New examples of template catalysis based processes: glycerol-like units as efficient promoters for dehydrative nucleophilic substitutions of ferrocenylmethanol

The direct high-yield synthesis without solvent and catalyst, under mild conditions, of eleven novel mono substituted ferrocenylmethyl ethers and amine derivatives from ferrocenemethanol and vicinal oxygenated alcohols and amines is here reported. The peculiar ability of these classes of non acidic compounds to favor the dehydrative nucleophilic substitution is attributed to the presence of vicinal oxygen atoms to the reactive group able to build a hydrogen bonding network with the reactant. The role of carbon dioxide and hexafluoroisopropanol was investigated to support the hypothesis that a template catalysis effect is occurring. The in vitro anti-fungal activity of some of these derivatives was tested on two plant fungi, Botrytis cinerea and Penicillium species, with moderate activity.     

Synthesis of tris and tetraisoxazole compounds

The syntheses of new tris (XII) and tetraisoxazole compounds (XIII and XIV) are reported; all synthons have been described. New isoxazole chlorooximes (V and VIII) have been prepared for this purpose and their behavior was examined.     

Development and validation of sensitive methods for determination of sibutramine hydrochloride monohydrate and direct enantiomeric separation on a protein-based chiral stationary phase

Sibutramine hydrochloride monohydrate, chemically 1-(4-chlorophenyl)-N,N-dimethyl-alpha-(2-methylpropyl) hydrochloride monohydrate (SB.HCI.H20), was approved by the U.S. Food and Drug Administration for the treatment of obesity. The objective of this study was to develop, validate, and compare methods using UV-derivative spectrophotometry (UVDS) and reversed-phase high-performance liquid chromatography (HPLC) for the determination of SB.HCI.H20 in pharmaceutical drug products. The UVDS and HPLC methods were found to be rapid, precise, and accurate. Statistically, there was no significant difference between the proposed UVDS and HPLC methods. The enantiomeric separation of SB was obtained on an alpha-1-acid glycoprotein column. The R- and S-sibutramine were eluted in < 5 min with baseline separation of the chromatographic peaks (alpha = 1.9 and resolution = 1.9).     

A 3-D phenomenological constitutive model for shape memory alloys under multiaxial loadings

This paper presents a new phenomenological constitutive model for shape memory alloys, developed within the framework of irreversible thermodynamics and based on a scalar and a tensorial internal variable. In particular, the model uses a measure of the amount of stress-induced martensite as scalar internal variable and the preferred direction of variants as independent tensorial internal variable. Using this approach, it is possible to account for variant reorientation and for the effects of multiaxial non-proportional loadings in a more accurate form than previously done. In particular, we propose a model that has the property of completely decoupling the pure reorientation mechanism from the pure transformation mechanism. Numerical tests show the ability to reproduce main features of shape memory alloys in proportional loadings and also to improve prediction capabilities under non-proportional loadings, as proven by the comparison with several experimental results available in the literature.     

Performance evaluation of shape-memory-alloy superelastic behavior to control a stay cable in cable-stayed bridges

This paper focuses on introducing and investigating the performance of a new passive control device for stay cable in cable-stayed bridges made with shape-memory alloys (SMA). The superelasticity and damping capability of SMA is sought in this study to develop a supplementary energy dissipation device for stay cable. A linear model of a sag cable and a one-dimensional constitutive model for the SMA are used. The problem of the optimal design of the device is studied. In the optimization problem, an energy criterion associated with the concept of optimal performance of the hysteretic connection is used. The maximum dissipation energy depends on the cross-sectional area, the length, and the location of the SMA on the cable. The effectiveness of the SMA damper in controlling the cable displacement is assessed. Furthermore, a study is conducted to determine the sensitivity of the cable response to the properties of the SMA device. The comparison between the SMA damper and a more classical passive control energy dissipation device, i.e., the tuned mass damper (TMD), is carried out. The numerical results show the effectiveness of the SMA damper to damp the high free vibration and the harmonic vibration better than an optimal TMD.     

A one-dimensional model for superelastic shape-memory alloys with different elastic properties between austenite and martensite

The present work addresses a one-dimensional model able to reproduce the shape-memory-alloy superelastic behavior, taking into account the different elastic properties between austenite and martensite. The model is based on a single scalar internal variable, the martensite fraction, for which evolutionary equations in rate form are proposed. The dependency of the elastic modulus in terms of the martensite fraction is computed through different homogenization techniques. Integration in time leads to the time-discrete evolutionary equations, for which a detailed analysis in terms of admissible roots is presented, together with the expression of the consistent tangent modulus. The solution of the time-discrete model is approached through a return map algorithm, properly modified for the case of phase transitions of the type occurring in shape-memory materials. Finally, the ability of the model to simulate one-dimensional experimental data is assessed.     

On the geometrically exact beam model: A consistent,effective and simple derivation from three-dimensional finite-elasticity

The goal of the present work is to emphasize some intrinsic features of the three-dimensional beam model originally proposed by Simo [Simo, J.C., 1985. A finite-strain beam formulation. The three-dimensional dynamic problem. Part I. Comput. Methods Appl. Mech. Eng. 49, 55–70] and to derive the model equations for the general finite-deformation case as well as for the finite-deformation small-strain case in a consistent but simpler way with respect to what it is generally done in the literature.     

A 3D finite strain phenomenological constitutive model for shape memory alloys considering martensite reorientation

Most devices based on shape memory alloys experience both finite deformations and non-proportional loading conditions in engineering applications. This motivates the development of constitutive models considering finite strain as well as martensite variant reorientation. To this end, in the present article, based on the principles of continuum thermodynamics with internal variables, a three-dimensional finite strain phenomenological constitutive model is proposed taking its basis from the recent model in the small strain regime proposed by Panico and Brinson (J Mech Phys Solids 55:2491–2511, 2007). In the finite strain constitutive model derivation, a multiplicative decomposition of the deformation gradient into elastic and inelastic parts, together with an additive decomposition of the inelastic strain rate tensor into transformation and reorientation parts is adopted. Moreover, it is shown that, when linearized, the proposed model reduces exactly to the original small strain model.