Microbial PolyHydroxyAlkanoate Biopolymers: Comparison
Please note this is a comparison between Version 2 by Camila Xu and Version 1 by Anindya Mukherjee.

PolyHydroxyAlkanoates (PHAs) fulfil every criterion set out in the definition of a natural polymer or a biopolymer. PHA biopolymers, a group of biopolyesters, are found in nature, and they are biosynthesized using renewable carbon in microbes. PHAs are biodegradable, because nature has the tools to convert them into CO2 and water and about 10% organic fertilizer or humus, the same as in the biodegradation of cellulose or cotton.

  • biopolymers
  • green chemistry principles
  • natural polymers
  • polyhydroxyalkanoates

1. Introduction

The increasing production and use of synthetic and recalcitrant polymeric materials of petrochemical origin for packaging, personal care, and other uses are currently responsible for several global threats: the accumulation of plastic waste in aqueous and terrestrial environments, the formation of highly recalcitrant, xenobiotic microplastic particles causing the death of marine animals, deteriorating ecosystems and negatively affecting human health, as recently demonstrated by studies confirming the presence of microplastic particles, even in human blood [1], placenta [2], and the digestive system [3]. Not all consumed microplastic is easily excreted by the body; it is estimated that microplastic intake by humans results to an irreversible accumulation of about 41 ng microplastic particles 1–10 µm in size per person until the age of 70 [4]. It is suspected that microplastics in our body may drive carcinogenic signaling [5]. Interestingly, in many environments, a so called “eco-corona” forms on the surface of microplastic particles, consisting of viruses, microbes, or organic toxins. This “eco-corona” facilitates the uptake of microplastic by human cells, where organisms and toxins unleash their toxic effects, and may even allow them to cross the blood–brain barrier [6].
In response to these threats, policies worldwide are striving to replace unsustainable linear economy approaches (“take-use-dispose”), like the production and use of fossil and persistent plastics, with circular alternatives (“take-use-recycle”). Legislations such as California Assembly Bill (AB) 1201 on “Solid waste: products: labelling: compostability and biodegradability” [7], Senate Bill (SB) 54 on “Solid waste: reporting, packaging, and plastic food service ware” [8], the European Commission’s Single Use Plastics Directive or SUPD (EU 904/2019) [9], the Plastics and Packaging Waster Directive (PPWR) [10], and the REACH Amendment on Intentionally Added Microplastics [11] go in this direction. The overarching goal of the current legislative efforts are to reduce virgin plastics use, their leakage into the environment, and the resulting pollution. In encouraging plastic recycling, policy makers seem to believe that the effects of persistent fossil plastics can be reduced or even eliminated. Recycling needs to be encouraged and improved; the sheer volume of fossil plastics used today (annual global production is estimated to be about 400 Mt and forecast to double by 2040) has no immediate replacement [12]. However, recycling only postpones the negative effects of fossil plastics by postponing the end of life of the materials. Chemical recycling is in its infancy, and mechanical recycling increases microplastics formation that are inherent in all plastics handling, processing, and use. These policies and legislations, while restricting fossil plastics, are also restricting the introduction of innovative alternatives. Policies and legislations are redefining words like “plastics” and “natural polymers” that are restricting the introduction of innovative, circular, and inherently sustainable alternatives. Instead, these policies need to focus on the circularity and sustainability of materials, through (a) renewable carbon use and from the (b) end-of life perspective of the material and not just the product, such as packaging or personal care items. Some examples of restrictive legislations have been mentioned above. Many of these legislations such as California SB 54 [8] and the European Union’s Single Use Plastics Directive (SUPD) [9] are focused on defining materials by redefining terminologies like “plastics” and “natural polymers” to restrict the use of these persistent fossil plastics with the aim of reducing harmful plastic pollution. Instead, it is believed that legislation needs to focus on the circularity and end-of-life profiles and options, rather than focusing on redefining established terminologies. For example, renewability, biodegradability and compostability should be emphasized, along with standards and certifications that allow for such materials to be used. A second area that these legislations should focus on are encouraging and mandating increased separation and collection, and composting infrastructure to facilitate increased organic recycling. Examples of such legislations, which allow for biodegradable and compostable materials are California Assembly Bill 1080—“Solid waste: packaging and products” [13], or California SB 270, which imposes a statewide ban on single-use plastic bags at large retail stores [14]. Here, it should be noted that no nation-wide regulations exist for the US. Since 20 December 2022, the manufacture and import for sale in Canada of checkout bags, cutlery, foodservice ware, stir sticks, and straws (i.e., straight straws), as defined in respective regulations, are prohibited [15]. In the People’s Republic of China, a policy document jointly issued by the National Development and Reform Commission (NDRC) and the Ministry of Ecology and Environment on 16 January 2020, developed the plastic ban that prohibits restaurants throughout the country from providing single-use plastic straws and stores in the major cities from providing plastic shopping bags; this ban took effect on 1 January 2021 [16]. In April 2022, the Act on the Promotion of Resource Circulation for Plastics was enacted in Japan to improve the circularity of plastics [17]. In summer 2022, India imposed a ban on single-use plastic to tackle pollution, including straws, cutlery, ear buds, packaging films, and cigarette packets, etc. [18].
These legislations have also restricted materials that are renewable, biodegradable, and domestically and industrially compostable—attributes that would reduce and eventually eliminate the accumulation of persistent and fossil polymers and the dangers that they cause. Indeed, many of these legislations consider plastic recycling an appropriate strategy to overcome today’s plastic pollution predicament [19]; however, plastic recycling rather postpones the problem, and does not provide a solution. Instead, real “Natural Polymers” should be forcefully promoted by legislation. Widespread adaptation of natural alternatives is currently impeded by higher production costs, insecure supply chains for raw materials, or cumbersome downstream processing; however, natural polymers as solutions exist or are in development that use inexpensive raw materials, ecologically friendly polymer production and extraction methods, in addition to being circular and sustainable from an end-of-life perspective [20].

