Polymer production is rapidly increasing, but there are no large-scale technologies available to effectively mitigate the massive accumulation of these recalcitrant materials. One potential solution is the development of a carbon-neutral polymer life cycle, where microorganisms convert plant biomass to chemicals, which are used to synthesize biodegradable materials that ultimately contribute to the growth of new plants. Realizing a circular carbon life cycle requires the integration of knowledge across microbiology, bioengineering, materials science, and organic chemistry, which itself has hindered large-scale industrial advances. This review addresses the biodegradation status of common synthetic polymers, identifying novel microbes and enzymes capable of metabolizing these recalcitrant materials and engineering approaches to enhance their biodegradation pathways. Design considerations for the next generation of biodegradable polymers are also reviewed, and finally, opportunities to apply findings from lignocellulosic biodegradation to the design and biodegradation of similarly recalcitrant synthetic polymers are discussed.

The development of degradable polymers has commanded significant attention over the past half century. Approaches have predominantly relied on ring-opening polymerization of cyclic esters (e.g., lactones, lactides) and N-carboxyanhydrides, as well as radical ring-opening polymerizations of cyclic ketene acetals. In recent years, there has been a significant effort applied to expand the family of degradable polymers accessible via olefin metathesis polymerization. Given the excellent functional group tolerance of olefin metathesis polymerization reactions generally, a broad range of conceivable degradable moieties can be incorporated into appropriate monomers and thus into polymer backbones. This approach has proven particularly versatile in synthesizing a broad spectrum of degradable polymers including poly(ester), poly(amino acid), poly(acetal), poly(carbonate), poly(phosphoester), poly(phosphoramidate), poly(enol ether), poly(azobenzene), poly(disulfide), poly(sulfonate ester), poly(silyl ether), and poly(oxazinone) among others. In this review, we will highlight the main olefin metathesis polymerization strategies that have been used to access degradable polymers, including (i) acyclic diene metathesis polymerization, (ii) entropy-driven and (iii) enthalpy-driven ring-opening metathesis polymerization, as well as (iv) cascade enyne metathesis polymerization. In addition, the livingness or control of polymerization reactions via different strategies are highlighted and compared. Potential applications, challenges and future perspectives of this new library of degradable polyolefins are discussed. It is clear from recent and accelerating developments in this field that olefin metathesis polymerization represents a powerful synthetic tool towards degradable polymers with novel structures and properties inaccessible by other polymerization approaches.

Polymer research is currently focused on sustainable and degradable polymers which are cheap, easy to synthesize, and environmentally friendly. Silicon-based polymers are thermally stable and can be utilized in various applications, such as columns and coatings. Poly(silyl ether)s (PSEs) are an interesting class of silicon-based polymers that are easily hydrolyzed in either acidic or basic conditions due to the presence of the silyl ether Si-O-C bond. Synthetically, these polymers can be formed in several different ways, and the most effective and environmentally friendly synthesis is dehydrogenative cross coupling, where the byproduct is H2 gas. These polymers have a lot of promise in the polymeric materials field due to their sustainability, thermal stability, hydrolytic degradability, and ease of synthesis, with nontoxic byproducts. In this review, we will summarize the synthetic approaches for the PSEs in the recent literature, followed by the properties and applications of these materials. A conclusion and perspective will be provided at the end.

Degradable polymers (both biomacromolecules and several synthetic polymers) for biomedical applications have been promising very much in the recent past due to their low cost, biocompatibility, flexibility, and minimal side effects. Here, we present an overview with updated information on natural and synthetic degradable polymers where a brief account on different polysaccharides, proteins, and synthetic polymers viz. polyesters/polyamino acids/polyanhydrides/polyphosphazenes/polyurethanes relevant to biomedical applications has been provided. The various approaches for the transformation of these polymers by physical/chemical means viz. cross-linking, as polyblends, nanocomposites/hybrid composites, interpenetrating complexes, interpolymer/polyion complexes, functionalization, polymer conjugates, and block and graft copolymers, are described. The degradation mechanism, drug loading profiles, and toxicological aspects of polymeric nanoparticles formed are also defined. Biomedical applications of these degradable polymer-based biomaterials in and as wound dressing/healing, biosensors, drug delivery systems, tissue engineering, and regenerative medicine, etc., are highlighted. In addition, the use of such nano systems to solve current drug delivery problems is briefly reviewed.

The anionic ring-opening copolymerization (ROCOP) of epoxides, namely of ethylene oxide (EO), with anhydrides (AH) generally produces strictly alternating copolymers. With triethylborane (TEB)-assisted ROCOP of EO with AH, statistical copolymers of high molar mass including ether and ester units could be obtained. In the presence of TEB, the reactivity ratio of EO (rEO), which is normally equal to 0 in its absence, could be progressively raised to values lower than 1 or higher than 1. Conditions were even found to obtain rEO equal or close to 1. Samples of P(EO-co-ester) with minimal compositional drift could be synthesized; upon basic degradation of their ester linkages, these samples afforded poly(ethylene oxide) (PEO) diol samples of narrow molar mass distribution. In other cases where rEO were lower or higher than 1, the PEO diol samples eventually isolated after degradation exhibited a broader distribution of molar masses because of the compositional drift of initial P(EO-co-ester) samples.

