Department of Chemistry, University of York, Heslington, York YO10 5DD, United Kingdom.
Department of Biology, University of York, Heslington, York YO10 5DD, United Kingdom.
ACS Biomater Sci Eng. 2022 May 9;8(5):1829-1840. doi: 10.1021/acsbiomaterials.1c01560. Epub 2022 Apr 1.
Hydrogels with spatio-temporally controlled properties are appealing materials for biological and pharmaceutical applications. We make use of mild acidification protocols to fabricate hybrid gels using calcium alginate in the presence of a preformed thermally triggered gel based on a low-molecular-weight gelator (LMWG) 1,3:2:4-di(4-acylhydrazide)-benzylidene sorbitol (DBS-CONHNH). Nonwater-soluble calcium carbonate slowly releases calcium ions over time when exposed to an acidic pH, triggering the assembly of the calcium alginate gel network. We combined the gelators in different ways: (i) the LMWG was used as a template to spatially control slow calcium alginate gelation within preformed gel beads, using glucono-δ-lactone (GdL) to lower the pH; (ii) the LMWG was used as a template to spatially control slow calcium alginate gelation within preformed gel trays, using diphenyliodonium nitrate (DPIN) as a photoacid to lower the pH, and spatial resolution was achieved by masking. The dual-network hybrid gels display highly tunable properties, and the beads are compatible with stem cell growth. Furthermore, they preserve the LMWG function of inducing in situ silver nanoparticle (AgNP) formation, which provides the gels with antibacterial activity. These gels have potential for eventual regenerative medicine applications in (e.g.) bone tissue engineering.
具有时空可控性能的水凝胶是生物和药物应用的理想材料。我们利用温和酸化方案,在预先形成的基于低分子量凝胶剂 (LMWG) 的热触发凝胶(1,3:2:4-二(4-酰肼基)-苄基山梨糖醇(DBS-CONHNH)的存在下,制造混合凝胶。当暴露于酸性 pH 时,非水溶性碳酸钙会随着时间的推移缓慢释放钙离子,触发藻酸钙凝胶网络的组装。我们以不同的方式组合了凝胶剂:(i)LMWG 被用作模板,通过使用葡萄糖酸-δ-内酯 (GdL) 降低 pH 值来空间控制预先形成的凝胶珠内的缓慢藻酸钙凝胶化;(ii)LMWG 被用作模板,通过使用二苯基碘鎓硝酸盐 (DPIN) 作为光酸来空间控制预先形成的凝胶盘中的缓慢藻酸钙凝胶化,通过掩蔽实现空间分辨率。双网络杂化凝胶显示出高度可调的性能,并且珠子与干细胞生长兼容。此外,它们保留了 LMWG 诱导原位银纳米颗粒 (AgNP) 形成的功能,这为凝胶提供了抗菌活性。这些凝胶有可能最终在(例如)骨组织工程中的再生医学应用中得到应用。