ABSTRACT
The present work shows an efficient strategy to assemble two types of functional nanoparticles onto mesoporous MCM-41 silica nanospheres with a high degree of spatial precision. In a first stage, magnetite nanoparticles are synthesized with a size larger than the support pores and grafted covalently through a peptide-like bonding onto their external surface. This endowed the silica nanoparticles with a strong superparamagnetic response, while preserving the highly ordered interior space for the encapsulation of other functional guest species. Second, we report the finely controlled pumping of preformed Pt nanoparticles (1.5 nm) within the channels of the magnetic MCM-41 nanospheres to confer an additional catalytic functionality to the multiassembled nanoplatform. The penetration depth of the metallic nanoparticles can be explained as a result of the interplay between the particle-wall electrostatic attraction and the repulsive forces between neighboring Pt nanoparticles. A detailed transmission electron microscopy and a 3D high-resolution high-angle annular dark-field detector electron tomography study were carried out to characterize the material and to explain the assembly mechanism. Finally, the performance of these multifunctional nanohybrids as magnetically recoverable catalysts has been evaluated in the selective hydrogenation of p-nitrophenol, a well-known pollutant and intermediate in multiple industrial processes.
ABSTRACT
BACKGROUND: Magnetic resonance imaging (MRI) plays an important role in tumor detection/diagnosis. The use of exogenous contrast agents (CAs) helps to improve the discrimination between lesion and neighbouring tissue, but most of the currently available CAs are non-specific. Assessing the performance of new, selective CAs requires exhaustive assays and large amounts of material. Accordingly, in a preliminary screening of new CAs, it is important to choose candidate compounds with good potential for in vivo efficiency. This screening method should reproduce as close as possible the in vivo environment. In this sense, a fast and reliable method to select the best candidate CAs for in vivo studies would minimize time and investment cost, and would benefit the development of better CAs. RESULTS: The post-mortem ex vivo relative contrast enhancement (RCE) was evaluated as a method to screen different types of CAs, including paramagnetic and superparamagnetic agents. In detail, sugar/gadolinium-loaded gold nanoparticles (Gd-GNPs) and iron nanoparticles (SPIONs) were tested. Our results indicate that the post-mortem ex vivo RCE of evaluated CAs, did not correlate well with their respective in vitro relaxivities. The results obtained with different Gd-GNPs suggest that the linker length of the sugar conjugate could modulate the interactions with cellular receptors and therefore the relaxivity value. A paramagnetic CA (GNP (E_2)), which performed best among a series of Gd-GNPs, was evaluated both ex vivo and in vivo. The ex vivo RCE was slightly worst than gadoterate meglumine (201.9 ± 9.3% versus 237 ± 14%, respectively), while the in vivo RCE, measured at the time-to-maximum enhancement for both compounds, pointed to GNP E_2 being a better CA in vivo than gadoterate meglumine. This is suggested to be related to the nanoparticule characteristics of the evaluated GNP. CONCLUSION: We have developed a simple, cost-effective relatively high-throughput method for selecting CAs for in vivo experiments. This method requires approximately 800 times less quantity of material than the amount used for in vivo administrations.
