Comprehensive conformational analysis of the nucleoside analogue 2'-beta-deoxy-6-azacytidine by DFT and MP2 calculations

A comprehensive conformational analysis of isolated 2'-beta-deoxy-6-azacytidine (d6AC), an analogue of therapeutically active 6-azacytidine (6AC), has been performed by means of ab initio calculations at the MP2/6-311++G(2df,pd)//DFT B3LYP/6-31G(d,p) level of theory. Among the 81 conformers located within a 7.83 kcal/mol Gibbs energy range at T = 298.15 K, 38 contain syn-oriented bases with respect to 2'-deoxyribose; the other conformers include anti-oriented bases. Energetic analysis of these conformers shows that conformational equilibrium of isolated d6AC at T = 298.15 K is shifted to syn conformation with a syn/anti ratio estimated as 61.4%:38.6%. As far as the sugar conformation is concerned, 40 conformers contain north (N) (with 0.3 degrees < or = P < or = 40.1 degrees), and the rest possess south (S) (with 157.1 degrees < or = P < or = 207.0 degrees) puckers, where P is the pseudorotational angle of the furanose ring. The S/N occupancy ratio is estimated as 80.2%:19.8% (T = 298.15 K). The two most stable conformers are energetically quasidegenerate and correspond to both C2'-endo/syn conformers differing only by orientation of the O3'H hydroxyl group. They are both stabilized by means of similar intramolecular H-bonds, i.e., O5'H...O2, C2'H2...O2, and C2'H2...O5'. As examined by AIM criteria, from 1 to 3 H-bonds per conformer were identified among 13 possible interactions: O5'H...O2, O5'H...N6, O3'H...O5', O5'H...O3', C1'H...O2, C2'H2...O2, C2'H2...O5', C3'H...O2, C3'H...N6, C5'H1...O2, C5'H2...O2, C5'H1...N6, and C5'H2...N6. The biological effect of d6AC is conceived as an inhibition of replicative DNA polymerase caused by an unusual orientation of the sugar residue against the base in the only A form DNA-like conformer.     

Mechanochemical synthesis of poly(2,5-dimethoxy aniline) nanobelts and its electrochemical performance in hybrid supercapacitors

A solvent-free mechanochemical route for the preparation of poly(2,5-dimethoxyaniline) hydrochloride nanostructures is developed and reported in the article. High conductivity, good crystallinity, and nanostructured morphology are observed for the prepared polymer. This polymeric powder is utilized as a cathode material in hybrid supercapacitor and its electrochemical performance is evaluated and discussed in this short report. The maximum specific capacitance of the poly(2,5-dimethoxyaniline) hydrochloride/activated carbon hybrid supercapacitor is found to be 125 F g⁻¹ at 1 mA cm⁻² current density. The cell delivers a specific energy as high as 50 Wh kg⁻¹ at a specific power of 97 W kg⁻¹ and also exhibits an excellent cycle performance with more than 99% coulombic efficiency and the maintenance of 85% of its initial capacitance after 1,000 cycles.     

Synthesis,growth, structure,spectral, thermal and first-order molecular hyperpolarizability of benzophenone-2-furoyl hydrazone single crystal

Single crystals of benzophenone-2-furoyl hydrazone are grown by slow evaporation solution growth technique from ethanol at room temperature. It belongs to monoclinic system with the space group P2₁/c and the cell parameters are, a = 6.1631(3) Å, b = 13.1397(8) Å, c = 18.0030(11) Å and V = 1457.72(14) Å³. NMR spectral studies reveal the structure and powder XRD indicates the crystallinity of the specimen. The characteristic functional groups present in the molecule are confirmed by Fourier transform infrared spectroscopy. The crystals are transparent in the visible region having a lower optical cut-off at ∼406 nm and the band gap energies are estimated by the application of Kubelka–Munk algorithm. Thermal analysis by TG/DTA indicates the stability of the material. The scanning electron microscopy studies reveal the surface morphology of the as-grown crystal. Theoretical calculations were performed using Hartree–Fock method with 6-31G(d,p) as the basis set for to derive the optimized geometry, dipole moment and first-order molecular hyperpolarizability (β) values.     

Enhancement of second harmonic generation efficiency: Cs(I)-doped tris(thiourea)zinc(II) sulphate crystals

The effect of dopant cesium (Cs(I)) over a concentration range from 1 to 10 mol% on the growth process, morphology, thermal and optical properties of tri(thiourea)zinc(II) sulfate (ZTS) single crystals grown by slow evaporation solution growth technique has been investigated. Incorporation of Cs(I) into the crystal lattice was well confirmed by energy dispersive X-ray spectroscopy (EDS). The lattice parameters of the as-grown crystals were obtained by single crystal X-ray diffraction analysis. The reduction in the intensities observed in powder X-ray diffraction patterns of doped specimen and slight shifts in vibrational frequencies in fourier transform infrared spectra (FT-IR) indicate the lattice stress as a result of doping. Thermal studies reveal the purity of the material and no decomposition is observed up to the melting point. High transmittance is observed in the visible region and the cut-off λ is ～280 nm. The surface morphology of the as-grown specimens was studied by scanning electron microscopy (SEM). The second harmonic generation (SHG) efficiency of the host crystal is enhanced greatly in the presence of high concentrations of the dopant.