SBA-15 supported Ni-Cu catalysts for hydrodeoxygenation of m-cresol to toluene.

Amidst concerns over fossil fuel dependency and environmental sustainability, the utilization of biomass-derived aromatic compounds emerges as a viable solution across diverse industries. In this scheme, the conversion of biomass involves pyrolysis, followed by a hydrodeoxygenation (HDO) step to reduce the oxygen content of pyrolysis oils and stabilize the end products including aromatics. In this study, we explored the properties of size controlled NiCu bimetallic catalysts supported on ordered mesoporous silica (SBA-15) for the catalytic gas-phase HDO of m-cresol, a lignin model compound. We compared their performances with monometallic Ni and Cu catalysts. The prepared catalysts contained varying Ni to Cu ratios and featured an average particle size of approximately 2 nm. The catalytic tests revealed that the introduction of Cu alongside Ni enhanced the selectivity for the direct deoxygenation (DDO) pathway, yielding toluene as the primary product. Optimal performance was observed with a catalyst composition comprising 5 wt.% Ni and 5 wr.% Cu, achieving 85 % selectivity to toluene. Further increasing the Cu content improved turnover frequency (TOF) values, but reduced DDO selectivity. These findings underscore the importance of catalyst design in facilitating biomass-derived compound transformations and offer insights into optimizing catalyst composition for more selective HDO reactions.

The Impact of Lignin Biopolymer Sources, Isolation, and Size Reduction from the Macro- to Nanoscale on the Performances of Next-Generation Sunscreen.

In recent years, concerns about the harmful effects of synthetic UV filters on the environment have highlighted the need for natural sun blockers. Lignin, the most abundant aromatic renewable biopolymer on Earth, is a promising candidate for next-generation sunscreen due to its inherent UV absorbance and its green, biodegradable, and biocompatible properties. Lignin's limitations, such as its dark color and poor dispersity, can be overcome by reducing particle size to the nanoscale, enhancing UV protection and formulation. In this study, 100-200 nm lignin nanoparticles (LNPs) were prepared from various biomass by-products (hardwood, softwood, and herbaceous material) using an eco-friendly anti-solvent precipitation method. Pure lignin macroparticles (LMPs) were extracted from beech, spruce, and wheat straw using an ethanol-organosolv treatment and compared with sulfur-rich kraft lignin (KL). Sunscreen lotions made from these LMPs and LNPs at various concentrations demonstrated novel UV-shielding properties based on biomass source and particle size. The results showed that transitioning from the macro- to nanoscale increased the sun protection factor (SPF) by at least 2.5 times, with the best results improving the SPF from 7.5 to 42 for wheat straw LMPs and LNPs at 5 wt%. This study underscores lignin's potential in developing high-quality green sunscreens, aligning with green chemistry principles.

Enhanced stability and photothermal efficiency of Indocyanine Green J-aggregates by nanoformulation with Calix[4]arene for photothermal therapy of cancers.

Photothermal therapy (PTT) is a method of growing attention, owing to its controllable process, high efficiency and minimal side effect. Indocyanine Green (ICG) is as Food and Drug Administration (FDA) approved agent that stands on the frontline of further developments of PTT toward clinics. However, the applicability of ICG-mediated PTT is limited by the rapid in vivo clearance and photo-degradation of ICG. To improve those parameters, nanosized ICG-loaded nanoparticles (ICG-J/CX) were fabricated in this study by co-assembly of anionic ICG J-aggregates (ICG-J) with cationic tetraguanidinium calix[4]arene (CX). This very simple approach produces ICG-J/CX with a well-defined nanometer range size and a close to neutral charge. The nanoparticles demonstrate high photothermal conversion efficiency (PCE) and dramatically improved photostability, as compared with ICG. The in vitro cellular uptake and cytotoxicity studies further demonstrated that the ICG-J/CX nanoparticles enhance uptake and photothermal efficiency in comparison with ICG or non-formulated ICG-J, overall demonstrating that ICG-J/CX mediated photothermal therapy have significant potential for attaining cancer treatment.

Lipid-coated mesoporous silica microparticles for the controlled delivery of ß-galactosidase into intestines.

