Proton-hole transfer

Figure 2.5 Relative energetics of the Grotthuss and proton-hole-transfer mechanisms as a function of the )Ka values. (Reproduced with permission from ref. 30.)...

A sketch of different stages of the interpolation in case of a proton and proton-hole transfer is depicted in Fig. 4.6. It can be seen that for a H-transfer the locator particle migrates into the same direction as the proton, whereas the directions are opposite in case of the proton-hole. 

Figure 7-4. Excess coordination number plots for (a) MEP (three-water-bridge) [27] and (b) PMF (H64 in ) [14] simulations for the proton transfer in CAII. Note that the MEP calculation follows a very concerted mechanism while PMF simulation follows a step-wise proton hole mechanism...

Experiments with methyl guanine (27), in which the acidic proton of the radical cation is exchanged by a methyl group, support this explanation [22]. With this base in a mismatch situation (strand 25) the hole transfer becomes efficient again because a deprotonation cannot occur (Fig. 15). 

These experiments demonstrate the importance of proton transfer processes during hole transfer through DNA. S. Steenken has already remarked that a proton shift between the G C bases stabilizes the positive charge [23]. If such a proton shift is coupled with the hole shift, a deuterium isotope effect should arise. Actually, H/D isotope effects are described by V. Shafiro-vich, M.D. Sevilla as well as H.H. Thorp in their articles of this volume. Experiments with our assay [22] also demonstrate (Fig. 16) that hole transfer in protonated DNA (H20 as solvent) is three times more efficient than in deuterated DNA (D20 as solvent). If this reflects a primary isotope effect, it shows that the charge transfer is coupled with a proton transfer. 

Fig. 16 Influence of the exchange of protons (H20) by deuterons (D20) on the efficiency of the hole transfer, measured by the product ratios Pqgg/Pg...

The low-temperature EPR experiments used to determine the DNA ion radical distribution make it very clear that electron and hole transfer occurs after the initial random ionization. What then determines the final trapping sites of the initial ionization events To determine the final trapping sites, one must determine the protonation states of the radicals. This cannot be done in an ordinary EPR experiment since the small hyperfine couplings of the radicals only contribute to the EPR linewidth. However, detailed low-temperature EPR/ENDOR (electron nuclear double resonance) experiments can be used to determine the protonation states of the low-temperature products [17]. These proto-nation/deprotonation reactions are readily observed in irradiated single crystals of the DNA base constituents. The results of these experiments are that the positively charged radical cations tend to deprotonate and the negatively charged radical anions tend to protonate. 

Ionization of DNA s solvation shell produces water radical cations (H20 ) and fast electrons. The fate of the hole is dictated by two competing reactions hole transfer to DNA and formation of HO via proton transfer. If the ionized water is in direct contact with the DNA (F < 10), hole transfer dominates. If the ionized water is in the next layer out (9 < r < 22), HO formation dominates [67,89,90]. The thermalized excess electrons attach preferentially to bases, regardless of their origin. Thus the yield of one-electron reduced bases per DNA mass increases in lockstep with increasing F, up to an F of 20-25. This means that when F exceeds 9, there will be an imbalance between holes and electrons trapped on DNA, the balance of the holes being trapped as HO . At F = 17, an example where the water and DNA masses are about equal, the solvation shell doubles the number of electron adducts, increasing the DNA-centered holes by a bit over 50% [91-93]. 

Very Shallow Traps. It has been proposed that the neutral Gua(Nl—H) radical, formed by proton transfer from the Gua radical by proton transfer from N1 of Gua to N3 of Cyt, is a shallow trap [143,144]. This proposal is based on projections from made on monomers in dilute aqueous solution, which predict that proton transfer is favored by 2.3 kJ/mol [22,145]. Ab initio calculations are in excellent agreement with this value [146,147]. So one expects that an energy of at least 0.025 eV is needed to activate the return of the proton to N1 Gua, reforming Gua . Once Gua is reformed, tunneling to nearby guanines is reestablished as a competitive pathway. Proton transfer therefore is a gate for hole transfer. Proton-coupled hole transfer describes the thermally driven transfer of holes from one Gua Cyt base pair to another. 

Proton Transfer Coupled to Electron or Hole Transfer... 

Temperature and Proton Transfer Effects on Electron Transfer.. . 106 Hole Transfer and Localization in DNA at Low Temperatures. .. 108 Hole Transfer from the Hydration Layer to DNA. 109... 

Transfer of radiation-induced electrons and holes (H20 ) from the hydration layer of DNA has been of considerable recent interest. Results from ESR experiments at low temperatures suggest that ionization of hydration water (reaction 4) results in hole transfer to the DNA (reaction 5) [4, 24-28]. Since the proton transfer reaction (reaction 6) to form the hydroxyl radical likely occurs on the timescale of a few molecular vibrations [29], it is competitive with and limits hole transfer to DNA [27]. 

Keywords DNA Oxidative damage Proton-coupled electron transfer Hole transfer Laser flash photolysis... 

Radical formation in a mixed crystal system of cytosine monohydrate doped with small amounts of thiocytosine (ca. 0.5%) was investigated on order to gain insight into hole transfer in a well-defined crystalline system.31 Also of interest was whether the protonation state of the thiocytosine radical(s) was the same as that of the cystosine radical(s). Crystals were X-irradiated (ca. 30 kGy) and ESR and ENDOR spectra recorded at ca. 15 K. After irradiation, many types of free radicals were formed. Among these, the low field resonance from a sulfur centered radical (42), with g-tensor (2.132, 2.004, 2.002), was clearly visible. Radical 42 constituted approximately 10% of the total cohort of radicals formed in the crystal and is apparently the only sulfur-centred radical observed in this experiment. Six weakly coupled protons were observed, two of which are shown... 

Cai Z, Gu Z, Sevilla MD (2001) Electron spin resonance study of electron and hole transfer in DNA effects of hydration, aliphatic amine cations and histone proteins. J Phys Chem B 105 6031-6041 Cai Z, Li X, Sevilla MD (2002) Excess electron transfer in DNA effect of base sequence and proton transfer. J Phys Chem B 106 2755-2762... 

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