Adaptive instant record signals applied to detection with time reversal operator decomposition

Time reversal arrays are becoming common tools whether for detection or tomography. These applications require the measurement of the response from the array to one or several receivers. The most natural way to record the impulse responses for several sources is to generate pulses successively from each emitting point and record simultaneously the signals from the receivers. However, this method is very time consuming or inefficient in terms of signal-to-noise ratio. To overcome this limitation quasi-orthogonal pseudonoise signals like Kasami sequences can be used. For guided wave propagation, a very high degree of orthogonality between the signal is necessary to allow an accurate measure of the whole multipath structure of the transfer function. Hence, in this work, we propose a new family of pseudo-orthogonal signals that is adapted to the environment and more specifically, to highly dispersive media. These adaptive instant records signals are used experimentally to detect targets using the time reversal operator decomposition method. The accuracy of the 15 x 15 transfer functions acquired simultaneously, and therefore the detection capability, are demonstrated in an experimental ultrasonic waveguide as a small-scale model of shallow water propagation including bottom absorption and reverberation.     

Reliability of Speaking and Maximum Voice Range Measures in Screening for Dysphonia

Speech range profile (SRP) is a graphical display of frequency-intensity occurring interactions during functional speech activity. Few studies have suggested the potential clinical applications of SRP. However, these studies are limited to qualitative case comparisons and vocally healthy participants. The present study aimed to examine the effects of voice disorders on speaking and maximum voice ranges in a group of vocally untrained women. It also aimed to examine whether voice limit measures derived from SRP were as sensitive as those derived from voice range profile (VRP) in distinguishing dysphonic from healthy voices. Ninety dysphonic women with laryngeal pathologies and 35 women with normal voices, who served as controls, participated in this study. Each subject recorded a VRP for her physiological vocal limits. In addition, each subject read aloud the "North Wind and the Sun" passage to record SRP. All the recordings were captured and analyzed by Soundswell's computerized real-time phonetogram Phog 1.0 (Hitech Development AB, T?by, Sweden). The SRPs and the VRPs were compared between the two groups of subjects. Univariate analysis results demonstrated that individual SRP measures were less sensitive than the corresponding VRP measures in discriminating dysphonic from normal voices. However, stepwise logistic regression analyses revealed that the combination of only two SRP measures was almost as effective as a combination of three VRP measures in predicting the presence of dysphonia (overall prediction accuracy: 93.6% for SRP vs 96.0% for VRP). These results suggest that in a busy clinic where quick voice screening results are desirable, SRP can be an acceptable alternate procedure to VRP.     

Pulse compression and fiber delivery of 45 fs Fourier transform limited pulses at 830 nm

A specific scheme is used for fiber delivery of ultrashort pulses using conventional elements. Starting from a standard femtosecond Ti:Al(2)O(3) oscillator (150 fs @ 830 nm), perfectly compressed ultrashort pulses with a duration of 45 fs are produced at the output of a standard two meter long single-mode fiber. The setup allows compensating independently and simultaneously second and third orders of chromatic dispersion as well as management of self-phase modulation in the fiber. It includes an optimized dispersion compensation line made of the assembly of diffraction gratings and prisms. The unsurpassed performances of the device are experimentally and numerically highlighted. Fiber delivery of sub-30 fs multinanojoule pulses is discussed.     

Characterization of porosity in a 19th century painting ground by synchrotron radiation X-ray tomography

The study of the early oeuvre of the Swiss painter Cuno Amiet (1868–1961) has revealed that, up to 1907, many of his grounds were hand applied and are mainly composed of chalk, bound in protein. These grounds are not only lean and absorbent, but also, as Synchrotron radiation X-ray microtomography has shown, porous. Our approach to the characterization of pore structure and quantity, their connectivity, and homogeneity is based on image segmentation and application of a clustering algorithm to high-resolution X-ray tomographic data. The issues associated with the segmentation of the different components of a ground sample based on X-ray imaging data are discussed. The approach applied to a sample taken from “Portrait of Max Leu” (1899) by Amiet revealed the presence of three sublayers within the ground with distinct porosity features, which had not been observed optically in cross-section. The upper and lower layers are highly porous with important connectivity and thus prone to water uptake/storage. The middle layer however shows low and nonconnected porosity at the resolution level of the X-ray tomography images, so that few direct water absorption paths through the entire sample exist. The potential of the method to characterize porosity and to understand moisture-related issues in paint layer degradation are discussed.     

