The Electronic Property Differences between dA::dG and dA::dGoxo. A Theoretical Approach

The dA::dGoxo pair appearing in nucleic ds-DNA can lead to a mutation in the genetic information. Depending on the dGoxo source, an AT→GC and GC→AC transversion might be observed. As a result, glycosylases are developed during the evolution, i.e., OGG1 and MutY. While the former effectively removes Goxo from the genome, the second one removes adenine from the dA::dGoxo and dA:dG pair. However, dA::dGoxo is recognized by MutY as ~6–10 times faster than dA:dG. In this article, the structural and electronic properties of simple nucleoside pairs dA:dG, dC:::dGoxo, dC:::dG, dA::dGoxo in the aqueous phase have been taken into theoretical consideration. The influence of solvent relaxation on the above is also discussed. It can be concluded that the dA::dGoxo nucleoside pair shows a lower ionization potential and higher electron affinity than the dA:dG pair in both a vertical and adiabatic mode. Therefore, it could be predicted, under electronic properties, that the electron ejected, for instance by a MutY 4[Fe-S]2+ cluster, is predisposed to trapping by the ds-DNA part containing the dA::dGoxo pair rather than by dA::dG.

A study on hybrid oligomeric type II photoinitiator

Preparing tailor-made hybrid photoinitiator (PI) for specific applications continues to gain momentum. The hybrid PIs comprising both H-abstraction chromophore and coinitiator moiety are the candidate materials with energy-saving and environment-protection in the photo-curing field. So two oligomeric photoinitiators (OMKs) containing benzophenone (BP) and aliphatic tert-amines chromophore in the main-chain (OMK-2) or side-chain (OMK-1) were synthesized and characterized respectively. Photophysical investigation showed that the absorption maxima of OMKs were around 340 nm, red shifted about 5-10 nm compared to BP. Their initiation efficiencies were found to be higher than that of BP and 4,4’-bis(dimethylamino)benzophenone(MK) respectively. The reaction proceeds via a simple electron-transfer/proton-transfer mechanism. Dynamic NMR data reveal that H-abstraction reacts predominantly via alpha H of aliphatic tertamines, as might be expected on the basis of the lower ionization potential and bond dissociation energy of aliphatic amines compared to aromatic amines. The reaction mechanism of H-abstraction was confirmed by using radical scavenger 2,2,6,6-tetramethylpiperidin-1-oxy(TEMPO), which acts as a probe under photolysis reaction conditions. The volatility and migration were tested under simulated conditions, the result show that OMKs exhibited very low volatility and significantly reduced migration compared to the low molecular analogs. Results showed that the OMKs are the promising candidate as higher efficient PIs with low volatile organic compounds (VOCs) emission and reduced migration. They are suitable for environmental-friendly formulations.

Impacts of Ionization Potentials and Megasonic Dispersion

It has been shown that megasonics can accelerate strip processes such as doped and plasma treated photoresist [1]. However, applied megasonic energy can also damage sensitive semiconductor devices. It was shown that adding a solvent such as IPA or lowering the temperature helps to control cavitation in semi-aqueous fluids [2]. Sonochemical reactions have been observed in various industries, however, there are no published observations in semiconductor cleaning. Ions may form in megasonic driven bubble collapse impacted by the characteristics of a gas or liquid that enters the bubble from the bulk liquid. Lower ionization potential gases or liquids may form ions earlier in the bubble collapse, so as to use up some of the total available energy through sonochemical reactions and possibly reducing the cavitations implosive energy. Here, tests are conducted to vary the liquid and gas type based on ionization potential to look into the impact this would have on cleaning and damage. It is shown that lower ionization or liquid additives lower the device damage.

The formation and reactions of aromatic dimer cations in a high pressure photoionization source

Aromatic dimer cations (M2+) have been generated for a series of aromatic compounds in a high pressure photoionization source. Relative third order rate constants for formation of M2+ have been obtained for benzene (1.0), benzene-d6 (2.7), toluene (0.8), o-xylene (1.5), p-xylene (0.7), fluorobenzene (0.3), m-fluorotoluene (0.5), m-chlorotoluene (0.7), p-chlorotoluene (0.5), and o-methoxytoluene (0.4). These values are consistent with and supplement previous data for such systems. Reagent ion monitoring has been used to determine the relative rates of reaction of both M2+ and the monomer ions, M+, with a series of (mainly) aromatic compounds (X). Reaction of C6H6+ is by charge transfer to compounds of lower ionization potential than C6H6. (C6H6)2+ reacts only by charge transfer, if the ionization potential of X is more than 0.5 eV lower than that of benzene. When the difference is smaller, mixed dimer cations are observed which are probably formed in a switching reaction (C6H6)2+ + X → (C6H6•X)+ + C6H6.

CHARGE TRANSFER IN THE RADIOLYSIS OF BINARY HYDROCARBON MIXTURES

The radiolysis of dilute solutions of ethane-dε, propane-d8, and n-butane-d10 in liquid hydrocarbons at 195 °K results in the production of D2 and HD in amounts which are determined by the relative ionization potentials of solvent and solute. Solvents of higher ionization potential enhance the production of D2 and HD from deuterated solutes of lower ionization potential. When the ionization potentials are in the reverse order the yields are diminished. This solute–solvent interaction, which is ionic in nature, is a general phenomenon in the radiolysis of mixtures of saturated hydrocarbons in the liquid phase and is consistent with charge transfer between solvent and solute.

The basic reactions in the upper atmosphere II. The theory of recombination in the ionized layers

Recombination in the ionized layers is discussed. It is pointed out that the results of recent work make the ionic recombination theory very difficult to maintain. Consideration is therefore given to two alternatives, the dust recombination theory and the molecular recombination theory. It is concluded that of these only the latter is at all promising. In the E layer the recombination process would be O + 2 + e → O׳ + O״, while in F 1 the effective reactions would be O + + XY → XY + + O XY + + e → X' + Y' }, N + 2 + e → N' + N'', and N + 2 + XY → XY + + N 2 XY + + e → X' + Y' }. The molecule XY possesses a lower ionization potential than O and need form only a very small fraction of the upper atmospheric content at the altitudes concerned. It is not identified but may be O 2 or NO. The reaction involving O + must be introduced, as otherwise the concentration of this ion would build up to impossibly large values. In F 2 the same reactions would be supposed to occur as in F 1 , but the reduced amount of XY would lead to a lower and pressure-dependent recombination coefficient. Confirmation of the theory must await proper determination of the reaction rates.