Zamora Rosario, Hidalgo Francisco J
Instituto de la Grasa, Consejo Superior de Investigaciones Científicas, Avenida Padre García Tejero 4, 41012 Sevilla, Spain.
Chem Res Toxicol. 2003 Dec;16(12):1632-41. doi: 10.1021/tx034126w.
Phosphatidylethanolamine and ethanolamine were incubated with 4,5(E)-epoxy-2(E)-heptenal to analyze the changes produced in amino phospholipids as a consequence of their reaction with this lipid oxidation product. The reactions, which were followed by GC/MS or HPLC/MS, produced in a first step the corresponding imines, which later evolved into two main products. These products, which were isolated and characterized by (1)H and (13)C NMR and mass spectrometry, resulted in the corresponding phosphatidylethanolpyrroles (PEPs) and phosphatidylethanol-2-(1-hydroxypropyl)pyrroles (PEHPs). PEPs were relatively stable, but PEHPs polymerized spontaneously. This polymerization, which was followed in 4,5(E)-epoxy-2(E)-heptenal/ethanolamine incubations with the detection of the corresponding dimers and trimers, was related to the brown color and fluorescence development produced. In addition, when hydroxyalkylpyrroles were incubated in the presence of single pyrroles, mixed polymers of the two pyrroles were obtained, and these polymers were produced in a higher extent than those derived exclusively from PEHP. These results confirm that lipid oxidation products are able to react with amino phospholipids analogously to protein amino groups, and therefore, both amino phospholipids and proteins may compete for lipid oxidation products. Although these results do not demonstrate the formation of pyrrolyzed phospholipids in vivo, they suggest that analogously to pyrrolyzed proteins, these modified phospholipids are likely to be produced during the phospholipid peroxidation process. In addition, these results also provide new bases for assessing the role of phospholipid modification in certain diseases, pathophysiological conditions, and aging.
将磷脂酰乙醇胺和乙醇胺与4,5(E)-环氧-2(E)-庚烯醛一起孵育，以分析氨基磷脂因与这种脂质氧化产物反应而产生的变化。这些反应通过气相色谱/质谱联用（GC/MS）或高效液相色谱/质谱联用（HPLC/MS）进行监测，第一步产生相应的亚胺，随后亚胺演变成两种主要产物。这些产物通过氢核磁共振（¹H NMR）、碳核磁共振（¹³C NMR）和质谱进行分离和表征，结果得到相应的磷脂酰乙醇基吡咯（PEP）和磷脂酰乙醇-2-(1-羟丙基)吡咯（PEHP）。PEP相对稳定，但PEHP会自发聚合。在4,5(E)-环氧-2(E)-庚烯醛/乙醇胺孵育过程中，通过检测相应的二聚体和三聚体来跟踪这种聚合反应，它与产生的棕色和荧光有关。此外，当羟烷基吡咯在单吡咯存在下孵育时，会得到两种吡咯的混合聚合物，并且这些聚合物的生成程度高于仅由PEHP衍生的聚合物。这些结果证实，脂质氧化产物能够与氨基磷脂发生类似于与蛋白质氨基的反应，因此，氨基磷脂和蛋白质可能会竞争脂质氧化产物。虽然这些结果并未证明体内会形成吡咯化磷脂，但它们表明，类似于吡咯化蛋白质，这些修饰的磷脂可能在磷脂过氧化过程中产生。此外，这些结果还为评估磷脂修饰在某些疾病、病理生理状况和衰老中的作用提供了新的依据。
