Ptasińska S, Denifl S, Scheier P, Märk T D
Institut für Ionenphysik, Leopold-Franzens Universität Innsbruck, Technikerstrasse 25, A-6020 Innsbruck, Austria.
J Chem Phys. 2004 May 8;120(18):8505-11. doi: 10.1063/1.1690231.
We have investigated experimentally the formation of anions and cations of deoxyribose sugar (C(5)H(10)O(4)) via inelastic electron interaction (attachment/ionization) using a monochromatic electron beam in combination with a quadrupole mass spectrometer. The ion yields were measured as a function of the incident electron energy between about 0 and 20 eV. As in the case of other biomolecules (nucleobases and amino acids), low energy electron attachment leads to destruction of the molecule via dissociative electron attachment reactions. In contrast to the previously investigated biomolecules dehydrogenation is not the predominant reaction channel for deoxyribose; the anion with the highest dissociative electron attachment (DEA) cross section of deoxyribose is formed by the release of neutral particles equal to two water molecules. Moreover, several of the DEA reactions proceed already with "zero energy" incident electrons. In addition, the fragmentation pattern of positively charged ions of deoxyribose also indicates strong decomposition of the molecule by incident electrons. For sugar the relative amount of fragment ions compared to that of the parent cation is about an order of magnitude larger than in the case of nucleobases. We determined an ionization energy value for C(5)H(10)O(4) (+) of 10.51+/-0.11 eV, which is in good agreement with ab initio calculations. For the fragment ion C(5)H(6)O(2) (+) we obtained a threshold energy lower than the ionization energy of the parent molecular ion. All of these results have important bearing for the question of what happens in exposure of living tissue to ionizing radiation. Energy deposition into irradiated cells produces electrons as the dominant secondary species. At an early time after irradiation these electrons exist as ballistic electrons with an initial energy distribution up to several tens of electron volts. It is just this energy regime for which we find in the present study rather characteristic differences in the outcome of electron interaction with the deoxyribose molecule compared to other nucleobases (studied earlier). Therefore, damage induced by these electrons to the DNA or RNA strands may start preferentially at the ribose backbone. In turn, damaged deoxyribose is known as a key intermediate in producing strand breaks, which are the most severe form of lesion in radiation damage to DNA and lead subsequently to cell death.
我们通过使用单色电子束结合四极质谱仪,对脱氧核糖(C₅H₁₀O₄)通过非弹性电子相互作用(附着/电离)形成阴离子和阳离子进行了实验研究。测量了离子产率作为入射电子能量在约0至20电子伏特之间的函数。与其他生物分子(核碱基和氨基酸)的情况一样,低能电子附着会通过解离电子附着反应导致分子破坏。与先前研究的生物分子不同,脱氢不是脱氧核糖的主要反应通道;脱氧核糖具有最高解离电子附着(DEA)截面的阴离子是通过释放等于两个水分子的中性粒子形成的。此外,一些DEA反应已经在“零能量”入射电子下进行。此外,脱氧核糖正离子的碎片化模式也表明分子被入射电子强烈分解。对于糖类,与母阳离子相比,碎片离子的相对量比核碱基的情况大约大一个数量级。我们确定C₅H₁₀O₄⁺的电离能值为10.51±0.11电子伏特,这与从头算计算结果吻合良好。对于碎片离子C₅H₆O₂⁺,我们获得的阈值能量低于母分子离子的电离能。所有这些结果对于活体组织暴露于电离辐射时会发生什么的问题具有重要意义。能量沉积到受辐照细胞中会产生电子作为主要的次级物种。在辐照后的早期,这些电子以具有高达几十电子伏特初始能量分布的弹道电子形式存在。正是在这个能量范围内,我们在本研究中发现,与其他核碱基(先前研究过)相比,电子与脱氧核糖分子相互作用的结果存在相当显著的差异。因此,这些电子对DNA或RNA链造成的损伤可能优先从核糖主链开始。反过来,受损的脱氧核糖是产生链断裂的关键中间体,链断裂是DNA辐射损伤中最严重的损伤形式,随后会导致细胞死亡。