The primary objective of this study is the development of nanofluids based on different diluent/dispersant ratios (DDR) for extra-heavy oil (EHO) viscosity reduction and its perdurability over time. Different diluents such as xylene, diesel, n-pentane, and n-heptane were evaluated for the formulation of the carrier fluid. Instability of asphaltenes was assessed for all diluents through colloidal instability index (CII) and Oliensis tests. Rheology measurements and hysteresis loop tests were performed using a rotational rheometer at 30 °C. The CII values for the alkanes type diluents were around 0.57, results that were corroborated with the Oliensis tests as asphaltenes precipitation was observed with the use of these diluents. This data was related to the viscosity reduction degree (VRD) reported for the different diluents. With the use of the alkanes, the VRD does not surpass the 60%, while with the use of xylene a VRD of approximately 85% was achieved. Dimethylformamide was used as a dispersant of the nanoparticles and had a similar VRD than that for xylene (87%). Subsequent experiments were performed varying the DDR (xylene/dimethylformamide) for different dosages up to 7 vol % determining that a DDR = 0.2 and a dosage of 5 vol % was appropriated for enhancing EHO VRD, obtaining a final value of 89%. Different SiO2 nanoparticles were evaluated in the viscosity reduction tests reporting the best results using 9 nm nanoparticles that were then included at 1000 mg·L−1 in the carrier fluid, increasing the VRD up to 4% and enhancing the perdurability based on the rheological hysteresis and the viscosity measurements for 30 days. Results showed a viscosity increase of 20 and 80% for the crude oil with the nanofluid and the carrier fluid after 30 days, respectively. The nanoparticles have a synergistic effect in the viscosity reduction and the inhibition of the viscoelastic network re-organization (perdurability) after treatment application which was also observed in the rheological modeling carried out with Cross and Carreau models as the reported characteristic relaxation time was increased almost a 20%. Moreover, the Vipulanandan rheological model denotes a higher maximum stress value reached by the EHO with the addition of nanofluids which is derived from the EHO internal structure rearrangement caused by the asphaltenes adsorption phenomenon.

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The development of cocoa flavor and aroma is a complex phenomenon that depends on how the fermentation and roasting processes are carried out. During fermentation, the formation of some compounds so-called “aroma and flavor precursors” takes place, which are finally expressed during the roasting stage. Therefore, the evaluation of aroma precursors such as the amino acids formed during fermentation is crucial in order to determine the quality of the cocoa. In this context, we developed and validated a method for the study of these compounds in cocoa samples. The amino acids were quantitatively converted into their trimethylsilyl derivatives before their determination by gas chromatography with mass spectrometry detection. The results were verified performing precision and accuracy studies. The inter and intra assay coefficients of variation (C.V, n = 5) were lower than 4.7% and 4%, respectively. The analytical recoveries (95% to 108% with C.V < 4.2, n = 5) demonstrated the high performance of the extraction procedure. The method was successfully applied to the analysis of the amino acids in 110 samples of Venezuelan Criollo cocoa during the three days of fermentation and roasting (110 °C for 25 min). All samples had an appreciable content of free amino acids ranging between 3.87 and 5.97 g/kg in the absence of fermentation. We observed degradation of the acidic amino acids during the first day of fermentation, while the rest of amino acids increased progressively during the fermentation process with a predominance of the hydrophobic ones, mainly leucine, phenylalanine, valine, alanine and isoleucine. Additionally, during the roasting stage a fraction of the amino acids, especially the hydrophobic ones, was partially degraded through Maillard reaction to form the compounds associated with the cocoa aroma and flavor.

Amino acids (AA) composition in cocoa beans can predict the synthesis of compounds which affect cocoa flavor. Thus, their determination is of great interest for the community implied in the commercialization and production of cocoa. In consequence, in this work, the analysis of AA produced during cocoa beans fermentation and roasting was carried out. A high-performance liquid chromatographic method with DAD detection at 254 nm was optimized and validated for their selective determination in six varieties of cocoa beans with different genotypes, all of them grown in Venezuela. AA were extracted by defatted milled cocoa powder ultrasonication using purified water at 70 ºC. Then, they were derivatized with phenyl isothiocyanate, and their derivatives were separated, using a reversed-phase column with gradient elution, achieving a satisfactory resolution among the peaks (greater than 1.0) in less than 29 min. 110 cocoa samples were analyzed. Results showed a significant content of free AA, ranging from 3.87 to 5.97 g/kg in absence of fermentation with a predominance of acidic AA. Moreover, there is a progressive increase in the AA content while fermentation process occurs, with a predominance of hydrophobic AA such as alanine, valine, isoleucine, leucine, phenylalanine, and tyrosine. On the other hand, all cocoa types showed a partial degradation of free AA during the roasting step, especially the hydrophobic ones.