Fully fluorinated imidodiphosphinate shells for visible- and NIR-Emitting lanthanides: Hitherto unexpected effects of sensitizer fluorination on lanthanide emission properties

In this paper we demonstrate that the effect of aromatic C-F substitution in ligands does not always abide by conventional wisdom for ligand design to enhance sensitisation for visible lanthanide emission, in contrast with NIR emission for which the same effect coupled with shell formation leads to unprecedented long luminescence lifetimes. We have chosen an imidodiphosphinate ligand, N-{P,P-di-(pentafluorophinoyl)}-P,P-dipentafluoro-phenylphosphinimidic acid (HF(20)tpip), to form ideal fluorinated shells about all visible- and NIR-emitting lanthanides. The shell, formed by three ligands, comprises twelve fully fluorinated aryl sensitiser groups, yet no-high energy X-H vibrations that quench lanthanide emission. The synthesis, full characterisation including X-ray and NMR analysis as well as the photophysical properties of the emissive complexes [Ln(F(20)tpip)(3)], in which Ln=Nd, Sm, Eu, Gd, Tb, Dy, Er, Yb, Y, Gd, are reported. The photophysical results contrast previous studies, in which fluorination of alkyl chains tends to lead to more emissive lanthanide complexes for both visible and NIR emission. Analysis of the fluorescence properties of the HF(20)tpip and [Gd(F(20)tpip)(3)] reveals that there is a low-lying state at around 715 nm that is responsible for partially quenching of the signal of the visible emitting lanthanides and we attribute it to a pi-sigma* state. However, all visible emitting lanthanides have long lifetimes and unexpectedly the [Dy(F(20)tpip)(3)] complex shows a lifetime of 0.3 ms, indicating that the elimination of high-energy vibrations from the ligand framework is particularly favourable for Dy. The NIR emitting lanthanides show strong emission signals in powder and solution with unprecedented lifetimes. The luminescence lifetimes of [Nd(F(20)tpip)(3)], [Er(F(20)tpip)(3)] and [Yb(F(20)tpip)(3)] in deuteurated acetonitrile are 44, 741 and 1111 mu s. The highest value observed for the [Yb(F(20)tpip)(3)] complex is more than half the value of the Yb ion radiative lifetime.

Three dimensional number density mapping in the plume of a low temperature laser ablated magnesium plasma

Simultaneous optical absorption and laser-induced fluorescence measurements have been used to map the three-dimensional number densities of ground-state ions and neutrals within a low-temperature KrF laser-produced magnesium plasma expanding into vacuum. Data is reported for the symmetry plane of the plasma, which includes the laser interaction point at a delay of 1 μs after the ∼30 ns KrF laser ablation pulse and for a laser fluence of 2 J cm−2 on target. The number density distributions of ion and neutral species within this plane indicate that two distinct regions exist within the plume; one is a fast component containing ions and neutrals at maximum densities of ∼3×1013 cm−3 and ∼4×1012 cm−3, respectively and the second is a high-density region containing slow neutral species, at densities up to ∼1×1015 cm−3.

Modeled structure of the whole regulator G-protein signaling-2

There is an increasing interest towards the mechanism by which regulators of G-protein signaling regulate signals of G-protein-coupled receptors. RGS2 is a regulator of Gq protein signaling (RGS), the N-terminal region of which is known to contain determinants for G protein-coupled receptor recognition, but its structure is still unknown. To understand the molecular basis for this recognition, the three-dimensional model of RGS2, including N-terminal region and RGS box, was modeled. For this, RGS4 box structure and data from circular dichroism study of RGS2 N-terminal region were used. Then, membrane-targeting activity of the RGS2 amphipathic helix contained in the N-terminal region was investigated. Furthermore, in cellulo study provided first evidence that an internal sequence within the N-terminal region of RGS2 is involved in RGS2 regulation of cholecystokinin receptor-2 signal. RGS2 modeled structure can now serve to study molecular recognition of RGS2 by signaling molecules. © 2006 Elsevier Inc. All rights reserved.

