Cationic -migrations

Capillary zone electrophoresis also can be accomplished without an electroosmotic flow by coating the capillary s walls with a nonionic reagent. In the absence of electroosmotic flow only cations migrate from the anode to the cathode. Anions elute into the source reservoir while neutral species remain stationary. 

The electrolyte thus formed can conduct electric current by the movement of ions under the influence of an electric field. A cell using an electrolyte as a conductor and a positive and a negative electrode is called an electrolysis cell. If a direct-current voltage is appHed to a cell having inert electrode material such as platinum, the hydrogen ions (cations) migrate to the cathode where they first accept an electron and then form molecular hydrogen. The ions... 

Base Sequence Effects on Radical Cation Migration in DNA -... 

The anthraquinone group of the UAQ sensitizer is intercalated on the 3 -side of its linkage site [15]. Use of UAQ permits assessment of the directionality of long-range radical cation migration. Both AQ and UAQ enable the selective and efficient introduction of a radical cation in duplex DNA, whose lifetime is controlled by its relatively slow bimolecular reaction primarily with H20. 

In the second limiting case, the rate of reaction with H20 is presumed to be much slower than the rate of radical cation migration and independent of the specific base pair sequence surrounding the GG step. Under these circumstances, each GG step will be equally reactive, and just as much strand cleavage will be observed at the GG step farthest from the AQ as at the one closest to it. 

In the intermediate circumstance where the rate of reaction with H20 and the rate of radical cation migration are comparable, then the amount of reaction detected is somehow related to the distance from the AQ to the GG step. 

Therefore, analysis of the efficiency and pattern of strand cleavage provides information on the relative rate of radical cation migration through different DNA sequences. This is powerful information for analysis of the charge migration mechanism. 

The Base Sequence and Distance Dependence of Radical Cation Migration... 

Fig. 4 Schematic representation of long-distance radical cation migration in DNA. In AQ-DNA(l), irradiation of the anthraquinone group linked at the 5 -terminus leads to reaction at GG steps that are 27 A and 44 A from the site of charge injection. The amount of reaction observed at each guanine is represented approximately by the length of the solid arrow. In UAQ-DNA(2), irradiation of the anthraquinone leads to reaction at each of the eight GG steps. However, replacement of a G by 7,8-dihydro-8-oxoguanine (8-OxoG) introduces a deep trap that inhibits reaction at guanines on the same side of the DNA as the trap...

GG8, the radical cation must traverse five A/T base pairs. Electrochemical measurements in solution have shown that the purine bases (A and G) have considerably lower Eox than the pyrimidines (C and T), with the Eox of G estimated to be about 0.25 V below that of A [20]. It is not very likely that the Eox of bases in DNA will be the same as they are in solution, but it is generally assumed that the order of Eox will remain the same. Consequently, the radical cation at Gi of AQ-DNA(l) must traverse a bridge of five A bases to reach GG8. The process whereby the radical cation crosses such bridges has been a major point of debate in consideration of long distance radical cation migration mechanisms in DNA this issue will be discussed fully below. 

Fig. 7 Structures of AQ-linked DNA oligomers containing a regularly repeating sequence of base pairs that were used to assess the effect of base sequence effects on long-distance radical cation migration...

The hole-resting-site and polaron-like hopping models can be distinguished by the distance and sequence behavior of radical cation migration. Analysis of the hole-resting-site model leads to the prediction that the efficiency of radical cation migration will drop ca. ten-fold for each A/T base pair that separates the G resting sites [33]. 

Having an ATA sequence between assigned polarons does not always create a high barrier for radical cation migration. In AQ-DNA(IO), we assign... 

The primary conclusion that follows from the effect of base sequence on the efficiency of radical cation migration through duplex DNA is that base pairs cannot be considered in isolation. For example, the effect of placing a T in a sequence of purines depends critically on the nature and number of purines. In this regard, the effect of base sequence on radical cation transport emerges from examination of collective properties of the DNA. This is a clear indication that the charge is delocalized over several base pairs, a conclusion that is supported by extensive quantum calculations. 

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