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A Review on Algal Biopolymers

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DOI: 10.15377/2409-983X.2017.04.2

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 Journal of Chemical Engineering Research Updates, 2017, 4, 7-14 7

A Review on Algal Biopolymers

Didem Özçimen*, Benan İnan, Ogün Morkoç and Aybüke Efe

Yıldız Technical University, Faculty of Chemical and Metallurgical Engineering, Bioengineering Department,
Esenler 34201, Istanbul, Turkey
Abstract: Polymers are the most important materials we use in many areas of daily life. Without them humanity could
not shape today’s world. However, major source of polymeric material is fossil fuels which decrease constantly.
Therefore, alternative resources are needed to be discovered especially from biological source for sustainable polymer
production. Biopolymers are polymers developed from renewable resources such as plant, animal, bacteria, fungi and
algae. They can also be useful in material and many other applications. Algae are one of the most promising organisms
in many aspects. Since they grow fast, contain variety of unique value added material and do not compete with food
resources, and also they have high bioenergy feedstock potential. In this study, algae are considered as feedstock for
biopolymer production and biopolymers derived from algae are investigated. Throughout this study algae derived
biopolymers were classified as three types. First type of polymer obtained from algae are natural polymers
(polysaccharides, lipids, extracellular polymeric substance). Especially polysaccharides from algae such as alginate and
agar are well known for their biotechnological applications. Second type is polyhydroxyalkanoates (PHA) which
accumulate in only cyanobacteria. And third type is bio-based polymers polymerized from algae derived monomer, they
can have same characteristics with conventional synthetic polymer. This review study will give an idea especially about
the algal biopolymers, their resources, properties, structures, application areas, production methods and their future
potentials.

Keywords: Algae, natural polymer, biopolymer, lipids, polysaccharides.

1. INTRODUCTION polymer constitutes first step for the classification. Also,

the term “bioplastic” is often used for the biopolymer.
Algae are alternative renewable sources for Nevertheless, bioplastic can be biodegradable but this
biopolymer production, because of their high growth does not mean that the polymer is derived from
rate, high photosynthetic efficiency and great potential biological resource. Some of the petroleum based
for carbon dioxide fixation [1]. Therefore, variety of polymers can also be biodegradable such as
biopolymers can be obtained from algae. Basically polycaprolactone (PCL) and poly (butylene succinate)
those are naturally occurring polymers (polysaccharide, (PBS) [3]. The term bio-based polymer is used for the
lipid, protein), bio-based polymers which are polymer obtained from renewable resources [2].
polymerized from algae derived monomer and naturally However, some bio-based polymers can also be non-
occurring polyester polyhydroxyalkanoates (PHA) biodegradable [2]. Nevertheless, of this contradiction in
which are accumulated only in cyanobacteria. Each terms our focus will be polymer obtained from
polymer type has different property and application in renewable resources.
many areas. For example, PHA and bio-based
polymers which are polymerized from algae derived Mainly, there are three methods to obtain
monomer have potential to replace fossil fuel based biopolymers from renewable resources; (1) Polymers
conventional polymer. And naturally occurring polymer extracted from biomass (Natural occurring polymers),
have many applications in medical, pharmaceutical and (2) Polymers produced by microorganism, (3) Polymer
food industries as a novel material. Therefore, algae synthesized by bio-derivative monomers [2, 3, 5].
derived biopolymer offers sustainable alternative
material for many usage areas. Natural polymers are produced by organisms and
they are essential polymers for all types of life and
However, the definition of biopolymer is not clear in synthesized by enzymatic pathway. They are divided
the literature. There are many terms exist for the into polysaccharides, lipids and proteins, and often
concept of biopolymer which have overlapping obtained by extraction methods. Polymers as second
meanings such as “biodegradable”, “bio-based”, type produced by microorganism, consist of mostly
“compostable”, “bioplastic”, “renewable polymer” and polyhydroxyalkanoates (PHAs) such as poly-3-
“green polymer” [2-4]. Mostly biodegradability of hydroxybutyrate. PHA is mainly produced by bacteria
and blue-green algae (cyanobacteria). This naturally
occurring polyester accumulated in this microorganism
*Address correspondence to this author at the Yıldız Technical University, against stress condition and their production require
Faculty of Chemical and Metallurgical Engineering, Bioengineering
Department, Esenler 34201, Istanbul, Turkey; Tel: +90 212 383 4635; elaborate culture condition [1-5].
Fax: 0212 383 4625; E-mail: ozcimen@yildiz.edu.tr

