Understanding the role of promoters in catalysis: operando XAFS/DRIFTS study of CeO_x/Pt/Al₂O₃ during CO oxidation

A combined operando XAFS/DRIFTS study on CeOx/Pt/Al2O3 catalysts has been performed during CO oxidation and provides insights into the changes in nanoparticle structure and adsorbed species during the reaction profile. The onset of CO2 formation is shown to be concurrent with a rapid re-oxidation of the Pt nanoparticles, evidenced by XAFS spectroscopy, and the loss of bridge bonded CO adsorbed on Pt, as shown by simultaneous DRIFTS acquisition. The continued appearance of linear bound CO on the catalyst surface is shown to remain long after catalytic light off. The interaction of Pt and CeOx is evidenced by the improved performance towards CO oxidation, compared to the non-CeOx modified Pt/Al2O3, and changes in the CO adsorption properties on Pt previously linked to Pt-CeO2 interfaces

Nanostructures based on monoolein or diolein and amphiphilic gadolinium complexes as MRI contrast agents

Highly ordered two or three dimensional mesophases in aqueous solution could be usefully obtained by using monoolein (MO) or diolein (DO) monomers. Nanostructures (also indicated as nanoparticles, NPs) of MO or DO containing different amounts (1%, 5%, 10% and 20%) of the synthetic amphiphilic gadolinium complex (C18)2DTPA(Gd) have been prepared and characterized for their relaxometric and structural behaviors. The nanostructure is found in the 110–200 nm range for all investigated systems, while the presence of the gadolinium containing monomer produces a partial loss of the cubic symmetry, as shown by Cryo-TEM images of NPs doped with 10% w/w of (C18)2DTPA(Gd). Gadolinium containing nanostructures display high relaxivity values (in the 10–15 mM1 s1 range at 25 and 20 MHz, with a further increase at 37°C for DO based NPs), and interesting relaxometric properties for their possible use as MRI contrast agents. NPs containing 10% w/w of (C18)2DTPA(Gd) (MO3-NPs and DO3-NPs) have been also derivatized by introducing 3% wt of (C18)2–Peg3000–FA to obtain targeted aggregates (MO3-NP–FA, DO3-NP–FA). A preferential uptake efficiency of DO3-NP–FA in IGROV-1 cells with respect to DO-NPs without folic acid is observed, specially when cells are incubated with low concentrations of nanostructures or at short incubation times, thus indicating its potential use as a target-selective delivery system for MRI contrast agents on tumor cells overexpressing the folate receptor

Polymerized mixed aggregates containing gadolinium complex and CCK8 peptide.

Two novel amphiphilic unimers contg. an aliph. hydrophobic chain (PDA) with two C C triple bonds and hydrophilic heads presenting the chelating agent DTPAGlu and the CCK8 bioactive peptide, resp., have been prepd. by solid phase synthesis. Aggregates obtained by mixing together PDA-DTPAGlu, or its Gd(III) complex, and PDA-L2-CCK8 in 70/30 molar ratio before and after a polymn. process carried out by UV irradn. have been structurally characterized by means of small angle neutron scattering. The relaxivity properties of aggregates contg. Gadolinium complexes have also been investigated. Elongated mixed micelles have been obsd., in which the relaxivity value r1p for each Gadolinium complex, measured at 20 MHz and 298 K, is around 12 mM-1s-1

Physicochemical properties of mixed micellar aggregates containing CCK peptides and Gd complexes designed as tumor specific contrast agents in MRI

