We report the synthesis and surface functionalization of MCM-41-like mesoporous silica nanoparticles (MSNs) with spheroidal shape and particle size of 141 ± 41 nm. The success of surface functionalization with aminopropyl and sodium ethylcarboxylate groups (giving amino-MSN and carboxy-MSN, respectively) was ascertained by infrared spectroscopy and ζ potential measurements. The former showed the decrease of surface silanol groups and the corresponding appearance of signals related to NH2 bending mode (δNH2) at 1595 cm(-1) and COO(-) stretching (νas and νsym) at 1562 and 1418 cm(-1). The latter showed a change in surface charge, in that the isoelectric point (IEP) changed from pH 3-4.5 to 8.5 when the MSN was functionalized with the amino groups, while carboxy-MSN showed a more negative charge in the whole pH range with respect to MSN. The hydrophilic character of the prepared materials was ascertained by quantitative microgravimetric measurements, allowing the calculation of the average isosteric adsorption heat (q[combining macron]st). This was found to be 51 ± 3 kJ mol(-1), 61 ± 4, and 65 ± 3 kJ mol(-1) for MSN, amino-MSN, and carboxy-MSN samples, respectively. The increase in q[combining macron]st after functionalization can be ascribed to the specific interaction of water molecules with the functionalizing agents, in agreement with a higher basicity with respect to silanol groups. Moreover, the possibility of multiple H-bonding interactions of water molecules with the carboxylate anion is put forward to account for the higher water uptake with respect to parent MSN.

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The interaction of water molecules with the surface of hybrid silica-based mesoporous materials is studied by Si, H and C solid-state NMR and IR spectroscopy, with the support of ab initio calculations. The surface of aminopropyl-grafted mesoporous silica nanoparticles is studied in the dehydrated state and upon interaction with controlled doses of water vapour. Former investigations described the interactions between aminopropyl and residual SiOH groups; the present study shows the presence of hydrogen-bonded species (SiOH to NH ) and weakly interacting "free" aminopropyl chains with restricted mobility, together with a small amount of protonated NH groups. The concentration of the last-named species increased upon interaction with water, and this indicates reversible and fast proton exchange from water molecules to a fraction of the amino groups. Herein, this is discussed and explained for the first time, by a combination of experimental and theoretical approaches.

A series of luminescent rare-earth ion-doped hexagonal II-type Gd oxycarbonate phosphors Gd2-xRExO2CO3 (RE = Eu(3+), Yb(3+), Dy(3+)) have been successfully synthesized by thermal decomposition of the corresponding mixed oxalates. The Yb(3+) doped Gd-oxycarbonate has evidenced a high persistent luminescence in the NIR region, that is independent from the temperature and makes this materials particular attractive as optical probes for bioimaging.