Cross-polarization/magic-angle-spinning nuclear magnetic resonance in selectively 13C-labeled synthetic eumelanins.
We report a solid-state NMR study of synthetic eumelanins prepared by oxidation of 5,6-dihydroxyindole (DHI) selectively 13C-labeled at positions 2 or 3 of the indole ring. The 13C-1H couplings have been used to quantify the carbons by selecting the non-protonated and protonated carbon resonances. By comparing the data of non-labeled melanin to that obtained using [2-(13)C]- and [3-(13)C]-enriched DHI, it was possible to clearly demonstrate the high chemical reactivity of position 2 and, to a lesser extent, position 3 of the DHI unit. These two sites together are responsible for three-quarters of the proton loss during polymerization. The cross-polarization/magic-angle-spinning spectra likewise point to a partial oxidation of positions 2 and 3 to the carboxyl and carbonyl oxidation states during the formation of melanin. Furthermore, it is shown that 13C-13C dipolar interactions in [2-(13)C]-enriched DHI melanins can be observed using radiofrequency-driven dipolar recoupling (RFDR) 2D experiments. An upper limit of about 4 A for the distance between the C-2 carbons is deduced from the RFDR experiments. This result is in agreement with the basic arrangement of the different atoms expected in the DHI melanins.
Reinheimer
P
P
Institut de Chimie, UMR 7510 CNRS, Bruker S.A., Université Louis Pasteur, Strasbourg, France.
Hirschinger
J
J
Granger
P
P
Breton
P
P
Lagrange
A
A
Gilard
P
P
Lefebvre
M A
MA
Goetz
N
N
D002247:Carbon Isotopes; D009682:Magnetic Resonance Spectroscopy / Q000379:methods*; D008543:Melanins / Q000737:chemistry*
D002247:Carbon Isotopes; D008543:Melanins; C041877:eumelanin