Integrating spatial dependence into stochastic frontier analysis

An approach to incorporate spatial dependence into stochastic frontier analysis is developed and applied to a sample of 215 dairy farms in England and Wales. A number of alternative specifications for the spatial weight matrix are used to analyse the effect of these on the estimation of spatial dependence. Estimation is conducted using a Bayesian approach and results indicate that spatial dependence is present when explaining technical inefficiency.

Path dependence and Britain’s "coal wagon problem"

This article explores the nature and impact of path dependence in British rail coal haulage before 1939. It examines the factors which locked Britain's railways into a system of small coal wagons with highly fragmented ownership, the cost penalties of this system, and the reasons that attempts at modernization were unsuccessful. The analysis highlights the importance of decentralized ownership of a highly durable installed base of complementary infrastructure. Technical and institutional interrelatedness blocked incremental modernization, while the political requirement to compensate private wagon owners for the loss of their wagon stock made wholesale rationalization financially unattractive.

Effect of salt on the compression of polyelectrolyte brushes in a theta solvent

Classical strong-stretching theory (SST) predicts that, as opposing polyelectrolyte brushes are compressed together in a salt-free theta solvent, they contract so as to maintain a finite polymer-free gap, which offers a potential explanation for the ultra-low frictional forces observed in experiments even with the application of large normal forces. However, the SST ignores chain fluctuations, which would tend to close the gap resulting in physical contact and in turn significant friction. In a preceding study, we examined the effect of fluctuations using self-consistent field theory (SCFT) and illustrated that high normal forces can still be applied before the gap is destroyed. We now look at the effect of adding salt. It is found to reduce the long-range interaction between the brushes but has little effect on the short-range part, provided the concentration does not enter the salted-brush regime. Consequently, the maximum normal force between two planar brushes at the point of contact is remarkably unaffected by salt. For the crossed-cylinder geometry commonly used in experiments, however, there is a gradual reduction because in this case the long-range part of the interaction contributes to the maximum normal force.

The dependence of contrail formation on the weather pattern and altitude in the North Atlantic

Aircraft flying through cold ice-supersaturated air produce persistent contrails which contribute to the climate impact of aviation. Here, we demonstrate the importance of the weather situation, together with the route and altitude of the aircraft through this, on estimating contrail coverage. The results have implications for determining the climate impact of contrails as well as potential mitigation strategies. Twenty-one years of re-analysis data are used to produce a climatological assessment of conditions favorable for persistent contrail formation between 200 and 300 hPa over the north Atlantic in winter. The seasonal-mean frequency of cold ice-supersaturated regions is highest near 300 hPa, and decreases with altitude. The frequency of occurrence of ice-supersaturated regions varies with large-scale weather pattern; the most common locations are over Greenland, on the southern side of the jet stream and around the northern edge of high pressure ridges. Assuming aircraft take a great circle route, as opposed to a more realistic time-optimal route, is likely to lead to an error in the estimated contrail coverage, which can exceed 50% for westbound north Atlantic flights. The probability of contrail formation can increase or decrease with height, depending on the weather pattern, indicating that the generic suggestion that flying higher leads to fewer contrails is not robust.

Synthesis of beaded poly(vinyl ether) solid supports with unique solvent compatibility

Poly(vinyl ether) gels SLURPS (Superior Liquid Uptake Resin for Polymer-supported synthesis) with low cross-linking levels have been synthesized for the first time in beaded form using a non-aqueous inverse suspension polymerisation approach. The synthetic protocol was optimized with regards to several parameters including reactions conditions, type and concentration of suspension stabilizer and controlled low temperature addition of co-initiator. Particle size measurements confirm the production of beads with average diameters of 700e950 mm. Optimization of the monomer composition of the poly (vinyl ether) gels resulted in a novel beaded polymer support with considerably improved as well as unique swelling characteristics in solvents ranging from hexane to water. The synthetic utility of the new gel was confirmed by carrying out a set of transformations with complete conversion leading to a useful amino and hydroxy terminated solid-phase precursor resin. Reaction progress could be monitored easily by 1H and 13C gel-phase NMR.

