Bioplastic

Bioplastics are a form of plastics derived from renewable biomass sources, such as vegetable
fats and oils, corn starch, pea starch,[1] or microbiota,[2] rather than fossil-fuel plastics which are
derived from petroleum. Some, but not all, bioplastics are designed to biodegrade.

Applications
Biodegradable bioplastics are used for disposable items, such as packaging and catering items
(crockery, cutlery, pots, bowls, straws). Biodegradable bioplastics are also often used for organic
waste bags, where they can be composted together with the food or green waste. Some trays and
containers for fruit, vegetables, eggs and meat, bottles for soft drinks and dairy products and
blister foils for fruit and vegetables are manufactured from bioplastics.
Nondisposable applications include mobile phone casings, carpet fibres, and car interiors, fuel
line and plastic pipe applications, and new electroactive bioplastics are being developed that can
be used to carry electrical current.[3] In these areas, the goal is not biodegradability, but to create
items from sustainable resources.
Plastic types
Starch-based plastics
Constituting about 50 percent of the bioplastics market, thermoplastic starch, such as Plastarch
Material, currently represents the most important and widely used bioplastic. Pure starch
possesses the characteristic of being able to absorb humidity, and is thus being used for the
production of drug capsules in the pharmaceutical sector. Flexibiliser and plasticiser such as
sorbitol and glycerine are added so the starch can also be processed thermo-plastically. By
varying the amounts of these additives, the characteristic of the material can be tailored to
specific needs (also called "thermo-plastical starch"). Simple starch plastic can be made at home
shown by this method.[4]
Industrially, starch based bioplastics are often blended with biodegradable polyesters. These
blends are mainly starch/polycaprolactone[5] or starch/Ecoflex[6] (polybutylene adipate-co-
terephthalate produced by BASF[7] ). These blends remain compostables. Other producers, such
as Roquette, have developed another strategy based on starch/polyeolefine blends. These blends
are no longer biodegradables, but display a lower carbon footprint compared to the
corresponding petroleum based plastics[8] .
[edit] Cellulose-based plastics

Packaging blister made from cellulose acetate, a bioplastic

Cellulose bioplastics are mainly the cellulose esters, (including cellulose acetate and
nitrocellulose) and their derivatives, including celluloid.
Some aliphatic polyesters
The aliphatic biopolyesters are mainly polyhydroxyalkanoates (PHAs) like the poly-3-
hydroxybutyrate (PHB), polyhydroxyvalerate (PHV) and polyhydroxyhexanoate PHH.
Polylactic acid (PLA) plastics

Mulch film made of polylactic acid (PLA)-blend bio-flex

Polylactic acid (PLA) is a transparent plastic produced from cane sugar or glucose. It not only
resembles conventional petrochemical mass plastics (like PE or PP) in its characteristics, but it
can also be processed easily on standard equipment that already exists for the production of
conventional plastics. PLA and PLA blends generally come in the form of granulates with
various properties, and are used in the plastic processing industry for the production of foil,
moulds, cups and bottles.
Poly-3-hydroxybutyrate (PHB)
The biopolymer poly-3-hydroxybutyrate (PHB) is a polyester produced by certain bacteria
processing glucose, corn starch[9] or wastewater[10] . Its characteristics are similar to those of the
petroplastic polypropylene. The South American sugar industry, for example, has decided to
expand PHB production to an industrial scale. PHB is distinguished primarily by its physical
characteristics. It produces transparent film at a melting point higher than 130 degrees Celsius,
and is biodegradable without residue.
Polyamide 11 (PA 11)
PA 11 is a biopolymer derived from natural oil. It is also known under the tradename Rilsan B,
commercialized by Arkema. PA 11 belongs to the technical polymers family and is not
biodegradable. Its properties are similar to those of PA 12, although emissions of greenhouse
gases and consumption of nonrenewable resources are reduced during its production. Its thermal
resistance is also superior to that of PA 12. It is used in high-performance applications like
automotive fuel lines, pneumatic airbrake tubing, electrical cable antitermite sheathing, flexible
oil and gas pipes, control fluid umbilicals, sports shoes, electronic device components, and
catheters.
