Quantum mechanical calculations of conformationally relevant 1H and 13C NMR chemical shifts of calixarene systems

[graphs: see text] QM GIAO calculations of 13C and 1H chemical shift values of the ArCH2Ar group have been performed, using the hybrid DFT functional MPW1PW91 and the 6-31G(d,p) basis set, on some representative calixarenes and on a series of simplified calixarene models allowing derivation of chemical shift surfaces versus phi and chi dihedral angles. A good reproduction of experimental data was obtained. The applicability of chemical shift surfaces in the study of calixarene conformational features is illustrated.     

Thermogravitational effect in macromolecular solutions

We have investigated in a thermogravitational apparatus the behavior of solutions containing macromolecular solutes and of suspensions of ultramicroscopic particles such as viruses and ribosomes. We have obtained very high separation ratios with all the solutes studied, the value of the separation being characteristic of each solution. The reproducibility of the results is good, and the dependence on the geometrical and physical parameters involved fits the predictions of the phenomenological theory. Our results prove that fractionation of very high molecular weight particles is feasible by this method, and also that the characterization of the macromolecular species and the determination of the mass and shape of the particles of the solute seem to be within the possibilities of the thermogravitational method when this is applied to very high molecular weight materials.     

Synthesis,Antibacterial, and Antioxidant Evaluation of Novel Series of Condensed Thiazoloquinazoline with Pyrido,Pyrano, and Benzol Moieties as Five- and Six-Membered Heterocycle Derivatives

A novel synthesis of thiazolo[2,3-b]quinazolines 4(a–e), pyrido[2′,3′:4,5]thiazolo[2,3-b]quinazolines {5(a–e), 6(a–e), and 7(a–e)}, pyrano[2′,3′:4,5]thiazolo[2,3-b]quinazolines 8(a–e), and benzo[4,5]thiazolo[2,3-b]quinazoloine9(a–e) derivatives starting from 2-(Bis-methylsulfanyl-methylene)-5,5-dimethyl-cyclohexane-1,3-dione 2 as efficient α,α dioxoketen dithioacetal is reported and the synthetic approaches of these types of compounds will provide an innovative molecular framework to the designing of new active heterocyclic compounds. In our study, we also present optimization of the synthetic method along with a biological evaluation of these newly synthesized compounds as antioxidants and antibacterial agents against the bacterial strains, like S. aureus, E. coli, and P. aeruginosa. Among all the evaluated compounds, it was found that some showed significant antioxidant activity at 10 μg/mL while the others exhibited better antibacterial activity at 100 μg/mL. The results of this study showed that compound 6(c) possessed remarkable antibacterial activity, whereas compound 9(c) exhibited the highest efficacy as an antioxidant. The structures of the new synthetic compounds were elucidated by elemental analysis, IR, ¹H-NMR, and ¹³C-NMR.     

Excess noise generation during spectral broadening in a microstructured fiber

We observe that nanojoule femtosecond pulses that are spectrally broadened in a microstructured fiber acquire excess noise. The excess noise is manifested as an increase in the noise floor of the rf spectrum of the photocurrent from a photodetector illuminated by the pulse train from the laser oscillator. Measurements are made of the intensity dependence of the excess noise for both 100 fs and sub-10 fs pulses. The excess noise is very strong for 100 fs pulses, but barely measurable for sub-10 fs pulses. A rigorous quantum treatment of the nonlinear propagation of ultrashort pulses predicts that, for a fixed generated bandwidth, the amount of excess noise decreases with pulse duration, in agreement with the experimental results.