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三苯基磷修饰花菁 H

花匠小妙招
2025-11-28 20:32

摘要:

光热治疗（PTT）通过光热剂（PTAs）吸收近红外光，将光激发产生的非辐射能量耗散到病灶部位，实现局部组织的热消融，为治疗肿瘤及细菌感染提供新途径。但开发兼具高效光热转换与精准靶向功能的有机 PTAs 面临挑战。本文聚焦七甲川花菁染料分子工程优化，提出聚集态调控与功能基团协同强化策略，在中性花菁骨架引入三苯基磷阳离子（TPP+），构建新型阳离子衍生物 Cy7T-TPP。其具三重优势：TPP+赋予细菌膜锚定与线粒体靶向能力；诱导 H-聚集体增强分子间紧密堆叠，光热转换效率达 51.65%；TPP+屏蔽活性氧攻击，提升稳定性。实验证实其抗肿瘤及抗菌效能优异，为高稳定、靶向性有机光热材料的开发提供分子工程新范式。

Abstract:

Photothermal therapy (PTT) uses photothermal agents (PTAs) to absorb near-infrared light and dissipate the non radiative energy generated by light excitation to the lesion site, achieving local tissue thermal ablation and providing a new approach for treating tumors and bacterial infections. However, developing organic PTAs that combine efficient photothermal conversion and precise targeting functions faces challenges. This article focuses on the molecular engineering optimization of heptamethylene cyanine dye, proposing a strategy of aggregation state regulation and synergistic strengthening of functional groups. A novel cationic derivative Cy7T-TPP is constructed by introducing triphenylphosphine cation (TPP+) into the neutral cyanine skeleton. It has three advantages: TPP + endows bacteria with membrane anchoring and mitochondrial targeting abilities; Inducing H-aggregates to enhance tight intermolecular stacking, achieving a photothermal conversion efficiency of 51.65%; TPP shields against reactive oxygen species attacks and enhances stability. Experimental results have confirmed its excellent anti-tumor and antibacterial efficacy, providing a new paradigm of molecular engineering for the development of highly stable and targeted organic photothermal materials.

图 1 Cy7T-TPP和Cy7T-Pr的合成路线

Figure 1. The synthetic routes of Cy7T-TPP and Cy7T-Pr

图 2 (a) 化合物Cy7T-Pr的核磁共振氢谱; (b)化合物Cy7T-TPP的核磁共振氢谱

Figure 2. (a) 1H NMR spectrum of compound Cy7T-TPP; (b)1H NMR spectrum of compound Cy7T-Pr

图 3 (a) Cy7T-TPP 和 (d) Cy7T-Pr 在水中的流体动力学粒径分布，(b) Cy7T-TPP和 (e) Cy7T-Pr自组装纳米粒子的TEM图像, (c) Cy7T-TPP和 (f) Cy7T-Pr自组装纳米粒子的AFM图像（化合物浓度10 μmol/L）

Figure 3. (a) Fluid dynamic particle size distribution of Cy7T TPP and (d) Cy7T Pr in water, (b) TEM images of Cy7T TPP and (e) Cy7T Pr self-assembled nanoparticles, (c) AFM images of Cy7T TPP and (f) Cy7T Pr self-assembled nanoparticles. (The concentration of both compounds is 10 μmol/L)

图 4 Cy7T-TPP和Cy7T-Pr自组装纳米粒子在水中的Zeta电位（化合物浓度10 μmol/L）

Figure 4. Zeta potentials of 10 μmol/L Cy7T-TPP and Cy7T-Pr self-assembled nanoparticles in water in water

图 5 (a) 5 μmol/L Cy7T-TPP和(b) Cy7T-Pr在不同溶剂中的紫外吸收光谱; 不同浓度的(c) Cy7T-TPP和(d) Cy7T-Pr在DMSO中的紫外-可见吸收光谱；(e) Cy7T-TPP和Cy7T-Pr在DMSO中浓度-吸光度的线性关系；不同浓度的(f) Cy7T-TPP和(g) Cy7T-Pr在水中的紫外-可见吸收光谱；(h) Cy7T-TPP和Cy7T-Pr在水中浓度-吸光度的线性关系

Figure 5. (a) UV absorption spectra of 5 μmol/L Cy7T-TPP and (b) Cy7T-Pr in different solvents; UV-vis absorption spectra of (c) Cy7T-TPP and (d) Cy7T-Pr at different concentrations in DMSO; (e) The linear relationship between concentration and absorbance of Cy7T-TPP and Cy7T-Pr in DMSO; UV-vis absorption spectra of (f) Cy7T-TPP and (g) Cy7T-Pr at different concentrations in water; (h) The linear relationship between concentration and absorbance of Cy7T-TPP and Cy7T-Pr in water

图 6 (a) Cy7T-TPP和 (b) Cy7T-Pr在水中不同浓度下的光热升温曲线; (c) Cy7T-TPP和 (d) Cy7T-Pr在水中不同功率下的光热升温曲线( 808 nm, 20 μmol/L )

Figure 6. (a) The photothermal heating curves of Cy7T-TPP and (b) Cy7T-Pr at different concentrations in water; (c) Photothermal heating curves of Cy7T-TPP and (d) Cy7T-Pr in water at different powers (808 nm, 20 μmol/L)

图 7 (a) Cy7T-TPP和 (b) Cy7T-Pr在水中的升温/冷却循环曲线( 808 nm, 0.5 W/cm2, 20 μmol/Lol/L)

Figure 7. (a) Cy7T-TPP and (b)Cy7T-Pr heating/cooling cycle curves in water (808 nm, 0.5 W/cm2, 20 μmol/L)

图 8 (a) Cy7T-TPP和 (b) Cy7T-Pr在水中的紫外吸收光谱随光照时间的变化；(c) Cy7T-TPP和 Cy7T-Pr在水中归一化的吸光度随光照时间的变化 (808 nm, 0.5 W/cm2)

Figure 8. (a) The UV absorption spectra of Cy7T-TPP and (b) Cy7T-Pr in water as a function of illumination time; (c) Normalized absorbance of Cy7T-TPP and Cy7T-Pr in water as a function of illumination time (808 nm, 0.5 W/cm2).

图 9 (a) Cy7T-TPP和 (b) Cy7T-Pr在水中的光热转换效率计算(808 nm, 0.5 W/cm2)

Figure 9. (a) Calculation of photothermal conversion efficiency of Cy7T-TPP and (b) Cy7T-Pr in water (808 nm, 0.5 W/cm2)

图 10 含有(a) Cy7T-Pr，(b) Cy7T-TPP 的 DPBF 水溶液以及不含光敏剂的 (c) DPBF 水溶液经激光照射（808 nm，0.5 W/cm2）后的吸收光谱；(d) DPBF 在 410 nm 处的归一化吸光度随照射时间的变化

Figure 10. The absorption spectra of DPBF aqueous solution containing (a) Cy7T-Pr, (b) Cy7T-TPP, and (c) DPBF aqueous solution without photosensitizer after laser irradiation (808 nm, 0.5 W/cm2); (d) Normalized absorbance of DPBF at 410 nm as a function of irradiation time

图 11 (a) Cy7T-TPP与(b)Cy7T-Pr的体外 PTT；(c) 活 / 死细胞双染成像（标尺 100 μm）；(d) 细胞光热图像及升温曲线 (808 nm, 0.5 W/cm2)。使用单因素方差分析来检验统计显著性（*P<0.05，**P<0.01，***P<0.001，****P< [3]

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