Trends in Biotechnology

Review
Designing Biobased Recyclable Polymers
for Plastics
Rajni Hatti-Kaul,1,* Lars J. Nilsson,2 Baozhong Zhang,3 Nicola Rehnberg,4 and Stefan Lundmark5

Several concurrent developments are shaping the future of plastics. A transition to a sustainable Highlights
plastics system requires not only a shift to fossil-free feedstock and energy to produce the car- Rational polymer design is impor-
bon-neutral building blocks for polymers used in plastics, but also a rational design of the poly- tant for desired functionality and
mers with both desired material properties for functionality and features facilitating their recy- recyclability.
clability. Biotechnology has an important role in producing polymer building blocks from
Increasing the glass transition
renewable feedstocks, and also shows potential for recycling of polymers. Here, we present stra-
temperature is an effective strategy
tegies for improving the performance and recyclability of the polymers, for enhancing degrad-
for enhancing the performance and
ability to monomers, and for improving chemical recyclability by designing polymers with
recyclability of biobased polymers.
different chemical functionalities.
Selective polymer depolymeriza-
tion and repolymerization of
The Need of the Hour monomers offers an important
At the start of 2018, the European Commission communicated ‘a European Strategy for Plastics in a route to plastic recycling.
Circular Economy’, emphasizing improved design and production of plastics and plastic products to
Microbial cells and enzymes
facilitate reuse, repair, and recycling. It also noted the need to decouple plastic production from fossil
constitute important tools for the
resources and reduce greenhouse gas (GHG) emissions in line with the commitments under the Paris
production as well as recycling of
Agreement on Climate Changei. Even though plastics provide economic and environmental benefits polymers.
during their use in various applications, they have come under close scrutiny for their negative envi-
ronmental impacts, in particular from littering and leakage into terrestrial and aquatic environments Feedstock sustainability is a
[1,2] (Box 1). Enormous amounts of plastic waste are generated globally [3,4], and only a fraction of concern and CO2 will become an
this waste is recycled (Box 2). The major portion of plastic waste goes for energy recovery and land- important alternative to biomass
filling [2,5], where landfilling is the less favored alternative and is being gradually phased out in Eu- for fossil-free polymers.

rope. Low recycling rates result in large losses of the material value to the economy [1]. Thus, plastics
are now at the top of the political agenda in Europe and across the world, and several initiatives are
being put forward to minimize plastic leakage and move towards a more circular plastics economy
[13]. This implies that plastics, instead of being discarded as waste, should re-enter the economy
as valuable commodities, hence retaining their economic value as well as conserving natural re-
sources, reducing waste, and minimizing their carbon footprint [1].

Transition to a circular economy (see Glossary) requires rethinking the entire plastics value chain from
raw materials and energy used for production to material design, recovery, and recycling options af-
ter their useful lifetime (Figure 1). In accordance with the aims of a circular economy as well as a bio-
economy to reduce the use of fossil resources [14,15], plastics based on renewable feedstocks are
already being developed as carbon-neutral alternatives to fossil-based products, and electricity sys-
tems are becoming fossil-free with increasing shares of renewable and variable power production.
However, the production volumes of biobased plastics remain <1% of the total plastics (335 million 1Biotechnology, Faculty of Engineering,

Lund University, SE-221 00 Lund, Sweden

tons in 2016ii). This can be attributed primarily to the competition with cheap virgin plastics made
2Environmental and Energy Systems
from low-cost fossil feedstock that go untaxed despite their carbon content. Biomass feedstock
Studies, Faculty of Engineering, Lund
sourcing and undeveloped recycling and/or disposal routes are additional challenges to biobased University, SE-221 00 Lund, Sweden
plastics. An important key to a sustainable plastics system lies in the rational design of nonfossil poly- 3Center for Analysis and Synthesis, Faculty

mers not only for achieving optimal material properties required for the target applications, but also of Engineering, Lund University, SE-221 00
Lund, Sweden
to facilitate recyclability of the material or to recover its energy and carbon content in cases where
4Bona Sweden AB, Murmansgatan 130,
recycling is difficult or not possible [16,17].
Box 210 74, SE-200 21, Malmö, Sweden
5Perstorp AB, Industriparken, 284 80
Here, we highlight the trends and challenges in the production of plastics from renewable feedstocks, Perstorp, Sweden
strategies for improving their performance and recycling, and the role of biotechnology as an *Correspondence:
enabling tool in production and its potential to drive a more sustainable plastics economy. We focus Rajni.Hatti-Kaul@biotek.lu.se

50 Trends in Biotechnology, January 2020, Vol. 38, No. 1 https://doi.org/10.1016/j.tibtech.2019.04.011

ª 2019 Elsevier Ltd. All rights reserved.
Trends in Biotechnology

Box 1. The Plastics Challenge Glossary

Plastics production accounts for an average of 6% of the global fossil feedstocks (approximately half as raw ma- Amorphous polymers: polymers
terial and half in the form of energy for the manufacturing process) [1], and reached a global production volume with a random structure that do
of 335 million tons in 2016 (www.plasticseurope.org/en/resources/publications/619-plastics-facts-2018), while not have a sharp melting point
the global generation of postconsumer plastic waste is estimated at present to be approximately 150 million and soften gradually with in-
tons per annum [3,4]. There are three basic routes for the disposal of collected plastic waste: mechanical recy- creases in temperature.
Biobased plastics: plastics
cling, landfilling, and incineration, the latter two accounting for the major forms of disposal [5]. Considerable
comprising, wholly or a significant
GHG emissions are associated with the production and some also with the disposal of plastics after use depend-
part thereof, renewable biological
ing on the route of disposal (e.g., incineration for energy recovery results in the direct release of the carbon, raw materials (such as plant, ani-
while release from landfilling can take a very long time). In 2012, these emissions amounted to 390 million mal, and marine materials),
tons of CO2 globally. If the plastic usage were to continue at the same rate, plastics are expected to account including products and residues
for 20% of total fossil oil consumption, with the related GHG emissions increasing to 15% of the global annual from agriculture and forestry.
carbon budget [6] by 2050 from the current figure of 1% [1]. Biodegradable plastic: a plastic
that is broken down by microor-
Recycling of plastics is inefficient; globally, only 2% of total plastic waste is recycled, while in Europe, 31.1% of the ganisms in the environment for
27.1 million tons of postconsumer plastic waste was collected for recycling in 2016, 41.6% was incinerated and use as a carbon and energy
27.3% went to landfill (www.plasticseurope.org/en/resources/publications/619-plastics-facts-2018). It is esti- source. Biodegradation can take
mated that 95% of the value of plastic packaging material (V70 million–V105 billion) is lost to the economy after place in many environments,
a very short first-use cycle (ec.europa.eu/environment/circular-economy/pdf/plastics-strategy-brochure.pdf). including soils, compost sites,
water treatment facilities, anaer-
Several of the chemical additives, such as plasticizers, flame retardants, stabilizers, antioxidants, and pigments, obic digestors, and marine envi-
included in plastic products to enhance their polymer properties and prolong their shelf life, are hazardous to ronments. Not all biobased plas-
the environment, humans, and other organisms. These additives can be released during recycling procedures, tics are biodegradable, and
biodegradable plastics are not
or can leak from plastic wastes in landfills into groundwater [2,7,8].
always biobased. PCL is an
Leakage of plastics into the oceans is estimated to be
8 million tons per annum and has led to a total plastics example of a biodegradable fos-
accumulation of 150 million tons, which has a deadly effect on marine organisms through physical entangle- sil-based plastic.
Bioeconomy: encompasses the
ment, ingestion of microplastics (plastic debris a few mm–500 mm in size, estimated at over 51 trillion pieces
production of renewable biolog-
weighing over 250 000 tons [9]), and the associated plastic additives [2,10].
ical resources and the conversion
of these resources and waste
streams into value-added prod-
mainly on polyesters because they cover a range of properties and applications from durable to ucts, such as food, feed, biobased
products, and bioenergy. The
biodegradable plastics, and their realm of applications can be further expanded by suitable polymer
Circular Bioeconomy combines
design and modifications. Moreover, most biobased polymers produced thus far are polyesters. the common features of bio-
economy and circular economy,
(i.e., improved resource and
ecoefficiency, low GHG footprint,
Box 2. Recycling of Plastics
reducing the demand for fossil
Mechanical recycling is the most common and economical method available for recycling postconsumer plastic carbon, and valorization of waste
waste, and involves sorting, grinding, washing, and extrusion of the material [3,4,11]. Given that the process and side streams).
results in varying degrees of polymer degradation, mechanical recycling is limited by the number of reprocess- Carbon-neutrality: generated
ing cycles. Mechanical recycling is operated in two modes: primary and secondary recycling. Primary or closed- CO2 is converted again to
biomass by photosynthesis.
loop recycling implies reprocessing of the plastic back to the product used for the same purpose as the original
Ceiling temperature: tempera-
plastic; the process makes use of almost clean waste or postconsumer waste of known origin. The only example
ture at which the rate of polymer-
of primary recycling is that of PET bottles, wherein the recycled PET is combined with virgin plastic because of a ization and depolymerization of a
reduction in polymer chain lengths caused by the recycling process. polymer are equal.
Circular economy: a concept of an
Secondary recycling is the most used route for recycling of PET, high-density polyethylene (HDPE), and low-
economy that is restorative or
density polyethylene (LDPE), and often yields products lower in value. The lower molecular weight recycled regenerative in contrast to the
PET is used for fiber production. The comparatively high thermal stability of polyethylenes allows HDPE and concept of end-of-life or waste
LDPE to be processed through several melt and remould cycles [3]. (www.ellenmacarthurfoundation.
org/circular-economy/concept). It
Chemical recycling uses a chemical process for the degradation of polymers into their chemical constituents, is based on a shift to renewable
which may either be repolymerized to the original product or converted into other useful products, such as basic energy, superior design of mate-
chemicals and/or polymers for new plastics or fuels. An example of chemical recycling is pyrolysis (thermolysis), rials and products without any
in which plastics are subjected to high temperatures in the presence of a catalyst to give a mixture of products toxic chemicals to allow their
that are normally difficult to separate. An alternative would be selective degradation of the polymer chains un- reuse or recycling, and innovative
der controlled conditions to the precursor building blocks that are purified and subsequently repolymerized to services and business models.
form the original polymer or repurposed as building blocks for new polymers [12]. Chemical recycling is not Composting: a process to break
down organic matter with the help
practiced to a large extent on an industrial scale because the present methods require a large energy input.
of microorganisms in a specific

