Lanthanide-containing metallomesogens with low transition temperatures

Lanthanide-containing liquid crystals exhibiting a mesophase close to room temperature were obtained by adduct formation between a long-chain salicylaldimine Schiff base and tris(2-thenoyltrifluoroacetonato)lanthanide( III) complexes or tris( benzoyltrifluoroacetonato) lanthanide( III) complexes. The mesophase was identified as a smectic A phase. The temperature range of the mesophase was found to decrease over the lanthanide series, and no mesophase was observed for the complexes of the smallest lanthanide ions. The photoluminescence of the europium( III), samarium( III), neodymium( III), and erbium( III) complexes was studied. It is shown that the clearing point can be detected by monitoring the luminescence decay time as a function of the temperature.

Chironomid-inferred Late-Glacial Summer Air Temperatures From Lough Nadourcan, Co. Donegal, Ireland.

Western Ireland, located adjacent to the North Atlantic, and with a strongly oceanic climate, is potentially sensitive to rapid and extreme climate change. We present the first high-resolution chironomid-inferred mean July temperature reconstruction for Ireland, spanning the late-glacial and early Holocene (LGIT, 15-10 ka BP). The reconstruction suggests an initial rapid warming followed by a short cool phase early in the interstadial. During the interstadial there are oscillations in the inferred temperatures which may relate to Greenland Interstadial events GI-1a-e. The temperature decrease into the stadial occurs in two stages. This two-stage drop can also be seen in other late-glacial chironomid-inferred temperature records from the British Isles. A stepped rise in temperatures into the Holocene, consistent with present-day temperatures in Donegal, is inferred. The results show strong similarities with previously published LGIT chironomid-inferred temperature reconstructions, and with the NGRIP oxygen-isotope curve, which indicates that the oscillations observed in the NGRIP record are of hemispherical significance. The results also highlight the influence of the North Atlantic on the Irish climate throughout the LGIT.

Lowest energy potentials of Li2 + F accessible at ultracold temperatures

Ab initio calculations for the strongly exoergic Li2+F harpoon reaction are presented using density-functional theory, complete active space self-consistent field, and multireference configuration interaction methods to argue that this reaction would be an ideal candidate for investigation with ultracold molecules. The lowest six states are calculated with the aug-correlation-consistent polarized valence triple-zeta basis set and at least two can be accessed by a ground rovibronic Li2 molecule with zero collision energy at all reaction geometries. The large reactive cross section (characteristic of harpoon reactions) and chemiluminescent products are additional attractive features of these reactions.

Analysis of Degradation Data of Poly(L-lactide-co-L,D-lactic actide) and Poly(L-lactide) Obtained at Elevated and Physiological Temperatures Using Mathematical Models

The degradation of resorbable polymeric devices often takes months to years. Accelerated testing at elevated temperatures is an attractive but controversial technique. The purposes of this paper include: (a) to provide a summary of the mathematical models required to analyse accelerated degradation data and to indicate the pitfalls of using these models; (b) to improve the model previously developed by Han and Pan; (c) to provide a simple version of the model of Han and Pan with an analytical solution that is convenient to use; (d) to demonstrate the application of the improved model in two different poly(lactic acid) systems. It is shown that the simple analytical relations between molecular weight and degradation time widely used in the literature can lead to inadequate conclusions. In more general situations the rate equations are only part of a complete degradation model. Together with previous works in the literature, our study calls for care in using the accelerated testing technique.

Exploitation of inherited weakness in fire-damaged building sandstone: the ‘fatiguing’ of ‘shocked’ stone

The problem of the long-term impact of historical fire on masonry is not clearly understood. Much research focuses on the damage that is caused by fire in isolation, and omits to investigate the subsequent exploitation of weaknesses inherited from fire events. Fire can, for example, cause significant physical, chemical and mineralogical change to sandstone, which may then be exploited by background environmental factors such as salt and freeze–thaw weathering. To explore this experimentally, blocks of Peakmoor Sandstone were subjected to a real fire (as well as lime rendering/removal and frost cycle pre-treatments), and their subsequent response to salt weathering cycles was monitored by weight loss and visual assessment of the pattern of surface damage. Results illustrate that the post-fire deterioration of sandstone is strongly conditioned by fracture networks and soot cover inherited from the fire. The exploitation of fractures can lead to spalling during salt weathering cycles — this takes place as granular dissagregation steadily widens cracks and salts concentrate and crystallise in areas of inherited weakness. Soot cover can have a profound effect on subsequent performance. It reduces surface permeability and can be hydrophobic in character, limiting salt ingress and suppressing decay in the short term. However, as salt crystals concentrate under the soot crust, detachment of this layer can occur, exposing fire-damaged stone beneath. Understanding the subsequent exploitation of stone exposed to fire damage by background environmental factors (for example, salt weathering/ temperature cycling) is key to the post-fire management of stone decay.

