Chlorostannate(II) Ionic Liquids: Speciation, Lewis Acidity, and Oxidative Stability

The anionic speciation of chlorostannate(II) ionic liquids, prepared by mixing 1-alkyl-3-methylimidazolium chloride and tin(II) chloride in various molar ratios, chi(SnCl2), was investigated in both solid and liquid states. The room temperature ionic liquids were investigated by Sn-119 NMR spectroscopy, X-ray photoelectron spectroscopy, and viscometry. Crystalline samples were studied using Raman spectroscopy, single-crystal X-ray crystallography, and differential scanning calorimetry. Both liquid and solid systems (crystallized from the melt) contained [SnCl3](-) in equilibrium with Cl- when chi(SnCl2) < 0.50, [SnCl3](-) in equilibrium with [Sn2Cl5](-) when chi(SnCl2) > 0.50, and only [SnCl3](-) when chi(SnCl2) = 0.50. Tin(II) chloride was found to precipitate when chi(SnCl2) > 0.63. No evidence was detected for the existence of [SnCl4](-) across the entire range of chi(SnCl2) although such anions have been reported in the literature for chlorostannate(II) organic salts crystallized from organic solvents. Furthermore, the Lewis acidity of the chlorostannate(II)-based systems, expressed by their Gutmann acceptor number, has been determined as a function of the composition, chi(SnCl2), to reveal Lewis acidity for chi(SnCl2) > 0.50 samples comparable to the analogous systems based on zinc(II). A change of the Lewis basicity of the anion was estimated using H-1 NMR spectroscopy, by comparison of the measured chemical shifts of the C-2 hydrogen in the imidazolium ring. Finally, compositions containing free chloride anions (chi(SnCl2) < 0.50) were found to oxidize slowly in air to form a chlorostannate(IV) ionic liquid containing the [SnCl6](2-) anion.

Disjoint mixing operators

Chan and Shapiro showed that each (non-trivial) translation operator acting on the Fréchet space of entire functions endowed with the topology of locally uniform convergence supports a universal function of exponential type zero. We show the existence of d-universal functions of exponential type zero for arbitrary finite tuples of pairwise distinct translation operators. We also show that every separable infinite-dimensional Fréchet space supports an arbitrarily large finite and commuting disjoint mixing collection of operators. When this space is a Banach space, it supports an arbitrarily large finite disjoint mixing collection of C0-semigroups. We also provide an easy proof of the result of Salas that every infinite-dimensional Banach space supports arbitrarily large tuples of dual d-hypercyclic operators, and construct an example of a mixing Hilbert space operator T so that (T,T2) is not d-mixing.

Mixing operators on spaces with weak topology

We prove that a continuous linear operator T on a topological vector space X with weak topology is mixing if and only if the dual operator T' has no finite dimensional invariant subspaces. This result implies the characterization of hypercyclic operators on the space $\omega$ due to Herzog and Lemmert and implies the result of Bayart and Matheron, who proved that for any hypercyclic operator T on $\omega$, $T\oplus T$ is also hypercyclic.

Hypercyclic and mixing operator semigroups

We describe a class of topological vector spaces admitting a mixing uniformly continuous operator group $\{T_t\}_{t\in\C^n}$ with holomorphic dependence on the parameter $t$. This result covers those existing in the literature. We also
describe a class of topological vector spaces admitting no supercyclic strongly continuous operator semigroups $\{T_t\}_{t\geq 0}$.

Characterizing Pb mobilization from upland soils to streams using (206)Pb/(207)Pb isotopic ratios

Anthropogenically deposited lead (Pb) binds efficiently to soil organic matter, which can be mobilized through hydrologically mediated mechanisms, with implications for ecological and potable quality of receiving waters. Lead isotopic ((206)Pb/(207)Pb) ratios change down peat profiles as a consequence of long-term temporal variation in depositional sources, each with distinctive isotopic signatures. This study characterizes differential Pb transport mechanisms from deposition to streams at two small catchments with contrasting soil types in upland Wales, U.K., by determining Pb concentrations and (206)Pb/(207)Pb ratios from soil core profiles, interstitial pore waters, and stream water. Hydrological characteristics of soils are instrumental in determining the location in soil profiles of exported Pb and hence concentration and (206)Pb/(207)Pb ratios in surface waters. The highest Pb concentrations from near-surface soils are mobilized, concomitant with high dissolved organic carbon (DOC) exports, from hydrologically responsive peat soils with preferential shallow subsurface flows, leading to increased Pb concentrations in stream water and isotopic signatures more closely resembling recently deposited Pb. In more minerogenic soils, percolation of water allows Pb, bound to DOC, to be retained in mineral horizons and combined with other groundwater sources, resulting in Pb being transported from throughout the profile with a more geogenic isotopic signature. This study shows that (206)Pb/(207)Pb ratios can enhance our understanding of the provenances and transport mechanisms of Pb and potentially organic matter within upland soils.

Conversion Ratios, Efficiency and Obfuscation: A Study of the Impact of Changed UK Charity Accounting Requirements on External Stakeholders

Key stakeholders in the UK charity sector have, in recent years, advocated greater accountability for charity performance. Part of that debate has focussed on the use of conversion ratios as indicators of efficiency, with importance to stakeholders being contrasted with charities’ apparent reluctance to report such measures. Whilst, before 2005, conversion ratios could have been computed from financial statements, changes in the UK charity SORP have radically altered the ability of users to do this. This article explores the impact on the visibility of such information through an analysis of the financial statements of large UK charities before and after the 2005 changes. Overall, the findings suggest that, despite the stated intention of increasing transparency in respect of charity costs, the application of the changes has resulted in charities ‘managing’ the numbers and limiting their disclosures, possibly to the detriment of external stakeholders.