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time frame in a controlled warm,

moist, aerobic environment to
produce nontoxic compost that
can be used as soil enhancer for
supporting plant growth.
Crystalline or semicrystalline
polymers: polymers with a signif-
icant fraction in the crystalline
state, which have a melting
temperature.
Elastomers: class of polymers that
can be repeatedly stretched to
more than twice their size without
any deformation and that can
recover their original shape.
Global carbon budget: de-
termines the input of CO2 to the
atmosphere by emissions from
human activities, balanced by
output (storage) in the carbon
reservoirs on land or in the ocean;
provides quantitative updates on
permissible emissions for given
climate stabilization targets (i.e.,
to remain below a 2 C increase in
global warming) [6].
Glass transition temperature (Tg):
temperature at which a material
changes from a glassy state to a
Trends in Biotechnology soft rubbery state. Tg is usually
applicable to wholly or partially
Figure 1. Presentation of the Production of Biobased Plastics and Their Recycling. amorphous plastics.
The carbon-neutral building blocks for polymers are produced from biomass or directly from CO2. The polymers Life cycle assessment (LCA): a
method for environmental
are designed to have features suited for different applications and also a specific mode of recycling after the
assessment of products and ser-
plastic is no longer used. The plastic can either be mechanically recycled to obtain the original material, or
vices, covering their life cycle from
depolymerized under specific conditions to obtain the building blocks that are then used for rebuilding the raw material extraction to waste
polymer or converted to another product (chemical recycling). A biodegradable polymer may be subjected to treatment (i.e., cradle-to-grave).
microbial degradation under aerobic (composting) or anaerobic conditions and the residue is used for Thermoplastics: plastics that can
supporting plant growth. be softened and melted by heat-
ing and can be processed in either
the heat-softened or liquid state.
Plastics from Renewable Feedstock
The global production capacity of biobased plastics in 2018 was estimated at 2.11 million tons, of
which 1.2 million tons were nonbiodegradable and the remaining biodegradableiii. The biodegrad-
able products currently on the market are thermoplastic starch and several aliphatic polyesters,
including poly(lactic acid) (PLA), polyhydroxyalkanoates (PHAs), and poly(butylene succinate) (PBS)
(Table 1) [18]. PLA is by far the most commercially developed, having reached an annual production
volume of
200 000 tons. Biodegradability has been considered to be a useful feature, providing a
solution to reducing plastic waste by way of their decomposition to CO2 (or CH4) and H2O. However,
their practical use is hampered by their relatively poor thermal, mechanical, and rheological proper-
ties, and lack of compatibility with the processing and recycling systems currently available, hence
requiring copolymerization or blending with other polymers and additives to achieve the desired
properties [19]. Furthermore, not all polymers are readily biodegradable; the time and products of
degradation vary depending on the environmental conditions as well as the plastic components [20].

An increasing trend in recent years has been to replace partly or wholly the fossil-based building
blocks of conventional plastics by identical molecules of renewable origin, the so-called ‘drop-ins’,
such as bio-poly(ethylene) (bio-PE) produced from bioethanol, poly(ethylene terephthalate) (bio-
PET) made using biobased ethylene glycol as the monomer, poly(trimethylene terephthalate) (bio-
PTT) with biobased 1,3-propanediol (1,3-PDO), and bio-polyamide from castor oil (Table 1) [12,21].
Being chemically identical to the products they replace, these biobased ‘greener’ alternatives can

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Table 1. Commercial Biobased and Biodegradable Polymers

Polymer Structure Biobased Annual Examples of Applications

content production trademark/
(%)a (tons)b company

Starch 100 384 000 Mater-Bi/Novamont Food packaging,

compostable films and
bags, disposable
eating utensils

PLA 100 217 000 Ingeo/NatureWorks; Packaging materials,

Luminy/Total medical implants, 3D
Corbion; Lacty/ printing polymers,
Shimadzu Cor.; textiles, electronics
Vyloecol/Toyobo

PHA 100 30 000 Minerv-PHATM/Bio- Packaging, compost

On; PHBHTM/Kaneka; bags, tissue
TephaFlex/Tepha; engineering
NodaxTM/Danimer
Scientific; AirCarbon/
Newlight Technologies

PBS Up to 100 97 000 GS PLA/Mitsubishi Films and sheets for

Chemical; BionolleTM food packaging and
1000/Showa Denko agriculture, compost
K.K.; Skygreen/SK bags, fishing nets,
Chemicals; BioPBSTM/ automotive industry
PTT MCC Biochem

Poly(butylene
50 BionolleTM 3000/ Films, sheets,

succinate-co-butylene Showa Denko K.K.; filaments, laminates in
adipate) (PBSA) Skygreen/SK agriculture, fishery,
Chemicals household goods, etc.

Poly(butylene adipate- 0 152 000 Ecoflex/BASF; Cling wraps for food

co-butylene Wango/Zhuhai Wango packaging,
terephthalate (PBAT) Chemical Co.; compostable plastic
Ecoworld/JinHui bags, water-resistant
ZhaoLong; Eastar Bio/ coatings
Eastman); Origo-Bi/
Novamont

Poly(ε-caprolactone 0 CAPATM/Perstorp until Packaging, bags, films,

(PCL) 2018, acquired by adhesives, footwear,
Ingevity biomedical
applications

Biobased, nonbiodegradable

Bio-poly(ethylene) 100 200 000 I’m greenTM/Braskem Mainly packaging,

(bio-PE) films and bags

(Continued on next page)

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Table 1. Continued

Polymer Structure Biobased Annual Examples of Applications

content production trademark/
(%)a (tons)b company

Bio-poly(ethylene 20 560 000 PlantBottleTM/Coca Packaging

terephthalate) (Bio- Cola
PET)

Poly(ethylene 100 Under Synvina/Total-Corbion Packaging:

furanoate) (PEF) development replacement for PET

Bio-poly(trimethylene 30 194 000 Sorona/DuPont Fiber for textiles and

terephthalate) (Bio- CorterraTM/Shell carpets, nonwoven
PTT) Chemicals fabrics

Bio-polyamide (Bio- Up to 100 245 000 EcoPAXX/DSM; Automotive, electrical

PA) Vestamid TERRA/ and electronics,
Evonik consumer goods,
sports, and leisure
a
The biobased content of the polymers is based on current information about commercially available products, and could be increased for polymers that are
presently partly or wholly fossil based.
b
The annual production volume of the polymers was obtained from www.european-bioplastics.org/market/

be processed using the existing infrastructure and made available to users already familiar with their
performance and applications. Efforts have also been under way to produce other high-value mono-
mers such as isoprene, propylene, styrene, acrylic acid, and terephthalic acid, for commonly used
plastics [22,23].

The conversion of biomass feedstocks allows us access to not only carbon-neutral alternatives, but
also a diversity of novel structures not easily obtained from fossil resources, such as furan-based
monomers and isosorbide. 2,5-Furan dicarboxylic acid (FDCA), produced by the oxidation of 5-hy-
droxymethylfurfural (5-HMF), a dehydration product of C6-sugar, is currently a building block of inter-
est for the production of a new recyclable fully biobased product poly(ethylene furanoate) (PEF), with
excellent thermal properties and superior barrier properties compared with PET (over six times higher
for O2, and twice as high for CO2 and water), which makes it an ideal substituent for the polymer in
packaging [24].

Cradle-to-grave life cycle assessment (LCA) of several bio- and fossil-based plastics has shown the
production and use of biobased plastics to be generally advantageous in terms of saving fossil re-
sources and reducing GHG emissions [25–28]. For example, significant savings of nonrenewable en-
ergy use (40–50%) and GHG emissions (45–55%) have been reported for the production of PEF
compared with the cradle-to-grave impact of PET [29]. The environmental impact of biobased plastics
production is typically dominated by primary agricultural feedstock production in terms of fossil fuel
and fertilizer inputs with resulting GHG emissions, acidification of soil, eutrophication, and strato-
spheric ozone depletion [25,26,30,31]. The water footprint of such plastics is also usually quite signif-
icant. Thus far, most commercial biobased plastics and their monomers are produced from first-gen-
eration agricultural feedstocks (e.g., cornstarch and sugar cane) that are easy to process and that,
besides the impacts described earlier, also bring up the issue of land use [25,26]. Although current
production is estimated to translate to 0.82 million ha of landiv, equivalent to only
0.07% of arable
land, the land-use issue will be a concern if hypothetically 100% and not just 1% of all plastics become
biobased. The current level of total plastic production would require
25–30 EJ of biomass feed-
stock, which is nearly half of all current biomass use for energy and a significant amount relative to
estimated global biomass potentials of 50–500 EJ [32].

