Journal of Bioscience and Bioengineering

VOL. 110 No. 6, 621 – 632, 2010

www.elsevier.com/locate/jbiosc

REVIEW

Current trends in biodegradable polyhydroxyalkanoates

Suchada Chanprateep⁎

Department of Microbiology, Faculty of Science, Chulalongkorn University, Phayathai Road, Patumwan, Bangkok 10330, Thailand

Received 5 April 2010; accepted 26 July 2010

Available online 17 August 2010

The microbial polyesters known as polyhydroxyalkanoates (PHAs) positively impact global climate change scenarios by
reducing the amount of non-degradable plastic used. A wide variety of different monomer compositions of PHAs has been
described, as well as their future prospects for applications where high biodegradability or biocompatibility is required. PHAs
can be produced from renewable raw materials and are degraded naturally by microorganisms that enable carbon dioxide and
organic compound recycling in the ecosystem, providing a buffer to climate change. This review summarizes recent research
on PHAs and addresses the opportunities as well as challenges for their place in the global market.
© 2010, The Society for Biotechnology, Japan. All rights reserved.

[Key words: Polyhydroxyalkanoates (PHAs); Microbial polyester; Biodegradable polymer]

THE NECESSITY OF BIODEGRADABLE POLYMER AS A SUSTAINABLE
STRATEGY FOR PROTECTING AGAINST CLIMATE CHANGE
Materials made from synthetic polymers are not biodegradable
and are often improperly discarded. These materials are typically
derived from petroleum-based plastics. Rapid progress in materials
science technology has created new plastic products with favorable
mechanical integrity and excellent durability. Nevertheless, plastic
products usually have single-use applications, especially in food
packaging and medical materials. Because these plastic products are
not biodegradable, they are extremely persistent and accumulate in
the ecosystem, resulting in a significant burden on solid waste
management. The total global capacity of commodity plastic produc-
tion dramatically increased from 1.5 million tons in 1950 to
245 million tons in 2008, an annual growth rate of 9%. The biggest
potential growth area is in the rapidly developing Asian countries
(excluding Japan), where current plastics consumption per capita is
only around 20 kg (The compelling facts about plastics, The
Association of Plastic Europe, 2009). It is very difficult to reduce the
consumption of plastic products due to their versatile properties, but
it is possible to replace petroleum-based plastics with alternative
materials that have polymer-like properties and that degrade after
being discarded.
Among the various types of biodegradable plastics, polyhydroxyalk-
anoates (PHAs) are among the most well known, being recognized as
completely biosynthetic and biodegradable with zero toxic waste, and
completely recyclable into organic waste. They are microbial polyesters
produced by a wide range of microorganisms, mostly as intracellular
storage compounds for energy and carbon (1,2). PHAs are among the
most fascinating and largest groups of biopolyesters, with over 150
⁎ Tel.: + 66 2 218 5070; fax: + 66 2 252 7576.
E-mail address: suchada.cha@chula.ac.th.
different types of monomer composition that provide different
properties and functionalities (3–6). Their properties span a wide
range, including materials that imitate thermoplastic properties and
others that possess electrometric properties. PHAs are efficiently
degraded in the environment because many microorganisms in soils
are able to secrete polyhydroxybutyrate (PHB) depolymerases, enzymes
that hydrolyze the ester bonds of a polymer into water-soluble
monomers and oligomers. Microorganisms then metabolize these
degradation products into water and carbon dioxide (7–9). There are
several intensive academic studies of PHA production and applications,
mostly based on seeking inexpensive carbon sources to reduce the cost
of production (10–17) and applying genetic engineering to improve
productivity (18–26). This knowledge is now at a bottleneck, being
largely unused to bring products to the market. Only a few PHAs, mainly
polyhydroxybutyrate (PHB), poly(3-hydroxybutyrate-co-3-hydroxyva-
lerate) (PHBV), and poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)
(PHBH), have proceeded to the production stage in large quantities (27).
This review aims to summarize the recent trends in biodegradable
polymers, based on the current situation of PHA-based plastic products
available on the market. The review also addresses global policy that
may be useful for turning academic research towards the current
demand for biodegradable plastics.
GLOBAL MARKETS AND POLICIES
Environmentally degradable polymers (biopolymers) are one of the
possible solutions to replace some petroleum-based polymers. Based on
the definition given by the European Bioplastics Association, biopolymers
are based on renewable resources complying with ASTM D-6866 and can
be degraded to comply with international standards such as EN13432,
ASTM D6400, and ISO17088. In Europe, the criteria for biodegradability
are set out within the standard EN13432, 2000, which is binding when
applied to compostable packing under the EU directive on Packaging and