Bio-derived polyethylene
The basic building block (monomer) of polyethylene is ethylene. This is just one small chemical
step from ethanol, which can be produced by fermentation of agricultural feedstocks such as
sugar cane or corn. Bio-derived polyethylene is chemically and physically identical to traditional
polyethylene - it does not biodegrade but can be recycled. It can also considerably reduce
greenhouse gas emissions. Brazilian chemicals group Braskem claims that using its route from
sugar cane ethanol to produce one tonne of polyethylene captures (removes from the
environment) 2.5 tonnes of carbon dioxide while the traditional petrochemical route results in
emissions of close to 3.5 tonnes.
Braskem plans to introduce commercial quantities of its first bio-derived high density
polyethylene, used in a packaging such as bottles and tubs, in 2010 and has developed a
technology to produce bio-derived butene, required to make the linear low density polethylene
types used in film production.[11]
Genetically modified bioplastics
Genetic modification (GM) is also a challenge for the bioplastics industry. None of the currently
available bioplastics - which can be considered first generation products - require the use of GM
crops, although GM corn is the standard feedstock.
Looking further ahead, some of the second generation bioplastics manufacturing technologies
under development employ the "plant factory" model, using genetically modified crops or
genetically modified bacteria to optimise efficiency.
Environmental impact
The production and use of bioplastics is generally regarded as a more sustainable activity when
compared with plastic production from petroleum (petroplastic), because it relies less on fossil
fuel as a carbon source and also introduces fewer, net-new greenhouse emissions if it
biodegrades. They significantly reduce hazardous waste caused by oil-derived plastics, which
remain solid for hundreds of years, and open a new era in packing technology and industry.[12]
However, manufacturing of bioplastic materials is often still reliant upon petroleum as an energy
and materials source. This comes in the form of energy required to power farm machinery and
irrigate growing crops, to produce fertilisers and pesticides, to transport crops and crop products
to processing plants, to process raw materials, and ultimately to produce the bioplastic, although
renewable energy can be used to obtain petroleum independence.
Italian bioplastic manufacturer Novamont[13] states in its own environmental audit[14] that
producing one kilogram of its starch-based product uses 500g of petroleum and consumes almost
80% of the energy required to produce a traditional polyethylene polymer. Environmental data
from NatureWorks,[15][16] the only commercial manufacturer of PLA (polylactic acid) bioplastic,
says that making its plastic material delivers a fossil fuel saving of between 25 and 68 per cent
compared with polyethylene, in part due to its purchasing of renewable energy certificates for its
manufacturing plant.
A detailed study examining the process of manufacturing a number of common packaging items
in several traditional plastics and polylactic acid carried out by Franklin Associates and
published by the Athena Institute shows the bioplastic to be less environmentally damaging for
some products, but more environmentally damaging for others.[17] This study however does not
consider the end-of-life of the products, thus ignores the possible methane emissions that can
occur in landfill due to biodegradable plastics.
While production of most bioplastics results in reduced carbon dioxide emissions compared to
traditional alternatives, there are some real concerns that the creation of a global bioeconomy
could contribute to an accelerated rate of deforestation if not managed effectively. There are
associated concerns over the impact on water supply and soil erosion.
Other studies showed that bioplastics represent a 42% reduction in carbon footprint.[18]
On the other hand, bioplastic can be made from agricultural byproducts [12] and also from used
plastic bottles and other containers using microorganisms.[19]
Bioplastics and biodegradation
The terminology used in the bioplastics sector is sometimes misleading. Most in the industry use
the term bioplastic to mean a plastic produced from a biological source. One of the oldest
plastics, cellulose film, is made from wood cellulose. All (bio- and petroleum-based) plastics are
technically biodegradable, meaning they can be degraded by microbes under suitable conditions.
However many degrade at such slow rates as to be considered non-biodegradable. Some
petrochemical-based plastics are considered biodegradable, and may be used as an additive to
improve the performance of many commercial bioplastics. [citation needed] Non-biodegradable
bioplastics are referred to as durable. The degree of biodegradation varies with temperature,
polymer stability, and available oxygen content. Consequently, most bioplastics will only
degrade in the tightly controlled conditions of industrial composting units. In compost piles or
simply in the soil/water, most bioplastics will not degrade (e.g. PH), starch-based bioplastics
will, however.[20] An internationally agreed standard, EN13432, defines how quickly and to what
extent a plastic must be degraded under commercial composting conditions for it to be called
biodegradable. This is published by the International Organization for Standardization ISO and is
recognised in many countries, including all of Europe, Japan and the US. However, it is designed
only for the aggressive conditions of commercial composting units. There is no standard
applicable to home composting conditions.
