showing 10 related works from this author
Complexation of phosphine ligands with peracetylated β-cyclodextrin in supercritical carbon dioxide: Effect of temperature and cosolvent on the equil…
2009
Abstract The interaction between peracetylated-β-cyclodextrin and tert-butyl and adamantyl functionalized triphenylphosphine derivatives was studied in supercritical carbon dioxide (scCO 2 ) based solvent media by UV–vis spectroscopy. The equilibrium constant for a 1:1 complexation reaction was obtained from titration spectra both in pure carbon dioxide and in the presence of methanol as a cosolvent in the temperature range 308–323 K to estimate the internal energy and entropy of the inclusion equilibrium. The values of the equilibrium constants were found significantly smaller than those obtained in aqueous solution with analogous phosphines and substantially independent of the nature of t…
Ring opening polymerization of $\varepsilon$-caprolactone in the presence of wet $\beta$-cyclodextrin: Effect of the operative pressure and of water …
2016
International audience; The ring opening polymerization (ROP) of $\varepsilon$-caprolactone (CL) in the presence of $\beta$-cyclodextrin ($\beta$-CD) wasperformed in batch reactors both at room pressure and with the reaction system pressurized with CO$_2$, N$_2$ orAr. Significant enhancements of the polymerization rate was observed when the ROP was carried out withwet $\beta$-CD under pressure. For example, after 24 hours at 120° C with a $\beta$-CD/CL molar ratio of about1/100, the monomer conversion increased from 4 to 98–99% when the pressure was changed from 0.1to 12.5–13.0 MPa independent of the nature of the compressing gas. MALDI-TOF analyses indicated thata major fraction of polymer…
Robust Mesoporous CoMo/γ-Al2O3 Catalysts from Cyclodextrin-Based Supramolecular Assemblies for Hydrothermal Processing of Microalgae: Effect of the P…
2018
Hydrothermal liquefaction (HTL) is a promising technology for the production of biocrude oil from microalgae. Although this catalyst-free technology is efficient under high-temperature and high-pressure conditions, the biocrude yield and quality can be further improved by using heterogeneous catalysts. The design of robust catalysts that preserve their performance under hydrothermal conditions will be therefore very important in the development of biorefinery technologies. In this work, we describe two different synthetic routes (i.e., impregnation and cyclodextrin-assisted one-pot colloidal approach), for the preparation in aqueous phase of six high surface area CoMo/γ-Al2O3 catalysts. Cat…
Complexation of phosphine ligands with peracetylated β-cyclodextrin in supercritical carbon dioxide: spectroscopic determination of equilibrium const…
2007
The interaction between peracetylated beta-cyclodextrin and several triphenyl phosphine derivatives was studied in supercritical carbon dioxide (scCO2) by UV-visible spectroscopy. The equilibrium constant for a 1:1 complexation reaction was obtained from titration spectra and calculated using two established mathematical models. The values of the equilibrium constants are 1-3 orders of magnitude smaller than those obtained in aqueous solution with analogous phosphines. This is likely due to the absence in scCO2 of the hydrophobic effect, which is replaced by a corresponding, but weaker, CO2-phobic effect. The largest value of Kf was found for complexes of diphenyl(4-adamantylphenyl)phosphin…
Host–guest inclusion complexes between peracetylated β-cyclodextrin and diphenyl(4-phenylphenyl)phosphine : computational studies
2006
PM3 and molecular dynamic calculations were performed upon the inclusion complexation of peracetylated β-cyclodextrin (Per-Ac-β-CD) with diphenyl(4-phenylphenyl)phosphine (DBP). Results show that the 4-phenylphenyl part of the DBP phosphine fits tightly in the cavity of the Per-Ac-β-CD, leading to the formation of stable inclusion complexes. Complexation energies indicate that the complex formed via the primary side of the Per-Ac-β-CD is more stable than that formed via the secondary side. Electrostatic potential mapping and frontier orbital analysis suggest that van der Waals interaction constitute a major driving force in the complexation of the DBP and Per-Ac-β-CD.