1389-1723/$ - see front matter © 2010, The Society for Biotechnology, Japan. All rights reserved.
doi:10.1016/j.jbiosc.2010.07.014
622 CHANPRATEEP
Packaging Waste (94/62/EC). In North America, similar criteria for
defining compostability have been established by the Institute for
Standards Research under ASTM D6400-99 Specification for Compo-
stable Plastics. Synthetic components, such as additives, colorants, or
glues, can be added to aid performance. Biopolymers can be classified
into three groups based on their biodegradable characteristics. The first
group consists of biopolymers that are not bio-based plastics but have
biodegradable or compostable properties. This group includes synthetic
biodegradable aliphatic–aromatic copolyesters, such as polybutylene
terephthalate adipate (PBTA), polybutylene terephthalate succinate
(PBTS), and polybutylene terephthalate glutarate (PBTG). The second
group includes bio-based polymers that are biodegradable or compo-
stable, for example (i) polylactide (PLA) (Ingeo™ by NatureWorks LLC,
USA), (ii) starch-based materials (Mater-Bi™ by Novamont S.p.A., Italy),
(iii) cellulose-based materials (NatureFlex™ by Innovia Films Ltd., UK),
(iv) PLA compounds and blends (Ecoflex® and Ecovio® by BASF, The
Chemical Company, Germany), and (v) PHAs (Mirel™ by Telles, USA).
The third group is composed of bio-based resources that are manufac-
tured into non-biodegradable polymers. This group includes bio-based
1,3 propanediol (PDO) from corn sugar (Bio-PDO™ by DuPont Tate &
Lyle Bio Products, LLC, USA), and bioethanol-based linear low-density
polyethylene (LLDPE) (Dowlex™ by Dow Chemical Company, USA) (27).
Alternatively, biopolymers can also be classified into four groups
based on their components. The first group is produced directly by
living organisms (e.g., cotton, silk, wool, other natural fibers, cellulose,
starch, lignin, oil proteins, natural rubber, and PHAs). The second
group is produced by polymerization of monomers that either exist in
nature or are derived from materials that exist in nature (e.g., PLA,
polytrimethylene glycol, soy-based polyols, and their derivatives).
The third group contains combinations of monomers from renewable
resources with petrochemical-derived monomers (e.g., isosorbate-
containing polycarbonates and soy-based urethanes). The last group
includes polymers produced from blends of renewable resources and
petroleum-based materials, such as blends of starch and polyvinyl
alcohol (Eco Flo® by Green Light Products Ltd., UK) (28). Table 1
summarizes the commercialized PHAs with their trade names and
manufacturing companies.
Members of the European Union have already established policies
against petroleum-based consumer packaging. For example, Belgium
has established an eco-tax of €3 kg−1 on packaging such as shopping
bags, whereas compostable shopping bags that conform to the European
Standard (EN) 13432 for compostable packaging material will be
exempted. The Netherlands has established a carbon-based packaging
tax based on CO2 emissions from the production of packaging material
and the embedded carbon content of the packaging. France, Italy, and
Spain are considering similar legislation. So far, two European countries
have established legislative measures for bioplastics and their deriva-
tives. Since June 2005, an interim regulation under the German
Packaging Directive exempts compostable packaging, enabling recycling
TABLE 1. The current and potential large volume manufacturers of polyhydroxyalkanoates (33).
Polymer Trade names
PHB Biogreen® Mitsubishi Gas Chemical Company Inc. (Japan)
PHB Mirel™
PHB Biocycle®
PHBV and PHB Biomer®
PHBV, PHBV + Ecoflex blend Enmat®
PHBH Nodax™
PHBH Nodax™
PHBH Kaneka PHBH
P(3HB-co-4HB) Green Bio
Polyhydroxyalkanoate from P&G Meredian
a
Bacteria to produce bioplastics, BIOPRO Baden-Württemberg GmbH, September 24, 2009 available at http://www.bio-pro.de/magazin/thema/04308/index.html?
lang=en&artikelid=/artikel/04310/index.html, accessed on March 2010.
b
Full-scale development of the world's first completely bio-based polymer with soft and heat resistant properties, Kaneka Corporation, March 10, 2009 available at
http://www.kaneka.co.jp/kaneka-e/news/pdf/090310.pdf, accessed on March 2010. n/a means price is not able to be found.
J. BIOSCI. BIOENG.,
without specific supporting documentation or measures. Since 2006 in
France, a regulation for the promotion of French agriculture requires
disposable retail bags to be biodegradable by 2010 (Political strategies
and statutory regulation, The European Bioplastics Association, 2010).
In the U.S., the San Francisco Board of Supervisors approved the
first-in-the nation legislation in 2007 that outlawed the use of non-
biodegradable plastic bags in large supermarkets within 6 months and
large chain pharmacies in about a year. Minnesota also bolstered its
ban on the disposal of yard trimmings in landfills recently when the
governor signed a bill forbidding the use of conventional plastic bags
for collecting yard trimmings in the Twin Cities area. This bill also
requires compostable bags to meet ASTM D6400 or be certified by an
independent organization. The law took effect on January 10, 2010
(Plastic Bags Legislation, The Council of State Governments/Eastern
Regional Conference, 2010).
Among Asian countries, Japan is the biotechnology leader in
biodegradable plastic. After ratification of the Kyoto Protocol in 2002,
the government announced two state measures, “Biotechnology
Strategic Scheme” and “Biomass Nippon Strategy,” to mitigate global
warming by promoting the use of renewable resources and applying
rapid advances in biotechnology (29). The Japan Bioplastic Association
(JBPA) classified bioplastics into two groups: (i) biodegradable plastics
(GreePla®) with biodegradable characteristics and biodegradable
synthetic high-polymer materials with an average molecular weight
of at least 1000 Da, including chemically modified starch- and
polyamino acid-based biodegradable high-polymer materials, and (ii)
biomass-based plastics (BiomassPla®) produced with either chemically
or biologically synthesized materials containing renewable organic
materials (excluding natural organic polymers that are not chemically
modified). The JBPA has estimated that demand for biomass-based
plastics will reach 20% of total plastic consumption in 2020. Thus, the
JBPA started the “Identification and Labeling System” in 2000 and has
certified about 900 biodegradable plastic products in Japan. The system
is based on a positive list system for all components, biodegradability
specifications based in Japanese Industrial Standards, safety certification
of all components, and proof of no hazardous effects to soil (http://
www.jbpaweb.net/english/english.htm). Standards for the biodegrad-
ability of plastics in the ISO have been proposed under TC61/SC5/WG22
(30). Table 2 shows the global policies that have been enacted stating a
requirement for biodegradable/compostable plastics.
CHALLENGES AND OPPORTUNITIES OF
POLYHYDROXYALKANOATES
Two of the most promising biopolymers are PLA and PHA. PLA has
received much attention as a potential alternative to existing materials
while PHA is challenging and price-competitive with petroleum-based
polymers. In the long term, bioplastics have significant potential for cost
reduction. The price of petroleum-based plastics could increase by 50–
Manufacturers Capacity (tons) Price (kg− 1)
(in 2010)
10,000 €2.5–3.0
Telles (US) 50,000 €1.50 a
PHB Industrial Company (Brazil) 50 n/a
Biomer Inc. (Germany) 50 €3.0–5.0
Tianan Biologic, Ningbo (China) 10,000 €3.26
P&G (US) 20,000–50,000 €2.50
Lianyi Biotech (China) 2000 €3.70
Kaneka Corporation (Japan) 1000 n/a b
Tianjin Gree Bio-Science Co/DSM 10,000 n/a
Meredian (US) 272,000 (2013) n/a
VOL. 110, 2010 CURRENT TRENDS IN BIODEGRADABLE POLYHYDROXYALKANOA 623

TABLE 2. The global policies and measures.

