Biochar from slow pyrolysis under controlled conditions is favorable in the transformation of waste into materials that serve as soil conditioners, and/or environmental remediation. Thus, this work aimed to produce and characterize biochar from cassava waste under different temperature conditions and evaluate interactions with Ca2+ and Pb2+ for agricultural and environmental applications. To investigate the efficiency of the interaction of biochar with nutrients (Ca) and contaminants (Pb), the influence of pH and contact time were evaluated. There was an increase in pH, pHzpc (zero point charge), and condensed aromatic structures in BC, due to the increase in pyrolysis temperature. Also, biochar demonstrated a Pb2+ adsorbed amount of 2.03 to 2.37 mg g-1 and a Ca2+ release capacity of 0.655 to 0.765 mg g-1. In this way, biochar produced from residues of cassava waste can be a viable strategy to enhance agricultural production and reduce environmental contaminants.

It is known that the reactivity of the nanocatalytic systems is related to the particle size and shape and also to the features of the capping agents on the nanostructures. In this study, gold nanorods (AuNRs) were synthesized by the seed-mediated method using different tetra-alkylammonium bromide salts as capping agents, that are, cetyltrimethylammonium (CTABr), N,N-dimethyl-N-cetyl-N-(2-hydroxyethyl)ammonium (HEA16Br), and N,N-dimethyl-N-cetyl-N-(2-hydroxypropyl)ammonium (HPA16Br), and used as catalyst for the chemical reduction of p-nitrophenol (PNP) in the presence of NaBH4. The catalytic systems were characterized by ultraviolet-visible (UV-Vis) absorption spectroscopy and transmission electron microscopy (TEM). The effect of the ammonium bromide-based capping agent on the catalytic activity of AuNRs was evaluated by performing the chemical reduction of p-nitrophenol in the presence of excess NaBH4 in aqueous medium. Under the reaction conditions employed, the catalytic systems displayed detectable subtle differences in terms of induction times and apparent activation energy (Ea) values. These results show that slight changes carried out in the chemical structure of the capping agent are able to imprint even slightly modification of the kinetic parameter of the catalytic reaction.

Catalysts were prepared by the heterogenization of the tributyltin(IV) methoxide (n-Bu3Sn(OMe)) and dibutyltin(IV) dimethoxide (n-Bu2Sn(OMe)2) on silica by two strategies: (i) anchoring of the organotin(IV) compounds on silica and (ii) anchoring of the organotin(IV) compounds on a silica gel functionalized with mercaptopropyl groups (SiO2–SH). The characterization results showed that, regardless of the method used to anchor the organotin species, the solids contained approximately 7-10% of Sn. The decrease or disappearance of the O–H and S–H stretching signals in the SiO2 and SiO2–SH spectra after the treatment with the organotin(IV) methoxide derivatives suggest the immobilization via O–Sn or S–Sn covalent bonds. The catalytic performance was evaluated in methanolysis of ethyl acetate, in comparison to the analogous homogeneous systems, and the order of reactivity is n-Bu2Sn(OMe)2 > n-Bu3Sn(OMe) > SiO2–SnBu2 > SiO2–S–SnBu2 > SiO2–SnBu3 > SiO2–S–SnBu3. The solids on which the organotin species were directly immobilized on activated SiO2 showed catalytic efficiencies slightly higher than those immobilized on thiol-functionalized silica. All of the solid catalysts were recovered and reused for recycling studies and characterized again after the reuse tests. A better interaction between n-Bu3Sn(OMe) and both supports was observed, as verified by the low leaching of Sn after the first catalytic reaction.

In this study an analytical method, based on gas chromatography with flame ionization detection, using a short column and response factor (GCSCRF), was validated for the quantification of fatty acid alkyl esters (methylic or ethylic). During the validation process, the proposed method was employed to analyze twenty samples of fatty acid methyl esters and fatty acid ethyl esters. Biodiesel samples were produced from soybean oil and the validated method was found to be selective, being able to separate and identify every ester species present in the samples according to its carbon number. When the method was submitted to some variations in the sample preparation procedure, it remained robust. Limits of detection and quantification were 6.76 and 20.4 mg mL-1, respectively. The suggested method also showed great precision when successive analyses were carried out for different analysts, with standard deviation (SD) 0.6 for repeatibility and relative standard deviation (RSD) percentage 7.3% for intermediate precision, excellent accuracy when compared to other reference methods (EN 14103 and high-performance liquid chromatography with ultraviolet dection (HPLC-UV)) and recovery studies.

