Influence of structural chemical characteristics on polymer chain dynamics

A comparative study of the dielectric relaxation behavior of two structurally close polymers containing aliphatic-aromatic side groups was carried out in order to get a better understanding on how slight differences in chemical structure affect the molecular responses to perturbation fields. Specifically, chain dynamics of poly(2-acryloyloxyethyl-2-naphthalene-2-ylacetate) and poly(2-methacryloyloxyethyl-2-naphthalene-2-ylacetate) were studied by broadband dielectric spectroscopy in the frequency range of 10(-2)-10(8) Hz and temperature window of 298-403 K. Also, the relaxation behavior of (2-acetyloxyethyl-2-naphthalene-2-ylacetate), model compound of the polymer side groups, was analyzed. The isotherms representing the dielectric loss in the frequency domain show important conductive contributions, especially at high temperature, which hide the low frequency side of the alpha relaxation. Conductivity also increases the real component of the complex permittivity in the low frequencies region. Retardation spectra were obtained by minimizing the sum of the squares of the difference between the experimental values of the complex permittivity for each frequency and the analytical ones, predicted by the linear phenomenological theory, using a Tikhonov regularization technique. The spectra present an apparent alpha peak with an excess wing at short time side resulting from the overlapping of the true alpha relaxation and a beta process. Three absorptions, named in increasing order of time gamma, beta, and alpha relaxations, are separated by deconvolution methods. The activation energies associated with the gamma process are 70.0+/-1.8, 68.0+/-1.4, and 74.8+/-0.8 kJ mol(-1) for (2-acetyloxyethyl-2-naphthalene-2-yl acetate), poly(2-acryloyloxyethyl-2-naphthalene-2-yl acetate) and poly(2-methacryloyloxyethyl-2-naphthalene-2-yl acetate), respectively. The respective activation energies associated with the beta relaxation are 121.7+/-2.4, 135.3+/-1.4, and 141.6+/-1.3 kJ mol(-1). Values of the shape parameters and the strengths of the relaxation processes were obtained as a function of temperature. The dynamic fragility of the polymers and the model compound was studied and compared with that reported for macromolecular and monomeric systems. Also, the evolution of the size of the correlated domains associated with the alpha relaxation was estimated. Finally, the gamma relaxation rather than the beta absorption obeys the criteria apparently held by the Johari-Goldstein beta processes.     

Sobolev estimates for constructive uniform-grid FFT interpolatory approximations of spherical functions

The fast Fourier transform (FFT) based matrix-free ansatz interpolatory approximations of periodic functions are fundamental for efficient realization in several applications. In this work we design, analyze, and implement similar constructive interpolatory approximations of spherical functions, using samples of the unknown functions at the poles and at the uniform spherical-polar grid locations \(\left (\frac {j\pi }{N}, \frac {k \pi }{N}\right )\), for j=1,…,N?1, k=0,…,2N?1. The spherical matrix-free interpolation operator range space consists of a selective subspace of two dimensional trigonometric polynomials which are rich enough to contain all spherical polynomials of degree less than N. Using the \({\mathcal {O}}(N^{2})\) data, the spherical interpolatory approximation is efficiently constructed by applying the FFT techniques (in both azimuthal and latitudinal variables) with only \({\mathcal {O}}(N^{2} \log N)\) complexity. We describe the construction details using the FFT operators and provide complete convergence analysis of the interpolatory approximation in the Sobolev space framework that are well suited for quantification of various computer models. We prove that the rate of spectrally accurate convergence of the interpolatory approximations in Sobolev norms (of order zero and one) are similar (up to a log term) to that of the best approximation in the finite dimensional ansatz space. Efficient interpolatory quadratures on the sphere are important for several applications including radiation transport and wave propagation computer models. We use our matrix-free interpolatory approximations to construct robust FFT-based quadrature rules for a wide class of non-, mildly-, and strongly-oscillatory integrands on the sphere. We provide numerical experiments to demonstrate fast evaluation of the algorithm and various theoretical results presented in the article.     

"Nonsolvent" applications of ionic liquids in biotransformations and organocatalysis

The application of room-temperature ionic liquids (RTILs) as (co)solvents and/or reagents is well documented. However, RTILS also have "nonsolvent" applications in biotransformations and organocatalysis. Examples are the anchoring of substrates to RTILs; ionic-liquid-coated enzymes (ILCE) and enzyme-IL colyophilization; the construction of biocatalytic ternary reaction systems; the combination of enzymes, RTILs, membranes, and (bio)electrochemistry; and ionic-liquid-supported organocatalysts. These strategies provide more robust, more efficient, and more enantioselective bio- and organocatalysts with many practical applications. As shown herein, RTILs offer a wide range of promising alternatives to conventional chemistry.     

Thermal induced phase transitions and structural relaxation in apoferritin encapsulated copper nanoparticles

Nanocrystalline metals display interesting basic and technological properties related to their chemical and structural properties. Among other properties, they display a richer phase diagram due to the additional degree of freedom introduced by the nanoparticles surface. Metal nanoparticles encapsulated within biological macromolecules have the additional advantage of biocompatibility. In this paper we investigate the thermal evolution of the structure and dynamics of apoferritin encapsulated nanocrystalline copper. We determined the occurrence of a yet unexpected phase transition from a low temperature FCC to a complex high temperature phase including a (putative) amorphous precursor. The occurrence of a FCC-icosahedral transition is also discussed as a possible explanation to our results. The lattice dynamics of the FCC phase (monitored by its Debye temperature) differs from the behaviour expected for nanosized structures.     

