Covalently Trapped Triarylamine-Based Supramolecular Polymers

C₃-Symmetric triarylamine trisamides (TATAs), decorated with three norbornene end groups, undergo supramolecular polymerization and further gelation by π–π stacking and hydrogen bonding of their TATA cores. By using subsequent ring-opening metathesis polymerization, these physical gels are permanently crosslinked into chemical gels. Detailed comparisons of the supramolecular stacks in solution, in the physical gel, and in the chemical gel states, are performed by optical spectroscopies, electronic spectroscopies, atomic force microscopy, electronic paramagnetic resonance spectroscopy, X-ray scattering, electronic transport measurements, and rheology. The results presented here clearly evidence that the core structure of the functional supramolecular polymers can be precisely retained during the covalent capture whereas the mechanical properties of the gels are concomitantly improved, with an increase of their storage modulus by two orders of magnitude.     

Unprecedented Reverse Volume Expansion in Spin-Transition Crystals

The current craze for research around the spin crossover phenomenon can be justified to some extent by the mechanical properties due to the decrease of volume associated with the transition of the metal ion from the HS state to the LS state. As demonstrated here, the molecular complex [Fe(PM-pBrA)₂(NCS)₂] exhibits, on the contrary, an increase of the unit-cell volume from HS to LS. This counter-intuitive and unprecedented behavior that concerns both the thermal and the photoexcited spin conversions is revealed by a combination of single-crystal and powder X-ray diffraction complemented by magnetic measurements. Interestingly, this abnormal volume change appears concomitant with the wide rotation of a phenyl ring which induces a drastic modification, though reversible, of the structural packing within the crystal. In addition, the light-induced HS state obtained through the Light-Induced Excited Spin-State Trapping shows a remarkably high relaxation temperature, namely T(LIESST), of 109 K, one of the highest so far reported. The above set of quite unusual characteristics opens up new fields of possibilities within the development of spin crossover materials.     

Silver ionic conductivity enhancement by network former mixed in oxide-based glasses

Glasses in the binary system xAg₂P₂O₆ − (1 − x)Ag₂Te₂O₅ have been prepared for 0 x 1. For each composition only one glass transition temperature is observed in the temperature range of 180–220 °C. All glasses appear homogeneous considering their optical and electrical properties. Nevertheless, in SEM observations, some glass compositions appear to be heterogeneous after decoration following short nitric acid etching. For each composition, conductivity data obtained in the temperature range of 25–200 °C using impedance techniques obey an Arrhenius relationship with a composition independent pre-exponential term. Variation of the conductivity activation energy with x induces correlative variations of isothermal conductivity curves leading to an increase of the ionic conductivity of about one order of magnitude compared with linearity at 25 °C. This behaviour is discussed with respect to the thermodynamic properties of the glassy solutions.     

A Runge-Kutta method for index 1 stochastic differential-algebraic equations with scalar noise

The paper deals with the numerical treatment of stochastic differential-algebraic equations of index one with a scalar driving Wiener process. Therefore, a particularly customized stochastic Runge-Kutta method is introduced. Order conditions for convergence with order 1.0 in the mean-square sense are calculated and coefficients for some schemes are presented. The proposed schemes are stiffly accurate and applicable to nonlinear stochastic differential-algebraic equations. As an advantage they do not require the calculation of any pseudo-inverses or projectors. Further, the mean-square stability of the proposed schemes is analyzed and simulation results are presented bringing out their good performance.     

Adductor spasmodic dysphonia: case reports withacoustic analysis following botulinum toxin injection and acupuncture

We analyzed frequency and duration parameters of voice and speech in two men with adductor spasmodic dysphonia (SD). One was treated with botulinum toxin injection; the other received acupuncture therapy. Im provement after acupuncture therapy in terms of standard deviation of fundamental frequency, acoustic perturbation measurements, durational measurements of voice and speech, and spectrographic analysis was comparable to the results achieved with botulinum toxin injection. Voice and speech parameters were stable I year after acupuncture therapy.     

Retaining positive definiteness in thresholded matrices

Positive definite (p.d.) matrices arise naturally in many areas within mathematics and also feature extensively in scientific applications. In modern high-dimensional applications, a common approach to finding sparse positive definite matrices is to threshold their small off-diagonal elements. This thresholding, sometimes referred to as hard-thresholding, sets small elements to zero. Thresholding has the attractive property that the resulting matrices are sparse, and are thus easier to interpret and work with. In many applications, it is often required, and thus implicitly assumed, that thresholded matrices retain positive definiteness. In this paper we formally investigate the algebraic properties of p.d. matrices which are thresholded. We demonstrate that for positive definiteness to be preserved, the pattern of elements to be set to zero has to necessarily correspond to a graph which is a union of complete components. This result rigorously demonstrates that, except in special cases, positive definiteness can be easily lost. We then proceed to demonstrate that the class of diagonally dominant matrices is not maximal in terms of retaining positive definiteness when thresholded. Consequently, we derive characterizations of matrices which retain positive definiteness when thresholded with respect to important classes of graphs. In particular, we demonstrate that retaining positive definiteness upon thresholding is governed by complex algebraic conditions.     

