Steady-State Spectroscopy to Single Out the Contact Ion Pair in Excited-State Proton Transfer.

Despite the outstanding relevance of proton transfer reactions, investigations of the solvent dependence on the elementary step are scarce. We present here a probe system of a pyrene-based photoacid and a phosphine oxide, which forms stable hydrogen-bonded complexes in aprotic solvents of a broad polarity range. By using a photoacid, an excited-state proton transfer (ESPT) along the hydrogen bond can be triggered by a photon and observed via fluorescence spectroscopy. Two emission bands could be identified and assigned to the complexed photoacid (CPX) and the hydrogen-bonded ion pair (HBIP) by a solvatochromism analysis based on the Lippert-Mataga model. The latter indicates that the difference in the change of the permanent dipole moment of the two species upon excitation is ∼3 D. This implies a displacement of the acidic hydrogen by ∼65 pm, which is in quantitative agreement with a change of the hydrogen bond configuration from O-H···O to -O···H-O+.

Structure and stability of propellane-like E[Formula: see text].

Propellane-like structures are an important building block for group-14 compounds. Therefore, in the present work, we study theoretically various such structures of the form E[Formula: see text] starting with the pure molecules for which E = E' = E″ = C, Si, Ge, or Sn. Subsequently, we study the systems with E ≠ E' = E″ and finally, we consider some selected cases molecules for which E, E', and E″ all are different. Special emphasis is put on identifying structural trends for the molecules with at least two different group-14 elements. The resulting scheme is, we believe, generally valid for group-14 based systems with more than one type of group-14 elements.

Doppler vortography: a color Doppler approach to quantification of intraventricular blood flow vortices.

We propose a new approach to quantification of intracardiac vorticity based on conventional color Doppler images -Doppler vortography. Doppler vortography relies on the centrosymmetric properties of the vortices. Such properties induce particular symmetries in the Doppler flow data that can be exploited to describe the vortices quantitatively. For this purpose, a kernel filter was developed to derive a parameter, the blood vortex signature (BVS), that allows detection of the main intracardiac vortices and estimation of their core vorticities. The reliability of Doppler vortography was assessed in mock Doppler fields issued from simulations and in vitro data. Doppler vortography was also tested in patients and compared with vector flow mapping by echocardiography. Strong correlations were obtained between Doppler vortography-derived and ground-truth vorticities (in silico: r2 = 0.98, in vitro: r2 = 0.86, in vivo: r2 = 0.89). Our results indicate that Doppler vortography is a potentially promising echocardiographic tool for quantification of vortex flow in the left ventricle.

Stolt's f-k migration for plane wave ultrasound imaging.

Ultrafast ultrasound is an emerging modality that offers new perspectives and opportunities in medical imaging. Plane wave imaging (PWI) allows one to attain very high frame rates by transmission of planar ultrasound wave-fronts. As a plane wave reaches a given scatterer, the latter becomes a secondary source emitting upward spherical waves and creating a diffraction hyperbola in the received RF signals. To produce an image of the scatterers, all the hyperbolas must be migrated back to their apexes. To perform beamforming of plane wave echo RFs and return high-quality images at high frame rates, we propose a new migration method carried out in the frequency-wavenumber (f-k) domain. The f-k migration for PWI has been adapted from the Stolt migration for seismic imaging. This migration technique is based on the exploding reflector model (ERM), which consists in assuming that all the scatterers explode in concert and become acoustic sources. The classical ERM model, however, is not appropriate for PWI. We showed that the ERM can be made suitable for PWI by a spatial transformation of the hyperbolic traces present in the RF data. In vitro experiments were performed to outline the advantages of PWI with Stolt's f-k migration over the conventional delay-and-sum (DAS) approach. The Stolt's f-k migration was also compared with the Fourier-based method developed by J.-Y. Lu. Our findings show that multi-angle compounded f-k migrated images are of quality similar to those obtained with a stateof- the-art dynamic focusing mode. This remained true even with a very small number of steering angles, thus ensuring a highly competitive frame rate. In addition, the new FFT-based f-k migration provides comparable or better contrast-to-noise ratio and lateral resolution than the Lu's and DAS migration schemes. Matlab codes for the Stolt's f-k migration for PWI are provided.

Unsupervised dealiasing and denoising of color-Doppler data.

Color Doppler imaging (CDI) is the premiere modality to analyze blood flow in clinical practice. In the prospect of producing new CDI-based tools, we developed a fast unsupervised denoiser and dealiaser (DeAN) algorithm for color Doppler raw data. The proposed technique uses robust and automated image post-processing techniques that make the DeAN clinically compliant. The DeAN includes three consecutive advanced and hands-off numerical tools: (1) statistical region merging segmentation, (2) recursive dealiasing process, and (3) regularized robust smoothing. The performance of the DeAN was evaluated using Monte-Carlo simulations on mock Doppler data corrupted by aliasing and inhomogeneous noise. Fifty aliased Doppler images of the left ventricle acquired with a clinical ultrasound scanner were also analyzed. The analytical study demonstrated that color Doppler data can be reconstructed with high accuracy despite the presence of strong corruption. The normalized RMS error on the numerical data was less than 8% even with signal-to-noise ratio as low as 10dB. The algorithm also allowed us to recover highly reliable Doppler flows in clinical data. The DeAN is fast, accurate and not observer-dependent. Preliminary results showed that it is also directly applicable to 3-D data. This will offer the possibility of developing new tools to better decipher the blood flow dynamics in cardiovascular diseases.