The development of solid acid catalysts, especially based on metal oxides and different magnetic nanoparticles, gained much awareness recently as a result of the development of different nano-based materials. Solid acid catalysts based on metal oxides are promising for the (trans)esterification reactions of different oils and waste materials for biodiesel production. This review gives a brief overview of recent developments in various solid acid catalysts based on different metal oxides, such as zirconia, zinc, titanium, iron, tungsten, and magnetic materials, where the catalysts are optimized for various reaction parameters, such as the amount of catalyst, molar ratio of oil to alcohol, reaction time, and temperature. Furthermore, yields and conversions for biodiesel production are compared. Such metal-oxide-based solid acid catalysts provide more sustainable, green, and easy-separation synthesis routes with high catalytic activity and reusability than traditionally used catalysts.

In this study, magnetic maghemite nanoparticles, which belong to the group of metal oxides, were functionalized with chitosan, a non-toxic, hydrophilic, biocompatible, biodegradable biopolymer with anti-bacterial effects. This was done using different synthesis methods, and a comparison of the properties of the synthesized chitosan functionalized maghemite nanoparticles was conducted. Characterization was performed using scanning electron microscopy (SEM) and vibrating sample magnetometry (VSM). Characterizations of size distribution were performed using dynamic light scattering (DLS) measurements and laser granulometry. A chitosan functionalization layer was confirmed using potentiometric titration on variously synthesized chitosan functionalized maghemite nanoparticles, which is important for further immobilization of bioactive compounds. Furthermore, after activation of chitosan functionalized maghemite nanoparticles with glutaraldehyde (GA) or pentaethylenehexamine (PEHA), immobilization studies of enzyme cholesterol oxidase (ChOx) and horseradish peroxidase (HRP) were conducted. Factors influencing the immobilization of enzymes, such as type and concentration of activating reagent, mass ratio between carrier and enzyme, immobilization time and enzyme concentration, were investigated. Briefly, microparticles made using the chitosan suspension cross-linking process (MC2) proved to be the most suitable for obtaining the highest activity of immobilized enzyme, and nanoparticles functionalized with chitosan using the covalent binding method (MC3) could compete with MC2 for their applications.

Graham flour is a form of whole wheat flour made by grinding the endosperm and is thus also the most nutritious. Generally, the enzyme polyphenol oxidase (PPO) catalyzes two different reactions in the presence of molecular oxygen: the hydroxylation of monophenols to ortho-diphenol and the oxidation of o-diphenol to o-quinone. The purpose of the work was to inactivate PPO activity to extend the shelf life of graham flour and at the same time preserve all the of its high-quality properties. The influence of supercritical CO₂ (scCO₂) treatment on PPO activity in graham flour was investigated. First, graham flour was exposed to scCO₂ conditions, then the proteins were extracted, and in the last step the concentration of total proteins and the specific activity of the PPO enzyme were determined by spectrophotometric assay. PPO activity decreased with an increase in treatment pressure. Furthermore, the flour quality characteristics that meet all needs for wheat end-use products after scCO₂ treatment have been preserved. No major changes in the structure of the granulate or shape of the flour particles were observed. A slightly reduced value of the moisture content in scCO₂-treated graham flour also implies an extension of the shelf life.

The objectives of this study were to inactivate the enzymes α-amylase, lipase, protease, and peroxidase in flour with supercritical carbon dioxide (scCO₂), and to optimize the enzymatic treatment conditions. Enzyme inactivation is important, due to the undesirability of certain flour enzymes that cause adverse reactions during storage as unpleasant rancidity of flour, and, at the same time, reduce the shelf life of flour. Therefore, crude enzymes and flour were initially exposed to scCO₂ to determine the effect on specific enzyme activity under appropriate conditions. The activity of the unwanted enzymes lipase and peroxidase decreased under optimal process conditions of scCO₂ exposure, lipase by 30%, and peroxidase by 12%, respectively. It was discovered that the inactivation of enzymes in wheat flour occurred, where, at the same time, this sustainable method allows the regulation of enzyme activity in the baking process. Afterwards, the effect of scCO₂ on the physicochemical properties of flour, morphological changes on starch granules, and content of total lipids was studied. In scCO₂-treated white wheat flour, the fat content decreased by 46.15 ± 0.5%, the grain structure was not damaged, and the bread as the final product had a lower specific surface volume. Therefore, this could be a promising technology for flour pretreatment, potentially impacting the prolonging of its shelf-life.

In this research, a new approach to enzyme inactivation in flour was presented by supercritical technology, considered a sustainable technology with lower energy consumption compared to other technologies that use ultra-high temperature processing. Total protein concentration and the activity of enzymes α-amylase, lipase, peroxidase, polyphenol oxidase, and protease were determined in flour pre-treated with scCO₂. During the study, it was observed that the activity of enzymes such as lipase and polyphenol oxidase, was significantly reduced under certain conditions of scCO₂ treatment, while the enzymes α-amylase and protease show better stability. In particular, polyphenol oxidase was effectively inactivated below the 60% of preserved activity at 200 bar and 3 h, whereas α-amylase under the same conditions retained its activity. Additionally, the moisture content of the scCO₂-treated spelt flour was reduced by 5%, and the fat content was reduced by 58%, while the quality of scCO₂-treated flour was maintained. In this regard, the sustainable scCO₂ process could be a valuable tool for controlling the enzymatic activity of spelt flour since the use of scCO₂ technology has a positive effect on the quality of flour, which was verified by the baking performance of spelt flour with the baked spelt bread as an indicator of quality.