Catalytic hydrogenation of tertiary amides at low temperatures and pressures using bimetallic Pt/Re-based catalysts

Hydrogenation of tertiary amides, in particular, N-methylpyrrolidin-2-one, can be efficiently facilitated by a TiO(2)-supported bimetallic Pt/Re catalyst at low temperatures and pressures. Characterisation of the catalysts and kinetic tests have shown that the close interaction between the Re and Pt is crucial to the high activity observed. DFT calculations were used to examine a range of metal combinations and show that the role of the uncoordinated Re is to activate the C=O and that of the Pt is as a hydrogenation catalyst, removing intermediates from the catalyst surface. The rate enhancement observed on the TiO(2) support is thought to be due to the presence of oxygen vacancies allowing adsorption and weakening of the C=O bond. (C) 2011 Elsevier Inc. All rights reserved.

The use of short time-on-stream in situ spectroscopic transient kinetic isotope techniques to investigate the mechanism of hydrocarbon selective catalytic reduction (HC-SCR) of NOx at low temperatures

The problem of differentiating between active and spectator species that have similar infrared spectra has been addressed by developing short time-on-stream in situ spectroscopic transient isotope experimental techniques (STOS-SSITKA). The techniques have been used to investigate the reaction mechanism for the reduction of nitrogen oxides (NOx) by hydrocarbons under lean-burn (excess oxygen) conditions on a silver catalyst. Although a nitrate-type species tracks the formation of isotopically labeled dinitrogen, the results show that this is misleading because a nitrate-type species has the same response to an isotopic switch even under conditions where no dinitrogen is produced. In the case of cyanide and isocyanate species, the results show that it is possible to differentiate between slowly reacting spectator isocyanate species, probably adsorbed on the oxide support, and reactive isocyanate species, possibly on or close to the active silver phase. The reactive isocyanate species responds to an isotope switch at a rate that matches that of the rate of formation of the main product, dinitrogen. It is concluded that these reactive isocyanates could potentially be involved in the reduction of NOx whereas there is no evidence to support the involvement of nitrate-type species that are observable by infrared spectroscopy.

Ab initio potentials of F + Li-2 accessible at ultracold temperatures

Ab initio calculations for the strongly exoergic Li-2 + F harpoon reaction are presented using density-functional theory, complete active space self-consistent field, and multireference configuration interaction methods to argue that this reaction would be an ideal candidate for investigation with ultracold molecules. The lowest six states are calculated with the aug-correlation-consistent polarized valence triple-zeta basis set and at least two can be accessed by a ground rovibronic Li-2 molecule with zero collision energy at all reaction geometries. The large reactive cross section (characteristic of harpoon reactions) and chemiluminescent products are additional attractive features of these reactions.

Effect of column base strength on steel portal frames in fire

This paper presents the findings of a project part sponsored by an ICE Research and Development grant on portal frames in fire. The research reported here has also lead to a sucessful research grant from the IStructE. The paper describes a non-linear elasto plastic dynamic finite element model that captures the collapse of a portal frame in fire. It demonstrates that current guidance on the column base stiffness and strength, to prevent collapse, may in some cases be unconservative.

An analysis of VUV C (IV) emission from the JET divertor giving measurements of electron temperatures

A description of the radiation emitted by impurities from within a plasma is crucial if spectral line intensities are to be used in detailed studies, such as the analysis of impurity transport. The simplest and most direct check that can be made on measurements of line intensities is to analyse their ratios with other lines from the same ion. This avoids uncertainties in determining the volume of the emitting plasma and the absolute sensitivity calibration of the spectrometer and, in some cases, the need even for accurate measurements of parameters such as electron density. Consistency is required between the measured line intensity ratios and the theoretical values. The expected consistency has not been found for radiation emitted from the JET scrape-off layer (e.g. Lawson et al 2009a JINST 4 P04013), meaning that the description of the spectral line intensities of impurity emission from the plasma edge is incomplete. In order to gain further understanding of the discrepancies, an analysis has been carried out for emission from the JET divertor plasma and this is reported in this paper. Carbon was the main low Z intrinsic impurity in JET and an analysis of spectral line intensity ratios has been made for the C (IV) radiation emitted from the JET divertor. In this case, agreement is found between the measured and theoretical ratios to a very high accuracy, namely to within the experimental uncertainty of similar to +/- 10%. This confirms that the description of the line intensities for the present observations is complete. For some elements and ionization stages, an analysis of line intensity ratios can lead to the determination of parameters such as the electron temperature of the emitting plasma region and estimates of the contribution of recombination to the electron energy level populations. This applies to C (IV) and, to show the value and possibilities of the spectral measurements, these parameters have been calculated for a database of Ohmic and additionally heated phases of a large number of pulses. The importance of dielectronic, radiative and charge-exchange recombination as well as ionization has been investigated. In addition, the development of T-e throughout two example discharges is illustrated. The presented results indicate a number of areas for further investigation.