E-ISSN: 2409-983X/17 © 2017 Avanti Publishers

8 Journal of Chemical Engineering Research Updates, 2017, Vol. 4 Didem et al.

Polymer synthesized by bio derivative monomers, differ in M and G contents as well as the length of each
their monomers are derived from monomers, which are block, and more than 200 different alginates are
from fatty acids and their derivatives, monomers currently being manufactured [10].
obtained by digestion of natural polymers such as
carbohydrates [4]. Also monomer can be derived from An extraction method of alginate is that 100 g algae
protein which serves as a building block for polymer are ground and left in a 0.1 M hydrogen chloride (HCl)
synthesis. Those monomers are obtained either by solution overnight. Then, it is washed in 1 L of 1%
chemical, biochemical and thermochemical processes sodium carbonate (Na2CO3) solution, stirred and
for further polymerization. During polymerization, filtered. The filtrate is collected and precipitated with
blending material can be added to enhance polymer IsPrOH in three volumes of residue. The resulting gel is
properties. Obtained polymer is often called as dried and milled [11].
bioplastic and it has same property with petroleum
2.1.2. Laminarin
based conventional polymer. Those polymers either
can be bio degradable or non-biodegradable [6]. The principal storage polysaccharides of brown
seaweeds are laminarin and representing up to 35% of
2. NATURAL POLYMERS EXTRACTED FROM the algal dry weight [6]. It is a linear polysaccharide
ALGAL BIOMASS
constituted by 25-50 glucose units. M and G are two
types of laminarin chains depending upon the reducing
2.1. Algal Polysaccharides
end. M chains end with 1-O-substituted D-mannitol,
The world’s surface encompasses more than 70% whereas G chains end with glucose as the reducing
water, and the vast diversity of marine organisms offers end [12]. For laminar extraction, 85% ethanol is applied
a rich source of natural products such as at 23°C and 70°C to separate the pigment and proteins
polysaccharides. Polysaccharides have been an arising from the milled algae. Then it is centrifuged. The
material in biomedical applications because of the fact solvent and pellet are separated from each other by
that they are functionally active, water soluble and vacuum filtration with a filter paper. The separated
biodegradable. Marine algae contain a large amount of pellet is treated with 2% CaCl2 at 70°C and centrifuged.
polysaccharides. These are cell wall structural Thus, alginates as well as fucoidan and laminarin are
polysaccharides, mucopolysaccharides and storage precipitated. The fucoidan is separated from the
polysaccharides [7]. The main polysaccharides in resulting pellet with 0.01 M HCl solution at pH 2 and
green algae seaweeds are ulnas, sulfuric acid 70°C and then centrifuged again. The pellet obtained
polysaccharides, xylan and sulfated galactans; those in after centrifugation is subjected to 3% Na2CO3 at 70°C
red seaweeds are xylan, carrageenan, fucoidan, water- for alginate extraction and centrifuged again. Last
soluble sulfated galactan, porphyran and product is laminarin [11].
mucopolysaccharides [8, 9]; and those in brown 2.1.3. Fucoidan
seaweeds are alginic acid, fucoidan, laminarin and
sargassan. They are sulfated polysaccharides. Sulfated Fucoidans are a group of polysaccharides (fucans)
polysaccharides are known to possess some biological essentially composed of sulfated L-fucose with less
activities with the inclusion of anticoagulant, antiviral, than 10% of other monosaccharides. It is a ramified
anticancer and immunoinflammatory [7]. sulfated polysaccharide [7]. The low molecular fucoidan
(LMF) is more bioavailable than high molecular
2.1.1. Alginate fucoidan (HMF) [12]. Fucoidan extraction from
Alginate is a polysaccharide which is obtained from macroalgae is carried out in hot water followed by
cell wall of brown algae (Phaeophyceae). The acid precipitation with organic solvents or salts. The process
form is a linear polyuronic one and referred to as has three crucial steps: milling seaweeds,
alginic acid. Alginate is both a biopolymer and a extraction/purification (which involves several,
polyelectrolyte [7]. Alginate is now known to be a whole extensive extractions with aqueous and acidic solutions
family of linear co-polymers containing blocks of (1,4)- and includes calcium to promote the alginate
linked β-D-mannuronate (M) and α-L-guluronate (G) precipitation), and drying/careful storage [7].
residues. The blocks are composed of consecutive G 2.1.4 Carrageenan
residues (GGGGGG), consecutive M residues
(MMMMMM), and alternating M and G residues Carrageenan is one of the major constituents of red
(GMGMGM). Alginates extracted from different sources seaweed cell wall representing 30–75% of the algal dry
A Review on Algal Biopolymers Journal of Chemical Engineering Research Updates, 2017, Vol. 4 9