Countries National policies and measures

Germany a German Packaging Directive has been in force (2005). The compostable packaging will be exempt from the requirements in § 6 of the Directive
France a A law for the promotion of French agriculture has been in force (2006) stating a requirement for biodegradability of disposable retail carry bags by 2010
Italyb,c Markets in Florence had been charging €0.10–0.20 per plastic bag (2009)
Ireland, Scotland, Denmark These countries have already imposed levies and taxes on non-degradable plastic bags
c
and Sweden
UKc,e In 2003, county Durham has been charging Ecotax per plastic bag
d,e
US San Francisco: in March 2007, the San Francisco Board of Supervisors approved first-in-the nation legislation that outlaws the use of non-biodegradable
plastic bags in large supermarkets within 6 months and large chain pharmacies in about a year
Canada d Toronto City Council: retailers will be required to charge a minimum of 5 cents for each plastic retail shopping bag that customers take (2008)
Japan f Law on Promoting Green Purchasing and Law on Recycling have been in force in 2001
India d Plastic is officially banned in Ladakh
d
Australia Thin non-biodegradable plastic shopping bags have been prohibited in South Australia from 4 May 2009
d
Bangladesh From the beginning of January 2002, the Bangladesh government is banning the use of plastic bags in Dhaka
a
The Association European Bioplastics, European Bioplastics e.V., Berlin, available at http://www.european-bioplastics.org/index.php?id = 307, accessed on March 2010.
b
Banning plastic bags, available at http://www.treehugger.com/files/2009/02/5-great-green-ways-us-cities-leading-by-example.php, accessed on March 2010.
c
Plastic carrier bag taxes in Europe, 13.05.04.09, Mepex Consult AS, Norway, available at The California Product Stewardship Council (http://www.calpsc.org/).
d
Seattle bag tax and Styrofoam ban, The Northwest economic policy seminar, available at http://www.seattlebagtax.org/california.html, accessed on March 2010.
e
Sand Francisco First city to ban plastic shopping bags, San Francisco Chronicle, Hearst newspapers, Hearst Communications Inc., available at http://www.sfgate.com/cgi-bin/
article.cgi?file=/c/a/2007/03/28/MNGDROT5QN1.DTL, accessed on March 2010.
f
Green purchasing and green procurement in motion, Japan for sustainability newsletter #004, December 2002, Japan for Sustainability (JFS), available at http://www.japanfs.org/
en_/newsletter/200212-2.html, accessed on March 2010.

80% in 2012, based on the increasing price of oil (The Plastics Exchange
LLC, 2010). Most manufacturers of biodegradable plastics are small-
scale facilities (about 1000–20,000 tons per year of production), and
they lack the economy of scale of a single polyethylene unit with a
capacity of 300,000 tons per year of production. The world's largest
lactic acid manufacturing facility belongs to NatureWorks LLC in Blair,
Nebraska, U.S.A. with a capacity of 140,000 tons. In 2003, NatureWorks
LLC started to produce Ingeo™ PLA resin. Afterwards, PLA became the
first bio-based plastic produced on a large scale. Among PHA-
manufacturing companies, the main company with a large production
is the U.S. biotech company Metabolix, Inc. in Cambridge, Massachu-
setts. In 2010, Telles, a joint venture company formed by the Archer
Daniels Midland Company (ADM) and Metabolix, Inc. opened the first
commercial-scale plant to produce a corn syrup-based PHA resin,
Mirel™, in Clinton, Iowa, U.S.A. It is expected to begin shipping PHA resin
in April of 2010 and would produce 50,000 tons per year at full capacity
(Plastics Q6 News, 10 March 2010).
The history of commercialized PHAs goes back to 1959. W. R. Grace
and Company produced PHB in the U.S. for possible commercial
applications (Baptist, J.N., (Assignor to W.R. Grace & Co., New York)
US Patent No. 3225766, 1965). However, the company shut down the
process due to low production efficiency and a lack of suitable
purification methods. In 1970, PHBV was commercialized by Imperial
Chemical Industries Ltd. (ICI/Zeneca BioProducts, Bellingham, UK)
under the trade name of Biopol™ (31). In 1996, the technology was
sold to Monsanto and then to Metabolix, Inc. The U.S. Department of
Commerce Advanced Technology Program funded a project to re-
engineer the central metabolism of Escherichia coli for more efficient
conversion of renewable sugars into PHB. In 2008, Metabolix, Inc.
announced the combined production of PHA Bio-based Polymers and
Biomass Energy with a target to obtain PHA from switchgrass at a level
of 20% of dry-cell weight, 75% of which could be recovered. Thus, if
switchgrass yields are 10 to 15 tons per acre, then each acre will yield 1.5
to 2.25 tons of PHA bio-based polymers or derived chemicals, and
1 million acres will yield 3.3 to 5 billion pounds of PHAs (32).
Procter and Gamble, in partnership with Kaneka Corporation, Tsinga
University in China, and the Riken Institute in Japan, has developed a
wide range of applications for PHB and PHBH (Nodax™) as fibers, non-
woven materials, aqueous dispersions, and disposable products.
However, Nodax technology was sold in 1993 (33). Recently, Kaneka
Corporation has announced its plan to launch the production of a plant-
derived soft polymer called Kaneka PHBH in 2010, with a production
capacity of 1000 tons per year at Takasago City, Hyogo, Japan (http://
www.kaneka.co.jp/kaneka-e/news/pdf/090310.pdf). A German compa-
ny, Biomer Inc. (Kraaling, Germany) produces PHB on a commercial scale
for special applications. In 1993, Biomer acquired expertise and microbes
for PHB products from the Austrian company Petrochemia Danubia and
registered the trade name Biomer™ in 1995 (34). In Brazil, one of the
largest sugar-exporting countries, PHB Industrial S.A. (Serrana) uses
sugar cane to manufacture PHB (Biocycle™) in a joint venture started in
1992 between a sugar producer (Irmaoes Biagi) and an alcohol producer
(the Balbo Group). The company has been running a pilot plant at
50 tons per year and plans to increase production capacity to 3000 tons
per year (35). In Canada, Biomatera Inc. specializes in the manufacture of
PHA by fermentation of agricultural residues. The biopolymers are used
in the manufacture of creams and gels that are used as slow-release
agents in drug manufacturing and as cosmetic agents and tissue matrix
regeneration (36). In Japan, Mitsubishi Gas Chemical has made progress
on the production of PHB from methanol fermentation (BioGreen™)
(33). Table 3 presents physical, mechanical and thermal properties of
commercialized PHAs, and Table 4 shows the potential of commercial-
ized PHA to replace some petroleum-based plastics (37).
COST COMPETITIVENESS
In 2006, the cost of PHB was in the range of €10 per 12 kg−1. This
price was much higher than that of starch polymers and other bio-based
polyesters due to high raw material costs, small production volumes,
and high processing costs, particularly for purification (33). It was
concluded that raw material accounts for 30–40% of the total cost of PHB
(38). The latest market price of Mirel™ is quoted at about €1.50 kg−1
(Plastics News, 10 March 2010). This product combines biodegradability
with premium pricing relative to most petroleum-based plastics. PHAs
will soon enter the market and become potential candidates for
commodity materials. In 2010, the market potential of the total
bioplastics market in the EU will reach 200,000–500,000 tons. The
main markets are short term application for packaging and agriculture.
By 2020, the bioplastics market in the EU is forecast to increase to 2–
5 million tons and to expand to the textile, automotive, and agricultural
sectors, including many durable applications (BioplasticsMarket Trends
andU.S.&E.U.Outlook, FUJ00024, p. 132, Fuji-Keizai,October 2007). The
summary of market prices for PHAs in 2010 is given in Table 1.
SUSTAINABILITY AND ENVIRONMENTAL IMPACT OF PHAS BASED
ON LIFE CYCLE ASSESSMENT
The sustainability of fossil resource depletion and its environmental
impacts (such as greenhouse emissions) are important subjects of
624 CHANPRATEEP J. BIOSCI. BIOENG.,