The oxidative polymerization of linseed oil was investigated comparing the classical catalysts cobalt(II) 2-ethylhexanoate and manganese(II) 2-ethylhexanoate and their derivatives modified by the presence of chelating nitrogen ligands, i.e., 2,2'-bipyridyl, 2-(acetyl-2,6-diisopropylphenylimine)-pyridine and [N-(2,6-diisopropylphenyl)imine]acenaphthoquinone. The suitable stoichiometries between the two precursor complexes with the three ligands were determined by UV-visible spectroscopy. All complexes were characterized by infrared spectroscopy, and one complex was characterized also by X-ray diffraction. The apparent kinetic constants of oxidative polymerization of linseed oil was determined, for each catalytic system, via the periodic measurements of the oil viscosity during the oxidation reaction. The results indicated that the modifications of the classical two complexes with the chelating nitrogen ligands improved the catalytic efficiency at least to the manganese complex.

Neste trabalho descrevemos um estudo teórico sobre a reação de polimerização do eteno catalisada por um complexo catiônico volumoso do tipo Ni(II)-α-diimina. Empregamos a combinação da teoria do funcional de densidade (DFT) e mecânica molecular (MM), contida na aproximação ONIOM, para avaliar as estruturas e energias envolvidas na polimerização do eteno, usando o sistema catalítico de Brookhart. Todas as estruturas intermediárias e de transição ao longo destes passos elementares foram tratadas como representativas do processo de polimerização. Discutimos a conformação do ligante em torno do sítio ativo ao longo das etapas da reação de polimerização, o ângulo de coordenação da olefina, complexo-p, e a formação de ramificações na cadeia polimérica em crescimento durante o processo de polimerização.

In this work we describe a theoretical investigation of the ethene polymerization reaction catalyzed by a bulky cationic α-diimine Ni(II) complex. We employed the combination of density functional theory (DFT) and molecular mechanics (MM), within the ONIOM approach, to evaluate the structures and energies involved on the most representative reactions observed on ethene polymerization, using the Brookhart catalytic system. All intermediates and transition state structures along these elementary steps were treated as representatives of the polymerization process. We discuss the conformation of the ligands around the active site along the polymerization reaction steps, the coordination angle of the coordinated olefin, p-complexes, and branch formation of the growing chain during the polymerization process.

Este trabalho trata da síntese e caracterização de um complexo de Cr(III) contendo o ligante N,N'-di-t-Bu-2,11-diaza [3.3] (2,6)-piridinofano (t-Bu-N4CrCl2+ Cl-) e posterior avaliação catalítica na polimerização de etileno e propileno, sob várias condições de reação, em presença de MAO (metilaluminoxana) ou Et3Al2Cl3 (sesquicloreto de etilalumínio - EASC), como cocatalisadores. O emprego do sistema catalítico t-Bu-N4CrCl2+ Cl-/Et3Al2Cl3 produziu copolímeros de etileno-propileno e de polietilenos, com bons rendimentos. A caracterização desses polímeros, através de várias técnicas analíticas, mostrou que os mesmos são essencialmente lineares e de alta massa molar.

Chromium (III) complex bearing N,N'- di-t-Bu-2, 11-diaza[3.3] (2,6)-pyridinophane ligand (t-Bu-N4CrCl2+ Cl) was synthesized and characterized. This complex was tested in ethylene and propylene polymerisation, under several reaction conditions, in the presence of MAO (metilaluminoxane) or Et3Al2Cl3 (ethyl aluminium sesquichloride), as cocatalysts. The use of the catalytic system t-Bu-N4CrCl2+ Cl -/Et3Al2Cl3 led to ethylene-propylene copolymers and polyethylene, with good yields. The polymers thus produced display high molar masses and narrow polydispersities.