Johny Melby, Schouder Constant A, Al-Refaie Ahmed, He Lanhai, Wiese Joss, Stapelfeldt Henrik, Trippel Sebastian, Küpper Jochen
Center for Free-Electron Laser Science CFEL, Deutsches Elektronen-Synchrotron DESY, Notkestrasse 85, 22607 Hamburg, Germany.
Center for Ultrafast Imaging, Universität Hamburg, Luruper Chaussee 149, 22761 Hamburg, Germany.
Phys Chem Chem Phys. 2024 May 1;26(17):13118-13130. doi: 10.1039/d3cp03471b.
Radiation-induced damage of biological matter is an ubiquitous problem in nature. The influence of the hydration environment is widely discussed, but its exact role remains elusive. Utilising well defined solvated-molecule aggregates, we experimentally observed a hydrogen-bonded water molecule acting as a radiation protection agent for ionised pyrrole, a prototypical aromatic biomolecule. Pure samples of pyrrole and pyrrole(HO) were outer-valence ionised and the subsequent damage and relaxation processes were studied. Bare pyrrole ions fragmented through the breaking of C-C or N-C covalent bonds. However, for pyrrole(HO), we observed a strong protection of the pyrrole ring through the dissociative release of neutral water or by transferring an electron or proton across the hydrogen bond. Overall, a single water molecule strongly reduces the fragmentation probability and thus the persistent radiation damage of singly-ionised pyrrole.
辐射引起的生物物质损伤是自然界中普遍存在的问题。水合环境的影响已得到广泛讨论,但其确切作用仍不明确。利用定义明确的溶剂化分子聚集体,我们通过实验观察到一个氢键结合的水分子作为原型芳香生物分子——离子化吡咯的辐射防护剂。对吡咯和吡咯(HO)的纯样品进行了外层价态电离,并研究了随后的损伤和弛豫过程。裸露的吡咯离子通过碳 - 碳或氮 - 碳共价键的断裂而碎片化。然而,对于吡咯(HO),我们观察到通过中性水的解离释放或通过氢键转移电子或质子对吡咯环有很强的保护作用。总体而言,单个水分子极大地降低了单电离吡咯的碎片化概率,从而减少了持续的辐射损伤。