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Polyhydroxyalkanoates: Synthesis and Application: Review
Polyhydroxyalkanoates: Synthesis and Application: Review
REVIEW
Polyhydroxyalkanoates: Synthesis and Application
Nguyen Nguyen Xuan Vu (BI236), Nguyen Tien Hoang (BI9107)
ABSTRACT
As the humanity is entering the plastic age, the waste from synthetic polymers
has become a major problem since it would take thousands of years for these
material to completely decompose in the environment after being discarded.
A solution that receives many attentions nowadays is developing bio-
degradable polymers that can replace petroleum-based polymers. Such
material includes polyhydroxyalkanoate, a family of polymers synthesized via
bacterial fermentation. The polymers show comparable properties with their
synthetic counterparts, and can be applied in a number of aspects including
food packaging, drug delivery, medical implantation…
temperature, oxygen, water), depending on the may include heavy metals, or cornstarch, to weaken
nature of the decomposition material. the texture and easily decay.
- Compostable: Can decompose by composting - Hydro-biodegradable plastic: Plastics can be of
under certain conditions, or according to defined biological origin like cornstarch, plants ... or minerals
standards. When a material is compostable, it but biodegradable. These materials are to be
means that it can biodegrade in a given time, under biodegradable, in industrialized areas, under
certain conditions. However, not all 100% of defined conditions, published in the standards for
biodegrable plastic can be composted, because the biodegradable materials.
composting components will lose the usage value of
compost. The production of petroleum based plastics has a big
- Degradable: All plastic materials are capable of disadvantage of generating non-degradable waste
decaying. It is possible to disintegrate plastic by products. The non-biodegradable nature of these
mechanical methods such as, crushing, crushing, products, due to their high molecular mass and
grinding, ... Some plastics are added with additives complex structure imparts a high environmental
to accelerate the decomposition process under burden as they can remain in water bodies, soil and
certain conditions. such as: Light (photodegradable landfill for many years. Concerns over the harmful
plastic) oxygen (Oxo-degradable plastic). effects of these petrochemical derived plastics by
Mechanical decay resins into micro or nano-plastic public and environmental bodies have been
fragments. In the case of chemical decay, the resin increased. This awareness prompted a global
reacts with oxygen in a humid environment, scientific drive to develop alternative green, eco-
promoted by the light into CO2 and water. friendly and biodegradable polyesters and plastics
substitutes such as PHA or PLA
- Oxo-biodegradable plastic: Plastic made from
traditional petroleum-based materials, mixed with Polyhydroxyalkanoates or PHAs are linear
special additives to force it to decay. This additive biopolyesters. They are biodegradable polyesters
produced and stored within cells as energy and
Polyhydroxyalkanoate review |3
suitable for treatment in well-managed home there are not any standards but they are applied via
composting installations; GreenPla program (responded about 60% of organic
- TUV OK biodegradable SOIL: Biodegradability in materials transform to CO2 in minimum). Here some
the soil offers huge benefits for agricultural and trademarks are popular such as ABA Compostable
horticultural products, as they can be left to break Seedling, TUV OK Compost, the DIN-Geprüft
down in situ after being used. The OK biodegradable Industrial Compostable Mark and BPI Compostable.
SOIL label is a guarantee a product will completely
biodegrade in the soil without adversely affecting According to the survey of patent registration based
the environment; on Thomson Innovation database, it shows:
- TUV OK biodegradable WATER: Products certified
for OK biodegradable WATER guarantee - About 1446 patents related to biodegradable
biodegradation in a natural fresh water plastic have been registered for protection (from
environment, and thus substantially contribute to 1977-2015). The first patent, in 1977, filed in France
the reduction of waste in rivers, lakes or any natural involved the design of making a box made from
fresh water. Note that this not automatically biodegradable plastic;
guarantees biodegradation in marine waters;
- From 1977-1989, the number of patents applied
- Din-Certo v: Din-Certo certify industrial
for registration was not much (<10 inventions/year),
compostable products accroding to EN 13432 and
soared in 1990 with nearly 30 patents and peaked in
other national and international standards, where
2002 with 92 patents;
applicable. DIN CERTCO Gesellschaft für
Konformitätsbewertung mbH offers certification for - Currently, patents related to biodegradable
products made from biodegradable materials which plastic are being applied for protection in about 42
are compatible with home and garden composting. countries around the world, mainly in Japan, China,
It awards the "DIN-Geprüft home compostable" USA, Korea and Germany.
mark for this, along with an individual registration
number. Compostability linked with In addition, there are currently about 180
biodegradability represents an important element enterprises specializing in manufacturing bioplastics
of the recycle management system. The in general and biodegradable plastics in particular.
internationally recognised "DIN-Geprüft" mark from Among them, there are 45 companies in Germany,
DIN CERTCO can now also be awarded to products USA and Japan. According to estimation, by 2020,
which can be composted in the garden. Certification the market share of the bioplastic industry has a
is possible on the basis of the following current turnover of about US $ 30 billion, by 2030 expected
standard: AS 5810, NF T 518000. to reach US $ 324 billion.
Products that stand on ASTM D6400 or D6868 This information shows that the development of
standard are considered biodegradable abilities. biodegradable plastic production technology has
However, in the marine environment, ASTM D6691 great potential and is the general development
is applied. In compost home case, some standards trend of the plastic industry worldwide.
are used such as: AS 5810 and AS 4736 in Australia,
NF T 51800 in France, EN 17427 in Europe,
certificates from TUV Din-Certo in Austria-Belgium
as: OK Compost Home, DIN-OK Compost Home, DIN-
Geprüft Home Compostable Mark and Australasian
Bioplastics Association (ABA) Home Compostable.
