Structure of tetraphenylarsonium tricyano- 2,2′,6′,2′′-terpyridylferrate(II), AsPh4[FeII(terpy)(CN)3]; and kinetics of oxidation of the complex anion by peroxodisulfate in water and in binary aqueous mixtures

The structure of the title compound has been determined by X-ray crystallography. The octahedral arrangement of ligands about the iron(II) centre is somewhat distorted, with the axial NC–Fe–CN bond angle being 174.3(4)°. The oxidation of the tricyano-2,2,6,2- terpyridylferrate(II) anion by the peroxodisulfate anion has been investigated in water and in binary aqueous mixtures. The reaction follows a second order rate law, with a second-order rate constant of 0.126± 0.001dm3mol–1s–1 at 295.2K. The enthalpy and entropy of activation in water are 51.3±1.8kJmol–1 and –89±5JK–1mol–1 respectively. The rate is retarded on addition of organic cosolvent. The transfer chemical potential of the initial state from water into mixed solvents has been determined from solubility measurements, and compared with the transfer potential of the transition state. Solvent effects on the reaction are discussed in terms of initial state versus transition state solvation.     

Experimental investigation of a bistable system in the presence of noise and delay

We experimentally analyze the behavior of a non-Markovian bistable system with noise, using a vertical cavity surface emitting laser with time-delayed optoelectronic feedback. The effects of the delayed feedback are observed in the probability distribution of the residence times of the two orthogonal polarization states, and in the polarization-resolved power spectrum. They agree well with recent theoretical predictions based on a two-state model with transition rates depending on an earlier state of the system. We also observe experimentally and explain theoretically that the residence time probability distribution deviates from exponential decay for residence times close to (and smaller than) the delay time.     

Mesomorphic properties of some laterally fluorinated 4-alkyl,4'-oxoalkyl 1,1': 4',1'terphenyls

The liquid crystalline behaviour and nematic viscosities of a series of laterally fluorinated alkyl-oxoalkyl terphenyls are reported. The mesomorphic behaviour and nematic viscosity can be influenced by the position of the oxygen atom in the oxoalkyl chain as well as the position of lateral fluorination. Compounds have been synthesized that are suitable for use in ferroelectric smectic C (S*_C) mixtures; the switching properties of a four component mixture are also reported.     

Highly Birefringent Nematic Liquid Crystals for Reflective STN Applications

Abstract

An important parameter of any LCD containing portable electronic device is a low power requirement. The reflective STN display mode offers a moderate to high information content display with low power consumption. One method to realise colour in this mode is to use a large retardation (dΔn) value in the cell. For a cell gap of 6 μm, and a retardation of ?1.5, a birefringence (Δn) of greater than +0.2 is necessary. To achieve such a value in an STN LC mixture, materials with broad nematic range, good solubility and a Δn value of <+0.25 are required.

A study of the trans-cyclohexyldifluorophenyltolane core structure was made and a large number of dialkyl, alkenyl-alkyl and alkoxy materials were synthesised and characterised. These materials possess low to moderate melting points, broad purely nematic mesophases, a high Δn and very good solubility in nematic LC hosts. They are suitable materials for inclusion in mixtures for colour reflective STN displays.     

Long-term influence of manure and mineral nitrogen applications on plant and soil 15N and 13C values from the Broadbalk Wheat Experiment

The Broadbalk Wheat Experiment at Rothamsted Research in the UK provides a unique opportunity to investigate the long-term impacts of environmental change and agronomic practices on plants and soils. We examined the influence of manure and mineral fertiliser applications on temporal trends in the stable N ((15)N) and C ((13)C) isotopes of wheat collected during 1968-1979 and 1996-2005, and of soil collected in 1966 and 2000. The soil delta(15)N values in 1966 and 2000 were higher in manure than the mineral N supplied soil; the latter had similar or higher delta(15)N values than non-fertilised soil. The straw delta(15)N values significantly decreased in all N treatments during 1968 to 1979, but not for 1996-2005. The straw delta(15)N values decreased under the highest mineral N supply (192 kg N ha(-1) year(-1)) by 3 per thousand from 1968 to 1979. Mineral N supply significantly increased to straw delta(13)C values in dry years, but not in wet years. Significant correlations existed between wheat straw delta(13)C values with cumulative rainfall (March to June). The cultivar Hereward (grown 1996-2005) was less affected by changes in environmental conditions (i.e. water stress and fertiliser regime) than Cappelle Desprez (1968-1979). We conclude that, in addition to fertiliser type and application rates, water stress and, importantly, plant variety influenced plant delta(13)C and delta(15)N values. Hence, water stress and differential variety response should be considered in plant studies using plant delta(13)C and delta(15)N trends to delineate past or recent environmental or agronomic changes.     

Simple Ion–Gas Mixtures as a Source of Key Molecules Relevant to Prebiotic Chemistry

Very simple chemistry can result in the rapid and high-yield production of key prebiotic inorganic molecules. The two reactions investigated here involve such simple systems, (a) carbon disulfide (CS₂) and acetate (CH₃COO¯) and (b) sulfur dioxide (SO₂) and formate (HCOO¯). They have been carried out under non-aqueous conditions, either in an organic solvent or with a powdered salt exposed to the requisite gas. Under such dry conditions the first reaction generated the thioacetate anion [CH₃COS]¯ while the second produced the radical [SO₂^·]¯anion. Anhydrous conditions are not rare and may have arisen on the early earth at sites where an interface between different phases (liquid/gas or solid/gas) could be generated. This is one way to rationalize the formation of molecules and ions (such as we have produced) necessary in the prebiotic world. Interpretation of our results provides insight into scenarios consistent with the more prominent theories of abiogenesis.     

Synthetic magnetic opals

We present studies of novel nanocomposites of BiNi impregnated into the structure of opals as well as inverse opals. Atomic force microscopy and high resolution elemental analyses show a highly ordered structure and uniform distribution of the BiNi filler in the matrix. These BiNi-based nanocomposites are found to exhibit distinct ferromagnetic-like ordering with transition temperature of about 675 K. As far as we know there exists no report in literature on any BiNi compound which is magnetic.     

Size selectivity of narrow pores

The selectivity of micropores and ion channels is examined for simple pore topologies within the framework of density functional theory of highly confined fluids. In an infinite cylindrical pore purely steric (excluded volume) effects are shown to lead to strong, nontrivial size selectivity, which is highly sensitive to the pore radius. A crude modeling of electrostatic effects does not alter the relative absorbance of Na+ and K+ ions in a significant way.