m NEED FOR BIODEGRADABLE PLASTICS.

m OVERVIEW OF BIODEGRADABLE POLYMERS.

m BACTERIAL POLYESTERS
æ INTRODUCTION
æ HISTORICAL DEVELOPMENT
æ BIOSYNTHESIS PATHWAYS
æ GENERAL PROPERTIES
æ ECONOMIC FACTORS
æ APPLICATIONS
m FUTURE PROSPECTS
m Use of conventional plastics raises environmental
concerns.
m Conventional plastics are made from
nonrenewable fossil fuels ± mostly natural gas ±
8% of world¶s oil production is used as raw
material for plastics.
m Plastics are the world¶s most used material ± an
estimated 350 billion pounds of new plastic is
produced annually, and this number is growing.
m Only a small percentage of plastic is recycled.
m Impediments to recycling include Quality Control
issues, health risk (food packaging), very labor
intensive, thermoset plastics cannot be melted ±
ground up as fillers.
m Biopolymers are obtained via polymerization of
bio-based raw materials through engineered
industrial processes.
m Types of Bio-polymers;
æ Polyesters: Polylactic acid (PLA), Polyhydroxyalkanoate
(PHAs).
æ Proteins: Silk, Soy proteins.
æ Polysaccharides: Xanthan, Cellulose, Starch, Chitin.
æ Polyphenols: Lignin, Tannin.
æ Lipids: Waxes, Surfactants.
m PHA are a family of optically active biological
polyesters which contain (R)-3HA monomer units.
m Produced under conditions of:
æ Low limiting nutrients (P, N, S, O)
æ Excess carbon.

m Highly stereoregular. Polymer completely isotactic.

m General formula
m Most well known member is PHB

m Average molecular weight as high as 20 MDa.

m PHA exist as discrete inclusions that are typically 0.2 0.5 mm in
diameter localized in the cell cytoplasm.
m PHA ž
ž
is amorphous, whereas extracellular PHA is crystalline.
æ No current theory explains what prevents ž
ž
crystallization.
æ 5-10% water associated with the PHA may act as a plasticizer.
m The surface of in vivo PHA inclusions is a dynamic boundary region
where the proteins involved in the biosynthesis (PHA synthase) and
degradation (intracellular PHA depolymerase) of PHA are located.
m PHA synthase enzyme shows a broad substrate
specificity and therefore a wide variety of
monomers can be polymerized.
m Microorganisms are capable of producing PHA
from various carbon sources ranging from
inexpensive, complex waste effluents like beet or
cane molasses, to plant oils, alkanes as well as
simple carbohydrates.
m Multiple pathways for PHB synthesis exist based
on the available carbon source. Ex. Sugars, Fatty
acids.
m Steps involved in synthesis of
monomer for PHB are as follows;
1. Conversion of selected carbon
source to acetate.
2. Attachment of co-enzyme (CoA)
via a thioester bond.
3. Formation of acetoacetyl CoA.
4. Reduction to a monomer unit 3-
hydroxybutyryl-CoA.
m The polymerization involves a polymerase with
two active thiol groups and the reaction proceeds
via a thioester oxyester interchange reaction.
m Most important property being; biodegradability.
m PHA is stored as an energy reserve there exists an
effective pathway to convert it to simple organic
compounds.
m A wide variety of bacteria and fungi can secrete PHA
depolymerase.
m Rate of degradation depends on many factors
æ Environmental: Moisture, pH, Temperature, nutrient supply
æ PHA properties: Composition, crystallinity, additives.
m Composition of PHA depolymerase enzyme.
æ Consists of 3 characteristic domains.
æ a catalytic domain, a substrate binding domain, a linking
region connecting these domains.
m Characteristics similar to polypropylene.
A comparison of the physical properties of PHB and some of its
copolymers with those of polypropylene (PP) and low density polyethylene
(LDPE)3.
m Properties can be improved by co-polymerization
with other PHAs.
m PHB co-polymerized with PHV have commercial
applications.

m Production requires specific substrate. Added

costs.
m Factors that affect cost include; PHA productivity,
content, yield, cost of carbon substrate, recovery
process.
æ Cost decreases with increase in productivity. As productivity in
synthesis using recombinant M
ž increased from 1.98 g l-1h-1
to 3.2 g l-1h-1 cost decreased from US $5.37 to $4.91/kg PHB.
æ Raw material cost remained the same whereas fixed capital
costs, labor costs and utilities decreased.
æ Cost of carbon source can account for 38% overall cost.
æ Crude carbon sources such as cane molasses, cheese whey
etc. can be used. Productivity with these substrates is often
not as high as with pure substrates.
æ Cost of substrates for co-polymers add to cost. These are
more costly than the primary substrate.
m Global consumption of bio-degradable polymers has increased from 149.6
million lbs in 2001 to 600 million lbs in 2007.
m PHAs have very low water permeability (21 g/m2 per day)which make
them very attractive in applications in food and packaging. More than 7
times lower than PLA and PCL ~ 172 g/m2 per day
m First commercial product was introduced in 1982 by ICI named µBiopol¶.

m Due to its bio-compatibility it

has potential applications in the medical
field including- drug delivery,
surgical sutures, osteosynthetic material.
m Crop plants are capable of producing large amounts of a number of useful
chemicals at a low cost compared to that of bacteria or yeast.
m Production of PHA on an agronomic scale, using transgenic crops, could allow
synthesis of biodegradable plastics in the million ton scale compared to
fermentation, which produces material in the thousand ton scale.
m It is estimated that this could reduce the cost of PHAs to $0.20±0.50/kg.
1. K.Sudesh, Y.Doi, Synthesis Structure and Properties of
Polyhydroxyalkanoates: Biological Polyesters, Prog.
Polym. Sci. 2000, 25, 1503-1555.
2. R.W.Lenz, R.H.Marcessault, Bacterial Polyesters:
Biosynthesis, Biodegradable plastics and Biotechnology,
AChS, 2005, 6
3. C.S.K.Reddy, V.C.Kalia, Polyhydroxyalkanoates-An
Overview, Bioresource Technology, 2003, 87, 137-146.
4. A. Steinbüchel, B. Füchtenbusch, Bacterial and Other
Biological Systems for Polyester Production.
5. I. Chodak, Polyhydroxyalkanoate: Origin, Properties and
Applications; Monomers Polymers and Composites from
Renewable sources, Elsevier, 2008.