High stability multiplexed fiber interferometer and its application on absolute displacement measurement and on-line surface metrology

We propose a self-reference multiplexed fibre interferometer (MFI) by using a tunable laser and fibre Bragg grating (FBG). The optical measurement system multiplexes two Michelson fibre interferometers with shared optical path in the main part of optical system. One fibre optic interferometer is used as a reference interferometer to monitor and control the high accuracy of the measurement system under environmental perturbations. The other is used as a measurement interferometer to obtain information from the target. An active phase tracking homodyne (APTH) technique is applied for signal processing to achieve high resolution. MFI can be utilised for high precision absolute displacement measurement with different combination of wavelengths from the tuneable laser. By means of Wavelength-Division-Multiplexing (WDM) technique, MFI is also capable of realising on-line surface measurement, in which traditional stylus scanning is replaced by spatial light-wave scanning so as to greatly improve the measurement speed and robustness.

In situ X-ray studies of crotyl alcohol selective oxidation over Au/Pd(1 1 1) surface alloys

The selective oxidation of crotyl alcohol to crotonaldehyde over ultrathin Au overlayers on Pd(1 1 1) and Au/Pd(1 1 1) surface alloys has been investigated by time-resolved X-ray photoelectron spectroscopy (XPS) and mass spectrometry. Pure gold is catalytically inert towards crotyl alcohol which undergoes reversible adsorption. In contrast, thermal processing of a 3.9 monolayer (ML) gold overlayer allows access to a range of AuPd surface alloy compositions, which are extremely selective towards crotonaldehyde production, and greatly reduce the extent of hydrocarbon decomposition and eventual carbon laydown compared with base Pd(1 1 1). XPS and CO titrations suggest that palladium-rich surface alloys offer the optimal balance between alcohol oxidative dehydrogenation activity while minimising competitive decomposition pathways, and that Pd monomers are not the active surface ensemble for such selox chemistry over AuPd alloys. Crown Copyright © 2008.

Alkali- and nitrate-free synthesis of highly active Mg-Al hydrotalcite-coated alumina for FAME production

Mg-Al hydrotalcite coatings have been grown on alumina via a novel alkali- and nitrate-free impregnation route and subsequent calcination and hydrothermal treatment. The resulting Mg-HT/AlO catalysts significantly outperform conventional bulk hydrotalcites prepared via co-precipitation in the transesterification of C-C triglycerides for fatty acid methyl ester (FAME) production, with rate enhancements increasing with alkyl chain length. This promotion is attributed to improved accessibility of bulky triglycerides to active surface base sites over the higher area alumina support compared to conventional hydrotalcites wherein many active sites are confined within the micropores. © 2014 The Royal Society of Chemistry.

Nanoengineering the active site in heterogeneous catalysis

Here we demonstrate the first application of time-resolved synchrotron X-ray absorption spectroscopy to simultaneously follow dynamic nanoparticle surface restructuring and the evolution of surface and gas-phase products during an organic reaction. Surface palladium oxide, and not metal, is identified as the catalytic species responsible for the selective oxidation (selox) of crotyl alcohol to crotonaldehyde. Elevated reaction temperatures facilitate reversible nanoparticle redox processes, and concomitant catalytic selectivity loss, in response to reaction conditions. These discoveries highlight the importance of stabilizing surface palladium oxide and minimizing catalyst reducibility in order to achieve high selox yields, and will aid the future design of Pd-derived selox catalysts. This discovery has important implications for the design of future liquid and vapor phase selox catalysts, and the thermochemical behavior of Pd nanostructures in general.

Surface catalysed Suzuki-Miyaura cross-coupling by Pd nanoparticles:an operando XAS study

Size-controlled, catalytically active PVP-stabilised Pd nanoparticles have been studied by operando liquid phase XAS during the Suzuki cross-coupling of iodonanisole and phenylboronic acid in MeOH-toluene using KOMe base. XAS reveals nanoparticles are stable to metal leaching throughout the reaction, with surface density Pd defect sites directly implicated in the catalytic cycle. The efficacy of popular selective chemical and structural poisons for distinguishing heterogeneous and homogeneous contributions in Pd catalysed cross-couplings is also explored. © 2010 The Royal Society of Chemistry.

