Effective discrimination of non-complementary nucleotides is an important factor to ensure the accuracy of hybridization-based nucleic acid analyses. The current study investigates the effects of the chemical nature, the positions, the numbers, and the cooperative behavior of mismatches as well as insertions on 20-mer and 30-mer duplexes. We observed the hybridization stability trend affected by mismatches: G:T ≈ G:G > G:A > A:A ≈ T:T > A:C ≈ T:C > C:C. The experimental data show that mismatches at the center of the oligonucleotide probes have a more profound destabilizing effect on the hybridization stability than those at either ends. Insertions also demonstrate a similar destabilizing effect as mismatches. These results provide useful information for designing DNA microarray nucleotide probes and for improving the discrimination accuracy of hybridization-based detections.
2,5-bis-(4-biphenyl)-yl-1,3,4-oxadiazole (1a), 2,5-bis-(4-(6,8-difluoro)-biphenyl)-yl-1,3,4-oxadiazole (1b) and 2,5-bis-(4-(spiro-fluorenyl)-phenyl)-yl-1,3,4-oxadiazole (1c) were designed, synthesized and characterized. 1a–c were easily obtained from Suzuki reactions between 2,5-bis-(4-bromo-phynyl)-[1,3,4]oxadiazole (2) and aromatic boronic acids (3). They were characterized by 1H-NMR, DSC, TGA, UV-Vis, photoluminescence (PL) spectrometry and CV. The melting temperatures (T m) of 1a–c are 237, 208 and 370 °C, respectively, much higher than that of 2-tert-butylphenyl-5-biphenyl-1,3,4-oxadiazole (PBD, T m = 136 °C). The oxidation potentials of 1a–c are 1.86, 1.94 and 1.18 V, and their reduction potentials are −2.31, −2.22 and −2.27 V, respectively, indicating that the introduction of electronegative oxadiazole unit lowers the electron density in molecules and enhances their stabilities. The LUMO/HOMO energy levels of 1a–c are as low as −2.39/−6.56, −2.48/−6.69 and −2.43/−5.88 eV, respectively. The good thermal stabilities and low orbital levels of 1a–c make them promising electron-transporting or hole-blocking materials for organic optoelectronic devices.
The size dependence of the nanocrystal melting temperature has been investigated based on a nonequilibrium thermodynamics approach. An expression has been derived for the melting temperature that, contrary to the classical Tomson formula, takes into account the metastable character of the crystal nucleus-melt shell equilibrium. Quantitative estimations have been carried out for small spherical particles of aluminum, tin, and lead.
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