The first bismuth(III)-catalyzed guanylation of thioureas

This work describes the first catalytic bismuth-promoted synthesis of polysubstituted guanidines in good yields through the guanylation reaction of N-benzoyl or N-phenylthioureas with primary and secondary amines, but now employing equimolar amounts of each organic reagent. Both bismuth iodine and bismuth nitrate were efficient as inorganic thiophiles at only 5 mol % in relation to substrates, being the first example of inorganic thiophiles acting in guanylation at catalytic levels.     

Long-range predictive adaptive fuzzy relational control

A class of long-range predictive adaptive fuzzy relational controllers is presented. The plant behavior is described over an extended time horizon by a fuzzy relational model which is identified based on input-output closed-loop observations of the plant variables. In this class of adaptive controllers the control law attempts to minimize a quadratic cost over an extended control horizon. When used with linear models, this approach has revealed a significant potential for overcoming the limitations of one-step ahead schemes, such as the stabilization of non-minimum phase plants. Here, a uniform framework is adopted for implementing both the fuzzy model and the fuzzy controller, namely distributed fuzzy relational structures gaining from their massive parallel processing features and from the learning capabilities typical of the connectivist approaches. Issues such as maintenance during the adaptation process of the meaning of linguistic terms used at both fuzzy systems interfaces are addressed, namely by introducing a new design methodology for on-line fuzzy systems interface adaptation. The examples presented reinforce the claim of the usefulness of this new approach.     

Titanosilicates as Supports for an Enzymatic Alcoholysis Reaction

Novel [Cr^III(amp)(bipy)(Cl)] (1) (H₂amp = N-(hydroxyphenyl)salicyldimine; bipy = 2,2-bipyridyl) and [Cr^III(app)(bipy)(Cl)]⁺ (2) (H₂app = N-(hydroxyphenyl)pyridine-2-carboxaldimine; bipy = 2,2-bipyridyl) complexes have been synthesized and characterized by physico-chemical methods. Complexes 1 and 2 have been employed as catalysts in the oxidation of both saturated and unsaturated hydrocarbons using tert-butylhydroperoxide (t-BuOOH). The significance of the results with respect to oxo-functionalization of C-H bonds both in unsaturated and saturated hydrocarbons is noted.     

A kinetic approach to homogeneous Ziegler type polymerization. Steady state

In this paper we present a kinetic approach to the analysis of steady-state homogeneous Ziegler-Natta polymerization activity data. The influence of the number of monomeric species that are coordinated to the active site on the apparent rate law is discussed and the equations are fitted to the experimental results.     

Preconcentration Systems Using Polyurethane Foam/Me-BDBD for Determination of Copper in Food Samples

A new reagent, 6-[2′-(6′-methyl-benzothiazolylazo)]-1,2-dihydroxy-3,5-benzenedisulfonic acid (Me-BDBD), was synthesised and used in on-line and off-line systems for copper preconcentration by solid-phase extraction. Spectrophotometry and Flame Atomic Absorption Spectrometry (FAAS) were the detection techniques. Polyurethane foam loaded with Me-BDBD packed in a minicolumn was used as sorbent in both systems. The spectral characteristics of Me-BDBD were investigated. The optimum pH values for maximum sorption of the metal are between 7.0 and 8.5. Copper was desorbed with 0.05 and 0.50 mol L⁻¹ hydrochloric acid solutions, for on-line and off-line systems, respectively. The effects of several foreign substances on the adsorption of copper are reported. The enrichment factors obtained were 7 (on-line) and 26 (off-line) for the systems. The proposed procedures allowed the determination of copper with detection limits of 3.4 and 1.4 μg L⁻¹ (0.85 and 0.35 μg per gram of sample) for on-line and off-line systems, respectively. The precision of the procedures was also calculated: 3.2 (on-line) and 1.9% (off-line). The validation of the procedures was carried out by analysis of certified reference material. The copper contents in corn and rice flour and black tea samples were determined by applying the proposed procedures.