‘Venus trapped, Mars transits’: Cu and Fe redox chemistry, cellular topography and in situ ligand binding in terrestrial isopod hepatopancreas

Woodlice efficiently sequester copper (Cu) in ‘cuprosomes’ within hepatopancreatic ‘S’ cells. Binuclear ‘B’ cells in the hepatopancreas form iron (Fe) deposits; these cells apparently undergo an apocrine secretory diurnal cycle linked to nocturnal feeding. Synchrotron-based m-focus X-ray spectroscopy undertaken on thin sections was used to characterize the ligands binding Cu and Fe in S and B cells of Oniscus asellus (Isopoda). Main findings were: (i) morphometry confirmed a diurnal B-cell apocrine cycle; (ii) X-ray fluorescence (XRF) mapping indicated that Cu was co-distributed with sulfur (mainly in S cells), and Fe was co-distributed with phosphate (mainly in B cells); (iii) XRF mapping revealed an intimate morphological relationship between the basal regions of adjacent S and B cells; (iv) molecular modelling and Fourier transform analyses indicated that Cu in the reduced Cuþ state is mainly coordinated to thiol-rich ligands (Cu–S bond length 2.3 A˚ ) in both cell types, while Fe in...