Miao Shuting, Guo Jing, Zhang Yuexin, Liu Peisheng, Chen Xiaojie, Han Qian, Wang Yingbo, Xuan Kun, Yang Peng, Tao Fei
Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, Xi'an Key Laboratory of Polymeric Soft Matter, International Joint Research Center on Functional Fiber and Soft Smart Textile, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an, 710119, China.
State Key Laboratory of Oral & Maxillofacial Reconstruction and Regeneration, National Clinical Research Center for Oral Diseases, Shaanxi Clinical Research Center for Oral Diseases, Department of Preventive Dentistry, School of Stomatology, The Fourth Military Medical University, Xi'an, 710032, China.
Adv Mater. 2025 Jun;37(22):e2416824. doi: 10.1002/adma.202416824. Epub 2025 Apr 7.
Intrafibrillar mineralization is essential not only as a fundamental process in forming biological hard tissues but also as a foundation for developing advanced composite fibril-based materials for innovative applications. Traditionally, only natural collagen fibrils have been shown to enable intrafibrillar mineralization, presenting a challenge in designing ordered hierarchical fibrils from common protein aggregation that exhibit similar high intrafibrillar mineralization activity. In this study, a mechanically directed two-step transformation method is developed that converts phase-transitioned protein nanofilms into crystalline, hierarchical amyloid-like fibrils with multilayer structures, which effectively control the growth and lateral organization of hydroxyapatite within adaptive gaps. The resulting mineralized HSAF achieves a hardness of 0.616 ± 0.007 GPa and a modulus of 19.06 ± 3.54 GPa-properties closely resembling native hard tissues-and exhibits exceptionally high bioactivity in promoting both native bone tissue growth and further intrafibrillar mineralization, achieving 76.9% repair in a mice cranial defect model after 8 weeks and outperforming other regenerative materials. This remarkable performance, stemming from the unique structure and composition of the fibers, positions HSAF as a promising candidate for biomedical and engineering applications. These findings advance the understanding of biomineralization mechanisms and establish a foundation for developing high-bioactivity materials for hard tissue regeneration.
纤维内矿化不仅是形成生物硬组织的基本过程，也是开发用于创新应用的先进复合纤维基材料的基础。传统上，只有天然胶原纤维被证明能够实现纤维内矿化，这给从具有相似高纤维内矿化活性的常见蛋白质聚集体设计有序分级纤维带来了挑战。在本研究中，开发了一种机械导向的两步转化方法，该方法将相转变蛋白纳米膜转化为具有多层结构的结晶、分级类淀粉样纤维，有效控制了羟基磷灰石在适应性间隙内的生长和横向组织。所得矿化的HSAF硬度达到0.616±0.007 GPa，模量为19.06±3.54 GPa，其性能与天然硬组织极为相似，并且在促进天然骨组织生长和进一步的纤维内矿化方面表现出极高的生物活性，在小鼠颅骨缺损模型中8周后实现了76.9%的修复，优于其他再生材料。这种卓越的性能源于纤维独特的结构和组成，使HSAF成为生物医学和工程应用的有希望的候选材料。这些发现推进了对生物矿化机制的理解，并为开发用于硬组织再生的高生物活性材料奠定了基础。
