Capillarity driven instability of a soft solid

We report the observation of a Plateau instability in a thin filament of solid gel with a very small elastic modulus. A longitudinal undulation of the surface of the cylinder reduces its area thereby triggering capillary instability, but is counterbalanced by elastic forces following the deformation. This competition leads to a nontrivial instability threshold for a solid cylinder. The ratio of surface tension to elastic modulus defines a characteristic length scale. The onset of linear instability is when the radius of the cylinder is one-sixth of this length scale, in agreement with theory presented here.     

The mechanisms of the homogeneous,unimolecular, elimination kinetics of several β‐substituted diethyl acetals in the gas‐phase

The rates of gas‐phase elimination of several β‐substituted diethyl acetals have been determined in a static system and seasoned with allyl bromide. The reactions, inhibited with toluene, are homogeneous, unimolecular, and follow first‐order law kinetics. These elimination processes involve two parallel reactions. The first parallel reaction yields ethanol and the corresponding ethyl vinyl ether. The latter product is an unstable intermediate and further decomposes to ethylene and the corresponding substituted aldehyde. The second parallel reaction gives ethane and the corresponding ethyl ester. The kinetics has been measured over the temperature range of 370–441 °C and pressure range of 23–160 torr. The rate coefficients are given by the following Arrhenius equations: The differences in the rates of ethanol formation may be attributed to electronic transmission of the β‐substituent. The comparative kinetic and thermodynamic parameters of the parallel reactions suggest two different concerted polar four‐membered cyclic transition state types of mechanisms. Copyright © 2010 John Wiley & Sons, Ltd.     

Second-Order Data Obtained by Time-Resolved Room Temperature Phosphorescence. A New Approach for PARAFAC Multicomponent Analysis

A second-order multivariate calibration approach, based on a combination of PARAFAC with time-resolved room temperature phosphorescence (RTP), has been applied to resolve a binary mixture of Phenanthrene and 1,10-Phenanthroline, as model compounds. The RTP signals were obtained in aqueous β-cyclodextrin solutions, in the presence of several heavy atom containing compounds. No deoxygenation was necessary to obtain the phosphorescence signals, which adds simplicity to the method. The resolution of the model compounds was possible in base to the differences in the delay-time of the RTP signals of the investigated analytes, opening a new approach for second-order data generation and subsequent second order multivariate calibration.     

Substituent effects in the Baeyer–Villiger reaction of acetophenones: a theoretical study

This paper reports the first complete theoretical study of substituent effects on the mechanism of the Baeyer– Villiger (BV) reaction in non‐polar solvents taking into account the lowest‐energy mechanism that has been proposed for this rearrangement which is non‐ionic and fully concerted. The BV reaction of p‐substituted acetophenones, p‐XC₆H₄COCH₃ (X = NO₂, CN, H, CH₃, OCH₃), with performic (PFA) and trifluoroperacetic (TFPAA) acids, catalyzed by formic (FA) and trifluoroacetic (TFAA) acids, respectively, using the MPWB1K functional and the 6‐311G(d,p) and 6‐311++G(d,p) basis sets, are studied. Solvent effects are taken into account by means of the PCM continuum model using dichloromethane as solvent. Electron‐donating substituents on the aryl group have a relatively small activation effect on the first step, but a pronounced activation effect on the second to the point of being able to change the rate‐determining step (RDS) of the reaction, as observed in the case of p‐methoxyacetophenone with TFPAA acids. After analyzing the changes in Gibbs free energy of activation, geometrical parameters, and charge distributions of the transition states (TSs), explanations are provided for the two distinct effects that substituents on the ketone have on the kinetics of the addition and migration steps of the BV oxidation. The effect of the acid/peracid pair used is also discussed. Copyright © 2008 John Wiley & Sons, Ltd.     