TABLE 3. The physical, mechanical and thermal properties of some commercialized PHAs (37).
PHB PHB copolymers PHBV PHBH
Biomer240 Biomer P226 MirelP1001 MirelP1002 Biocycle100 Biocycle24005 Kaneka

Application grade Injection mold Injection mold Extrusion and injection Foam mold

Physical properties
Melt flow rate (g/10 min) 5–7 9–13 10–12 15–25 5–10
Density (g/cm3) 1.17 1.25 1.39 1.30 1.22 1.20 1.2
Crystallinity (%) 60–70 60–70 50–60

Mechanical properties
Tensile strength (MPa) 18–20 24–27 28 26 30–40 25–30 10–20
Elongation (%) 10–17 6–9 6 13 2.5–6 20–30 10–100
Flexural strength (MPa) 17 35 46 35
Flexural modulus (GPa) 3.2 1.9 0.8–1.8

Thermal properties
Melting temperature (°C) 170–175
VICAT softening point (°C) 53 96 148 137 120–125

ongoing scientific and political argument. An attempt to develop
biotechnological processes to produce chemical commodities from
renewable agricultural resources is one advocated approach that has
recently gained much attention. PHAs are currently included in these
considerations. Thus, it is necessary to ascertain whether the manufac-
turing processes preserve non-renewable resources and benefit the
environment as intended. Life Cycle Assessment (LCA) is a well-
established approach for identifying best practices within the complex-
ity of choices confronting society and industry. The LCA is an objective
procedure for evaluating the environmental impacts associated with a
product through every step of its life cycle starting from raw materials,
making it in a factory, selling it in a store, using it in the workplace or at
home, and disposing of it or recycling it into a new product (39,40). The
LCA methodology has been standardized under the ISO-14040 series,
and it distinguishes four phases: goal and scope definition, inventory
analysis, impact assessment, and interpretation (41). LCA evaluations
have been investigated, for example, in a notorious argument between
paper and plastic (42,43). It was found that although LCA usually leads
to a definite conclusion, its results can easily be reversed under different
environmental impacts, different inventory parameters, and/or differ-
ent boundaries of the study. For example, one may look at energy, solid
waste, or water. The number of published LCAs for PHAs is limited, and
only a few environmental analyses have been undertaken. Thus, this
article offers examples of LCAs that use different parameters to compare
between PHAs and synthetic plastics (or other bioplastics) with respect
to specific environmental impacts.
In earlier studies, most of the published LCAs of PHAs focused on the
consumption of fuel and non-renewable energy. In 1998, Heyde (44)
reported that the energy requirements for PHB production can exceed
the energy requirements for conventional plastics of high density
polyethylene (HDPE) and polystyrene (PS) (44). Likewise, Gerngross
(45) conducted a cradle-to-grave analysis of theoretical large-scale
PHA production from corn-based glucose versus a conventional PS
process. It was concluded that the replacement of conventional
polymers with fermentation-derived PHAs did not appear to be a
useful approach if the sustainable production of polymers is the
TABLE 4. The potential of commercialized PHA to replace the petroleum-based
plastics (33).
LPDE PP HPDE PS HI-PS PVC PET PA PBT
Mirel™ ++ + ++ ± + ++ ± −
Biomer® − ++ ++ + − − − − −
Nodax™ + ++ ++ − − + + − −
Biocycle® − ++ ++ + − − − − −
(++) Means probable; (+) means possible; (±) means doubtful; (−) means unlikely.
desired outcome. The biodegradability and biocompatibility benefits of
PHAs could justify the use of fossil resources; however, those benefits
have to be quantified and evaluated separately. A high level of energy
consumption from cradle-to-factory gate is an environmental burden
associated with corn cultivation (45). This assessment has led to
several LCA studies that adopted similar inventory analyses and
environmental impact assessments. These studies noted the high level
of energy consumption and negative environmental impacts from
plant cultivation (46–48). Kim and Dale (49) suggested that some
approaches to reducing the environmental burdens of agricultural
processes are necessary to achieve better profiles for photochemical
smog, acidification, and eutrophication associated with plant cultiva-
tion (49). In 2008, Kim and Dale (50) conducted an LCA evaluation
using information from Telles on site-specific processes such as corn
wet milling, PHB fermentation, and recovery. In this specific case, most
of the energy used in corn wet milling, PHB fermentation, and recovery
processes was generated in a cogeneration power plant in which corn
stover is burned to generate electricity and steam. In this case, PHB
derived from corn grain offers environmental advantages over
petroleum-derived polymers in terms of non-renewable energy
consumption and greenhouse gas emissions. Furthermore, PHB
provides greenhouse gas credits, and thus PHB use reduces greenhouse
gas emissions compared to petroleum-derived polymers (50).
Pietrini et al. (51) pointed out a different challenge of cradle-to-
grave environmental LCA comparisons of PHB-based composites with
petrochemical plastics. In this study, the end products were cathode ray
tube monitor housings produced from high-impact polystyrene and the
internal panels of an average car produced from glass-fiber-filled
polypropylene. The environmental impact was evaluated for non-
renewable energy use and global warming potential over a 100-year
time horizon. On a cradle-to-factory gate basis, all PHB composites
appeared to be environmentally superior to conventional polymers for
both chosen applications. When the analysis was extended to cradle-to-
grave (including the use phase, post-consumer waste incineration, and
energy recovery), PHB composites scored better only for the CRT
monitor housing. In the case of the automotive application, the weight of
the functional unit becomes overriding, and no substantial savings are
observed regarding environmental impact (51).
Mixed bacterial culture PHA production has the potential to produce
large amounts of PHAs at low cost due to lower sterility, equipment and
control requirements, and the ability to utilize a wide range of cheap
substrates (including industrial and agriculture wastes) (52–54).
However, Rhu et al. (53) reported that the production cost of PHA
from fermented food waste would be about US $13 per kg, meaning that
the production costs would exceed the existing disposal costs, making
PHA production an unattractive option (53). Gurieff and Lant (55)
VOL. 110, 2010 CURRENT TRENDS IN BIODEGRADABLE POLYHYDROXYALKANOA
conducted a comparative LCA and a financial analysis of mixed-culture
PHA production. The analysis was performed for industrial wastewater
treatment technology, and the conditions used for mixed-culture PHA
were compared with biogas production that utilizes the same waste
resource. It was concluded that mixed-culture PHA production was
preferable to biogas production for treating the specified industrial
effluent, and it was financially attractive in comparison to pure-culture
PHA production. In addition, the mixed-culture and pure-culture PHA
production processes had similar environmental impacts that were
significantly lower than HDPE production.
In 2009, Zhong et al. (56) investigated the environmental impacts of
three manufacturing processes for PHA production. The processes
studied were microbial PHA manufacturing using (a) glucose as a
carbon source, (b) cheese whey as a carbon source, and (c) PHA
