Chemistry (PhD)

The project will develop synthetic routes to novel bridged bicyclic amines, non-racemic three-dimensional drug-like scaffolds, using flexible and scalable catalysis. It will extend chemistry we have previously reported in Chem. Commun. 2012, 48, 4836 and Chem. Commun. 2013, 49, 8931.

Self-funding applicants are welcome. In addition to tuition fees, bench fees of £6.000 per annum are required.

Home/EU -June 30th/October 31st and Overseas May 31st/September 30th

• Dr Duncan Gill

Nuclear Magnetic Resonance (NMR) is an incredibly powerful and versatile analytical technique. Providing structural and dynamic information at the atomic level NMR is ubiquitous within the physical sciences but development of new applications, or even routine exploitation in the case of volume limited samples, is hindered by low intrinsic sensitivity. NMR sensitivity can be boosted by transferring ‘spin polarization’ from unpaired electrons. Whilst such transfer has conventionally been achieved using microwave pumping of electronic transitions in so-called dynamic nuclear polarization (DNP) experiments, there are major technical challenges to this approach. Recently we have demonstrated a method using optical excitation instead of microwave irradiation. This not only overcomes a number of technical challenges, but also potentially offers much higher sensitivity gains above the maximum possible in microwave DNP. This PhD project will build upon the recent proof of principle demonstration of optically pumped DNP, investigating multiple factors such as illumination time, illumination wavelength, magnetic field strength and choice of polarizing agent. The theory underpinning the technique will also be tested and new numerical models devised. This will allow development of the methodology from proof of principle to real-world application.

Self-funding applicants are welcome. In addition to tuition fees, bench fees of £6,000 per annum are required.

Home/EU -June 30th/October 31st and Overseas May 31st/September 30th

• Dr Christopher Wedge

This project involves the combination of thermal analysis and ambient ionisation mass spectrometry (specifically, DART-MS). A new integrated system has been developed that allows for investigation of the behaviour of complex materials as a function of temperature. The successful candidate will further develop and refine the system and investigate its wide-ranging applications.

Self-funding applicants are welcome. In addition to tuition fees, bench fees of £3,000 per annum are required.

Home/EU -June 30th/October 31st and Overseas May 31st/September 30th

• Dr Lindsay Harding
• Dr Gareth Parkes

Transition metal complexes have attracted enormous interest for their photophysical and photochemical properties which make them amenable for a range of applications including photovoltaics, artificial photosynthesis and solar fuels, photocatalysis, electronic display and artificial lighting and in biomedical areas such photodynamic therapy. In this latter area, photochemically reactive complexes have been targeted for application in photoactivated chemotherapy in which a non-toxic complex undergoes photochemical ligand release to yield toxic fragments, inducing cancer cell death in a highly targeted manner. Despite the potential importance of these photochemical processes, relatively little has been known about the key excited state responsible for mediating these processes. Projects are available, supervised by Prof Paul Elliott, for the investigation of these fundamentally important processes and the characterization of the key excited states involved. See publications from our group at https://www.hud.ac.uk/ourstaff/profile/index.php?staffid=222

Self-funding applicants are welcome. In addition to tuition fees, bench fees of £5,000 per annum are required.

Home/EU -June 30th/October 31st and Overseas May 31st/September 30th

• Dr Paul Elliott
• Mr Paul Scattergood

In this project novel polysaccharides will be identified, purified, fully characterised. One major concern is that a large amount of work has previously been carried out on crude material and not on highly purified or well characterised polysaccharide components which makes conclusions on functionality difficult.

Self-funding applicants are welcome. In addition to tuition fees, bench fees of £6,000 per annum are required.

