Electronic Circular Dichroism Spectra of DNA Quadruple Helices Studied by Molecular Dynamics Simulations and Excitonic Calculations including Charge Transfer States

We here investigate the Electronic Circular Dichroism (ECD) Spectra of two representative Guanine-rich sequences folded in a Quadruple helix (GQ), by using a recently developed fragment diabatisation based excitonic model (FrDEx). FrDEx can include charge transfer (CT) excited states and consider the effect of the surrounding monomers on the local excitations (LEs). When applied to different structures generated by molecular dynamics simulations on a fragment of the human telomeric sequence (Tel21/22), FrDEx provides spectra fully consistent with the experimental one and in good agreement with that provided by quantum mechanical (QM) method used for its parametrization, i.e., TD-M05-2X. We show that the ECD spectrum is moderately sensitive to the conformation adopted by the bases of the loops and more significantly to the thermal fluctuations of the Guanine tetrads. In particular, we show how changes in the overlap of the tetrads modulate the intensity of the ECD signal. We illustrate how this correlates with changes in the character of the excitonic states at the bottom of the La and Lb bands, with larger LE and CT involvement of bases that are more closely stacked. As an additional test, we utilised FrDEx to compute the ECD spectrum of the monomeric and dimeric forms of a GQ forming sequence {"type":"entrez-nucleotide","attrs":{"text":"T30695","term_id":"612793"}}T30695 (5′TGGGTGGGTGGGTGGG3′), i.e., a system containing up to 24 Guanine bases, and demonstrated the satisfactory reproduction of the experimental and QM reference results. This study provides new insights on the effects modulating the ECD spectra of GQs and, more generally, further validates FrDEx as an effective tool to predict and assign the spectra of closely stacked multichromophore systems.     

Synthesis and evaluation of thermal, electrical, and electrochemical properties of Ba0.5Sr0.5Co0.04Zn0.16Fe0.8O3�C�� as a novel cathode material for IT-SOFC applications

Ba_0.5Sr_0.5[Co_xZn_0.2-x]Fe_0.8O_3?C??, (x?=?0, 0.04, 0.08, 0.12) cathode formulations were successfully synthesized by solid state reactions and the effect of cobalt doping at Zn site of Ba_0.5Sr_0.5Zn_0.2Fe_0.8O_3?C?? (BSZF0.2) on the electrical conductivity, the polarization resistance and electrochemical behavior was evaluated. X-ray diffraction patterns indicate that a single cubic perovskite phase of Ba_0.5Sr_0.4Co_0.8Fe_0.2O_3?C?? oxide is successfully obtained. Ba_0.5Sr_0.5Co_0.04Zn_0.16Fe_0.8O_3?C?? (BSCZF0.16) exhibited a high electrical conductivity of 10 S/cm at 400 °C in comparison to the BSZF0.2 showing 5.5 S/cm. Further, BSCZF0.16 also possess a low polarization resistance as low as 0.22, 0.38, 0.87, and 1.55 ?? cm² at 750, 700, 650, and 600 °C in air, respectively. Accordingly, a low activation energy value of 149.8 kJ/mol for BSCZF0.16 in comparison to 159.4 kJ/mol for BSZF0.2 indicates high catalytic efficiency. Enhancement of desirable properties such as electrical conductivity in combination with low-polarization resistance and low-activation energy values can be attributed to the coexistence of Co and Zn in the B-site of BSCZF0.16 leading to the multivalent states which contributes to the enhanced electron transport properties demonstrating BSCZF0.16 as a better cathode for intermediate temperature solid oxide fuel cells applications.