List 229: Irish and English Dendrochronology

These results cover dating undertaken since the last published list of dated building from Ireland (Brown (2002)); one English church building is also included in the list. Thanks are due to the owners of the buildings and especially to everyone who assisted in taking of the samples: Phil Barrett, Sapphire Mussen, Charles Lyons, Jon Pilcher and Mike Baillie, Amanda Pedlow, Caimin O’Brien and Martin Timoney. Most of the descriptions of the buildings are taken from the National Inventory of Architectural Heritage http://www.buildingofi reland.ie/. The correlation values were generated by CROSS84 (Munro, 1984), which provides a signifi cance level for the date to be correct; *** (extremely signifi cant), ** (very signifi cant), * (signifi cant), nsm (not signifi cant). Estimated felling date ranges are based on the Belfast sapwood estimate of 32 ± 9 years. Date ranges have been calculated by adding and subtracting 9 years from the calculated estimated felling dates. Timbers from the following buildings could not be dated. Cork: St Finbarre’s Cathedral (W 675 715); Dublin: Christchurch Cathedral (O 152 341); Galway: Cloghan Castle (M 972 119); Kilkenny: Rothe House (S 506 563); Offaly: Boveen House (S 075 956); Waterford: Christchurch Cathedral (S 616 121). Generally only single oak samples were recovered from these structures. References: D.Brown, ‘Dendrochronological dating building from Ireland’, VA 33 (2002), 71–3; M. Munro, ‘An improved algorithm for crossdating tree-ring series’, Tree-Ring Bulletin 44 (1984), 17–27.

Effect of pioglitazone on endothelial function in impaired glucose tolerance

Aim: Flow-mediated dilation (FMD) is a surrogate marker of endothelial function, which has been proposed as a barometer of vascular health. Impaired microvascular response to reactive hyperaemia is thought to be the mechanism behind reduced shear stress and subsequently impaired FMD, which has been associated with cardiovascular events. This study aims to assess the effect of pioglitazone on the vasculature of patients with impaired glucose tolerance (IGT).

Materials and Methods: Forty IGT patients with no cardiovascular disease were compared with 24 healthy age- and sex-matched controls. Endothelial function was assessed using FMD of the brachial artery. Adiponectin (ADN) levels were measured and insulin sensitivity was calculated using homeostasis model assessment of insulin resistance (HOMA-IR). A randomised double-blind placebo-controlled trial of the IGT subjects was then performed, with subjects receiving either pioglitazone 30 mg od or matched placebo for 12 weeks before the measurements were repeated.

Results: The IGT subjects had a significantly impaired FMD compared with the controls (p < 0.001). Diastolic shear stress (DSS) was also significantly reduced in IGT (p = 0.04). High molecular weight (HMW) ADN was significantly lower in the IGT group than in controls (p = 0.03). On analysis of the IGT group after 12 weeks treatment, FMD was significantly increased in the pioglitazone group compared with placebo (p = 0.03) as was endothelium-independent dilation (EID) (p = 0.03). A significant increase in total ADN (p < 0.001), HMW ADN (p < 0.001) and HMW/total ratio (p = 0.001) occurred in the pioglitazone group compared with placebo.

Conclusions: Pioglitazone improved endothelial function in IGT. Treatment with pioglitazone may reduce the risk of cardiovascular disease in this patient group.

A short proof of existence of disjoint hypercyclic operators

We give a short proof of existence of disjoint hypercyclic tuples of operators of any given length on any separable infinite dimensional Fr\'echet space. Similar argument provides disjoint dual hypercyclic tuples of operators of any length on any infinite dimensional Banach space with separable dual.

An efficient neural network approach for nanoscale FinFET modelling and circuit simulation

The present paper demonstrates the suitability of artificial neural network (ANN) for modelling of a FinFET in nano-circuit simulation. The FinFET used in this work is designed using careful engineering of source-drain extension, which simultaneously improves maximum frequency of oscillation f(max) because of lower gate to drain capacitance, and intrinsic gain A(V0) = g(m)/g(ds), due to lower output conductance g(ds). The framework for the ANN-based FinFET model is a common source equivalent circuit, where the dependence of intrinsic capacitances, resistances and dc drain current I-d on drain-source V-ds and gate-source V-gs is derived by a simple two-layered neural network architecture. All extrinsic components of the FinFET model are treated as bias independent. The model was implemented in a circuit simulator and verified by its ability to generate accurate response to excitations not used during training. The model was used to design a low-noise amplifier. At low power (J(ds) similar to 10 mu A/mu m) improvement was observed in both third-order-intercept IIP3 (similar to 10 dBm) and intrinsic gain A(V0) (similar to 20 dB), compared to a comparable bulk MOSFET with similar effective channel length. This is attributed to higher ratio of first-order to third-order derivative of I-d with respect to gate voltage and lower g(ds), in FinFET compared to bulk MOSFET. Copyright (C) 2009 John Wiley & Sons, Ltd.

