Department of Food Science and Biotechnology, Ewha Womans University, Seoul, 03760, Republic of Korea.
Division of Chemical Engineering and Materials Science, and Graduate Program in System Health Science and Engineering, Ewha Womans University, Seoul, 03760, Republic of Korea.
Sci Rep. 2022 Jun 7;12(1):9397. doi: 10.1038/s41598-022-13406-8.
Photobiocatalysis is a growing field of biocatalysis. Especially light-driven enzyme catalysis has contributed significantly to expanding the scope of synthetic organic chemistry. However, photoenzymes usually utilise a rather narrow wavelength range of visible (sun)light. Triplet-triplet annihilation-based upconversion (TTA-UC) of long wavelength light to shorter wavelength light may broaden the wavelength range. To demonstrate the feasibility of light upconversion we prepared TTA-UC poly(styrene) (PS) nanoparticles doped with platinum(II) octaethylporphyrin (PtOEP) photosensitizer and 9,10-diphenylanthracene (DPA) annihilator (PtOEP:DPA@PS) for application in aqueous solutions. Photoexcitation of PtOEP:DPA@PS nanoparticles with 550 nm light led to upconverted emission of DPA 418 nm. The TTA-UC emission could photoactivate flavin-dependent photodecarboxylases with a high energy transfer efficiency. This allowed the photodecarboxylase from Chlorella variabilis NC64A to catalyse the decarboxylation of fatty acids into long chain secondary alcohols under green light (λ = 550 nm).
光生物催化是生物催化领域的一个新兴分支。特别是光驱动的酶催化在扩展有机合成化学的范围方面做出了重大贡献。然而，光酶通常利用可见光（太阳）光相当窄的波长范围。基于三重态-三重态湮灭的上转换（TTA-UC）可以将长波长光转换为短波长光，从而拓宽波长范围。为了证明光上转换的可行性，我们制备了掺杂有铂(II)八乙基卟啉（PtOEP）光敏剂和 9,10-二苯基蒽（DPA）猝灭剂的 TTA-UC 聚苯乙烯（PS）纳米粒子（PtOEP:DPA@PS），用于水溶液中的应用。用 550nm 的光激发 PtOEP:DPA@PS 纳米粒子，导致 DPA 的上转换发射 418nm。TTA-UC 发射可以用光转移效率高的黄素依赖性光脱羧酶进行光激活。这使得来自 Chlorella variabilis NC64A 的光脱羧酶能够在绿光（λ=550nm）下催化脂肪酸脱羧生成长链仲醇。