Double-quantum filtered MAS NMR in the presence of chemical shielding anisotropies and direct dipolar and J couplings

Double-quantum filtered MAS NMR spectra of an isolated homonuclear spin-1/2 pair are considered, at and away from rotational resonance conditions. The pulse sequence used is the solid-state NMR equivalent of double-quantum filtered COSY, known from solution-state NMR. The 119Sn spin pair in [(chex3Sn)2S] is characterized by a difference in isotropic chemical shielding smaller than the two chemical shielding anisotropies and by direct dipolar and isotropic J-coupling constants of similar magnitudes. At rotational resonance, one-dimensional double-quantum filtered 119Sn lineshapes yield the relative orientation of the two 119Sn chemical shielding tensors. Good double-quantum filtration efficiencies are found at and away from rotational resonance conditions, despite the presence of large chemical shielding anisotropies. Numerical simulations illustrate the interplay of the direct dipolar and J-coupling pathways and identify the latter as the main pathway even at rotational resonance conditions.     

Development of intermolecular potential models for electrolyte solutions using an electrolyte SAFT-VR Mie equation of state

ABSTRACT

We present a theoretical framework and parameterisation of intermolecular potentials for aqueous electrolyte solutions using the statistical associating fluid theory based on the Mie interaction potential (SAFT-VR Mie), coupled with the primitive, non-restricted mean-spherical approximation (MSA) for electrolytes. In common with other SAFT approaches, water is modelled as a spherical molecule with four off-centre association sites to represent the hydrogen-bonding interactions; the repulsive and dispersive interactions between the molecular cores are represented with a potential of the Mie (generalised Lennard-Jones) form. The ionic species are modelled as fully dissociated, and each ion is treated as spherical: Coulombic ion–ion interactions are included at the centre of a Mie core; the ion–water interactions are also modelled with a Mie potential without an explicit treatment of ion–dipole interaction. A Born contribution to the Helmholtz free energy of the system is included to account for the process of charging the ions in the aqueous dielectric medium. The parameterisation of the ion potential models is simplified by representing the ion–ion dispersive interaction energies with a modified version of the London theory for the unlike attractions. By combining the Shannon estimates of the size of the ionic species with the Born cavity size reported by Rashin and Honig, the parameterisation of the model is reduced to the determination of a single ion–solvent attractive interaction parameter. The resulting SAFT-VRE Mie parameter sets allow one to accurately reproduce the densities, vapour pressures, and osmotic coefficients for a broad variety of aqueous electrolyte solutions; the activity coefficients of the ions, which are not used in the parameterisation of the models, are also found to be in good agreement with the experimental data. The models are shown to be reliable beyond the molality range considered during parameter estimation. The inclusion of the Born free-energy contribution, together with appropriate estimates for the size of the ionic cavity, allows for accurate predictions of the Gibbs free energy of solvation of the ionic species considered. The solubility limits are also predicted for a number of salts; in cases where reliable reference data are available the predictions are in good agreement with experiment.     

Commissioning of a multi‐beamline femtoslicing facility at SOLEIL

The investigation of ultrafast dynamics, taking place on the few to sub‐picosecond time scale, is today a very active research area pursued in a variety of scientific domains. With the recent advent of X‐ray free‐electron lasers (XFELs), providing very intense X‐ray pulses of duration as short as a few femtoseconds, this research field has gained further momentum. As a consequence, the demand for access strongly exceeds the capacity of the very few XFEL facilities existing worldwide. This situation motivates the development of alternative sub‐picosecond pulsed X‐ray sources among which femtoslicing facilities at synchrotron radiation storage rings are standing out due to their tunability over an extended photon energy range and their high stability. Following the success of the femtoslicing installations at ALS, BESSY‐II, SLS and UVSOR, SOLEIL decided to implement a femtoslicing facility. Several challenges were faced, including operation at the highest electron beam energy ever, and achievement of slice separation exclusively with the natural dispersion function of the storage ring. SOLEIL's setup also enables, for the first time, delivering sub‐picosecond pulses simultaneously to several beamlines. This last feature enlarges the experimental capabilities of the facility, which covers the soft and hard X‐ray photon energy range. In this paper, the commissioning of this original femtoslicing facility is reported. Furthermore, it is shown that the slicing‐induced THz signal can be used to derive a quantitative estimate for the degree of energy exchange between the femtosecond infrared laser pulse and the circulating electron bunch.     