On the active site in heterogeneous palladium selox catalysts

The nature of the active site in the Pd-catalysed aerobic selective oxidation of cinnamyl and crotyl alcohols has been directly probed by bulk and surface X-ray techniques. The importance of high metal dispersions and the crucial role of surface palladium oxide have been identified. © The Royal Society of Chemistry 2006.

High stability multiplexed fibre interferometer and its application on absolute displacement measurement and on-line surface metrology

We propose a self-reference multiplexed fibre interferometer (MFI) by using a tunable laser and fibre Bragg grating (FBG). The optical measurement system multiplexes two Michelson fibre interferometers with shared optical path in the main part of optical system. One fibre optic interferometer is used as a reference interferometer to monitor and control the high accuracy of the measurement system under environmental perturbations. The other is used as a measurement interferometer to obtain information from the target. An active phase tracking homodyne (APTH) technique is applied for signal processing to achieve high resolution. MFI can be utilised for high precision absolute displacement measurement with different combination of wavelengths from the tuneable laser. By means of Wavelength-Division-Multiplexing (WDM) technique, MFI is also capable of realising on-line surface measurement, in which traditional stylus scanning is replaced by spatial light-wave scanning so as to greatly improve the measurement speed and robustness. © 2004 Optical Society of America.

InP-based active and passive components for communication systems at 2 μm

Progress on advanced active and passive photonic components that are required for high-speed optical communications over hollow-core photonic bandgap fiber at wavelengths around 2 μm is described in this paper. Single-frequency lasers capable of operating at 10 Gb/s and covering a wide spectral range are realized. A comparison is made between waveguide and surface normal photodiodes with the latter showing good sensitivity up to 15 Gb/s. Passive waveguides, 90° optical hybrids, and arrayed waveguide grating with 100-GHz channel spacing are demonstrated on a large spot-size waveguide platform. Finally, a strong electro-optic effect using the quantum confined Stark effect in strain-balanced multiple quantum wells is demonstrated and used in a Mach-Zehnder modulator capable of operating at 10 Gb/s.

Identification of the degradation mechanisms of organic solar cells:active layer and interfacial layers

Organic Solar Cells (OSCs) represent a photovoltaic technology with multiple interesting application properties. However, the establishment of this technology into the market is subject to the achievement of operational lifetimes appropriate to their application purposes. Thus, comprehensive understanding of the degradation mechanisms occurring in OSCs is mandatory in both selecting more intrinsically stable components and/or device architectures and implementing strategies that mitigate the encountered stability issues. Inverted devices can suffer from mechanical stress and delamination at the interface between the active layer, e.g. poly(3-hexylthiophene):[6,6]-phenyl-C61-butyric acid methyl ester (P3HT:PCBM), and the hole transport layer, e.g. poly(3,4-ethylenedioxythiophene):poly(p-styrene sulfonate) (PEDOT:PSS). This work proposes the incorporation of a thin adhesive interlayer, consisting of a diblock copolymer composed of a P3HT block and a thermally-triggerable, alkyl-protected PSS block. In this context, the synthesis of poly(neopentyl p-styrene sulfonate) (PNSS) with controlled molar mass and low dispersity (Ð ≤ 1.50) via Reversible Addition-Fragmentation chain Transfer (RAFT) polymerisation has been extensively studied. Subsequently, Atomic Force Microscopy (AFM) was explored to characterise the thermal deprotection of P3HT-b-PNSS thin layers to yield amphiphilic P3HT-b-PSS, indicating that surface deprotection prior to thermal treatment could occur. Finally, structural variation of the alkyl protecting group in PSS allowed reducing the thermal treatment duration from 3 hours (P3HT-b-PNSS) to 45 minutes for the poly(isobutyl p-styrene sulfonate) (PiBSS) analogous copolymer. Another critical issue regarding the stability of OSCs is the sunlight-driven chemical degradation of the active layer. In the study herein, the combination of experimental techniques and theoretical calculations has allowed identification of the structural weaknesses of poly[(4,4’- bis(2-ethylhexyl) dithieno [3,2-b:2’,3’-d]silole)-2,6-diyl-alt-(4,7-bis(2-thienyl)-2,1,3-benzothiadiazole)-5,5’-diyl], Si-PCPDTBT, upon photochemical treatment in air. Additionally, the study of the relative photodegradation rates in air of a series of polymers with systematically modified backbones and/or alkyl side chains has shown no direct correlation between chemical structure and stability. It is proposed instead that photostability is highly dependent on the crystalline character of the deposited films. Furthermore, it was verified that photostability of blends based on these polymers is dictated by the (de)stabilising effect that [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) has over each polymer. Finally, a multiscale analysis on the degradation of solar cells based on poly[4,4' bis(2- ethylhexyl) dithieno[3,2-b:2',3'-d]silole)-2,6-diyl-alt-[2,5 bis(3 tetradecylthiophen 2-yl)thiazole[5,4-d]thiazole)-1,8-diyl] and PCBM, indicated that by judicious selection of device layers, architectures, and encapsulation materials, operational lifetimes up to 3.3 years with no efficiency losses can be successfully achieved.