production using genetically engineered plants. These processes were
compared with respect to ten indicators under three categories (i)
human health (carcinogenic effects, climate change, ozone layer
depletion, radiation, inorganic, and organic respiratory effects), (ii)
ecosystem quality (acidification/nitrification and eco-toxicity), and (iii)
sufficient supply of resources (fuels and minerals). It was concluded that
PHA manufacturing from transgenic plants was less beneficial over the
full cradle-to-gate life cycle than microbial PHA manufacturing with
glucose and whey. The main cause of this high life cycle impact was high
steam consumption. However, it was suggested that CO2 intake at the
corn forming stage can more than compensate for its CO2 emissions, and
its polymer extraction and compounding processes consume much less
power than the fermentation and recovery processes in microbial PHA
manufacturing. Using a renewable energy resource would make PHA
manufacturing from transgenic plants significantly better. One recom-
mended solution is using the residual corn stover, after extraction, for
electricity and steam (56). The available LCA results show that PHAs
could have advantages over petrochemical polymers in several
environmental impact categories (cogeneration power plant, green-
house gas credits etc.) but are less favorable in other categories
(eutrophication, acidification, etc.). This is a common occurrence in LCA
comparisons of different raw materials and products. In addition, the
different environmental impact categories are usually not regarded as
being of equal weight in terms of seriousness of the effect on the
environment. Under the current manufacturing technology, a number of
LCA reports have indicated that petrochemical polymers can have
equivalent or better eco-profiles than PHAs. The main factors influenc-
ing this assessment were energy for polymer manufacture, the effects of
the number of recycling loops, and end-of-life disposal (especially
methane generation in landfill). However, PHA manufacturing is
generally small-scale at present. It is likely that as the scale increases,
technical improvements and environmental economies of scale includ-
ing recycling potential will accrue for PHAs. At this stage, PHAs could
contribute to sustainability and help engage the public in environmental
awareness.
THE RESEARCH-TO-MARKET BOTTLENECK
PHA-producing microorganisms The microorganism of choice
for the industrial production of PHA varies depending on factors that
include the cell's ability to utilize an inexpensive carbon source (recent
attention has been paid to agricultural wastes and industrial by-
products), the cost of the medium, the growth rate, the polymer
synthesis rate, the quality and quantity of PHAs, and the cost of
downstream processes (57). Although more than 300 different
microorganisms synthesize PHAs (3–6), only a few, such as Cupriavi-
dus necator (formerly known as Ralstonia eutropha or Alcaligenes
eutrophus), Alcaligenes latus, Azotobacter vinelandii, Pseudomonas oleo-
vorans, Paracoccus denitrificans, Protomonas extorquens, and recombi-
nant E. coli, are able to produce sufficient PHA for large-scale production
625
(58). Some examples of patented PHA-producing bacterial strains
currently used in industrial-scale production are reviewed below.
In 1970, ICI Ltd. initiated the production of PHB and PHBV on an
industrial scale (200,000 l) (59). The process utilized a mutant of C.
necator, NCIB 11599 (60, Henman, T. J. and Holmes, P. A., ICI PLC (GB),
European Patent Application EP0052946, 1982). The fermentation was
carried out in a two-step fed-batch culture with glucose as the sole carbon
source, and phosphate as the limiting element to enhance PHB production.
The final biomass was 100 g/l with a productivity of 2.5 g/l h. The PHBV
was produced by providing a mixed feed of glucose and propionic acid in
the polymer accumulation phase. The content of 3-hydroxyvalerate (HV)
was regulated by adjusting the ratio of the two substrates in the feed (61).
In 1996, the PHA production process was acquired by The Monsanto
Company in the U.S., which stopped the production of PHB and PHBV at
the end of 1998 (62). Metabolix, Inc. developed recombinant E. coli K12 for
the overexpression of PHB, and this bacterial strain can produce 100 g/l of
PHB in 40 h (63).
Another industrial process for the production of PHB was
developed at the Biotechnologische Forchungsgesellchaft Company
in Linz, Austria (64). The process was based on A. latus DSM1124,
which can accumulate PHB at up to 80% of dry-cell weight in a one-
step fed-batch fermentation process using a mineral-salt medium
with sucrose as the sole carbon source. Although a biomass density of
60 g/l was achieved, the company stopped the production of PHB in
1993 (65).
Several academic research groups have focused on producing PHA
with high productivity and high yield to reduce the overall costs. Fed-
batch and continuous cultivation have been carried out to improve
productivity, either because of the difficulty of developing cultivation
strategies using unusual or expensive carbon substrates, or due to the
lack of applications to justify the high production costs (66–71). Several
strategies have been developed in academia for the efficient production
of PHA employing C. necator H16. By maintaining the glucose
concentration at 10–20 g/l during a fed-batch culture, a total biomass
of 164 g/l, a PHB concentration of 121 g/l, and a PHB content of 76%
could be obtained in 50 h, resulting in a peak productivity of 2.42 g/l h.
Using the same cultivation strategy, more than 110 g/l of PHBV could be
produced by feeding a mixture of glucose and propionic acid (68).
Several carbon sources other than glucose have also been used as
substrates for PHA production. Ethanol was tested for the production of
PHB by a mutant strain of C. necator, but the highest concentration of
PHB obtained was 47 g/l (72).
Several researchers (73–77) have tried to improve PHB production
by controlling the fermentation conditions. They developed mathemat-
ical models to maximize PHB production and used suboptimal
procedures such as maintaining a constant nutrient concentration.
The optimal feed profiles of glucose and ammonium hydroxide were
calculated using a model, and a final cell concentration of 141 g/l and a
PHB concentration of 105 g/l in 40 h of fed-batch culture were achieved
with C. necator, for a productivity of 2.63 g/l h (74). To date, the highest
PHB productivity (of 5.13 g/l h) was obtained in the short cultivation
time of 16 h using a fed-batch culture of A. latus DSM1123 under
nitrogen limitation (78).
In addition to high productivity, one concern (particularly in PHBV
production) is the rigorous control of HV content by the development of
an on-line feeding strategy for fed-batch cultivation. A series of studies
developed a novel multivariable control strategy for alcohol (ethanol
and n-pentanol) concentrations during the production of PHBV by P.
denitrificans ATCC 1774. This development coincided with an improve-
ment of the quality of PHAs produced. A simple metabolic reaction (MR)
model based on flux distribution analysis was constructed (75,76,79).
Fig. 1 shows the metabolic map for PHBV biosynthesis in P. denitrificans
ATCC17741 based on the consumption rates of ethanol and n-pentanol
as described previously (75). Next, a model predictive controller (MPC)
was developed and used for the on-line estimation of the specific
626 CHANPRATEEP J. BIOSCI. BIOENG.,