weight. They are linear hydrophilic polysaccharides is mainly composed of glucose, rhamnose, xylose,
which have 3-linked β -D-galactopyranose (G-units) glucuronic acid, iduronic acid and sulfate with smaller
and 4-linked α-D-galactopyranose (D-units) or 4-linked amounts of mannose, arabinose and galactose. The
3,6-anhydro-α-D-galactopyranose (DA-units) as two major kinds of Ulvan that have been identified are
alternating units with additional sulphate group [13]. the water-soluble Ulvan and the insoluble cellulose-like
The number and position of sulphate groups in the material [7]. Ulvan is mostly homogeneously distributed
repeating galactose units allow the classification of throughout the frond being more predominant within
carrageenan in three main commercially relevant the intercellular space and in the fibrillar wall [14].
families, namely, kappa (k), iota (i), and lambda (l). The
chemical reactivity of carrageenan is mainly because of 3. POLYMERS EXTRACTED FROM
the sulfate groups, and its structural diversity justifies CYANOBACTERIA
its wide application [7, 13].
3.1. Polyhydroxyalkanoates (PHA)
In extraction process, the algae are collected, dried
quickly and then baled to protect its freshness. The Polyhydroxyalkanoates (PHA) are one of the most
dried algae are mechanically ground, sieved to remove promising biopolymer which can be alternative to
foreign matter such as sand and salt, and thoroughly petroleum based polymer (synthetic polymer).
washed to improve quality. A two-stage treatment Synthetic polymers have various applications in all
process is applied for the disposal of cellulosic areas of industry and variety of daily products. The
materials. First, the dissolved carrageenan mixture is main properties of synthetic polymers are that they can
centrifuged to remove the cellulosic particles. Following be shaped easily and have high chemical resistance.
this, filtration is applied to separate smaller particles However synthetic polymers have an important
and the solution is concentrated by evaporation and drawback that their disposal is very difficult since they
removal of water. The carrageenan is then recovered are nondegradable [15-17]. Polyhydroxyalkanoates are
by one of the two process methods. The first method is biodegradable biopolymer which have same polymer
to deposit the carrageenan solution in the potassium characteristics with synthetic polymer due to their high
chloride solution. This application increases the molecular weight and other properties like
gelation temperature and thus allows the filtrate to gel thermoplastic processability and hydrophobicity.
immediately. The gel is then frozen and compressed to Therefore, biodegradability and good material
remove excess water during thawing. In the other properties of PHAs give PHA very useful characters
method, the concentrated carrageenan solution is that they can be used instead of synthetic polymers.
precipitated in isopropyl alcohol. As the carrageenan is However, the production cost of PHA is higher than
not soluble in alcohol, it becomes a clot (coagulum) synthetic polymer. Thus, their applications are limited.
between alcohol and water. This clot is compacted to New techniques and development are necessary to
remove the liquid content and is vacuum dried to lower the cost of PHA production [17, 18].
remove the alcohol completely. The drying process is
completed on a drying strip and the dried coagulum is PHA are bio polyesters which can be synthesized
milled and blended [11]. and accumulated inside the cell as insoluble granules
for energy and carbon storage by various prokaryotic
2.1.5. Agar
organism. There are two species reported to
Agar is a mixture of polysaccharides, composed of accumulate PHA; bacteria mostly chemoautotrophic
agarose and agaropectin, with interchangeable bacteria and cyanobacteria known as blue-green algae.
structural and functional properties as carrageenan [7]. Also, genetically engineered higher plants can produce
Agar extraction from algae has following steps in PHA [17, 19, 20]. Main producers of PHA are bacteria.
general manner: washing the seaweed to remove the PHA content in bacteria reachs at most 90% of cell dry
foreign matters, boiling in water to dissolve the agar, weight. Depend on conditions of organism PHA can
filtering, cooling the product to obtain jelly structure. have different structure up to date 150 different
Than the remaining water has been removed with structure, identified most well-known monomers are 3-
various techniques to obtain the final product [12]. hydroxypropionate, 3-hydroxybutyrate, 3-hydroxy-
valerate, 3-hydroxyhexanoate, 3-hydroxyoctanoate,
2.1.6. Ulvan
3-hydroxydecanoate, 3-hydroxydodecanoate, 3-hydr-
Ulvan are the major constituents of green seaweed oxytetradecanoate and 4-hydroxybutyrate. Within those
cell walls representing 8-29% of the algal dry weight. It monomers homopolymers, random copolymers or
10 Journal of Chemical Engineering Research Updates, 2017, Vol. 4 Didem et al.

