Bottom-Up Approach to Eumelanin Photoprotection: Emission Dynamics in Parallel Sets of Water-Soluble 5,6-Dihydroxyindole-Based Model Systems

A. Corani, Jannetje Maria Huijser, A. Iadonise, A. Pezzella, V. Sundström, M. d'Ischa

Research output: Contribution to journalArticleAcademicpeer-review

20 Citations (Scopus)

Abstract

The molecular mechanisms by which the black eumelanin biopolymers exert their photoprotective action on human skin and eyes are still poorly understood, owing to critical insolubility and structural heterogeneity issues hindering direct investigation of excitation and emission behavior. Recently, we set up strategies to obtain water-soluble 5,6-dihydroxyindole (DHI)-based polymers as useful models for disentangling intrinsic photophysical properties of eumelanin components from aggregation and scattering effects. Herein, we report the absorption properties and ultrafast emission dynamics of two separate sets of DHI-based monomer–dimer–polymer systems which were made water-soluble by means of poly(vinyl alcohol) or by galactosyl-thio substitution. Data showed that dimerization and polymerization of DHI result in long-lived excited states with profoundly altered properties relative to the monomer and that glycosylation of DHI imparts monomer-like behavior to oligomers and polymers, due to steric effects hindering planar conformations and efficient interunit electron communication. The potential of S-glycation as an effective tool to probe and control emission characteristics of eumelanin-like polymers is disclosed.
Original languageEnglish
Pages (from-to)13151-13158
JournalJournal of physical chemistry B
Volume116
Issue number44
DOIs
Publication statusPublished - 2012

Fingerprint

Polymers
Water
polymers
monomers
Monomers
water
Glycosylation
Dimerization
biopolymers
Biopolymers
Emission control
dimerization
oligomers
Oligomers
Excited states
excitation
Conformations
Skin
alcohols
Alcohols

Keywords

  • IR-84719
  • METIS-289281
  • PhysicsTechnological sciencesOptics (see also 3311)Overig onderzoek in de civiele sectorProduktie van instrumenten

Cite this

@article{da01e7d74d4644c6bf9875f81dabe663,
title = "Bottom-Up Approach to Eumelanin Photoprotection: Emission Dynamics in Parallel Sets of Water-Soluble 5,6-Dihydroxyindole-Based Model Systems",
abstract = "The molecular mechanisms by which the black eumelanin biopolymers exert their photoprotective action on human skin and eyes are still poorly understood, owing to critical insolubility and structural heterogeneity issues hindering direct investigation of excitation and emission behavior. Recently, we set up strategies to obtain water-soluble 5,6-dihydroxyindole (DHI)-based polymers as useful models for disentangling intrinsic photophysical properties of eumelanin components from aggregation and scattering effects. Herein, we report the absorption properties and ultrafast emission dynamics of two separate sets of DHI-based monomer–dimer–polymer systems which were made water-soluble by means of poly(vinyl alcohol) or by galactosyl-thio substitution. Data showed that dimerization and polymerization of DHI result in long-lived excited states with profoundly altered properties relative to the monomer and that glycosylation of DHI imparts monomer-like behavior to oligomers and polymers, due to steric effects hindering planar conformations and efficient interunit electron communication. The potential of S-glycation as an effective tool to probe and control emission characteristics of eumelanin-like polymers is disclosed.",
keywords = "IR-84719, METIS-289281, PhysicsTechnological sciencesOptics (see also 3311)Overig onderzoek in de civiele sectorProduktie van instrumenten",
author = "A. Corani and Huijser, {Jannetje Maria} and A. Iadonise and A. Pezzella and V. Sundstr{\"o}m and M. d'Ischa",
year = "2012",
doi = "10.1021/jp306436f",
language = "English",
volume = "116",
pages = "13151--13158",
journal = "Journal of physical chemistry B",
issn = "1520-6106",
publisher = "American Chemical Society",
number = "44",

}

Bottom-Up Approach to Eumelanin Photoprotection: Emission Dynamics in Parallel Sets of Water-Soluble 5,6-Dihydroxyindole-Based Model Systems. / Corani, A.; Huijser, Jannetje Maria; Iadonise, A.; Pezzella, A.; Sundström, V.; d'Ischa, M.

In: Journal of physical chemistry B, Vol. 116, No. 44, 2012, p. 13151-13158.

Research output: Contribution to journalArticleAcademicpeer-review

TY - JOUR

T1 - Bottom-Up Approach to Eumelanin Photoprotection: Emission Dynamics in Parallel Sets of Water-Soluble 5,6-Dihydroxyindole-Based Model Systems

AU - Corani, A.

AU - Huijser, Jannetje Maria

AU - Iadonise, A.

AU - Pezzella, A.

AU - Sundström, V.

AU - d'Ischa, M.

PY - 2012

Y1 - 2012

N2 - The molecular mechanisms by which the black eumelanin biopolymers exert their photoprotective action on human skin and eyes are still poorly understood, owing to critical insolubility and structural heterogeneity issues hindering direct investigation of excitation and emission behavior. Recently, we set up strategies to obtain water-soluble 5,6-dihydroxyindole (DHI)-based polymers as useful models for disentangling intrinsic photophysical properties of eumelanin components from aggregation and scattering effects. Herein, we report the absorption properties and ultrafast emission dynamics of two separate sets of DHI-based monomer–dimer–polymer systems which were made water-soluble by means of poly(vinyl alcohol) or by galactosyl-thio substitution. Data showed that dimerization and polymerization of DHI result in long-lived excited states with profoundly altered properties relative to the monomer and that glycosylation of DHI imparts monomer-like behavior to oligomers and polymers, due to steric effects hindering planar conformations and efficient interunit electron communication. The potential of S-glycation as an effective tool to probe and control emission characteristics of eumelanin-like polymers is disclosed.

AB - The molecular mechanisms by which the black eumelanin biopolymers exert their photoprotective action on human skin and eyes are still poorly understood, owing to critical insolubility and structural heterogeneity issues hindering direct investigation of excitation and emission behavior. Recently, we set up strategies to obtain water-soluble 5,6-dihydroxyindole (DHI)-based polymers as useful models for disentangling intrinsic photophysical properties of eumelanin components from aggregation and scattering effects. Herein, we report the absorption properties and ultrafast emission dynamics of two separate sets of DHI-based monomer–dimer–polymer systems which were made water-soluble by means of poly(vinyl alcohol) or by galactosyl-thio substitution. Data showed that dimerization and polymerization of DHI result in long-lived excited states with profoundly altered properties relative to the monomer and that glycosylation of DHI imparts monomer-like behavior to oligomers and polymers, due to steric effects hindering planar conformations and efficient interunit electron communication. The potential of S-glycation as an effective tool to probe and control emission characteristics of eumelanin-like polymers is disclosed.

KW - IR-84719

KW - METIS-289281

KW - PhysicsTechnological sciencesOptics (see also 3311)Overig onderzoek in de civiele sectorProduktie van instrumenten

U2 - 10.1021/jp306436f

DO - 10.1021/jp306436f

M3 - Article

VL - 116

SP - 13151

EP - 13158

JO - Journal of physical chemistry B

JF - Journal of physical chemistry B

SN - 1520-6106

IS - 44

ER -