Ring-strain effects on the oxidation potential of enediynes and enediyne complexes

The metal-enediyne complexes [(eta 5-C5H5)Fe[eta 5-1,2-C5H3C identical to C(CH2)nC identical to]] (4, n = 4; 5, n = 5) and [(eta 5-C5H5)-Fe[eta 5-1,2-C5H3(C identical to C Me)2]] (6) were prepared from 1,2-diethynylferrocene (3). Complexes 4 and 5 were characterized in the solid state by X-ray crystallographic analysis. The structures of 4 and 6 were determined by computation using ab initio methods. A correlation was observed between ring-strain and increased ease of electrochemical oxidation along the series 6 (+0.164 V) to 5(+0.152 V) to 4 (+0.123 V). A similar trend in ionization potentials was identified in both the gas phase and in solution by computational methods.     

A wireless magnetoelastic biosensor for the direct detection of organophosphorus pesticides

An organophosphorus (OP) pesticide sensor was fabricated by applying a pH-sensitive polymer coating and organophosphorus hydrolase (OPH) enzyme onto the surface of a magnetoelastic sensor, the magnetic analogue of the better-known surface acoustic wave sensor. Organophosphorus hydrolase catalyses the hydrolysis of a wide range of organophosphorus compounds, which changes the pH in the hydrogel. This article describes the application of the magnetoelastic sensor for the detection of OP pesticides by measuring the changes in viscoelasticity caused by the swelling/shrinking of the pH-responsive polymer when exposed to the pesticides. The sensor was successfully used to detect paraoxon and parathion down to a concentration of 1 x 10(-7) and 8.5 x 10(-7) M respectively.     

Modeling and simulation of the motion of nanoparticles in cylindrical capillaries allowing particle‐to‐wall interactions

The process of transporting nanoparticles at the blood vessels level stumbles upon various physical and physiological obstacles; therefore, a Mathematical modeling will provide a valuable means through which to understand better this complexity. In this paper, we consider the motion of nanoparticles in capillaries having cylindrical shapes (i.e., tubes of finite size). Under the assumption that these particles have spherical shapes, the motion of these particles reduces to the motion of their centers. Under these conditions, we derive the mathematical model, to describe the motion of these centers, from the equilibrium of the gravitational force, the hemodynamic force and the van der Waals interaction forces. We distinguish between the interaction between the particles and the interaction between each particle and the walls of the tube. Assuming that the minimum distance between the particles is large compared with the maximum radius R of the particles and hence neglecting the interactions between the particles, we derive simpler models for each particle taking into account the particles‐to‐wall interactions. At an error of order O(R) or O(R³)(depending if the particles are 'near' or 'very near' to the walls), we show that the horizontal component of each particle's displacement is solution of a nonlinear integral equation that we can solve via the fixed point theory. The vertical components of the displacement are computable in a straightforward manner as soon as the horizontal components are estimated. Finally, we support this theory with several numerical tests. Copyright © 2016 John Wiley & Sons, Ltd.     

A regioregular polyalkylthiophene bearing covalently-linked biotin, and its interaction with avidin in solution and in thin films

A regioregular copolymer of 3-hexylthiophene and 3-(6-hydroxyhex-1-yl)thiophene has been functionalised with biotin hydrazide; binding of avidin to the biotin moieties causes drastic changes to the absorption spectrum of the polymer in solution, and to the electrochemistry and conductivity of the polymer in thin films.     

Time-periodic solutions of the time-dependent Ginzburg-Landau equations of superconductivity

The problem of existence of time-periodic solutions for the time-dependent Ginzburg-Landau equations of superconductivity is discussed. It is assumed that the applied magnetic field H is -periodic in time, and so is the associated dynamical process. We prove the existence of -periodic solutions in time, which are exactly the fixed points of the associated period mapping.     

Design and characterization of new advanced energetic biopolymers based on surface functionalized cellulosic materials

A new class of energetic biopolymers, which contain nitrate ester (O-NO₂) and nitramine (N-NO₂) as explosophoric groups, was successfully synthesized by surface modification of renewable pristine cellulose (PC) and microcrystalline cellulose (MCC) via epichlorohydrin-mediated amination followed by nitration process to produce new promising energetic aminated and nitrated cellulose and microcrystalline cellulose (APCN and AMCCN). Their structural, thermal, crystallinity and morphological features were examined and compared to those of the common cellulose nitrate. Furthermore, their energetic performances were evaluated by EXPLO5 V6.04 software. Experimental results confirm the successful chemical functionalization process to develop insensitive APCN and AMCCN with outstanding features such as nitrogen content of 15.01% and 15.39%, density of 1.692 g/cm³ and 1.708 g/cm³, and detonation velocity of 7526 m/s and 7752 m/s, respectively, which are significantly higher than those of the nitrated unmodified cellulosic biopolymers. The present investigation provides a suitable pathway to design new insensitive and energy-rich dense cellulosic biopolymers for potential application in high-performance solid propellants and composite explosives.

     

Estimation of a class of quasi‐resonances generated by multiple small particles with high surface impedances

We deal with the stationary acoustic waves propagating in a cluster of small particles enjoying high contrasts. Such contrasts allow the appearance of (complex valued) resonances that are close to the real line as the size of the particles becomes small. For single (but not necessarily small) particles, we derive the characteristic equation that generates a class of these resonances (the ones for which the corresponding eigenfunctions are uniformly constant). For multiple and small particles, we provide sufficient conditions on the contrasts that generates quasi‐resonances for which the corresponding eigenfunctions are uniformly constant. Precisely, we show that, if we distribute the particles on a uniform line, then the existence of such quasi‐resonances is related to the eigenvalues of the Harary matrix. To show these results, we take, as the small contrasted particles, small obstacles with high surface impedances λ of the form λ: = βa^?1 ? αβa^{?1 + h} where a is the maximum radi of the particles, with a < <1, and β is a universal and positive constant depending only on the shape of the particles (but not on their size). In this case, if the relative constant α is an eigenvalue of the Harary matrix, then the used frequency is a quasi resonance of the cluster of the small particles where the error of approximation is of the order for h ∈ (0,1) as a < <1.     

Active learning for spectroscopic data regression

In this work, we introduce an active learning approach for the estimation of chemical concentrations from spectroscopic data. Its main objective is to opportunely collect training samples in such a way as to minimize the error of the regression process while minimizing the number of training samples used, and thus to reduce the costs related to training sample collection. In particular, we propose two different active learning strategies developed for regression approaches based on partial least squares regression, ridge regression, kernel ridge regression, and support vector regression. The first strategy uses a pool of regressors in order to select the samples with the greatest disagreements among the different regressors of the pool, while the second one is based on adding samples that are distant from the current training samples in the feature space. For support vector regression, a specific strategy based on the selection of the samples distant from the support vectors is proposed. Experimental results on three different real data sets are reported and discussed. Copyright © 2012 John Wiley & Sons, Ltd.