1. MOLECULAR STRUCTURE OF PHA PHA granules are accumulated inside the bacteria in
the presence of an excess carbon source and a
PHAs are polyhydroxyesters of 3, 4, 5 and 6-
deprivation of other elements, such as nitrogen [2].
hydroxylalkanoic acids. The monomers are either
There are three factors could affect the products:
achiral or chiral with R configuration (Figure 2) [1].
the microorganism used, the carbon source and the
fermentation condition.
PHA synthases are the crucial enzymes of the
biosynthesis of PHA. Therefore, only bacteria strains
that contain this type of enzyme could be used to
produce PHA, such as Alcaligenes, Pseudomonas,
Enterobacter, Necator, Rhodobacter, Ralstonia and
Cupriavidus. Under suitable condition, certain
cyanobacteria and halophiles can also accumulate
PHAs [3].
It is also stated that, not only the biocatalysts are
responsible for the structure, composition and
Figure 2. General structure of PHAs and
properties of PHAs but also the carbon substrate
some examples.
used to growth them. Since the substrate molecules
The PHA polymers are sorted into 2 types: short- need to be transported through the rigid thick cell
chain-length PHA (scl-PHA) and medium-chain- wall of the microorganism, it is preferred for the
length PHA (mcl-PHA). 3-hydroxylbutyrate (3HB), 3- molecules to be small. Large polymeric molecules
hydroxylvalerate (3HV) and 4-hydroxylbutyrate need to be pretreated extracellularly either by a
(4HB) are the most common building blocks chemical process or by the microorganism itself to
representing for scl-PHA. The mcl-PHAs are made up become smaller for utilization. Generally, the
of building block of at least 6 carbon atoms. substrates can be categorized into three types:
Examples of the monomers are 3- simple sugars, triacylglycerol and hydrocarbons.
hydroxylhexanoate (HHx) and 3-hydroxyloctanoate Simple sugars can be used by most of the PHA-
(HO). In addition to these simple representatives, producing bacteria, and triacylglycerol is usable for
the side chains of mcl-PHAs can contain chemical a limited range of microorganism. Only
functionalities such as double bonds, aromatic rings, Pseudomonas species can undergo hydrocarbon
functional groups or chemical elements like metabolism. Using a same substrate, different
halogens, nitrogen, sulfur…[1] microorganism can produce different PHAs
composition. The information about substrates and
2. BIOSYNTHESIS AND PRODUCTION
their corresponding bacteria and products is
Briefly, PHAs are synthesized from various bacterial summarized in Figure 3 [4].
strains and renewable organic carbon sources.
Most of the carbon sources used in recent industrial
Under limited-nutrient condition, the bacteria can
manufacturing of PHAs are food-based, namely food
stack carbon inside their cells as energy reservoir or
crops, sugar cane and vegetable oils, as listed in
fat under the form of PHAs. The PHAs are then
Table 1. This results in a competition between the
purified and collected for further processing. By
production of carbon source and food supply
changing the bacteria family and carbon source,
production. For example, 34,000 tons of PHA
different PHAs can be produced.
produced per year would utilize about 126,000 tons
2.1. Biosynthesis of corn [4]. Thus a matter of interest now is to find
Polyhydroxyalkanoate review |6
Figure 3. A summary of the substrate and microorganism that can biosynthesis PHAs. Blue arrows
indicate substrates added later during the fermentation process to make copolymers.
a non-food-based carbon source, or better, recycle production wastes; and lipids from plant and animal
the wasted carbon. These carbon source could be waste (M. Koller, 2014).
molasses; lactose from whey; cellulose hydrolysates
Another crucial factor is the fermentation process.
from the reject fiber wastes from the paper
At first the bacteria strain is cultivated in mineral
industry; glycerol and methanol from biodiesel
medium which contains all necessary elements for
Polyhydroxyalkanoate review |7
the growth of the bacteria, namely phosphor (from be considered are: pH, temperature, shaking rate,
phosphate salts), nitrogen (from urea) and some fermentation scheme. These factors, in combination
metal ions, along with an excess amount of carbon with microorganism strains and carbon sources
from a carbon source like sugar or fatty acid. After would determine the composition of PHAs as
other elements are depleted, the microorganism illustrated by examples listed in Table 2 [3].
starts to accumulate the carbon intracellularly
under the form of PHAs [5]. Parameters that need to
harmless substances like CO2 and water. The PHAs [6] G. D. Christian et al., “Production of
are biosynthesized using a group of bacteria Microbial Polyesters :,” Managing, vol. 71,
containing PHA synthases. The polymers are no. 4, p. 10, 2001.
accumulated intracellularly as a carbon stock of the [7] K. Khosravi-Darani and D. Z. Bucci,
cells as others nutrient components are depleted. “Application of poly(hydroxyalkanoate) in
The PHAs having many commons in term of food packaging: Improvements by
physicochemical and thermomechanical properties nanotechnology,” Chem. Biochem. Eng. Q.,
with their petroleum-based counterparts like PP vol. 29, no. 2, pp. 275–285, 2015.
and PE. By changing the production condition, these
[8] “Production of Polyhydroxyalkanoates , a
properties can be controlled. bacterial biodegradable polymer,” vol. 3, no.
Since the PHAs family covers a wide range of January, pp. 18–24, 2004.
materials, it can be implemented in a variety of [9] D. Z. Bucci, L. B. B. Tavares, and I. Sell, “PHB
aspects, from food containers to biological devices. packaging for the storage of food products,”
However, the high cost of production remains as a vol. 24, pp. 564–571, 2005.
barrier for wide application of PHA.
[10] D. Z. Ã. Bucci, L. B. B. Tavares, and I. Sell,
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