Preparation and characterization of PdO nanoparticles on trivalent metal (B, Al and Ga) substituted MCM-41: excellent catalytic activity in supercritical carbon dioxide.

Palladium oxide (PdO) nanoparticles supported on B, Al and Ga modified mesoporous MCM-41with different Si/M ratios (where, M=B, Al or Ga) varied from 100 to 5 was synthesized in one-pot. Developed materials were characterized by several techniques such as XRD, TEM, UV-Vis, XPS and TG-DTA. A highly ordered structure was revealed by XRD for all the support materials depending on Si/M ratio. TEM analysis evidenced the presence of spherical PdO particles. Interestingly, the particle sizes correlated well with Si/M ratio as well as the nature of M. Spectroscopic characterization of calcined materials suggested the presence of Pd(2+), whereas XPS confirmed the existence of Pd(2+) in PdO form. The catalytic activity of resultant materials was investigated by the chemoselective hydrogenation of chloronitrobenzene in supercritical carbon dioxide. All the materials exhibit excellent conversion of chloronitrobenzene and selectivity to chloroaniline within the reaction time of 50 min. at 35 °C. Substitution of Si by trivalent metal cation improved the catalytic performance of B and Ga containing catalysts. Among the three catalysts, superior catalytic activity was observed for Pd/B-MCM-41 with highest conversion (100%) and selectivity to chloroaniline (100%) and thus, followed the reactivity order of PdO/B>PdO/Ga>PdO/Al. Considering o-, m- and p-chloronitrobenzene, for all the materials conversion followed the order of p->m->o-, whereas selectivity to chloroaniline for all three isomers were strongly influenced by the trivalent metal ion in the support material.

Preparation of N-acetylneuraminic acid from delipidated egg yolk.

Egg yolk, a large proportion of the egg, was studied for the preparation of N-acetylneuraminic acid (Neu5Ac). The delipidated hen egg yolk (DEY; 500 kg containing 0.2% w/w, Neu5Ac) was hydrolysed with HCl (pH 1.4) at 80 degrees C and neutralized with NaOH (pH 6.0). The mixture was filtered and electrodialysed until the conductivity was 240 microS cm-1. The filtrate was applied on a column of Dowex HCR-W2 (20-50 mesh), followed by a column of Dowex 1-X8 (200-400 mesh). The latter column was washed with water, and then eluted with a linear gradient of HCO2H (0-2 M). The eluates containing Neu5Ac were concentrated using a reverse osmosis membrane and, finally, rotary evaporated at 40 degrees C. The residue was then lyophilized to yield 500 g Neu5Ac. The purity of Neu5Ac was > 98% (TBA method). HPLC, NMR spectroscopy and TLC chromatography of the product obtained from the DEY showed that Neu5Ac was the sole derivative present in egg yolk. The DEY, a byproduct from egg processing plants, was found to be an excellent source for the large-scale preparation of Neu5Ac.