Comparative study of dissolved organic matter from groundwater and surface water in the Florida coastal Everglades using multi-dimensional spectrofluorometry combined with multivariate statistics

Dissolved organic matter (DOM) in groundwater and surface water samples from the Florida coastal Everglades were studied using excitation–emission matrix fluorescence modeled through parallel factor analysis (EEM-PARAFAC). DOM in both surface and groundwater from the eastern Everglades S332 basin reflected a terrestrial-derived fingerprint through dominantly higher abundances of humic-like PARAFAC components. In contrast, surface water DOM from northeastern Florida Bay featured a microbial-derived DOM signature based on the higher abundance of microbial humic-like and protein-like components consistent with its marine source. Surprisingly, groundwater DOM from northeastern Florida Bay reflected a terrestrial-derived source except for samples from central Florida Bay well, which mirrored a combination of terrestrial and marine end-member origin. Furthermore, surface water and groundwater displayed effects of different degradation pathways such as photodegradation and biodegradation as exemplified by two PARAFAC components seemingly indicative of such degradation processes. Finally, Principal Component Analysis of the EEM-PARAFAC data was able to distinguish and classify most of the samples according to DOM origins and degradation processes experienced, except for a small overlap of S332 surface water and groundwater, implying rather active surface-to-ground water interaction in some sites particularly during the rainy season. This study highlights that EEM-PARAFAC could be used successfully to trace and differentiate DOM from diverse sources across both horizontal and vertical flow profiles, and as such could be a convenient and useful tool for the better understanding of hydrological interactions and carbon biogeochemical cycling.

Development of a surface-enhanced raman spectroscopy method for the detection of benzodiazepines in urine

Benzodiazepines are among the most prescribed compounds for anti-anxiety and are present in many toxicological screens. These drugs are also prominent in the commission of drug facilitated sexual assaults due their effects on the central nervous system. Due to their potency, a low dose of these compounds is often administered to victims; therefore, the target detection limit for these compounds in biological samples is 10 ng/mL. Currently these compounds are predominantly analyzed using immunoassay techniques; however more specific screening methods are needed. ^ The goal of this dissertation was to develop a rapid, specific screening technique for benzodiazepines in urine samples utilizing surface-enhanced Raman spectroscopy (SERS), which has previously been shown be capable of to detect trace quantities of pharmaceutical compounds in aqueous solutions. Surface enhanced Raman spectroscopy has the advantage of overcoming the low sensitivity and fluorescence effects seen with conventional Raman spectroscopy. The spectra are obtained by applying an analyte onto a SERS-active metal substrate such as colloidal metal particles. SERS signals can be further increased with the addition of aggregate solutions. These agents cause the nanoparticles to amass and form hot-spots which increase the signal intensity. ^ In this work, the colloidal particles are spherical gold nanoparticles in aqueous solution with an average size of approximately 30 nm. The optimum aggregating agent for the detection of benzodiazepines was determined to be 16.7 mM MgCl2, providing the highest signal intensities at the lowest drug concentrations with limits of detection between 0.5 and 127 ng/mL. A supported liquid extraction technique was utilized as a rapid clean extraction for benzodiazepines from urine at a pH of 5.0, allowing for clean extraction with limits of detection between 6 and 640 ng/mL. It was shown that at this pH other drugs that are prevalent in urine samples can be removed providing the selective detection of the benzodiazepine of interest. ^ This technique has been shown to provide rapid (less than twenty minutes), sensitive, and specific detection of benzodiazepines at low concentrations in urine. It provides the forensic community with a sensitive and specific screening technique for the detection of benzodiazepines in drug facilitated assault cases.^

