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Initiating redox reactions by ionizing radiation: A versatile, selective and quantitative tool 电离辐射引发氧化还原反应:一种多功能、选择性和定量的工具
Pub Date : 2023-05-09 DOI: 10.1016/j.rbc.2023.100004
Peter Wardman

The absorption of ionizing radiation initiates redox reactions, producing chemical species resulting from single electron loss or electron gain. Radiation chemists have developed methods to study individual redox species selectively and to monitor their reactions in real time. This has provided an enormous resource of kinetic, thermodynamic and spectroscopic information concerning the characteristics and reactions of free radicals and their redox reactions, mainly in aqueous solution. While the techniques are specialized and exploiting them is certainly more difficult than initiating redox changes by simple mixing of two chemicals or adding a reagent to a biological target, it is useful to gain an understanding of the basic mechanisms and approaches involved in exploiting radiation chemistry in the wider context of redox reactions in biochemistry, chemistry, and biology. This should enable readers both to appreciate the reliance which can be placed on the kinetic and other information resulting from such studies, as well as identify potential new applications of the technique which might be exploited in their research, by seeking partners who have access to the necessary specialized equipment or just basic irradiation facilities. This review outlines how radiation can be used to initiate selective redox reactions, mainly in water, and helps point readers to resources which should be useful in considering such reactions in a wider context.

电离辐射的吸收引发氧化还原反应,产生单电子损失或电子增益产生的化学物质。辐射化学家已经开发出选择性研究单个氧化还原物种并实时监测其反应的方法。这为主要在水溶液中的自由基及其氧化还原反应的特性和反应提供了大量的动力学、热力学和光谱信息。虽然这些技术是专门的,利用它们肯定比通过简单混合两种化学物质或向生物靶标添加试剂来引发氧化还原变化更困难,但在生物化学、化学和生物学中更广泛的氧化还原反应背景下,了解利用辐射化学的基本机制和方法是有用的。这应使读者既能理解对此类研究产生的动力学和其他信息的依赖,又能通过寻找能够获得必要专业设备或基本辐照设施的合作伙伴,确定该技术在研究中可能被利用的潜在新应用。这篇综述概述了如何使用辐射来引发选择性氧化还原反应,主要是在水中,并帮助读者找到在更广泛的背景下考虑此类反应时应该有用的资源。
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引用次数: 2
In Memoriam: Emeritus Professor Robin L. Willson 纪念:名誉教授罗宾·威尔逊
Pub Date : 2023-04-01 DOI: 10.1016/j.rbc.2022.100001
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引用次数: 0
Cross-linking between cysteine and lysine, tryptophan or tyrosine in peptides and proteins treated with hypochlorous acid and other reactive halogens 用次氯酸和其他活性卤素处理的多肽和蛋白质中半胱氨酸和赖氨酸、色氨酸或酪氨酸之间的交联
Pub Date : 2023-04-01 DOI: 10.1016/j.rbc.2023.100002
Nicholas J. Magon, Rufus Turner, Anthony J. Kettle, Christine C. Winterbourn

Cysteine residues are the most favored targets for oxidation by hypochlorous acid and other reactive halogen species. The end-products of cysteine oxidation are usually considered to be reversibly formed disulfides and the more highly oxidized sulfinic and sulfonic acids. However, reactive halogen species are capable of generating additional products in which cysteine is cross-linked to other amino acids. Here we have treated a range of peptides with hypochlorous acid (HOCl) and hypobromous acid (HOBr), and used mass spectrometry to demonstrate sulfenamide, sulfinamide and sulfonamide formation with lysine residues, as well as –S(O)- and –S(O2)- linkages with tyrosine, tryptophan and arginine residues. The -(SO2)- products were more prevalent with HOCl than HOBr, reflecting its higher oxidizing ability. There was also considerable variation between peptides in efficiency of cross-linking compared with other modifications. The –S(O)- and –S(O2)- forms were much more resistant than the disulfide to reduction by dithiothreitol. Using calprotectin as a representative cysteine-containing protein, we show that a range of products containing each of these cross-links is formed when the protein is treated with HOCl. Two of the identified cysteine-lysine calprotectin cross-links were also detected in bronchoalveolar lavage fluid from children with cystic fibrosis. Our results imply that cross-linked species would be formed when cysteine-containing proteins are exposed to reactive halogen species, with the nature of the specific products depending on structural features around the cysteine residue. Cross-linking could have a modulatory effect on protein function or be detrimental in causing oligomerization and aggregation.

半胱氨酸残基是次氯酸和其他活性卤素物质氧化的最有利靶点。半胱氨酸氧化的最终产物通常被认为是可逆形成的二硫化物以及氧化程度更高的亚磺酸和磺酸。然而,活性卤素物种能够产生半胱氨酸与其他氨基酸交联的额外产物。在这里,我们用次氯酸(HOCl)和次溴酸(HOBr)处理了一系列肽,并使用质谱法证明了与赖氨酸残基形成的亚磺酰胺、磺酰胺和磺酰胺,以及与酪氨酸、色氨酸和精氨酸残基结合的-S(O)和-S(O2)键。HOCl中的-(SO2)-产物比HOBr更普遍,反映出其更高的氧化能力。与其他修饰相比,肽之间的交联效率也有相当大的差异。-S(O)-和-S(O2)-形式比二硫化物更耐二硫苏糖醇还原。使用钙卫蛋白作为一种代表性的含半胱氨酸蛋白质,我们发现当用HOCl处理蛋白质时,会形成一系列含有这些交联的产物。在患有囊性纤维化的儿童的支气管肺泡灌洗液中也检测到两种已鉴定的半胱氨酸-赖氨酸钙卫蛋白交联。我们的结果表明,当含半胱氨酸的蛋白质暴露于活性卤素物种时,会形成交联物种,特定产物的性质取决于半胱氨酸残基周围的结构特征。交联可能对蛋白质功能有调节作用,或对引起低聚和聚集有害。
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引用次数: 1
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Redox Biochemistry and Chemistry
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