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Peer-reviewedCC BYMaterials

Understanding Polycaprolactone Degradation: Molecular Mechanisms and Implications for Biomedical Device Design

Abstract

Polycaprolactone (PCL) is a widely used biodegradable polyester in tissue engineering, drug delivery, and temporary implant design. While its favorable processability, biocompatibility, and low melting temperature are highly advantageous, its slow and condition-dependent degradation remains a major limitation for precise temporal control in biomedical applications. Despite extensive literature on PCL, a critical knowledge gap remains in linking fundamental molecular chain scission directly to macroscopic structural evolution, mechanical failure, and predictable in vivo device performance. To address this, this review provides a comprehensive synthesis of PCL degradation mechanisms, with a particular emphasis on PCL-bioceramic composites designed for hard tissue engineering. We elucidate the progressive degradation pathway-distinguishing between initial hydrolytic chain scission, oligomer formation, the generation of low-molecular-weight degradation products, and their subsequent metabolic fate under physiological conditions. Furthermore, this review critically evaluates how fundamental variables-specifically molecular weight, crystallinity, bioceramic fillers, device geometry, and physiological environments-alter degradation kinetics. By connecting molecular weight reduction to subsequent mass loss, thermal behavior, and mechanical deterioration, we establish a framework for understanding how structural reorganization and crystallinity evolution govern material failure. This review bridges the gap between simplified in vitro models and complex in vivo realities, supporting the rational design of composite biomedical devices with tailored, predictable resorption profiles.

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BibTeX
@article{dziemianczyk2026understanding,
  title = {{Understanding Polycaprolactone Degradation: Molecular Mechanisms and Implications for Biomedical Device Design}},
  author = {Paulina Dziemiańczyk and Dawid Łysik and François Vernay and Joanna Mystkowska},
  journal = {Materials},
  year = {2026},
  month = sep,
  doi = {10.3390/ma19183894},
  url = {https://hal.science/hal-05772569v1},
  note = {CC BY},
}
RIS
TY  - JOUR
TI  - Understanding Polycaprolactone Degradation: Molecular Mechanisms and Implications for Biomedical Device Design
AU  - Paulina Dziemiańczyk
AU  - Dawid Łysik
AU  - François Vernay
AU  - Joanna Mystkowska
PY  - 2026
DA  - 2026/09/12
JO  - Materials
DO  - 10.3390/ma19183894
UR  - https://hal.science/hal-05772569v1
AB  - Polycaprolactone (PCL) is a widely used biodegradable polyester in tissue engineering, drug delivery, and temporary implant design. While its favorable processability, biocompatibility, and low melting temperature are highly advantageous, its slow and condition-dependent degradation remains a major limitation for precise temporal control in biomedical applications. Despite extensive literature on PCL, a critical knowledge gap remains in linking fundamental molecular chain scission directly to macroscopic structural evolution, mechanical failure, and predictable in vivo device performance. To address this, this review provides a comprehensive synthesis of PCL degradation mechanisms, with a particular emphasis on PCL-bioceramic composites designed for hard tissue engineering. We elucidate the progressive degradation pathway-distinguishing between initial hydrolytic chain scission, oligomer formation, the generation of low-molecular-weight degradation products, and their subsequent metabolic fate under physiological conditions. Furthermore, this review critically evaluates how fundamental variables-specifically molecular weight, crystallinity, bioceramic fillers, device geometry, and physiological environments-alter degradation kinetics. By connecting molecular weight reduction to subsequent mass loss, thermal behavior, and mechanical deterioration, we establish a framework for understanding how structural reorganization and crystallinity evolution govern material failure. This review bridges the gap between simplified in vitro models and complex in vivo realities, supporting the rational design of composite biomedical devices with tailored, predictable resorption profiles.
SN  - 1996-1944
ER  -