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甲基丙烯酸化淀粉与少量甲基丙烯酸化壳聚糖的混合生物墨水可实现用于复杂组织支架的高精度3D打印。

Hybrid bioink of methyacrylated starch with minimal methacrylated chitosan enables high-precision 3D printing for complex tissue scaffolds.

作者信息

Zhou Xingping, Wu Silin, Liu Peng, Wang Liming, Xie Fengwei

机构信息

School of Chemistry and Chemical Engineering, Guangzhou University, Guangzhou Higher Education Mega Center, Guangzhou, Guangdong 510006, China.

School of Chemistry and Chemical Engineering, Guangzhou University, Guangzhou Higher Education Mega Center, Guangzhou, Guangdong 510006, China.

出版信息

Carbohydr Polym. 2025 Nov 1;367:124023. doi: 10.1016/j.carbpol.2025.124023. Epub 2025 Jul 6.

DOI:10.1016/j.carbpol.2025.124023
PMID:40817551
Abstract

Starch-based gels represent promising bioinks for 3D-printed cell scaffolds due to their biosafety, biocompatibility, and biodegradability. However, their widespread adoption has been hindered by inadequate formability and poor self-supporting properties. Here, we introduce an innovative starch-dominated hydrogel system achieved through dual methacrylation of normal corn starch and chitosan, enabling the fabrication of biodegradable cell scaffolds. While methacrylated starch alone (substitution degree: 0.013) exhibited insufficient printing accuracy even with UV assistance, the optimized 10:1 (starch/chitosan, w/w) blend of methacrylated chitosan (substitution degree: 0.27) demonstrated dramatically enhanced 3D printing formability and precision when combined with UV crosslinking. Rheological analysis demonstrated that blending methacrylated starch with methacrylated chitosan reduced flow stress (τ), improving printability while retaining shear-thinning behavior. Incorporation of 10 % glycerol enhanced biomacromolecular compatibility, as evidenced by rheological results and homogenous microstructures in SEM, enabling high-fidelity printing of intricate architectures. UV-cured scaffolds exhibited tunable compressive strength (150-200 kPa) and deformation rate (50-60 %), balancing mechanical compliance with tissue safety. The material's hydrophilic surface (contact angle: 30-60°) supported robust cell adhesion, while in vitro assays confirmed exceptional biocompatibility (96 % cell viability) and controlled biodegradation in α-amylase/lysozyme solutions. This work establishes starch as a primary matrix for bioinks, advancing sustainable, high-precision 3D printing in biomedicine.

摘要

基于淀粉的水凝胶由于其生物安全性、生物相容性和生物可降解性,是用于3D打印细胞支架的有前景的生物墨水。然而,其广泛应用受到可成型性不足和自支撑性能差的阻碍。在此,我们介绍一种创新的以淀粉为主的水凝胶系统,该系统通过普通玉米淀粉和壳聚糖的双重甲基丙烯酸酯化实现,能够制造可生物降解的细胞支架。虽然单独的甲基丙烯酸酯化淀粉(取代度:0.013)即使在紫外线辅助下打印精度也不足,但优化后的甲基丙烯酸酯化壳聚糖(取代度:0.27)与甲基丙烯酸酯化淀粉以10:1(淀粉/壳聚糖,w/w)混合时,与紫外线交联相结合,显示出显著增强的3D打印可成型性和精度。流变学分析表明,将甲基丙烯酸酯化淀粉与甲基丙烯酸酯化壳聚糖混合可降低流动应力(τ),提高可打印性,同时保持剪切变稀行为。加入10%的甘油增强了生物大分子的相容性,流变学结果和扫描电子显微镜中的均匀微观结构证明了这一点,从而能够对复杂结构进行高保真打印。紫外线固化的支架表现出可调的抗压强度(150 - 200 kPa)和变形率(50 - 60%),在机械顺应性与组织安全性之间取得平衡。该材料的亲水性表面(接触角:30 - 60°)支持强大的细胞粘附,而体外试验证实了其优异的生物相容性(96%的细胞活力)以及在α -淀粉酶/溶菌酶溶液中的可控生物降解性。这项工作将淀粉确立为生物墨水的主要基质,推动了生物医学中可持续、高精度的3D打印。

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