Beer is commonly produced with four inputs: water, malt, hops, yeast and, in some cases, brewing adjuncts. Industrial and artisanal processes essentially follow the same steps and may undergo minor changes due to the style of beer. Despite this, many consumers attribute higher quality to craft beer compared to industrial ones. In this study, we applied the analytical techniques of infrared (IR), hydrogen nuclear magnetic resonance (1H NMR) and mass spectrometry (ESI(±)FT-ICR MS) to discriminate craft beers from industrial ones (brands common to the Brazilian market). In addition, Partial Least Squares (PLS) and Support Vector Machine (SVR) regression were used to estimate some beer properties (pH, total acidity (meq·L-1, color (EBC), bitterness (IBU), alcohol content (%v/v) and density (g·mL-1)). The use of the IR allowed the identification of vibrations attributed to chemical compounds common to beverages, such as water (3320 and 1640 cm-1), carbohydrates (1500 cm-1) and ethanol (1050-1040 and 875-865 cm-1). 1H NMR showed good applicability in identifying classes of organic compounds in the beverage, where signs attributed to alcohols, organic acids, carbohydrates and amino acids were observed. The ESI(+)FT-ICR MS allowed the identification of chemical compounds present in beverages, allowing the construction of a fingerprint of the beers. In addition, the application of chemometric tools enabled the prediction of physicochemical properties, presenting promising results in the prediction of alcohol content (RMSEC 0.2430 and RMSEP 0.3929) and bitterness (RMSEC 1.3022 and RMSEP 1.6008), and also in the classification regarding the manufacturing process (craft and industrial beer).

The correlation between iron distribution in octahedral or tetrahedral sites in synthetic magnetite and zinc spinel ferrites and their catalytic properties were investigated in this work. The zinc-doped nanomagnetites were prepared by co-precipitation method and annealed at 420 °C. X-ray diffraction, UV-Vis, X-ray absorption and 57Fe Mössbauer spectroscopies were used to identify iron sites. The obtained results showed that ZnII replaces the relatively smaller FeIII cation in the tetrahedral sites, increasing the cubic lattice dimension, and this replacement remarkably enhances the catalytic effectiveness of the Zn-spinel ferrite towards the indigo carmine degradation compared to undoped magnetite. The indigo carmine degradation experiments were carried out using photo-Fenton method in which 50 mL of indigo carmine dye aqueous solutions (20 mg L−1, pH 3.0), 20 mg ZnxFe(3-x)O4, and 2.0 mL H2O2 (aqueous solution at 0.028 mol L−1) were placed under UV light at 25 °C. Under these experimental conditions the degradation rate of indigo carmine was superior to 98%.

To choose among the variety of oleaginous plants for biodiesel production, the oil content of several matrices was determined through different low-field ¹H nuclear magnetic resonance (NMR) experiments with varied pulse sequences, namely single-pulse, spin-echo, CPMG, and CWFP. The experiments that involved the first three sequences showed high correlation with each other and with the solvent extraction method. The quality of the vegetable oils was also evaluated on the basis of the existing correlation between the T2 values of the oils and their properties, such as viscosity, iodine index, and cetane index. These analyses were performed using HCA and PCA chemometric tools. The results were sufficiently significant to allow separation of the oleaginous matrices according to their quality. Thus, the low-field ¹H NMR technique was confirmed as an important tool to aid in the selection of oleaginous matrices for biodiesel production.

Neste trabalho foi desenvolvida uma nova metodologia de reciclagem química do poli(tereftalato de etileno) grau garrafa pós-consumo, PETpc, através da reação de despolimerização em meio alcalino (solução de hidróxido de sódio, NaOH, de 7,5 mol L-1 a 100 ºC) e como catalisador o tensoativo catiônico brometo de hexadeciltrimetrilamônio, CTAB (1 × 10-2 mol L-1). A presença de CTAB aumentou o rendimento da reação em cerca de 85% e reduziu o tempo reacional de 6 para 2 h, quando utilizado em mistura NaOH/CTAB na proporção de 4:1 (% v/v) com 2 g de PETpc. O produto final, o monômero ácido tereftálico, TPA, foi caracterizado por análise termogravimétrica, calorimetria diferencial varredura, espectroscopia na região do infravermelho com transformada de Fourier e espectrometria de massas. Os resultados foram comparados com os da matéria-prima, PETpc. Além disso, o catalisador CTAB permaneceu no meio reacional (fase aquosa), sem interferir no processo de purificação do TPA.