Solvent-dependent modulation of metal–metal electronic interactions in a dinuclear cyanoruthenate complex: a detailed electrochemical, spectroscopic and computational study

The dinuclear complex [{Ru(CN)4}2(μ-bppz)]4− shows a strongly solvent-dependent metal–metal electronic interaction which allows the mixed-valence state to be switched from class 2 to class 3 by changing solvent from water to CH2Cl2. In CH2Cl2 the separation between the successive Ru(II)/Ru(III) redox couples is 350 mVand the IVCT band (from the UV/Vis/NIR spectroelectrochemistry) is characteristic of a borderline class II/III or class III mixed valence state. In water, the redox separation is only 110 mVand the much broader IVCT transition is characteristic of a class II mixed-valence state. This is consistent with the observation that raising and lowering the energy of the d(π) orbitals in CH2Cl2 or water, respectively, will decrease or increase the energy gap to the LUMO of the bppz bridging ligand, which provides the delocalisation pathway via electron-transfer. IR spectroelectrochemistry could only be carried out successfully in CH2Cl2 and revealed class III mixed-valence behaviour on the fast IR timescale. In contrast to this, time-resolved IR spectroscopy showed that the MLCTexcited state, which is formulated as RuIII(bppz˙−)RuII and can therefore be considered as a mixed-valence Ru(II)/Ru(III) complex with an intermediate bridging radical anion ligand, is localised on the IR timescale with spectroscopically distinct Ru(II) and Ru(III) termini. This is because the necessary electron-transfer via the bppz ligand is more difficult because of the additional electron on bppz˙− which raises the orbital through which electron exchange occurs in energy. DFT calculations reproduce the electronic spectra of the complex in all three Ru(II)/Ru(II), Ru(II)/Ru(III) and Ru(III)/Ru(III) calculations in both water and CH2Cl2 well as long as an explicit allowance is made for the presence of water molecules hydrogen-bonded to the cyanides in the model used. They also reproduce the excited-state IR spectra of both [Ru(CN)4(μ-bppz)]2– and [{Ru(CN)4}2(μ-bppz)]4− very well in both solvents. The reorganization of the water solvent shell indicates a possible dynamical reason for the longer life time of the triplet state in water compared to CH2Cl2.

Formation of vesicles through solvent assisted self-assembly of hydrophobic pentapeptides: encapsulation and pH responsive release of dyes by the vesicles

In the biomimetic design two hydrophobic pentapetides Boc-Ile-Aib-Leu-Phe-Ala-OMe ( I) and Boc-Gly-Ile-Aib-Leu-Phe-OMe (II) (Aib: alpha-aminoisobutyric acid) containing one Aib each are found to undergo solvent assisted self-assembly in methanol/water to form vesicular structures, which can be disrupted by simple addition of acid. The nanovesicles are found to encapsulate dye molecules that can be released by the addition of acid as confirmed by fluorescence microscopy and UV studies. The influence of solvent polarity on the morphology of the materials generated from the peptides has been examined systematically, and shows that fibrillar structures are formed in less polar chloroform/petroleum ether mixture and vesicular structures are formed in more polar methanol/water. Single crystal X-ray diffraction studies reveal that while beta-sheet mediated self-assembly leads to the formation of fibrillar structures, the solvated beta-sheet structure leads to the formation of vesicular structures. The results demonstrate that even hydrophobic peptides can generate vesicular structures from polar solvent which may be employed in model studies of complex biological phenomena.

Assessment of surface winds over the Atlantic, Indian and Pacific Ocean sectors of the Southern Ocean in CMIP5 models: historical bias, forcing response, and state dependence

