Tight-binding parameters for charge transfer along DNA

We systematically examine all the tight-binding parameters pertinent to charge transfer along DNA. The $\pi$ molecular structure of the four DNA bases (adenine, thymine, cytosine, and guanine) is investigated by using the linear combination of atomic orbitals method with a recently introduced parametrization. The HOMO and LUMO wavefunctions and energies of DNA bases are discussed and then used for calculating the corresponding wavefunctions of the two B-DNA base-pairs (adenine-thymine and guanine-cytosine). The obtained HOMO and LUMO energies of the bases are in good agreement with available experimental values. Our results are then used for estimating the complete set of charge transfer parameters between neighboring bases and also between successive base-pairs, considering all possible combinations between them, for both electrons and holes. The calculated microscopic quantities can be used in mesoscopic theoretical models of electron or hole transfer along the DNA double helix, as they provide the necessary parameters for a tight-binding phenomenological description based on the $\pi$ molecular overlap. We find that usually the hopping parameters for holes are higher in magnitude compared to the ones for electrons, which probably indicates that hole transport along DNA is more favorable than electron transport. Our findings are also compared with existing calculations from first principles.Comment: 15 pages, 3 figures, 7 table

Suppression in Melt Viscosity of the Homogeneously Mixed Blends of Polypropylene (iPP-UHMWiPP) in the Presence of an Oxalamide

Here we report on the influence of an aliphatic oxalamide-based nucleating agent (OXA3,6) on the viscoelastic and mechanical properties of isotactic polypropylene (iPP) blended with ultrahigh molecular weight iPP (UHMWiPP). The linear viscoelastic properties are investigated by using a plate-plate rheometer; the presence of only 0.5 wt % of OXA3,6 in the iPP-UHMWiPP blends results in a reduction of the complex viscosity in the entire frequency domain examined. This observation holds irrespective of the UHMWiPP weight fraction, up to 25 wt %. The viscosity suppression is attributed to an acceleration of the reorientation times of the chains, especially the longer ones, due to partial alignment of their molecular segments. Furthermore, SAXS measurements on cooled, injection molded samples hint that OXA3,6-containing samples display enhanced alignment under processing conditions (injection molding). Compared to samples without OXA, an increase in the SAXS intensity along the equator is observed in the OXA3,6 samples, implying an enhanced ability of shish-kebab formation. Such a morphological development results in higher yield stress while maintaining the elastic behavior