FIG. 1. Metabolic map for PHBV biosynthesis in Paracoccus denitrificans ATCC17741 based on consumption rates of ethanol and n-pentanol (75).

consumption rate and control of the alcohol concentration in fed-batch
cultures. The Multi-Input and Multi-Output (MIMO) controller success-
fully controlled alcohol concentration, and the 3HV mole fraction units
reached a given set point in the range of 0–70 mol%. The MPC was used
to optimize PHBV production with a target mole fraction of 3 HV units.
The amount of PHBV was maximized with a given mole fraction of 3 HV
units at the final cultivation step (76). Afterward, the random and block
polymers of PHBV that produced in a range of 0–90 mol% using two
feeding strategies were characterized using a non-isothermal kinetics
study. The exponent function quantified by Osawa's equation in block
PHBV was similar to that for PHB because the majority of the
components in the block polymer were the 3HB unit. The rate of non-
isothermal crystallization of block PHBV was faster than that of random
PHBV but slower than that of PHB. Using the conventional method, the
simultaneous feeding of ethanol and n-pentanol and the MPC system to
control alcohol concentrations precisely, the availability of ethanol and

FIG. 2. Control results of ethanol and n-pentanol concentrations (a) and 3HV mole fraction units (b) by Multi-Input and Multi-Output Controller under C/N of 50 (74). The SEM
micrographs of the surface of film made of random PHBV consisting of 5 mol% 3HV units (c) and 3-D images obtained from AFM analysis (d) (81).
VOL. 110, 2010
n-pentanol can be maintained throughout the cultivation time. The
recent evidence from PHA samples produced by the optimization
method has tended to demonstrate the possibility of producing block
PHBV. The combined strategy may affect the polymerization step by
natural dynamic changes of preferential consumption between ethanol
and n-pentanol due to the switching of the carbon to nitrogen (C/N)
ratio and the feeding strategy (80,81). Finally, their biodegradation rates
were also compared in an in vitro study. Scanning electron microscopy
(SEM) and trapping mode atomic force microscopy (AFM) were used for
high resolution imaging of the surface structure (Figs. 2 and 3). It was
observed that the surfaces of block PHBV samples are remarkably
different from those of random PHBV samples. The highest degradation
rate (of 2.6% per day) was observed for random PHBV produced by the
conventional method consisting of 38 mol% of HV units. The degrada-
tion rates of random PHBVs were about two times faster than those of
PHBVs produced by the optimized method (81). These observations
indicate that the development of a feeding strategy could affect the
quality of PHA produced and in turn change the physical and biological
properties of the biopolymer.
New bacterial strains identified in the laboratory have been reported
regularly, but research groups have struggled to optimize PHA
production with inexpensive carbon sources. There have been a few
reports on the production of the terpolymer poly(3-hydroxybutyrate-
co-3-hydroxyvalerate-co-4-hydroxybutyrate), P(3HB-co-3HV-co-4HB).
Chanprateep and Kulpreecha (82) were the first to report the pro-
duction and characterization of terpolymer P(3HB-co-3HV-co-4HB) by
the newly isolated C. necator strain A-04. A transmission electron
micrograph of an ultra-thin section of C. necator strain A-04 containing
PHB granules is shown in Fig. 4. The highest terpolymer content, 68%,
was produced at 60 h. The terpolymer with the highest (93 mol%) 4HB
FIG. 3. Control results of ethanol and n-pentanol concentrations (a) and 3HV mole fraction units (b) by a Model Predictive Controller under optimal strategy (74). The SEM
micrographs of the surface of film made of block PHBV consisting of 7 mol% 3HV units (c) and 3-D images obtained from AFM analysis (d) (81).
CURRENT TRENDS IN BIODEGRADABLE POLYHYDROXYALKANOA 627
mole fraction units was produced when the cultivation time was
extended to 96 h. The terpolymer P(4%3HB-co-3%3HV-co-93%4HB)
showed an elongation of 430%, a toughness of 33 MPa, and a Young's
modulus of 127 MPa, similar to those of low-density polyethylene, as
shown in Table 5. The terpolymer P(11%3HB-co-34%3HV-co-55%4HB)
showed a Young's Modulus of 618 MPa, similar to that of polypropylene,
as shown in Table 6 (82). The kinetics of P(3HB-co-4HB) production by
C. necator strain A-04 was also investigated in detail; the synthesis of
4HB units was growth-associated under nitrogen-sufficient
conditions. Fig. 5 shows the effect of the C/N ratio on the relationship
between specific growth rate and specific production rate of PHA when
the ratio of γ-hydroxybutyric acid in the feed was between 50 wt.% and
95 wt.%. The synthesis of 3HB units was enhanced under nitrogen-
deficient conditions. The mole fraction of 4HB units could be changed
from 0 to 70 mol% by adjusting the ratio of substrate and the mole ratio
of C/N. The total P(3HB-co-4HB) content was 71 wt.% with a 4HB unit
mole fraction of 30 mol% in the copolymer (83).
SELECTION OF CARBON SOURCES
There are a number of literature reviews on the selection of suitable
carbon sources for efficient PHA production, for which the total cost of
bioprocessing must meet economic requirements (5,10,11,13). The
most frequently reported factor that influences the price of PHA is the
cost of the carbon source. Fortunately, most microorganisms are
saprophytes that can metabolize a wide range of carbon sources.
However, the selection of carbon sources should not focus only on
market prices but also on availability and global price consistency. In
addition, inexpensive carbon sources such as agricultural wastes and
industrial by-products may incur additional costs due to pre-treatment
628 CHANPRATEEP J. BIOSCI. BIOENG.,

TABLE 6. Mechanical properties of terpolymer produced by C. necator strain A-04

comparing with P(3HB-co-3HV) and P(3HB-co-4HB) (82).
PHAs composition Toughness Young's modulus Tensile strength Elongation
(MPa) (MPa) (MPa) (%)

P(3HB) – 3500 40 0.4

P(3HB-co-3HV)
3% 3HV – 2900 38 –
9% 3HV – 1620 190 37
14% 3HV – 1500 150 35
20% 3HV – 1450 120 32
25% 3HV – 1370 70 30
P(3HB-co-4HB)
3% 4HB – – 28 45
10% 4HB – – 24 242
16% 4HB – – 26 444
44% 4HB – – 10 511
64% 4HB – 30 17 591
90% 4HB – 100 65 1080
P(3HB-co-3HV-co-4HB)
10% 3HB 40% 0.22 503 9 4
3HV 50% 4HB
11% 3HB 34% 0.26 618 10 3
3HV 55% 4HB
11% 3HB 23% 0.32 392 9 5
3HV 66% 4HB
12% 3HB 12% 0.39 142 4 9
3HV 76% 4HB
10% 3HB 6% 3HV 20 118 9 300
84% 4HB
4% 3HB 3% 3HV 33 127 14 430
93% 4HB
Petroleum based plastic
Plactic bag (HDPE) 62 640 19 576
Plactic bag (PP) 64 590 27 435
Plactic bag (LDPE) 15 156 13 126
FIG. 4. Transmission electron micrograph of ultra-thin section of C. necator strain A-04 UV degradable bag 60 674 24 384
(a) typical short rod cells ranging from 0.6 to 1.0 μm. Bar, 1 μm. (b) C. necator strain A-
04 containing PHB granules (white fractions). Bar, 200 nm (83).

