{"title":"利用高频EPR光谱研究光系统I中的电子转移。纪念克劳斯教授Möbius(1936-2024)。","authors":"Vasily V. Ptushenko, Alexey Y. Semenov","doi":"10.1134/S0006297925601091","DOIUrl":null,"url":null,"abstract":"<p>Klaus Möbius, Professor at the Free University of Berlin, was an outstanding physical chemist and biophysicist. He was a pioneer in the development of high-field/high-frequency EPR spectroscopy methods and their application in the study of photosynthesis. Among the most essential are the applications in studying the charge transfer kinetics and properties of the ion-radical pairs in photosynthetic reaction centers (RC). Under his leadership and with his direct participation a unique setup allowing registration of the kinetics of the electron transfer between the (bacterio)chlorophyll dimer and quinone in the bacterial photosynthetic RC and plant photosystem I (PSI) was created. This setup also allowed precise determining of the distance between separated charges based on measuring the frequencies of the Electron Spin Echo Envelope Modulation (ESEEM). This setup made it possible to prove that electron transfer in PSI occurs mainly along the <i>A</i> branch of redox cofactors. The kinetics of backward electron transfer reaction (reoxidation of the phyllosemiquinone anion A<sub>1</sub><sup>−</sup> and reduction of the photooxidized chlorophyll dimer P<sub>700</sub><sup>+</sup>) in PSI were measured under the same conditions. The essential data on the bioprotective effect of the disaccharide trehalose on the kinetics of forward and backward electron transfer in PSI complexes were obtained. A significant slowdown in the kinetics of electron transfer due to the restriction of protein conformational mobility, as well as long-term maintaining of functional activity of PSI dried in a vitreous trehalose matrix at room temperature (i.e., subjected to a reversible anhydrobiosis) was demonstrated. These results obtained in collaboration with Prof. Möbius and Prof. Venturoli (Bologna) allowed elucidating the role of hydrogen bond network and the conformational mobility of the protein subunits in facilitating electron transfer in the photosynthetic RC.</p>","PeriodicalId":483,"journal":{"name":"Biochemistry (Moscow)","volume":"90 )\nGuest","pages":"830 - 839"},"PeriodicalIF":2.2000,"publicationDate":"2025-07-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Study of Electron Transfer in Photosystem I Using High-Frequency EPR Spectroscopy. 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This setup also allowed precise determining of the distance between separated charges based on measuring the frequencies of the Electron Spin Echo Envelope Modulation (ESEEM). This setup made it possible to prove that electron transfer in PSI occurs mainly along the <i>A</i> branch of redox cofactors. The kinetics of backward electron transfer reaction (reoxidation of the phyllosemiquinone anion A<sub>1</sub><sup>−</sup> and reduction of the photooxidized chlorophyll dimer P<sub>700</sub><sup>+</sup>) in PSI were measured under the same conditions. The essential data on the bioprotective effect of the disaccharide trehalose on the kinetics of forward and backward electron transfer in PSI complexes were obtained. A significant slowdown in the kinetics of electron transfer due to the restriction of protein conformational mobility, as well as long-term maintaining of functional activity of PSI dried in a vitreous trehalose matrix at room temperature (i.e., subjected to a reversible anhydrobiosis) was demonstrated. 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引用次数: 0
摘要
Klaus Möbius,柏林自由大学教授,杰出的物理化学家和生物物理学家。他是开发高场/高频EPR光谱方法及其在光合作用研究中的应用的先驱。其中最重要的应用是研究光合反应中心(RC)离子自由基对的电荷转移动力学和性质。在他的领导下,在他的直接参与下,建立了一个独特的装置,允许在细菌光合RC和植物光系统I (PSI)中(细菌)叶绿素二聚体和醌之间的电子转移动力学的注册。通过测量电子自旋回波包络调制(ESEEM)的频率,该装置还可以精确地确定分离电荷之间的距离。这种设置使得证明PSI中的电子转移主要沿着氧化还原辅助因子的A支发生成为可能。在相同条件下,测定了PSI中叶半醌阴离子A1-的再氧化和光氧化叶绿素二聚体P700+的还原反应动力学。获得了双糖海藻糖对PSI配合物中正向和反向电子转移动力学的生物保护作用的基本数据。由于蛋白质构象迁移率的限制,电子转移动力学的显著放缓,以及在室温下(即,遭受可逆的无水作用)在玻璃体海藻糖基质中干燥的PSI的功能活性的长期维持。这些结果是与Möbius教授和Venturoli教授(博洛尼亚)合作获得的,可以阐明氢键网络和蛋白质亚基的构象迁移率在促进光合作用RC中的电子转移中的作用。
Study of Electron Transfer in Photosystem I Using High-Frequency EPR Spectroscopy. In Memory of Professor Klaus Möbius (1936-2024)
Klaus Möbius, Professor at the Free University of Berlin, was an outstanding physical chemist and biophysicist. He was a pioneer in the development of high-field/high-frequency EPR spectroscopy methods and their application in the study of photosynthesis. Among the most essential are the applications in studying the charge transfer kinetics and properties of the ion-radical pairs in photosynthetic reaction centers (RC). Under his leadership and with his direct participation a unique setup allowing registration of the kinetics of the electron transfer between the (bacterio)chlorophyll dimer and quinone in the bacterial photosynthetic RC and plant photosystem I (PSI) was created. This setup also allowed precise determining of the distance between separated charges based on measuring the frequencies of the Electron Spin Echo Envelope Modulation (ESEEM). This setup made it possible to prove that electron transfer in PSI occurs mainly along the A branch of redox cofactors. The kinetics of backward electron transfer reaction (reoxidation of the phyllosemiquinone anion A1− and reduction of the photooxidized chlorophyll dimer P700+) in PSI were measured under the same conditions. The essential data on the bioprotective effect of the disaccharide trehalose on the kinetics of forward and backward electron transfer in PSI complexes were obtained. A significant slowdown in the kinetics of electron transfer due to the restriction of protein conformational mobility, as well as long-term maintaining of functional activity of PSI dried in a vitreous trehalose matrix at room temperature (i.e., subjected to a reversible anhydrobiosis) was demonstrated. These results obtained in collaboration with Prof. Möbius and Prof. Venturoli (Bologna) allowed elucidating the role of hydrogen bond network and the conformational mobility of the protein subunits in facilitating electron transfer in the photosynthetic RC.
期刊介绍:
Biochemistry (Moscow) is the journal that includes research papers in all fields of biochemistry as well as biochemical aspects of molecular biology, bioorganic chemistry, microbiology, immunology, physiology, and biomedical sciences. Coverage also extends to new experimental methods in biochemistry, theoretical contributions of biochemical importance, reviews of contemporary biochemical topics, and mini-reviews (News in Biochemistry).