New amphiphilic molecules containing a bioactive peptide or a claw moiety have been prepared in order to obtain mixed micelles as target-specific contrast agents in magnetic resonance imaging. The first molecule, C18H37CONH(AdOO)2-G-CCK8 (C18CCK8), contains a C18 hydrophobic moiety bound to the C-terminal cholecystokinin octapeptide amide (CCK 26-33 or CCK8). The second amphiphilic compound, C18H37CONHLys(DTPAGlu)CONH2 (C18DTPAGlu) or its gadolinium complex, (C18DTPAGlu- (Gd)), contains the same C18 hydrophobic moiety bound, through a lysine residue, to the DTPAGlu chelating agent. The mixed aggregates as well as the pure C18DTPAGlu aggregate, in the presence and absence of Gd, have been fully characterized by surface tension measurements, FT-PGSE-NMR, fluorescence quenching, and small-angle neutron scattering measurements. The structural characterization of the mixed aggregates C18DTPAGlu(Gd)-C18CCK8 indicates a spherical arrangement of the micelles with an external shell of 21 Å and an inner core of 20 Å. Both the DTPAGlu(Gd) complexes and the CCK8 peptides point toward the external surface. The measured values for relaxivity in saline medium at 20 MHz proton Larmor frequency and 25 °C are 18.7 mM-1 s-1. These values show a large enhancement in comparison with the isolated DTPAGlu(Gd) complex

Size determination and quantification of engineered cerium oxide nanoparticles by flow field-flow fractionation coupled to inductively coupled plasma mass spectrometry

Facing the lack of studies on characterization and quantification of cerium oxide nanoparticles (CeO2 NPs), whose consumption and release is greatly increasing, this work proposes a method for their sizing and quantification by Flow Field-flow Fractionation (FFFF) coupled to Inductively Coupled Plasma-Mass Spectrometry (ICP-MS). Two modalities of FFFF (Asymmetric Flow- and Hollow Fiber-Flow Field Flow Fractionation, AF4 and HF5, respectively) are compared, and their advantages and limitations discussed. Experimental conditions (carrier composition, pH, ionic strength, crossflow and carrier flow rates) are studied in detail in terms of NP separation, recovery, and repeatability. Size characterization of CeO2 NPs was addressed by different approaches. In the absence of feasible size standards of CeO2 NPs, suspensions of Ag, Au, and SiO2 NPs of known size were investigated. Ag and Au NPs failed to show a comparable behavior to that of the CeO2 NPs, whereas the use of SiO2 NPs provided size estimations in agreement to those predicted by the theory. The latter approach was thus used for characterizing the size of CeO2 NPs in a commercial suspension. Results were in adequate concordance with those achieved by transmission electron microscopy, X-ray diffraction and dynamic light scattering. The quantification of CeO2 NPs in the commercial suspension by AF4-ICP-MS required the use of a CeO2 NPs standards, since the use of ionic cerium resulted in low recoveries (99 ± 9% vs. 73 ± 7%, respectively). A limit of detection of 0.9 µg L-1 CeO2 corresponding to a number concentration of 1.8 × 1012 L-1 for NPs of 5 nm was achieved for an injection volume of 100 µL

Tailoring gold nanoparticle characteristics and the impact on aqueous-phase oxidation of glycerol

Poly(vinyl alcohol) (PVA)-stabilized Au nanoparticles (NPs) were synthesized by colloidal methods in which temperature variations (−75 to 75 °C) and mixed H2O/EtOH solvent ratios (0, 50, and 100 vol/vol) were used. The resulting Au NPs were immobilized on TiO2 (P25), and their catalytic performance was investigated for the liquid phase oxidation of glycerol. For each unique solvent system, there was a systematic increase in the average Au particle diameter as the temperature of the colloidal preparation increased. Generation of the Au NPs in H2O at 1 °C resulted in a high observed activity compared with current Au/TiO2 catalysts (turnover frequency = 915 h−1). Interestingly, Au catalysts with similar average particle sizes but prepared under different conditions had contrasting catalytic performance. For the most active catalyst, aberration-corrected high angle annular dark field scanning transmission electron microscopy analysis identified the presence of isolated Au clusters (from 1 to 5 atoms) for the first time using a modified colloidal method, which was supported by experimental and computational CO adsorption studies. It is proposed that the variations in the populations of these species, in combination with other solvent/PVA effects, is responsible for the contrasting catalytic properties