Tandem RCM-isomerization-cyclopropanation reactions

A new triple tandem process has been discovered in which simple acyclic substrates can be transformed into bicyclic compounds via RCM-double bond isomerization-cyclopropanation. This process is catalyzed by second generation Grubb's catalyst without the requirement of other reactives or additives. In addition, a one-pot RCM-isomerization reaction followed by cyclopropanation with CHCl3/NaOH allows the synthesis of products related to iNOS (nitric oxide synthase) inhibitors, which are currently under clinical evaluation.     

Study of ageing of ketone resins used as picture varnishes by FTIR spectroscopy,UV–Vis spectrophotometry,atomic force microscopy and scanning electron microscopy X-ray microanalysis

This paper presents a study of thin films of the commercial ketone resins Laropal K80, Keton N and MS2A, attempting to reproduce the pictorial layers and protective finishes commonly present in contemporary paintings. Chemical and morphological changes due to the degradation effect of environmental agents have been specially considered. For this purpose, three different accelerated ageing processes were applied to a series of specimens prepared from the studied commercial products: thermal, UV light and ageing in an SO(2)-polluted chamber. Spectroscopic techniques such as FTIR spectroscopy and UV-Vis spectrophotometry were applied in combination with microscopic examination techniques, namely, AFM and scanning electron microscopy energy dispersive X-ray microanalysis (SEM-EDX). Chemical changes due to UV light and thermal ageing are in good agreement with those previously reported in the literature. Bleaching exhibited by the three commercial products after exposure to a SO(2)-saturated atmosphere has been related to the diffusion of SO(2)-rich water vapour into the film. This effect was particularly strong in the MS2A resin due to the higher content of hydroxyl groups in this product.     

Study of the kinetics of the transport of Cu(II), Cd(II) and Ni(II) ions through a liquid membrane

The coupled transport of Cu(II), Cd(II) and Ni(II) ions through a bulk liquid membrane (BLM) containing pyridine-2-acetaldehyde benzoylhydrazone (2-APBH) as carrier dissolved in toluene has been studied. Once the optimal conditions of extraction of each metal were established, a comparative study of the transport kinetics for these metals was performed by means of a kinetic model involving two consecutive irreversible first-order reactions. The kinetic parameters (apparent rate constants of the metal extraction and re-extraction reactions (k ₁, k ₂), the maximum reduced concentration of the metal in the liquid membrane (), the time of the maximum value of R _o ( t _max) and the maximum entry and exit fluxes of the metal through the liquid membrane ( and ) of the extraction and stripping reactions were evaluated and results showed good agreement between experimental data and theoretical predictions. Complete transport through the membrane took place according to the following order: Cd(II)>Cu(II)>Ni(II), with similar kinetic parameters obtained for Cu(II) and Cd(III). The transport behaviour of Ni(II) was different to that of Cu(II) and Cd(III), probably due to the different stoichiometry of the nickel complex compared to those of the other metal ions and the different chemical conditions required for its formation. The influence of the sample salinity on the transport kinetics was studied. k ₁ values decreased slightly when the feed solution salinity was increased for Cu(II) and Ni(II), but not for Cd(II). Values of k ₂ were practically unaffected. The proposed BLM was applied to the preconcentration and separation of metal ions (prior to their determination) in water samples with different saline matrices (CRM, river water and seawater), and good agreement with the certified values was obtained.     

Comparing stage-scenario with nodal formulation for multistage stochastic problems

To solve real life problems under uncertainty in Economics, Finance, Energy, Transportation and Logistics, the use of stochastic optimization is widely accepted and appreciated. However, the nature of stochastic programming leads to a conflict between adaptability to reality and tractability. To formulate a multistage stochastic model, two types of formulations are typically adopted: the so-called stage-scenario formulation named also formulation with explicit non-anticipativity constraints and the so-called nodal formulation named also formulation with implicit non-anticipativity constraints. Both of them have advantages and disadvantages. This work aims at helping the scholars and practitioners to understand the two types of notation and, in particular, to reformulate with the nodal formulation a model that was originally defined with the stage-scenario formulation presenting this implementation in the algebraic language GAMS. In addition, this work presents an empirical analysis applying the two formulations both without any further decomposition to perform a fair comparison. In this way, we show that the difficulties to implement the model with the nodal formulation are somehow reworded making the problem tractable without any decomposition algorithm. Still, we remark that in some other applications the stage-scenario formulation could be more helpful to understand the structure of the problem since it allows to relax the non-anticipativity constraints.

     

Cycloisomerization of dienes and enynes catalysed by a modified ruthenium carbene species

Cycloisomerization is a totally atom economic procedure which converts dienes and enynes into cyclic molecules. Modification of Grubbs' 2nd generation catalysts by reaction with dimethylformamide provides a new species able to catalyse this transformation. Selection of suitable conditions allowed high yields and selectivity. Studies performed in order to identify the catalytic species point to a non-carbenic ruthenium complex that has lost the phosphine. No hydride signals appeared. In addition, the reaction works with enynes and the new species catalyses efficiently crossed cyclotrimerizations of alkynes with diynes.     

Medium-sized and strained heterocycles from non-catalysed and gold-catalysed conversions of β-carbolines

2-Allyl-1-vinyl-β-carbolines and dihydropyrrolo-β-carbolines react with activated internal alkynes through novel rearrangement reactions leading to complex polycyclic structures. Favored reaction pathways depend on reaction conditions and on the presence of gold catalysts. In particular, upon reaction with 2 equiv. of the alkyne, new hexacyclic structures 10 are formed with total stereocontrol.