Surface morphology and composition of c-, a- and m-sapphire surfaces in O2 and H2 environments

This paper reports that monitoring the composition of the c(0 0 0 1), a(11–20) and m(10–10) sapphire surfaces is essential for a proper interpretation of the surface morphologies obtained after annealing at 1253 and 1473 K in ArH₂ or ArO₂ atmospheres. Our experimental investigations, which have used Auger electron spectroscopy (AES) and atomic force microscopy (AFM) on the surfaces of 99.99% pure sapphire wafers, have led to the following original conclusions: (i) Calcium segregates at the c-surface of sapphire both under ArO₂ and ArH₂. (ii) Potassium adsorption enhances the kinetics of step-bunching on the c-surface under ArO₂. (iii) The step edges on the a-surface may develop a comb-like morphology made of parallel strips along the [10–10] direction. (iv) At 1253 K, clean m-surfaces may be stable. (v) Under ArH₂, alumina surface diffusion is much slower than under ArO₂ for all surface orientations, the surface concentration of impurities is low, and the Al–O ratio of the AES signals at the surface is significantly larger.     

Feasibility of using ultrasound contrast agents to increase the size of thermal lesions induced by non-focused transducers: in vitro demonstration in tissue mimicking phantom

Miniature flat ultrasound transducers have shown to be effective for a large variety of thermal therapies, but the associated superficial heating implicates developing original strategies in order to extend therapeutic depth. The goal of the present paper is to use ultrasound contrast agents (UCA) to increase remote attenuation and heating. Theoretical simulations demonstrated that increasing attenuation from 0.27 to 0.8 Np/cm at 10 MHz beyond a distance of 18 mm from the transducer should result in longer thermal damages due to protein coagulation in a tissue mimicking phantom. Contrast agents (BR14, Bracco, Plan-les-Ouates, Switzerland) were embedded in thermo-sensitive gel and attenuations ranging from 0.27 to 1.33 Np/cm were measured at 10 MHz for concentrations of BR14 between 0 and 4.8%. Thermal damages were then induced in several gels, which had different layering configurations. Thermal damages, 12.8 mm in length, were obtained in homogeneous gels. When mixing contrast agents at a concentration of 3.2% beyond a first 18 mm-thick layer of homogeneous gel, the thermal damages reached 21.5 mm in length. This work demonstrated that contrast agents can be used for increasing attenuation remotely and extending therapeutic depth induced by a non-focused transducer. Additional work must be done in vivo in order to verify the remote-only distribution of bubbles and associated increase in attenuation.     

Controlled Space Radiation concept for mesh-free semi-analytical technique to model wave fields in complex geometries

Numerical modelling of the ultrasonic wave propagation is important for Structural Heath Monitoring and System Prognosis problems. In order to develop intelligent and adaptive structures with embedded damage detector and classifier mechanisms, detailed understanding of scattered wave fields due to anomaly in the structure is inevitably required. A detailed understanding of the problem demands a good modelling of the wave propagation in the problem geometry in virtual form. Therefore, efficient analytical, semi-analytical or numerical modelling techniques are required. In recent years a semi-analytical mesh-free technique called Distributed Point Source Method (DPSM) is being used for modelling various ultrasonic, electrostatic and electromagnetic wave field problems. In the conventional DPSM approach point sources are placed along the transducer faces, problem boundaries and interfaces to model incident and scattered fields. Every point source emits energy in all directions uniformly. Source strengths of these 360° radiation sources are obtained by satisfying interface and boundary conditions of the problem. In conventional DPSM modelling approach it is assumed that the shadow zone does not require any special consideration. 360° Radiation point sources should be capable of properly modelling shadow zones because all boundary and interface conditions are satisfied. In this paper it is investigated how good this assumption is by introducing the ‘shadow zone’ concept at the point source level and comparing the results generated by the conventional DPSM and by this modified approach where the conventional 360° radiation point sources are replaced by the Controlled Space Radiation (CSR) sources.     

Essential countability of treeable equivalence relations

We establish a dichotomy theorem characterizing the circumstances under which a treeable Borel equivalence relation E is essentially countable. Under additional topological assumptions on the treeing, we in fact show that E   is essentially countable if and only if there is no continuous embedding of _E1${\mathbb{E}}_1$ into E. Our techniques also yield the first classical proof of the analogous result for hypersmooth equivalence relations, and allow us to show that up to continuous Kakutani embeddability, there is a minimum Borel function which is not essentially countable-to-one.