Enzymatic polymerization is a potential area in polymer research, providing a sustainable and adaptable alternative to conventional polymerization processes. Its capacity to manufacture polymers with exact structures in mild circumstances opens up new possibilities for material design and application, helping to progress both research and industry. It is a novel and sustainable method of synthesizing polymers that utilizes the catalytic properties of enzymes to both initiate and regulate the polymerization process. It works under mild circumstances, usually at room temperature and pressure as well as in aqueous environments, in contrast to conventional chemical polymerization techniques that frequently need for harsh conditions and harmful reagents. This approach allows fine control over the structure and functionality of polymers while simultaneously consuming less energy and having a less environmental impact. [1] [2]
This polymerization technique has the considerable advantage of being compatible with renewable resources. Many of the monomers utilized in these procedures come from natural sources, which aligns with the ideas of green chemistry and sustainability. [3] This alignment is especially crucial given growing environmental concerns and the quest for more sustainable industrial operations. The potential applications of polymers produced via enzymatic polymerization are vast, spanning the fields of biomedicine, materials science, and environmental engineering. For example, biodegradable polymers produced using this method are very useful for medical applications such as drug delivery systems, biosensors and tissue engineering scaffolds. Furthermore, enzymatic polymerization opens up fascinating possibilities for the production of innovative biomaterials with tailored characteristics for specific industrial applications. [4] [5] [6] [7]
Enzymatic polymerization can happen in a variety of ways, including:
Condensation Polymerization: Enzymes such as lipases and proteases catalyze the step-growth polymerization of monomers by establishing ester, amide, or peptide bonds, releasing tiny molecules such as water or alcohol as waste. [8] [9]
Addition Polymerization: This method includes radical-mediated processes, in which enzymes such as peroxidases initiate polymerization by producing radical species that propagate the polymer chain. [10]
Ring-Opening Polymerization: Enzymes help to open cyclic monomers to produce linear polymers, which is a typical process for synthesizing polyesters and polyamides. [11]
Polymerases, or polymerase enzymes, can catalyze the synthesis of different kinds of polymers. Key enzymes involved include: Lipases are used in the synthesis of polyesters and polyamides, lipases accelerate esterification and transesterification processes, which are required for polymer chain formation [12] [13] . In oxidative polymerization, peroxidases aid in the polymerization of phenolic and aniline derivatives, resulting in the production of conductive polymers [14] . Glycosyltransferases are necessary for polysaccharide formation because they catalyze the transfer of sugar moieties to create glycosidic linkages [15] . Proteases are enzymes that help create peptide bonds, allowing amino acid monomers to be polymerized into polyamides or proteins. [16]
In polymer chemistry, polymerization, or polymerisation, is a process of reacting monomer molecules together in a chemical reaction to form polymer chains or three-dimensional networks. There are many forms of polymerization and different systems exist to categorize them.
Transesterification is the process of exchanging the organic functional group R″ of an ester with the organic group R' of an alcohol. These reactions are often catalyzed by the addition of an acid or base catalyst. Strong acids catalyze the reaction by donating a proton to the carbonyl group, thus making it a more potent electrophile. Bases catalyze the reaction by removing a proton from the alcohol, thus making it more nucleophilic. The reaction can also be accomplished with the help of other enzymes, particularly lipases.
A polyamide is a polymer with repeating units linked by amide bonds.
In chemistry, initiation is a chemical reaction that triggers one or more secondary reactions. Initiation creates a reactive centre on a molecule which produces a chain reaction. The reactive centre generated by initiation is usually a radical, but can also be cations or anions. Once the reaction is initiated, the species goes through propagation where the reactive species reacts with stable molecules, producing stable species and reactive species. This process can produce very long chains of molecules called polymers, which are the building blocks for many materials. After propagation, the reaction is then terminated. There are different types of initiation, with the two main ways being thermal initiation and photo-initiation (light).
End groups are an important aspect of polymer synthesis and characterization. In polymer chemistry, they are functional groups that are at the very ends of a macromolecule or oligomer (IUPAC). In polymer synthesis, like condensation polymerization and free-radical types of polymerization, end-groups are commonly used and can be analyzed by nuclear magnetic resonance (NMR) to determine the average length of the polymer. Other methods for characterization of polymers where end-groups are used are mass spectrometry and vibrational spectrometry, like infrared and raman spectroscopy. These groups are important for the analysis of polymers and for grafting to and from a polymer chain to create a new copolymer. One example of an end group is in the polymer poly(ethylene glycol) diacrylate where the end-groups are circled.
