A relationship between amide hydrogen bond strength and quinone reduction potential: Implications for photosystem I and bacterial reaction center quinone function

A series of 11 simple phylloquinone derivatives, each lacking the extended phytyl side chain but featuring H-bond donor amides at one or both peri positions, were prepared and some salient physical properties were measured. A correlation between both IR frequency and NMR peak position, as indicators of internal H-bond strength, and the quinone half-wave reduction potential, was observed. These data are consistent with the prevailing hypothesis that quinone carbonyl H-bonding in general, and stronger H-bonds in particular, favorably bias the endogenous quinone’s electrochemical potential toward easier reduction.

Graphical abstractPeri-amide-substituted naphthoquinones were synthesized and their reduction potentials, N–H IR and N–H 1H NMR absorptions were recorded.Figure optionsDownload full-size imageDownload as PowerPoint slide