Enzymatic synthesis of short-chain flavor esters from natural sources using tailored magnetic biocatalysts.

Immobilized lipases are excellent biocatalysts for the enzymatic synthesis of short- and medium-chain fatty esters used as food flavor compounds. Herein a new approach for a magnetic core-shell biocatalyst by immobilization of Candida antarctica B lipase is reported, coating single-core magnetic nanoparticles with an organic shell, preferably poly(benzofurane-co-arylacetic acid), followed by the covalent attachment of the enzyme and embedment of the primary biocatalyst in a silica layer. Although covalent and sol-gel immobilization were efficient on their own, their combination can ensure additional operational stability through multi-point linkages. Moreover, silanes holding glycidoxy groups, which can also form covalent linkages, have been successfully used as precursors for the silica coating layer. The structural, magnetic and morphological characteristics were assessed by TEM, SEM-EDX, X-ray photoelectron spectroscopy and vibrating sample magnetometry. The new biocatalysts demonstrated high catalytic efficiency in the solventless synthesis of isoamyl esters of natural carboxylic acids, also in multiple reaction cycles.

Refinement of Magnetite Nanoparticles by Coating with Organic Stabilizers.

Magnetite nanoparticles are of great importance in nanotechnology and nanomedicine and have found manifold applications. Here, the effect of coating of magnetite nanoparticles with organic stabilizers, such as O-phosphoryl ethanolamine, glycerol phosphate, phospho-l-ascorbic acid, phospho-d,l-serine, glycolic acid, lactic acid, d,l-malic acid, and d,l-mandelic acid was studied. Remarkably, this procedure led to an improvement of saturation magnetization in three cases rather than to an unfavorable decrease as usually observed. Detailed X-ray powder diffraction investigations revealed that changes in the average crystallite occurred in the coating process. Surprisingly, changes of the average crystallite sizes in either direction were further observed, when the exposure time to the stabilizer was increased. These results imply a new mechanism for the well-known coating of magnetite nanoparticles with stabilizers. Instead of the hitherto accepted simple anchoring of the stabilizers to the magnetite nanoparticle surfaces, a more complex recrystallization mechanism is likely, wherein partial re-dispersion of magnetite moieties from the nanoparticles and re-deposition are involved. The results can help producers and users of magnetite nanoparticles to obtain optimal results in the production of core shell magnetite nanoparticles.

Cryptands with 1,3,5-tris(1',3'-dioxan-2'-yl)-benzene units: synthesis and structural investigations.

Various cryptands based on 1,3-dioxane decorated 1,3,5-trisubstituted-benzene building blocks, connected by different chains (exhibiting ester, ether, or triazol groups) to several units with C3 symmetry, are reported. The structure of the compounds was investigated by single crystal X-ray diffraction, NMR, and MS. The role of the 1,3-dioxane units was targeted to ensure the preorganization of the substrate for the macrocyclization reactions on one side, and for easier NMR assignment of the structure of the cryptands on the other side.