steps, extended cultivation times, and purification. Simple carbon carbon sources for large-scale PHB production, due to its availability in
sources such as sugar and starch from crops seem to be superior to the market. Metabolix, Inc. and ADM selected corn syrup to produce
complex carbon sources, but they are also a primary source of human Mirel™ resin from recombinant E. coli using a fully biological fermen-
food and animal feed (84). Because the price of fossil fuels continues to tation process. In academic research, the greatest success with PHA
increase, using some of these carbohydrates for biofuel production is production from sugar has been reported by Kim et al. (86) They used
unavoidable. Given the limits on agricultural capacity and the increasing recombinant E. coli K12 (ATCC 23716) harboring the plasmid pSYL104,
demand for crops as bioenergy resources, researchers need to seek ways which contains 8.8 kb of a PHB operon and an ampicillin-resistant gene,
of using non-food crops for biodegradable production (85). Below, I and grew the bacterial cultures to 101 g/l of biomass on glucose while
provide information on conventional raw materials and optional raw maintaining the specific growth rate at 0.1 h−1. The kinetic information is
materials for PHA production. Table 7 shows the current global market fully available and ready for industrial-scale production (86).
prices of substrates and their theoretical PHB yields. Starches Starches are also an abundant carbon source. Many
Sugars Carbon sources are needed by all living organisms, and research groups are interested in utilizing starch for PHA production.
sugars are among the simplest. Pure sucrose is one of the most suitable Starch has also been used as a bio-based polymer for various types of
bioplastics. However, microorganisms often display low productivity
when grown directly on raw starch, and additional costs from
TABLE 5. Thermal properties of terpolymer comparing with copolymers produced by C. liquefaction and saccharification steps limit the potential use of starch.
necator strain A-04 (82). R. eutropha NCIMB 11599 was able to produce PHB from saccharified
PHAs composition (mol%) Tg (°C) Tm (°C) MW MN PDI potato starch waste with phosphate limitation. The biomass produced
PHB 10 177 – 7.82 × 105 1.8 was 179 g/l and 94 g/l of PHB for a productivity of 1.47 g/l h (87). Kim
P(3HB-co-3HV) and Chang (38) investigated PHB production from starch in flask, batch,
24% 3HV −6 138 – 1.38 × 105 1.9 and fed-batch cultures of Azotobacter chroococcum. In flask cultures,
45% 3HV − 10 75 – 4.00 × 105 2.4 PHB content reached 74% of dry-cell weight. In batch cultures, PHB
71% 3HV − 13 87 – 2.54 × 105 2.0
content reached 44% with O2 limitation. In fed-batch cultures, 71 g/l of
P(3HB-co-4HB)
11% 4HB – 160 – 2.23 × 105 2.5 biomass with 20% PHB was obtained without O2 limitation, whereas
17% 4HB – 152 – 3.32 × 105 2.4 54 g/l of biomass with 46% PHB was obtained with O2 limitation (38).
82% 4HB – 40 – 1.29 × 105 2.4 Extruded rice bran was utilized to obtain a cell concentration of 140 g/l,
P(3HB-co-3HV-co-4HB)
a PHA concentration of 77.8 g/l, and a PHA content of 55.6 wt.% in a
10% 3HB 40% 3HV 50% 4HB − 13.7 87.6 1.10 × 106 9.67 × 105 1.13
11% 3HB 34% 3HV 55% 4HB − 15.9 99.9 5.98 × 105 2.99 × 105 2.00 repeated fed-batch fermentation. In 2006, Huang et al. (88) reported
11% 3HB 23% 3HV 66% 4HB − 17.7 91.8 6.62 × 105 1.90 × 105 3.46 that when extruded corn starch was used as the major carbon source,
12% 3HB 12% 3HV 76% 4HB − 21.1 87.3 5.51 × 105 1.73 × 105 3.18 62.6 g/l of biomass was obtained with 24.2 g/l of PHA (38.7 wt.%) (88).
10% 3HB 6% 3HV 84% 4HB − 47.1 54.3 1.77 × 105 6.27 × 104 2.82 Halami screened for bacterial strains that could utilize starch to produce
4% 3HB 3% 3HV 93% 4HB − 51.6 54.8 4.15 × 105 1.33 × 105 3.11
PHB. It was found that the isolated Bacillus cereus could secrete the
VOL. 110, 2010 CURRENT TRENDS IN BIODEGRADABLE POLYHYDROXYALKANOA 629

FIG. 5. The effect of C/N ratio on the relationship between μ and ρ when the ratio of γ-hydroxybutyric acid in the feed was 50 wt.% (a), 75 wt.% (b), and 95 wt.% (c), respectively.
Symbols: closed square, specific production rate of 4HB monomer unit; open triangle, specific production rate of 3HB monomer unit; closed circle, specific production rate of
copolymer of P(3HB-co-4HB) (83).

enzyme amylase and simultaneously produce PHB at 0.48 g/l (89); TABLE 7. The global market prices of substrates in 2010 and estimated substrate cost for
however, industrial-scale production still awaits optimization of the production of PHA based on yield (59,98,101).

