Differential reactivities of hypochlorous and hypobromous acids with purified Escherichia coli phospholipid:: formation of haloamines and halohydrins
Differential reactivities of hypochlorous and hypobromous acids with purified Escherichia coli phospholipid:: formation of haloamines and halohydrins
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DOI：
10.1016/s0005-2760(98)00038-1
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发表时间：
1998-06-15
期刊：
影响因子：
--
通讯作者：
Winterbourn, CC
中科院分区：
文献类型：
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作者：
Carr, AC;van den Berg, JJM;Winterbourn, CC
次氯酸（HOCl）和次溴酸（HOBr）是来自髓过氧化物酶和嗜酸性粒细胞过氧化物酶的强氧化剂，髓过氧化物酶和嗜酸性粒细胞过氧化物酶分别是中性粒细胞和嗜酸性粒细胞的主要抗菌酶。这些氧化剂与各种生物分子具有高度反应性。在生理pH下，HOCl和HOBr都容易与胺反应形成卤代胺，并与脂肪酸的不饱和键反应形成卤代醇。我们已经调查了这些反应发生与磷脂酰乙醇胺（PE），大肠杆菌的主要磷脂。用TLC和比色法测定卤代胺的形成，用TLC和GC-MS测定卤代醇的形成。用HOCl，氯胺是更优选的产物，只有当HOCl超过将胺转化为二氯胺所需的量时，才形成大量的氯代醇。所有浓度的HOBr。溴胺和溴代醇同时形成，表明与不饱和脂肪酸的相对反应性大于与HOCl的相对反应性。发现PE和其它伯胺的溴胺衍生物比等效的氯胺更具反应性，并且能够溴化脂肪酸的不饱和键。因此，溴醇（直接形成或通过溴胺的作用形成）可能是体内产生HOBr的合适生物标志物。(C)1998年Elsevier Science B.V.
Hypochlorous (HOCl) and hypobromous (HOBr) acids are strong oxidants derived from myeloperoxidase and eosinophil peroxidase, the major antimicrobial enzymes of neutrophils and eosinophils, respectively. These oxidants are highly reactive with a wide range of biomolecules. At physiological pH, both HOCl and HOBr react readily with amines to form haloamines and with the unsaturated bonds of fatty acids to form halohydrins. We have investigated which of these reactions occur with phosphatidylethanolamine (PE), the predominant phospholipid of Escherichia coli. The formation of haloamines was determined by TLC and colorimetrically and the formation of halohydrins was determined by TLC and GC-MS. With HOCl, chloramines were much the preferred product and chlorohydrins were formed in substantial amounts only when HOCl was in excess of the amount required to convert the amine to the dichloramine. With HOBr at all concentrations. bromamines and bromohydrins were formed concurrently, indicating a greater relative reactivity with unsaturated fatty acids than with HOCl, The bromamine derivatives of PE, and other primary amines, were found to be more reactive than the equivalent chloramines, and were able to brominate the unsaturated bonds of fatty acids. Bromohydrins (formed directly or through the action of bromamines) may, therefore, be suitable biomarkers for the production of HOBr in vivo. (C) 1998 Elsevier Science B.V.