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Utilization of by-products and waste flows as raw materials or integrating production in a biorefinery
would provide a dramatic ecological advantage as well as reduce pressure on arable land [26,31,33–
35]. Wood and other lignocellulosic residues from agriculture and forestry are expected to be more
sustainable alternatives because they are a major source of polysaccharides and lignin in nature for
providing both aliphatic and aromatic chemical platforms for the chemical and material industries.
Here, the need for pretreatment and fractionation of the recalcitrant feedstock and depolymerization
of the polysaccharides to sugar monomers adds significantly to the energy and process costs and, in
the case of lignin, there is also a challenge in terms of the downstream processing of its degradation
products [36]. By contrast, research on the utilization of industrial wastes, both organic and gaseous
(syngas, CO2, and CH4), as the future feedstocks for nonfossil products has gained momentum [37–
39]. Production of PHA from diverse biomass streams, municipal wastewater, CO2, and CH4 is an
important case in point [40–45]. Transformation of CO2 and CH4 provides further benefits of utilizing
GHGs to form useful products.

Industrial Biotechnology: The Key Enabling Technology for Biobased Plastics

Irrespective of the polymers being biodegradable or nonbiodegradable, or the feedstock used, in-
dustrial biotechnology is a key enabler for the production of most biobased plastics, starting from
providing tools for the first step of biomass deconstruction to simpler entities, to the production of
building blocks and also polymers [18,22,46–49]. Enormous efforts have gone into the screening
and development of enzymes that hydrolyze the different components of the lignocellulosic biomass
[50,51]. However, because enzymatic hydrolysis adds to the process costs, the approach gaining favor
is that of consolidated bioprocessing, which involves the development of microbial strains with engi-
neered polysaccharide-degrading activities or the design of co-cultures that would allow direct con-
version of the biomass to the target molecule [52,53]. Accessing the diverse aromatic monomers in
lignin is still a puzzle being solved, for which the selectivity of various microbial lignin-depolymerizing
enzymes is of interest [54].

The production of polymer building blocks, including aliphatic diols, dicarboxylic acids, hydroxya-
cids, diamines, and aromatic molecules, from biomass components, including sugars, oils, and glyc-
erol, invariably relies on the use of microorganisms [22,47,48,55–60] and, in case of PHAs, the whole
polymer with a variable monomer composition is accumulated by the microbial cells [61–65]. For
many building blocks (e.g., FDCA, terephthalic acid, acrylic acid, isosorbide, etc.), integration of
biotechnology processes based on microbial or enzymatic transformation with chemical processes
offers a potential production route [66–69]. While microorganisms, with a genetic makeup to produce
the target product naturally, may be further developed by evolutionary engineering to utilize a spe-
cific feedstock and to increase product concentrations and yields [70], metabolic engineering, sup-
ported by systems biology and synthetic biology tools, is being increasingly used for the develop-
ment of cell factories for the production of several natural and non-natural chemicals [55,56,71,72].
Examples of the production of polymer building blocks are represented in Figure 2. The metabolic
engineering strategies could include construction of a new pathway, elimination of competing path-
ways, altering substrate preference, facilitating transport of metabolites, ensuring redox balance,
improving resistance to inhibition by product, pH, and so on, with a target to achieve high product
yields and selectivity. So far, only a limited number of microorganisms are amenable to engineering
and to serve as large-scale production hosts; thus, there is near-unlimited scope for expanding the
microbial toolbox for the production of chemicals and materials. Moreover, efforts are still needed
to build processes with high yields and productivities, and with efficient product recovery techniques
to make the production of biobased products resource efficient and cost competitive.

Biological systems also offer different routes for CO2 reduction and methane oxidation operating at
ambient temperatures [37,39,40,78,79]. While various biological CO2 sequestration methods using
algae, photosynthetic bacteria, or autotrophic bacteria are being developed, the approach that
has gained considerable interest is that of microbial electrosynthesis performed in a bio-
electrochemical cell using renewable electricity to provide electrons for autotrophic microbes to
catalyze the CO2 reduction to chemical building blocks [79–81].

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Finally, the use of enzymes as selective catalysts for polymer synthesis and modification has been well
documented [18,48,82]. Synthesis of both natural and synthetic polymers, including polysaccharides,
polyesters, polyamides, and polyphenols, has been demonstrated [83]. Free or immobilized lipases
and cutinases have been successfully used to produce aliphatic polyesters with significant molecular
weights via polycondensation and ring-opening reactions [48,49,84,85]. However, their industrial
application has been limited due to the high cost and low stability of the biocatalysts under the harsh
conditions needed for polymer syntheses.

Designing Biobased Polymers for Enhanced Performance

High performance biobased polymers with desirable material features that are retained even when
subjected to processing and recycling, are in demand. The glass transition temperature (Tg) is

(A) (C)

(D)

(B)

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(Figure legend at the bottom of the next page)

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one of the most important thermal properties of amorphous plastic materials, determining their phys-
ical, mechanical, and rheological properties and, hence, their range of applications, while the melting
temperature, Tm, is important for semicrystalline plastics [86,87]. PET, the most widely recycled plas-
tic, has a Tg of
74 C, but undergoes a loss of molecular mass during recycling (Box 2). Commercial
biodegradable polymers generally have a low Tg, the highest value being 55 C for PLA [88]. Tg of PHA
with aliphatic monomers varies widely, from, for example, 5 C for short chain-length (scl-PHA) ther-
moplastics to –47 C for middle chain-length (mcl-PHA) elastomers, the type of PHA produced de-
pending on the bacterial host and the carbon source used during their cultivation [89]. Introduction
of aromatic units (e.g., phenyl, phenoxy, nitrophenoxy, benzoyl, etc.) in the PHA chain significantly
increases the Tg of the polymer to 10–30 C, depending on the aromatic group [90].

Improvements in Tg of aliphatic polyesters are an effective strategy for increasing their performance
and recycling possibilities, and even their optical transparency. Polymers with high Tg values have
rigid backbones, which restricts their rotational flexibility [91]; thus, an increase in Tg is achieved by
introducing rigid ring structures (e.g., aromatic or cycloaliphatic moieties) into the polymer backbone
to impart high conformational barriers and strong polar associations, or by making substituents along
or near the polymer chain that limit the chain rotation through steric interactions [86,92] (Table 2).

Aromatic units from lignin (e.g., ferulic acid, coumaric acid, vanillic acid, and syringic acid) and tannins
(gallic acid) or produced by engineering of the metabolic route (shikimate pathway) for the produc-
tion of aromatic amino acids from sugars, constitute useful renewable components for biobased poly-
esters with high Tg [86,93–96]. Use of larger aromatic structures can result in a larger increase in Tg, as
known for polyethylene naphthalate (PEN, Tg
120 C). Thus, biopolyesters with excellent thermal
properties could be produced from an indole derivative [97], an aromatic heterocyclic compound
formed as an intermediate in the shikimate pathway for tryptophan biosynthesis. Even aromatic di-
mers produced by coupling monomers also serve as novel building blocks for fully biobased high
Tg aromatic polyesters, as shown with divanillin produced by laccase-catalyzed coupling of vanillin
molecules [98]. Interestingly, the fully biobased PEF, with a 5-membered furan ring as a monomer
unit, has a higher Tg (86 C) than PET [86], and the use of the FDCA dimer, 2,20 -bifuran-5,50 -dicarbox-
ylate, as the monomer increases the Tg further to 107 C [99].

Figure 2. Examples of Metabolic Pathways for the Production of Biobased Building Blocks from Sugar.
(A) 1,3-Propanediol (1,3-PDO) is naturally produced from glycerol by Lactobacillus [57], Klebsiella, Citrobacter, Enterobacter, and Clostridium species [73],
by a pathway involving dehydration catalyzed by vitamin B12-dependent glycerol dehydratase (dhaB1-3) to 3-hydroxypropionaldehyde, which is reduced
using NADH in a reaction catalyzed by 1,3-PDO oxidoreductase. Production from glucose is achieved using metabolically engineered Escherichia coli
involving conversion via a series of reactions to glycerol-3-phosphate, which is converted by glycerol 3-phosphate dehydrogenase (DAR1) and glycerol-
3-phosphatase (GPP2) to glycerol that is subsequently converted to 1,3-PDO using dhaB1-3 and E. coli oxidoreductase yqhD [73]. Further engineering
involves replacing the glucose transport system with an ATP-dependent glucose phosphorylation system, downregulation of the gene encoding
glyceraldehyde 3-phosphate dehydrogenase (gap), and also deletion of the competing pathways (genes encoding glycerol kinase and glycerol
dehydrogenase) for glycerol metabolism. (B) Glycolic acid is produced via an engineered glyoxylate cycle in acid-tolerant Saccharomyces cerevisiae and
Kluyveromyces lactis by introducing genes encoding glyoxylate reductase (GLYR1) and deleting genes encoding malate synthase (MLS1) and isocitrate
dehydrogenase (IDP2) while simultaneously expressing the gene encoding isocitrate lyase (ICL1) [74]. (C) Vanillin is produced mainly from lignin and
guaiacol, but there exist several biosynthetic routes from ferulic acid, eugenol, isoeugenol, and glucose [75]. Production of vanillin from glucose involves
creating a diversion from the shikimic acid pathway by introducing 3-dehydroshikimic dehydratase, which catalyzes the dehydration of the intermediate
3-dehydroshikimic acid to protocatechuic acid (PCA). Subsequently, PCA is converted to vanillic acid by introducing the gene encoding catechol-O-
methyltransferase (COMT) into the cells, followed by a reductive step to form vanillin in vitro using aromatic carboxylic acid reductase (ACAR).
Alternatively, full in vivo conversion is achieved in S. cerevisiae by the introduction of ACAR in combination with a phosphopantetheinyl transferase to
reduce PCA to protocatechuic aldehyde, which is converted to vanillin by COMT [75]. (D) Adipic acid production from glucose is possible via different
metabolic routes, including: (i) via PCA [biosynthesis of which is similar to that described in (C)], which is converted by protocatechuic acid
decarboxylase to catechol, which in turn is converted to cis-cis-muconic acid using catechol 1,2-dioxygenase; and (ii) via glucaric acid, which is produced
from glucose through several reaction steps. myo-Inositol-phosphate synthase encoded by a heterologous Ino1 gene catalyzes the production of myo-
inositol-phosphate from glucose-6-phosphate formed as a result of glucose transport by the phosphoenolpyruvate (PEP)-dependent
phosphotransferase (PTS) system. myo-Inositol-phosphate is hydrolytically dephosphorylated to produce myo-inositol, which is then converted by
another recombinant enzyme, myo-inositol oxygenase (MIOX), to D-glucuronic acid using molecular oxygen. Subsequently, D-glucuronic acid is
oxidized using uronate dehydrogenase to D-glucaric acid [76,77]. Both muconic acid and glucaric acid are chemically hydrogenated to form adipic acid.

