2-Methylisoxazolin-5-ones III. Curboxylic. Acids and their Derivatives

Carbethoxy-substituted 12-methylisoxazolin-5-ones and several functional derivatives have been prepared. Spectral properties of the corresponding carboxylic acids are discussed. These acids ant stronger when the carboxy group is in position 3 than when in position 4 of the heterocycle.     

Metal-cinnamic acids interactions. Part III. Synthesis and study of copper(II) complexes of 3, 4- and 3, 5-dimenthoxycinnamic acid

Summary Copper(II) complexes derived from substituted cinnamic acids 3, 4-dimethoxycinnamic acid (3, 4-DMCH) and 3, 5-dimethoxycinnamic acid (3, 5-DMCH), of the formula [Cu(3, 4-DMC)₂]·H₂O (1), [Cu(3, 5-DMC)₂]·H₂O (2) were prepared. The magnetic properties of the complexes suggest dimeric structures typical of copper(II) acetate monohydrate-like complexes. X-band e.s.r. spectra of polycrystalline samples at low temperature are typical of triplet state systems S=1. Their ability to catalyze the aerial oxidation of 3, 5-di-t-butylcatechol was measured spectrophotometrically at 30°C. The complexes are models for oxidases.     

Synthese, 13C-NMR-Spektren und räumliche Struktur von ‘Push-Pull’-Diacetylenen

Synthesis, ¹³C-NMR Spectra, and X-Ray Investigation of ‘Push-Pull’ Diacetylenes Phenyl-substituted ‘push-pull’ diacetylenes 1f and 1g have been prepared by acetylation and benzoylation of the appropriate lithiodiynylamines 4 (Scheme 2). ¹³C-NMR spectra of diacetylenes 1a–g (Table 1) are discussed with respect to the expected polarisation of the diacetylene unit by ‘push’ and ‘pull’ substituents. X-Ray investigations of 1c , 1e , and 1f have been performed in view of the planned solid-state polymerisation of ‘push-pull’ diacetylenes. In the crystalline state, diacetylenes 1c and 1f are stacked, however, the stacking parameters do not allow a solid-state polymerisation.     

Unexpected Secondary Nucleation in Poly(Vinyl acetate) Nanoparticle Synthesis by Ab Initio Batch Emulsion Polymerization Using Poly(Vinyl alcohol) as Surfactant

Kinetic aspects of the vinyl acetate ab initio batch emulsion polymerization using poly(vinyl alcohol) to produce polymer nanoparticles are studied. The initial nucleation step is followed by limited coagulation and then by the generation of new particles. It seems that this is the first report of secondary nucleation phenomenon occurring in the system under study in batch mode. To explain this phenomenon, a mathematical model that allows to determine whether certain polymerization conditions and the presence/absence of a steric barrier, can lead or not to significant secondary nucleation is developed. It is deduced that the effect of such steric barrier on the free‐radical entry process plays a key role on the observed phenomenon.     

Multielemental analyses of Lonomia obliqua (Lepidoptera,Saturniidae) caterpillar using EDXRF and INAA techniques

In this study, multielemental analysis of Lonomia obliqua (Lepidoptera, Saturniidae) caterpillar was performed using energy dispersive X-ray fluorescence and instrumental neutron activation analysis techniques. This caterpillar is poisonous and has the ability to cause fatal hemorrhagic effects in humans after contact. The need of this study is related to morphological changes (mainly size and color) observed in some caterpillars used for preparation of antilonomic serum (antivenom). The samples were classified as healthy (caterpillars of control) and unhealthy (caterpillars visibly modified). The XRF measurements were performed in an energy dispersive X-ray fluorescence spectrometer and the instrumental neutron activation analysis using the IEA-R1 nuclear reactor at IPEN. The results show significant differences for several elements (mainly, P, Cl, Ca, Ti, Mn, Fe, Ni, and Zn) in unhealthy caterpillars that can affect the development of this species as well as the quality and yield of the antivenom. Furthermore, its elemental characterization contributes for the understanding the potential pharmacological (procoagulant and antithrombotic) in the prevention of life-threatening blood clots.     

Bond-based peridynamic modelling of singular and nonsingular crack-tip fields

A static meshfree implementation of the bond-based peridynamics formulation for linearly elastic solids is applied to the study of the transition from local to nonlocal behavior of the stress and displacement fields in the vicinity of a crack front and other sources of stress concentration. The long-range nature of the interactions between material points that is intrinsic to and can be modulated within peridynamics enables the smooth transition from the square-root singular stress fields predicted by the classical (local) linear theory of elasticity, to the nonsingular fields associated with nonlocal theories. The accuracy of the peridynamics scheme and the transition from local to nonlocal behavior, which are dictated by the lattice spacing and micromodulus function, are assessed by performing an analysis of the boundary layer that surrounds the front of a two dimensional crack subjected to mode-I loading and of a cracked plate subjected to far-field tension.     

Kinetic Study of the Thermopolymerization of Furfuryl Methacrylate in Bulk by Mathematical Modeling. Part A: Simulation of Experimental Data and Sensitivity Analysis of Kinetic Parameters

Mathematical modeling of the thermopolymerization of FM and CMFMA was carried out using a cross‐linked kinetic model proposed for the photo‐initiated polymerization of acryl‐furanic compounds. In this model, the photochemical initiation step was substituted by a thermal one and it was assumed that the constant of radical termination was time‐dependent, which allowed the gel effect (Trommsdorff) at high monomer conversion to be simulated. Optimization of all kinetic constants was achieved and the results of simulation suitably fitted the experimental data of the monomer conversion. The contribution of each step in the mechanism and its dependence on the experimental conditions were estimated by a sensitivity analysis technique.

     

Colored diffusion-limited aggregation for urban migration

In this paper we study the growth probability and cluster morphologies which emerge in an off-lattice, two-dimensional, colored diffusion-limited aggregation model for urban dynamics, particularly migration. To reach this goal, three immobile interacting clusters that include the geographical concept of gravity are studied by exact enumeration. In our simulations we find a strong correlation between the seed’s distance, migration rules and number of aggregated particles. The growth probability of a certain angular subset and its rate and route of convergence to a Normal distribution when migration cost is acting are also shown. We search how all the factors mentioned above determine the cluster morphologies.