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A comprehensive study of the photophysical properties of a series of monoaza[5]helicenes is presented on the basis of joint optical spectroscopy and quantum chemistry investigations. The molecules have been characterized by absorption and CW/time-resolved luminescence measurements. All quantities related to spin-orbit-coupling processes, such as intersystem crossing rates and radiative phosphorescence lifetimes, were found to depend strongly on the nitrogen position within the carbon backbone. Density functional theory and semiempirical quantum-chemical methods were used to evaluate the molecular geometries, the characteristics of the excited singlet and triplet states, and the spin-orbit coupling matrix elements. We demonstrate that the magnitude of spin-orbit coupling is directly correlated with the degree of deviation from planarity. The trends from the calculated photophysical quantities, namely, radiative fluorescence and phosphorescence decay rates and intersystem crossing rates, of the mono-aza-helicenes are fully consistent with experiment.

Background-Pulmonary hypertension is a disease characterized by an elevation in pulmonary arterial pressure that is diagnosed invasively via right heart catheterization. Such pathological altered pressures in the pulmonary vascular system should lead to changes in blood flow patterns in the main pulmonary artery. Methods and Results-Forty-eight subjects (22 with manifest pulmonary hypertension, 13 with latent pulmonary hypertension, and 13 normal control subjects) underwent time-resolved 3D magnetic resonance phase-contrast imaging of the main pulmonary artery. Velocity fields that resulted from measurements were calculated, visualized, and analyzed with dedicated software. Main findings were as follows: (1) Manifest pulmonary hypertension coincides with the appearance of a vortex of blood flow in the main pulmonary artery (sensitivity and specificity of 1.00, 95% confidence intervals of 0.84 to 1.00 and 0.87 to 1.00, respectively), and (2) the relative period of existence of the vortex correlates significantly with mean pulmonary arterial pressure at rest (correlation coefficient of 0.94). To test the diagnostic performance of the vortex criterion, we furthermore investigated 55 patients in a blinded prospective study (22 with manifest pulmonary hypertension, 32 with latent pulmonary hypertension, and 1 healthy subject), which resulted in a sensitivity of 1.00 and specificity of 0.91 (95% confidence intervals of 0.84 to 1.00 and 0.76 to 0.98, respectively).Comparison of catheter-derived mean pulmonary artery pressure measurements and calculated mean pulmonary artery pressure values resulted in a standard deviation of differences of 3.6 mm Hg. Conclusions-Vortices