An Endoglycosidase is an enzyme that releases oligosaccharides from glycoproteins or glycolipids. It may also cleave polysaccharide chains between residues that are not the terminal residue, although releasing oligosaccharides from conjugated protein and lipid molecules is more common.
Polyester is a category of polymers that contain the ester functional group in every repeat unit of their main chain. As a specific material, it most commonly refers to a type called polyethylene terephthalate (PET). Polyesters include naturally occurring chemicals, such as in plants and insects, as well as synthetics such as polybutyrate. Natural polyesters and a few synthetic ones are biodegradable, but most synthetic polyesters are not. Synthetic polyesters are used extensively in clothing.
The enzyme horseradish peroxidase (HRP), found in the roots of horseradish, is used extensively in biochemistry applications. It is a metalloenzyme with many isoforms, of which the most studied type is C. It catalyzes the oxidation of various organic substrates by hydrogen peroxide.
Polyphenol oxidase, an enzyme involved in fruit browning, is a tetramer that contains four atoms of copper per molecule.
In biochemistry, a cross-linked enzyme aggregate is an immobilized enzyme prepared via cross-linking of the physical enzyme aggregates with a difunctional cross-linker. They can be used as stereoselective industrial biocatalysts.
In enzymology, a lignin peroxidase (EC 1.11.1.14) is an enzyme that catalyzes the chemical reaction
Biodegradable polymers are a special class of polymer that breaks down after its intended purpose by bacterial decomposition process to result in natural byproducts such as gases (CO2, N2), water, biomass, and inorganic salts. These polymers are found both naturally and synthetically made, and largely consist of ester, amide, and ether functional groups. Their properties and breakdown mechanism are determined by their exact structure. These polymers are often synthesized by condensation reactions, ring opening polymerization, and metal catalysts. There are vast examples and applications of biodegradable polymers.
The enzyme cutinase is a member of the hydrolase family. It catalyzes the following reaction:
Oxazoline is a five-membered heterocyclic organic compound with the formula C3H5NO. It is the parent of a family of compounds called oxazolines, which contain non-hydrogenic substituents on carbon and/or nitrogen. Oxazolines are the unsaturated analogues of oxazolidines, and they are isomeric with isoxazolines, where the N and O are directly bonded. Two isomers of oxazoline are known, depending on the location of the double bond.
Syringic acid is a naturally occurring phenolic compound and dimethoxybenzene that is commonly found as a plant metabolite.
Poly(p-phenylene oxide) (PPO), poly(p-phenylene ether) (PPE), poly(oxy-2,6-dimethyl-1,4-phenylene), often referred to simply as polyphenylene oxide, is a high-temperature thermoplastic with the general formula (C8H8O)n. It is rarely used in its pure form due to difficulties in processing. It is mainly used as blend with polystyrene, high impact styrene-butadiene copolymer or polyamide. PPO is a registered trademark of SABIC Innovative Plastics B.V. under which various polyphenylene ether resins are sold.
Polyaspartic acid (PASA) is a biodegradable, water-soluble condensation polymer based on the amino acid aspartic acid. It is a biodegradable replacement for water softeners and related applications. PASA can be chemically crosslinked with a wide variety of methods to yield PASA hydrogels. The resulting hydrogels are pH-sensitive such that under acidic conditions, they shrink, while the swelling capacity increases under alkaline conditions.
A sequence-controlled polymer is a macromolecule, in which the sequence of monomers is controlled to some degree. This control can be absolute but not necessarily. In other words, a sequence-controlled polymer can be uniform or non-uniform (Ð>1). For example, an alternating copolymer synthesized by radical polymerization is a sequence-controlled polymer, even if it is also a non-uniform polymer, in which chains have different chain-lengths and slightly different compositions. A biopolymer with a perfectly-defined primary structure is also a sequence-controlled polymer. However, in the case of uniform macromolecules, the term sequence-defined polymer can also be used.
PETases are an esterase class of enzymes that catalyze the breakdown (via hydrolysis) of polyethylene terephthalate (PET) plastic to monomeric mono-2-hydroxyethyl terephthalate (MHET). The idealized chemical reaction is:
Synthetic biopolymers are human-made copies of biopolymers obtained by abiotic chemical routes. Synthetic biopolymer of different chemical nature have been obtained, including polysaccharides, glycoproteins, peptides and proteins, polyhydroxoalkanoates, polyisoprenes.