Methane is an abundant material that presents huge potential as a feedstock for chemicals synthesis. It is widely available as the major constituent of natural gas, but becomes also increasingly more obtainable from sustainable sources, such as biogas and landfill gas, and unconventional sources, such as shale gas, coalbed methane and methane hydrates. Moreover, it has more than 25 times higher 100-year global warming potential to that of CO2, so the need to develop efficient methane utilization methods towards value-added products is more than clear. Among many uses, methane has been identified as a very promising raw material for the production of ethylene. The latter is the most widely produced base chemical, used e.g. for polymers, but its production depends on crude oil, generating the vast majority of CO2 process emissions in the UK chemical industry. In fact, under the Kyoto Protocol and the UK Climate Change Act, UK has specific international and domestic targets for reducing greenhouse gas emissions. 11% of these are represented by methane originating from agriculture, waste management and the energy industry, hence the production of ethylene from methane can be a promising process with multiple benefits for these sectors. The high temperatures needed, though, for the activation of the stable methane molecule via thermal-catalysis, in conjunction with the use of oxidants to facilitate thermodynamically favourable routes, result in significant amounts of undesired carbon oxide by-products in the currently applied upgrading methods. The combination of non-thermal plasma with catalysis has recently emerged as a promising technology to enable catalysts to operate at low temperatures. In non-thermal plasmas, the overall gas temperature is as low as ambient, however electrons are highly energetic resulting in collisions that easily break down molecule bonds, producing various reactive species like free radicals, excited states and ions that participate in subsequent reactions. The strong non-equilibrium character of these plasmas has been shown to even allow thermodynamically unfavourable reactions to occur under ambient conditions. Being able to carry out direct methane coupling towards ethylene at low temperatures at non-oxidative conditions would present significant benefits, ranging from carbon oxides-free products to drastically reduced energy requirements and would enable alternate production routes towards polymers and high octane-number fuels. Combining the high reactivity of plasma with the high selectivity of the catalytic surface has a huge potential to unravel these benefits, which can further be enhanced by the use of sustainable electricity for the generation of the plasma. Nonetheless, the interaction between non-thermal plasma and catalysts is a highly complex phenomenon. There has been a considerable amount of experimental work aimed at understanding the underlying elementary processes, however most mechanistic details are not yet elucidated. The combination of experimental, theoretical and modelling studies is needed to gain a more fundamental insight. Microkinetic modelling is proposed as a novel approach to enhance the understanding and enable the optimisation of plasma-assisted heterogeneous catalytic reaction systems. With support from BASF, UK and a carefully designed experimental program, the novelty of the proposed project lies on the, for the first time, systematic consideration of all elementary reaction processes taking place in the plasma phase and on the catalyst surface and the explicit description of the interactions among them. The project is very timely, addressing topics in EPSRC's portfolio in relation to energy efficiency and alternative fuels and sources of chemicals. Successful implementation will result in the development of predictive computational tools that can be used to accelerate the design of new processes, reducing the needs for experimentation and associated costs.

Oilseed rape (OSR) crops in the UK are threatened by two main fungal diseases: light leaf spot (LLS) caused by Pyrenopeziza brassicae (lineage 1) and Phoma caused by Plenodomus lingam / Plenodomus biglobosus. In the UK, Phoma and LLS each cause >£100M in crop losses despite costly fungicide applications (primarily DeMethylation Inhibitors (DMIs)). New variants and fungicide resistant strains of these pathogens have been reported recently from other geographic regions and may threaten UK OSR crops should they emerge there. The first P. brassicae risk relates to decreased fungicide sensitivity, where DMI resistance was found in European P. brassicae populations including the UK. Decreased DMI sensitivity is mediated by alterations in the CYP51 gene, including point mutations in the coding region (G460S or S508T) and inserts in the upstream control (promoter) region. Fungal isolates from Ireland with a G460S+S508T genotype had a much reduced DMI sensitivity. Therefore, work is required to monitor for changes in the fungicide sensitivity status of UK P. brassicae populations and screen for the G460S+S508T genotype. An additional risk from P. brassicae has recently