Synthesis of β,γ-unsaturated primary amides from α,β-unsaturated acids and investigation of the mechanism

α,β-Unsaturated acids, through their acid chlorides, react with tritylamine in the presence of triethylamine under mild conditions, to afford in high yield and high regioselectivity the corresponding β,γ-unsaturated tritylamides. Detritylation with TFA generates quantitatively β,γ-unsaturated primary amides. An investigation of this deconjugative isomerization was performed.     

Thermoanalytical, magnetic and structural study of Co(II) complexes with substituted salicylaldehydes and neocuproine

In this study, simultaneous TG/DTG-DTA technique was used for two cobalt(II) complexes with neocuproine(neoc) and the anion of a substituted salicylaldehyde ligand (X-salo) (X?=?3-OCH₃, or 5-CH₃) with the general formula [Co(X-salo)₂(neoc)], to determine their thermal degradation in inert atmosphere, which was found to be a multi-step decomposition related to the release of the ligand molecules. The solid material at 1300?°C (verified with PXRD) was a mixture of carbonaceous metal cobalt. Evolved gas analysis by coupled TG-MS verified the elimination of a formaldehyde molecule in the first decomposition stage, initially proposed by the percentage mass loss data. By single-crystal X-ray diffraction analysis an octahedral geometry of the complex [Co(3-OCH₃-salo)₂(neoc)] was found. The variable temperature magnetic susceptibility measurements showed a paramagnetic nature of the complexes, in accordance with their molecular structure. Finally, for the determination of the activation energy (E) two different methods (the isoconversional methods of Ozawa, Flynn and Wall (OFW) and Friedman) were used comparatively.     

Physical interpretation of a modified Lorentz dielectric function for metals based on the Lorentz–Dirac force

It is proposed that a recently used ad hoc modified Lorentz dielectric function for metals can be physically interpreted via the Lorentz–Dirac force. The Lorentz–Dirac force considers the radiation reaction of electrons, an effect that is ignored in classical dispersion relationships. A suitable reduced order form of the Lorentz–Dirac force that does not suffer from pre-acceleration and runaway artifacts is employed in the derivation of the modified dispersion model. The frequency characteristics and the causality of the Lorentz–Dirac dielectric model are studied in detail. Furthermore, the superiority of the Lorentz–Dirac dielectric function as a means of improved fitting of experimental data is demonstrated for gold, silver, and silicon in the infrared and optical region.     

Mass hierarchy, mass gap and corrections to Newton’s law on thick branes with Poincaré symmetry

We consider a scalar thick brane configuration arising in a 5D theory of gravity coupled to a self-interacting scalar field in a Riemannian manifold. We start from known classical solutions of the corresponding field equations and elaborate on the physics of the transverse traceless modes of linear fluctuations of the classical background, which obey a Schrödinger-like equation. We further consider two special cases in which this equation can be solved analytically for any massive mode with $m^2\ge 0$ , in contrast with numerical approaches, allowing us to study in closed form the massive spectrum of Kaluza–Klein (KK) excitations and to analytically compute the corrections to Newton’s law in the thin brane limit. In the first case we consider a novel solution with a mass gap in the spectrum of KK fluctuations with two bound states—the massless 4D graviton free of tachyonic instabilities and a massive KK excitation—as well as a tower of continuous massive KK modes which obey a Legendre equation. The mass gap is defined by the inverse of the brane thickness, allowing us to get rid of the potentially dangerous multiplicity of arbitrarily light KK modes. It is shown that due to this lucky circumstance, the solution of the mass hierarchy problem is much simpler and transparent than in the thin Randall–Sundrum (RS) two-brane configuration. In the second case we present a smooth version of the RS model with a single massless bound state, which accounts for the 4D graviton, and a sector of continuous fluctuation modes with no mass gap, which obey a confluent Heun equation in the Ince limit. (The latter seems to have physical applications for the first time within braneworld models). For this solution the mass hierarchy problem is solved with positive branes as in the Lykken–Randall (LR) model and the model is completely free of naked singularities. We also show that the scalar–tensor system is stable under scalar perturbations with no scalar modes localized on the braneworld configuration.     

Application of an effective medium theory for modeling ultrasound wave propagation in healing long bones

Quantitative ultrasound has recently drawn significant interest in the monitoring of the bone healing process. Several research groups have studied ultrasound propagation in healing bones numerically, assuming callus to be a homogeneous and isotropic medium, thus neglecting the multiple scattering phenomena that occur due to the porous nature of callus. In this study, we model ultrasound wave propagation in healing long bones using an iterative effective medium approximation (IEMA), which has been shown to be significantly accurate for highly concentrated elastic mixtures. First, the effectiveness of IEMA in bone characterization is examined: (a) by comparing the theoretical phase velocities with experimental measurements in cancellous bone mimicking phantoms, and (b) by simulating wave propagation in complex healing bone geometries by using IEMA. The original material properties of cortical bone and callus were derived using serial scanning acoustic microscopy (SAM) images from previous animal studies. Guided wave analysis is performed for different healing stages and the results clearly indicate that IEMA predictions could provide supplementary information for bone assessment during the healing process. This methodology could potentially be applied in numerical studies dealing with wave propagation in composite media such as healing or osteoporotic bones in order to reduce the simulation time and simplify the study of complicated geometries with a significant porous nature.     