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Rigid cycloaliphatic diols, such as 1,4-cyclohexanedimethanol (CHDM) and cis/trans-2,2,4,4-tetra-

methyl-1,3-cyclobutanediol (CBDO),have proven useful in developing copolyesters with excellent
thermal properties with terephthalate and furan dicarboxylate esters, respectively [100–104]. Both di-
ols are used in the production of high-performance terephthalate-based copolyesters TritanTM (Tg
108–116 C; Eastman), and in several high-Tg polymer compositions involving FDCA, exhibiting
good barrier and mechanical properties, and biodegradability. Biobased rigid diols comprising
1,4:3,6-dianhydrohexitols (isohexides) including isosorbide, isomannide, and isoidide derived from
corresponding C6-sugar alcohols (sorbitol, mannitol, and iditol, respectively), also increase the ther-
mal stability of polymers [105–108]. Isosorbide is the only product industrially available and, hence, is
used more extensively in the synthesis of high-Tg homo- and copolyesters with aliphatic and aromatic
structures [109–115], although the low reactivity of the exposed secondary hydroxyl groups generally
leads to low-molecular-weight polymers. By contrast, high-molecular-weight, high-Tg polyesters
could be produced using a rigid sugar alcohol derivative with exposed primary alcohols, produced
by acetalization of the secondary alcohol groups forming fused dioxane rings [116].

Spirocyclic acetal or cyclic ketal structures provide options to design other unique rigid biobased diol
monomers for polymers with favorable thermal and mechanical properties, particularly when used in
combination with aromatic molecules (Table 2) [86,117,118]. An example of a spirocyclic acetal-
bearing product is AkestraTM (Perstorp AB), a partially biobased thermoplastic terephthalate-based
copolyester with Tg in the range of 90–110 C, suitable for heat-resistant packaging. High-Tg aliphatic
polyesters with tunable properties have also been generated by copolymerization of cyclic anhy-
drides with epoxides [119].

Design for Enhanced Degradation

Although biodegradable plastics appear to be less favored than nonbiodegradable ones, biode-
gradability is a useful feature for certain applications where recovery of the plastics is difficult or
impossible and leakage into the environment is difficult to avoid, such as in agricultural mulch films,
fishing nets, or cosmetics. Biodegradability could also be used as a means to enable polymer recy-
cling. However, a major bottleneck when designing degradable polymers is to achieve good proper-
ties and stability during their useful lifetime while at the same time being 100% degradable after
disposal in a reasonable time frame to harmless degradation products that do not accumulate in
the environment.

Commercial biodegradable polymers have variable degradation rates [120]. For example, compar-
ison of the polyesters with short side chains, PLA, polyhydroxybutyrate (PHB) and polycaprolac-
tone (PCL; currently a fossil-based polymer) shows that their sensitivity to hydrolysis decreases
in the order PLA>PHB>PCL, and the biodegradation rate for PHB is the fastest, followed by
PCL and PLA [119]. In fact, the biodegradation rate of PHA and PLA polymers and also the for-
mation and assimilation of their low-molecular-weight degradation products are influenced by
their stereochemistry.

Degradation of polymers is a complex process that depends on the nature of the backbone and the
individual bonds as well as biotic and abiotic factors in the environment [121]. One important factor is
the degree of polymer crystallinity [120,122,123]. Amorphous polyesters undergo faster hydrolysis,
and degradation of semicrystalline polyesters starts with water diffusion in the less organized amor-
phous regions; only after the amorphous regions are degraded does the hydrolysis continue into the
crystalline domains. The semicrystalline PLA, containing 100% L-lactide units, exhibits the longest
degradation time, with a half-life of 110 weeks, which decreases dramatically to 10 weeks by incorpo-
ration of 50% D-lactide units, and to 3 weeks on copolymerization with 25% glycolic acid [124]. Even
the degradation rate of PHAs is determined by their monomer composition and crystallinity [125].
Longer side chains of the monomers (e.g., 3-hydroxyhexanoate) increases the amorphous fraction
in the polymer, making the polymer more prone to degradation by PHA depolymerase and lipase en-
zymes [126,127]. PHA copolymer poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) degrades
faster than the homopolymer of PHB [128]. Similarly, incorporating a dicarboxylic acid unit with a

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Table 2. Examples of Monomers Yielding Polyesters with High Glass Transition Temperatures

Monomer 1 Other monomer(s) Tg Other properties Refs

Aromatic

Hydroxyethylferulic acid L-lactide 64–107 C Increasing ratio of aromatic units led to [93]
polymers with decreasing molecular
weights and increasing thermal stability

Indole dicarboxylate 1,3-propanediol 93 C Mn (number average molecular [97]

weight) =35 800 g/mol, Mw (weight
average molecular weight): 71 700 g/
mol

Neopentyl glycol 99  C Mn=41 100 g/mol, Mw: 112 300 g/mol;

polyesters are amorphous and form
transparent flexible films

Divanillin Dimethyl terephthalate 102 C High thermal stability of polymers [98]

2,5-furandimethylester 139 C

2,20 -bifuran-5,50 -dicarboxylate Ethylene glycol 107 C Polyester has Tm of 240 C and Td [99]
(temperature at maximum weight loss
rate) of 429 C, excellent barrier and
good UV radiation-blocking properties

Cycloaliphatic diol

1,4-cyclohexane dimethanol (CHDM) Dimethyl terephthalate and ethylene 102 C Replacement of part of CHDM with more [103]
glycol rigid CBDO increased Tg further to
118 C. Copolyesters exhibit increased
fragility and oxygen permeability

2,2,4,4-Tetramethyl-1,3- Dimethyl terephthalate + C2-C4 diols 80–168 C High UV stability, good thermal and [100]
cyclobutanediol (CBDO) photooxidative stability, high impact
Terephthaloyl chloride 185 C
resistance and optical clarity

Dimethyl furan-2,5-dicarboxylate and 88.9– Copolyesters had better mechanical [104]

ethylene glycol 94.3 C properties, good barrier properties, and
better clarity

Isosorbide FDCA dichloride derivative 173–194 C Polyesters with Mn in the range of 9000– [110,109]
25 000 g/mol

1,4-Cyclohexane dicarboxylic acid 122–145 C Homopolyester with Mn of 11 000 g/mol; [111]

dichloride (CHDA) copolyester with succinyl chloride gave
maximum Tg of 112 C

(Continued on next page)

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Table 2. Continued

Monomer 1 Other monomer(s) Tg Other properties Refs


CHDA 131 C Polyester with Mn 14 300 and Mw of 71 [112]
000; acetylation of isosorbide decreased
steric hindrance during reaction

Terephthalic acid, ethylene glycol and 93–143 C High degree of polymerization, Mn=25 [113]
CHDM 400 and Mw=65 400 g/mol

Dimethyl furan-2,5-dicarboxylate, 81–119 C Terpolyesters of high molecular weight [115]

ethylene glycol and CHDM (50 800 g/mol). Use of CHDM increased
low reactivity of furan monomer with
isosorbide

Succinyl chloride and isophthaloyl 75-180 C Biodegradable polyester with Mn of [114]

chloride 7000–15 000 g/mol

2,4:3,5-di-o-methylene-D-mannitol Dimethyl terephthalate 137 C Polyesters have Mw in range of 30 000– [116]

(Manx) 52 000 g/mol and are thermally stable up
Butyleneterephthalate Up to
to almost 370 C
100 C

Spiroglycol Terephthalic acid and ethylene glycol 90-110 C Spiroglycol obtained from reaction of [117]
biobased pentaerythritol with two
equivalents of hydroxypivaldehyde.
Copoly(ester acetal) is heat resistant,
hydrolytically stable, has comparable
transmittance, mechanical properties
and lower density compared with PET

Ketal monomer made from 1,4- Dimethyl furan dicarboxylate 96 C Mn: 8600 g/mol; Td: 320 C [118]
cyclohexanedione and glycerol

Terpene-based cyclic anhydride Propylene oxide 83–106 C High thermal stability of polymers; [119]
Mn=55 400 g/mol

longer carbon chain as the monomer resulted in higher enzymatic degradability of poly(butylene suc-
cinate adipate) (PBSA) compared with the homopolymers PBS and poly(butylene adipate) (PBA) [129].
The same is also true for aromatic-aliphatic polyesters, such as poly(butylene adipate-co-tere-
phthalate) (PBAT), a commercially available biodegradable polymer resin (currently fossil based)
with good mechanical and thermal properties suitable for various packaging applications [130] (Table
1). A relatively large spacing between the ester linkages (such as that obtained with adipic, azelaic,
and sebacic acids) and a suitable hydrophilic–hydrophobic balance of the materials are important fac-
tors for the susceptibility of isosorbide-based polyesters to enzymatic degradation [131]. Copolymer-
ization of isosorbide with aliphatic and aromatic dicarboxylic acids provides readily biodegradable
polyesters with good thermal properties and Tg up to180 C, which is better than most commercial
engineered plastics [116].

