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-A_(1), 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.
展开▼
机译:由于其强烈的DNA切割活性,副植物天然产物是癌症或白血病的有效药物。生物保养触发器Masamune-Bergman对其脱卤物质的脱卤部分的环化,并摘要来自脱氧氧化物的两个氢。 Esperamicin-A_(1)的MALDI质谱,首批分离的脱炔烯抗生素之一,含有硫醇的基质(2,5-二氨基-1,4-苯并二醇),得到三硫化物与硫醇的裂解的峰( M / z 1248)和循环分析物( m / z 1250,esperamicin-z)。但是,包括2,3-二氨基萘醇的三种基质没有给予Esperamicin-z的峰,而它使 M / Z 1248.结果表明,基质的硫醇基对脱炔烯部分的环化机制有影响。
展开▼