identified a lineage 2 variant responsible for chlorotic leaf spot outbreaks in the US Pacific northwest. There lineage 2 appears to be a recent introduction that has undergone rapid invasive spread. This damaging variant now threatens adjacent Canadian OSR production and could affect European OSR production, particularly given the unknown implications of lineages 1 and 2 coming into contact and increasing use of brassica cover crop seed produced in the US Pacific northwest. Research is thus required to monitor the lineages currently present in UK pathogen populations. For Phoma, one threat to UK OSR comes from fungicide resistant P. lingam / P. biglobosus. Until 2015, in vitro testing had shown both pathogens to be sensitive to DMIs. However, recent work has shown DMI resistance in 15-24% of the P. lingam population in Australia and the Czech Republic. Such resistance is associated with inserts in the CYP51 promoter region. Whether DMI resistance has also emerged in P. lingam, and also P. biglobosus, pathogen populations in the UK requires investigation. A further Phoma threat relates to the recent discovery in Europe of the P. biglobosus 'canadensis' subclade. Prior to this only the P. biglobosus 'brassicae' subclade had been reported in Europe. There is increasing evidence that the P. biglobosus subclade variants pose different risks to OSR health, that may require distinct disease management strategies. Data is thus required on the pathogen population structure of subclades present in the UK OSR crops. In the proposed project, we will work with our collaborator, BASF who will collect OSR leaves from field trials showing Phoma (Jan 23) and LLS (Mar 23) symptoms. At least ten trials will be sampled from the UK and potentially some additional EU locations. Samples will be sent to RRes for fungal isolation, with the aim of collecting 50-100 isolates each of P. brassicae, P. lingam, and P. biglobosus . These isolates will be deposited into the RRes and OREGIN culture collections. Isolate DNA will be extracted, and P. brassicae strains lineage typed via lineage-specific amplification. Plenodomus isolates will be typed using species-specific DNA primers specific for P. lingam / P. biglobosus. For P. biglobosus isolates, the internal transcribed spacer (ITS) region will be sequenced to determine subclade (subgroup) identities. Isolates of all three species will be screened in vitro for sensitivity to fungicides, including DMIs (prothioconazole-desthio, mefentrifluconazole) and a QoI (pyraclostrobin), and for the least DMI sensitive isolates, CYP51 will be examined molecularly to explore possible resistance mechanisms.

Pressurised gyration processes, which are the focus of this grant application is an emerging technique that utilises centrifugal force and the dynamic fluid flow to jet out advanced functional materials consistently. This technique has shown great potential in overcoming the limitations of the existing techniques to manufacture functional materials and structures that can safely, consistently and cost-effectively be up-scaled. Thus in the past 5 years pressurised gyration, and several sister-processes (infusion gyration, melt pressurised gyration, pressure-coupled infusion gyration) have been developed and applied to prepare functional materials for different applications. The overall motivation of this research is to manufacture a wide variety of "core-sheath" structures, that are not fully exploited commercially in functional applications (e.g. healthcare) simply because of lack of innovative manufacturing. The overall aim of the project is to develop pressurised gyration as a novel means of effective manufacturing of multi-material core-sheath structures. Therefore, a very significant aspect of this project is to develop a pressurised gyration technique based on exploratory experimental evidence, to generate core-sheath structures on a large scale. A newly created exploratory device containing two chambers has been used to manufacture a wide range of polymer nanofibres with different polymers in both aqueous and non-aqueous solutions as core and sheath components at various concentrations, pressures and rotating speeds. In addition antibacterial metallic nanoparticles loaded nanofibres were also produced using this device. The manufacturing of core-sheath structure has been demonstrated by using a high speed camera and microscopy. Thus, the proposed research pays attention on developing a new high yield device for manufacturing layered core-sheath structures based on our existing preliminary device. Also a considerable effort will be devoted to analyse the new process to make quantitative assessment in order to understand the theoretical issues. It will focus on investigating the forming of core-sheath fibres and core-shell capsules from micro-nanoscale. Functionalising those core-sheath structures produced with additions of other, organic, inorganic and particulate materials will be an important feature. The processed core-sheath structures will be characterised with advanced tools to explore their unique physical, chemical and biological properties.

