Stelmaszyńska T, Zgliczynski J M
Eur J Biochem. 1978 Dec 1;92(1):301-8. doi: 10.1111/j.1432-1033.1978.tb12748.x.
The chlorination of dipeptides by the myeloperoxidase/H2O2/Cl- system takes place at the N-terminal amino group, whereas no chlorination of the amide nitrogen of the peptide bond can be observed. The N-terminal amino group is chlorinated to N-monochloroamine or/and N-dichloroamine. N-Monochloropeptides were the main products at higher pH values, at lower pH at mixture of N-monochloropeptides and N-dichloropeptides was formed owing to the dismutation of N-monochloroamine to N-dichloroamine. N-Monochloropeptides decompose, yielding NH3 and the corresponding N-(2-oxoacyl)amino acids. N-Dichlorodipeptides decompose faster but to nitriles and the free C-terminal amino acids. N-Dichloroglycyl-amino acid decomposes through a relatively stable intermediate (cyano-formylamino acid) to hydrogen cyanide, cyanogen chloride and the free C-terminal amino acid. Insulin chlorination also yields N-terminal glycyl and phenylalanyl N-monochloro derivatives, which deaminate to glyoxylyl and phenylpyruvyl residues.
髓过氧化物酶/H₂O₂/Cl⁻系统对二肽的氯化作用发生在N端氨基上，而肽键的酰胺氮未观察到氯化现象。N端氨基被氯化为N-一氯胺或/和N-二氯胺。在较高pH值下，N-一氯肽是主要产物，在较低pH值下，由于N-一氯胺歧化为N-二氯胺，会形成N-一氯肽和N-二氯肽的混合物。N-一氯肽分解，产生NH₃和相应的N-(2-氧代酰基)氨基酸。N-二氯二肽分解更快，但生成腈和游离的C端氨基酸。N-二氯甘氨酰氨基酸通过相对稳定的中间体（氰基甲酰氨基酸）分解为氰化氢、氯化氰和游离的C端氨基酸。胰岛素氯化还产生N端甘氨酰和苯丙氨酰N-一氯衍生物，它们脱氨基生成乙醛酰基和苯丙酮酰基残基。
