Cooperative catalysis by silica-supported organic functional groups

Hybrid inorganic–organic materials comprising organic functional groups tethered from silica surfaces are versatile, heterogeneous catalysts. Recent advances have led to the preparation of silica materials containing multiple, different functional groups that can show cooperative catalysis; that is, these functional groups can act together to provide catalytic activity and selectivity superior to what can be obtained from either monofunctional materials or homogeneous catalysts. This tutorial review discusses cooperative catalysis of silica-based catalytic materials, focusing on the cooperative action of acid–base, acid–thiol, amine–urea, and imidazole–alcohol–carboxylate groups. Particular attention is given to the effect of the spatial arrangement of these organic groups and recent developments in the spatial organization of multiple groups on the silica surface

The rational development of molecularly imprinted polymer-based sensors for protein detection.

The detection of specific proteins as biomarkers of disease, health status, environmental monitoring, food quality, control of fermenters and civil defence purposes means that biosensors for these targets will become increasingly more important. Among the technologies used for building specific recognition properties, molecularly imprinted polymers (MIPs) are attracting much attention. In this critical review we describe many methods used for imprinting recognition for protein targets in polymers and their incorporation with a number of transducer platforms with the aim of identifying the most promising approaches for the preparation of MIP-based protein sensors (277 references)

High-Resolution Contact Printing with Chemically Patterned Flat Stamps Fabricated by Nanoimprint Lithography

Chemically patterned flat stamps provide an effective solution to avoid mechanical stamp-stability problems currently encountered in microcontact printing. A new method is developed to fabricate chemical patterns on a flat PDMS stamp using nanoimprint lithography. Sub-100 nm gold patterns are successfully replicated by these chemically patterned flat PDMS stamps. \ud \u

Fabrication of hydrophobic inorganic coatings on natural lotus leaves for nanoimprint stamps

Hydrophobic inorganic films were obtained by direct deposition of copper or silicon onto natural lotus leaves by ion beam sputtering deposition technique. Scanning electron microscopy observations showed a lotus-leaf-like surface structure of the deposited inorganic films. Hydrophobic nature of the inorganic films on lotus leaves had been improved compared to the inorganic films deposited on flat silicon substrates. Water contact angles measured on the lotus-leaf-like copper and silicon films were 136.3 \pm 8{\deg} and 117.8 \pm 4.4{\deg}, respectively. The hydrophobic lotus-leaf-like inorganic films had been repeated used as nanoimprint stamps. Negative structures of lotus-leaf-like inorganic films were obtained on the polystyrene resist layers.Comment: 14 pages, 6 figure

Unraveling deformation mechanisms around FCC and BCC nanocontacts through slip trace and pileup topography analyses

Nanocontact loadings offer the potential to investigate crystal plasticity from surface slip trace emissions and distinct pileup patterns where individual atomic terraces arrange into hillocks and symmetric rosettes. Our MD simulations in FCC Cu and Al nanocontacts show development of specific dislocation interception, cross-slip and twin annihilation mechanisms producing traces along characteristic and directions. Although planar slip is stabilized through subsurface dislocation interactions, highly serrated slip traces always predominate in Al due to the advent of cross-slip of the surfaced population of screw dislocations, leading to intricate hillock morphologies. We show that the distinct wavy hillocks and terraces in BCC Ta and Fe nanocontacts are due to dislocation double-kinking and outward spreading of surfaced screw segments, which originate from dislocation loops induced by twin annihilation and twin-mediated nucleation processes in the subsurface. Increasing temperature favors terrace formation in BCCs whereas the enhancement of surface decorations in FCCs limits hillock definition. It is found that material bulging against the indenter-tip is a distinctive feature in nanocontact plasticity associated with intermittent defect bursts. Bulging is enhanced by recurrent slip traces introduced throughout the contact surface, as in the case of the strongly linear defect networks in FCC Al, and by specific twin arrangements at the vicinity of BCC nanocontacts. Defect patterning also produces surface depressions in the form of vertexes around FCC nanoimprints. While the rosette morphologies are consistent with those assessed experimentally in greater FCC and BCC imprints, local bulging promoted during tip removal becomes more prominent at the nanoscale.Peer ReviewedPostprint (author's final draft