The pedunculopontine tegmental nucleus and the nucleus basalis magnocellularis: Do both have a role in sustained attention?

Background  

It is well established that nucleus basalis magnocellularis (NbM) lesions impair performance on tests of sustained attention. Previous work from this laboratory has also demonstrated that pedunculopontine tegmental nucleus (PPTg) lesioned rats make more omissions on a test of sustained attention, suggesting that it might also play a role in mediating this function. However, the results of the PPTg study were open to alternative interpretation. We aimed to resolve this by conducting a detailed analysis of the effects of damage to each brain region in the same sustained attention task used in our previous work. Rats were trained in the task before surgery and post-surgical testing examined performance in response to unpredictable light signals of 1500 ms and 4000 ms duration. Data for PPTg lesioned rats were compared to control rats, and rats with 192 IgG saporin infusions centred on the NbM. In addition to operant data, video data of rats' performance during the task were also analysed.     

Carbon–chalcogen bond formation initiated by [Al(NONDipp)(E)]− anions containing Al–E{16} (E{16} = S,Se) multiple bonds

Multiply-bonded main group metal compounds are of interest as a new class of reactive species able to activate and functionalize a wide range of substrates. The aluminium sulfido compound K[Al(NON^Dipp)(S)] (NON^Dipp = [O(SiMe₂NDipp)₂]²⁻, Dipp = 2,6-ⁱPr₂C₆H₃), completing the series of [Al(NON^Dipp)(E)]⁻ anions containing Al–E{16} multiple bonds (E{16} = O, S, Se, Te), was accessed via desulfurisation of K[Al(NON^Dipp)(S₄)] using triphenylphosphane. The crystal structure showed a tetrameric aggregate joined by multiple K⋯S and K⋯π(arene) interactions that were disrupted by the addition of 2.2.2-cryptand to form the separated ion pair, [K(2.2.2-crypt)][Al(NON^Dipp)(S)]. Analysis of the anion using density functional theory (DFT) confirmed multiple-bond character in the Al–S group. The reaction of the sulfido and selenido anions K[Al(NON^Dipp)(E)] (E = S, Se) with CO₂ afforded K[Al(NON^Dipp)(κ²E,O-EC{O}O)] containing the thio- and seleno-carbonate groups respectively, consistent with a [2 + 2]-cycloaddition reaction and C–E bond formation. An analogous cycloaddition reaction took place with benzophenone affording compounds containing the diphenylsulfido- and diphenylselenido-methanolate ligands, [κ²E,O-EC{O}Ph₂]²⁻. In contrast, when K[Al(NON^Dipp)(E)] (E = S, Se) was reacted with benzaldehyde, two equivalents of substrate were incorporated into the product accompanied by formation of a second C–E bond and complete cleavage of the Al–E{16} bonds. The products contained the hitherto unknown κ²O,O-thio- and κ²O,O-seleno-bis(phenylmethanolate) ligands, which were exclusively isolated as the cis-stereoisomers. The mechanisms of these cycloaddition reactions were investigated using DFT methods.

Reaction of Al–E (E = S, Se) multiple bonds with C O functionalities generates new C–E bonds.     

Design of Oligourea-Based Foldamers with Antibacterial and Antifungal Activities

There is an urgent need to develop new therapeutic strategies to fight the emergence of multidrug resistant bacteria. Many antimicrobial peptides (AMPs) have been identified and characterized, but clinical translation has been limited partly due to their structural instability and degradability in physiological environments. The use of unnatural backbones leading to foldamers can generate peptidomimetics with improved properties and conformational stability. We recently reported the successful design of urea-based eukaryotic cell-penetrating foldamers (CPFs). Since cell-penetrating peptides and AMPs generally share many common features, we prepared new sequences derived from CPFs by varying the distribution of histidine- and arginine-type residues at the surface of the oligourea helix, and evaluated their activity on both Gram-positive and Gram-negative bacteria as well as on fungi. In addition, we prepared and tested new amphiphilic block cofoldamers consisting of an oligourea and a peptide segment whereby polar and charged residues are located in the peptide segment and more hydrophobic residues in the oligourea segment. Several foldamer sequences were found to display potent antibacterial activities even in the presence of 50% serum. Importantly, we show that these urea-based foldamers also possess promising antifungal properties.