2. Definition of “Natural Polymers”—Clarifying Existing Ambiguities

When it comes to sustainable and circular materials, nature is the best teacher. What nature makes, nature unwinds and remakes. Therefore, the prefix “bio” is frequently used to connect an object or a product to nature. Several such words exist:
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Bio-based—Denoting a chemical compound or material produced from renewable carbon sources. “Bio-based” does not specify whether the product or material is synthesized chemically or biologically in plants, organisms, and animals.
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Biosynthesis—The synthesis of a chemical or material through the actions in living organisms (plants, microorganisms, or animals) or parts thereof (enzymes). A biosynthesized polymer implies having been produced in plants, microorganisms, or animals through the action of enzymes in vivo. The word “polymerization” implies a synthetic or an anthropogenic process for generation of polymers from building blocks that are either bio-based, synthesized, or chemically synthesized.
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Biodegradation—This implies the breakdown of a chemical or material through the actions of naturally occurring enzymes in vivo or by extracellular enzymes that are secreted by plants, microorganisms, or animals. Generally, breaking down chemicals or materials involves the eventual transformation to carbon dioxide (CO2) and water and complex biomass called humus, also known as organic fertilizer. Hence, “biodegradation” can be understood as nature’s way of material recycling.
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Biocompatibility—Implies chemicals or materials that do not exert harmful effects on the environment or on living systems, including humans.
Materials that fulfil these criteria are well known, such as cellulose, starch, chitin, alginates, proteins, and nucleic acids (DNA, RNA). All these are also macromolecules and are excellent examples of “Natural Polymers”, also called a “Biopolymers”. Therefore, “Natural Polymers” are defined as those that are simultaneously:
  • Derived from renewable carbon such as sugar from sugar cane, fatty acids like canola oil or carbon dioxide, or methane from biogas or the atmosphere.
  • Biosynthesized in plants, microorganisms, and animals.
  • Biodegradable or turn into CO2, water, and humus.
  • Are biocompatible.

3. PolyHydroxyAlkanoates Are Natural Polymers

PolyHydroxyAlkanoates (PHAs) fulfil every criterion set out in the definition of a natural polymer or a biopolymer. PHA biopolymers, a group of biopolyesters, are found in nature, and they are biosynthesized using renewable carbon in microbes. PHAs are biodegradable, because nature has the tools to convert them into CO2 and water and about 10% organic fertilizer or humus, the same as in the biodegradation of cellulose or cotton. PHAs are biocompatible, they are harmless to all living beings, and can be used in vivo as medical devices such as scaffolds, stents or as meshes. They will eventually be absorbed by the body with no traces of the PHAs remaining [21].

Evidence: PHAs Are a Natural Polymer

We spoke of nature knowing best when it comes to the circularity of chemicals and materials that are found in nature. For what nature creates, nature also develops ways to degrade and recycle. This is especially true for cellulose as well as PHAs. After their end of life, PHAs become mineralized or biodegraded by natural hydrolytic depolymerase enzymes to exactly those chemical building blocks from which they were once made in nature. These include CO2 and water, which then, through photosynthesis, are converted into sugar (sugarcane or corn) or lipids (canola oil or palm oil), used today to produce PHAs. This demonstrates that the formation and degradation of PHAs is inherently circular. Figure 1 illustrates the fact that PHA biopolyesters are entirely embedded in nature’s closed material cycles, which is vividly exemplified by the old quote attributed to Lavoisier, a pioneer in the field of chemistry, when he explained that in nature “Nothing gets lost, nothing gets created, everything gets transformed.” [22].
Figure 1.
Circularity of natural PHA biopolyesters.
Table 1 summarizes the aspects, which are integral to defining polymeric materials as “natural”, and how PHAs meet these requirements. In addition, Table 2 examines PHA manufacturing in the context of the 12 Principles of Green Chemistry, mentioned in individual sections of the text.
Table 1.
Comparison of different natural/non-natural polymers.

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