Radiation-induced binding of methanol, ethanol and 1-butanol to haemoglobin

Aqueous solutions of haemoglobin were irradiated under N2 and under N2O in the presence of methanol, ethanol and 1-butanol, which were partly 14C-labelled. The amount of bound alcohol was measured after gel filtration on Sephadex G-100 and with sodium dodecyl sulphate on Sepharose 6B-CL. All alcohols became covalently linked to haemoglobin. After radiolysis under N2 the G values for the three different alcohols were very similar, but under N2O the yield of cross-linking of haemoglobin with 1-butanol is twice that of methanol or ethanol. The high degree of modification by butanol results in extensive dissociation to dimers. Possible mechanisms yielding covalent cross-links between alcohols and haemoglobin are discussed. The high G value for cross-linking with butanol suggests that butanol radicals can add very efficiently to double bonds.