Impact of co-adsorbed oxygen on crotonaldehyde adsorption over gold nanoclusters:a computational study

Crotonaldehyde (2-butenal) adsorption over gold sub-nanometer particles, and the influence of co-adsorbed oxygen, has been systematically investigated by computational methods. Using density functional theory, the adsorption energetics of crotonaldehyde on bare and oxidised gold clusters (Au , d = 0.8 nm) were determined as a function of oxygen coverage and coordination geometry. At low oxygen coverage, sites are available for which crotonaldehyde adsorption is enhanced relative to bare Au clusters by 10 kJ mol. At higher oxygen coverage, crotonaldehyde is forced to adsorb in close proximity to oxygen weakening adsorption by up to 60 kJ mol relative to bare Au. Bonding geometries, density of states plots and Bader analysis, are used to elucidate crotonaldehyde bonding to gold nanoparticles in terms of partial electron transfer from Au to crotonaldehyde, and note that donation to gold from crotonaldehyde also becomes significant following metal oxidation. At high oxygen coverage we find that all molecular adsorption sites have a neighbouring, destabilising, oxygen adatom so that despite enhanced donation, crotonaldehyde adsorption is always weakened by steric interactions. For a larger cluster (Au, d = 1.1 nm) crotonaldehyde adsorption is destabilized in this way even at a low oxygen coverage. These findings provide a quantitative framework to underpin the experimentally observed influence of oxygen on the selective oxidation of crotyl alcohol to crotonaldehyde over gold and gold-palladium alloys. © 2014 the Partner Organisations.

Microwave properties of an inhomogeneous optically illuminated plasma in a microstrip gap

The optical illumination of a microstrip gap on a thick semiconductor substrate creates an inhomogeneous electron-hole plasma in the gap region. This allows the study of the propagation mechanism through the plasma region. This paper uses a multilayer plasma model to explain the origin of high losses in such structures. Measured results are shown up to 50 GHz and show good agreement with the simulated multilayer model. The model also allows the estimation of certain key parameters of the plasma, such as carrier density and diffusion length, which are difficult to measure by direct means. The detailed model validation performed here will enable the design of more complex microwave structures based on this architecture. While this paper focuses on monocrystalline silicon as the substrate, the model is easily adaptable to other semiconductor materials such as GaAs.

Application of long-period-grating sensors to respiratory plethysmography

A series of in-line curvature sensors on a garment are used to monitor the thoracic and abdominal movements of a human during respiration. These results are used to obtain volumetric tidal changes of the human torso in agreement with a spirometer used simultaneously at the mouth. The curvature sensors are based on long-period gratings (LPGs) written in a progressive three-layered fiber to render the LPGs insensitive to the refractive index external to the fiber. A curvature sensor consists of the fiber long-period grating laid on a carbon fiber ribbon, which is then encapsulated in a low-temperature curing silicone rubber. The sensors have a spectral sensitivity to curvature, dλ/dR from ∼7-nm m to ∼9-nm m. The interrogation technique is borrowed from derivative spectroscopy and monitors the changes in the transmission spectral profile of the LPG's attenuation band due to curvature. The multiplexing of the sensors is achieved by spectrally matching a series of distributed feedback (DFB) lasers to the LPGs. The versatility of this sensing garment is confirmed by it being used on six other human subjects covering a wide range of body mass indices. Just six fully functional sensors are required to obtain a volumetric error of around 6%. © 2007 Society of Photo-Optical Instrumentation Engineers.

CO adsorption over Pd nanoparticles:a general framework for IR simulations on nanoparticles

CO vibrational spectra over catalytic nanoparticles under high coverages/pressures are discussed from a DFT perspective. Hybrid B3LYP and PBE DFT calculations of CO chemisorbed over Pd4 and Pd13 nanoclusters, and a 1.1 nm Pd38 nanoparticle, have been performed in order to simulate the corresponding coverage dependent infrared (IR) absorption spectra, and hence provide a quantitative foundation for the interpretation of experimental IR spectra of CO over Pd nanocatalysts. B3LYP simulated IR intensities are used to quantify site occupation numbers through comparison with experimental DRIFTS spectra, allowing an atomistic model of CO surface coverage to be created. DFT adsorption energetics for low CO coverage (θ → 0) suggest the CO binding strength follows the order hollow > bridge > linear, even for dispersion-corrected functionals for sub-nanometre Pd nanoclusters. For a Pd38 nanoparticle, hollow and bridge-bound are energetically similar (hollow ≈ bridge > atop). It is well known that this ordering has not been found at the high coverages used experimentally, wherein atop CO has a much higher population than observed over Pd(111), confirmed by our DRIFTS spectra for Pd nanoparticles supported on a KIT-6 silica, and hence site populations were calculated through a comparison of DFT and spectroscopic data. At high CO coverage (θ = 1), all three adsorbed CO species co-exist on Pd38, and their interdiffusion is thermally feasible at STP. Under such high surface coverages, DFT predicts that bridge-bound CO chains are thermodynamically stable and isoenergetic to an entirely hollow bound Pd/CO system. The Pd38 nanoparticle undergoes a linear (3.5%), isotropic expansion with increasing CO coverage, accompanied by 63 and 30 cm− 1 blue-shifts of hollow and linear bound CO respectively.

EDC-mediated oligonucleotide immobilization on a long period grating optical biosensor

We present the development and simplification of label-free fiber optic biosensors based on immobilization of oligonucleotides on dual-peak long period gratings (dLPGs). This improvement is the result of a simplification of biofunctionalization methodology. A one-step 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC)-mediated reaction has been developed for the straightforward immobilization of unmodified oligonucleotides on the glass fiber surface along the grating region, leading to covalent attachment of a 5´-phosphorylated probe oligonucleotide to the amino-derivatized fiber grating surface. Immobilization is achieved via a 5´phosphate-specific linkage, leaving the remainder of the oligonucleotide accessible for binding reactions. The dLPG has been tested in different external media to demonstrate its inherent ultrahigh sensitivity to the surrounding-medium refractive index (RI) achieving 50- fold improvement in RI sensitivity over the previously-published LPG sensor in media with RI’s relevant to biological assays. After functionalization, the dLPG biosensor was used to monitor the hybridization of complementary oligonucleotides showing a detectable oligonucleotide concentration of 4 nM. The proposed one-step EDC reaction approach can be further extended to develop fiber optic biosensors for disease analysis and medical diagnosis with the advances of label-free, real-time, multiplex, high sensitivity and specificity.