The selective oxidative conversion of seven representative fully characterized biomasses recovered as secondary feedstocks from the agroindustry is reported. The reaction system, known as the “OxFA process,” involves a homogeneous polyoxometalate catalyst (H8PV5Mo7O40), gaseous oxygen, p-toluene sulfonic acid, and water as solvent. It took place at 20 bar and 90 °C and transformed agro-industrial wastes, such as coffee husks, cocoa husks, palm rachis, fiber and nuts, sugarcane bagasse, and rice husks into biogenic formic acid, acetic acid, and CO2 as sole products. Even though all samples were transformed; remarkably, the reaction obtains up to 64, and 55% combined yield of formic and acetic acid for coffee and cocoa husks as raw material within 24 h, respectively. In addition to the role of the catalysts and additive for promoting the reaction, the influence of biomass components (hemicellulose, cellulose and lignin) into biogenic formic acid formation has been also demonstrated. Thus, these results are of major interest for the application of novel oxidation techniques under real recovered biomass for producing value-added products. Graphical abstract
Cocoa pod shell is an essential agricultural residue in Ecuador, and this study addressed its potential valorization for bioethanol production. For this, three types of pretreatments, acid, alkaline, and autohydrolysis, were applied to pod shells from two different cocoa types, national and CCN-51. to remove the lignin. Untreated and treated biomasses were characterized by composition, thermal stability, Fourier transformed infrared spectroscopy (FITR), and scanning electron microscopy (SEM). The treated biomass was then enzymatically hydrolyzed with cellulase. Reducing sugars were quantified after pretreatments and enzymatic hydrolysis, and the pretreatment liquors and the enzymatic hydrolysates were subjected to alcoholic fermentation with Saccharomyces cerevisiae. There were substantial differences in composition between both biomasses, particularly in lignin content, with national cocoa having the lowest values. All pretreatment conditions had significant effects on biomass composition, structure, and thermal properties. After alkaline pretreatment, the biomass presented the highest cellulose and lowest lignin contents, resulting in the highest reducing sugar concentration in the pretreatment liquor. The highest lignin content was found after the acid pretreatment, which resulted in low, reducing sugar concentrations. Autohydrolysis produced similar results as the acid pretreatment; however, it resulted in the highest sugar concentration after enzymatic hydrolysis, while the acid-treated sample had negligible levels. After fermentation, there were no differences in productivity among the pretreatment liquors, but autohydrolysis had the largest ethanol yield. In the hydrolysates, it was also autohydrolysis that resulted in higher productivity and yield. Thus, there is an indication of the formation of inhibitors, both enzymatic activity and ethanol production, in the acid and alkaline pretreatments, and this should be tackled in future research. Nonetheless, given the crucial changes observed in biomass, we believe that cocoa pod shell pretreatment has potential for the generation of reducing sugars that could be further used in different bioprocesses, nor only bioethanol production.
Colloidal matrices of native and oxidized pectin were developed to improve iron bioavailability through the digestive tract. Ferrous bisglycinate (Gly-Fe), obtained by precipitation of glycine chelation to Fe2+, was mixed with native and peroxide-oxidized citrus pectin, and subsequently lyophilized. Controls included matrices with iron and glycine without chelation. The resulting samples were characterized through FTIR, SEM, and TGA/DSC before and after in vitro digestion, which was performed in simulated salivary, gastric, and intestinal fluids. During these digestions, swelling capacity and iron release were assessed. All matrix formulations were porous, and while pectin oxidation did not alter architecture, it changed their properties, increasing thermal stability, likely due to greater number of interaction possibilities through carbonyl groups generated during oxidation. This also resulted in lower swelling capacity, with greater stability observed when using the chelated complex. Higher swelling was found in gastric and intestinal fluids. Pectin oxidation also increased retention of the chelated form, contrary to what was observed with unchelated iron. Thus, there is an important effect of pectin oxidation combined with iron in the form of ferrous biglyscinate on matrix stability and iron release through the digestive tract. These matrices could potentially improve iron bioavailability, diminishing organoleptic changes in fortified iron foods.
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