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研究论文

Mn2+离子/二聚体差异化热响应的CaF2纳米探针实现多模式光学测温

刘文素, 江莎*, 王渝童, 谢林林, 张登翔, 谭力伟, 汪永杰   

  1. 重庆邮电大学 电子科学与工程学院 重庆 400065
  • 投稿日期:2025-07-11
  • 基金资助:
    国家自然科学基金项目(No. 11604037), 重庆市教委科学技术研究项目(Nos. KJQN202300652, KJZD-K202300612), 重庆市自然科学基金项目(CSTB2025NSCQ-LZX0080)和重庆市留学人员回国创业创新支持计划(CX2024081)资助.

CaF2 nanoprobes with Mn2+ ions/dimers exhibiting differential thermal responses for multimodal optical thermometry

Liu Wensu, Jiang Sha*, Wang Yutong, Xie Linlin, Zhang Dengxiang, Tan Liwei, Wang Yongjie   

  1. School of Electronic Science and Engineering, Chongqing University of Posts and Telecommunications, Chongqing 400065
  • Received:2025-07-11
  • Contact: * E-mail: jiangsha@cqupt.edu.cn
  • Supported by:
    National Natural Science Foundation of China (No. 11604037), the Scientific and Technological Research Program of Chongqing Municipal Education Commission (Nos. KJQN202300652, KJZD-K202300612), Natural Science Foundation of Chongqing (CSTB2025NSCQ-LZX0080) and the Venture and Innovation Support Program for Chongqing Overseas Returnees (CX2024081).

近年来,基于无机纳米材料的光学测温技术因其高灵敏度、非接触测量和良好的生物相容性等优势,在生物医学温度传感领域展现出重要应用前景.本研究通过溶剂热法成功制备了CaF2:Mn2+纳米颗粒,并系统研究了其温度依赖的光学特性.实验结果表明:该纳米颗粒的发光强度、发射峰位置和荧光寿命均表现出显著的温度响应特性.进一步研究发现:在近红外第一生物窗口内(650-950 nm),CaF2:Mn2+纳米颗粒呈现出Mn2+-Mn2+二聚体的特征发射(680-950 nm),且其热猝灭效应强于Mn2+离子的发光.基于上述实验结果,我们建立了基于CaF2:Mn2+纳米颗粒的多模式光学温度传感策略.其中,Mn2+-Mn2+二聚体发光强度、发光强度比(Mn2+离子/Mn2+-Mn2+二聚体)和Mn2+-Mn2+二聚体寿命模式在生理温度内(300-330 K)表现出最佳测温性能,其相对灵敏度分别为2.82% K-1(330 K)、0.79% K-1(305 K)和0.65% K-1(330 K),这为生物测温提供了可靠的多模式测量方案.本研究不仅证实了CaF2:Mn2+纳米颗粒在生物温度传感领域中的应用潜力,更为开发新型高灵敏度的生物测温探针提供了重要理论参考和实验依据.

关键词: CaF2:Mn2+纳米颗粒, Mn2+-Mn2+二聚体, 发光强度比, 生物测温, 多模式测温

In recent years, optical thermometry based on inorganic nanomaterials has demonstrated significant application potential in biomedical temperature sensing due to its high sensitivity, non-contact measurement capability, and excellent biocompatibility. Compared with a single temperature sensing mode, the development of a multi-mode optical temperature sensing strategy is expected to significantly improve the accuracy and reliability of temperature detection, which has become an important research direction in this field. In this work, a series of CaF2:Mn2+ nanoparticles with particle size of about 10-20 nm have been successfully prepared through a solvothermal approach. In order to further reveal the structure-activity relationship of CaF2: Mn2+, its structural composition and microscopic morphology were systematically characterized by X-ray diffraction, X-ray photoelectron spectroscopy and transmission electron microscopy. The luminescence properties and temperature-dependent response behavior of CaF2:Mn2+ were explored in detail by spectroscopic analysis. On this basis, the potential application prospects of the material in the field of optical temperature sensing are further discussed. The experimental results demonstrate that the nanoparticles exhibit significant temperature-dependent characteristics in luminescence intensity, emission peak position, and fluorescence lifetime. Further investigation revealed that the CaF2:Mn2+ nanoparticles exhibited characteristic emission from Mn2+-Mn2+ dimers (680-950 nm) within the first near-infrared biological window (650-950 nm), and showed stronger thermal quenching effects compared to Mn2+ ions. Based on these experimental results, we have established a multimodal optical temperature sensing strategy utilizing CaF2:Mn2+ nanoparticles. Among these, the temperature sensing models based on luminescence intensity of the Mn2+-Mn2+ dimer, the luminescence intensity ratio (Mn2+ ions / Mn2+-Mn2+ dimer), and the lifetime of the Mn2+-Mn2+ dimer demonstrate optimal temperature sensing performance within the physiological temperature range (300-330 K). Corresponding relative sensitivities are 2.82% K-1 (330 K), 0.79% K-1 (305 K), and 0.65% K-1 (330 K), respectively, providing a reliable multi-mode measurement scheme for biological thermometry. This study not only confirms the application potential of CaF2:Mn2+ nanoparticles in the field of biological temperature sensing, but also provides important theoretical references and experimental basis for the development of novel high-sensitivity biothermometry probes.

Key words: CaF2:Mn2+ nanoparticles, Mn2+-Mn2+ dimers, luminescence intensity ratio, biothermometry, multimodal thermometry