block copolymers can be formed. This diversity give based polymer. The polymer that is produced from
them various material properties like physical and those processes can be biodegradable or
thermal properties [16, 17]. Also, the type and ratio of nonbiodegradable. They often called as bioplastic
monomers namely material properties can be which suits the definition of American Society for
controlled by optimizing culture conditions [20]. Testing and Materials ASTM D6866-06, since they are
obtained from biological resource [22]. Algal biomass is
PHAs are environmentally friendly plastics and have excellent source for production of various chemicals.
an application in many areas. Their main advantages With suitable treatment, these chemicals serve as a
are their biodegradability, non-toxicity and material monomer for polymer production. Currently majority of
property similarity with conventional plastic. Some conventional polymers are polyethylene (PE),
applications of PHA; for example, in biomedical polyethylene terephthalate (PET), and polypropylene
industry it can be used as biomedical material as carbonate (PPC), and their monomer (ethylene,
implant, wound dressing, surgical suture or in drug propylene, benzene) derived from fossil fuel [23].
delivery, in tissue engineering application even used as However, there is a huge concern about sustainability
direct drug monomer. Other examples of PHAs are that of fossil fuel and their non-environmental friendly
they can be used as bioplastic for packaging, manner [24]. Therefore, renewable biomass gains
laminates, film, coating material and consumer goods. importance to become as alternative source to fulfill
Disposable products used in the food industry or it can energy demand and need for valuable chemical to act
be used as animal feed, bioenergy source or smart as monomer for bio based polymer production having
material [16, 2]. theoretically low greenhouse gas emissions [25]. With
chemical synthesis, almost all chemical building block
3.2. Poly-(Hydroxybutyrate) (PHB)
of polymer can be produced from biomass and these
Apart from bacteria, cyanobacteria are potential building blocks have same property of petrochemical
host for PHA production. Because cyanobacteria counterpart. Those polymers are called ‘drop-in’
requires minimum nutrient, can fix CO2 as a sole bioplastic [26]. Also, new kind of chemical building
carbon source. Use of cyanobacteria as PHA block can be produced from biomass which have
producing host has many advantages over bacteria different property and cannot be synthesized from
since cyanobacteria use waste CO2 and sunlight as petrochemicals such as lactic acid [6]. Mainly these
carbon and energy source. Therefore, cyanobacteria polymers, can be produced by converting algal
can provide environmentally friendly biopolymer which biomass into ethanol by fermentation, which can be
can be used as bioplastic. However, PHA content is used as feedstock for variety of polymer like as
low in percentage cell dry weight to compare with polylactide (biodegradable polyester) [2, 27].
bacteria. The possible reason for low content might be
As pointed earlier, algal biomass have advantages
due to larger cell size and thicker cell wall of
over first and second generations of biomass since
cyanobacteria restrain downstream processing of PHA
they utilize CO2 from atmosphere and convert it to
extraction [20]. PHB poly-(hydroxybutyrate) is the most
carbon source. One of the major advantages of using
abundant PHA which is homopolymer of
algal biomass is its potential to reduce biomass cost [6,
hydroxybutyrate that presents in various cyanobacteria
23, 24, 27].
such as Chlorogloea fritschii, Spirulina spp.,
Aphanothece spp., Gloeothece spp. and However, this process may include many steps and
Synechococcus spp. Synechocystis sp, Gloeocapsa those steps can be different for different kinds of
sp, Spirulina platensis, Phormidium sp etc. [17, 18, polymer which cannot be economically feasible. Also,
19, 21]. polymer production yield is very low to compensate
polymer demand. Therefore, it is important to design
4. POLYMER SYNTHESIZED FROM ALGAE
DERIVED MONOMER modest process to fulfill the economic requirement and
environmentally friendly manner. On the other hand,
So far natural polymer from algae and PHA from biopolymer synthesis researches from biomass are
cyanobacteria are discussed. Apart from them algal mostly conducted in laboratory scale hence, industrial
biomass can be utilized by chemical, thermochemical, application is not common. Dongda Zhang et al.
mechanical and biochemical processes for production analyses 20 polymer synthesis pathways from biomass
of monomer for further polymerization of green bio including algal biomass to find most promising pathway
and they found that polyethylene (PE) is the most
A Review on Algal Biopolymers Journal of Chemical Engineering Research Updates, 2017, Vol. 4 11

