Atomic-scale assembly of a heterogeneous catalytic site

The distance between surface Pd atoms has been shown to control the catalytic formation of vinyl acetate from ethylene and acetic acid by AuPd catalysts. Here, we use the bulk alloy's thermodynamic properties, as well as the surface lattice spacing of a AuPd(100) alloy single-crystal model catalyst to control and optimize the concentration of the active site (Pd atom pairs at a specific Pd-Pd distance with Au nearest-neighbors). Scanning tunneling microscopy reveals that sample annealing has a direct effect on the surface Pd arrangements: short-range order preferentially forms Pd pairs located in the c(2 x 2) sites, which are known to be optimal for vinyl acetate synthesis. This effect could be harnessed for future industrial catalyst design.     

Promising compact wavelength-tunable optical add-drop multiplexer in dense wavelength-division multiplexing systems

We design and model a highly compact and tunable optical add-drop multiplexer (OADM) device that consists of long-period gratings and piezoelectric ceramic fiber stretchers. The proposed OADM shows that 50 dense wavelength-division multiplexing channel signals can be selected in the wavelength range from 1526.25 to 1563.75 nm with 0.75-nm channel spacing, which covers the whole C-band gain spectrum of an erbium-doped fiber amplifier. The cross talk between channels is less than -39 dB, and the total insertion loss of the device is approximately 0.24 dB, which includes the splicing losses, the mode mismatching loss, and the expected losses in the two side-by-side coupled fibers.     

Effect of blend ratio and nanofiller localization on the thermal degradation of graphite nanoplatelets-modified PLA/PCL

A variety of poly(lactic acid) (PLA)-poly(ε-caprolactone) (PCL) samples with different PLA:PCL ratios, containing different contents of graphite nanoplatelets (GrP), were analysed in a thermogravimetric analyser (TG) under, respectively, nitrogen and oxygen atmospheres, and in a differential scanning calorimeter (DSC) in a nitrogen atmosphere. Their respective morphologies were determined through scanning electron microscopy. The TG analyses in nitrogen gave fairly predictable results, but the analyses in oxygen gave complex results that seemed to be dependent on the respective morphologies of the blend samples and on the presence and amount of GrP in the respective samples. It was observed that, depending on the blend or nanocomposite morphologies, the GrP could have played the role of catalysing the degradation process, or inhibiting the onset of degradation by immobilizing the polymer or free radical chains and by delaying the evolution of the degradation products from the respective samples. The DSC results clearly showed the influence of the respective components in the blends and composites on the crystallization behaviour and crystallinities of the two polymers.

     

Inhibition of human neutrophil elastase activity by encapsulated serum (serumsome™) therapy

In order to inhibit human leukocyte proteolytic activity as a means of arresting the inflammatory response in tissues in vivo, we have designed a novel antiprotease carrier named serumsomes^™. Stabilized human serum was added to a flask containing a film of dried, purified lipids (phosphatidylcholine/dicetyl phosphate/cholesterol, 70∶20∶10) and hand-shaken for 10 min. Equal volumes of human neutrophils, and either serumsomes^™ (in stabilized human serum) or stabilized human serum alone were mixed together. Following 2 h of incubation at 37°C, the total elastase content of the neutrophils was reduced to 60±15% and 83±7% of the original activity by serumsomes^™ and stabilized human serum, respectively. Analysis of β-glucuronidase activity, a nonproteolytic lysosomal marker enzyme, revealed no diminution of activity during either of these incubations. These experiments demonstrate that human neutrophils are capable of interacting with serumsomes^™ in vitro, selectively inhibiting the lysosomal protease elastase. By administering serumsomes^™ in vivo, one may potentially preload blood leukocytes with serum antiproteases prior to their migration to inflammatory sites and thus possibly reduce the extent of tissue injury.     

Highly selective chromium-based ethylene trimerisation catalysts with bulky diphosphinoamine ligands

In situ prepared chromium catalysts containing bulky diphosphinoamine (PNP) ligands, upon activation with MAO, are extremely efficient catalysts for the trimerisation of ethylene to 1-hexene.     