Sensory systems and spatial memory in the fruit bat Rousettus aegyptiacus

The megachiropteran fruit bat Rousettus aegyptiacus is able to orient and navigate using both vision and echolocation. These two sensory systems have different environmental constraints however, echolocation being relatively short range when compared with vision. Despite this difference, an experiment testing their memory of a perch location demonstrates that once the location of a perch is learned R. aegyptiacus is not influenced by the movement of local landmark cues in the vicinity of the perch under either light or dark conditions. Thus despite the differing constraints of vision and echolocation, this suggests a place is remembered as a location in space and not by associations with landmarks in the vicinity. A decrease in initial performance when the task was repeated in the dark suggested the possibility that a memory of a location learned using vision does not generalize to echolocation.

Sequential antimicrobial therapy: treatment of severe lower respiratory tract infections in children

Although there have been a number of studies in adults, to date there has been little research into sequential antimicrobial therapy (SAT) in paediatric populations. The present study evaluates the impact of a SAT protocol for the treatment of severe lower respiratory tract infection in paediatric patients. The study involved 89 paediatric patients (44 control and 45 SAT). The SAT patients had a shorter length of hospital stay (4.0 versus 8.3 days), shorter duration of inpatient antimicrobial therapy (4.0 versus 7.9 days) with the period of iv therapy being reduced from a mean of 5.6 to 1.7 days. The total healthcare costs were reduced by 52%. The resolution of severe lower respiratory tract infection with a short course of iv antimicrobials, followed by conversion to oral therapy yielded clinical outcomes comparable to those achieved using longer term iv therapy. SAT proved to be an important cost-minimizing tool for realizing substantial healthcare costs savings.

Tetrahexahedral Pt Nanocrystal Catalysts Decorated with Ru Adatoms and Their Enhanced Activity in Methanol Electrooxidation

Tetrahexahedral Pt nanocrystals (THH Pt NCs) bound by well-defined high index crystal planes offer exceptional electrocatalytic activity, owing to a high density of low-coordination surface Pt sites. We report, herein, on methanol electrooxidation at THH Pt NC electrodes studied by a combination of electrochemical techniques and in situ FTIR spectroscopy. Pure THH Pt NC surfaces readily facilitate the dissociative chemisorption of methanol leading to poisoning by strongly adsorbed CO. Decoration of the stepped surfaces by Ru adatoms increases the tolerance to poisoning and thereby reduces the onset potential for methanol oxidation by over 100 mV. The Ru modified THH Pt NCs exhibit greatly superior catalytic currents and CO2 yields in the low potential range, when compared with a commercial PtRu alloy nanoparticle catalyst. These results are of fundamental importance in terms of model nanoparticle electrocatalytic systems of stepped surfaces and also have practical significance in the development of surface tailored, direct methanol fuel cell catalysts.

An enantio-selective chromatographic stationary phase for S-ibuprofen prepared by stoichiometric molecular imprinting

Molecularly Imprinted Polymers (MIPs) against S-ibuprofen were synthesised using a tailor made functional monomer, 2-acrylamido-4-methylpyridine, following extensive pre-polymerisation studies of template-monomer complexation. An apparent association constant of 340 +/- 22 M-1 was calculated that was subsequently corrected to account for dimerisation of ibuprofen (K-dim = 320 +/- 95 M-1) resulting in an intrinsic association constant of 715 +/- 16 M-1, consistent with previously reported values. Using the synthesised imprinted polymer as a stationary phase, complete resolution of a racemic mixture of ibuprofen was achieved in predominantly aqueous mobile phases. An imprinting factor of 10 was observed, and was found to be in agreement with the difference in the average number of binding sites between MIP and blank polymers, calculated by staircase frontal chromatography. The imprinted polymers exhibited enhanced selectivity for the templated drug over structurally related NSAIDs. When applied as sorbents in solid-phase extraction of ibuprofen from commercial tablets, urine and blood serum samples, recoveries up to 92.2% were achieved. © The Royal Society of Chemistry 2012