Using a one-step procedure we have prepared magnetic fluids comprising of polyelectrolyte stabilized magnetite nanoparticles. These nanocomposites are comprised of linear, chain-like assemblies of magnetic nanoparticles, which can be aligned in parallel arrays by an external magnetic field. We have shown the potential use of these materials as contrast agents by measuring their MR response in live rats. The new magnetic fluids have demonstrated good biocompatibility and potential for in vivo MRI diagnostics.
Hierarchically porous hybrid microparticles, strikingly reminiscent in their structure of the silica skeletons of single-cell algae, diatoms, but composed of titanium dioxide, and the chemically bound amphiphilic amino acids or small proteins can be prepared by a simple one-step biomimetic procedure, using hydrolysis of titanium alkoxides modified by these ligands. The growth of the hierarchical structure results from the conditions mimicking the growth of skeletons in real diatoms--the self-assembly of hydrolysis-generated titanium dioxide nanoparticles, templated by the microemulsion, originating from mixing the hydrocarbon solvent and water on action of amino acids as surfactants. The obtained microsize nanoparticle aggregates possess remarkable chemical and thermal stability and are promising substrates for applications in drug delivery and catalysis. They can be provided with pronounced surface chirality through application of chiral modifying ligands. They display also high selectivity in sorption of phosphorylated biomolecules or medicines as demonstrated by (1)H and (31)P NMR studies and by in vitro modeling using (32)P-marked ATP as a substrate. The release of the adsorbed model compounds in an inert medium is a very slow process directed by desorption kinetics. It is enhanced, however, noticeably in contact with biological fluids modeling those of the tissues suffering inflammation, which makes the produced material highly attractive for application in medical implants. The developed synthetic approach has been applied successfully also for the preparation of analogous hybrid microparticles based on zirconium dioxide or aluminum sesquioxide.
Recyclable organocatalysts: The first chiral DMAP analogue immobilized on magnetic nanoparticles is a highly active catalyst that is capable of the acylation of racemic sec-alcohols under convenient, process-scale friendly conditions (room temperature, 5 mol % loading, with acetic anhydride as the acylating agent) with excellent enantiodiscrimination. The catalyst is easily recovered and possesses unprecedented recyclability-in this study it was demonstrated to retain excellent activity and selectivity over 32 iterative cycles.
A systematic study concerning the immobilisation onto magnetic nanoparticles of three useful classes of chiral organocatalyst which rely on a confluence of weak, easily perturbed van der Waals and hydrogen bonding interactions to promote enantioselective reactions has been undertaken for the first time. The catalysts were evaluated in three different synthetically useful reaction classes: the kinetic resolution of sec-alcohols, the conjugate addition of dimethyl malonate to a nitroolefin and the desymmetrisation of meso anhydrides. A chiral bifunctional 4-N,N-dialkylaminopyridine derivative could be readily immobilised; the resulting heterogeneous catalyst is highly active and is capable of promoting the kinetic resolution of sec-alcohols with synthetically useful selectivity under process-scale friendly conditions and has been demonstrated to be reusable in a minimum of 32 consecutive cycles. The immobilisation of a cinchona alkaloid-derived urea-substituted catalyst proved considerably less successful in terms of both catalyst stability and product levels of enantiomeric excess. An immobilised cinchona alkaloid-derived sulfonamide catalyst was also prepared, with mixed results: the catalyst exhibits outstanding recyclability on a par with that associated with the successful N,N-dialkylaminopyridine analogue, however product enantiomeric excess is consistently lower than that obtained using the corresponding homogeneous catalyst. While no physical deterioration of the heterogeneous catalysts was detected on analysis after multiple recycles, in the cases of both the conjugate addition to nitroolefins and the desymmetrisation of meso anhydrides, significant levels of background catalysis by the nanoparticles in the absence of the organocatalyst was detected, which explains in part the poor performance of the immobilised organocatalysts in these reactions from a stereoselectivity standpoint. It seems clear that the immobilisation of sensitive chiral organocatalysts onto magnetite nanoparticles does not always result in heterogeneous catalysts with acceptable activity and selectivity profiles, and that consequently the applicability of the strategy must be ascertained (until more data is available) on a case-by-case basis.
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