Stéphane Isabettini

Hierarchical high-silica zeolites as superior base catalysts

For more than four decades, the design of zeolite base catalysts has relied on the application of aluminium-rich frameworks exchanged with alkali metal cations (preferably Cs+). However, moderate activity associated with access and diffusion limitations, and high manufacturing costs associated with high caesium content (typically over 30%) have hampered their industrial implementation so far. Herein, we have discovered that high-silica USY zeolites outperform their Al-rich counterparts in a variety of base-catalysed reactions of relevance in the fine chemical industry, as well as in the upgrading of biofuels. The benefits of this class of materials are amplified upon the alleviation of diffusion constraints through the introduction of a network of intracrystalline mesopores by post-synthetic modification. For example, the resulting cation-free hierarchical USY provides an up to 30-fold Knoevenagel condensation activity compared to the benchmark Cs–X, and similar observations were made upon application in liquid-phase (nitro)aldol reactions. Moreover, in the gas-phase aldol condensation of propanal, high-silica zeolites provide superior activity, selectivity, and lifetime compared to caesium-containing zeolites and even a strong solid base such as MgO. We decouple the complex interplay between mesoporosity and intrinsic zeolitic properties such as crystallinity, and quantify the increase in catalyst effectiveness upon hierarchical structuring as a function of reactant size. The obtained results are a major step to resolve the drawbacks of zeolites catalysis and thereby revitalise their potential for industrial application.

Tailoring Bicelle Morphology and Thermal Stability with Lanthanide-Chelating Cholesterol Conjugates.

Bicelles composed of DMPC and phospholipids capable of chelating lanthanide ions, such as 1,2-dimyristoyl-sn-glycero-3-phospho-ethanolamine-diethylene triaminepentaacetate (DMPE-DTPA), are highly tunable magnetically responsive soft materials. Further doping of these systems with cholesterol-DTPA conjugates complexed to a lanthanide ion considerably enhances the bicelles size and magnetic alignability. The high value of these cholesterol conjugates for bicelle design remains largely unexplored. Herein, we examine how molecular structural alterations within the cholesterol-DTPA conjugates lead to contrasting self-assembled polymolecular aggregate structures when incorporated into DMPC/DMPE-DTPA/Tm(3+) bilayers. The nature of the linker connecting the DTPA-chelating moiety to the sterol backbone is examined by synthesizing conjugates of various linker lengths and polarities. The incorporation of these compounds within the bilayer results in polymolecular aggregate geometries of higher curvature. The increasing degrees of freedom for conformational changes conveyed to the chelator headgroup with increasing linker atomic length reduce the cholesterol-DTPA conjugates critical packing parameter. Consequently, an inverse correlation between the number of carbon atoms in the linker and the bicelle radius is established. The introduction of polarity into the carbon chain of the linker did not cause major changes in the polymolecular aggregate architecture. Under specific conditions, the additives permit the formation of remarkably temperature-resistant bicelles. The versatility of design offered by these amphiphiles gives rise to new and viable tools for the growing field of magnetically responsive soft materials.

Ion-Induced Hydrogel Formation and Nematic Ordering of Nanocrystalline Cellulose Suspensions

Nanocrystalline cellulose (NCC) is a promising material for formation of hydrogels and nematic liquid crystals. While salt addition is known to facilitate hydrogel formation, it remains unclear whether this originates from cationic bridging or charge screening effects. Herein, we demonstrate the effect of mono- and divalent salts on NCC gelation and nematic ordering. A strong correlation of NCC suspension zeta-potential and rheological behavior was found. Lower concentrations of divalent cations were needed to decrease NCC zeta-potential and form hydrogels. The same zeta-potentials and gel strengths were achieved at higher concentrations of monovalent salts. Salt-induced NCC aggregation is thus caused by intermolecular attractive forces rather than cationic bridging. Against excluded volume argumentation, salt addition was found to promote NCC nematic phase formation. Increased nematic ordering was observed in a transition regime of moderate salt addition before complete aggregation occurs. This regime is governed by an equilibrium of repulsive and attractive forces. Small angle neutron scattering suggests lateral orientation of NCC. Hence, NCC gelation and nematic ordering can be modulated via its zeta-potential by targeted salt addition.

Development of Smart Optical Gels with Highly Magnetically Responsive Bicelles

Hydrogels delivering on-demand tailorable optical properties are formidable smart materials with promising perspectives in numerous fields, including the development of modern sensors and switches, the essential quality criterion being a defined and readily measured response to environmental changes. Lanthanide ion (Ln3+)-chelating bicelles are interesting building blocks for such materials because of their magnetic responsive nature. Imbedding these phospholipid-based nanodiscs in a magnetically aligned state in gelatin permits an orientation-dependent retardation of polarized light. The resulting tailorable anisotropy gives the gel a well-defined optical signature observed as a birefringence signal. These phenomena were only reported for a single bicelle-gelatin pair and required high magnetic field strengths of 8 T. Herein, we demonstrate the versatility and enhance the viability of this technology with a new generation of aminocholesterol (Chol-NH2)-doped bicelles imbedded in two different types of gelatin. The highly magnetically responsive nature of the bicelles allowed to gel the anisotropy at commercially viable magnetic field strengths between 1 and 3 T. Thermoreversible gels with a unique optical signature were generated by exposing the system to various temperature conditions and external magnetic field strengths. The resulting optical properties were a signature of the gels environmental history, effectively acting as a sensor. Solutions containing the bicelles simultaneously aligning parallel and perpendicular to the magnetic field directions were obtained by mixing samples chelating Tm3+ and Dy3+. These systems were successfully gelled, providing a material with two distinct temperature-dependent optical characteristics. The high degree of tunability in the magnetic response of the bicelles enables encryption of the gels optical properties. The proposed gels are viable candidates for temperature tracking of sensitive goods and provide numerous perspectives for future development of tomorrows smart materials and technologies.

