Controlling Reaction Selectivity over Hybrid Plasmonic Nanocatalysts.

The localized surface plasmon resonance (LSPR) excitation in plasmonic nanoparticles has been used to accelerate several catalytic transformations under visible-light irradiation. In order to fully harness the potential of plasmonic catalysis, multimetallic nanoparticles containing a plasmonic and a catalytic component, where LSPR-excited energetic charge carriers and the intrinsic catalytic active sites work synergistically, have raised increased attention. Despite several exciting studies observing rate enhancements, controlling reaction selectivity remains very challenging. Here, by employing multimetallic nanoparticles combining Au, Ag, and Pt in an Au@Ag@Pt core-shell and an Au@AgPt nanorattle architectures, we demonstrate that reaction selectivity of a sequential reaction can be controlled under visible light illumination. The control of the reaction selectivity in plasmonic catalysis was demonstrated for the hydrogenation of phenylacetylene as a model transformation. We have found that the localized interaction between the triple bond in phenylacetylene and the Pt nanoparticle surface enables selective hydrogenation of the triple bond (relative to the double bond in styrene) under visible light illumination. Atomistic calculations show that the enhanced selectivity toward the partial hydrogenation product is driven by distinct adsorption configurations and charge delocalization of the reactant and the reaction intermediate at the catalyst surface. We believe these results will contribute to the use of plasmonic catalysis to drive and control a wealth of selective molecular transformations under ecofriendly conditions and visible light illumination.

Can pain influence the proprioception and the motor behavior in subjects with mild and moderate knee osteoarthritis?

BACKGROUND: Osteoarthritis (OA) is a chronic disease, usually characterized by pain, which is associated with reduced muscle strength, disability and progressive loss of function. However, the pain influence over proprioception and motor behaviour remains unclear. Thus, the purpose of the study was to identify the levels of pain, the proprioceptive acuity and the pattern of muscle recruitment during stair ascent and descent in elderly patients with mild and moderate osteoarthritis (OA) compared to healthy subjects. METHODS: The study participants included 11 healthy elderly subjects (7 women and 4 men) and 31 elderly patients with knee OA (19 women and 12 men). The functional capacity was assessed by the Western Ontario and McMaster Universities (WOMAC) osteoarthritis index; the pain was evaluated by Wong-Baker faces pain rating scale (WBS) and pressure pain threshold (PPT); the proprioceptive acuity was based on the joint position sense evaluated by electrogoniometer; and the electromyographic (EMG) activity of the major muscles of the lower limb were evaluated during a task of stair ascent and descent of 15 cm. For statistical analysis it was used Statistic for Windows software (StatSoft Inc., version 5.0). Data from the WOMAC index, WBS, the proprioceptive acuity and IEMG (for each muscle in each phase) were analyzed using the Mann-Whitney U test and data from PPT was used Kruskal-Wallis test. RESULTS: Higher scores were found in the WOMAC index and WBS whereas lower scores were seen in PPT in patients with knee OA compared to healthy subjects. In contrast, there were no significant differences in the proprioceptive acuity and EMG results of most muscles analyzed between the groups. CONCLUSION: The presence of pain does not influence the proprioception and the motor behavior of the thigh muscles during stair ascent and descent in subjects with mild and moderate knee OA.

A green approach to DDT degradation and metabolite monitoring in water comparing the hydrodechlorination efficiency of Pd, Au-on-Pd and Cu-on-Pd nanoparticle catalysis.

DDT (1,1,1-trichloro-2,2-bi(p-chlorophenyl)-ethane) and its metabolites (DDD, 1,1-dichloro-2,2-bis-(4'-chlorophenyl)ethane, and DDE, 1,1-dichloro-2,2-bis-(4'-chlorophenyl)ethylene) are persistent organic pollutants that can be catalytically degraded into a less toxic and less persistent compound. In this work, ecofriendly methodologies for catalyst synthesis, catalytic degradation of DDT and reaction monitoring have been proposed. Three types of Pd-based nanoparticles, NPs, (Pd, Au-on-Pd and Cu-on-Pd) were synthesized and used for catalytic hydrodechlorination of DDT and its metabolites. The structural and electronic properties of NPs were investigated using TEM and XAS spectroscopy. Au-on-Pd showed the highest hydrodechlorination efficiency within 1 h of reaction. To obtain the best reaction conditions, the effects of H2 flow and base addition Au-on-Pd NPs activity were investigated. To study the effectiveness of the different NPs, a solvent-free analytical method was optimized to detect and measure DDT and its by-products. The SPME-GC-MS method provided low detection limits (0.03 µg L-1) and high recovery (≥88.75%) and was a valuable tool for the NP degradation study. In this way, a green method for degradation and monitoring of DDT and its by-products in water was achieved.

Core-shell PdCu bimetallic colloidal nanoparticles in Sonogashira cross-coupling reaction: mechanistic insights into the catalyst mode of action.

Core-shell PdCu nanoparticles with different metal proportions were synthesized using a one-pot methodology and characterized by STEM, HRTEM, XANES and EXAFS analysis. The bimetallic nanoparticles were applied as catalysts in the Sonogashira cross-coupling reaction to investigate the mode of action of the PdCu in the reaction. The copper content directly influenced the generation of the cross-coupling product, shaping the performance of the catalyst. A quasi-homogeneous reaction pathway was evidenced by kinetics and poisoning experiments as well as XAS, HRTEM and HRMS analysis. These findings help to elucidate the mode of action of the PdCu nanocatalysts in the, as yet, unrevealed Sonogashira mechanism and the potential development of new nanocatalysts.

A mechano-colloidal approach for the controlled synthesis of metal nanoparticles.

A mechano-colloidal approach was developed to produce Au nanotadpoles. It comprises the generation of seeds by ball-milling from a solid mixture containing a precursor, reductant, and capping agent, followed by the dispersion of this mixture in water leading to seeded-growth to generate the target nanoparticle morphology.

Combining active phase and support optimization in MnO2-Au nanoflowers: Enabling high activities towards green oxidations.

Among the several classes of chemical reactions, the green oxidation of organic compounds has emerged as an important topic in nanocatalysis. Nonetheless, examples of truly green oxidations remain scarce due to the low activity and selectivity of reported catalysts. In this paper, we present an approach based on the optimization of both the support material and the active phase to achieve superior catalytic performances towards green oxidations. Specifically, our catalysts consisted of ultrasmall Au NPs deposited onto MnO2 nanoflowers. They displayed hierarchical morphology, large specific surface areas, ultrasmall and uniform Au NPs sizes, no agglomeration, strong metal-support interactions, oxygen vacancies, and Auδ+ species at their surface. These features led to improved performances towards the green oxidations of CO, benzene, toluene, o-xylene, glucose, and fructose relative to the pristine MnO2 nanoflowers, commercial MnO2 decorated with Au NPs, and other reported catalysts. We believe that the catalytic activities, stabilities, and mild/green reaction conditions described herein for both gas and liquid phase oxidations due to the optimization of both the support and active phase may inspire the development of novel catalytic systems for a wealth of sustainable transformations.