ß-Galactosidase has been drawing increasing attention for the treatment of lactose intolerance, but its delivery has been impeded by degradation under gastric conditions. We have demonstrated that the coating of mesoporous silica microparticles (diameter ≈ 9 µm, pore size ≈ 25 nm) with dioleoylphosphatidylcholine membranes significantly improved the loading capability and protected the enzymes from the loss of function under simulated gastric conditions. Once the particles are transferred to simulated intestinal conditions, the digestion of phosphatidylcholine with pancreatin led to the release of functional ß-galactosidase. The coating of mesoporous silica nanoparticles with a single phospholipid bilayer opens up a large potential towards the controlled release of orally administrated drugs or enzymes to the intestines.

Silica-based systems for oral delivery of drugs, macromolecules and cells.

According to the US Food and Drug Administration and the European Food Safety Authority, amorphous forms of silica and silicates are generally recognized to be safe as oral delivery ingredients in amounts up to 1500mg per day. Silica is used in the formulation of solid dosage forms, e.g. tablets, as glidant or lubricant. The synthesis of silica-based materials depends on the payload nature, drug, macromolecule or cell, and on the target release (active or passive). In the literature, most of the examples deal with the encapsulation of drugs in mesoporous silica nanoparticles. Still to date limited reports concerning the delivery of encapsulated macromolecules and cells have been reported in the field of oral delivery, despite the multiple promising examples demonstrating the compatibility of the sol-gel route with biological entities, likewise the interest of silica as an oral carrier. Silica diatoms appear as an elegant, cost-effective and promising alternative to synthetic sol-gel-based materials. This review reports the latest advances silica-based systems and discusses the potential benefits and drawbacks of using silica for oral delivery of drugs, macromolecules or cells.

Effect of Meso vs Macro Size of Hierarchical Porous Silica on the Adsorption and Activity of Immobilized ß-Galactosidase.

ß-Galactosidase (ß-Gal) is one of the most important enzymes used in milk processing for improving their nutritional quality and digestibility. Herein, ß-Gal has been entrapped into a meso-macroporous material (average pore size 9 and 200 nm, respectively) prepared by a sol-gel method from a silica precursor and a dispersion of solid lipid nanoparticles in a micelle phase. The physisorption of the enzyme depends on the concentration of the feed solution and on the pore size of the support. The enzyme is preferentially adsorbed either in mesopores or in macropores, depending on its initial concentration. Moreover, this selective adsorption, arising from the oligomeric complexation of the enzyme (monomer/dimer/tetramer), has an effect on the catalytic activity of the material. Indeed, the enzyme encapsulated in macropores is more active than the enzyme immobilized in mesopores. Designed materials containing ß-Gal are of particular interest for food applications and potentially extended to bioconversion, bioremediation, or biosensing when coupling the designed support with other enzymes.

Spin State As a Probe of Vesicle Self-Assembly.

A novel system of paramagnetic vesicles was designed using ion pairs of iron-containing surfactants. Unilamellar vesicles (diameter ≈ 200 nm) formed spontaneously and were characterized by cryogenic transmission electron microscopy, nanoparticle tracking analysis, and light and small-angle neutron scattering. Moreover, for the first time, it is shown that magnetization measurements can be used to investigate self-assembly of such functionalized systems, giving information on the vesicle compositions and distribution of surfactants between the bilayers and the aqueous bulk.

Core-shell microcapsules of solid lipid nanoparticles and mesoporous silica for enhanced oral delivery of curcumin.

Newly designed microcapsules (MC) combining a core of solid lipid nanoparticle (SLN) and a mesoporous silica shell have been developed and explored as oral delivery system of curcumin (CU). CU-loaded MC (MC-CU) are 2 µm sized and have a mesoporous silica shell of 0.3 µm thickness with a wormlike structure as characterized by small angle X-ray scattering (SAXS), nitrogen adsorption/desorption and transmission electron microscopy (TEM) measurements. It was found that SLN acts as reservoir of curcumin while the mesoporous shell insures the protection and the controlled release of the drug. MC-CU displayed a pH-dependent in vitro release profile with marked drug retention at pH 2.8. Neutral red uptake assay together with confocal laser scanning microscopy (CLSM) showed a good cell tolerance to MC-CU at relatively high concentration of inert materials. Besides, the cell-uptake test revealed that fluorescent-MC were well internalized into Caco-2 cells, confirming the possibility to use MC for gut cells targeting. These findings suggest that organic core-silica shell microcapsules are promising drug delivery systems with enhanced bioavailability for poorly soluble drugs.

