Monitoring pattern formation in drying and wetting dispersions of gold nanoparticles by ESEM

We report an investigation of the self-assembly of patterns from functionalized gold nanoparticles (GNPs) by monitoring the process in situ by environmental scanning electron microscopy (ESEM) during both evaporation and condensation of the dispersant. As this method limits the choice of dispersants to water, GNPs functionalized with hydrophilic thiol ligands, containing poly(ethylene)glycol (PEG) groups, were used on a variety of substrates including pre-patterned ones. Particular emphasis was given to early stage deposition of GNPs, as well as redispersion and lift-off upon condensation of water droplets. ESEM presents a unique opportunity of directly imaging such events in situ. It was found that attractive interactions between the substrate and the GNPs are often stronger than expected once the particles have been deposited. The role of nickel perchlorate as a highly water-soluble additive was studied. It was found that entropically driven deposition of particles and decoration of surface features was enhanced in its presence, as expected.</p

Catalytic Enantioselective Synthesis of Tetrahydocarbazoles and Exocyclic Pictet-Spengler-Type Reactions

A synthetic strategy for the synthesis of chiral tetrahydrocarbazoles (THCAs) has been developed. The strategy relies on two types of 6-<i>exo-trig</i> cyclization of 3-substituted indole substrates. Enantioselective domino Friedel–Crafts-type reactions leading to THCAs can be catalyzed by chiral phosphoric acid derivatives (with up to >99% ee), and the first examples of exocyclic Pictet–Spengler reactions to form THCAs are reported

Turnover Rate of Metal-Catalyzed Hydroconversion of 2,5-Dimethylfuran: Gas-Phase Versus Liquid-Phase

Hydroconversion (hydrogenation and hydrogenolysis) of biomass-derived furanic compounds giving furan ring-hydrogenation and ring-cleavage products attracts interest for sustainable production of chemicals and fuels. Here, the hydroconversion of 2,5-dimethylfuran (DMF), chosen as a model furanic compound, was investigated at a gas-solid interface over carbon-supported Pt, Pd, Rh and Ru metal catalysts in a fixed-bed reactor at 70&ndash;90 &deg;C and ambient pressure. Pt/C was mainly active in ring cleavage of DMF to produce 2-hexanone as the primary product, followed by its hydrogenation to 2-hexanol and hexane. In contrast, Pd/C, Rh/C and Ru/C selectively hydrogenated the furan ring to 2,5-dimethyltetrahydrofuran (DMTHF). The turnover frequency (TOF) of metal sites in the gas-phase DMF hydroconversion was determined from zero-order kinetics in the absence of diffusion limitations. The TOF values decreased in the sequence Pt &gt; Rh &gt; Pd &gt;&gt; Ru, similar to the liquid-phase reaction. The TOF values for the gas-phase reaction were found to be one order of magnitude greater than those for the liquid-phase reaction. This indicates that the gas-phase process is potentially more efficient than the liquid-phase process. TOF values for hydroconversion of ring-saturated furan derivatives, tetrahydrofuran and DMTHF, on Pt/C, were much lower than those for DMF

Local sensing of absolute refractive index during protein-binding using microlasers with spectral encoding

Funding: Engineering and Physical Sciences Research Council - EP/P030017/1; Alexander von Humboldt-Stiftung; European Research Council - 640012; Royal Society - DH160102.Multiplexed, specific, and sensitive detection of antigens is critical for the rapid and accurate diagnosis of disease and the informed development of personalized treatment plans. Here, it is shown that polymer microsphere lasers can be used as photonic sensors to monitor and quantify direct surface binding of biomolecules via changes in the refractive index. The unique spectral signature of each individual laser can be used to find their size and effective refractive index which adds a new encoding dimension when compared to conventional fluorescent beads. Antibody-functionalized microlasers selectively detect protein binding, as demonstrated for Immunoglobulin G and C-reactive protein, and have the ability to resolve different stages of the multilayer surface modification. Moreover, by continuously monitoring single lasers, the possibility of real-time monitoring of binding dynamics between antigens in solution phase and the immobilized antibodies is demonstrated. For multiplexed detection, the microlasers are employed in a flow cytometer configuration, with fast spectral detection and identification of microlasers with and without antigen binding. It is envisioned that by combining microlasers with well-established surface modification chemistries and flow geometries, the multiplexing ability of microbead immunoassays can be strongly increased while also opening avenues for single-cell profiling within heterogeneous cell populations.Publisher PDFPeer reviewe