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The polymer degradation rate may also be increased by introducing a functional group that degrades
by another mechanism, to provide polyester fragments with increased susceptibility to hydrolysis
through a decrease of molecular weight, resulting in an open structure for water to enter and facilitate
both enzymatic and nonenzymatic hydrolysis. The introduction of acetal functionalities in polyesters is
a good example, and has two new routes for degradation besides the hydrolysis of ester bonds: reg-
ular acid-promoted hydrolysis and light-induced radical decay. The latter could result in a polymer of
reduced molecular weight, increased polarity, loss of mechanical and barrier properties, and frag-
ments digestible by microorganisms or enzymes. Polyoxalates, a special group of polyesters with
two adjacent ester groups produced by reacting an acetal-based diol with an oxalic acid derivative,
have high Tg (attributable to an aromatic and a cyclic acetal group) and also hydrolyze easily under
mild acidic to neutral conditions owing to increased electrophilicity of the carbonyl group caused
by the proximity of the other [132].

Towards Recyclable Polymers and Monomers

In addition to mechanical recycling, there is increasing attention being paid towards developing
technologies for recovering the building blocks from plastics for repolymerization to the original
polymer or conversion to another product, in a process referred to as chemical recycling [3,12,133]
(Box 2). The traditional process of chemical recycling by pyrolysis, in which plastics are subjected
to high temperatures in the presence of a catalyst, gives a mixture of smaller molecules that are diffi-
cult to separate. Selective depolymerization under milder conditions would be useful even for
enabling facile separation of polymers from blends, as in textiles and mixed plastic wastes [134].
Achieving selectivity is a challenge in this approach besides the paradox of combining the suscepti-
bility of a polymer to depolymerization with its material properties [135].

Different strategies for selectively triggering polymer degradation using temperature, light, or other
stimuli by incorporating suitable functional groups have been proposed. An interesting approach
makes use of the thermodynamics of polymerization and depolymerization related to the ceiling tem-
perature (Tc); that is, temperatures below and above Tc favoring polymerization and depolymeriza-
tion, respectively. Polymers designed with a favorable Tc, such that polymerization and depolymer-
ization are achieved in a reasonable temperature range, are interesting in this regard. Polyesters
derived from cyclic esters or lactones have real potential to meet these requirements [136–140]; poly-
mers with five-membered g-butyrolactone as monomer have so far demonstrated complete and in-
finite chemical recyclability [135].

Thermal degradation of PLA and PHA has shown the catalyst to be important in promoting selective
depolymerization under milder conditions and the products formed [141–145]. Thermal degradation
of PHA using a catalyst such as dibutyltin dimethoxide in solution results in a cyclic ester that can be
repolymerized to the original polymer [142], while the use of alkali earth compound catalysts yields
vinyl monomers that can be subjected to microbial repolymerization to homo- or copolymers
[143,144], or further reacted to form other high Tg polymer products [146] (Figure 3).

Chemical bonds, such as esters, acetals, amides, and ethers, in a polymer are susceptible to hydro-
lysis or enzymatic cleavage; thus, incorporating the building blocks with the functionalities needed for
creating such bonds in the polymer and performing depolymerization under controlled conditions in
a closed system would allow reclamation of the monomers. Polymers with weak covalent bonds [e.g.,
poly(hemiacetal ester)s] undergo thermal depolymerization, and their dissociation temperature can
be controlled by molecular design of the dicarboxylic acid monomers [146].

Reports of the microbial degradation of synthetic nondegradable plastics have attracted consider-
able public attention. Given that their degradation ability is attributed to the enzymatic activity, mi-
crobial enzymes are potential catalysts for the recycling of both synthetic and biobased plastic wastes
[147,148]. Lipases and cutinases are the most studied enzymes for the hydrolysis of polyesters and
polycarbonates [18,48,82]. Studies with PET have shown thermostable cutinases to give the highest
degree of polymer hydrolysis, especially when combined with a thermostable carboxylesterase

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Trends in Biotechnology

Figure 3. Different Strategies for the Biotic and/or Abiotic Recycling of polyhydroxyalkanoate (PHA).
The polymer is produced from a varied feedstock, such as sugar, oil, organic wastes, CO2, or CH4. The PHA product can be biodegraded under aerobic or
anaerobic conditions to yield CO2 or CH4, which can be utilized again for PHA biosynthesis. An alternative strategy is the catalytic depolymerization of PHA
at high temperature to yield a mixture of 2-alkenoates (e.g., crotonic acid) and 3-hydroxyalkanoate monomers and oligomers that can be repolymerized by
bacteria to PHA copolymers either directly or with methane. Alternatively, 2-alkenoates can be copolymerized with other monomers to another copolymer.
Yet another route is to transform polyhydroxybutyrate (PHB) by catalytic ring-closing depolymerization to a cyclic monomer that can be polymerized back to
PHB.

[149] or lipase B [150]. Several site-directed mutagenesis approaches (e.g., to improve the adsorption
of cutinase to the polymer surface, to vary the size and hydrophobicity of residues around the catalytic
site, and also to make it resistant to product inhibition) have led to improvements in PET hydrolysis.
Even the polyesterase from a recently discovered PET-degrading bacterium Ideonella sakaiensis was
shown to have features resembling cutinase and lipase [151]. This enzyme also degrades PEF but not
aliphatic polyesters. Recycling of biodegradable polyesters, including PCL, PLA, PHB, PBS, and pol-
y(butylene adipate), and their copolymers by lipase-catalyzed depolymerization to cyclic oligomers
and repolymerization to readily form the polyester has been shown to be possible [152,153]. Polymer
degradation was significantly promoted by the addition of supercritical CO2 in the reaction medium
[153]. Microbial PHA depolymerases, which have a catalytic domain with an esterase sequence and a
substrate-binding domain for adsorption to the hydrophobic surface of the polymer [154], are other
enzymes of interest for processing PHAs.

Among other synthetic polymers, degradation of polyurethanes is catalyzed by proteases, esterases

and ureases [155], while limited degradation of polyethylene has been observed using lignin-degrad-
ing enzymes (e.g., laccases and peroxidases) [156]. The features of a polymer that govern the effi-
ciency of enzymatic depolymerization include its surface properties, surface area, and crystallinity
[147].

Concluding Remarks and Future Perspectives

Plastic materials are crucial to modern life and society, and their continued importance in multiple
applications is undisputed. Given the damaging environmental effects of the current linear plastics

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economy and also the future material demands for the growing global population (estimated to be 9
Outstanding Questions
billion by 2050), a major shift to a sustainable plastics system based on renewable feedstocks and en-
How can polymers be produced
ergy, and material recycling is essential [5]. Here, we argue that polymer design should be an inte-
and recycled in a future closed-
grated part of the development of biobased plastics, and we present approaches for improving
loop biogenic carbon economy?
the material performance and recyclability of biobased plastics that can be applied individually or
in combination for designing plastics for the future. However, a primary requirement is to make avail- What tools are needed for
able a portfolio of carbon-neutral building blocks needed for plastics for different applications and a improving the production of bio-
defined recycling route (see Outstanding Questions). aromatic monomers from lignin as
well as sugars?

Priority could be given to biobased alternatives for aromatic and long-chain aliphatic monomers that How do we overcome the limita-
are currently missing from the market, perhaps because of their low productivities due to challenges tions for facilitating a shift from fos-
involved in their production related to, for example, their solubility, cellular transport, toxicity, or sil fuels to renewable electricity and
complexity of pathways. Availability of PHAs with such monomers can be an important development microbial electrosynthesis on a
in this direction [90]. In general, further work is needed to develop a platform of diverse microbial pro- large scale?

duction hosts with necessary genetic tools as well as innovative bioprocess strategies to improve the Can we develop efficient biological
resource and energy efficiency of production to promote high product yields and productivity. catalysts for the degradation of
Furthermore, the potential to improve biocatalysts by protein engineering for the efficient synthesis crystalline domains of polymers,
as well as selective degradation of polymers needs to be further investigated and their applications and efficient processes for plastic
developed in suitable bioreactor systems. biodegradation and recycling?

What do the life cycles of polymers

To reduce their environmental footprint, continued efforts are needed to adapt plastic production to look like in a fossil-free world?
varied feedstocks with lower land-use impacts, including wastes, biomethane, and CO2 [34,64,65],
along with the use of renewable electricity in the production processes. In addition, it would require
integrating plastic production in biorefineries that can make multiple products from the available
feedstock.

Acknowledgments
The authors are among the academic and industry representatives of a research program ‘Sustain-
able Plastics and Transition Pathways (STEPS) supported by the Swedish Foundation for Strategic
Environmental Research (Mistra) L.J.N. also acknowledges funding from the EU Horizon2020 project
REINVENT (No. 730053). Thanks are due to Smita Mankar and Adel Abouhmad for assistance with
some tables and figures.