Evaluation of in Situ DGT Measurements for Predicting the Concentration of Cd in Chinese Field-Cultivated Rice: Impact of Soil Cd:Zn Ratios

DGT (diffusive gradients in thin-films) has been proposed as a tool for predicting Cd concentrations in rice grain, but there is a lack of authenticating data. To further explore the relationship between DGT measured Cd and concentrations in rice cultivated in challenging, metal degraded, field locations with different heavy metal pollutant sources, 77 paired soil and grain samples were collected in Southern China from industrial zones, a "cancer village" impacted by mining waste and an organic farm. In situ deployments of DGT in flooded paddy rice rhizospheres were compared with a laboratory DGT assay on dried and rewetted soil. Total soil concentrations were a very poor predictor of plant uptake. Laboratory and field deployed DGT assays and porewater measurements were linearly related to grain concentrations in all but the most contaminated samples where plant toxicity occurred. The laboratory DGT assay was the best predictor of grain Cd concentrations, accommodating differences in soil Cd, pollutant source, and Cd:Zn ratios. Field DGT measurements showed that Zn availability in the flooded rice rhizospheres was greatly diminished compared to that of Cd, resulting in very high Cd:Zn ratios (0.1) compared to commonly observed values (0.005). These results demonstrate the potential of the DGT technique to predict Cd concentrations in field cultivated rice and demonstrate its robustness in a range of environments. Although, field deployments provided important details about in situ element stoichiometry, due to the inherent heterogeneity of the rice rhizosphere soils, deployment of DGT in dried and homogenized soils offers the best possibility of a soil screening tool.

Improving the Fuel Economy of a Tuned 600cc FSAE Engine

To maintain its relevance, motorsport cannot be exempt from
the trend of increasing fuel economy. This bears obvious
competitive benefits as well, either in decreasing the
frequency of pit stops or the mass of fuel carried. Given the
increased points weighting of fuel economy for the Formula
Student (FS) competition, a complete analysis was performed
on the Queen's Formula Racing 600cc motorcycle engine in
preparation for the 2011 competition.
The criteria for such high performance fuel economy differ to
a degree from most mass transportation counterparts and were
divided into three distinct regimes; full load, part load and no
load conditions.
Full load positions naturally demand maximum torque for
performance but that does not imply that fuel savings cannot
be made whilst preserving this. The point at which maximum
torque is produced with minimum air -fuel ratio, Leanest
mixture for Best Torque (LBT), was therefore sought and
mapped for full load.
At part load, torque is less of a concern, and maintaining a
sustainable engine temperature and transient response become
more important. With decreasing AFR, engine temperatures
can rise dramatically so temperatures were measured close to
the exhaust port for a wide range of air-fuel ratios.
Competition track data was analysed to highlight key part load
operating regions and these were mapped according to
measured safe temperature limits. Torque response to a step
throttle change was also measured to ensure suitable engine
transient performance was maintained.
At no load conditions, with low engine speed only idle
conditions need to be satisfied. In the situation where the
engine is still at high speed without load, the engine is being
motored and no fuel is required. An overrun fuel cut was
employed to reflect this giving significant fuel savings. The
effect on torque and engine pickup was measured.
Modifications were also made to the fuel injector location to
improve fuel mixing and evaporation at this lower air flow
condition.
These mapping regimes were implemented and tested using
fully transient lap simulations using competition track data
and a four quadrant AC engine dynamometer. The experiment
indicated a reduction in fuel consumption for 22 laps of the FS
track from 5.08litres to 3.67litres, around 27% in total. The
actual fuel used at the 2011 competition was 3.6 litres while
placing 8th in the endurance event, further validating the
benefits of these mapping regimes.

Harmonic generation and wave mixing in nonlinear metamaterials and photonic crystals (Invited paper)

The basic concepts and phenomenology of wave mixing and harmonic generation are reviewed in context of the recent advances in the enhanced nonlinear activity in metamaterials and photonic crystals. The effects of dispersion, field confinement and phase synchronism are illustrated by the examples of the on-purpose designed artificial nonlinear structures. (c) 2012 Wiley Periodicals, Inc. Int J RF and Microwave CAE 22:469482, 2012.

Gaussian pulse mixing and scattering by finite nonlinear layered structures

Multiple Gaussian pulse interactions and scattering in the nonlinear layered dielectric structures have been examined. The Gaussian pulses with different centre frequencies and lengths are incident at oblique angles on the finite stack of nonlinear dielectric layers. The properties of the reflected and refracted waveforms and the effects of the structure and the incident pulses' parameters on the mixing process are discussed. It is shown that the efficiency of forward emission at the combinatorial frequency can be considerably increased when the wavelengths of interacting pulses are close to the edges of electromagnetic bandgap. © 2012 IEEE.

Gaussian pulse mixing by nonlinear photonic crystals

The properties of mixing and scattering of two non-collinear Gaussian pulses with different centre frequencies and lengths, incident on the finite nonlinear periodic layered dielectric structures, have been analysed. It is shown that at the backward emission grows with the number of layers and can reach the level of the forward emission in the direction of combinatorial frequency scattering.

Wave mixing by periodic nonlinear semiconductor multilayers

The properties of the combinatorial frequency generation and wave scattering by periodic stacks of nonlinear passive semiconductor layers are explored. It is demonstrated that the nonlinearity in passive weakly nonlinear semiconductor medium has the resistive nature associated with the dynamics of carriers. The features of the combinatorial frequency generation and the effects of the pump wave scattering and parameters of the constituent semiconductor layers on the efficiency of the frequency mixing are discussed and illustrated by the examples. © 2013 IEICE.