Fluctuation analysis for the loss from default

We analyze the fluctuation of the loss from default around its large portfolio limit in a class of reduced-form models of correlated firm-by-firm default timing. We prove a weak convergence result for the fluctuation process and use it for developing a conditionally Gaussian approximation to the loss distribution. Numerical results illustrate the accuracy and computational efficiency of the approximation.     

Detection of multiple cardiac markers with an integrated acoustic platform for cardiovascular risk assessment

This work describes the application of a newly emerged biosensing configuration incorporating a Surface Acoustic Wave device integrated with a multi-channel microfluidic module for the rapid and efficient analysis of cardiac markers. The examined cardiac markers of creatine kinase MB (CK-MB), cardiac reactive protein (CRP), D-dimer and pregnancy-associated plasma protein A (PAPP-A), comprise a group of both established and emerging heart disease proteins, that has never been probed before with any kind of biochip-related platform. The four markers were successfully detected; kinetics and affinity studies on their interactions with the surface immobilized antibodies are also presented. A concentration detection limit of less than 1 nM was achieved, with a dynamic range of more than two orders of magnitude, covering some of the pathological and healthy areas of interest. Mixtures of biomarkers applied to the device surface were used to prove the specificity of each binding event and investigate the microsystem's performance in the presence of complex fluids, towards future utilization with real samples. The simplicity and multiplexing ability of the integrated platform render the system ideal as a potential diagnostic tool for cardiovascular risk assessment, where simultaneous analysis of various protein markers is required.     

In situ SAXS investigation of dibromomethane adsorption in ordered mesoporous silica

A SAXS/WAXS apparatus with the aid of a specially designed sample cell capable for performing both SAXS and WAXS experiments was used for adsorption studies in nanoporous materials. The applicability of the instrument for structural investigations and its ability for adsorption experiments because of the advanced sample environment were demonstrated by carrying out in situ SAXS measurements during gas physisorption. SAXS profiles of ordered mesoporous silica were measured at selected equilibrium points alongside a dibromomethane (CH₂Br₂) adsorption isotherm at 293 K. SBA-15 was the adsorbent of choice because it consists of a regular 2D hexagonal array of cylindrical mesopores that gives rise to Bragg reflections in the small-angle regime. CH₂Br₂ was selected as a contrast-matching fluid because it has almost the same electron density as silica. We obtained high-quality data comparable to those resulting from experiments performed in synchrotron light sources which produce intense beams of x-rays and support advanced instrumentation for high-resolution diffraction and SAXS studies. The Bragg peaks of the pore lattice are clearly visible for the evacuated sample and at the early stages of the adsorption process. The intensity decrease and the elimination of the Bragg peaks for the saturated sample suggest that an almost perfect contrast matching was achieved. A model has been used for monitoring the fluid condensation and evaporation regime in SBA-15 by taking into account both the Bragg scattering and the diffuse scattering for spatially random pore filling. The results show the absence of spatial correlations between filled pores suggesting random pore filling.     

In situ small angle X-ray scattering and benzene adsorption on polymer-based carbon hollow fiber membranes

The structural changes and the mechanism of benzene adsorption on microporous carbon hollow fiber membranes with different surface and pore network properties have been investigated by in situ small-angle X-ray scattering (SAXS) and benzene adsorption. Benzene adsorption measurements have been carried out in situ with SAXS alongside an adsorption/desorption isotherm cycle at 293 K with the aid of a specially constructed adsorption sample cell. In addition low-pressure C₆H₆ and high-pressure CO₂, CH₄ and N₂ adsorption isotherms have been performed. Two carbon hollow fiber membranes, both prepared by controlled pyrolysis procedures of polyimide membrane precursor, were under study. During benzene adsorption the intensity of the SAXS curves changes in a way that depends on how the pores are filled and the contrast fluctuations occur. The SAXS data have been modeled by evaluating the form factor of lamellar micropores upon filling with C₆H₆. The existence of ultra micropores within the surrounding matrix was also taken into account. The results suggest that the arrangement of the ultra micropores on the non-activated membrane is in such a way that the access of benzene to the micropores is restricted, resulting in an incomplete filling. On the other hand, the activation process generates a more accessible pore network where the micropores are completely filled.