チオール含有マトリックスを用いた抗腫瘍抗生物質のMALDI-MS分析

抄録

The diynene natural products are effective drugs for cancer or leukemia owing to their strong DNA cleavage activity. Bioreduction triggers Masamune–Bergman cyclization of their diynene portion producing a 1,4-dehydrobenzene diradical species, and it abstracts two hydrogens from deoxyribose. MALDI mass spectrum of Esperamicin-A₁, one of the first isolated diynene antibiotics, with thiol containing matrix (2,5-diamino-1,4-benzenedithiol) gave peaks of the cleavage of the trisulfide with thiols (m/z 1248) and cyclized analyte (m/z 1250, Esperamicin-Z).However, three matrices including 2,3-diaminonaphthol gave no peaks of Esperamicin-Z, while it gave peaks of m/z 1248. The results suggested that thiol group of matrix has influence on cyclization mechanism of the diynene portion.