An assessment of the fifth Coupled Models Intercomparison Project (CMIP5) models’ simulation of the near-surface westerly wind jet position and strength over the Atlantic, Indian and Pacific sectors of the Southern Ocean is presented. Compared with reanalysis climatologies there is an equatorward bias of 3.7° (inter-model standard deviation of ± 2.2°) in the ensemble mean position of the zonal mean jet. The ensemble mean strength is biased slightly too weak, with the largest biases over the Pacific sector (-1.6±1.1 m/s, 27 -22%). An analysis of atmosphere-only (AMIP) experiments indicates that 41% of the zonal mean position bias comes from coupling of the ocean/ice models to the atmosphere. The response to future emissions scenarios (RCP4.5 and RCP8.5) is characterized by two phases: (i) the period of most rapid ozone recovery (2000-2049) during which there is insignificant change in summer; and (ii) the period 2050-2098 during which RCP4.5 simulations show no significant change but RCP8.5 simulations show poleward shifts (0.30, 0.19 and 0.28°/decade over the Atlantic, Indian and Pacific sectors respectively), and increases in strength (0.06, 0.08 and 0.15 m/s/decade respectively). The models with larger equatorward position biases generally show larger poleward shifts (i.e. state dependence). This inter-model relationship is strongest over the Pacific sector (r=-0.89) and insignificant over the Atlantic sector (r=-0.50). However, an assessment of jet structure shows that over the Atlantic sector jet shift is significantly correlated with jet width whereas over the Pacific sector the distance between the sub-polar and sub-tropical westerly jets appears to be more important.

‘What Price Solidarity? Nuclear Dependence in NATO, 1949-1967’

Archive-based study of the dependence of NATO member states on the USA as nuclear guarantor, and the problems this entailed.

Lightly branched comb polyesters: application in fast drying solvent-borne coating formulations

Novel oxazoline-based comb-polymers possessing linoleyl or oleic side chains have been synthesized and used to produce low viscosity coatings. Inclusion of the polymers in model paint formulations results in coatings that exhibit faster drying times than commercially available alkyd resin formulations. The comb polymers were produced from diol substituted oxazoline monomers that were synthesized through a scalable, solvent free protocol and purified by simple recrystallisation. Co-polymerisation of the oxazolines with adipic acid at 160 °C in the bulk resulted in the targeted polyester comb type polymers. The polymers were soluble in a range of organic solvents and compatible with commercial alkyd resins. Model paint formulations containing up to 40 wt% of the linoleyl-based comb polymers exhibited a dramatic reduction in viscosity (from 35 to 13 Poise at 25 °C) with increasing quantities of polymer added. Dynamic mechanical analysis (DMA) studies revealed that the drying rate of the model paint formulations containing the comb polymers was enhanced when compared with that of commercial alkyd resins.

Dependence of winter precipitation over Portugal on NAO and baroclinic wave activity

The relationship between winter (DJF) rainfall over Portugal and the variable large scale circulation is addressed. It is shown that the poles of the sea level pressure (SLP) field variability associated with rainfall variability are shifted about 15° northward with respect to those used in standard definitions of the North Atlantic Oscillation (NAO). It is suggested that the influence of NAO on rainfall dominantly arises from the associated advection of humidity from the Atlantic Ocean. Rainfall is also related to different aspects of baroclinic wave activity, the variability of the latter quantity in turn being largely dependent on the NAO. A negative NAO index (leading to increased westerly surface geostrophic winds into Portugal) is associated with an increased number of deep (ps<980 hPa) surface lows over the central North Atlantic and of intermediate (980

The dependence of southern ocean meridional overturning on wind stress

An eddy-resolving numerical model of a zonal flow, meant to resemble the Antarctic Circumpolar Current, is described and analyzed using the framework of J. Marshall and T. Radko. In addition to wind and buoyancy forcing at the surface, the model contains a sponge layer at the northern boundary that permits a residual meridional overturning circulation (MOC) to exist at depth. The strength of the residual MOC is diagnosed for different strengths of surface wind stress. It is found that the eddy circulation largely compensates for the changes in Ekman circulation. The extent of the compensation and thus the sensitivity of the MOC to the winds depend on the surface boundary condition. A fixed-heat-flux surface boundary severely limits the ability of the MOC to change. An interactive heat flux leads to greater sensitivity. To explain the MOC sensitivity to the wind strength under the interactive heat flux, transformed Eulerian-mean theory is applied, in which the eddy diffusivity plays a central role in determining the eddy response. A scaling theory for the eddy diffusivity, based on the mechanical energy balance, is developed and tested; the average magnitude of the diffusivity is found to be proportional to the square root of the wind stress. The MOC sensitivity to the winds based on this scaling is compared with the true sensitivity diagnosed from the experiments.