Exciton Absorption and Luminescence in i-Motif DNA

We have studied the excited-state dynamics for the i-motif form of cytosine chains (dC)10, using the ultrafast fluorescence up-conversion technique. We have also calculated vertical electronic transition energies and determined the nature of the corresponding excited states in a model tetramer i-motif structure. Quantum chemical calculations of the excitation spectrum of a tetramer i-motif structure predict a significant (0.3 eV) red shift of the lowest-energy transition in the i-motif form relative to its absorption maximum, which agrees with the experimental absorption spectrum. The lowest excitonic state in i-(dC)10 is responsible for a 2 ps red-shifted emission at 370 nm observed in the decay-associated spectra obtained on the femtosecond time-scale. This delocalized (excitonic) excited state is likely a precursor to a long-lived excimer state observed in previous studies. Another fast 310 fs component at 330 nm is assigned to a monomer-like locally excited state. Both emissive states form within less than the available time resolution of the instrument (100 fs). This work contributes to the understanding of excited-state dynamics of DNA within the first few picoseconds, which is the most interesting time range with respect to unraveling the photodamage mechanism, including the formation of the most dangerous DNA lesions such as cyclobutane pyrimidine dimers.

О зонной структуре Bi-=SUB=-2-=/SUB=-Te-=SUB=-3-=/SUB=-

For p -Bi_2Te_3 crystals grown by the Czochralski method, the temperature dependences of the conductivity, Hall coefficient, thermoelectric power (α), and transverse Nernst–Ettingshausen coefficient are obtained experimentally in the temperature range 77–450 K. The transmittance spectrum in the range 400–5250 cm^–1 is recorded at room temperature. It is shown that, to interpret the temperature dependences of the scattering parameter r and the ratio of the thermoelectric power to temperature (α/ T ), it is essential to take into account the complex valence-band structure and the contribution of heavy holes to transport phenomena. Estimations of the energy band parameters in the context of the two-band model give a hole effective mass close to the free electron mass and the energy gap between nonequivalent extrema at a level of several hundredths of eV. In the absorption spectrum derived from the transmittance spectrum, a sharp increase in absorption defined by indirect interband transitions with the band gap E _ g ≈ 0.14 eV is observed in the region of frequencies ν ≥ 1000 cm^–1. The absorption spectrum calculated from the reflectance data using the Kramers–Kronig relations is in agreement with the experimental absorption spectrum.