锰掺杂磷酸钙纳米团簇多级结构的构建及性能研究

doi:10.15541/jim20260004

摘要/Abstract

摘要： 锰(Mn)因其多价态特性在抗肿瘤和促成骨等生物医学领域应用广泛, 在肿瘤治疗中仍面临着催化与光热性能难以协同提升的挑战。本研究以(2.50±0.64) nm的锰掺杂磷酸钙纳米团簇(Mn:nCaP)为结构单元, 采用赖氨酸(Lys)偶联及pH调控策略构建纳米团簇多级结构聚集体(Mn:nCaP@Lys), 探究多级结构化对Mn:nCaP光热转换和催化性能的影响, 以期优化Mn的生物学效应。实验结果表明, 采用1-乙基-(3-二甲基氨基丙基)碳二亚胺盐酸盐/N-羟基琥珀酰亚胺(0.09 mol/L)介导的Lys (0.04 mol/L)偶联反应, 通过调控pH(7.0~11.0)成功构建了系列尺度的Mn:nCaP@Lys; 随着pH从7.0增加到11.0, 实现了Mn:nCaP@Lys尺寸从(57.27±7.83) nm至(95.70±14.16) nm的可控调节。与Mn:nCaP相比, Mn:nCaP@Lys在4 h内展现出更高的催化活性, pH 9.0条件下催化活性达到最强。多级结构在pH 9.0条件下保留了良好的升温能力, 但在pH 10.0、11.0条件下升温能力弱于单体。Mn:nCaP@Lys具有良好的生物安全性, 与Mn:nCaP相比展现出增强的肿瘤细胞抑制效果以及化疗增敏效应。本研究为优化Mn的生物学效应提供了一种有效的技术方案, 有助于推动Mn在生物医学领域的应用。

关键词: 纳米磷酸钙, 锰离子, 多级结构, 尺寸效应

Abstract: Manganese (Mn), with its unique multivalent nature, has been widely used in biomedical applications, including anticancer therapy and bone formation. However, in cancer treatment, it still faces challenges in achieving synergistic improvements in both catalytic and photothermal properties. In this study, a hierarchical structure (Mn:nCaP@Lys) was constructed through lysine (Lys) coupling and pH control utilizing manganese-doped calcium phosphate nanoclusters (Mn:nCaP, (2.50±0.64) nm) as structural units. Influence of hierarchical structuring on the photothermal conversion and catalytic performance of Mn:nCaP was discussed to optimize its biological effects. Experimental results showed that various Mn:nCaP@Lys samples with different particle sizes were successfully constructed by adjusting pH using a method of 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride/N-hydroxysuccinimide (0.09 mol/L)-mediated Lys (0.04 mol/L) coupling reaction. By increasing pH from 7.0 to 11.0, the particle size of Mn:nCaP@Lys was controllably increased from (57.27±7.83) nm to (95.70±14.16) nm. Compared to Mn:nCaP, Mn:nCaP@Lys showed better catalytic activity over 4 h. Moreover, the hierarchical structure material synthesized at pH 9.0 exhibited the strongest catalytic activity and good heating capacity, but its heating capacity was weaker than that of Mn:nCaP at pH 10.0 and 11.0. Biocompatible Mn:nCaP@Lys displayed enhanced tumor cell inhibition and increased chemo-therapeutic sensitization compared to Mn:nCaP. This study presents an effective method for improving the biological effects of Mn, supporting its application in biomedical fields.

Key words: nano-calcium phosphate, manganese ion, hierarchical structure, size effect

中图分类号:

TQ318

陈俊锐, 汤新丽, 曹妩青, 韩颖超. 锰掺杂磷酸钙纳米团簇多级结构的构建及性能研究[J]. 无机材料学报, DOI: 10.15541/jim20260004.

CHEN Junrui, TANG Xinli, CAO Wuqing, HAN Yingchao. Manganese-doped Calcium Phosphate Nanoclusters with Hierarchical Structure: Construction and Performance[J]. Journal of Inorganic Materials, DOI: 10.15541/jim20260004.

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