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Catalytic Deuterium Evolution and H/D Exchange in DNA
ChemElectroChem ( IF 3.5 ) Pub Date : 2018-11-30 , DOI: 10.1002/celc.201801214 Vlastimil Dorčák 1 , Emil Paleček 1
ChemElectroChem ( IF 3.5 ) Pub Date : 2018-11-30 , DOI: 10.1002/celc.201801214 Vlastimil Dorčák 1 , Emil Paleček 1
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Recently, it has been shown that DNA catalyzes the hydrogen evolution reaction (HER) at mercury‐containing electrodes, which provide voltammetric and chronopotentiometric stripping (CPS) peaks 
, allowing label‐free DNA determination at very low concentrations. Here, we compared DNA catalytic HER in H2O with catalytic deuterium evolution reaction (DER) in D2O. We show that in D2O single‐stranded (ss) and double‐stranded (ds) DNAs produced CPS peaks 
due to DER. Compared to peaks 
obtained in H2O, peaks 
were smaller and appeared at more negative potentials. Under conditions where dsDNA did not produce any peak 
in D2O, this DNA produced in H2O peak 
. These results suggested a lack of accessible bases in the D2O surface‐attached dsDNA. This might be attributed to the greater stability of deuterated dsDNA, better resisting the electric field effects at the negatively charged interface. The process of protonation of deuterated ssDNA was very fast in contrast to that of dsDNA, which was much slower and could be followed by CPS in a time range of tens of minutes.
中文翻译：
DNA中的催化氘演化和H / D交换
最近，有研究表明，DNA可以在含汞电极上催化氢释放反应（HER），从而提供伏安和计时电位溶出（CPS）峰
，从而可以在非常低的浓度下测定无标记的DNA。这里，我们比较DNA催化HER H中2 ö与d催化氘析出反应（DER）2 O.我们表明，在d 2 ö单链（ss）和双链（DS）的DNA所产生的峰值CPS由于DER。与在H 2 O中获得的峰相比，峰更小并且出现在更大的负电位上。在dsDNA在D 2 O中不产生任何峰的条件下，该DNA在H中产生2 O峰
。这些结果表明，D 2 O表面附着的dsDNA中缺少可及的碱基。这可能归因于氘代dsDNA的稳定性更高，可以更好地抵抗带负电荷的界面处的电场效应。与dsDNA相比，氘代ssDNA的质子化过程非常快，而dsDNA质子化过程要慢得多，并且CPS可能会在数十分钟的时间范围内使质子化。
更新日期：2018-11-30
, allowing label‐free DNA determination at very low concentrations. Here, we compared DNA catalytic HER in H2O with catalytic deuterium evolution reaction (DER) in D2O. We show that in D2O single‐stranded (ss) and double‐stranded (ds) DNAs produced CPS peaks due to DER. Compared to peaks obtained in H2O, peaks were smaller and appeared at more negative potentials. Under conditions where dsDNA did not produce any peak in D2O, this DNA produced in H2O peak
. These results suggested a lack of accessible bases in the D2O surface‐attached dsDNA. This might be attributed to the greater stability of deuterated dsDNA, better resisting the electric field effects at the negatively charged interface. The process of protonation of deuterated ssDNA was very fast in contrast to that of dsDNA, which was much slower and could be followed by CPS in a time range of tens of minutes.
中文翻译：
DNA中的催化氘演化和H / D交换
最近，有研究表明，DNA可以在含汞电极上催化氢释放反应（HER），从而提供伏安和计时电位溶出（CPS）峰
，从而可以在非常低的浓度下测定无标记的DNA。这里，我们比较DNA催化HER H中2 ö与d催化氘析出反应（DER）2 O.我们表明，在d 2 ö单链（ss）和双链（DS）的DNA所产生的峰值CPS由于DER。与在H 2 O中获得的峰相比，峰更小并且出现在更大的负电位上。在dsDNA在D 2 O中不产生任何峰的条件下，该DNA在H中产生2 O峰
。这些结果表明，D 2 O表面附着的dsDNA中缺少可及的碱基。这可能归因于氘代dsDNA的稳定性更高，可以更好地抵抗带负电荷的界面处的电场效应。与dsDNA相比，氘代ssDNA的质子化过程非常快，而dsDNA质子化过程要慢得多，并且CPS可能会在数十分钟的时间范围内使质子化。
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