紫質衍生物生物無機化學：從生物感測、小分子活化、到能源應用

Bioinorganic Chemistry of Porphyrin Analogues: Biosensor, Small-molecule Activation, and Energy Conversion Applications

莊川弘(Chuan-Hung Chuang) ； 許凱淳(Kai-Chun Hsu) ； 李向(Hsiang Lee) ； 洪政雄(Chen-Hsiung Hung)

《化學》 77卷4期 (2019/12) Pp. 379-395

https://doi.org/10.6623/chem.201912_77(4).007

摘要

紫質及類紫質分子在生物系統扮演電子傳遞、分子攜帶及活化、以及光吸收的角色。在紫質合成化學漸進成熟的過程中，紫質及類紫質分子在各領域的應用上也逐漸開花結果。由典型的四吡咯紫質結構出發並且引入官能基的修飾，加深了紫質分子在生物模擬的研究深度。除此之外，異原子雜環的引入取代部分吡咯環以及擴大或縮減四吡咯環狀結構，皆開啟了紫質化學研究的新章節。環狀分子共軛結構的擴張更延伸了紫質化學的研究觸角，以拓樸學的角度合理闡述了特殊大環π共軛系統的芳香性（aromaticity）。本文從類紫質分子的合成出發，進一步發揮每一個紫質衍生物的特殊化學性質，分別將其應用在鋅離子感測、氧氣活化、亞硝酸根至亞硝基的還原反應、亞硝基至氧化亞氮的還原反應、染料敏化太陽能電池、以及鈣鈦礦太陽能電池元件的研究。

關鍵字

紫質 ； 生物無機 ； 異位紫質 ； 生物感測 ； 太陽能電池

並列摘要

Porphyrins and porphyrin analogues play crucial roles, including electron-transfer mediator, small-molecule carrier and activation center, and light harvester, in the biological systems. On account of the successful development of synthetic porphyrin chemistry, the versatile applications of porphyrin analogues are achieved. The introduction of functional groups into classical tetrapyrrolic porphyrin deepens the biomimetic study. On the other hand, the remarkable chemical properties from replacing part of pyrrolic rings with other heterocyclic rings, expending and contracting the tetrapyrrolic ring size also broaden the research scope of porphyrin chemistry. Moreover, molecular topology rationalizes the distinct aromaticity/stability of the π-conjugated expansion in expending porphyrins with highly flexible ring conformations. Herein, the synthesis of porphyrin analogues is described, and also the respective applications of the porphyrin analogues include zinc-ion biosensor, biomimetic reduction of nitrite to nitric oxide, reduction of nitric oxide to nitrous oxide, dye-sensitized solar cell, and hole-transporting material in perovskite solar cell.

並列關鍵字

Porphyrin ； Bioinorganic ； N-confused porphyrin ； Biosensor ； Solar cell