Particulate immunotherapy holds promise to vaccinate or treat a broad array of illnesses, including cancer, infectious diseases, and autoimmune disorders. The rate of antigen release from nano/microparticles (MPs) can impact both the type and quality of the immune response they elicit. The lysosomes of antigen-presenting cells are highly oxidizing. Thus, an oxidation-sensitive vehicle could enable a significant advancement in effective MP immunotherapy. One promising class of materials being developed toward this end is aryl-boronate-modified dextran polymers. The boronic esters used for oxidation-sensitive materials and sensors are typically made using pinacol (Pin) as a diol. However, Pin-based aryl-boronate-modified polymers are capable of transesterifying with biogenic diols, which can lead to undesirable interactions and poor material properties. To solve this, pinanediol (PD) was used in place of Pin in the synthesis of an aryl-boronate-modified dextran polymer (PDB-Dex), yielding a highly stable boronic ester. This modified dextran reverses its water solubility as desired, and improves on Pin-based materials by maintaining its solubility in organic solvents. MPs could be prepared by emulsion, nanoprecipitation, and electrospray techniques. The hydrogen peroxide-triggered degradation of microparticles was quantified colorimetrically, and the mechanism was probed using 1H NMR. Preliminary in vitro studies show low cytotoxicity and the ability to deliver an immunostimulatory agent.

Globally, over 100,000 tons of antibiotics are consumed each year with a significant proportion discharged into the environment. As antibiotic usage continues to rise, there is a pressing need to reduce antibiotic pollution by developing antimicrobials whose activity can be switched off after the material has served its intended purpose. We have reported a series of imidazolium polymers incorporating pH-degradable linkers. The polymers show excellent antimicrobial activity across a range of Gram-positive and Gram-negative bacteria and fungi. The introduction of pH-degradable linkers was demonstrated to facilitate environmental degradation of the polymers to inactive small molecules. Both polymers and their degradation products do not induce bacterial resistance and display moderate biodegradation in surface water.

Herein, we develop a well-defined antibacterial polymer based on poly(2-hydroxyethyl methacrylate) (PHEMA) and a derivative of vitamin B1, easily degradable into inactive and biocompatible compounds. Hence, thiazole moiety was attached to HEMA monomer through a carbonate pH-sensitive linkage and the resulting monomer was polymerized via reversible addition-fragmentation chain transfer (RAFT) polymerization. N-alkylation reaction of the thiazole groups leads to cationic polymer with thiazolium groups. This polymer exhibits excellent antibacterial activity against methicillin-resistant Staphylococcus aureus (MRSA) with an MIC value of 78 µg mL-1, whereas its degradation product, thiazolium small molecule, was found to be inactive. Hemotoxicity studies confirm the negligible cytotoxicity of the degradation product in comparison with the original antibacterial polymer. The degradation of the polymer at physiological pH was found to be progressive and slow, thus the cationic polymer is expected to maintain its antibacterial characteristics at physiological conditions for a relative long period of time before its degradation. This degradation minimizes antimicrobial pollution in the environment and side effects in the body after eradicating bacterial infection.

Two approaches to obtain fast-degrading polymer films based on poly(sebacic anhydride) (PSA) are presented, both of which target polymer films with a lower degree of crystallinity than pure PSA homopolymer: first, thin films were prepared from poly(adipic anhydride)/poly(sebacic anhydride) blends at different ratios, and second, films were made from the copolymer poly(salicylic acid-co-sebacic acid). These films are intended as sacrificial layers for self-regenerating functional coatings, for example to regenerate antimicrobial surface activity. The degradation kinetics of these films were analyzed by surface plasmon resonance spectroscopy (SPR). The results of the blends approach indicate that the blend degradation rate was accelerated only in the initial degradation phase (compared to PSA). The degradation kinetics study of the poly(salicylic-acid-co-sebacic acid) film shows that this copolymer degraded faster than poly(sebacic anhydride) initially, releasing antimicrobial salicylic acid in the process. However, its degradation rate slowed down at a mass loss > 60% and approached the PSA degradation curve at longer degradation times. When tested as sacrificial layer in self-regenerating antimicrobial polymer stacks, it was found that the degradation rate was too low for successful layer shedding.

There is compelling evidence that the degradation kinetics of thin polymer films differ significantly from those of bulk materials, as interfacial effects become dominant. Therefore, it is crucial to investigate these kinetics separately. Qualitative analytics of thin film degradation exist, e.g. by scanning electron microscopy or atomic force microscopy (AFM), but a quantitative study is so far missing. In this work, poly(sebacic anhydride) (PSA), an aliphatic polyanhydride, is used as a model system for a quantitative degradation study. PSA was spin-coated onto silicon or gold substrates. The degradation of these PSA films was monitored by ellipsometry, surface-plasmon resonance spectroscopy (SPR), and Fourier transform infrared spectroscopy (FTIR). Two kinetic regimes were observed when plotting the relative layer thickness determined by FTIR and SPR against the degradation time. The data obtained by FTIR showed a single process for the rate of ester bond cleavage. Overall, the degradation rate constants of PSA determined by the different methods were consistent. The degradation rate constants of PSA film up to 378 nm thickness were constant. Several thicker free-standing samples studied gravimetrically had a degradation rate constant that was one order of magnitude slower, thus confirming thickness-dependent degradation rate constants.