Cold physical plasmas are emerging tools for wound care and cancer control that deliver reactive oxygen species (ROS) and nitrogen species (RNS). Alongside direct effects on cellular signaling processes, covalent modification of biomolecules may contribute to the observed physiological consequences. The potential of ROS/RNS generated by two different plasma sources (kINPen and COST-Jet) to introduce post-translational modifications (PTMs) in the peptides angiotensin and bradykinin was explored. While the peptide backbone was kept intact, a significant introduction of oxidative PTMs was observed. The modifications cluster at aromatic (tyrosine, histidine, and phenylalanine) and neutral amino acids (isoleucine and proline) with the introduction of one, two, or three oxygen atoms, ring cleavages of histidine and tryptophan, and nitration/nitrosylation predominantly observed. Alkaline and acidic amino acid (arginine and aspartic acid) residues showed a high resilience, indicating that local charges and the chemical environment at large modulate the attack of the electron-rich ROS/RNS. Previously published simulations, which include only OH radicals as ROS, do not match the experimental results in full, suggesting the contribution of other short-lived species, i.e., atomic oxygen, singlet oxygen, and peroxynitrite. The observed PTMs are relevant for the biological activity of peptides and proteins, changing polarity, folding, and function. In conclusion, it can be assumed that an introduction of covalent oxidative modifications at the amino acid chain level occurs during a plasma treatment. The introduced changes, in part, mimic naturally occurring patterns that can be interpreted by the cell, and subsequently, these PTMs allow for prolonged secondary effects on cell physiology.

中文翻译：

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冷等离子体衍生的活性氧和氮物种对肽的非酶促翻译后修饰

冷物理等离子体是用于伤口护理和癌症控制的新兴工具，可提供活性氧 (ROS) 和氮 (RNS)。除了对细胞信号过程的直接影响外，生物分子的共价修饰可能有助于观察到的生理后果。探索了由两种不同的血浆来源（kINPen 和 COST-Jet）产生的 ROS/RNS 在肽血管紧张素和缓激肽中引入翻译后修饰 (PTM) 的潜力。虽然肽骨架保持完整，但观察到氧化性 PTM 的显着引入。修饰聚集在芳香族（酪氨酸、组氨酸和苯丙氨酸）和中性氨基酸（异亮氨酸和脯氨酸）处，引入一个、两个或三个氧原子，组氨酸和色氨酸的环裂解，主要观察到硝化/亚硝基化。碱性和酸性氨基酸（精氨酸和天冬氨酸）残基显示出高弹性，表明局部电荷和化学环境在很大程度上调节了富含电子的 ROS/RNS 的攻击。先前发表的模拟仅包括 OH 自由基作为 ROS，与实验结果不完全匹配，表明其他短寿命物种的贡献，即原子氧、单线态氧和过氧亚硝酸盐。观察到的 PTM 与肽和蛋白质的生物活性、改变极性、折叠和功能有关。总之，可以假设在氨基酸链水平引入共价氧化修饰发生在等离子体处理期间。部分引入的变化，