Electron spin resonance investigation of small spin probes in aqueous and vesicle phases of mixed membranes made from poly(oxyethylene) hydrogenated castor oil and hexadecane

Small spin probes in the vesicle and aqueous phases of mixed membranes made from poly(oxyethylene) hydrogenated castor oil (HCO) and hexadecane were investigated by ESR (electron spin resonance) spectroscopy. Partitioning (partition coefficients), rotational correlation times, and activation energies of the spin probes in the vesicle phase were determined. The quantitative results obtained by an ESR simulation indicated that the spin probe DTBN (di-tert-butyl nitroxide), in the vesicle of the mixed membrane, was partitioned similar to that of TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl) at 50 degrees C, and the partitioning for both probes showed no abrupt change across the temperatures examined. The results differed considerably from conventional analyses of the high-field signal intensities. Activation energies obtained by the simulation for DTBN and TEMPO were 21 and 20 kJ/mol, respectively. In addition, the hyperfine values of 15.8 (DTBN) and 16.1 G (TEMPO) in the vesicle phase were consistent with the activation energies and supported the probe environments in the membrane. Thus, the present ESR results provided detailed information regarding the probe behavior in the membrane.