The reaction of styrene oxide with DNA components was studied using se
paration by capillary zone electrophoresis (CZE) and detection by nega
tive-ion electrospray mass spectrometry (MS). The CZE-MS interface was
built for a sector field mass spectrometer. The reaction of styrene o
xide with mononucleotides (dGMP, dAMP) was used to optimize the releva
nt separation parameters and to gather the first information about the
behaviour of the possible products. With these mixtures, sample stack
ing procedures were developed and the scope of collision-induced disso
ciations were studied. From the fragments recorded, information about
the reaction sites in the nucleotides was obtained. Further, the react
ion with intact calf thymus DNA was investigated. The DNA was digested
into oligonucleotides using the previously described approach with Be
nzonase, an unspecific nuclease, and alkaline phosphatase. Styrene oxi
de mono-adducts in dinucleotides, trinucleotides and tetranucleotides
were detected, whereas pentanucleotides exhibit mono- and discernible
amounts of di-adducts. The hexanucleotides were generally modified twi
ce. The alkylated species moved faster than the unmodified oligomers.