Degradation mechanisms of bioresorbable polyesters. Part 1. Effects of random scission, end scission and autocatalysis
Open accessAbstract
A mathematical model was developed to relate the degradation trend of bioresorbable polymers to different underlying hydrolysis mechanisms, including noncatalytic random scission, autocatalytic random scission, noncatalytic end scission or autocatalytic end scission. The effect of each mechanism on molecular weight degradation and potential mass loss was analysed. A simple scheme was developed to identify the most likely hydrolysis mechanism based on experimental data. The scheme was first demonstrated using case studies, then used to evaluate data collected from 31 publications in the literature to identify the dominant hydrolysis mechanisms for typical biodegradable polymers. The analysis showed that most of the experimental data indicates autocatalytic hydrolysis, as expected. However, the study shows that the existing understanding on whether random or end scission controls degradation is inappropriate. It was revealed that pure end scission cannot explain the observed trend in molecular weight reduction because end scission would be too slow to reduce the average molecular weight. On the other hand, pure random scission cannot explain the observed trend in mass loss because too few oligomers would be available to diffuse out of a device. It is concluded that the chain ends are more susceptible to cleavage, which produces most of the oligomers leading to mass loss. However, it is random scission that dominates the reduction in molecular weight.
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SEM voids may correspond to areas where significant auto-catalysis has occurred, resulting in pockets of low molecular weight oligomers that diffuse slowly out through the polymer matrix.
“This is consistent with SEM observations, where the voids seen may correspond to areas where significant auto-catalysis has occurred, resulting in pockets of low molecular weight oligomers which diffuse slowly out through the polymer matrix [21, 47].”
From Tuning structural relaxations, mechanical properties, and degradation timescale of PLLA during hydrolytic degradation by blending with PLCL-PEG (2019) · cites this paper as [47]
The Introduction (page unavailable) links faster degradation in the cores of large samples to oligomers and monomers acting as catalysts, and Section 3 says these water-soluble chains may diffuse out of a device. The paper does not identify SEM voids as sites of autocatalysis or describe them as pockets of oligomers that diffuse slowly through the polymer matrix. (LLM, conf=0.82)
Experimental — accuracy not yet measuredThe accelerated degradation of the blend is attributable to auto-catalytic behaviour: faster degrading PLCL-PEG breaks down, accumulating catalytic oligomers formed by hydrolysis, which then catalyse degradation of PLLA and further degradation of PLCL-PEG.
“This can be attributed to auto-catalytic behaviour [47, 48] - as the faster degrading PLCL-PEG breaks down, there is an accumulation of catalytic oligomers formed by hydrolysis, which then catalyse degradation of PLLA as well as further degradation of PLCL-PEG.”
From Tuning structural relaxations, mechanical properties, and degradation timescale of PLLA during hydrolytic degradation by blending with PLCL-PEG (2019) · cites this paper as [47]
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Experimental — accuracy not yet measuredThe hydrolytic degradation rate of LA/CL copolymers is strongly influenced by composition and increases with increasing LA amount and degree of randomness.
“the hydrolytic degradation rate of the copolymers of LA and CL is strongly influenced by the composition, as a consequence of the degree of crystallinity and the hydrophobicity. It was found that the degradation rate increase by increasing the LA amount and by the degree of randomness in the case of CL/LA copolymers [21].”
From Thermo-Rheological and Shape Memory Properties of Block and Random Copolymers of Lactide and ε-Caprolactone (2021) · cites this paper as [21]
Table 2 (Conclusions; page unavailable) includes a 90PLA:10PCL sample, but does not compare LA/CL compositions or their degradation rates. The discussion of random scission in §3.1 concerns where polymer chains break, not the degree of randomness of a copolymer. Searches for LA content, copolymer randomness, crystallinity, and hydrophobicity found no passage establishing the claimed trend. (LLM, conf=0.74)
Experimental — accuracy not yet measured
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“It was found that the degradation rate increase by increasing the LA amount and by the degree of randomness in the case of CL/LA copolymers [21].”
Background
- Authors
- Gleadall, A., Pan, J., Kruft, M.-A., & Kellomäki, M.
- Affiliations
- University of Nottingham (GB)
- University of Leicester (GB)
- Corresponding author
- Pan, Jingzhe
- Venue
- Acta Biomaterialia
- Publisher
- Elsevier BV
- Published
- 2014-05
- Volume
- 10
- Issue
- 5
- Pages
- 2223-2232
- ISSN
- 1742-7061 (ISSN-L)
- OpenAlex
- W2030708200
- Cited by
- 165
- References
- 53
- Citations by year
- 2026: 18 · 2025: 14 · 2024: 17 · 2023: 10 · 2022: 12 · 2021: 15 · 2020: 14 · 2019: 25 · 2018: 11 · 2017: 12 · 2016: 5 · 2015: 7 · 2014: 5
- FWCI
- 3.67
- Type
- journal article
- Language
- en
- Open access
- green
- figshare.com
- Licence
- cc-by-nc-nd
- www.elsevier.com/tdm/userlicense/1.0/ (tdm)
- Locations
- Acta Biomaterialia (publishedVersion)
- PubMed (publishedVersion)
- Figshare (submittedVersion, cc-by-nc-nd)
- Loughborough University Institutional Repository (Loughborough University) (submittedVersion, cc-by-nc-nd)
- Loughborough University Research Repository (Loughborough University) (submittedVersion, cc-by-nc-nd)
- Leicester Research Archive (University of Leicester) (submittedVersion, other-oa)
- Topics
- Physical Sciences › Materials Science › Biomaterials › biodegradable polymer synthesis and properties
- Physical Sciences › Materials Science › Biomaterials › Magnesium Alloys: Properties and Applications
- Life Sciences › Biochemistry, Genetics and Molecular Biology › Molecular Medicine › Hydrogels: synthesis, properties, applications
- Keywords
- biodegradable polymers, hydrolysis mechanism, random chain scission, autocatalytic hydrolysis, molecular weight degradation, mass loss, mathematical model
- MeSH terms
- Biocompatible Materials, Catalysis, Computer Simulation, Hydrolysis, Models, Theoretical, Molecular Weight, Polyesters, Time Factors
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