PMID- 29738111 OWN - NLM STAT- MEDLINE DCOM- 20190408 LR - 20190408 IS - 1755-148X (Electronic) IS - 1755-1471 (Linking) VI - 31 IP - 6 DP - 2018 Nov TI - Raman spectroscopy quantification of eumelanin subunits in natural unaltered pigments. PG - 673-682 LID - 10.1111/pcmr.12707 [doi] AB - Eumelanins are large polymers composed of 5,6-dihydroxyindole (DHI) and 5,6-dihydroxyindole-2-carboxylic acid (DHICA). Reactive oxygen species generation is higher during the synthesis of DHI than during the synthesis of DHICA; thus, the production of eumelanins with high relative DHI contents may compromise the viability of cells and organisms. Here, we show that dispersive Raman spectroscopy allows a noninvasive direct detection and quantification of DHI and DHICA in unaltered eumelanins that can be applied to the analysis of natural pigments in biological tissues. Using synthetic eumelanins purely composed of DHI or DHICA, we develop a model to determine the differential contribution of these subunits to the Raman spectra of mixed eumelanins, and exemplify the predictive capacity of the model with natural eumelanins deposited in black and gray feathers of fowl. We found that the wavenumber ranges of 550-1,200 and 1,650-2,300 cm(-1) are significant to predict the DHI:DHICA ratio in unknown samples. CI - (c) 2018 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd. FAU - Galvan, Ismael AU - Galvan I AUID- ORCID: 0000-0002-6523-8592 AD - Departamento de Ecologia Evolutiva, Estacion Biologica de Donana, CSIC, Sevilla, Spain. FAU - Araujo-Andrade, Cuauhtemoc AU - Araujo-Andrade C AD - ICFO - Institut de Ciencies Fotoniques, The Barcelona Institute of Science and Technology, Castelldefels, Spain. AD - Unidad Academica de Fisica, Universidad Autonoma de Zacatecas, Zacatecas, Mexico. FAU - Marro, Monica AU - Marro M AD - ICFO - Institut de Ciencies Fotoniques, The Barcelona Institute of Science and Technology, Castelldefels, Spain. FAU - Loza-Alvarez, Pablo AU - Loza-Alvarez P AD - ICFO - Institut de Ciencies Fotoniques, The Barcelona Institute of Science and Technology, Castelldefels, Spain. FAU - Wakamatsu, Kazumasa AU - Wakamatsu K AUID- ORCID: 0000-0003-1748-9001 AD - Department of Chemistry, Fujita Health University School of Health Sciences, Toyoake, Japan. LA - eng GR - RYC-2012-10237/Spanish Ministry of Economy, Industry and Competitiveness (MINECO)/International GR - SEV-2015-0522/Spanish Ministry of Economy, Industry and Competitiveness (MINECO)/International GR - FIS2016-80455-R/Spanish Ministry of Economy, Industry and Competitiveness (MINECO)/International GR - EU-H2020 654148/H2020 Framework/International GR - 424/C/2014/Fundacio la Marato de TV3/International GR - Fundacio Cellex Barcelona/International GR - Generalitat de Catalunya/International PT - Journal Article PT - Research Support, Non-U.S. Gov't DEP - 20180524 PL - England TA - Pigment Cell Melanoma Res JT - Pigment cell & melanoma research JID - 101318927 RN - 0 (Indoles) RN - 0 (Melanins) RN - 12627-86-0 (eumelanin) RN - 4790-08-3 (5,6-dihydroxy-2-indolylcarboxylic acid) RN - Z3OC8499KG (5,6-dihydroxyindole) SB - IM MH - Animals MH - Birds MH - Calibration MH - Feathers/chemistry MH - Indoles/analysis MH - Melanins/chemistry/*metabolism MH - Pigmentation MH - Reproducibility of Results MH - Spectrum Analysis, Raman/*methods OTO - NOTNLM OT - DHI OT - DHICA OT - ROS OT - Raman spectroscopy OT - eumelanins OT - melanogenesis EDAT- 2018/05/09 06:00 MHDA- 2019/04/09 06:00 CRDT- 2018/05/09 06:00 PHST- 2018/03/02 00:00 [received] PHST- 2018/04/19 00:00 [revised] PHST- 2018/04/20 00:00 [accepted] PHST- 2018/05/09 06:00 [pubmed] PHST- 2019/04/09 06:00 [medline] PHST- 2018/05/09 06:00 [entrez] AID - 10.1111/pcmr.12707 [doi] PST - ppublish SO - Pigment Cell Melanoma Res. 2018 Nov;31(6):673-682. doi: 10.1111/pcmr.12707. Epub 2018 May 24.