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Simulation of EPR Spectra as a Tool for Interpreting the Degradation Pathway of Hyaluronan

机译:EPR光谱模拟作为解释透明质酸降解途径的工具

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Electron paramagnetic resonance (EPR) spin trapping is one of the choice techniques for identifying free radicals and is often used in the study of biological systems. However, its sensitivity can result in a typical complicated EPR spectrum. The accurate simulation of these systems is essential for correct identification of the radical species, whenever more than one species contributes to the spectrum. Programs implementing the linear combination of single simulations allow the interpretation of EPR spectra without modifying experimental conditions. In this study, this approach was used to investigate the influence of the ferrous ion and the role of oxygen, as well on the formation of transient radical species, in the whole mechanism of hyaluronan degradation. Degradation was carried out under different environmental conditions (air, O2, Ar, N2, N2 + CO2) and EPR spin trapping studies were performed. The advantages of the simulation of multiple species EPR spectra were applied to the obtained results and some aspects of hyaluronan degradation mechanism were elucidated. The depolymerization reaction pathway has been defined according to two possible subsequent steps: the first is consistent with formation of an amidyl radical that induces a series of strand scissions, which stabilize at two different levels of molecular weight. The second step occurs when the molecular weight is lower than before and two different adducts are generated. E. Busi and V. Travagli equally contributed to this work.
机译:电子顺磁共振(EPR)自旋俘获是识别自由基的一种选择技术,通常用于研究生物系统。但是,其灵敏度会导致典型的复杂EPR频谱。这些系统的精确模拟对于正确识别自由基种类至关重要,只要有一个以上种类对光谱有贡献即可。实现单个模拟的线性组合的程序允许在不修改实验条件的情况下解释EPR光谱。在这项研究中,此方法用于研究透明质酸降解的整个机理中亚铁离子和氧的作用以及对瞬态自由基物种形成的影响。降解是在不同的环境条件下进行的(空气,O 2 ,Ar,N 2 ,N 2 + CO 2 )和EPR自旋陷阱研究进行了。将多种EPR谱模拟的优势应用于获得的结果,并阐明了透明质酸降解机理的某些方面。解聚反应途径已根据两个可能的后续步骤进行了定义:第一个步骤与酰胺基的形成相一致,该酰胺基会诱导一系列链断裂,并稳定在两个不同的分子量水平。当分子量低于之前的分子量并生成两种不同的加合物时,发生第二步。 E. Busi和V. Travagli同样为这项工作做出了贡献。

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