promising polymer since number of reaction step to process is that remaining residue, containing lipid and
produce PE is lower than others [23]. algal cell after flash hydrolysis of protein, can be used
as feedstock for other application like as biofuel
Algae contain high amount of carbohydrate, oil and production [29]. Polyurethane is biocompatible polymer
protein. Some species contain high amount of which have various applications due to their easiness
carbohydrate for example red algae that their to modify properties such as coating, adhesive,
carbohydrate amount reach up to 75-80% of its dry
sealants, adhesives, elastomers and foams [32].
weight [1]. On the other hand, some microalgae
species like as Phaeodactylum tricornutum contain 4.3. Thermomechanical Polymerization of
high amount of lipid [28]. And some of the species Microalgal Biomass
contain high amount of protein (~30–65 %) like as
Scenedesmus spp. [29]. Therefore, depend on species’ Another approach is using thermomechanical
different characteristics, chemical building block of polymerization technique. It is possible to use
polymer can be obtained from algal biomass. In this microalgae as a raw material to produce polymer which
section, examples of some polymer synthesized from is also biodegradable. Spirulina and Chlorella
algae derived monomer are investigated. microalgae are mostly used since they contain high
amount of protein (e.g. dried spirulina contain 51-71%
4.1. Polyester Production
and chlorella contain 51-58% protein) [22, 33]. The
process of thermomechanical molding is usually done
One of the aspects of the obtaining polyester is
with addition of plasticizer such as glycerol to increase
utilizing macroalgal polysaccharides. Agar is natural
mechanical properties of polymer such as increasing
polysaccharide and highly reactive. Therefore, it can be
converted into 5-hydroxymethylfurfural (HMF). From viscoelastic properties of polymer, and also blending
HMF common polyester building block 2,5- with polyethylene enhances mechanical properties of
furandicarboxylic acid (FDCA) can be synthesized [1, polymer [22, 33, 34]. Throughout the
30, 31]. And, various polyesters can be produced from thermomechanical molding, heat and pressure are
FDCA [1]. applied which lead to formation of new intermolecular
bonds, and addition of plasticizer stabilizes the three-
Another chemical building block is 1,2-propanediol dimensional structure [22].
(propylene glycol) which is also used in production of
polyester. 1,2-propanediol usually produced from Also, apart from thermomechanical polymerization
petrochemical can also be obtained biologically from polysaccharide from macro and microalgae such as
renewable biomass. Microorganisms like bacteria and carrageenan’s are polymerized with addition of
yeast, known for their ability to produce 1,2-propanediol reinforcement material to improve their mechanical and
from fermentable sugar like fucose and rhamnose thermal properties. S. A. Rodriguez et al. showed
which are abundant in structure of EPS, which can be production of nanocomposite material from
used as feedstock [30, 31]. Carrageenan [35]. Furthermore, M. Nizar Machmud et
al. (2013) use red algae Eucheuma Cottonii directly as
4.2. Polyurethane Production
a raw material to produce polymer with filtration
technique and with addition of plasticizer [36].
Protein is highly abundant in some microalgal
species. However, as microalgal biomass mostly used There are many commercial attempts to produce
for biofuel production the protein present in algae bioplastic from algae. To do this few companies aimed
degraded and incorporated into biofuel. On the other to produce biopolymer from thermochemical
hand, it is possible to extract protein from algae and processing of microalgae. These are; Algix and
convert it into polyurethane. S. Kumar et al. (2008), Algaeplast. Algix produces algae based bioplastic resin
demonstrate the process pathway. Firstly, algal protein pellets [37]. Another attempt is project SPLASH
is removed by flash hydrolysis (280°C, 10 s) process. (Sustainable Polymers from Algae Sugars and
After filtration and freeze drying amino acid residues, Hydrocarbons) which is funded by EU. The aim of the
peptide are obtained. Then, obtained peptide and project is to develop process to convert algal biomass
amino acid residues are treated with diamine and into biopolymer and plastic product and enhance
ethylene. Finally polyol, which is polymerized to cooperation with business and researcher [26, 38].
polyurethane, is obtained. The main advantage of this
12 Journal of Chemical Engineering Research Updates, 2017, Vol. 4 Didem et al.