In this work, a new analytical methodology has been developed for the chemical recycling of post-consumption bottle-grade poly(ethylene terephthalate), PETpc through depolymerization reaction in alkaline solution (NaOH solution of 7.5 mol L-1 at 100 ºC), using the surfactant cetyl trimethyl ammonium bromide (CTAB, 1 × 10-2 mol L-1) as catalyst. The presence of CTAB increased the reaction performance by ca. 85%, while the reaction time was decreased from 6 to 2 h when the mixture NaOH/CTAB was used in a proportion of 4:1 (% v/v) with 2 g of PETpc. The final product, the monomer terephthalic acid (TPA), was characterized by thermogravimetry analysis, differential scanning calorimetry, Fourier transform infrared spectroscopy and mass spectrometry. The results were compared with those for the raw material, PETpc. Furthermore, the catalyst CTAB remained in the alkaline environment (aqueous phase), without interfering with the TPA purification process.

O potencial da técnica de espectroscopia de infravermelho com transformada de Fourier e acessório de reflexão total atenuada (FTIR-ATR) foi avaliado para o monitoramento da degradação da poliamida 11 (PA-11) usada em dutos flexíveis. As amostras foram submetidas a envelhecimento em reatores com pressão controlada e atmosfera inerte. Os corpos de prova foram imersos em água deionizada (pH 7), nas temperaturas de 110, 120 e 140 ºC por um período de até 50 dias. A técnica recomendada para monitoramento da degradação da PA-11 é a viscosimetria, através de medidas da viscosidade inerente corrigida (VIC) e a análise termogravimétrica (TGA). O comportamento observado para a VIC e TGA durante o envelhecimento possibilitou a construção de modelos que correlacionam com a técnica de FTIR-ATR. A partir dos resultados de FTIR-ATR, a variação na intensidade da banda atribuída à fase amorfa, 1161 cm-1, possibilitou o monitoramento do envelhecimento quando associamos a técnica a modelos quimiométricos como o de regressão dos mínimos quadrados parciais, PLS. Portanto, a técnica FTIR-ATR pode ser uma nova alternativa no monitoramento da degradação hidrolítica da PA-11, eliminando assim o uso de solventes orgânicos tóxicos e reduzindo, consequentemente, o tempo de análise.

The potential of the infrared spectroscopy with the attenuated total reflection technique (FTIR-ATR) was evaluated to monitor degradation of polyamide 11, PA-11, applied in flexible pipes. The samples were subjected to aging on reactors with controlled pressure and atmosphere. The samples were immersed in deionized water, pH 7, at temperatures of 110, 120 and 140 ºC over a period of up to 50 days. The typical technique recommended for monitoring PA-11 degradation is viscometry from inherent viscosity corrected (VIC) and thermogravimetric (TGA) measurements. TGA and VIC results allowed the use of chemometric models that can be related to FTIR-ATR spectra, with assignment of a band to the amorphous phase (1161 cm-1) of PA-11. The chemometric model generated from PLS data was satisfactory in predicting the aging of PA-11. Therefore, FTIR-ATR can be used as a new analytical methodology to monitor PA-11 degradation, thus eliminating the use of toxic organic solvents and reducing the time required for the analysis.

Antimony is a common catalyst in the synthesis of polyethylene terephthalate used for food-grade bottles manufacturing. However, antimony residues in final products are transferred to juices, soft drinks or water. The literature reports mentions of toxicity associated to antimony. In this work, a green, fast and direct method to quantify antimony, sulfur, iron and copper, in PET bottles by X-ray fluorescence spectrometry is presented. 2.4 to 11 mg Sb kg-1 were found in 20 samples analyzed. The coupling of the multielemental technique to chemometric treatment provided also the possibility to classify PET samples between bottle-grade PET/recycled PET blends by Fe content.

Utiliza-se o método coordenada geradora Hartree-Fock para gerar bases Gaussianas adaptadas para os átomos de Li (Z=3) até Xe (Z=54). Neste método, integram-se as equações de Griffin-Hill-Wheeler-Hartree-Fock através da técnica de discretização integral. Comparam-se as funções de ondas geradas neste trabalho com as funções de ondas Roothaan-Hartree-Fock de Clementi e Roetti (1974) e com outros conjuntos de bases relatados na literatura. Para os átomos estudados aqui, os erros em nossas energias totais relativos aos limites numéricos Hartree-Fock são sempre menores que 7,426 milihartree.

The generator coordinate Hartree-Fock method is used to generate adapted Gaussian basis sets for the atoms from Li (Z=3) through Xe (Z=54). In this method the Griffin-Hill-Wheeler-Hartree-Fock equations are integrated through the integral discretization technique. The wave functions generated in this work are compared with the widely used Roothaan-Hartree-Fock wave functions of Clementi and Roetti (1974), and with other basis sets reported in the literature. For all atoms studied, the errors in our total energy values relatively to the numerical Hartree-Fock limits are always less than 7.426 mhartree.