有机自由基材料在生物医学领域的研究进展

doi:10.6023/cjoc202508018

摘要/Abstract

有机自由基材料因其特殊的开壳电子结构, 展现出独特的磁学、光学和氧化还原特性, 已在生物医学领域得到广泛应用. 但多数有机自由基寿命极短, 难以实现分离, 目前仅能通过立体化学等少数策略获得稳定的自由基材料. 因此, 如何开发稳定的自由基材料一直是近年来研究的重点和难点. 综述了有机自由基材料的分类、分子设计和基本特性, 论述了该材料在生物医学领域的应用, 尤其是在生物成像、光动力治疗、光热治疗以及协同治疗等方面的应用. 此外, 讨论了这些有机自由基材料目前所面临的各种挑战及未来发展机遇.

关键词: 稳定自由基, 生物成像, 光动力治疗, 光热治疗, 协同治疗

Organic radical materials, due to their special open-shell electronic structure, possess unique magnetic, optical, and redox properties, and have been widely applied in the field of biomedicine. However, the lifetime of most radicals is too short to be separated, and only a few radicals can maintain their stable radical form via stereochemical strategies. Therefore, how to develop stable organic radical materials has been the focus and difficulty of research in recent years. This review summarizes the classification, molecular design, and fundamental properties of organic radical materials, and discusses their biomedical applications, particularly in bioimaging, photodynamic therapy, photothermal therapy, and synergistic therapy. Additionally, the article also discusses the various challenges and future opportunities that these organic radical materials are currently facing.

Key words: stable radical, bioimaging, photodynamic therapy, photothermal therapy, synergistic therapy

引用此文

杨建业, 周佩, 申起飞, 张珮娟, 胥艳子, 赵炳捷, 党东锋. 有机自由基材料在生物医学领域的研究进展[J]. 有机化学, 2025, 45(11): 4013-4025.

Jianye Yang, Pei Zhou, Qifei Shen, Peijuan Zhang, Yanzi Xu, Bingjie Zhao, Dongfeng Dang. Progress of Organic Radical Materials in Biomedical Applications[J]. Chinese Journal of Organic Chemistry, 2025, 45(11): 4013-4025.

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图/表 10

图1. (a)闭壳分子和(b)开壳分子发光示意图

Figure 1. Schematic illustration of luminescence in (a) closed- shell molecules and (b) open-shell molecules

图2. 有机自由基的分类

Figure 2. Classification of organic radical

图3. 稳定自由基构筑策略

Figure 3. Stable radical construction strategies

图4. (a)有机自由基造影剂(ORCA)结构示意图和小鼠注射ORCA 90 min后T1加权MRI; (b) BASP-ORCAs结构示意图和注射BASP-ORCA前后的T2加权MRI; (c)氮氧自由基网络结构和小鼠腿部MRI

Figure 4. (a) Structural diagram of organic radical contrast agent (ORCA) and T1-weighted MRI of mouse 90 min after injection with ORCA; (b) Chemical structure of BASP-ORCAs and T2-weighted MRI before and after injection of BASP-ORCA; (c) Nitroxide radical network structure and MRI of mouse leg

图5. (a) HOPE71的化学结构及其刺激响应EPR谱图; (b) MCP与MCPH的相互转化结构及MCP对照组与DEM处理组的EPR成像

Figure 5. (a) Chemical structure of HOPE71 and its stimulus-responsive EPR spectrum; (b) Interconversion structures between MCP and MCPH, and EPR imaging of MCP control group versus DEM-treated group

图6. (a) P6阳离子自由基的制备和P•+⊂CB[7]在不同细胞中的线粒体共定位成像; (b) P8和P9的化学结构以及小鼠活体荧光成像; (c) TTM-Cz-Br的化学结构及其纳米粒子的制备

Figure 6. (a) Preparation process of P cation radical and mitochondrial co-localization imaging of P•+⊂CB[7] in different cells; (b) Chemical structures of P8 and P9 and in vivo fluorescence imaging of mice; (c) Chemical structure of TTM-Cz-Br and preparation of its nanoparticles

图7. 闭壳和开壳光敏剂活性氧产生机制

Figure 7. ROS production mechanisms of closed-shell and open-shell photosensitizers

图8. (a) Cy-TEMPO和Cy-DENT的化学结构, 以及(b) PTM- TPA的化学结构和不同浓度PTM-TPA纳米粒子电子顺磁共振波谱

Figure 8. Chemical structures of Cy-TEMPO and Cy-DENT; (b) Chemical structures of PTM-TPA and electron paramagnetic resonance spectra of PTM-TPA nanoparticles at different concentrations

图9. (a) BPDI3－, (b) NDI-2CB[7].－, (c) CRbio, (d) CR-(DPA)3-T, (e) DRM的化学结构, 以及(f) SFA-BTM的化学结构及其自由基纳米粒子在光热治疗中的应用

Figure 9. Chemical structures of (a) BPDI3－, (b) NDI-2CB[7].－, (c) CRbio, (d) CR-(DPA)3-T, and (e) DRM; (f) Chemical structure of SFA-BTM and its application of radical nanoparticles in photothermal therapy

图10. (a) HTB, (b) TTMIndoOMe和(c) 2PhNVDPP的化学结构

Figure 10. Chemical structures of (a) HTB, (b) TTMIndoOMe, and (c) 2PhNVDPP

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