# Thermoresponsive Behavior, Degradation, and Bioactivity of Nanohydroxyapatite on Graphene Oxide Nanoscroll-Enhanced Poly(N-isopropylacrylamide)-Based Scaffolds

## TL;DR

This study develops thermoresponsive scaffolds with antioxidant properties to improve bone regeneration in oxidative environments caused by diseases like osteoarthritis and bone cancer.

## Contribution

A quantitative framework for designing oxidation-resilient scaffolds using nanohydroxyapatite on graphene oxide nanoscrolls is introduced.

## Key findings

- P5G scaffolds showed reversible swelling and sustained antioxidant activity under oxidative conditions.
- PN5GP scaffolds had enhanced calcium deposition but suffered from accelerated mass loss due to PCL.
- P5G is identified as the most promising formulation for bone repair in oxidative environments.

## Abstract

Osteoarthritis and metastatic bone cancers create pathological oxidative environments characterized by elevated reactive oxygen species (ROS). ROS impair bone regeneration by degrading the scaffold and suppressing mineralization. To address these challenges, we fabricated thermoresponsive scaffolds based on poly(N-isopropylacrylamide) (PNIPAAm) incorporating in situ-grown nanohydroxyapatite on graphene oxide nanoscrolls (nHA-GONS) using stereolithography (SLA). Three scaffold formulations were studied: pure PNIPAAm (PNP), PNIPAAm with 5 wt.% nHA-GONS (P5G), and PNIPAAm with 5 wt.% nHA-GONS reinforced with polycaprolactone (PCL) microspheres (PN5GP). Each scaffold was evaluated for (i) swelling and lower critical solution temperature (LCST) using differential scanning calorimetry (DSC); (ii) oxidative degradation assessed using Fourier-transform infrared spectroscopy (FTIR), mass loss, and antioxidant assays; and (iii) mineralization and morphology via immersion in simulated body fluid followed by microscopy. The PN5GP and P5G scaffolds demonstrated reversible swelling, sustained antioxidant activity, and enhanced calcium deposition, which enable redox stability and mineralization under oxidative environments, critical for scaffold functionality in bone repair. PNP scaffolds exhibited copper accumulation, while PN5GP suffered from accelerated mass loss driven by the PCL phase. These findings identify the P5G formulation as a promising scaffold. This study introduces a quantitative framework that enables the predictive design of oxidation-resilient scaffolds.