Resources
i
ec.europa.eu/environment/circular-economy/pdf/plastics-strategy-brochure.pdf
ii
www.plasticseurope.org/en/resources/publications/619-plastics-facts-2018
iii
www.european-bioplastics.org/market/
iv
www.european-bioplastics.org/bioplastics/Feedstock/

References
1. Ellen MacArthur Foundation et al.. (2016) The New 7. North, E.J. and Halden, R.U. (2013) Plastics and
Plastics Economy – Rethinking the Future of environmental health: the road ahead. Rev. Environ.
Plastics, Ellen MacArthur Foundation Health 28, 1–8
2. Thompson, R.C. et al. (2009) Plastics, the 8. Hahladakis, J.N. et al. (2018) An overview of the
environment and human health: current consensus chemical additives present in plastics: migration,
and future trends. Philos. Trans. R. Soc. B Biol. Sci. release, fate and environmental impact during their
364, 2153–2166 use, disposal and recycling. J. Hazard. Mater. 344,
3. Rahimi, A. and Garcia, J.M. (2017) Chemical 179–199
recycling of waste plastics for new materials 9. Eriksen, M. et al. (2014) Plastic pollution in the
production. Nat. Rev. 1, 1–11 world0 s oceans: more than 5 trillion plastic pieces
4. Regaert, K. et al. (2017) Mechanical and chemical weighing over 250,000 tons afloat at sea. PLoS One
recycling of solid plastic waste. Waste Manag. 69, 9, e111913
24–58 10. Hermabessiere, L. et al. (2017) Occurrence and
5. Hillmyer, M.A. (2017) The promise of plastics from effects of plastic additives on marine environments
plants. Science 358, 868–870 and organisms: a review. Chemosphere 182, 781–793
6. Candela, J. and Carlson, D. (2017) The annual 11. Al-Salem, S.M. et al. (2009) Recycling and recovery
global carbon budget. World Metereological routes of plastic solid waste (PSW): a review. Waste
Organization Bulletin, 66, XXX–YYY. Manag. 29, 2625–2643

Trends in Biotechnology, January 2020, Vol. 38, No. 1 63

Trends in Biotechnology

12. Hong, M. and Chen, E.Y.-X. (2017) Chemically 35. Ahorsu, R. et al. (2018) Significance and challenges
recyclable polymers: a circular economy approach of biomass as a suitable feedstock for bioenergy
to sustainability. Green Chem. 19, 3692–3706 and biochemical production: a review. Energies 11,
13. UNEP. (2018) Single-Use Plastics: A Roadmap for 3366
Sustainability, UNEP 36. Xu, C. et al. (2014) Lignin depolymerization
14. European Commission. (2012) Innovating for strategies: towards valuable chemicals and fuels.
Sustainable Growth. A Bioeconomy for Europe, Chem. Soc. Rev. 43, 7485–7500
European Commission 37. Dürre, P. and Eikmanns, B.J. (2015) C1-carbon
15. Carus, M. and Dammer, L. (2018) The ‘Circular sources for chemical and fuel production by
Bioeconomy’ – Concepts, Opportunities and microbial gas fermentation. Curr. Opin. Biotechnol.
Limitations, Nova Institute 35, 63–72
16. Mani, T. et al. (2015) Microplastics profile along the 38. Ampelli, C. et al. (2015) CO2 utilization: an enabling
Rhine river. Sci. Rep. 5, 17988 element to move to a resource- and energy-efficient
17. UNEP. (2015) Plastic in Cosmetics. Are We Polluting chemical and fuel production. Philos. Trans. R. Soc.
the Environment with Our Personal Care?, UNEP A 373, 20140177
18. Debuissy, T. et al. (2018) Biotic and abiotic synthesis 39. Crumbley, A.M. and Gonzalez, R. (2018) Cracking
of renewable aliphatic polyesters from short ‘economies of scale’: biomanufacturing on
building blocks obtained from biotechnology. methane-rich feedstock. In Methane Biocatalysis:
ChemSusChem 11, 3836–3870 Paving the Way to Sustainability (Kalyuzhnaya, M.
19. Ma, P. et al. (2012) Toughening of poly(lactic acid) and Xing, X.H. eds), pp. 271–292, Springer
by ethylene-co-vinyl acetate copolymer with 40. Strong, P.J. et al. (2016) The opportunity for high-
different vinyl acetate contents. Eur. Polym. J. 48, performance biomaterials from methane.
146–154 Microorganisms 4, 11
20. Iwata, T. (2015) Biodegradable and bio-based 41. Bluemink, E.D. et al. (2016) Bio-plastics (poly-
polymers: future prospects of eco-friendly plastics. hydroxy-alkanoate) production from municipal
Angew. Chem. Int. Ed. 54, 3210–3215 sewage sludge in the Netherlands; a technology
21. Pagacz, J. et al. (2016) Bio-polyamides based on push or a demand driven process? Water Sci.
renewable raw materials. Glass transition and Technol. 74, 353–358
crystallinity studies. J. Thermal Anal. Calor. 123, 42. Pagliano, G. et al. (2017) Integrated systems for
1225–1237 biopolymers and bioenergy production from
22. Harmsen, P.F.H. et al. (2014) Green building blocks organic waste and by-products: a review of
for bio-based plastics. Biofuels Bioprod. Biorefin. 8, microbial processes. Biotechnol. Biofuels 10, 113
306–324 43. Troschi, C. et al. (2017) Cyanobacterial PHA
23. de Jong, E. et al. (2012) Bio-Based Chemicals. Value production – review of recent advances and a
Added Products from Biorefineries, IEA Bioenergy summary of three years0 working experience
24. Sousa, A.F. et al. (2015) Biobased polyesters and running a pilot plant. Bioengineering 4, 26
other polymers from 2,5-furandicarboxylic acid: a 44. Sciarria, T.P. et al. (2018) Bio-electrorecycling of
tribute to furan excellency. Polym. Chem. 6, 5961– carbon dioxide into bioplastics. Green Chem. 20,
5983 4058–4066
25. Gironi, F. and Piemonte, V. (2011) Bioplastics and 45. López, J.C. et al. (2018) Biogas-based
petroleum-based plastics: strengths and polyhydroxyalkanoates production by
weaknesses. Energy Sources, Part A Recover. Util. Methylocystis hirsute: a step further in
Environ. Eff. 33, 1949–1959 anaerobic digestion biorefineries. Chem. Eng. J.
26. Weiss, M. et al. (2012) A review of the environmental 333, 529–536
impacts of biobased materials. J. Ind. Ecol. 16, 46. Erickson, B. et al. (2012) Perspectives on
S169–S181 opportunities in industrial biotechnology in
27. Zhu, Y. et al. (2016) Sustainable polymers from renewable chemicals. Biotechnol. J. 7, 176–185
renewable resources. Nature 540, 354–362 47. Tsuge, Y. et al. (2016) Engineering cell factories for
28. Broeren, M.L.M. et al. (2017) Environmental impact producing building block chemicals for bio-
assessment of six starch plastics focusing on polymer synthesis. Microb. Cell Factories 15, 19
wastewater-derived starch and additives. Resour. 48. Pellis, A. et al. (2016) Renewable building blocks
Conserv. Recycl. 127, 246–255 for sustainable polyesters: new biotechnological
29. Eerhart, A.J.J.E. et al. (2012) Replacing fossil based route for greener plastics. Polym. Int. 65,
PET with biobased PEF; process analysis, energy 861–871
and GHG balance. Energy Environ. Sci. 5, 6407– 49. Kobayashi, S. (2015) Enzymatic ring-opening
6422 polymerization and polycondensation for green
30. Harding, K.G. et al. (2007) Environmental analysis of synthesis of polyesters. Polym. Adv. Technol. 26,
plastic production processes: comparing 677–686
petroleum-based polypropylene and polyethylene 50. Cragg, S.M. et al. (2015) Lignocellulose degradation
with biologically-based poly-b-hydroxybutyric acid mechanisms across the Tree of Life. Curr. Opin.
using life cycle analysis. J. Biotechnol. 130, 57–66 Chem. Biol. 29, 108–119
31. Narodoslawsky, M. et al. (2015) LCA of PHA 51. Andlar, M. et al. (2018) Lignocellulose degradation:
production - identifying the ecological an overview of fungi and fungal enzymes involved in
potential of bio-plastic. Chem. Biochem. Eng. Q. 29, lignocellulose degradation. Eng. Life Sci. 18,
299–305 768–778
32. Bauer, F. et al. (2018) Climate Innovations in the 52. Olson, D.G. et al. (2012) Recent progress in
Plastics Industry: Prospects for Decarbonisation, consolidated bioprocessing. Curr. Opin.
Lund: Miljö-och Energisystem, Lunds Universitet Biotechnol. 23, 396–405
33. Koller, M. et al. (2013) Biopolymer from industrial 53. Brethauer, S. and Studer, M.H. (2014) Consolidated
residues: life cycle assessment of bioprocessing of lignocellulose by a microbial
poly(hydroxyalkanoates) from whey. Resour. consortium. Energy Environ. Sci. 7, 1446–1453
Conserv. Recycl. 73, 64–71 54. Gall, D.L. et al. (2017) In vitro enzymatic
34. Cherubini, F. and Ulgiati, S. (2010) Crop residues as depolymerization of lignin with release of syringyl,
raw materials for biorefinery systems. Appl. Energy guaiacyl, and tricin units. Appl. Environ. Microbiol.
87, 47–57 84, AEM.02076-17

