HERFD XAS/ATR-FTIR batch reactor cell

An autoclave reactor was modified to perform simultaneously high energy resolution fluorescence detected X-ray absorption spectroscopy (HERFD XAS) and attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy measurements without altering the reactor design. This operando cell allows one to follow changes in the electronic and geometric structure of the catalyst with HERFD XAS and relate them to the simultaneously detected activity and reaction species with ATR-FTIR formed during the reaction in the liquid phase. The capability of the cell is demonstrated by two studies. The first shows the reduction of Au/CeO(2) precursors in different solvents. The second shows that mainly Au(0) is present in the hydrogenation of nitrobenzene over Au/CeO(2).     

Origin of Fluorescence Lifetimes in Human Serum Albumin. Studies on Native and Denatured Protein

Human serum albumin consists of a single polypeptide of 585 amino acid residues with 1 Trp residue. In the present work, we measured fluorescence lifetimes of the protein in both native and denatured states. The results indicate that Trp emission occurs with three lifetimes in both states. Lifetimes values and contribution to the global emission decay differ between the two states. Data are interpreted as the results of an emission occurring from three substructures of the tryptophan formed in the excited state. Two of these substructures are already present for the tryptophan free in solution. The third lifetime is the result of the interaction between the tryptophan residue and surrounding microenvironment. The populations of these substructures characterized by the pre-exponential parameters of the fluorescence lifetimes are dependent on the fluorophore microenvironment and on the global protein structure.     

Monitoring membrane rafts in colorectal cancer cells by means of correlative fluorescence electron microscopy (CFEM)

Detergent-resistant membrane (DRM) rafts have been shown to play a pivotal role in regulating key cell biological processes, such as signal transduction, cellular transport and cell survival. The fine structure of membrane rafts are studied using various different imaging approaches and the outcomes are largely dependent on the detection methodology applied. All these microscopy techniques which employ light-, laser- and photon-optics, electrons as well as atomic force probing are characterized on their turn by their strengths and limitations for membrane raft identification. This explains in part the diversity of definitions available to describe these peculiar membrane structures. We present herewith an alternative and uncomplicated microscopy tool to study fluorescently labelled DRMs with information at the transmission electron microscopical level of the same cell, enabling us to obtain a snapshot of the morpho-functional relationships between the cell's interior and DRMs. The proposed approach of correlative fluorescence electron microscopy (CFEM) can therefore be considered as an additional alternative imaging approach to unravel DRM structure–function relationships from micro- to nanometre length scales, from the cell to the molecule.     

New luminescence measurement facilities in retrospective dosimetry

This paper gives a review of recent developments in luminescence measurement facilities on the Risø TL/OSL reader including radio-luminescence (RL), exo-electron and violet stimulation attachments, and a method for characterising and if necessary correcting for beta irradiation source non-uniformity.We first describe improvements to the existing RL option to allow near infra-red detection (NIR) during irradiation by the built-in ⁹⁰Sr/⁹⁰Y beta source. The RL optical signal is collected by a liquid light guide through an F34-901 interference filter and detection is based on a dedicated thermoelectrically cooled NIR sensitive PMT (detection window peak at 855 nm, FWHM 27 nm). Software and electronics have been modified to allow standard TL and OSL measurements in the same sequence as RL measurements. Together with a new bleaching source based on a high-power UV LED (395 nm; 700 mW/cm²), this facility has been used to measure natural doses in feldspar using the decaying NIR RL signal.Secondly, we present a method for mapping radiation field of the built-in ⁹⁰Sr/⁹⁰Y β-source and estimating grain-location specific dose-rates. This is important for the accuracy of single grain results, when radiation field is spatially non-uniform across the sample area. We document the effect of this correction method and further investigate on the effect of lifting the source to achieve a better dose-rate uniformity.Finally we summarise two recently-developed novel facilities to help investigate (i) the time scales involved in OSL processes (time-resolved exo-electron detection) and (ii) extending the age range (violet stimulated signals from deep quartz OSL traps).     

Evaluation of the performance of high temperature conversion reactors for compound-specific oxygen stable isotope analysis

In this study conversion conditions for oxygen gas chromatography high temperature conversion (HTC) isotope ratio mass spectrometry (IRMS) are characterised using qualitative mass spectrometry (IonTrap). It is shown that physical and chemical properties of a given reactor design impact HTC and thus the ability to accurately measure oxygen isotope ratios. Commercially available and custom-built tube-in-tube reactors were used to elucidate (i) by-product formation (carbon dioxide, water, small organic molecules), (ii) 2nd sources of oxygen (leakage, metal oxides, ceramic material), and (iii) required reactor conditions (conditioning, reduction, stability). The suitability of the available HTC approach for compound-specific isotope analysis of oxygen in volatile organic molecules like methyl tert-butyl ether is assessed. Main problems impeding accurate analysis are non-quantitative HTC and significant carbon dioxide by-product formation. An evaluation strategy combining mass spectrometric analysis of HTC products and IRMS ¹⁸O/¹⁶O monitoring for future method development is proposed.     

An efficient decision feedback equalizer for the ATSC DTV receiver

In this paper an efficient decision feedback equalizer is presented for the equalization of the received signal in the eight level vestigial sideband, Advanced Television Systems Committee, digital television system, adopting a novel detection rule for symbol detection at the output of the equalizer. The conventional hard limiter is replaced by an efficient symbol detection algorithm, based on the underlying trellis coded modulated coding of the transmitted symbols. The proposed decision device has a marginal computational cost and it can be implemented using simple combinatorial and sequential logic circuitry. When the equalizer operates in the decision directed mode, the normalized least mean squared algorithm is utilized for the adaptation of the equalizer coefficients, in a “stop-and-go” like mode, triggered by a reliability signal associated to the detected symbols. The performance of the proposed method is illustrated by typical computer simulation.     

Constraining Si Particles within Graphene Foam Monolith: Interfacial Modification for High‐Performance Li+ Storage and Flexible Integrated Configuration

Pulverization of electrode materials and loss of electrical contact have been identified as the major causes for the performance deterioration of alloy anodes in Li‐ion batteries. This study presents the hierarchical arrangement of spatially confining silicon nanoparticles (Si NPs) within graphene foam (GF) for alleviating these issues. Through a freeze‐drying method, the highly oriented GF monolith is engineered to fully encapsulate the Si NPs, serving not only as a robust framework with the well‐accessible thoroughfares for electrolyte percolation but also a physical blocking layer to restrain Si from direct exposure to the electrolyte. In return, the pillar effect of Si NPs prevents the graphene sheets from restacking while preserving the highly efficient electron/Li⁺ transport channels. When evaluated as a binder‐free anode, impressive cycle performance is realized in both half‐cell and full‐cell configurations. Operando X‐ray diffraction and in‐house X‐ray photoelectron spectroscopy confirm the pivotal protection of GF to sheathe the most volume‐expanded lithiated phase (Li₁₅Si₄) at room temperature. Furthermore, a free‐standing composite film is developed through readjusting the pore size in GF/Si monolith and directly integrated with nanocellulose membrane (NCM) separator. Because of the good electrical conductivity and structural integrity of the GF monolith as well as the flexibility of the NCM separator, the as‐developed GF/Si‐NCM electrode showcases the potential use in the flexible electronic devices.