Surface properties of water ice at 150-191 K studied by elastic helium scattering

A highly surface sensitive technique based on elastic scattering of low-energy helium atoms has been used to probe the conditions in the topmost molecular layer on ice in the temperature range of 150-191 K. The elastically scattered intensity decreased slowly as the temperature was increased to about 180 K, followed by a rapid decrease at higher temperatures. An effective surface Debye temperature of 185+/-10 K was calculated from the data below 180 K. The changes in the ice surface above 180 K are interpreted as the onset of an anomalous enhancement of the mean square vibrational amplitude for the surface molecules and/or the onset of a limited amount of disorder in the ice surface. The interpretation is consistent with earlier experimental studies and molecular dynamics simulations. The observed changes above 180 K can be considered as the first sign of increased mobility of water molecules in the ice surface, which ultimately leads to the formation of a quasiliquid layer at higher temperatures. A small shift and broadening of the specular peak was also observed in the range of 150-180 K and the effect is explained by the inherent corrugation of the crystalline ice surface. The peak shift became more pronounced with increasing temperature, which indicates that surface corrugation increases as the temperature approaches 180 K. The results have implications for the properties and surface chemistry of atmospheric ice particles, and may contribute to the understanding of solvent effects on the internal molecular motion of hydrated proteins and other organic structures such as DNA.     

General theory of indirect detection in chromatography

Indirect detection is used in liquid chromatography to detect sample components that more or less lack detectable properties. A detectable component, the probe, is added to the mobile phase and the sample containing the components is injected. Every solute, even those not normally detectable, will give rise to detectable peaks due to the presence of the probe. The theory currently used to describe this situation is different for different adsorption isotherm models and also restrictions have to be imposed on the adsorption isotherm parameters. We present a general theory that describes both the retention times and areas of the detected peaks without making any a priori adsorption isotherm assumptions. Our general theory is compared with the current theory and validated by computer simulations. An alternative quantification method is suggested based on the measurement of the relative areas of the sample components without the requirement of having standard curves of known solutions of the sample components. Using this approach, the new theory is able to predict the solute concentrations in cases when the current theory did not, i.e., when the saturation capacities of the sample components and the probe differed from each other. In addition, a new application is proposed: the estimation of adsorption isotherm parameters.     

Electrospray ionization from a gap with adjustable width

In this paper, we present a new concept for electrospray ionization mass spectrometry, where the sample is applied in a gap which is formed between the edges of two triangular-shaped tips. The size of the spray orifice can be changed by varying the gap width. The tips were fabricated from polyethylene terephthalate film with a thickness of 36 microm. To improve the wetting of the gap and sample confinement, the edges of the tips forming the gap were hydrophilized by means of silicon dioxide deposition. Electrospray was performed with gap widths between 1 and 36 microm and flow rates down to 75 nL/min. The gap width could be adjusted in situ during the mass spectrometry experiments and nozzle clogging could be managed by simply widening the gap. Using angiotensin I as analyte, the signal-to-noise ratio increased as the gap width was decreased, and a shift towards higher charge states was observed. The detection limit for angiotensin I was in the low nM range.     

A longitudinal study of ethanol and acetaldehyde in the exhaled breath of healthy volunteers using selected-ion flow-tube mass spectrometry

Selected-ion flow-tube mass spectrometry (SIFT-MS) has been used to monitor the volatile compounds in the exhaled breath of 30 volunteers (19 male, 11 female) over a 6-month period. Volunteers provided breath samples each week between 8:45 and 13:00 (before lunch), and the concentrations of several trace compounds were obtained. In this paper the focus is on ethanol and acetaldehyde, which were simultaneously quantified by SIFT-MS using H3O+ precursor ions. The mean ethanol level for all samples was 196 parts-per-billion (ppb) with a standard deviation of 244 ppb, and the range of values for breath samples analysed is 0 to 1663 ppb. The mean acetaldehyde level for all samples was 24 ppb with a standard deviation of 17 ppb, and the range of values for breath samples analysed is 0 to 104 ppb. Background (ambient air) levels of ethanol were around 50 ppb, whereas any background acetaldehyde was usually undetectable. Increased ethanol levels were observed if sweet drink/food had been consumed within the 2 h prior to providing the breath samples, but no increase was apparent when alcohol had been consumed the previous evening. The measured endogenous breath ethanol and acetaldehyde levels were not correlated. These data relating to healthy individuals are a prelude to using breath analysis for clinical diagnosis, for example, the recognition of bacterial overload in the gut (ethanol) or the possibly of detecting tumours in the body (acetaldehyde).     

