9e1c5aca19d1ffc1eac9e130d831d26b ijms_a2017v18n10p2169.pdf c553f9fed77136df10a5f5ba4178d0dc24400c9d ijms_a2017v18n10p2169.pdf f1f79e3a677972290e4bb97886f7eb53a044a761f6d742d977c71f9b45c4122f ijms_a2017v18n10p2169.pdf Title: Replacing Nitrogen by Sulfur: From Structurally Disordered Eumelanins to Regioregular Thiomelanin Polymers Subject: The oxidative polymerization of 5,6-dihydroxybenzothiophene (DHBT), the sulfur analog of the key eumelanin building block 5,6-dihydroxyindole (DHI), was investigated to probe the role of nitrogen in eumelanin build-up and properties. Unlike DHI, which gives a typical black insoluble eumelanin polymer on oxidation, DHBT is converted to a grayish amorphous solid (referred to as thiomelanin) with visible absorption and electron paramagnetic resonance properties different from those of DHI melanin. Mass spectrometry experiments revealed gradational mixtures of oligomers up to the decamer level. Quite unexpectedly, nuclear magnetic resonance (NMR) analysis of the early oligomer fractions indicated linear, 4-, and 7-linked structures in marked contrast with DHI, which gives highly complex mixtures of partially degraded oligomers. Density functional theory (DFT) calculations supported the tendency of DHBT to couple via the 4- and 7-positions. These results uncover the role of nitrogen as a major determinant of the structural diversity generated by the polymerization of DHI, and point to replacement by sulfur as a viable entry to regioregular eumelanin-type materials for potential applications for surface functionalization by dip coating. Keywords: eumelanin; polydopamine; bioinspired polymers; bioinspired coatings; thiomelanin Author: Mariagrazia Iacomino, Juan Mancebo-Aracil, Mireia Guardingo, Raquel Martín, Gerardino D’Errico, Marco Perfetti, Paola Manini, Orlando Crescenzi, Félix Busqué, Alessandra Napolitano, Marco d’Ischia, Josep Sedó and Daniel Ruiz-Molina Creator: LaTeX with hyperref package Producer: pdfTeX-1.40.17 CreationDate: Wed Oct 18 10:35:43 2017 CEST ModDate: Wed Oct 18 10:35:43 2017 CEST Tagged: no UserProperties: no Suspects: no Form: none JavaScript: no Pages: 16 Encrypted: no Page size: 595.276 x 841.89 pts (A4) Page rot: 0 File size: 2936613 bytes Optimized: no PDF version: 1.5 name type encoding emb sub uni object ID ------------------------------------ ----------------- ---------------- --- --- --- --------- EGWTME+URWPalladioL-Ital Type 1 Custom yes yes no 66 0 JRQXZO+URWPalladioL-Bold Type 1 Custom yes yes no 67 0 XWOCXD+VnURWPalladioL-Bold Type 1 Custom yes yes no 68 0 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