The term "biodegradable plastic" has also been used by producers of specially modified
petrochemical-based plastics which appear to biodegrade.[21] Biodegradable plastic bag
manufacturers that have misrepresented their product's biodegradability may now face legal
action in the US state of California for the misleading use of the terms biodegradable or
compostable[22] Traditional plastics such as polyethylene are degraded by ultra-violet (UV) light
and oxygen. To prevent this process manufacturers add stabilising chemicals. However with the
addition of a degradation initiator to the plastic, it is possible to achieve a controlled
UV/oxidation disintegration process. This type of plastic may be referred to as degradable
plastic or oxy-degradable plastic or photodegradable plastic because the process is not initiated
by microbial action. While some degradable plastics manufacturers argue that degraded plastic
residue will be attacked by microbes, these degradable materials do not meet the requirements of
the EN13432 commercial composting standard. The bioplastics industry has widely criticized
oxo-biodegradable plastics, which the industry association says do not meet its requirements.
Oxo-biodegradable plastics - known as "oxos" - are conventional petroleum-based products with
some additives that initiate degradation. The ASTM standard used by oxo producers is just a
guideline. It requires only 60% biodegradation, P-Life is an oxo plastic claiming biodegradability
in soil at a temperature of 23 degrees Celsius reaches 66% after 545 days. Dr Baltus of the
National Innovation Agency, has said that there is no proven evidence that bio-organisms are
really able to consume and biodegrade oxo plastics.
Recycling
There are also concerns that bioplastics will damage existing recycling projects. Packaging such
as HDPE milk bottles and PET water and soft drinks bottles is easily identified and hence setting
up a recycling infrastructure has been quite successful in many parts of the world, although only
27% of all plastics actually get recycled.[23] The rest are in landfills and oceans.[24] However,
plastics like PET do not mix with PLA, yielding unusable recycled PET if consumers fail to
distinguish the two in their sorting. The problem could be overcome by ensuring distinctive
bottle types or by investing in suitable sorting technology. However, the first route is unreliable,
and the second costly.
MARINE BIOACTIVE COMPOUNDS AND THEIR APPLICATIONS IN MARICULTURE
A.P. LIPTON,
Vizhinjam Research Centre of CMFRI, Vizhinjam
Introduction
Marine bioactive compounds or Marine natural products (MNPs) are organic compounds produced by
microbes, sponges, seaweeds, and other marine organisms. The host organism synthesizes these
compounds as non-primary or secondary metabolites to protect themselves and to maintain homeostasis
in their environment. Between 1977 and 1987, around 2500 new metabolites (MNPs) were reported from
marine organisms ranging from microbes to fish, which accounts for less than 1.0% of the total marine
organisms. Review of literature reveals that even the seawater has bactericidal properties. This could be
attributed to the production of antibiotics by planktonic algae and bacteria respectively.
In the case of aquaculture or Mariculture activities, diseases are frequently encountered in all the stages
(from the egg stage onwards). Disease control using antibiotic substances has inherent limitations.
Recently, the Marine Products Export Development Authority (MPEDA) of India has restricted the usage
of many antibiotics in aquaculture, particularly in shrimp farming. The common problems of antibiotic use
include: development of drug resistant bacteria, environmental contamination and possible residues in the
tissues of fish/shellfish. Disease management using vaccines has limitation as they are specific. If the
causative agent is different, the vaccine will not work. Considering the potential of marine bioactive
substances, and the avenues for developing potent new drugs and other useful products, a holistic
approach is required to develop fish/ shellfish therapeutics, immunostimulants and other feed additives.