Bell Peppers (Capsicum annum L.) Losses and Wastes: Source for Food and Pharmaceutical Applications

Currently, the high added-value compounds contained in plant by-products and wastes offer a wide spectrum of opportunities for their reuse and valorization, contributing to the circular economy. The bell pepper (Capsicum annum L.) is an exotic vegetable with high nutritional value that, after processing, leaves wastes (peel, seeds, and leaves) that represent desirable raw material for obtaining phytochemical compounds. This review summarizes and discusses the relevant information on the phytochemical profile of bell peppers and their related biological properties as an alternative to revalorize losses and wastes from bell peppers for their application in the food and pharmaceutical industries. Bell pepper fruits, seeds, and leaves contain bioactive compounds (phenols, flavonoids, carotenoids, tocopherol, and pectic polysaccharides) that exhibit antioxidant, antibacterial, antifungal, immunosuppressive and immunostimulant properties, and antidiabetic, antitumoral and neuroprotective activities, and have a potential use as functional food additives. In this context, the revalorization of food waste is positioned as a technological and innovative research area with beneficial effects for the population, the economy, and the environment. Further studies are required to guarantee the safety use of these compounds and to understand their mechanisms of action.     

Reduced carbon solubility in Fe nanoclusters and implications for the growth of single-walled carbon nanotubes

Fe nanoclusters are becoming the standard catalysts for growing single-walled carbon nanotubes via chemical vapor decomposition. Contrary to the Gibbs-Thompson model, we find that the reduction of the catalyst size requires an increase of the minimum temperature necessary for the growth. We address this phenomenon in terms of solubility of C in Fe nanoclusters and, by using first-principles calculations, we devise a simple model to predict the behavior of the phases competing for stability in Fe-C nanoclusters at low temperature. We show that, as a function of particle size, there are three scenarios compatible with steady state growth, limited growth, and no growth of single-walled carbon nanotubes, corresponding to unaffected, reduced, and no solubility of C in the particles.     

Hot and cold electron dynamics following high-intensity laser matter interaction

The characteristics of fast electrons laser accelerated from solids and expanding into a vacuum from the rear target surface have been measured via optical probe reflectometry. This allows access to the time- and space-resolved dynamics of the fast electron density and temperature and of the energy partition into bulk (cold) electrons. In particular, it is found that the density of the hot electrons on the target rear surface is bell shaped, and that their mean energy at the same location is radially homogeneous and decreases with the target thickness.     

Transition to Fulde-Ferrel-Larkin-Ovchinnikov phases near the tricritical point: an analytical study

We explore analytically the nature of the transition to the Fulde-Ferrel-Larkin-Ovchinnikov superfluid phases in the vicinity of the tricritical point, where these phases begin to appear. We make use of an expansion of the free energy up to an overall sixth order, both in order parameter amplitude and in wavevector. We first explore the minimization of this free energy within a subspace, made of arbitrary superpositions of plane waves with wavevectors of different orientations but same modulus. We show that the standard second order FFLO phase transition is unstable and that a first order transition occurs at higher temperature. Within this subspace we prove that it is favorable to have a real order parameter and that, among these states, those with the smallest number of plane waves are preferred. This leads to an order parameter with a cos( ^. ) dependence, in agreement with preceding work. Finally we show that the order parameter at the transition is only very slightly modified by higher harmonics contributions when the constraint of working within the above subspace is released. Received 20 February 2002 / Received in final form 4 June 2002 Published online 13 August 2002     

Asymptotic linearization and stabilization for a class of nonlinear systems

This paper presents a nonlinear output feedback which asymptotically linearizes the class of nonlinear, continuous-time, affine in the control systems having relative degree equal to the state space dimension. Moreover, we show that any set of eigenvalues can be assigned for the asymptotic closed-loop linear system. The controller is based on a nonlinear observer, presented in a previous paper, and on the linearizing state feedback proposed by Isidori and computed in the estimated state. The main result obtained is equivalent to the separation theorem in the linear case.This work was supported by the Italian Ministry for University and Scientific and Technological Research.