Supramolecular hydrogels with a three-dimensional cross-linked macromolecular network have attracted growing scientific interest in recent years because of their ability to incorporate high loadings of bioactive molecules such as drugs, proteins, antibodies, peptides, and genes. Herein, we report a versatile approach for the confinement of Candida antarctica lipase B (CALB) within a silica-strengthened cyclodextrin-derived supramolecular hydrogel and demonstrate its potential application in the selective oxidation of 2,5-diformylfuran (DFF) to 2,5-furandicarboxylic acid (FDCA) under mild conditions. The enzymatic nanoreactor was deeply characterized using thermogravimetric analysis, Fourier transform infrared spectroscopy, N2-adsorption, dynamic light scattering, UV–visible spectroscopy, transmission electron microscopy, scanning electron microscopy, and confocal laser scanning microscopy, while the reaction products were established on the basis of 1H nuclear magnetic resonance spectroscopy combined with high-performance liquid chromatography. Our results revealed that while CALB immobilized in conventional sol–gel silica yielded exclusively 5-formylfuran-2-carboxylic acid (FFCA), confinement of the enzyme in the silicified hydrogel imparted a 5-fold increase in DFF conversion and afforded 67% FDCA yield in 7 h and almost quantitative yields in less than 24 h. The hierarchically interconnected pore structure of the host matrix was found to provide a readily accessible diffusion path for reactants and products, while its flexible hydrophilic–hydrophobic interface was extremely beneficial for the interfacial activation of the immobilized lipase.

The environmental context causes the use of renewable energy to increase, with the aim of finding alternatives to fossil-based products such as fuels. Biodiesel, an alternative to diesel, is now a well-developed solution, and its production from renewable resources makes it perfectly suitable in the environmental context. In addition, it is biodegradable, non-toxic and has low greenhouse gas emissions: reduced about 85% compared to diesel. However, the feedstock used to produce biodiesel competes with agriculture and the application of chemical reactions is not advantageous with a “green” process. Therefore, this review focuses only on bioprocesses currently taking an important place in the production of biodiesel and allow high yields, above 90%, and with very few produced impurities. In addition, the use of waste oils as feedstock, which now accounts for 10% of feedstocks used in the production of biodiesel, avoids competition with agriculture. To present a complete life-cycle of oils in this review, a second part will focus on the valorization of the biodiesel by-product, glycerol. About 10% of glycerol is generated during the production of biodiesel, so it should be recovered to high value-added products, always based on bioprocesses. This review will also present existing techniques to extract and purify glycerol. In the end, from the collection of feedstocks to the production of CO2 during the combustion of biodiesel, this review presents the steps using the “greener” possible processes.

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Surface modification plays a key role in the fabrication of highly active and stable enzymatic nanoreactors. In this study, we report for the first time the effect of various functional groups (epoxy, amine, trimethyl, and hexadecyl) on the catalytic performance of lipase B from Candida antarctica (CALB) incorporated within a monolithic supramolecular hydrogel with multiscale pore architecture. The supramolecular hydrogel formed by host-guest interactions between α-cyclodextrin (α-CD) and Pluronic F127 was first silicified to provide a hierarchically porous material whose surface was further modified with different organosilanes permitting both covalent anchoring and interfacial activation of CALB. The catalytic activity of nanoreactors was evaluated in the liquid phase cascade oxidation of 2,5-diformylfuran (DFF) to 2,5-furandicarboxylic acid (FDCA) under mild conditions. Results showed that high FDCA yields and high efficiency conversion of DFF could be correlated with the ability of epoxy and amine moieties to keep CALB attached to the carrier, while the trimethyl and hexadecyl groups could provide a suitable hydrophobic-hydrophilic interface for the interfacial activation of lipase. Cationic cross-linked β-CD was also evaluated as an enzyme-stabilizing agent and was found to provide beneficial effects in the operational stability of the biocatalyst. These supramolecular silicified hydrogel monoliths with hierarchical porosity may be used as promising nanoreactors to provide easier enzyme recovery in other biocatalytic continuous flow processes.