Guanine sites, oxidized

Electron and Hole Transfer to Oxidized Guanine Sites. 124... 

In addition to the sugar oxidations at A, T, and C, the guanine sites show enhanced cleavage upon piperidine treatment. This result is consistent with a second pathway involving oxidation of the guanine... 

Primary reduction sites of adenine, cytosine, and guanine and oxidation sites of adenine and guanine are shown in the Watson-Crick base pairing scheme (Figure lA). 

Since the results of our experiments with isolated rat liver fractions supported a reaction sequence Initiated by microsomal oxidation of the nitrosamine leading to formation of a carbonium ion, the results of the animal experiment suggested that in the intact hepatocyte, one of the earlier electrophilic intermediates (II, III or V, Figure 1) is intercepted by nucleophilic sites in DNA (exemplified here by the N7 position of guanine) before a carbocation is formed. 

With the site-selective hole injection and the hole trapping device established, the efficiency of the hole transport between the hole donor and acceptor, especially with respect to the distance and sequence dependence, were examined. Our experiments showed that hole transport between two guanines was extremely inefficient when the intervening sequence consisted of more than 5 A-T base pairs [1]. Hole injection into the DNA n-stack using photoexcited dCNBPU was accompanied by the formation of dCNBPU anion radical. Therefore, hole transport would always compete with the back electron transfer (BET). To minimize the effect of BET, we opted for hole transport between G triplets, that are still lower in oxidation potential than G doublet. With this experimental system, we researched the effect of the bridging sequence between two G triplets on the efficiency of hole transport [2]. 

Fig. 9 Illustrations of the charge transport in duplex 37/38, a in the absence and b in the presence of BamH I. Horizontal arrows and the numbers shown on the site of guanine oxidation indicate the band intensity relative to that of G24 in the protein bound duplex... 

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