Rigid biodegradable photopolymer structures of high resolution using deep-UV laser photocuring

Abstract

Recently there has been increasing effort in using microstereolithography to produce scaffolds of crosslinkable and biodegradable polymers, with desired configurations of high spatial resolution, able to regulate the growth and distribution of cells and consequently the tissue development and engineering on them. The use of deep-UV radiation allows high resolution both in the transversal plane (optical resolution) and in the vertical direction (curing depth) due to the intrinsic large absorption of polymers in this region of the electromagnetic spectrum. Herein we present high-resolution photocrosslinking of the biodegradable poly(propylene fumarate) (PPF) and diethyl fumarate (DEF), using pulsed laser light at 248 nm. The curing depth can be modulated between a few hundreds of nanometers (nm) and a few micrometers (µm) by adjusting the energy dose, the number of incident pulses and the weight ratios of PPF, DEF and photoinitiator in the photocrosslinkable mixtures. The lateral resolution is evaluated by projecting a pattern of a grid with a specified line width and line spacing, and is found to be a few µm. Young's modulus of the cured parts is measured and found to be several GPa, high enough to support bone formation. The results presented here demonstrate that the proposed technique is suitable for the fabrication of stiff and biocompatible structures with defined patterns of micrometer resolution in all three spatial dimensions, setting the first step toward deep-UV laser microstereolithography.