Scanning Kelvin probe imaging of the potential profiles in fixed and dynamic planar LECs

We measure the potential profiles of both dynamic and fixed junction planar light-emitting electrochemical cells (LECs) using Scanning Kelvin Probe Microscopy (SKPM) and compare the results against models of LEC operation. We find that, in conventional dynamic junction LECs formed using lithium trifluoromethanesulfonate (LiTf), poly(ethylene oxide) (PEO), and the soluble alkoxy-PPV derivative poly[2-methoxy-5-(3',7'-dimethyl-octyloxy)-p-phenylenevinylene (MDMO-PPV), the majority (>90%) of the potential is dropped near the cathode with little potential drop across either the film or the anode/polymer interface. In contrast, when examining fixed junction LECs where the LiTf is replaced with [2-(methacryloyloxy)ethyl] trimethylammonium 2-(methacryloyloxy)ethane-sulfonate (METMA/MES), the potential is dropped at both contacts during the initial poling. The potential profile evolves over a period of approximately 60 min under bias to achieve a final profile similar to that obtained in the LiTf systems. In addition to elucidating the differences between conventional dynamic LECs and fixed LECs incorporating cross-linkable ion pair monomers, the results on both systems provide direct evidence for a primarily "p-type" LEC consistent with the emitting junction near the cathode and relatively small electric fields across the bulk of the device for these two material systems.     

Confirmatory analysis of malachite green, leucomalachite green, crystal violet and leucocrystal violet in salmon by liquid chromatography-tandem mass spectrometry

A method has been developed to analyse for malachite green (MG), leucomalachite green (LMG), crystal violet (CV) and leucocrystal violet (LCV) residues in salmon. Salmon samples were extracted with acetonitrile:McIIIvain pH 3 buffer (90:10 v/v), sample extracts were purified on a Bakerbond strong cation exchange solid phase extraction cartridge. Aliquots of the extracts were analysed by LC-MS/MS. The method was validated in salmon, according to the criteria defined in Commission Decision 2002/657/EC. The decision limit (CCalpha) was 0.17, 0.15, 0.35 and 0.17 microg kg(-1), respectively, for MG, LMG, CV and LCV and for the detection capability (CCbeta) values of 0.30, 0.35, 0.80 and 0.32 microg kg(-1), respectively, were obtained. Fortifying salmon samples (n=6) in three separate assays, show the accuracy to be between 77 and 113% for MG, LMG, LCV and CV. The precision of the method, expressed as RSD values for the within-laboratory reproducibility, for MG, LMG and LCV at the three levels of fortification (1, 1.5 and 2.0 microg kg(-1)), was less than 13%. For CV a more variable precision was obtained, with RSD values ranging between 20 and 25%.     

Stereoselective synthesis of 2-dienyl-substituted piperidines using an eta4-dienetricarbonyliron complex as the stereocontrolling element in a double reductive amination cascade

In the presence of NaBH(OAc)(3), a 1,5-keto-aldehyde, contained within a side-chain of an eta(4)-dienetricarbonyliron complex, undergoes a double reductive amination sequence with a series of primary amines, to provide the corresponding piperidine products in good to excellent yield. The dienetricarbonyliron complex functions as a powerful chiral auxiliary in this cascade process, exerting complete control over the stereoselectivity of the reaction, with the formation of a single diastereoisomeric product. The sense of stereoinduction has been confirmed by X-ray crystallography. Removal of the tricarbonyliron moiety can be effected with CuCl(2) to afford the corresponding 2-dienyl-substituted piperidine in excellent yield. Attempted extension of this cyclisation strategy to the corresponding azepane ring system using a 1,6-keto-aldehyde as the cyclisation precursor was unsuccessful; in this case, the reaction stopped after a single reductive amination on the aldehyde to provide an acyclic keto-amine product.     

pH‐Responsive Non‐Ionic Diblock Copolymers: Ionization of Carboxylic Acid End‐Groups Induces an Order–Order Morphological Transition

A carboxylic acid based reversible additionfragmentation transfer (RAFT) agent is used to prepare gels composed of worm‐like diblock copolymers using two non‐ionic monomers, glycerol monomethacrylate (GMA) and 2‐hydroxypropyl methacrylate (HPMA). Ionization of the carboxylic acid end‐group on the PGMA stabilizer block induces a worm‐to‐sphere transition, which in turn causes immediate degelation. This morphological transition is fully reversible as determined by TEM and rheology studies and occurs because of a subtle change in the packing parameter for the copolymer chains. A control experiment where the methyl ester derivative of the RAFT agent is used to prepare the same diblock copolymer confirms that no pH‐responsive behavior occurs in this case. This end‐group ionization approach is important for the design of new pH‐responsive copolymer nano‐objects as, unlike polyacids or polybases, only a minimal amount of added base (or acid) is required to drive the morphological transition.     

