
revealed that polysaccharides extracted
from Gracilaria is a highly methylated agar
while Hypnea/Eucheuma contain essentially
-carrageenan.
We have also attempted to analyse the
contents of green algae species such as ulva
available abundantly on out east coast.

These species are protein rich and contain

saccharides such as rhamnose, glucuronic
acid, etc.
II Semi-pilot scale growth of Gracillaria
species
For a sustainable development of a seaweed
industry in Mauritius, the land-based culture
of species studied such as Gracilaria was
investigated (Fig. 35).
Our preliminary studies have shown that a
number of parameters need to be optimized
for successful growth. These parameters
are:
Salinity
Nutrient concentration (added nutrient)
pH control
Temperature control
Water quality
BOD level
Light intensity

Table 15. SEC-LS-Viscometry results for commercial and extracted carrageenans.

Sample
name
Iota
Kappa
Eu 15
Eu 9
Hp 15

Mw (LS)
[D]
316 00
268 000
315 000
202 000
169 000

Mn (LS)
[D]
140 000
184 000
173 000
135 000
84 000

Mw (conv)*
820 000
666 000
626 000
436 000
272 000

Mn (conv)*
[D]
233 000
135 000
127 000
119 000
83 000

[] bulk
[mg/g]
638
513
481
293
170

<Rg.> [nm]
68
48
89
46
52

conv stands for conventional SEC data analysis based on pullulan standards

Fig. 35. Semi-pilot land based culture of

Gracilaria

44

Biopolymers:
Carrageenan
s,
Agar,
Ulvans

OH
HOH2C

O
H O

H
H

H
O

O
H
H

OH
H

OH

Fig. 33. 1H-NMR spectrum of (A) commercial agar and (B) extracted agar.

OSO3-

HOH2C

H O

O
H
H

H
H

OH
H

OH

Fig. 34. 1H NMR spectrum of product extracted from Hypnea recorded in D2O at 25C.

Publication
Jhurry D, Bhaw-Luximon A, Mardamootoo T, Ramanjooloo A
Biopolymers from the Mauritian Marine Environment
Macromolecular Symposia (2006) 231(1), 16-27
45