Inclusion complexes of triphenylphosphine derivatives and peracetylated-β-cyclodextrin in supercritical carbon dioxide
2008
The supramolecular chemistry of peracetylated-β-CD (perAc-β-CD) as a host for triphenyphosphine derivatives has been studied in supercritical (scCO2) using UV absorption spectroscopy. It was found that the association constant in scCO2 at 40°C and 300 bar is 10 to 1000 times smaller compared to analogous systems in aqueous solvent. Studies of the thermodynamics of the inclusion process found an enthalpy of association of -30 kJ/mole and an entropy of -55 J/moleK. This difference with respect to water is attributed to the absence of the hydrophobic effect in scCO2 due to the much smaller polarity of scCO2 versus water. To further explore the effect of the solvent on the association constant,…
Peracetylated β‐cyclodextrin as solubilizer of arylphosphines in supercritical carbon dioxide
2006
Abstract Effect of peracetylated β-cyclodextrin on the solubility of diphenyl(4-phenylphenyl)phosphine in supercritical carbon dioxide medium has been investigated. As shown by gravimetric measurements, the presence of cyclodextrin (CD) (1 equivalent) allows to increase the solubility of phosphine (P) in supercritical carbon dioxide (scCO 2 ) (40 °C, 35.2 MPa, nominal system density 0.89 g/mL). This solubility enhancement was attributed to host–guest interactions in scCO 2 as the P was recovered in the form of an inclusion complex. Furthermore, a diffuse reflectance spectroscopy study on the samples recovered after the experiments and on various CD/P solid mixtures obtained by co-grinding i…
Hydroformylation of 1-Octene in Supercritical Carbon Dioxide: Can Alkylation of Arylphosphines with tertButyl Groups Lead to Soluble and Active Catal…
2008
Abstract The possibility of increasing the solubility and activity of rhodium catalysts in the hydroformylation of 1-octene in supercritical carbon dioxide (scCO2) by attachment of tertbutyl (tBu) groups to the triarylphosphine ligand was investigated. The solubility of the parent and monoalkylated ligands in a mixture of gaseous components (CO2/CO/H2) was evaluated by visual observation in a view cell. In the case of triphenylphosphine, introduction of one tertbutyl group does not seem to affect the solubility of the phosphine. When the behaviour of (diphenyl)biphenylphosphine and (para-tertbutyldiphenyl)biphenylphosphine was compared a clear solubilising effect of the tBu group was observ…
Asymmetric hydrogenation of ethyl pyruvate over aqueous dispersed Pt nanoparticles stabilized by a cinchonidine-functionalized β-cyclodextrin
2021
International audience; Cinchonidine-functionalized β-cyclodextrin was used as stabilizing agent for platinum nanoparticles dispersed in water, but also as chiral modifier for the asymmetric hydrogenation of ethyl pyruvate at 30 °C under 40 bar of hydrogen. This functionalized cyclodextrin allowed getting more stable, more catalytically active and also more enantioselective Pt nanoparticles compared to control catalytic systems. NMR and MALDI-MS analyses clearly showed the reduction of the vinyl group of the cinchonidine graft during the nanoparticles preparation. Under hydrogen pressure, the hydrogenation of the quinolinic moiety was also proven and can be responsible for the difficul…
Interesterification of triglycerides with methyl acetate for biodiesel production using a cyclodextrin-derived SnO@γ-Al2O3 composite as heterogeneous…
2022
International audience; Particle morphology and surface properties of metal oxides are topics of great importance in the field of heterogeneous catalysis. Herein, we have developed a molecular-colloidal coassembly approach combined with an ultrasonic-assisted precipitation method to fabricate SnO@γ-Al2O3 composites with tuneable pore size and well-defined octahedral-shape crystal structure. The supramolecular assemblies formed between the randomly methylated β-cyclodextrin (RaMeβCD) and Pluronic F127 were employed as template to tailor the size and shape of γ-Al2O3 nanoparticles and direct their assembly almost exclusively on the surface of micrometer-sized SnO single …