Continuous Paranematic Ordering of Rigid and Semiflexible Amyloid-Fe3O4 Hybrid Fibrils in an External Magnetic Field

External magnetic field is a powerful approach to induce orientational order in originally disordered suspensions of magneto-responsive anisotropic particles. By small angle neutron scattering and optical birefringence measurement technology, we investigated the effect of magnetic field on the spatial ordering of hybrid amyloid fibrils with different aspect ratios (length-to-diameter) and flexibilities decorated by spherical Fe3O4 nanoparticles. A continuous paranematic ordering from an initially isotropic suspension was observed upon increasing magnetic field strength, with spatial orientation increasing with colloidal volume fraction. At constant dimensionless concentration, stiff hybrid fibrils with varying aspect ratios and volume fractions, fall on the same master curve, with equivalent degrees of ordering at identical magnetic fields. However, the semiflexible hybrid fibrils with contour length close to persistence length exhibit a lower degree of alignment. This is consistent with Khokhlov-Semenov theoretical predictions. These findings sharpen the experimental toolbox to design colloidal systems with controllable degree of orientational ordering.

Methods for Generating Highly Magnetically Responsive Lanthanide-Chelating Phospholipid Polymolecular Assemblies

Mixtures of 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) and its lanthanide ion (Ln3+) chelating phospholipid conjugate, 1,2-dimyristoyl-sn-glycero-3-phospho-ethanolamine-diethylene triaminepentaacetate (DMPE-DTPA), assemble into highly magnetically responsive polymolecular assemblies such as DMPC/DMPE-DTPA/Ln3+ (molar ratio 4:1:1) bicelles. Their geometry and magnetic alignability is enhanced by introducing cholesterol into the bilayer in DMPC/Cholesterol/DMPE-DTPA/Ln3+ (molar ratio 16:4:5:5). However, the reported fabrication procedures remain tedious and limit the generation of highly magnetically alignable species. Herein, a simplified procedure where freeze thawing cycles and extrusion are replaced by gentle heating and cooling cycles for the hydration of the dry lipid film was developed. Heating above the phase transition temperature Tm of the lipids composing the bilayer before cooling back below the Tm was essential to guarantee successful formation of the polymolecular assemblies composed of DMPC/DMPE-DTPA/Ln3+ (molar ratio 4:1:1). Planar polymolecular assemblies in the size range of hundreds of nanometers are achieved and deliver unprecedented gains in magnetic response. The proposed heating and cooling procedure further allowed to regenerate the highly magnetically alignable DMPC/Cholesterol/DMPE-DTPA/Ln3+ (molar ratio 16:4:5:5) species after storage for one month frozen at -18 °C. The simplicity and viability of the proposed fabrication procedure offers a new set of highly magnetically responsive lanthanide ion chelating phospholipid polymolecular assemblies as building blocks for the smart soft materials of tomorrow.

Understanding the Enhanced Magnetic Response of Aminocholesterol Doped Lanthanide-Ion-Chelating Phospholipid Bicelles

Cholesterol (Chol-OH) and its conjugates are powerful molecules for engineering the physicochemical and magnetic properties of phospholipid bilayers in bicelles. Introduction of aminocholesterol (3β-amino-5-cholestene, Chol-NH2) in bicelles composed of 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) and the thulium-ion-chelating phospholipid 1,2-dimyristoyl-sn-glycero-3-phospho-ethanolamine-diethylene triaminepentaacetate (DMPE-DTPA/Tm3+) results in unprecedented high magnetic alignments by selectively tuning the magnetic susceptibility Δχ of the bilayer. However, little is known on the underlying mechanisms behind the magnetic response and, more generally, on the physicochemical forces governing a Chol-NH2 doped DMPC bilayer. We tackled this shortcoming with a multiscale bottom-up comparative investigation of Chol-OH and Chol-NH2 mixed with DMPC. First, simplified monolayer models on a Langmuir trough were employed to compare the two steroid molecules at various contents in DMPC. In a second step, a molecular dynamics (MD) simulation allowed for a more representative model of the bicelle bilayer while monitoring the amphiphiles and their interactions on the molecular level. In a final step, we moved away from the models and investigated the effect of temperature on the structure and magnetic alignment of Chol-NH2 doped bicelles by SANS. The DMPC/steroid monolayer studies showed that Chol-OH induces a larger condensation effect than Chol-NH2 at steroid contents of 16 and 20 mol %. However, this tendency was inversed at steroid contents of 10, 30, and 40 mol %. Although the MD simulation with 16 mol % steroid revealed that both compounds induce a liquid-ordered state in DMPC, the bilayer containing Chol-NH2 was much less ordered than the analogous system containing Chol-OH. Chol-NH2 underwent significantly more hydrogen bonding interactions with neighboring DMPC lipids than Chol-OH. It seems that, by altering the dynamics of the hydrophilic environment of the bicelle, Chol-NH2 changes the crystal field and angle of the phospholipid-lanthanide DMPE-DTPA/Tm3+ complex. These parameters largely determine the magnetic susceptibility Δχ of the complex, explaining the SANS results, which show significant differences in magnetic alignment of the steroid doped bicelles. Highly magnetically alignable DMPC/Chol-NH2/DMPE-DTPA/Tm3+ (molar ratio 16:4:5:5) bicelles were achieved up to temperatures of 35 °C before a thermoreversible rearrangement into nonalignable vesicles occurred. The results confirm the potential of Chol-NH2 doped bicelles to act as building blocks for the development of the magnetically responsive soft materials of tomorrow.