(Appendix B) Dinoflagellate cysts in Southeast Pacific Ocean surface sediments

orty-eight surface sediment samples from the southeast (SE) Pacific (25-53°S) are investigated for the determination of the spatial distribution of organic-walled dinoflagellate cysts along the western South American continental margin. Fifty-five different taxa are recorded and reflect oceanic or coastal assemblages. The oceanic assemblages are characterised by low cyst concentrations and the dominance of autotrophs, while the coastal assemblages generally contain a higher number of cysts, which are mainly produced by heterotrophic species. Highest cyst concentrations are observed in the active upwelling system offshore Concepción (35-37°S). Brigantedinium spp., Echinidinium aculeatum, Echinidinium granulatum/delicatum and cysts of Protoperidinium americanum dominate assemblages related to upwelling. Echinidinium aculeatum appears to be the best indicator for the presence of all year round active upwelling cells. Other protoperidinioid cysts may also occur in high relative abundances in coastal regions outside active upwelling systems, if the availability of nutrients, co-responsible for the presence/absence of their main food sources such as diatoms and other protists, is sufficient. The importance of nutrient availability as a determining environmental variable influencing cyst signals on a regional scale (SE Pacific) is demonstrated through statistical analyses of the data. Because of the importance of nutrients, uncertainties about the outcomes of quantitative sea-surface temperature (SST) reconstructions (Modern Analogue Technique) based on dinoflagellate cysts may arise, since no interaction between different hydrographical variables is considered in this approach. The combination of the SE Pacific surface sample dataset with other published cyst data from the Southern Hemisphere resulted in a database which includes 350 samples: the 'SH350 database'. This database is used to test the accuracy of the quantitative reconstructions by calculating and comparing the estimated versus observed values for each site. An attempt to perform quantitative SST reconstructions on the last 25 cal ka of site ODP1233 (41°S; 74°27'W) is made and again stresses the importance of other environmental variables such as nutrient availability in determining the dinoflagellate cyst assemblages.

Surface characteristics and metazoa occurrence at ice station PS67/006-1 during POLARSTERN cruise ANT-XXII/2 (Nov 2004-Jan 2005)

The surface and sub-ice layer habitats and their metazoan fauna were studied on a drifting pack-ice floe in the western Weddell Sea from 29 November 2004 to 1 January 2005 during the "Ice Station POLarstern" (ISPOL). Flooding of the floe occurred at some places, and the establishment of surface layers with a brownish colour due to growing algae was observed at several sampling sites. The average surface-layer temperature, brine salinity and brine volume were -1.4 °C, 25.3 and 54%, respectively. The temperature-salinity relationship in the surface layer was seldom at equilibrium conditions. Chlorophyll a (Chl a) concentrations in the brine varied between 1.0 and 53.5 µg /L. Surface-layer thickness, salinity, Chl a concentration and copepod abundances were generally higher at the edge of the floe than in the inner part. The sympagic copepod species Drescheriella glacialis/racovitzai and Stephos longipes, with abundances ranging between 0 and 3830 ind/L (median: 2 ind/L) and 0 and 1293 ind/L (median: 4 ind/L), respectively, were the dominant members of the surface-layer meiofauna. Their populations consisted mainly of adults and early naupliar stages, which points to an active reproduction of these species within the surface layer. Other taxa found in the surface layer were undetermined turbellarians, the gastropod Tergipes antarcticus, and, for the first time, the ctenophore Callianira antarctica, and the amphipods Eusirus antarcticus and Eusirus tridentatus. During the course of our study, slight melting at the ice underside took place, releasing sympagic organisms to the water column. Chl a concentrations in the sub-ice water layer were very low (0.1-0.5 µg /L), except for 25 December when the Chl a concentration at 0 m depth increased to 2.3 µg /L. The most dominant sympagic copepod species found in the sub-ice layer was Ectinosoma sp., with abundances ranging between 1 and 599 ind/m**3 (median: 25 ind/m**3). Other sympagic copepod species occurring regularly in this habitat were D. glacialis/racovitzai, Diarthrodes cf. lilacinus, Idomene antarctica and S. longipes. All of these sympagic species were generally found in higher abundances at 0 m depth underneath the ice than at 5 m depth, in contrast to pelagic copepod species that occurred more frequently at 5 m depth. Niche separation and probable life-cycle strategies of dominant sympagic metazoans are discussed.