Photonic crystal nanocavities in GaAs/AlGaAs with oxidised bottom cladding

We present a solution to the difficult task of removing an oxide-based hard mask from a photonic crystal fabricated in the GaAs/AlGaAs system. We use a polymer backfill technique to seal the AlGaAs layer, thereby making it inaccessible to the wet-etch solution. This allows us to use a GaAs active layer for the photonic crystal placed on an oxidised AlGaAs layer which provides mechanical and thermal support. Using this technique, we fabricated GaAs-based photonic crystal cavities and measured respectable quality factors (Q ≈ 2200) despite the intrinsic asymmetry of the system. The technique presents a viable method for producing electrically injected photonic crystal cavities for operation on a mechanically stable and thermally conducting buffer layer.     

A general and modular synthesis of monoimidouranium(IV) dihalides

The conproportionation reaction between the dimeric diimidouranium(V) species [U(N(t)Bu)(2)(I)((t)Bu(2)bpy)](2) ((t)Bu(2)bpy = 4,4'-di-tert-butyl-2,2'-bipyridyl) and UI(3)(THF)(4) in the presence of additional (t)Bu(2)bpy yields U(N(t)Bu)(I)(2)((t)Bu(2)bpy)(THF)(2) (2), an unprecedented example of a monoimidouranium(IV) dihalide complex. The general synthesis of this family of uranium(IV) derivatives can be achieved more readily by adding 2 equiv of MN(H)R (M = Li, K; R = (t)Bu, 2,6-(i)PrC(6)H(3), 2-(t)BuC(6)H(4)) to UX(4) in the presence of coordinating Lewis bases to give complexes with the general formula U(NR)(X)(2)(L)(n) (X = Cl, I; L = (t)Bu(2)bpy, n = 1; L = THF, n = 2). The complexes were characterized by (1)H NMR spectroscopy and single-crystal X-ray diffraction analysis of compounds 2 and {U[N(2,6-(i)PrC(6)H(3))](Cl)(2)(THF)(2)}(2) (4). (The X-ray structures of 5 and 6 are reported in the Supporting Information.)     

On L-spaces and left-orderable fundamental groups

Examples suggest that there is a correspondence between L-spaces and three-manifolds whose fundamental groups cannot be left-ordered. In this paper we establish the equivalence of these conditions for several large classes of manifolds. In particular, we prove that they are equivalent for any closed, connected, orientable, geometric three-manifold that is non-hyperbolic, a family which includes all closed, connected, orientable Seifert fibred spaces. We also show that they are equivalent for the twofold branched covers of non-split alternating links. To do this we prove that the fundamental group of the twofold branched cover of an alternating link is left-orderable if and only if it is a trivial link with two or more components. We also show that this places strong restrictions on the representations of the fundamental group of an alternating knot complement with values in $\text{ Homeo}_+(S^1)$ .     

Investigating the neural correlates of pathological cortical networks in Alzheimer's disease using heterogeneous neuronal models

This paper describes an investigation into the pathophysiological causes of abnormal cortical oscillations in Alzheimer's disease (AD) using two heterogeneous neuronal network models. The effect of excitatory circuit disruption on the beta band power (13-30 Hz) using a conductance-based network model of 200 neurons is assessed. Then, the neural correlates of abnormal cortical oscillations in different frequency bands based on a larger network model of 1000 neurons consisting of different types of cortical neurons are also analyzed. EEG studies in AD patients have shown that beta band power (13-30 Hz) decreased in the early stages of the disease with a parallel increase in theta band power (4-7 Hz). This abnormal change progresses with the later stages of the disease but with decreased power spectra in other fast frequency bands plus an increase in delta band power (1-3 Hz). Our results show that, despite the heterogeneity of the network models, the beta band power is significantly affected by excitatory neural and synaptic loss. Second, the results of modeling a functional impairment in the excitatory circuit shows that beta band power exhibits the most decrease compared with other bands. Previous biological experiments on different types of cultural excitatory neurons show that cortical neuronal death is mediated by dysfunctional ionic behavior that might specifically contribute to the pathogenesis of β-amyloid-peptide-induced neuronal death in AD. Our study also shows that beta band power was the first affected component when the modeled excitatory circuit begins to lose neurons and synapses.     

Gold-catalysed oxyarylation of styrenes and mono- and gem-disubstituted olefins facilitated by an iodine(III) oxidant

1-Hydroxy-1,2-benziodoxol-3(1H)-one (IBA) is an efficient terminal oxidant for gold-catalysed, three-component oxyarylation reactions. The use of this iodine(III) reagent expands the scope of oxyarylation to include styrenes and gem-disubstituted olefins, substrates that are incompatible with the previously reported Selectfluor-based methodology. Diverse arylsilane coupling partners can be employed, and in benzotrifluoride, homocoupling is substantially reduced. In addition, the IBA-derived co-products can be recovered and recycled.     

Static and dynamic analysis of side-mode suppression of widely tunable sampled grating DBR (SG-DBR) lasers

Side-mode suppression is an important issue for widely tunable laser design and applications. In this paper, we have developed a relatively simple algorithm to analyze side-mode suppression of widely tunable sampled grating distributed Bragg reflector (SG-DBR) lasers by using the Transfer Matrix Method (TMM) in combination with multimode rate equations. The dependence of gain spectrum on wavelength is also included in this model, and its effects on tuning characteristics of the devices are investigated for the first time. Static tuning characteristics and dynamic behaviors of wavelength switching are simulated. Results agree well with the experimental results reported.