An Autocatalytic System of Photooxidation‐Driven Substitution Reactions on a FeII4L6 Cage Framework

The functions of life are accomplished by systems exhibiting nonlinear kinetics: autocatalysis, in particular, is integral to the signal amplification that allows for biological information processing. Novel synthetic autocatalytic systems provide a foundation for the design of artificial chemical networks capable of carrying out complex functions. Here we report a set of Fe^II₄L₆ cages containing BODIPY chromophores having tuneable photosensitizing properties. Electron‐rich anilines were observed to displace electron‐deficient anilines at the dynamic‐covalent imine bonds of these cages. When iodoaniline residues were incorporated, heavy‐atom effects led to enhanced ¹O₂ production. The incorporation of (methylthio)aniline residues into a cage allowed for the design of an autocatalytic system: oxidation of the methylthio groups into sulfoxides make them electron‐deficient and allows their displacement by iodoanilines, generating a better photocatalyst and accelerating the reaction.     

A review on immobilised aptamers for high throughput biomolecular detection and screening

The discovery of Systematic Evolution of Ligands by Exponential Enrichment (SELEX) assay has led to the generation of aptamers from libraries of nucleic acids. Concomitantly, aptamer-target recognition and its potential biomedical applications have become a major research endeavour. Aptamers possess unique properties that make them superior biological receptors to antibodies with a plethora of target molecules. Some specific areas of opportunities explored for aptamer-target interactions include biochemical analysis, cell signalling and targeting, biomolecular purification processes, pathogen detection and, clinical diagnosis and therapy. Most of these potential applications rely on the effective immobilisation of aptamers on support systems to probe target species. Hence, recent research focus is geared towards immobilising aptamers as oligosorbents for biodetection and bioscreening. This article seeks to review advances in immobilised aptameric binding with associated successful milestones and respective limitations. A proposal for high throughput bioscreening using continuous polymeric adsorbents is also presented.     

Propane σ‐Complexes on PdO(101): Spectroscopic Evidence of the Selective Coordination and Activation of Primary C?H Bonds

Achieving selective C H bond cleavage is critical for developing catalytic processes that transform small alkanes to value‐added products. The present study clarifies the molecular‐level origin for an exceptionally strong preference for propane to dissociate on the crystalline PdO(101) surface via primary C H bond cleavage. Using reflection absorption infrared spectroscopy (RAIRS) and density functional theory (DFT) calculations, we show that adsorbed propane σ‐complexes preferentially adopt geometries on PdO(101) in which only primary C H bonds datively interact with the surface Pd atoms at low propane coverages and are thus activated under typical catalytic reaction conditions. We show that a propane molecule achieves maximum stability on PdO(101) by adopting a bidentate geometry in which a H Pd dative bond forms at each CH₃ group. These results demonstrate that structural registry between the molecule and surface can strongly influence the selectivity of a metal oxide surface in activating alkane C H bonds.     

Simulating periodic trends in the structure and catalytic activity of coinage metal nanoribbons

We present a systematic density functional theory (DFT) study of the structure and catalytic activity of group 10 (Ni, Pd, Pt) and group 11 (Cu, Ag, Au) coinage metal nanoribbons. These infinite, periodic, quasi‐one‐dimensional structures are conceptually important as intermediates between small metal clusters and close‐packed metal surfaces, and have been shown experimentally to be practical catalysts. We find that nanoribbons have significantly higher predicted H₂ dissociation activity than close‐packed metal surfaces consistent with their lower coordination numbers. Computed periodic trends are reasonable, with late transition states and low barriers for H₂ dissociation over late group 10 nanoribbons, suggesting their promise as practical catalysts. These trends are consistent with the isolated nanoribbons' computed molecular electrostatic potentials. Calculations also predict nearly linear Brønsted–Evans–Polanyi relationships between the nanoribbons' H₂ dissociation energies and dissociation barriers. We also test new meta‐generalized gradient approximation (GGA) and hybrid DFT approximations for H₂ dissociation over these nanoribbons. These new functionals increase the (generally underestimated) dissociation barriers predicted by standard GGAs, motivating their continued application in surface chemistry. © 2015 Wiley Periodicals, Inc.     

Survey of UV Emissions from Sunbeds in the UK

Increased use of indoor tanning for cosmetic purposes has led to concerns for its impact on the risk of cutaneous cancers. The effects on UVR on skin depend on radiant dose, i.e. combination of irradiance and exposure duration. While a number of studies surveyed accessible emission from sunbeds, majority did not include the information on doses received during tanning sessions. Spectral irradiance of 195 sunbeds in five areas of the United Kingdom was measured in order to assess the radiant doses for comparison with the SED. Erythema weighted irradiance of more than 85% of all tested solaria exceeded 0.3 W m^?2, consistent with the findings of other studies. However, evaluation of radiant doses showed no evidence of increasing exposure per session in the United Kingdom in the last decade despite the increasing sunbed emission levels. Use of sunbeds for cosmetic purposes should be discouraged, with effective enforcement of the ban on under‐18 use, strict control on tanning duration and promotion of information on health risks of sunbed use. Such an integrated approach on safe equipment, safe use, and information should reduce the risk of detrimental impact of sunbed use on public health.     

International Intercomparison of Solar UVR Spectral Measurement Systems in Melbourne in 2013

Monitoring ambient solar UVR levels provides information on how much there is in both real time and historically. Quality assurance of ambient measurements of solar UVR is critical to ensuring accuracy and stability and this can be achieved by regular intercomparisons of spectral measurement systems with those of other organizations. In October and November of 2013 a solar UVR spectroradiometer from Public Health England (PHE) was brought to Melbourne for a campaign of intercomparisons with a new Bentham spectrometer of Australian Radiation Protection and Nuclear Safety Agency (ARPANSA) and one at the Australian Bureau of Meteorology (BOM), supported by New Zealand's National Institute for Water and Atmosphere (NIWA). Given all three spectroradiometers have calibrations that are traceable to various national standards, the intercomparison provides a chance to determine measurement uncertainties and traceability that support UV measurement networks in Australia, New Zealand and the UK. UV Index measurements from all three systems were compared and ratios determined for clear sky conditions when the scans from each instrument were within 2 min of each other. While wavelengths below 305 nm showed substantial differences between the PHE unit and the two other systems, overall the intercomparison results were encouraging, with mean differences in measured UV Index between the BOM/NIWA and those of PHE and ARPANSA of <0.1% and 7.5%, respectively.