The proposed research describes a novel engineering approach to point-of-need delivery of controlled release medications for wound and burn treatment, based on an innovative portable device which allows in situ generation of nano-/micro fibrous meshes. These fibres can contain multiple layers of active pharmaceutical ingredients (APIs) in a core-shell configuration (potentially up to at least four layers), allowing compartmentalisation of agents ranging from proteins to low molecular weight antibiotics and including innovative therapeutic oligosaccharides. Nano- and microfibres with compartmentalised structures are currently attracting a great deal of interest within the drug delivery arena due to the advantages of high surface area, high fluid permeation, ready separation of incompatible drugs into physically distinct environments, the ability to tune drug release rates via incorporation into controlled release polymers and the physical flexibility and versatility of the macroscopic mesh structure. Furthermore, given recent emphasis on combination therapies, the possibility of generating compartmentalised systems using, for example, coaxial and multi-axial electrohydrodynamic (EHD) technology is highly attractive. One example of such an application is the treatment of wounds and burns, whereby the flexibility of shape of the meshes to neatly fill the lesion, the high fluid permeation of the mesh facilitating tissue regrowth, the tunable release of therapeutic agents and the biodegradation of the mesh are all perfectly feasible attributes that would render a drug-loaded nanofibre approach highly advantageous. A further possibility, not yet realised in practice, is the generation of micro/nanofibres in situ at the point of trauma. Were this to be possible, then valuable time to treatment would be saved as agents designed to stop bleeding, prevent infection, reduce pain or promote healing could be administered quickly in a form which could be applied to a wide range of lesion architectures and areas. Indeed, a portable system could also be used in conflict situations, for patients with mobility difficulties being treated at home for conditions such as diabetic ulcer or for otherwise medically inaccessible regions such as refugee camps, while the use of biodegradable polymer bases would allow the mesh to simply be resorbed over a period of time without damage to the lesion associated with dressing removal. Moreover, the capability to generate highly permeable microfibrous meshes at point-of-need enables an alternative nasal route for sustained and controlled drug release when oral/intravenous drug delivery is rendered impractical during emergencies where the patient may be unconscious with poor vein access (e.g. heroin overdose) or may even be having a seizure (e.g. status epilepticus). Overall, therefore, a 'field' system for simple and inexpensive administration of complex drug-loaded fibre meshes would have huge patient benefit for a wide range of conditions and would represent a significant breakthrough in engineering-led therapeutic development. Clearly, however, such a system would present a series of profound engineering challenges. Despite recent advances in fibre production technology, the generation of fibres with compartmentalised systems requires bulky, expensive (>£20k), bench-top high voltage supply and syringe pumps that are confined to a laboratory or factory environment. Developing a portable, hand-held, cheaper (<£2k), miniature EHD device that can generate multilayered therapeutic materials could revolutionise the practical applicability of micro/nanofibres. We believe, based on our work to date, that such an approach is now possible and the project outlined here, which focuses on the engineering issues associated with the development of our prototype device and the challenges of drug incorporation, would lay the foundation for the use of this approach in a wide range of therapeutic applications.

Oilseed rape, grown for the production of edible vegetable oil, biodiesel and animal feed, was until recently the UK's third most valuable crop and its principal oil crop. However, pressure from the crop pest, cabbage flea stem beetle (CSFB), has resulted in large losses in yield and profits. Furthermore, as a consequence of the war in the Ukraine, imports of edible oils from the Ukraine and Russia (the world's two biggest exporters) are at an all-time low (https://www.economist.com/business/2022/05/07/the-war-in-ukraine-is-rocking-the-market-for-edible-oils). Thus, it has never been more timely to begin measures to restore yields of oilseed rape crops in the UK. This proposal focuses on mitigating the damaging effects of the CSFB by developing a model to predict the occurrence and abundance of the pest so that prevention measures can be taken to protect the crop when it is most vulnerable. The CSFB has several life stages, e.g. egg, larvae, pupae, adult, which affect the crop in different ways. For example, the adults eat the newly planted crops in Autumn, whereas larvae burrow into the leaf stems causing damage to plants over winter and into the following spring. Furthermore, the timing of the life stages depends on local weather conditions. Air temperature is known to affect the developmental rates - e.g. the time taken for the eggs to hatch, the larvae to mature to adulthood etc, and wind speed and temperature affect the ability of the adults to migrate to new crops. Our model is process-based, meaning that when we run the model it steps forward through time and tells us the current life stage and abundance of the pest at every moment in time. Currently we only have a simple prototype model of the CSFB life cycle which does not contain information on how local weather affects the pest phenology. One aspect of this proposal is to code weather dependency into the model so that we can predict year-to-year variability and the effects of climate change on pest damage to oilseed rape. Another aspect of the proposal is collating all data currently available for CSFB and using this for building or validating our new model. The long-term aim is that our model will be developed into a decision support system (DSS) that can be used by farmers and agronomists for crop management. To this end, knowledge transfer is a key component of our project. A stakeholder group will be formed and will meet at least twice during the lifetime of the project; once at the start of the project and once in the second half of the project. The stakeholder group will be made up of representatives from the industry partners, BASF and Frontier and other interested parties. These stakeholders represent important industry actors that are influential in the development and use of DSS for pest management. The initial workshop will enable stakeholders to influence the design of the model from an early stage; the second workshop will allow stakeholders to trial the model in its development and hence inform on how the model can be further developed be applicable in real situations. Via ADAS, the model will be socialised with growers and advisors attending ADAS Farming Association conferences. There are several ADAS Farming Associations across England, and their membership consists of local farmers and agronomists. As such, these events represent an ideal opportunity to receive feedback from those tackling the issue of CSFB first-hand. Thus, this proposal combines industry partners (BASF and Frontier), biologists with knowledge of CSFB and its chemical and non-chemical control (HAU and ADAS) along with mathematical modellers and statisticians (BioSS) to provide a fully inter-disciplinary approach to restoring yields of oilseed rape through mitigation of the CSFB.