Polysaccharide/Silica Microcapsules Prepared via Ionic Gelation Combined with Spray Drying: Application in the Release of Hydrophilic Substances and Catalysis.

Polysaccharide/silica hybrid microcapsules were prepared using ionic gelation followed by spray-drying. Chitosan and alginate were used as biopolymer matrices, and in situ prepared silica was used as a structuring additive. The prepared microparticles were used in two very different applications: the encapsulation of hydrophilic molecules, and as a support for palladium nanoparticles used as catalysts for a model organic reaction, namely the reduction of p-nitrophenol by sodium borhydride. In the first application, erioglaucine disodium salt, taken as a model hydrophilic substance, was encapsulated in situ during the preparation of the microparticles. The results indicate that the presence of silica nanostructures, integrated within the polymer matrix, affect the morphology and the stability of the particles, retarding the release of the encapsulated substance. In the second application, chloropalladate was complexed on the surface of chitosan microparticles, and palladium(II) was subsequently reduced to palladium(0) to obtain heterogeneous catalysts with an excellent performance.

Magnetically enhanced polymer-supported ceria nanocatalysts for the hydration of nitriles.

The heterogeneous catalysis of the hydration of nitriles to amides is a process of great industrial relevance in which cerium(IV) oxide (also referred to as ceria) has shown an outstanding catalytic performance. The use of non-supported ceria nanoparticles is related to difficulties in the purification of the product and the recovery and recyclability of the catalyst. Therefore, in this work, ceria nanoparticles are supported on a polymer matrix either by synthesizing polymer particles by so-called Pickering miniemulsions while using ceria nanoparticles as emulsion stabilizers or, as a comparison, by in-situ crystallization on preformed polymer particles. The former strategy presents significant advantages over the latter in terms of time and consumption of resources, and it facilitates an easier scale-up of the process. In both strategies, the incorporation of a magnetoresponsive core within the polymer matrix allows the recovery and the recycling of the catalyst by simple application of a magnetic field and offers an enhancement of the catalytic efficiency.

Colloidally Confined Crystallization of Highly Efficient Ammonium Phosphomolybdate Catalysts.

Nanodroplets in inverse miniemulsions provide a colloidal confinement for the crystallization of ammonium phosphomolybdate (APM), influencing the resulting particle size. The effects of the space confinement are investigated by comparing the crystallization of analogous materials both in miniemulsion and in bulk solution. Both routes result in particles with a rhombododecahedral morphology, but the ones produced in miniemulsion have sizes between 40 and 90 nm, 3 orders of magnitude smaller than the ones obtained in bulk solution. The catalytic activity of the materials is studied by taking the epoxidation of cis-cyclooctene as a model reaction. The miniemulsion route yields APM particles catalytically much more active than analogous samples produced in bulk solution, which can be explained by their higher dispersibility in organic solvents, their higher surface area, and their higher porosity. Inorganic phosphate salt precursors are compared with organic phosphate sources. APM nanoparticles prepared in miniemulsion from d-glucose-6-phosphate and O-phospho-dl-serine yield a conversion in the epoxidation reaction of more than 90% after only 1 h, compared to 30% for materials prepared in bulk solution. In addition, the catalysts prepared in miniemulsion display a promising recyclability.

Zirconium oxocluster/polymer hybrid nanoparticles prepared by photoactivated miniemulsion copolymerization.

The photoactivated free radical miniemulsion copolymerization of methyl methacrylate (MMA) and the zirconium oxocluster Zr4O2(methacrylate)12 is used as an effective and fast preparation method for polymer/inorganic hybrid nanoparticles. The oxoclusters, covalently anchored to the polymer network, act as metal-organic cross-linkers, thus improving the thermomechanical properties of the resulting hybrid nanoparticles. Benzoin carbonyl organic compounds were used as photoinitiators. The obtained materials are compared in terms of cross-linking, effectiveness of cluster incorporation, and size distribution with the analogous nanoparticles produced by using conventional thermally induced free radical miniemulsion copolymerization. The kinetics of the polymerization process in the absence and in the presence of the oxocluster is also investigated.

DFT Study on the Interaction of Tris(benzene-1,2-dithiolato)molybdenum Complex with Water. A Hydrolysis Mechanism Involving a Feasible Seven-Coordinate Aquomolybdenum Intermediate.

In the present work, the reactivity of the tris(benzene-1,2-dithiolato)molybdenum complex ([Mo(bdt)3]) toward water is studied by means of the density functional theory (DFT). DFT calculations were performed using the M06, B3P86, and B3PW91 hybrid functionals for comparison purposes. The M06 method was employed to elucidate the reaction pathway, relative stability of the intermediate products, nature of the Mo-S bond cleavage, and electronic structure of the involved molybdenum species. This functional was also used to study the transference of electrons from the molybdenum center toward the ligands. The reaction pathway confirms that [Mo(bdt)3] undergoes hydrolysis, yielding dihydroxo-bis(benzene-1,2-dithiolato)molybdenum complex ([Mo(OH)2(bdt)2]) and benzenedithiol. The reaction takes place through seven transition structures, one of them involving an aquo seven-coordinate molybdenum intermediate stabilized by a lone pair (LP) LPO→LPMo hyperconjugative interaction. This heptacoordinate species allows understanding of the observed oxygen atom exchange between water and tertiary phosphines mediated by these complexes. Calculations also show that [Mo(C2H4S2)3] and [Mo(OH)2(C2H4S2)2] have d2 and d0 electronic configuration, and hence an electron pair must be transferred during the course of the hydrolysis. The frontier molecular orbital (FMO) analysis concludes that the electron pair is transferred in the rupture of the second Mo-S bond, from the occupied donating Mo dx2-y2 orbital to the unoccupied C2H4(SH)2 S-C σ* ligand orbital. This result is supported by the bond dissociation energy calculations, which demonstrate that the neutral dissociation of the second Mo-S bond is energetically the more favorable.