system's productivity. Carbon source Price per kg Yield of PHB (g g− 1) Cost of C-source per kg of PHA
Alcohols Alcohols are sterile carbon substrates, and PHA fermen- Sucrose a €0.35 0.40 €0.87
tation processes using alcohols as substrates could possibly reduce the Glucose b €0.41 0.38 €1.07
chance of contamination. There is considerable experience in methanol Ethanol c €0.31 0.50 €0.63
Methanol d €0.28 0.43 €0.58
fermentation technology because methlylotrophic bacteria have been
Cassava starch e €0.19 0.20 €0.94
considered for the large-scale industrial production of single-cell Cane molasses b €0.10 0.42 €0.24
proteins. Some methalotrophic and methanotrophic bacteria are Palm oil f €0.79 0.65 €1.22
promising for PHB production purposes. Pseudomonas sp. K was Soya oil g €0.92 0.70 €1.31
cultivated in a fed-batch process with nitrogen deficiency to a cell a
London Daily Sugar Price.
b
density as high as 233 g/l dry-cell weight with a PHB content of 64%, USDA Economic Research Service.
c
resulting in a product yield of 0.2 g g−1 (48). P. extorquens was grown to d
CME Fuel Ethanol Futures.
Methanex methanol price sheet.
cell densities of 190 g/l dry-cell weight with a PHB content of 60% (67). e
The Tapioca Trade Association (TTTA).
The methlylotrophic bacteria P. denitrificans and M. extorquens are able f
Crude, cif North West Europe.
to synthesize copolyester PHBV when methanol and n-amyl alcohol are g
Dutch, fob ex-mill.
630 CHANPRATEEP
fed simultaneously in nitrogen-limited medium. The 3HV content
reached 91.5 mol% depending on the ratio of substrate used (76,81,90).
P. denitrificans ATCC 17741 can produce a homopolymer of PHV (24% w/
w) when grown on n-pentanol (91). A microcomputer-aided, automatic
fed-batch culture system under potassium-limited conditions was set
up for PHB production with M. organophilum using methanol as the
substrate (92). However, alcohols have become very important as
alternative energy sources to replace fossil oils.
Industrial by-products Molasses, an industrial by-product of
sugar production, is one potentially inexpensive carbon source for PHA
production. However, molasses values over the past year have risen to
unprecedented levels at both origin and destination. The price of U.S.
blackstrap cane molasses is approximately double its historical level.
Sharply reduced production of molasses in India and Pakistan explain
the surge in prices. At the same time, the expanding use of molasses in
fuel ethanol programs is boosting global molasses demand. Molasses
production in Pakistan and Thailand for 2009–2010 is forecasted to rise
only slightly (Quarterly Market Outlook, International Sugar Organiza-
tion, November 2009). Chen et al. (93) reported on the production of
PHB from beet molasses by an A. vinelandii UWD mutant in two-stage
fed-batch cultures. The amount of PHB produced was 36 g/l with
productivity higher than 1 g/l h (93). Liu et al. (94) have successfully
replaced glucose with beet molasses to produce PHB by a recombinant
Escherichia coli strain (HMS174/pTZ18u-PHB). The final dry-cell weight,
PHB content, and PHB productivity were 39.5 g/l, 80% (w/w), and 1 g/l h
after 31.5 h of fed-batch fermentation with constant pH and dissolved
O2 content (94).
There are a number of reports on using cane molasses for PHA
production. Gouda, et al. (95) reported that Bacillus megaterium was
able to produce PHB from cane molasses in shaken flask cultivation.
Briefly, 46.2% PHB was produced when 3% (w/v) of sugar cane molasses
was supplied (95). Kulpreecha et al. (96) reported an attempt to
produce PHB from sugar cane molasses by Bacillus sp. BA019. The
optimal feeding medium in this system required a higher total sugar
concentration of 400 g/l and a C/N molar ratio of 10. Under these
conditions, the biomass was 72.6 g/l and PHB productivity was 1.27 g/l h
(96). However, the cost of downstream decolorization processes
becomes the limiting factor for cost competitiveness. In addition, the
recent trend toward utilizing molasses was based on projected profits
from bioethanol production.
Fatty acids and vegetable oils are also potential substrates for PHA
production because it was reported that the theoretical yield of PHA
production from fatty acids is 0.65 g g− 1 (97), whereas the theoretical
yield of PHA production from glucose ranges between 0.30–0.40 g g− 1
(98). It was reported that Rhodobacter sphaeroides (IFO 12203) could
utilize palm oil mill for PHA production, and a PHA yield of 0.50 g g− 1 of
organic acid consumed was obtained, resulting in PHA content of 67%
(99). Kahar et al. (100) reported the use of soybean oil for PHA production
by C. necator H16 and its recombinant strain PHB-4 harboring the Aero-
monas caviae PHA synthase gene. The production of PHA by C. necator H16
was 118–126 g/l, and the PHB content was 72–76%. The recombinant
strain could produce PHA from soybean oil with high cell density (128–
138 g/l) and high PHA content (71–74%). The yield obtained from these
experiments was as high as 0.72 to 0.76 g g− 1 (100). The Pseudomas sp.
strain DR2 isolated by Song et al. (16) was able to utilize corn oil, and it
produced 37.34% PHA that consisted of 3-hydroxyoctanoic, 3-hydro-
xydecanonic, and 3-hydroxydodecanoic. Strain DR2 also could utilize
vegetable oil as a carbon source for PHA production with a content of
23.52% (16). Recently, waste glycerol, a by-product from the biodiesel
industry, has received much interest from many researchers as an
inexpensive organic source for PHA production. As reported by Cavalheiro
et al. (17), C. necator was used to produce PHB using waste glycerol. A total
of 68.8 g/l of biomass was obtained with a PHB content of 38%. Finally, by
decreasing the biomass concentration, a PHB content of 50% with a
productivity of 1.1 g/l h was achieved (17). It is therefore reasonable to
J. BIOSCI. BIOENG.,
develop bioprocesses based on waste carbon resources. Finally, the world
market price of each substrate and the estimated substrate cost based on
the PHA production yield are listed in Table 7.
PHA is undoubtedly one of the potential candidates for replacing
petroleum-based plastics. However, only a few biodegradable plastic
products made from PHAs are available on the market (Mirel™,
Biocycle™, Biomer™, etc.). Although the current price of PHA is an
ongoing impediment to its widespread use, the additional cost provides a
completely biodegradable product that leaves zero hazardous waste in the
environment. National polices and legal measures are also important
factors that contribute to market initiatives for PHA. International
Standards (ISO) and Certified Labeling and Environmental Product
Declarations (EPD) are required to communicate the environmental
credentials of PHAs to consumers and businesses. Further research and
technical development is needed to build a wider range of applications, to
characterize the greenhouse gas emissions from PHAs, to obtain new data
for LCA models of the environment impacts of PHAs as feedback
information for further research, and to develop new polymers that can
be recycled after a first use. Altogether, the prospects for PHAs look bright.
The potential usefulness of PHAs should expand further as new market
niches open.
ACKNOWLEDGMENTS
The author wishes to express her appreciation to the Society for
Biotechnology (Japan), which awarded the Young Asian Biotechnol-
ogist Prize to her in 2009. The research done for this review was
supported in part by the “Joint Program in the Field of Biotechnology”
under the National Research Council of Thailand, the National Science
and Technology Development Agency of Thailand, and the Japan
Science and Technology Agency. The author would like to extend her
respectful thanks to Professor Suteaki Shioya (Sojo University),
Professor Hiroshi Shimizu (Osaka University), Professor Takuya Nihira
(Osaka University), Professor Wattanalai Panbangred (Mahidol
University), and Professor Yoshio Katakura (Kansai University) for
their invaluable discussions and supports.
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