Solvent-Free Aerobic Oxidative Cleavage of Methyl Oleate to Biobased Aldehydes over Mechanochemically Synthesized Supported AgAu Nanoparticles.

The performance of mechanochemically synthesized supported bimetallic AgAu nanoalloy catalysts was evaluated in the oxidative cleavage of methyl oleate, a commonly available unsaturated bio-derived raw material. An extensive screening of supports (SiO2 , C, ZrO2 , Al2 O3 ), metallic ratios (Ag : Au), reaction times, temperatures, and use of solvents was carried out. The performance was optimized towards productivity and selectivity for the primary cleavage products (aldehydes and oxoesters). The optimal conditions were achieved in the absence of solvent, using Ag8 Au92 /SiO2 as catalyst, at 80 °C, reaction time of 1 h, substrate to catalyst=555 and 10 bar of molecular oxygen. A strong support effect was observed: the selectivity to aldehydes was best with silica as support, and to esters was best using zirconia. This shows not only that mechanochemical preparation of bimetallic catalysts is a powerful tool to generate useful catalyst compositions, but also that a safe, green, solventless synthesis of bio-derived products can be achieved by aerobic oxidative cleavage.

Mechanochemical Strategies for the Preparation of SiO2-Supported AgAu Nanoalloy Catalysts.

Silver-gold nanoalloys were prepared from their metal salts precursors through bottom-up mechanochemical synthesis, using one-pot or galvanic replacement reaction strategies. The nanostructures were prepared over amorphous SiO2 as an inert supporting material, facilitating their stabilization without the use of any stabilizing agent. The nanomaterials were extensively characterized, confirming the formation of the bimetallic nanostructures. The nanoalloys were tested as catalysts in the hydrogenation of 2-nitroaniline and exhibited up to 4-fold the rate constant and up to 37% increased conversion compared to the respective single metal nanoparticles. Our approach is advantageous to produce nanoparticles with clean surfaces with available catalytic sites, directly in the solid-state and in an environmentally friendly manner.

Stimuli-Responsive Regulation of Biocatalysis through Metallic Nanoparticle Interaction.

The remote control of biocatalytic processes in an extracellular medium is an exciting idea to deliver innovative solutions in the biocatalysis field. With this purpose, metallic nanoparticles (NPs) are great candidates, as their inherent thermal, electric, magnetic, and plasmonic properties can readily be manipulated upon external stimuli. Exploring the unique NP properties beyond an anchoring platform for enzymes brings up the opportunity to extend the efficiency of biocatalysts and modulate their activity through triggered events. In this review, we discuss a set of external stimuli, such as light, electricity, magnetism, and temperature, as tools for the regulation of nanobiocatalysis, including the challenges and perspectives regarding their use. In addition, we elaborate on the use of combined stimuli that create a more refined framework in terms of a multiresponsive system. Finally, we envision this review might instigate researchers in this field of study with a set of promising opportunities in the near future.

Visible light plasmon excitation of silver nanoparticles against antibiotic-resistant Pseudomonas aeruginosa.

The interaction of metallic nanoparticles with light excites a local surface plasmon resonance (LSPR). This phenomenon enables the transfer of hot electrons to substrates that release Reactive Oxygen Species (ROS). In this context, the present study aimed at enhancing the antibacterial effect of citrate-covered silver nanoparticles (AgNPs) by LSPR excitation with visible LED. AgNPs possess excellent antimicrobial properties against Pseudomonas aeruginosa, one of the most refractory organisms to antibiotic treatment. The Minimum Inhibitory Concentration (MIC) of the AgNPs was 10 µg/ml under dark conditions and 5 µg/ml under light conditions. The combination of light and AgNPs led to 100% cell death after 60 min. Flow cytometry quantification showed that bacteria treated with LSPR-stimulated AgNPs displayed 4.8 times more ROS. This significant increase in ROS possibly accounts for most of the antimicrobial effect of the AgNPs. In addition, light exposition caused a small release of silver ions (0.4%) suggesting that silver ions may play a secondary role in P. aeruginosa death. Overall, the results presented here show that LSPR stimulation of AgNPs by visible light enhances the antimicrobial activity of silver nanoparticles and can be an alternative for the treatment of topic infections caused by antibiotic-resistant bacteria such as P. aeruginosa.

Multifunctional nanostructured Co-doped ZnO: Co spatial distribution and correlated magnetic properties.

In this report we present a systematic structural and magnetic analysis of Co-doped ZnO nanoparticles prepared via a microwave-assisted hydrothermal route. The structural data confirm the incorporation of Co ions into the wurtzite ZnO lattice and a Co concentration mainly near/at the surface of the nanoparticles. This Co spatial distribution is set to passivate the surface of the ZnO nanoparticles, inhibiting the nanoparticle growth and suppressing the observation of a ferromagnetic phase. Based on experimental and theoretical results we propose a kinetic-thermodynamic model for the processes of nucleation and growth of the Co-doped ZnO nanoparticles, and attribute the observed ferromagnetic order to a ferromagnetism associated with specific defects and adsorbed elements at the surface of the nanoparticle. Our findings give valuable contribution to the understanding of both the doping process at the nanoscale and the nature of the magnetic properties of the Co-doped ZnO system.