Nanoparticle-Enabled Interfacial Kinetic Control of Bond-Exchange Reactions: Insights from Biomedical Poly(ε-caprolactone)-Based Dynamic Polymers.
4 affiliations
- 1Faculty of Mechanical Engineering, University of Maribor, SI-2000Maribor, Slovenia.
- 2Faculty of Chemistry and Chemical Engineering, University of Maribor, SI-2000Maribor, Slovenia.
- 3Polymer Competence Center Leoben GmbH , AT-8700Leoben, Austria.
- 4Institute of Chemistry of Polymeric Materials, Technical University of Leoben, AT-8700Leoben, Austria.
Abstract
Poly(ε-caprolactone) (PCL)-based dynamic polymers are promising adaptive biomaterials due to their biocompatibility, biodegradability, and high chain mobility; however, the onset temperature for bond-exchange reactions, often referred to as topology-freezing temperature, Tv, remains difficult to control and is typically treated as a bulk property governed by catalyst selection and network structure. Consequently, many reported dynamic polymers operate at temperatures well above the biomedical operating window, limiting their biomedical applicability. Here, we propose an interfacial kinetic engineering strategy in which nanoparticle-polymer interfaces act as localized kinetic regulators of dynamic covalent bond exchange. By tailoring nanoparticle (NP) surface chemistry, including functional group density, polarity, and catalytic activity, the activation energy (Ea) can be modulated at the nanoscale, enabling programmable control of Tv. Exchange kinetics in PCL-based dynamic polymers are expected to be highly sensitive to the local chemical environment, indicating that interfacial effects can decouple dynamic behavior from bulk composition. This perspective establishes NP-dynamic polymer interfaces as a programmable kinetic design parameter for controlling bond-exchange reactions in dynamic polymer networks, opening a pathway toward spatially defined covalent adaptable materials with application-specific and programmable dynamic behavior.
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BibTeX
@article{cresnar2026nanoparticleenabled,
title = {{Nanoparticle-Enabled Interfacial Kinetic Control of Bond-Exchange Reactions: Insights from Biomedical Poly(ε-caprolactone)-Based Dynamic Polymers.}},
author = {Klementina Pušnik Črešnar and Tadej Slatinek and Lidija Fras Zemljič and Sandra Schlögl},
journal = {ACS macro letters},
year = {2026},
month = oct,
doi = {10.1021/acsmacrolett.6c00292},
url = {https://europepmc.org/article/MED/42899718},
note = {CC BY},
}
RIS
TY - JOUR
TI - Nanoparticle-Enabled Interfacial Kinetic Control of Bond-Exchange Reactions: Insights from Biomedical Poly(ε-caprolactone)-Based Dynamic Polymers.
AU - Klementina Pušnik Črešnar
AU - Tadej Slatinek
AU - Lidija Fras Zemljič
AU - Sandra Schlögl
PY - 2026
DA - 2026/10/01
JO - ACS macro letters
DO - 10.1021/acsmacrolett.6c00292
UR - https://europepmc.org/article/MED/42899718
AB - Poly(ε-caprolactone) (PCL)-based dynamic polymers are promising adaptive biomaterials due to their biocompatibility, biodegradability, and high chain mobility; however, the onset temperature for bond-exchange reactions, often referred to as topology-freezing temperature, Tv, remains difficult to control and is typically treated as a bulk property governed by catalyst selection and network structure. Consequently, many reported dynamic polymers operate at temperatures well above the biomedical operating window, limiting their biomedical applicability. Here, we propose an interfacial kinetic engineering strategy in which nanoparticle-polymer interfaces act as localized kinetic regulators of dynamic covalent bond exchange. By tailoring nanoparticle (NP) surface chemistry, including functional group density, polarity, and catalytic activity, the activation energy (Ea) can be modulated at the nanoscale, enabling programmable control of Tv. Exchange kinetics in PCL-based dynamic polymers are expected to be highly sensitive to the local chemical environment, indicating that interfacial effects can decouple dynamic behavior from bulk composition. This perspective establishes NP-dynamic polymer interfaces as a programmable kinetic design parameter for controlling bond-exchange reactions in dynamic polymer networks, opening a pathway toward spatially defined covalent adaptable materials with application-specific and programmable dynamic behavior.
SN - 2161-1653
ER -