Marine bacteria
Rosenfeld and Zobell (1947) demonstrated that marine bacteria produce anti-microbial substances. The
first documented identification of a bioactive marine bacterial metabolite was the highly brominated
pyrrole antibiotic, isolated by Burkholder and co-workers from a bacterium obtained from the surface of
the Caribbean Sea grass Thalassia (Burkholder et al., 1966). Subsequently, this unique metabolite was
identified by x-ray crystallographic methods, which composed of more than 70% bromine by weight
(Lovell, 1966). The metabolite exhibited impressive in vitro antibiotic properties against Gram-positive
bacteria, with minimum inhibitory concentration (MIC) ranging from 0.0063 to 0.2 g/ml. However, it was
inactive for Gram-negative bacteria and animal assays. As more evidence is obtained, it is becoming
abundantly clear that bacteria form highly specific, symbiotic relationships with marine plants and animals.
Experience in this area arose from a study of the pathogen resistance of the estuarine shrimp Palaemon
macrodactylus. Gil-Turnes et al., (1989) observed that the eggs of P. dactylus possess significant
bacterial epibionts, which, when removed by treatment with antibiotics, leads to the rapid infestation of the
eggs by pathogenic fungi, especially of Lagenidium callinectes. It could be due to the anti-fungal agents
produced by bacteria. Studies on marine bacterial products in Mariculture are therefore essential.
Marine fungi
Although terrestrial fungi have represented a major biomedicinal resource (penicillin from Penicillium, for
example), studies to develop the biomedicinal potential of marine fungi were less The isolation of a small
lactone, leptosphaerin from Leptosphaeria oraemaris by Schiehser (1980) demonstrated that marine fungi
may form important resource for unique metabolites. Later, the useful chemical, Gliovictin was isolated
from marine fungus, Asteromyces cruciatus (Shin and Fenical, 1987). Since then more than twenty useful
bioactive compounds have been derived from marine fungi.
Marine Microalgae
Microalgae are significant resource for bioactive metabolites, particularly cytotoxic agents with
applications in cancer chemotherapy (Moore et al., 1988). From the marine microalgae such as from the
blooms of Phaeocystis sp., antibiotic substances were listed. Phaeocystis pouchetii is reported to produce
chemicals such as Acrylic acid, which constitutes about 7.0% of the dry weight. The antibiotic substances
thus produced are transferred throughout the food chain and found in the digestive tract of Antartic
penguins (Sieburth, 1961). Production of carotene and vitamins by the halotolerant alga Dunaliella sp.,
is documented. These compounds have much importance for the Mariculture activities.
Marine Macroalgae
Of the total marine algae so far evaluated, about 25.0% showed one or the other biological activity. The
metabolites of green algae were reported to contain 1,4 diacetoxic butadiene moiety, which exhibited
icthyotoxic property. Among the red algae, halogenated lipids have been isolated, particularly from the
Laurencia sp. The rare chemical prostaglandin was also reported to occur in Gracilaria pichenoids. Ulva
meal supplementation was found to provide disease resistance to red sea bream in Japan (Satoh et al,
1986). Similar results were also reported from Japan on the use of Ulva meal supplementation towards
disease resistance and high growth rate in black sea bream (Nakagawa et al, 1987). The polysaccharide
fractions from marine algae, Porphyra yezoensis (PASF) was found to stimulate the in vivo and in vitro
murine phagocytic function. The purified fractions of PASF gave stronger phagocytic activity (Yoshizawa
et al. 1995). Some of the macro algal crude extracts indicated their potential therapeutic nature when
challenged with potential pathogens among fish and shellfish. The cellular and humoral responses of the
fish/shellfish towards the algal metabolites were investigated (Lipton, 2001).
Marine Sponges
The wider biosynthetic capability of sponges could be attributed to their biological association with other
symbionts. According to Bertrand and Vacelet (1971), about 38% of the sponge body comprises of
microorganisms. A wide variety of secondary metabolites were isolated from sponges and these have
been associated with antibacterial, antimicrobial, antiviral, antifouling, HIV-protease inhibitory, HIV reverse
transcriptase inhibitory, immuno- suppressent and cytotoxic activities. In addition to potential anticancer
applications, the MNPs of sponges have a myriad of activities ranging from antibiotic activity including
anticoagulant, antithrombin, anti-inflammatory, as well as imunomodulatory activities.
