Suppressing Nonradiative Decay in BF2 Formazanates via Donor Bromination for Cancer Phototheranostics.

IF 16 1区材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY

ACS Nano Pub Date : 2025-10-01 DOI:10.1021/acsnano.5c12563

Hanming Dai,Jinjun Shao,Dan Lei,Kang Xu,Tian Zhang,Anqing Mei,Peng Chen,Yuxin Guo,Xiaochen Dong

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引用次数: 0

Abstract

Dominant nonradiative decay pathways in second-near-infrared (NIR-II) small-molecule fluorescent dyes critically impair both radiative emission and intersystem crossing (ISC) efficiencies, limiting their utility in fluorescence imaging (FLI) and phototherapy. Herein, we report a donor bromination strategy to suppress nonradiative decay in a boron difluoride (BF2) formazanate dye BDFTBr for NIR-II FLI-guided tumor photothermal and photodynamic therapy. Compared with the unbrominated analogue BDFTH, BDFTBr with donor bromination maintains a stereoscopic conformation and suppresses intramolecular vibrations, reducing vibrationally induced nonradiative heat dissipation and enhancing the fluorescence quantum yield by ∼3.75-fold. Additionally, donor bromination narrows the singlet-triplet energy gap (ΔES-T) and facilitates ISC, leading to the improved generation of multiple reactive oxygen species, even under the hypoxic tumor microenvironment. In vitro and in vivo studies confirm that BDFTBr nanoparticles enable efficient NIR-II FLI-guided tumor ablation with minimal systemic toxicity. This work provides a generalizable strategy for suppressing nonradiative decay in NIR-II small-molecule fluorescent dyes, advancing their potential in multimodal cancer phototheranostics.

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通过供体溴化抑制BF2甲酸盐的非辐射衰变用于癌症光疗。

次近红外（NIR-II）小分子荧光染料的主要非辐射衰变途径严重损害了辐射发射和系统间交叉（ISC）效率，限制了它们在荧光成像（FLI）和光治疗中的应用。在此，我们报告了一种供体溴化策略，以抑制二氟化硼（BF2）甲酸酯染料BDFTBr的非辐射衰变，用于NIR-II fl引导的肿瘤光热和光动力治疗。与未溴化的类似物BDFTH相比，具有溴化供体的BDFTBr保持了立体构象，抑制了分子内振动，减少了振动诱导的非辐射散热，并将荧光量子产率提高了约3.75倍。此外，供体溴化缩小了单重态-三重态能隙（ΔES-T），促进了ISC，即使在低氧肿瘤微环境下，也能促进多种活性氧的生成。体外和体内研究证实，BDFTBr纳米颗粒能够有效地实现NIR-II fl引导的肿瘤消融，并且具有最小的全身毒性。这项工作为抑制NIR-II小分子荧光染料的非辐射衰变提供了一种通用策略，提高了它们在多模式癌症光疗中的潜力。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

ACS Nano 工程技术-材料科学：综合

CiteScore

26.00

自引率

4.10%

发文量

1627

审稿时长

1.7 months

期刊介绍： ACS Nano, published monthly, serves as an international forum for comprehensive articles on nanoscience and nanotechnology research at the intersections of chemistry, biology, materials science, physics, and engineering. The journal fosters communication among scientists in these communities, facilitating collaboration, new research opportunities, and advancements through discoveries. ACS Nano covers synthesis, assembly, characterization, theory, and simulation of nanostructures, nanobiotechnology, nanofabrication, methods and tools for nanoscience and nanotechnology, and self- and directed-assembly. Alongside original research articles, it offers thorough reviews, perspectives on cutting-edge research, and discussions envisioning the future of nanoscience and nanotechnology.