Halometallate ionic liquids and deep eutectic solvents

Ionic liquids and deep eutectic solvents have engendered wide and increasing research interest in recent years due to their interesting and tunable physical, chemical and solvation properties. The addition of metal halide salts to ionic liquids and deep eutectic solvents results in HMILs (halometallate ionic liquids) and HMDESs (halometallate deep eutectic solvents). A detailed understanding of these systems is vital to develop a relationship between chemical structure and properties which would enhance the useful application of HMILs and HMDESs. In this work bismuth based HMILs and nickel based HMDESs were studied via DFT calculations. The aims of studying both systems were: to understand the speciation in solution, and the driving forces determining speciation; to analyse the intermolecular interactions present; and to investigate the electronic structure of the systems. In the bismuth HMIL system the anionic speciation was elucidated; Cl{ , [BiCl4]{ , [BiCl5]2{ , [Bi2Cl7]{ , [Bi2Cl8]2{ , and [Bi2Cl9]3{ anions can be accessed by varying the mole fraction of BiX3 added to the ionic liquid (X = Cl, Br, I). An associative halide exchange mechanism was found, with a low barrier to reaction indicating that rapid exchange of halide atoms is likely to occur in solution. Experimental valence band XPS was reproduced, indicating that the theoretical method describes the electronic structure of HMILs well. In the nickel HMDES system speciation was found to be in uenced by both enthalpic and entropic factors. Highly charged complexes were enthalpically favoured over neutral species due to stronger intermolecular interactions, including doubly ionic hydrogen bonds. The previously reported thermochemical equilibrium between octahedral (low temperature) and tetrahedral (high temperature) species was rationalised via thermochemical analysis; the octahedral species is enthalpically favoured and the tetrahedral species entropically favoured. As temperature is a factor in the entropic part of Gibbs free energy the tetrahedral species becomes favoured at elevated temperatures.Open Acces

The Beginning of the End: A Look at the Causes of the Schism in the Methodist Episcopal Church

Examines the Methodist Episcopal Church schism of 1844, especially the role of differing northern and southern views of slavery. The PDF includes the author\u27s entry submission essay

Second fiddle: a review of lesser-known volatile binding media in conservation

This paper is published in the book ‘Subliming Surfaces: Volatile Binding Media in Heritage Conservation’, ed. Christina Rozeik (University of Cambridge Museums, 2018), pp. 13-20.While cyclododecane (CDD) is well known to conservators as a versatile material for temporary treatments, other volatile binding media have also been tested for use in conservation. Camphene, tricyclene and menthol have all been suggested as alternatives, each having slightly different properties that can make them more suitable for some applications. This paper reviews the literature about these materials and summarises what is known about their characteristics. Concern about possible health effects from CDD has led to recent interest in the alternatives, particularly menthol. Menthol is inexpensive, has good working properties and forms a fine-grained film. It has potential uses particularly for moulding and on archaeological sites, where it may even perform better than CDD in slightly damp conditions. These benefits need to be offset against its strongly irritant vapour. Camphene and tricyclene sublime rapidly and once seemed promising materials for very short term treatments. However, camphene is unstable and requires an antioxidant additive, which may leave residues after sublimation. It is also now recognised as more hazardous than previously thought. Recent research suggests that menthyl lactate and cyclododecanone also have potential as alternatives to CDD, though more work is needed to understand these materials fully.Non

Genotype-environment associations support a mosaic hybrid zone between two tidal marsh birds

Local environmental features can shape hybrid zone dynamics when hybrids are bounded by ecotones or when patchily distributed habitat types lead to a corresponding mosaic of genotypes. We investigated the role of marsh-level characteristics in shaping a hybrid zone between two recently diverged avian taxa – Saltmarsh (Ammodramus caudacutus) and Nelson\u27s (A. nelsoni) sparrows. These species occupy different niches where allopatric, with caudacutus restricted to coastal marshes and nelsoni found in a broader array of wetland and grassland habitats and co-occur in tidal marshes in sympatry. We determined the influence of habitat types on the distribution of pure and hybrid sparrows and assessed the degree of overlap in the ecological niche of each taxon. To do this, we sampled and genotyped 305 sparrows from 34 marshes across the hybrid zone and from adjacent regions. We used linear regression to test for associations between marsh characteristics and the distribution of pure and admixed sparrows. We found a positive correlation between genotype and environmental variables with a patchy distribution of genotypes and habitats across the hybrid zone. Ecological niche models suggest that the hybrid niche was more similar to that of A. nelsoni and habitat suitability was influenced strongly by distance from coastline. Our results support a mosaic model of hybrid zone maintenance, suggesting a role for local environmental features in shaping the distribution and frequency of pure species and hybrids across space

Genotype-environment associations support a mosaic hybrid zone between two tidal marsh birds

Local environmental features can shape hybrid zone dynamics when hybrids are bounded by ecotones or when patchily distributed habitat types lead to a corresponding mosaic of genotypes. We investigated the role of marsh-level characteristics in shaping a hybrid zone between two recently diverged avian taxa – Saltmarsh (Ammodramus caudacutus) and Nelson\u27s (A. nelsoni) sparrows. These species occupy different niches where allopatric, with caudacutus restricted to coastal marshes and nelsoni found in a broader array of wetland and grassland habitats and co-occur in tidal marshes in sympatry. We determined the influence of habitat types on the distribution of pure and hybrid sparrows and assessed the degree of overlap in the ecological niche of each taxon. To do this, we sampled and genotyped 305 sparrows from 34 marshes across the hybrid zone and from adjacent regions. We used linear regression to test for associations between marsh characteristics and the distribution of pure and admixed sparrows. We found a positive correlation between genotype and environmental variables with a patchy distribution of genotypes and habitats across the hybrid zone. Ecological niche models suggest that the hybrid niche was more similar to that of A. nelsoni and habitat suitability was influenced strongly by distance from coastline. Our results support a mosaic model of hybrid zone maintenance, suggesting a role for local environmental features in shaping the distribution and frequency of pure species and hybrids across space

A Scale-Explicit Framework for Conceptualizing the Environmental Impacts of Agricultural Land Use Changes

Demand for locally-produced food is growing in areas outside traditionally dominant agricultural regions due to concerns over food safety, quality, and sovereignty; rural livelihoods; and environmental integrity. Strategies for meeting this demand rely upon agricultural land use change, in various forms of either intensification or extensification (converting non-agricultural land, including native landforms, to agricultural use). The nature and extent of the impacts of these changes on non-food-provisioning ecosystem services are determined by a complex suite of scale-dependent interactions among farming practices, site-specific characteristics, and the ecosystem services under consideration. Ecosystem modeling strategies which honor such complexity are often impenetrable by non-experts, resulting in a prevalent conceptual gap between ecosystem sciences and the field of sustainable agriculture. Referencing heavily forested New England as an example, we present a conceptual framework designed to synthesize and convey understanding of the scale- and landscape-dependent nature of the relationship between agriculture and various ecosystem services. By accounting for the total impact of multiple disturbances across a landscape while considering the effects of scale, the framework is intended to stimulate and support the collaborative efforts of land managers, scientists, citizen stakeholders, and policy makers as they address the challenges of expanding local agriculture

Expanding the Miscanthus market in the UK:Growers in profile and experience, benefits and drawbacks of the bioenergy crop

Research Funding Biotechnology and Biological Sciences Research Council. Grant Number: BB/V011553/1 EPSRC Centre for Doctoral Training in Additive Manufacturing. Grant Number: EP/S000771/1 UK Supergen Bioenergy Hub. Grant Number: RG15855Peer reviewedPublisher PD