Thick porous tungsten trioxide films by anodization of tungsten in fluoride containing phosphoric acid electrolyte

In the present work, we report on the formation of mesoporous thick tungsten trioxide films grown on tungsten foil by anodization in fluoride containing concentrated phosphoric acid (85%) electrolyte. Under optimized experimental conditions, mesoporous WO₃ films with a thickness up to approximately 2 μm are formed. SEM shows the films to consist of a connected network with a typical pore and feature diameter of ca 50 nm. These films as formed are amorphous and can be annealed to orthorhombic WO₃ structure. These thick porous films can show significant enhanced electrochromic and improved photocatalytic properties.     

Improved efficiency of TiO2 nanotubes in dye sensitized solar cells by decoration with TiO2 nanoparticles

In the present work we investigate the effect of TiCl₄ treatments on the photoconversion efficiency of TiO₂ arrays used in dye sensitized solar cell. The results clearly show that by an appropriate treatment the decoration of the TiO₂ nanotube arrays with TiO₂ nanocrystallites of a typical size of 3 nm can be achieved. These particles can be converted to mixture of anatase and rutile phase by annealing in air. This decoration of the TiO₂ nanotubes leads to a significantly higher specific dye loading and, for certain annealing treatments, to a doubling of the solar cell efficiency (in our case from 1.9% to 3.8% of AM 1.5 conditions) can be achieved.     

A new approach to the characterization of the nano-surface structure by using factor analysis

The study provides a new approach to explore the existence of a nanostructure on the benzoic acid-modified glassy carbon electrode (BA-GC) system by applying factor analysis with varimax rotation of factors. The infrared spectra (IR) spectra of the bare glassy carbon electrodes (GC) and the BA-GC electrode systems with benzoic acid-nanofilm (BA-FILM) were obtained by using 10 different surface modification experiments. The IR data of the bare GC, BA-GC and BA-FILM were categorized into three series corresponding to the GC, BA-GC and BA-FILM. The factor analysis method was separately applied to each group to extract the factor loadings. By making use of these loadings, the rotated factor loadings corresponding to the first two factors were computed to estimate the relationship among and within groups. The results provided by the factor analysis method indicate the existence of the BA-FILM on the BA modified glassy carbon electrode.     

How to distinguish between specular and retroconfigurations for Andreev reflection in graphene rings

We numerically investigate Andreev reflection in a graphene ring with one normal conducting and one superconducting lead by solving the Bogoliubov-de Gennes equation within the Landauer-Büttiker formalism. By tuning chemical potential and bias voltage, it is possible to switch between regimes where electron and hole originate from the same band (retroconfiguration) or from different bands (specular configuration) of the graphene dispersion, respectively. We find that the dominant contributions to the Aharonov-Bohm conductance oscillations in the subgap transport are of period h/2e in retroconfiguration and of period h/e in specular configuration, confirming the predictions obtained from a qualitative analysis of interfering scattering paths. Because of the robustness against disorder and moderate changes to the system, this provides a clear signature to distinguish both types of Andreev reflection processes in graphene.     

Phonon-induced backscattering in helical edge states

A single pair of helical edge states as realized at the boundary of a quantum spin Hall insulator is known to be robust against elastic single particle backscattering as long as time reversal symmetry is preserved. However, there is no symmetry preventing inelastic backscattering as brought about by phonons in the presence of Rashba spin orbit coupling. In this Letter, we show that the quantized conductivity of a single channel of helical Dirac electrons is protected even against this inelastic mechanism to leading order. We further demonstrate that this result remains valid when Coulomb interaction is included in the framework of a helical Tomonaga Luttinger liquid.