Table 1: SWOT Analysis for Algal Biopolymers

• Biopolymers obtained from algae have potential to replace fossil fuel based polymers.

• They have sustainable and bioeconomical approach.

• Algae provide alternative, cheap, sustainable resource for biopolymer production because of their
high growth rate, without need of arable land and lack of competition with food resources.
• Algal biopolymer production is a new market.
Strengths
• With biopolymer production, CO 2 can be utilized from the environment.
• Biopolymers with different characteristics and properties can be obtained from different algae
species (e.g. therapeutic property, high mechanical property).

• Produced biopolymers can be biodegradable or non-biodegradable both of them have their own
advantages.

• Biopolymer production cost is still high mainly due to complex production process.

• Biopolymer production yield is low to fulfill the polymer demand in the market.
• Information present in literature is not very enough for production of biopolymer from algae.
Weaknesses • Controlling monomer composition of biopolymer is relatively difficult.

• Accumulation or secretion of desired product from microalgae need stress condition which also
decrease cell growth rate.

• Some difficulties in commercially algae production.

• Novel bio composite polymers can be produced with blending of algal biopolymer or biomass with
another polymer.

• Some algae species can also grow in waste water with designing suitable process, so that both
waste water is disposed and a useful product is obtained.
• Biorefinery approach for algae utilization provides to lower production cost with zerowaste concept.
Opportunities
• Algae species are prone to genetically engineering modification which let high yielded biopolymer.

• International investments and collobrations are possible to enhance algal biopolymer production,

• New job oppurtunities for algal biopolymer production are available.

• New patents for algal biopolymer production are available.

• Weakness of algal biopolymer may prevent their further commercialization.

Threats • Very low cost of fossil fuel based polymers prevents awareness of necessity to find and use
alternative sources for biopolymer production.

The polymer produced from algae have advantages advantages over first and second generation
and disadvantages over conventional polymers which feedstocks such as their high growth rate,
demonstrated on SWOT analysis (Table 1). Therefore, noncompetitiveness with food, need of less area for
further researches and projects are needed to reveal growth, fixation of CO2 from environment and lack of
more information about algal biomass production and having recalcitrant compartment like lignin, and they
feasible process to convert this biomass into various are more suitable for mainly biofuel and bioderived
biopolymer for different kind of applications. polymer productions. In conclusion, by means of this
review, the types of algal biopolymers and many
different processes to produce commercial bio-based
CONCLUSIONS polymers from algal biomass were presented to give
point of view for using sustainable and renewable
Algae are used as food, feed and fertilizer sources, sources.
and feedstocks for biofuel production. They can be also
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Received on 02-12-2017 Accepted on 05-12-2017 Published on 13-07-2017

DOI: http://dx.doi.org/10.15377/2409-983X.2017.04.2

© 2017 Didem et al; Avanti Publishers.

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