In Situ Small-Angle X-ray Scattering Investigation of the Formation of Dual-Mesoporous Materials.

The formation of a 2D-hexagonal (p6m) silica-based hybrid dual-mesoporous material is investigated in situ by using synchrotron time-resolved small-angle X-ray scattering (SAXS). The material is synthesized from a mixed micellar solution of a nonionic fluorinated surfactant, R(F) 8 (EO)9 (EO=ethylene oxide) and a nonionic triblock copolymer, P123. Both mesoporous networks, with pore dimensions of 3.3 and 8.5 nm respectively, are observed by nitrogen sorption, transmission electron microscopy (TEM), and SAXS. The in situ SAXS experiments reveal that mesophase formation occurs in two steps. First the nucleation and growth of a primary 2D-hexagonal network (N1), associated with mixed micelles containing P123, then subsequent formation of a second network (N2), associated with micelles of pure R(F) 8 (EO)9 . The data obtained from SAXS and TEM suggest that the N1 network is used as a nucleation center for the formation of the N2 network, which would result in the formation of a grain with two mesopore sizes. Understanding the mechanism of the formation of such materials is an important step towards the synthesis of more-complex materials by fine tuning the porosity.

Role of Solvent and Effect of Substituent on Azobenzene Isomerization by Using Room-Temperature Ionic Liquids as Reaction Media.

The effects of a para substituent, as the electron-donating -OCH3 and -OtBu groups and the electron-withdrawing -Br and -F atoms, on azobenzene isomerization have been investigated in a series of imidazolium ionic liquids (BMIM PF6, BMIM BF4, BMIM Tf2N, EMIM Tf2N, BM2IM Tf2N, and HMIM Tf2N). The thermal cis-trans conversion tends to be improved in the presence of the substituent, as pointed out by the first-order rate constants measured at 25 °C. Both the rotation and the inversion mechanisms occur in BMIM Tf2N, EMIM Tf2N, and HMIM Tf2N, as highlighted by typical V-shape Hammett plots, but only rotation takes place in BMIM PF6, BMIM BF4, and BM2IM Tf2N. The possible interactions between the cation and the anion of the solvent and both the isomers of the azobenzene derivatives have been studied by small-wide-angle X-ray scattering (SWAXS). The calculated cis population in the photostationary state and the hardness parameter η of the trans isomer show that azobenzene and F-azobenzene are the less reactive molecules for the trans-cis conversion in all the investigated ionic liquids.

A meso-macro compartmentalized bioreactor obtained through silicalization of "green" double emulsions: W/O/W and W/SLNs/W.

We report a straightforward approach for both structuring and entrapping enzymes into hierarchical silica materials with hexagonally ordered mesopores (12 nm) and tailored macroporosity by converting a double emulsion colloidal template (tens of microns) into solid lipid nanoparticles (hundreds of nanometres). The supported biocatalyst efficiently catalyzes the methanolysis of colza oil.

Liquid-crystalline polymers from cationic dendronized polymer-anionic lipid complexes.

The use of cationic dendronized polymers as a polyelectrolytic system for templating thermotropic liquid-crystalline phases (LC) via complexation and self-assembly with counter-charged ionic lipids is described. The topology of the LC phases resulting from the self-assembly process, their lattice parameter, and the interpenetration of lipid chains is discussed via birefringency analysis and small-angle X-ray scattering. Depending on the generation of the dendronized polymer and the length of the alkyl chains, amorphous, lamellar, and columnar tetragonal phases are observed. A structural model is proposed which accounts for the systematic variations of alkyl chain length as well as polymer generation. Owing to the reversible nature of the ionic complexation, this process proves high relevance for nanoporous channels, biomimetic, transport, and nanotemplating applications.