(Z)-3-p-tolylsulfinylacrylonitriles as chiral dipolarophiles: reactions with diazoalkanes

[reaction: see text] The dipolarophilic reactivity of enantiopure (Z)-3-p-tolylsulfinylacrylonitriles (1) has been evaluated with diazoalkanes. 3-Cyanopyrazoles are obtained when R = H, but with R = alkyl (Bn, n-Bu, and t-Bu) only one cycloadduct (4 or 5) is formed in high yield under mild conditions, therefore evidencing a complete control of the regioselectivity and the endo/exo and pi-facial selectivities. These reactions are a new straightforward entry to the synthesis of pyrazolines and related structures and reveal the excellent dipolarophilic features of (Z)-sulfinylacrylonitriles.     

Byte structure variable length coding (BS-VLC): a new specific algorithm applied in the compression of trajectories generated by molecular dynamics

Molecular dynamics is a well-known technique very much used in the study of biomolecular systems. The trajectory files produced by molecular dynamics simulations are extensive, and the classical lossless algorithms give poor efficiencies in their compression. In this work, a new specific algorithm, named byte structure variable length coding (BS-VLC), is introduced. Trajectory files, obtained by molecular dynamics applied to trypsin and a trypsin:pancreatic trypsin inhibitor complex, were compressed using four classical lossless algorithms (Huffman, adaptive Huffman, LZW, and LZ77) as well as the BS-VLC algorithm. The results obtained show that BS-VLC nearly triplicates the compression efficiency of the best classical lossless algorithm, preserving a near lossless behavior. Compression efficiencies close to 50% can be obtained with a high degree of precision, and the maximum efficiency possible (75%), within this algorithm, can be performed with good precision.     

Dependence of pulser driving responses on electrical and motional characteristics of NDE ultrasonic probes

Acoustic performance in ultrasonic transmitters can be improved by means of a suitable electrical driving response and matching/tuning networks. It is important to predict this electrical response, but doing so is not easy because it departs notably from the nominal pattern with the loading probes. In practice, the analysis of HV pulser spikes in NDE applications requires fairly complex models in the transient regime and, in addition, non-linear problems could arise, especially in the case of tuned transmitters. In this paper, the most relevant influences of loading characteristics of NDT ultrasonic probes on the pulser electrical driving responses are evaluated in time and frequency domains. Conventional pulse generators and typical NDE pulsers are considered. Driving responses are analysed across commercial ultrasonic probes and, alternatively, across similar purely electrical loads. Distinct influences on pulser responses from electrical and motional sections of the probes are identified. All these aspects are studied on the basis of experimental and computer results.     

Effects of temperature on the relaxation to equilibrium and stationary nonequilibrium states of some Langevin systems

We investigate the effects of temperature on the properties of the time relaxation to equilibrium and nonequilibrium steady states of correlation functions of some Langevin harmonic systems. We consider commonly used dissipative and conservative Langevin dynamics, and show that the time relaxation rate depends on the temperature in the case of thermal reservoirs at different temperatures connected to the system, but it does not happen in the case of relaxation to equilibrium, i.e., if all the heat bath are at the same temperature. Our formalism maps the initial stochastic problem on a noncanonical quantum field theory, and the calculations of the relaxation rates are based on a perturbative analysis. We argue to show the reliability of the perturbative computation.     

Poly(vinyl acetate) paints in works of art: A photochemical approach. Part 1

The photochemistry of poly(vinyl acetate), PVAc, homopolymer, of PVAc mixtures with selected pigments and fillers, and of accurate historic reproductions based on the colours prepared by Portuguese artist Joaquim Rodrigo and on those supplied by the company A Favrel was studied. The systems, applied as films, were irradiated at λ ≥ 300 nm and the changes followed by size exclusion chromatography, infrared spectroscopy, and colorimetry.PVAc as homopolymer or as an emulsion paint proved to be very stable to light, and after 5000 h of irradiation no gel fraction was observed. Φ_R (λ_irr = 313 nm) for chain scission for PVAc was determined to be 7 × 10⁻⁸. This value indicates that the mechanism/s operating when irradiating at λ ≥ 300 nm are different from those previously published with irradiation involving 254 nm. No side-group scission was observed, and main chain scission is the foremost photodegradation mechanism. Also, the metal ions present in the pigments do not affect the photochemical stability of the polymer.     

Numerical solution of reaction–diffusion equations by compact operators and modified equation methods

A system of reaction–diffusion equations which governs the propagation of an ozone decomposition laminar flame in Lagrangian co-ordinates is analysed by means of compact operators and modified equation methods. It is shown that the use of fourth-order accurate compact operators yields very accurate solutions if sufficient numbers of grid points are located at the flame front, where very steep gradients of temperature and species concentrations exist. Modified equation methods are shown to impose a restriction on the time step under certain conditions. The solutions obtained by means of compact operators and modified equation methods are compared with solutions obtained by other methods; good agreement is obtained.     

Inversion of the Bessel potential operator in weighted variable Lebesgue spaces

We study the inversion problem of the Bessel potential operator within the frameworks of the weighted Lebesgue spaces with variable exponent. The inverse operator is constructed by using approximative inverse operators. This generalizes some classical results to the variable exponent setting.     

Electric field gradient in nanostructured SnO2 studied by means of PAC spectroscopy using 111Cd or 181Ta as probe nuclei

Electric quadrupole interactions were studied in pure and Mn-doped powder samples and thin films of SnO₂ using perturbed γγ angular correlation spectroscopy (PAC). The powder samples were prepared by Sol gel method and the thin film were prepared on the Si (100) substrate by sputtering technique using Sn in the oxygen atmosphere. The samples were characterized by x-ray diffraction, energy dispersive spectroscopy and scanning electron microscopy. The thickness of the film was 100 nm. The average particle size of the SnO₂ powder samples was determined to be smaller than 60 nm. The radioactive ¹¹¹In and ¹⁸¹Hf tracers were introduced in the powder samples during the sol gel chemical process. Radioactive ¹¹¹In was implanted on the SnO₂ thin films using the University of Bonn ion implanter (BONIS). PAC measurements were carried out in a four BaF₂ detector spectrometer in the temperature range of 77–973 K for samples annealed at different temperatures. The PAC results for both nuclear probes show the presence of two electric quadrupole interactions. The major fractions in both cases correspond to the substitutional sites in the rutile phase of SnO₂. The results are compared with previous PAC measurements.