<br>基于四苯乙基的分子笼与辅酶 FAD：面向光催化辅助光动力疗法的构象异构体络合,Journal of the American Chemical Society

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基于四苯乙基的分子笼与辅酶 FAD：面向光催化辅助光动力疗法的构象异构体络合
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2024-10-21 , DOI: 10.1021/jacs.4c09508
Qingfang Li ₁ , Chaochao Yan ₁ , Peijuan Zhang ₂ , Pingxia Wang ₁ , Kaige Wang ₁ , Wanni Yang ₁ , Lin Cheng ₁ , Dongfeng Dang ₂ , Liping Cao ₁

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黄素腺嘌呤二核苷酸（FAD）作为一种光吸收辅酶因子，可以在不同酶内发生构象异构体络合，形成各种酶-辅酶复合物，这些复合物表现出在生理过程中起关键作用的光催化功能。使用 FAD 或其衍生物构建人工光功能系统不仅可以开发具有优异活性的生物相容性光催化系统，还可以进一步增强我们对 FAD 在生物系统中的作用的理解。在这里，我们展示了一种在水中构建具有光诱导催化功能的人工酶-辅酶型主-客体复合物的超分子方法。首先，我们设计并合成了一种基于水溶性四苯基烯（TPE）的八分子笼（1），该分子笼具有大而灵活的腔，它可以自适应地封装两个具有“U 形”构象（uFAD）的 FAD 分子，在水中形成 1：2 的主客体复合物（1⊃uFAD₂）。其次，基于 FAD 在 1 内的构象异构络合，1⊃uFAD₂ 复合物在白光照射下促进电子和能量转移到分子氧，有效地产生活性氧（ROS），例如超氧自由基（O₂^•–）和单线态氧（¹O₂）。据我们所知，1⊃uFAD₂ 复合物充当光催化剂，通过水介质中的光诱导超氧自由基催化机制实现 NADH 光催化氧化反应的最高周转频率（TOF）为 35.6 ^min-1。最后，结合 ROS 的细胞毒作用和涉及 NADH 的细胞内氧化还原平衡的破坏，1⊃uFAD₂ 作为超分子光敏剂在缺氧肿瘤中显示出优异的氧非依赖性光催化辅助光动力疗法。

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Tetraphenylethene-Based Molecular Cage with Coenzyme FAD: Conformationally Isomeric Complexation toward Photocatalysis-Assisted Photodynamic Therapy

Flavin adenine dinucleotide (FAD), serving as a light-absorbing coenzyme factor, can undergo conformationally isomeric complexation within different enzymes to form various enzyme–coenzyme complexes, which exhibit photocatalytic functions that play a crucial role in physiological processes. Constructing an artificial photofunctional system using FAD or its derivatives can not only develop biocompatible photocatalytic systems with excellent activities but also further enhance our understanding of the role of FAD in biological systems. Here, we demonstrate a supramolecular approach for constructing an artificial enzyme–coenzyme-type host–guest complex with photoinduced catalytic function in water. First, we have designed and synthesized a water-soluble tetraphenylethene (TPE)-based octacationic molecular cage (1) with a large and flexible cavity, which can adaptively encapsulate with two FAD molecules with “U-shaped” conformation (uFAD) to form a 1:2 host–guest complex (1⊃uFAD₂) in water. Second, based on the conformationally isomeric complexation of FAD within 1, the 1⊃uFAD₂ complex facilitates electron and energy transfers to molecular oxygen upon the white-light illumination, efficiently producing reactive oxygen species (ROS) such as superoxide radical (O₂^•–) and singlet oxygen (¹O₂). To our knowledge, the 1⊃uFAD₂ complex acts as a photocatalyst to achieve the highest turnover frequency (TOF) of 35.6 min^–1 for the photocatalytic oxidation reaction of NADH via a photoinduced superoxide radical catalysis mechanism in an aqueous medium. At last, combining the cytotoxic effects of ROS and the disruption of the intracellular redox balance involving NADH, 1⊃uFAD₂ as a supramolecular photosensitizer displays an excellent oxygen-independent photocatalysis-assisted photodynamic therapy in hypoxic tumors.

更新日期：2024-10-21

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