In-situ photoelectron spectroscopy with online activity measurement for catalysis research

We report Ambient pressure X-ray Photoelectron Spectroscopy Endstation with an integrated chemical analytical system that consists of a residual gas analyzer in the 2nd differential pumping stage and a new low-reactive sample holder heating assembly. This system has a linear response to the reaction chamber gas pressure. The sample heating assembly also has a low dark reaction rate up to 400 °C for H₂ and CO oxidation. We expect this chemical analytical system will expand our capabilities in conducting in-operando catalysis research.     

CO oxidation on nanostructured SnO(x)/Pt(111) surfaces: unique properties of reduced SnO(x)

We have investigated surface CO oxidation on "inverse catalysts" composed of SnO(x) nanostructures supported on Pt(111) using X-ray photoelectron spectroscopy (XPS), low-energy ion scattering spectroscopy (LEISS) and temperature-programmed desorption (TPD). Nanostructures of SnO(x) were prepared by depositing Sn on Pt(111) pre-covered by NO(2) layers at low temperatures. XPS data show that the SnO(x) nanoparticles are highly reduced with Sn(II)O being the dominant oxide species, but the relative concentration of Sn(II) in the SnO(x) nanoparticles decreases with increasing Sn coverage. We find that the most active SnO(x)/Pt(111) surface for CO oxidation has smallest SnO(x) coverage. Increasing the surface coverage of SnO(x) reduces CO oxidation activity and eventually suppresses it altogether. The study suggests that reduced Sn(II)O, rather than Sn(IV)O(2), is responsible for surface CO oxidation. The occurrence of a non-CO oxidation reaction path involving reduced Sn(II)O species at higher SnO(x) coverages accounts for the decreased CO oxidation activity. From these results, we conclude that the efficacy of CO oxidation is strongly dependent on the availability of reduced tin oxide sites at the Pt-SnO(x) interface, as well as unique chemical properties of the SnO(x) nanoparticles.     

Selective functionalisation of PDMS-based photonic lab on a chip for biosensing

A comparative study of different approaches for the selective immobilisation of biomolecules on the surface of poly(dimethylsiloxane) (PDMS) is reported. The motivation of this work is to set a robust and reliable protocol for the easy implementation of a biosensor device in a PDMS-based photonic lab-on-a-chip (PhLoC). A hollow prism configuration, previously reported for the colorimetric detection of analytes was chosen for this study. Here, the inner walls of the hollow prism were initially modified by direct adsorption of either polyethylene glycol (PEG) or polyvinyl alcohol (PVA) linear polymers as well as by carrying out a light chemical oxidation step. All these processes introduced hydroxyl groups on the PDMS surface to a different extent. The hydroxyl groups were further silanised using a silane containing an aldehyde end-group. The interaction between this group and a primary amine moiety enabled the selective covalent attachment of a biomolecule on the PDMS surface. A thorough structural characterisation of the resulting modified-PDMS substrates was carried out by contact angle measurements, X-ray photoelectron spectroscopic (XPS) analysis and atomic force microscopy (AFM) imaging. Using horseradish peroxidase as a model recognition element, different biosensor approaches based on each modification process were developed for the detection of hydrogen peroxide target analyte in a concentration range from 0.1 μM to 100 μM. The analytical performance was similar in all cases, a linear concentration range between 0.1 μM and 24.2 μM, a sensitivity of 0.02 a.u. μM(-1) and a limit of detection around 0.1 μM were achieved. However, important differences were observed in the reproducibility of the devices as well as in their operational stability, which was studied over a period of up to two months. Considering all these studies, the PVA-modified approach appeared to be the most suitable one for the simple fabrication of a biosensor device integrated in a PDMS PhLoC.     

The evaluation of 1-tetralone and 4-chromanone derivatives as inhibitors of monoamine oxidase

Molecular Diversity - Monoamine oxidase (MAO) is of much clinical relevance, and inhibitors of this enzyme are used in the treatment for neuropsychiatric and neurodegenerative disorders such as...