Cao Wei, Mao Haochuan, McCallum Naneki C, Zhou Xuhao, Sun Hao, Sharpe Christopher, Korpanty Joanna, Hu Ziying, Ni Qing Zhe, Burkart Michael D, Shawkey Matthew D, Wasielewski Michael R, Gianneschi Nathan C
Department of Chemistry, Northwestern University Evanston Illinois 60208 USA
Department of Materials Science and Engineering, Northwestern University Evanston Illinois 60208 USA.
Chem Sci. 2023 Mar 31;14(15):4183-4192. doi: 10.1039/d2sc06418a. eCollection 2023 Apr 12.
Herein, we investigate synthetic routes to a close mimic of natural pheomelanin. Three different oxidative polymerization routes were attempted to generate synthetic pheomelanin, each giving rise to structurally dissimilar materials. Among them, the route employing 5-cysteinyl-dihydroxyphenylalanine (5-CD) as a monomer was verified as a close analogue of extracted pheomelanin from humans and birds. The resulting biomimetic and natural pheomelanins were compared various techniques, including solid-state Nuclear Magnetic Resonance (ssNMR) and Electron Paramagnetic Resonance (EPR). This synthetic pheomelanin closely mimics the structure of natural pheomelanin as determined by parallel characterization of pheomelanin extracted from multiple biological sources. With a good synthetic biomimetic material in hand, we describe cation-π interactions as an important driving force for pheomelanogenesis, further advancing our fundamental understanding of this important biological pigment.
在此，我们研究了合成天然褐黑素类似物的路线。尝试了三种不同的氧化聚合路线来生成合成褐黑素，每种路线都产生了结构不同的材料。其中，以5-半胱氨酰二羟基苯丙氨酸（5-CD）为单体的路线被证实是从人类和鸟类中提取的褐黑素的近似类似物。通过包括固态核磁共振（ssNMR）和电子顺磁共振（EPR）在内的各种技术对所得的仿生褐黑素和天然褐黑素进行了比较。通过对从多种生物来源提取的褐黑素进行平行表征，确定这种合成褐黑素紧密模拟天然褐黑素的结构。有了一种良好的合成仿生材料，我们将阳离子-π相互作用描述为褐黑素生成的重要驱动力，进一步深化了我们对这种重要生物色素的基本认识。
