Hong Bo Min, Park Su A, Park Won Ho
1Department of Advanced Organic Materials and Textile System Engineering, College of Engineering, Chungnam National University, Daejeon, 34134 South Korea.
2Department of Nature-Inspired Nanoconvergence Systems, Korea Institute of Machinery and Materials, Daejeon, 34103 South Korea.
Biomater Res. 2019 Nov 21;23:21. doi: 10.1186/s40824-019-0170-1. eCollection 2019.
Photocrosslinking systems of polymers have been widely studied using UV or visible light irradiation. However, the photodegradation behavior derived from light irradiation was rarely reported, comparing with the photocrosslinking. In this study, the tyramine-modified hyaluronic acid (HA/Tyr) hydrogel was prepared using riboflavin (RF) as a photoinitiator, and the degradation behavior of HA by the reactive oxygen species (ROS) generated in photochemical process was investigated.
The HA/Tyr conjugate was synthesized by EDC/NHS chemistry to introduce phenol group. Degree of substitution (DS, %) of phenol group to HA molecule was about 25%. The structural change of HA/Tyr was measured by proton nuclear magnetic resonance (H-NMR) and attenuated total reflectance infrared spectroscopy (ATR-FTIR), and the rheological properties of photocrosslinked HA/Tyr hydrogel were investigated by rheometer.
The HA/Tyr solution with 25% substitution formed a stable hydrogel via visible light irradiation in the presence of RF photoinitiator. Rheological data of HA/Tyr solution showed that the storage modulus (G') was increased with increasing HA concentration. Additionally, it was found that RF initiated by visible light irradiation induced the degradation of HA molecular chain, and consequently reduced the viscosity of HA/Tyr solutions.
The results indicate that RF-based photoinitiator system caused the degradation of HA molecule by ROS generated in photochemical process as well as the crosslinking of HA/Tyr.
聚合物的光交联体系已通过紫外线或可见光照射得到广泛研究。然而,与光交联相比,光照射引起的光降解行为鲜有报道。在本研究中,以核黄素(RF)作为光引发剂制备了酪胺修饰的透明质酸(HA/Tyr)水凝胶,并研究了光化学过程中产生的活性氧(ROS)对HA的降解行为。
通过EDC/NHS化学法合成HA/Tyr共轭物以引入酚基。酚基在HA分子上的取代度(DS,%)约为25%。通过质子核磁共振(H-NMR)和衰减全反射红外光谱(ATR-FTIR)测定HA/Tyr的结构变化,并通过流变仪研究光交联的HA/Tyr水凝胶的流变性能。
在存在RF光引发剂的情况下,取代度为25%的HA/Tyr溶液通过可见光照射形成了稳定的水凝胶。HA/Tyr溶液的流变学数据表明,储能模量(G')随HA浓度的增加而增加。此外,发现可见光照射引发的RF诱导了HA分子链的降解,从而降低了HA/Tyr溶液的粘度。
结果表明,基于RF的光引发剂体系在光化学过程中产生的ROS导致了HA分子的降解以及HA/Tyr的交联。