5,6-Dihydroxyindole-2-carboxylic-Acid-TiO2 Charge Transfer Complexes in the Radical Polymerization of Melanogenic Precursor(s)

被引:37
作者
Vitiello, Giuseppe [1 ,2 ]
Pezzella, Alessandro [3 ,4 ]
Calcagno, Vincenzo [5 ]
Silvestri, Brigida [1 ]
Raiola, Luca [5 ]
D'Errico, Gerardino [2 ,3 ]
Costantini, Aniello [1 ]
Branda, Francesco [1 ]
Luciani, Giuseppina [1 ]
机构
[1] Univ Naples Federico II, Dept Chem Mat & Prod Engn, Ple V Tecchio 80, I-80125 Naples, Italy
[2] Consorzio Interuniv Sviluppo Sistemi & Grande Int, CSGI, Via Lastruccia 3, I-50019 Florence, Italy
[3] Univ Naples Federico II, Dept Chem Sci, Via Cintia 4, I-80126 Naples, Italy
[4] CNR, IPCB, Via Campi Flegrei 34, I-80078 Naples, Italy
[5] IIT, Ctr Adv Biomat Hlth Care CRIB, Via Largo Barsanti & Matteucci 53, I-80125 Naples, Italy
关键词
AEROBIC OXIDATION; TIO2; SURFACES; MELANIN; ACID; PHOTOCATALYSIS; EUMELANIN; NANOPARTICLES; POLYDOPAMINE; REDUCTION; MECHANISM;
D O I
10.1021/acs.jpcc.6b00226
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
A combination of biomedical and technological applications is generating, over the past decades, the well established interest toward melanins and melanogenesis. Several compounds have been explored to promote/catalyze oxidative polymerization of melanogenic precursors, such as 5,6-dihydroxyindole-2-carboxylic acid (DHICA), to melanin-like biopolymers in vitro. TiO2 has shown a photocatalytic activity driving DHICA polymerization and leading to the formation of melanin-TiO2 hybrid nanostructures with unique biocide behavior even under visible light. However, the mechanism of melanin formation in those hybrids is not yet well understood although a ligand to metal charge transfer (LMCT) process involving DHICA and Ti4+ ions was hypothesized. Here, we focus on melanin formation and apply a complementary analysis, by using photoluminescence (PL), UV-vis, electron paramagnetic resonance (EPR), and nuclear magnetic resonance (NMR) spectroscopy to reveal the mechanism of DHICA polymerization in the presence of a TiO2-sol. This study discloses TiO2 potentialities to drive and template DHICA polymerization to melanin via LMCT-based photo-oxidative process.
引用
收藏
页码:6262 / 6268
页数:7
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