Excited state intramolecular proton transfer emission in bent core liquid crystals

We report the photophysics of two bent-core liquid crystals (BLCs), C56H67NO9 (BLC1) and C55H65NO9 (BLC2), containing a Schiff-base and two long alkyl chains at its two ends. The ground state dipole moment and the electronic structures of the BLCs were calculated using density functional theory (DFT). The dipole moments of the liquid crystals were estimated experimentally via solvatochromic shift of the absorption and fluorescence spectra. The dipole moments obtained experimentally are in quite good agreement with theoretically calculated values. In the fluorescence spectra of both the BLCs show an interesting feature, i.e., dual emission. This dual emission is explained via the presence of two tautomeric forms (keto and enol) of the BLCs in the excited state. The band at similar to 390-450 nm is assigned to the emission due to the keto-form, whereas the band at similar to 340-370 nm is due to the emission from the enol-form. Irrespective of the solvents used, the keto-band is more intense than the enol-emission-band. This intense emission from the keto-form of the tautomers is demonstrated via the excited state intramolecular proton transfer (ESIPT). From the time resolved fluorescence spectroscopy studies, a longer lifetime is obtained for the keto-band. The associated vibrational states observed in the emission spectrum are responsible for this longer lifetime. Our finding of the dual emissive nature of the liquid crystals in the visible range is potentially useful for high temperature liquid crystal display and sensing applications. (C) 2018 Elsevier B.V. All rights reserved

Present address: Ultrasound and Elasticity Imaging Laboratory, Columbia University 630 W 168th St., Physicians and Surgeons 19-418

Abstract Arterial stiffness is a well-established biomarker for cardiovascular risk, especially in the case of hypertension. The progressive stages of an abdominal aortic aneurysm (AAA) have also been associated with varying arterial stiffness. Pulse wave imaging (PWI) is a noninvasive, ultrasound imagingbased technique that uses the pulse wave-induced arterial wall motion to map the propagation of the pulse wave and measure the regional pulse wave velocity (PWV) as an index of arterial stiffness. In this study, the clinical feasibility of PWI was evaluated in normal, hypertensive, and aneurysmal human aortas. Radiofrequency-based speckle tracking was used to estimate the pulse waveinduced displacements in the abdominal aortic walls of normal (N = 15, mean age 32.5 ± 10.2 years), hypertensive (N = 13, mean age 60.8 ± 15.8 years), and aneurysmal (N = 5, mean age 71.6 ± 11.8 years) human subjects. Linear regression of the spatio-temporal variation of the displacement waveform in the anterior aortic wall over a single cardiac cycle yielded the slope as the PWV and the coefficient of determination r 2 as an approximate measure of the pulse wave propagation uniformity. The aortic PWV measurements in all normal, hypertensive, and AAA subjects were 6.03 ± 1.68, 6.69 ± 2.80, and 10.54 ± 6.52 m s −1 , respectively. There was no significant difference (p = 0.15) between the PWVs of the normal and hypertensive subjects while the PWVs of the AAA subjects were significantly higher (p < 0.001) compared to those of the other two groups. Also, the average r 2 in the AAA subjects was significantly lower (p < 0.001) than that in the normal and hypertensive subjects. These preliminary results suggest that the regional PWV and the pulse wave propagation uniformity (r 2 ) obtained using PWI, in addition to the PWI images and spatio-temporal maps that provide qualitative visualization of