64 Trends in Biotechnology, January 2020, Vol. 38, No. 1

Trends in Biotechnology

55. Lee, J.W. et al. (2011) Microbial production of popular plant flavor and its de novo biosynthesis in
building block chemicals and polymers. Curr. Opin. the vanilla orchid. Mol. Plant 8, 40–57
Biotechnol. 22, 758–767 76. Kruyer, N.S. and Peralta-Yahya, P. (2017) Metabolic
56. Lee, S.Y. et al. (2019) A comprehensive metabolic engineering strategies to bio-adipic acid
map for production of bio-based chemicals. Nat. production. Curr. Opin. Biotechnol. 45, 136–143
Catal. 2, 18–33 77. Moon, T.S. et al. (2009) Production of glucaric acid
57. Dishisha, T. et al. (2014) Flux analysis of the from a synthetic pathway in recombinant
Lactobacillus reuteri propanediol-utilization Escherichia coli. Appl. Environ. Microbiol. 75,
pathway for production of 3- 589–595
hydroxypropionaldehyde, 3-hydroxypropionic acid 78. Yu, J. (2014) Bio-based products from solar
and 1,3-propanediol from glycerol. Microb. Cell energy and carbon dioxide. Trends Biotechnol. 32,
Factories 13, 76 5–10
58. Sayed, M. et al. (2019) Selective oxidation of 5- 79. Mohan, S.V. et al. (2016) A circular bioeconomy with
hydroxymethylfurfural to 5-hydroxymethyl-2- biobased products from CO2 sequestration. Trends
furancarboxylic acid using Gluconobacter oxydans. Biotechnol. 34, 506–518
ACS Sustain. Chem. Eng. 7, 4406–4413 80. Nevin, K.P. et al. (2010) Microbial electrosynthesis:
59. Kind, S. et al. (2014) From zero to hero - production feeding microbes electricity to convert carbon
of bio-based nylon from renewable resources using dioxide and water to multicarbon extracellular
engineered Corynebacterium glutamicum. Metab. organic compounds. mBio 1, e00103–e00110
Eng. 25, 113–123 81. ElMekawy, A. et al. (2016) Technological advances
60. Noda, S. and Kondo, A. (2017) Recent advances in in CO2 conversion electro-biorefinery: a step
microbial production of aromatic chemicals and towards commercialization. Bioresour. Technol.
derivatives. Trends Biotechnol. 35, 785–796 215, 357–370
61. Sudesh, K. et al. (2000) Synthesis, structure and 82. Pellis, A. et al. (2015) The closure of the cycle:
properties of polyhydroxyalkanoates: biological enzymatic synthesis and functionalization of bio-
polyesters. Prog. Polym. Sci. 25, 1503–1555 based polyesters. Trends Biotechnol. 34, 316–328
62. Quillaguaman, J. et al. (2008) Poly(3- 83. Kadokawa, J.-I. and Kobayashi, S. (2010) Polymer
hydroxybutyrate) production by Halomonas synthesis by enzymatic catalysis. Curr. Opin. Chem.
boliviensis in fed-batch culture. Appl. Microbiol. Biol. 14, 145–153
Biotechnol. 78, 227–232 84. Juais, D. et al. (2010) Isosorbide polyesters from
63. Koller, M. (2017) Advances in polyhydroxyalkanoate enzymatic catalysis. Macromolecules 43, 10315–
(PHA) production. Bioengineering 4, 88 10319
64. Kourmentza, C. et al. (2017) Recent advances and 85. Douka, A. et al. (2018) A review on enzymatic
challenges towards sustainable polymerization to produce polycondensation
polyhydroxyalkanoate (PHA) production. polymers: the case of aliphatic polyesters,
Bioengineering 4, 55 polyamides and polyesteramides. Prog. Polym. Sci.
65. Koller, M. et al. (2017) Producing microbial 79, 1–25
polyhydroxyalkanoate (PHA) biopolyesters in a 86. Nguyen, H.T.H. et al. (2018) The quest for high glass
sustainable manner. New Biotechnol. 37, 24–38 transition temperature bioplastics. J. Mater. Chem.
66. Dijkman, W.P. et al. (2014) Enzyme-catalyzed A 6, 9298–9331
oxidation of 5-hydroxymethylfurfural to furan-2,5- 87. Farah, S. et al. (2016) Physical and mechanical
dicarboxylic acid. Angew. Chem. Int. Ed. 53, 6515– properties of PLA, and their functions in widespread
6518 applications – a comprehensive review. Adv. Drug
67. McKenna, S.M. et al. (2017) The continuous Deliv. Rev. 107, 367–392
oxidation of HMF to FDCA and the immobilization 88. Benabdillah, K.M. et al. (2000) Can the glass
and stabilization of periplasmic aldehyde oxidase transition temperature of PLA polymers be
(PaoABC). Green Chem. 19, 4660–4665 increased? In Polymers from Renewable Resources
68. Collias, D.I. et al. (2014) Biobased terephthalic acid (Scholz, C. et al. eds), pp. 200–220, ACS
technologies: a literature review. Ind. Biotechnol. 89. Koller, M. and Braunegg, G. (2015) Biomediated
10, 91–105 production of structurally diverse
69. Dishisha, T. et al. (2015) Bio-based 3- poly(hydroxyalkanoates) from surplus streams of
hydroxypropionic- and acrylic acid production from the animal processing industry. Polimery 60,
biodiesel glycerol via integrated microbial and 298–308
chemical catalysis. Microb. Cell Factories 14, 200 90. Ishii-Hyakutake, M. et al. (2018) Biosynthesis and
70. Winkler, J.D. and Kao, K.C. (2014) Recent advances characteristics of aromatic polyhydroxyalkanoates.
in the evolutionary engineering of industrial Polymers 10, 1267
biocatalysts. Genomics 104, 406–411 91. Privalko, V.P. and Lipatov, Y.S. (1974) Glass
71. Chen, Y. and Nielsen, J. (2013) Advances in transition and chain flexibility of linear polymers.
metabolic pathway and strain engineering paving J. Macromol. Sci. B 9, 551–564
the way for sustainable production of chemical 92. Yu, X. et al. (2018) Unravelling substituent effects on
building blocks. Curr. Opin. Biotechnol. 24, 965–972 the glass transition temperatures of biorenewable
72. Chung, H. et al. (2015) Bio-based production of polyesters. Nat. Commun. 9, 2880
monomers and polymers by metabolically 93. Nguyen, H.T.H. et al. (2017) Copolymerization of
engineered microorganisms. Curr. Opin. lactones and bioaromatics via concurrent ring-
Biotechnol. 36, 73–84 opening polymerization/polycondensation. Green
73. Nakamura, C.E. and Whited, G.M. (2003) Metabolic Chem. 19, 1877–1888
engineering for the microbial production of 1,3- 94. Goto, T. et al. (2019) Synthesis and characterization
propanediol. Curr. Opin. Biotechnol. 14, 454–459 of biobased polyesters containing anthraquinones
74. Kolvistoinen, O.M. et al. (2013) Glycolic acid derived from gallic acid. Biomacromolecules 20,
production in the engineered yeasts 318–325
Saccharomyces cerevisiae and Kluyveromyces 95. Nguyen, H.D. et al. (2016) Fermentation of aromatic
lactis. Microb. Cell Factories 12, 82 lactate monomer and its polymerization to produce
75. Gallage, N.J. and Möller, B.L. (2015) Vanillin – highly thermoresistant bioplastics. Polym. J. 48,
bioconversion and bioengineering of the most 81–89

