Interference of Solvatochromic Twist in Amyloid Nanostructure for Light-Driven Biocatalysis,ACS Applied Energy Materials

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Interference of Solvatochromic Twist in Amyloid Nanostructure for Light-Driven Biocatalysis
ACS Applied Energy Materials ( IF 5.4 ) Pub Date : 2020-01-02 00:00:00 , DOI: 10.1021/acsaem.9b02303
Giyeong Son ₁ , Jinhyun Kim ₁ , Chan Beum Park ₁

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Amyloid self-assembly is a powerful bottom-up approach for the synthesis of sophisticated organic nanostructures that possess fascinating structural flexibility. This study adds a dimension to the research on amyloid self-assembly by expanding its scope to the field of photobiocatalysis. We demonstrate visible-light-driven regeneration of nicotinamide adenine dinucleotide (NAD⁺) using solvatochromic Congo red (CR) hybridized with an amyloid-derived peptide (Fmoc-FF) nanostructure. In the course of an in situ self-assembly process of Fmoc-FF peptides, CR molecules were hybridized into a Fmoc-FF nanofiber network through π–π interactions between the nonpolar fluorenyl group of Fmoc-FF and the aromatic moieties of CR. This hybridization made CR dyes capable of photoredox catalysis because the planarization of CR induced by the Fmoc-FF degenerated the twisted intramolecular charge-transfer state of the dye; the incorporation of CR into the Fmoc-FF nanostructure increased CR’s fluorescence intensity 9 times and generated a photocurrent by 400 nA cm^–2. The photocatalytic Fmoc-FF/CR hydrogel facilitated O₂ reduction-coupled NAD⁺ regeneration under visible light. The NAD⁺ regeneration yield of the Fmoc-FF/CR hybrid was 5 times higher than that of free CR. Furthermore, the in situ regenerated NAD⁺ activated NAD⁺-dependent redox enzymes for alcohol oxidation; the Fmoc-FF/CR hybrid achieved a substantially high total turnover number of enzymes of 42 953, which was 5.8 times larger than that with free CR.

中文翻译：

淀粉样纳米结构中溶剂变色扭曲对光驱动生物催化的干扰

淀粉样蛋白自组装是一种强大的自下而上的方法，用于合成具有引人入胜的结构灵活性的复杂有机纳米结构。该研究通过将淀粉样蛋白自组装的范围扩展到光生物催化领域，为淀粉样自组装的研究增添了新的内容。我们展示了烟酰胺腺嘌呤二核苷酸（NAD ⁺），使用与淀粉样蛋白衍生的肽（Fmoc-FF）纳米结构杂交的溶剂化刚果红（CR）。在Fmoc-FF肽的原位自组装过程中，CR分子通过Fmoc-FF的非极性芴基与CR的芳香族基团之间的π-π相互作用，杂交成Fmoc-FF纳米纤维网络。这种杂交使CR染料能够进行光氧化还原催化，因为Fmoc-FF诱导的CR的平面化使染料的扭曲的分子内电荷转移状态退化。将CR掺入Fmoc-FF纳米结构中可使CR的荧光强度提高9倍，并产生400 nA cm ^–2的光电流。光催化Fmoc-FF / CR水凝胶促进O ₂还原偶联NAD ⁺在可见光下再生。Fmoc-FF / CR杂种的NAD ⁺再生产量比游离CR高5倍。此外，用于酒精氧化的原位再生NAD ⁺活化的NAD ⁺依赖性氧化还原酶。Fmoc-FF / CR杂种获得的酶的总周转率很高，为42 953，这是游离CR酶的5.8倍。

更新日期：2020-01-02

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