Are luminous radio-loud active galactic nuclei triggered by galaxy interactions?

We present the results of a comparison between the optical morphologies of a complete sample of 46 southern 2 Jy radio galaxies at intermediate redshifts (0.05 < z < 0.7) and those of two control samples of quiescent early-type galaxies: 55 ellipticals at redshifts z ≤ 0.01 from the Observations of Bright Ellipticals at Yale (OBEY) survey, and 107 early-type galaxies at redshifts 0.2 < z < 0.7 in the Extended Groth Strip (EGS). Based on these comparisons, we discuss the role of galaxy interactions in the triggering of powerful radio galaxies (PRGs). We find that a significant fraction of quiescent ellipticals at low and intermediate redshifts show evidence for disturbed morphologies at relatively high surface brightness levels, which are likely the result of past or on-going galaxy interactions. However, the morphological features detected in the galaxy hosts of the PRGs (e.g. tidal tails, shells, bridges, etc.) are up to 2 mag brighter than those present in their quiescent counterparts. Indeed, if we consider the same surface brightness limits, the fraction of disturbed morphologies is considerably smaller in the quiescent population (53 per cent at z < 0.2 and 48 per cent at 0.2 ≤ z < 0.7) than in the PRGs (93 per cent at z < 0.2 and 95 per cent at 0.2 ≤ z < 0.7 considering strong-line radio galaxies only). This supports a scenario in which PRGs represent a fleeting active phase of a subset of the elliptical galaxies that have recently undergone mergers/interactions. However, we demonstrate that only a small proportion (≲20 per cent) of disturbed early-type galaxies are capable of hosting powerful radio sources.

Investigation of electrically active defects at the interface of high-k dielectrics and compound semiconductors

As silicon based devices in integrated circuits reach the fundamental limits of dimensional scaling there is growing research interest in the use of high electron mobility channel materials, such as indium gallium arsenide (InGaAs), in conjunction with high dielectric constant (high-k) gate oxides, for Metal-Oxide-Semiconductor Field Effect Transistor (MOSFET) based devices. The motivation for employing high mobility channel materials is to reduce power dissipation in integrated circuits while also providing improved performance. One of the primary challenges to date in the field of III-V semiconductors has been the observation of high levels of defect densities at the high-k/III-V interface, which prevents surface inversion of the semiconductor. The work presented in this PhD thesis details the characterization of MOS devices incorporating high-k dielectrics on III-V semiconductors. The analysis examines the effect of modifying the semiconductor bandgap in MOS structures incorporating InxGa1-xAs (x: 0, 0.15. 0.3, 0.53) layers, the optimization of device passivation procedures designed to reduce interface defect densities, and analysis of such electrically active interface defect states for the high-k/InGaAs system. Devices are characterized primarily through capacitance-voltage (CV) and conductance-voltage (GV) measurements of MOS structures both as a function of frequency and temperature. In particular, the density of electrically active interface states was reduced to the level which allowed the observation of true surface inversion behavior in the In0.53Ga0.47As MOS system. This was achieved by developing an optimized (NH4)2S passivation, minimized air exposure, and atomic layer deposition of an Al2O3 gate oxide. An extraction of activation energies allows discrimination of the mechanisms responsible for the inversion response. Finally a new approach is described to determine the minority carrier generation lifetime and the oxide capacitance in MOS structures. The method is demonstrated for an In0.53Ga0.47As system, but is generally applicable to any MOS structure exhibiting a minority carrier response in inversion.