Trends in Biotechnology, January 2020, Vol. 38, No. 1 65

Trends in Biotechnology

96. Suvannasara, P. et al. (2014) Biobased polyimides high Tg engineering plastics. J. Polym. Sci. Part A:
from 4-aminocinnamic acid photodimer. Polym. Chem. 51, 2464–2471
Macromolecules 47, 1586–1593 115. Kim, T. et al. (2017) Sustainable terpolyester of high
97. Wang, P. et al. (2018) Indole as a new sustainable Tg based on bioheterocyclic monomer of dimethyl
aromatic unit for high quality biopolyesters. Polym. furan-2,5-dicarboxylate and isosorbide. Polymer
Chem. 9, 4706–4710 132, 122–132
98. Llevot, A. et al. (2015) Renewable (semi)aromatic 116. Lavilla, C. et al. (2012) Bio-based aromatic
polyesters from symmetrical vanillin-based dimers. polyesters from a novel bicyclic diol derived from D-
Polym. Chem. 6, 6058–6066 mannitol. Macromolecules 45, 8257–8266
99. Kainulainen, T.P. et al. (2018) UV-blocking synthetic 117. Hufendiek, A. et al. (2019) Thermoplastic
biopolymer from biomass-based bifuran diester polyacetals: chemistry from the past for a
and ethylene glycol. Macromolecules 51, 1822– sustainable future? Polym. Chem. 10, 9–33
1829 118. Lingier, S. et al. (2017) Rigid polyurethanes,
100. Kelsey, D.R. et al. (2000) High impact, amorphous polyesters, and polycarbonates from renewable
terephthalate copolyesters of rigid 2,2,4,4- ketal monomers. Macromolecules 50, 5346–5352
tetramethyl-1,3-cyclobutanediol with flexible diols. 119. Sanford, M.J. et al. (2016) Alternating
Macromolecules 33, 5810–5818 copolymerization of propylene oxide and
101. Hoppens, N.C. et al. (2004) Aliphatic–aromatic cyclohexene oxide with tricyclic anhydrides: access
copolyesters derived from 2,2,4,4-tetramethyl-1,3- to partially renewable aliphatic polyesters with high
cyclobutanediol. J. Polym. Sci. Part A: Polym. Chem. glass transition temperatures. Macromolecules 49,
42, 3473–3478 6394–6400
102. Chen, T. et al. (2015) Alkali resistance of 120. Hakkarainen, M. (2002) Aliphatic polyesters: abiotic
poly(ethylene terephthalate) (PET) and and biotic degradation and degradation products.
poly(ethylene glycol-co-1,4- Adv. Polym. Sci. 157, 113–138
cyclohexanedimethanol terephthalate) (PETG) 121. Albertsson, A.-C. and Hakkarainen, M. (2017)
copolyesters: the role of composition. Polym. Designed to degrade. Science 358, 872–873
Degrad. Stab. 120, 232–243 122. Huang, J.C. et al. (1990) Biodegradable plastics: A
103. Iyer, K.A. (2017) Chain mobility, secondary review. Adv. Polym. Technol. 10, 23–30
relaxation, and oxygen transport in terephthalate 123. Mochizuki, M. et al. (1997) Structural effects upon
copolyesters with rigid and flexible cyclic diols. enzymatic hydrolysis of poly(butylene succinate-co-
Polymer 129, 117–126 ethylene succinate)s. Macromolecules 30, 7403–
104. Wang, J. et al. (2017) Synthesis of bio-based 7407
poly(ethylene 2,5-furandicarboxylate) copolyesters: 124. Li, S.M. et al. (1990) Structure-property relationships
Higher glass transition temperature, better in the case of the degradation of massive aliphatic
transparency, and good barrier properties. poly-(a-hydroxy acids) in aqueous media. J. Mater.
J. Polym. Sci., Part A: Polym. Chem. 55, 3298–3307 Sci. Mater. Med. 1, 123–130
105. Ristic, I.S. et al. (2012) Synthesis and characterisation 125. Ong, S.Y. (2017) Degradation of
of polyester based on isosorbide and butanedioic polyhydroxyalkanoate (PHA): a review. J. Siber. Fed.
acid. J. Polym. Environ. 20, 519–527 Univ. Biol. 10, 211–225
106. Vilela, C. et al. (2014) The quest for sustainable 126. Li, Z. et al. (2007) Study of enzymatic degradation of
polyesters – insights into the future. Polym. Chem. microbial copolyesters consisting of 3-
5, 3119–3141 hydroxybutyrate and medium-chain-length 3-
107. Fenouillot, F. et al. (2010) Polymers from renewable hydroxyalkanoates. Polym. Degrad. Stab. 92, 1708–
1,4:3,6-dianhydrohexitols (isosorbide, isomannide 1714
and isoidide): a review. Prog. Polym. Sci. 35, 127. Iwata, T. et al. (1999) Structure and enzymatic
578–622 degradation of poly(3-hydroxybutyrate) copolymer
108. Gustini, L. et al. (2016) Isohexide and sorbitol- single crystals with an extracellular PHB
derived, enzymatically synthesized renewable depolymerase from Alcaligenes faecalis T1. Int. J.
polyesters with enhanced Tg. Biomacromolecules Biol. Macromol. 25, 169–176
17, 3404–3416 128. Mergaert, J. et al. (1993) Microbial degradation of
109. Storbeck, R. and Ballauff, M. (1993) Synthesis and poly(3-hydroxybutyrate) and poly(3-
properties of polyesters based on 2,5- hydroxybutyrate-co-3-hydroxyvalerate) in soils.
furandicarboxylic acid and 1,4:3,6- Appl. Environ. Microbiol. 59, 3233–3238
dianhydrohexitols. Polymer 34, 5003–5006 129. Nikolic, M.S. et al. (2001) Synthesis and
110. Gandini, A. et al. (2009) Materials from renewable characterization of biodegradable poly(butylene
resources based on furan monomers and furan succinate-co-butylene adipate)s. Polym. Degrad.
chemistry: work in progress. J. Mater. Chem. 19, Stab. 74, 263–270
8656–8664 130. Shah, A.A. et al. (2008) Biological degradation of
111. Garaleh, M. et al. (2010) (Co-)polyesters derived plastics: a comprehensive review. Biotechnol. Adv.
from isosorbide and 1,4-cyclohexane dicarboxylic 26, 246–265
acid and succinic acid. Macromol. Chem. Phys. 211, 131. Okada, M. et al. (2000) Biodegradable polymers
1206–1214 based on renewable resources. IV. Enzymatic
112. Yoon, W.J. et al. (2013) Advanced polymerization degradation of polyesters composed of
and properties of biobased high Tg polyester of 1,4:3.6-dianhydro-D-glucitol and aliphatic
isosorbide and 1,4-cyclohexanedicarboxylic acid dicarboxylic acid moieties. J. Appl. Polym. Sci. 77,
through in situ acetylation. Macromolecules 46, 338–346
2930–2940 132. Kwon, J. et al. (2013) Inflammation-responsive
113. Yoon, W.J. et al. (2013) Synthesis and characteristics antioxidant nanoparticles based on a polymeric
of a biobased high-Tg terpolyester of isosorbide, prodrug of vanillin. Biomacromolecules 14, 1618–
ethylene glycol, and 1,4-cyclohexane dimethanol: 1626
effect of ethylene glycol as a chain linker on 133. Schneiderman, D.K. and Hillmyer, M.C. (2017) 5oth
polymerization. Macromolecules 46, 7219–7231 anniversary perspective: there is a great future in
114. Chatti, S. et al. (2013) Copolyesters of isosorbide, sustainable polymers. Macromolecules 50, 3733–
succinic acid, and isophthalic acid: biodegradable, 3749

66 Trends in Biotechnology, January 2020, Vol. 38, No. 1

Trends in Biotechnology

134. Sánchez, A.C. and Collinson, S.R. (2011) The 146. Otsuka, H. and Endo, T. (1999) Poly(hemiacetal
selective recycling of mixed plastic waste of ester)s: new class of polymers with thermally
polylactic acid and polyethylene terephthalate by dissociative units in the main chain.
control of process conditions. Eur. Polym. J. 47, Macromolecules 32, 9059–9061
1970–1976 147. Wei, R. and Zimmermann, W. (2017) Microbial
135. Zhu, J.-B. et al. (2018) A synthetic polymer system enzymes for the recycling of recalcitrant petroleum-
with repeatable chemical recyclability. Science 360, based plastics: how far are we? Microb. Biotechnol.
398–403 10, 1308–1322
136. Tang, X. and Chen, E.Y.-X. (2019) Towards infinitely 148. Zhang, X. et al. (2018) Catalysis as an enabling
recyclable plastics derived from renewable cyclic science for sustainable polymers. Chem. Rev. 118,
esters. Chem 5, 1–29 839–885
137. Brutman, J.P. et al. (2016) Renewable, 149. Barth, M. et al. (2016) A dual enzyme system
degradable, and chemically recyclable cross- composed of a polyester hydrolase and a
linked elastomers. Ind. Eng. Chem. Res. 55, 11097– carboxylesterase enhances the biocatalytic
11106 degradation of polyethylene terephthalate films.
138. Hong, M. and Chen, E.Y.-X. (2016) Towards truly Biotechnol. J. 11, 1082–1087
sustainable polymers: a metal-free recyclable 150. Carniel, A. et al. (2017) Lipase from
polyester from biorenewable non-strained g- Candida antarctica (CALB) and cutinase from
butyrolactone. Angew. Chem. Int. Ed. 55, 4188– Humicola insolens act synergistically for PET
4193 hydrolysis to terephthalic acid. Proc. Biochem. 59,
139. Hong, M. and Chen, E.Y.-X. (2016) Completely 84–90
recyclable biopolymers with linear and cyclic 151. Austin, H.P. et al. (2018) Characterization and
topologies via ring-opening polymerization of g- engineering of a plastic-degrading aromatic
butyrolactone. Nat. Chem. 8, 42–49 polyesterase. PNAS 115, E4350–E4357
140. De Hoe, G.X. et al. (2018) Sustainable polyester 152. Kobayashi, S. et al. (2000) Lipase-catalyzed
elastomers from lactones: synthesis, properties, and degradation of polyesters in organic solvents. A
enzymatic hydrolyzability. J. Am. Chem. Soc. 140, new methodology of polymer recycling
963–973 using enzyme as catalyst. Biomacromolecules 1,
141. Kopinke, F.D. et al. (1996) Thermal decomposition 3–5
of biodegradable polyesters -II. Poly(lactic acid). 153. Osanai, Y. et al. (2006) Enzymatic transformation of
Polym. Degrad. Stab. 53, 329–342 aliphatic polyesters into cyclic oligomers using
142. Melchiors, M. et al. (1996) Depolymerization of poly enzyme packed column under continuous flow of
[-3-hydroxybutyrate] to cyclic oligomers and supercritical carbon dioxide with toluene. Sci.
polymerization of the cyclic trimer: an example of Technol. Adv. Mater. 7, 202–208
thermodynamic recycling. Macromolecules 29, 154. Kasuya, K. et al. (1999) Substrate and
6442–6451 binding specificities of bacterial
143. Myung, J. et al. (2014) Disassembly and reassembly polyhydroxybutyrate depolymerase. Int. J. Biol.
of polyhydroxyalkanoates: recycling through abiotic Macromol. 24, 329–336
depolymerization and biotic repolymerization. 155. Cregut, M. et al. (2013) New insights into
Bioresour. Technol. 170, 167–174 polyurethane biodegradation and realistic
144. Flanagan, J.C.A. et al. (2016) prospects for the development of a sustainable
Poly(hydroxyalkanoate)s from waste biomass: a waste recycling process. Biotechnol. Adv. 31, 1634–
combined chemical-biological approach. Chem. 1647
Select 1, 2327–2331 156. Krueger, M.C. et al. (2015) Prospects for
145. Ariffin, H. et al. (2010) Chemical recycling of microbial solutions to environmental pollution
polyhydroxyalkanoates as a method towards with plastics. Appl. Microbiol. Biotechnol. 99, 8857–
sustainable development. Biotechnol. J. 5, 484–492 8874

Trends in Biotechnology, January 2020, Vol. 38, No. 1 67