Presence of specific symbiont morphologies of bacteria within specific sponges has been reported. These
specific bacteria, which live symbiotically with sponges, passed through their feeding chambers without
being digested. This suggested some sort of encapsulation or recognition process. In the demosponge,
Halichondria panicea, an association with the microbe Pseudomonas insolita was suggested to be lectin-
based (Mller et al., 1981). Wilkinson found an immunological basis for symbiosis in some sponges,
which he claimed as evidence of a Precambrian origin for many symbioses (Wilkinson, 1984).
A major problem with the early studies on sponge-microbe symbiosis was that most microorganisms were
uncultured or unculturable. The application of molecular biology to spongemicrobe symbiosis is now
yielding results that could not have been obtained by classical microbiological methods. The discovery of
a member of the Archaea living specifically within a sponge similar to Axinella mexicana was particularly
worth to mention (Preston et al., 1997).
Avenues for further research and development in relevance to Mariculture:
Perusal of literature indicates that during the last three decades number of diverse biologically active
compounds has been isolated from marine organisms, but the number of compounds taken-up for the
field trial/clinical use are scanty. Some of the future requirements are listed below:
1. Microbial Isolation/screening and culture techniques: required as new symbiotic microbes are difficult to
culture under laboratory conditions. Basic Research in Marine Microbiology is essential. Without
considerable attention to developing the basic biology of marine microorganisms, explorations for new
bioactive metabolites would be limited to those few classes of microorganisms, which are readily isolated
and grown under "standard" conditions. Unfortunately, little is known about the specific nutrients and
growth factors required by most of the marine microbes. For example, the common media components
such as peptone, sugars etc., are unrealistic marine nutrients as complex carbon sources such as chitin,
sulphated polysaccharides, marine protein etc., are found in the marine habitat. In addition, information is
lacking on some of the uncommon inorganic elements such as lithium, silicon etc., abundant in the marine
sediments. As a result of these difficulties, it is seen that less than 5% of the available microbial
population is only culturable under the standard laboratory conditions. Presently, this condition, certainly
limits the scope and ability to isolate and culture majority of the interesting and new microbes.
2. Preparation of crude extracts for bioactivity: as the goal is to obtain the widest possible screening for
each crude extract so that no useful compound is over looked. Solvents such as methanol, chloroform or
ether as independent solvents or as combinations can be used depending upon the nature of the MNPs.
As soon as the crude extracts are obtained, there is need for immediate and simple in vitro assays such
as: i. Antimicrobial and ii. Enzyme inhibition assay (very low quantity of sample only is required). This in
turn helps in the `bioassay guided fractionation and purification process.
3. Purification: Once bioactivity is detected in the crude extract, the next step is to purify the same. It is
important to employ non-destructive method such as spectroscopic method, which conserves the
materials for further bioassays. In addition, techniques such as: TLC, MS/IR/uv and H nMR (for
structural elucidations) are to be adopted for purification of the crude extract and for determining the
structure.
4. Pharmacological screening: The next step after purification and structural elucidation is
pharmacological screening. Studies such as determining the LD50 of the extracts in mice, in addition to
brine shrimp assay, fertilized sea urchin assay and starfish assay are to be carried out in established
laboratories. Further tests such as: antiviral (AIDS/anti- HIV), cytotoxic, anti-inflammatory, anti-tumor,
tumor promoter (protein kinase), analgesic, anti-coagulant / anti-thrombic (ex: heparin), anti-ulcer, anti-
cholesterol / anti-lipemic, wound dressing, anti-parasitic, anti-protozoa are to be conducted.
5. Commercial development of bioactive (MNP) products: The `co-operative drug development
programme as suggested by Dr. Faulkner is the best method, which will solve the problems arising on
issues such as: patent rights, academic freedom and industrial secrecy.
6. Conservational aspects of source organisms: Eco-friendly collection of the source organism and
required supply of them in bulk for scaling-up process.
7. The role of Industry and Academia: Considering the less microbiological and intensive pharmacological
training to the industrial personnel, relevant microbiological training has to be imparted to the industrial
pharmacologists. New isolation methods, media development etc., are to be included in the curricula of
academic/research institutes. Collaborative programmes which combine biomedical and microbiological
expertise of the pharmaceutical industry with the marine microbiological resources available in the marine
R&D Institutes will in the long run help in the better utilization of the marine resources for biotechnological
aspects.