A series of n-alkyl hydroperoxides are separated by HPLC and detected
by their postcolumn reaction with horseradish peroxidase and p-hydroxy
phenylacetic acid (HPAA) to yield a fluorescent product; several secon
dary and tertiary hydroperoxides, some 1-hydroxyalkyl hydroperoxides,
and a few branched hydroperoxides are also examined, n-Alkyl hydropero
xides up to at least C-18 react with the enzyme with only minimally re
duced efficiency at greater alkyl chain length, The effects of the col
umn, the eluent, and the pH of the sample reaching the detector are de
scribed, The detection limit with gradient elution ranges from 0.4 mu
mol L-1 for n-hexyl hydroperoxide to 1 mu mol L-1 for n-octadecyl hydr
operoxide.