Lipases are ubiquitous enzymes whose physiological role is the hydrolysis of triacylglycerol into fatty acids. They are the most studied and industrially interesting enzymes, thanks to their versatility to promote a plethora of reactions on a wide range of substrates. In fact, depending on the reaction conditions, they can also catalyze synthesis reactions, such as esterification, acidolysis and transesterification. The latter is particularly important for biodiesel production. Biodiesel can be produced from animal fats or vegetable oils and is considered as a biodegradable, non-toxic and renewable energy source. The use of lipases as industrial catalysts is subordinated to their immobilization on insoluble supports, to allow multiple uses and use in continuous processes, but also to stabilize the enzyme, intrinsically prone to denaturation with consequent loss of activity. Among the materials that can be used for lipase immobilization, mesoporous silica nanoparticles represent a good choice due to the combination of thermal and mechanical stability with controlled textural characteristics. Moreover, the presence of abundant surface hydroxyl groups allows for easy chemical surface functionalization. This latter aspect has the main importance since lipases have a high affinity with hydrophobic supports. The objective of this work is to provide an overview of the recent progress of lipase immobilization in mesoporous silica nanoparticles with a focus on biodiesel production.

An immobilization protocol of a model enzyme into silica nanoparticles was applied. This protocol exploited the use of the bifunctional molecule triethoxysilylpropylisocyanate (TEPI) for covalent binding through a linker of suitable length. The enzyme β-glucosidase (BG) was anchored onto wrinkled silica nanoparticles (WSNs). BG represents a bottleneck in the conversion of lignocellulosic biomass into biofuels through cellulose hydrolysis and fermentation. The key aspect of the procedure was the use of an organic solvent (anhydrous acetone) in which the enzyme was not soluble. This aimed to restrict its conformational changes and thus preserve its native structure. This approach led to a biocatalyst with improved thermal stability, characterized by high immobilization efficiency and yield. It was found that the apparent K_M value was about half of that of the free enzyme. The V_max was about the same than that of the free enzyme. The biocatalyst showed a high operational stability, losing only 30% of its activity after seven reuses.

Fungal cellulases generally contain a reduced amount of β-glucosidase (BG), which does not allow for efficient cellulose hydrolysis. To address this issue, we implemented an easy co-immobilization procedure of β-glucosidase and cellulase by adsorption on wrinkled mesoporous silica nanoparticles with radial and hierarchical open pore structures, exhibiting smaller (WSN) and larger (WSN-p) inter-wrinkle distances. The immobilization was carried out separately on different vectors (WSN for BG and WSN-p for cellulase), simultaneously on the same vector (WSN-p), and sequentially on the same vector (WSN-p) in order to optimize the synergy between cellulase and BG. The obtained results pointed out that the best biocatalyst is that prepared through simultaneous immobilization of BG and cellulase on the same vector (WSN-p). In this case, the adsorption resulted in 20% yield of immobilization, corresponding to an enzyme loading of 100 mg/g of support. 82% yield of reaction and 72 μmol/min·g activity were obtained, evaluated for the hydrolysis of cellulose extracted from Eriobotrya japonica leaves. All reactions were carried out at a standard temperature of 50 °C. The biocatalyst retained 83% of the initial yield of reaction after 9 cycles of reuse. Moreover, it had better stability than the free enzyme mixture in a wide range of temperatures, preserving 72% of the initial yield of reaction up to 90 °C.

Mesostructured silica nanoparticles offer a unique opportunity in the field of biocatalysis thanks to their outstanding properties. The tunable pore size in the range of mesopores allows for immobilizing bulky enzyme molecules. The large surface area improves the catalytic efficiency by increasing enzyme loading and finely dispersing the biocatalyst molecules. The easily tunable pore morphology allows for creating a proper environment to host an enzyme. The confining effect of mesopores can improve the enzyme stability and its resistance to extreme pH and temperatures. Benefits also arise from other peculiarities of nanoparticles such as Brownian motion and easy dispersion. Fossil fuel depletion and environmental pollution have led to the need for alternative sustainable and renewable energy sources such as biofuels. In this context, lignocellulosic biomass has been considered as a strategic fuel source. Cellulases are a class of hydrolytic enzymes that convert cellulose into fermentable sugars. This review is intended to survey the immobilization of cellulolytic enzymes (cellulases and β-glucosidase) onto mesoporous silica nanoparticles and their catalytic performance, with the aim to give a contribution to the urgent action required against climate change and its impacts, by biorefineries’ development.

In this paper, for the first time, inexpensive waterglass solutions are exploited as a new, simple and ecofriendly chemical approach for promoting the formation of a silica-based coating on hemp fabrics, able to act as a thermal shield and to protect the latter from heat sources. Fourier Transform Infrared (FTIR) and solid-state Nuclear Magnetic Resonance (NMR) analysis confirm the formation of –C–O–Si– covalent bonds between the coating and the cellulosic substrate. The proposed waterglass treatment, which is resistant to washing, seems to be very effective for improving the fire behavior of hemp fabric/epoxy composites, also in combination with ammonium polyphosphate. In particular, the exploitation of hemp surface treatment and Ammonium Polyphosphate (APP) addition to epoxy favors a remarkable decrease of the Heat Release Rate (HRR), Total Heat Release (THR), Total Smoke Release (TSR) and Specific Extinction Area (SEA) (respectively by 83%, 35%, 45% and 44%) as compared to untreated hemp/epoxy composites, favoring the formation of a very stable char, as also assessed by Thermogravimetric Analysis (TGA). Because of the low interfacial adhesion between the fabrics and the epoxy matrix, the obtained composites show low strength and stiffness; however, the energy absorbed by the material is higher when using treated hemp. The presence of APP in the epoxy matrix does not affect the mechanical behavior of the composites.