Sugumaran M, Semensi V, Dali H, Nellaiappan K
Department of Biology, University of Massachusetts, Boston 02125.
Arch Insect Biochem Physiol. 1991;16(1):31-44. doi: 10.1002/arch.940160105.
The oxidation of 3,4-dihydroxybenzyl alcohol, one of the sclerotizing precursors for the tanning of the ootheca of cockroach Periplaneta americana, is reported for the first time. Mushroom tyrosinase catalyzed oxidation of 3,4-dihydroxybenzyl alcohol generated the corresponding quinone which was found to be unstable and readily transformed to produce 3,4-dihydroxybenzaldehyde as the stable product probably through the intermediary formation of a quinone methide. Phenoloxidase isolated from the left collateral gland of P. americana also catalyzed this new reaction. When the enzymatic oxidation of 3,4-dihydroxybenzyl alcohol was performed in the presence of a test protein such as lysozyme, the reactive species formed, caused the oligomerization of test protein. Similar studies with collateral gland proteins, failed to generate oligomers, but produced insoluble polymeric proteins. The probable fate of 3,4-dihydroxybenzyl alcohol for the tanning of cockroach ootheca is discussed.
首次报道了3,4-二羟基苄醇（美洲大蠊卵鞘鞣制的硬化前体之一）的氧化反应。蘑菇酪氨酸酶催化3,4-二羟基苄醇氧化生成相应的醌，发现该醌不稳定，可能通过醌甲基化物的中间形成，容易转化生成稳定产物3,4-二羟基苯甲醛。从美洲大蠊左附腺分离的酚氧化酶也催化了这一新反应。当在诸如溶菌酶等测试蛋白存在下进行3,4-二羟基苄醇的酶促氧化时，形成的反应性物种会导致测试蛋白寡聚化。对附腺蛋白进行的类似研究未能产生寡聚物，但产生了不溶性聚合蛋白。讨论了3,4-二羟基苄醇在美洲大蠊卵鞘鞣制中的可能命运。
