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Inelastic electron interaction (attach ment/ionization) with deoxyribose

机译:与脱氧核糖的非弹性电子相互作用(附着/电离)

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We have investigated experimentally the formation of anions and cations of deoxyribose sugar (C_5H_(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_5H_(10)O_4~+ of 10.51+-0.11 eV,which is in good agreement with ab initio calculations.For the fragment ion C_5H_6O_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.
机译:我们使用单色电子束结合四极质谱仪,通过非弹性电子相互作用(附着/电离),通过实验研究了脱氧核糖(C_5H_(10)O_4)的阴离子和阳离子的形成,并测量了离子收率与功能的关系。大约在0至20 eV之间的入射电子能量。与其他生物分子(核碱基和氨基酸)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脱氢相反并不是脱氧核糖的主要反应通道;脱氧核糖的最大离解电子附着(DEA)截面阴离子是由释放等于两个水分子的中性粒子形成的。此外,几个DEA反应已经以“零”进行了能量”入射电子。此外,带正电的脱氧离子的碎裂模式核糖也表明分子被入射电子强烈分解。对于糖,碎片离子的数量相对于母体阳离子的相对数量大约比核碱基的数量大一个数量级。我们确定了C_5H_( 10)O_4〜+为10.51 + -0.11 eV,与从头算相符。对于碎片离子C_5H_6O_2〜+,我们获得的阈值能量低于母体分子离子的电离能,所有这些结果均得到对于活体组织暴露于电离辐射中会发生什么的问题具有重要意义。能量沉积到受辐照的细胞中会产生电子作为主要的次要物种。在辐射后的早期,这些电子以弹道电子的形式存在,初始能量分布高达数个数十个电子伏特。正是这种能量机制,我们在本研究中发现,与其他核碱基相比(先前研究),脱氧核糖分子具有更大的相互作用。因此,这些电子对DNA或RNA链引起的破坏可能优先从核糖主链开始。反过来,受损的脱氧核糖被认为是产生链断裂的关键中间体。 ,这是辐射损伤DNA并导致细胞死亡的最严重形式的病变。

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