ABSTRACT
The ultrafast UV-induced processes of the neutral, anionic and dianionic forms of trans- and cis-ferulic acid (FA) in aqueous solution were studied by static and femtosecond time-resolved emission and absorption spectroscopy combined with quantum chemical calculations. In all cases, initial excitation populates the first 1ππ* state. For the dianionic cis-isomer cFA2-, electronic deactivation takes place with a time constant of only 1.4 ps, whereas in all other cases, excited-state deactivation happens more than ten times slower, on a time scale of ≈20 ps. The data suggest sequential de-excitation pathways, where initial sub-picosecond solvent rearrangement and structural changes are followed by internal conversion to an intermediate excited electronic state from which deactivation to the ground state proceeds. Considering the time scales, barrierless excited-state pathways are suggested only in the case of cFA2-, where the observed formation of the isomerisation photoproduct tFA2- provides clear evidence for a cis â trans isomerisation coordinate. In the other cases, pathways with an excited-state energy barrier, presumably along the same coordinate, are likely, given the longer excited-state lifetimes.
ABSTRACT
PURPOSE: To provide multidimensional velocity compensation for real-time phase-contrast flow MRI. METHODS: The proposed method introduces asymmetric gradient echoes for highly undersampled radial FLASH MRI with phase-sensitive image reconstruction by regularized nonlinear inversion (NLINV). Using an adapted gradient delay correction the resulting image quality was analyzed by simulations and experimentally validated at 3 Tesla. For real-time flow MRI the reduced gradient-echo timing allowed for the incorporation of velocity-compensating waveforms for all imaging gradients at even shorter repetition times. RESULTS: The results reveal a usable degree of 20% asymmetry. Real-time flow MRI with full velocity compensation eliminated signal void in a flow phantom, confirmed flow parameters in healthy subjects and demonstrated signal recovery and phase conservation in a patient with aortic valve insufficiency and stenosis. Exemplary protocols at 1.4-1.5 mm resolution and 6 mm slice thickness achieved total acquisition times of 33.3-35.7 ms for two images (7 spokes each) with and without flow-encoding gradient. CONCLUSION: Asymmetric gradient echoes were successfully implemented for highly undersampled radial trajectories. The resulting temporal gain offers full velocity compensation for real-time phase-contrast flow MRI which minimizes false-positive contributions from complex flow and further enhances the temporal resolution compared with acquisitions with symmetric echoes.