Home/EU -June 30th/October 31st and Overseas May 31st/September 30th

• Dr Gordon Morris
• Dr Alan Smith

In comparison to traditional composite materials, nanocomposites exhibit enhanced properties through the incorporation of nanofillers. Polymer-based nanocomposites combine the benefits of polymers, such as low cost and ease of processing, with the unique features of the nanomaterials, such as high surface to volume ratio, high aspect ratio, excellent toughness and strength and improved electrical and thermal conductivities. In the last few years, polymer nanocomposites with enhanced optical, mechanical, electrical and thermal properties have been developed. A key challenge for nanocomposites is to prevent agglomeration of the nanofillers, in order to optimise property enhancement. Potential applications of nanocomposites include aerospace, automotive, marine, sports materials, construction, structures, electrical and electronic systems, biomedical devices, thermal management systems, adhesives, paints and coatings, industrial tooling and other general consumer products. In parallel with these developments, the discovery of graphene has been heralded as a game-changer for many areas of science and engineering, including materials science. The power of graphene is that it combines a range of exceptional properties in one material. A key challenge for promoting practical applications of graphene is to translate these properties into macro-structured materials. Putting these two concepts together, graphene-polymer nanocomposites utilise graphene as the nanofiller such that they combine the benefits of nanocomposites with the unique properties of graphene. Further to this, the synergistic effect of incorporating two or more nanofillers to form ‘hybridised nanocomposites’ has also been proposed for additional enhancement of properties. For example, the remarkable synergetic effect between graphene platelets and multiwalled carbon nanotubes has been observed to greatly improve the mechanical properties and thermal conductivity of nanocomposites. However, graphene-polymer and hybridised nanocomposites are at an early stage of development and their properties and behaviour are not fully understood. As such, there is great scope for further work and exploitation of these materials. This project will examine the processing of a range of graphene-polymer nanocomposites, test mechanical properties, assess thermal stability and examine breakage characteristics, in order to understand and optimise the behaviour of these materials.

Self-funding applicants are welcome. In addition to tuition fees, bench fees of £5,000 per annum are required.

Home/EU -June 30th/October 31st and Overseas May 31st/September 30th

• Dr Daniel Belton
• Dr Simon Barrans

Autoxidation is one of the main mechanisms of oxidative degradation of active pharmaceutical ingredients (APIs). It can result in a reduced shelf life for a pharmaceutical product, the need for low temperature storage and shipments or the inclusion of antioxidants in a formulation. When a new API enters development understanding the risk of autoxidation is therefore crucial. The autoxidation mechanism is well-known; an initially formed radical combines with oxygen from air to form a peroxyl radical. The peroxyl radical can then abstract any weakly bound hydrogen atom, to generate a new radical that can propagate the chain reaction. In principle, the chain reaction can be fast as long as the breaking CH bond is weaker than the OH bond that is formed in the hydrogen transfer. The CH bond dissociation energy can be accurately calculated for a hydrogen atom in any molecule and if autoxidation occurs these values are very good at predicting the site at which it will occur. However, the absolute value is not the sole predictor of whether autoxidation occurs at all. The ability of the chain mechanism to propagate seems key, with the subsequent formation of both carbon based and oxygen based radicals. Electron Paramagnetic Resonance (EPR) spectroscopy is a powerful tool for studying free radical formation and as such can be used to investigate autoxidative degradation mechanisms in APIs. Building on previous work in which EPR was validated as a tool for non-destructive investigation of the extent of API oxidation in this PhD project EPR will be used to investigate the factors allowing autoxidation reactions to propagate, and ways in which autoxidation can be prevented.

Self-funding applicants are welcome. In addition to tuition fees, bench fees of £6,000 per annum are required.

Home/EU -June 30th/October 31st and Overseas May 31st/September 30th

• Dr Christopher Wedge

Most geochemical processes occur at the mineral-fluid interfaces. Characterization of these interfaces and their interaction with contaminants (including radionuclides and heavy metals) and pollutants is therefore crucial to the understanding and the control of any interface process whether involved in geochemical processes or in any industrial and technological approaches that see mineral phases at the heart of their applications. This PhD will address the modelling challenges in the field, covering approaches that are capable of gaining insights into the structure and the processes, including but not limited to adsorption, transport and reactivity, at the interfaces of minerals with the surrounding environment. Applications to contaminants and pollutants remediation, construction, mineral formation and uptake in biological media, human healthcare and of course geochemistry could all be considered. The PhD student will undertake novel research using multiscale computational approaches to contaminants and pollutants at mineral/material interfaces with focus on the role of structure, adsorption and reactivity. The details of the project will be discussed with the candidate and the project will be tailored based on the candidate’s research interest. All research outputs: https://scholar.google.co.uk/citations?user=jAUrSBQAAAAJ&hl=en Examples of research outputs for this PhD are listed below: Sorptive Characteristics of Organomontmorillonite toward Organic Compounds: A Combined LFERs and Molecular Dynamics Simulation Study. https://pubs.acs.org/doi/10.1021/es200211r Toward Modeling Clay Mineral Nanoparticles: The Edge Surfaces of Pyrophyllite and Their Interaction with Water. https://pubs.acs.org/doi/10.1021/jp5070853 Modelling the effects of surfactant loading level on the sorption of organic contaminants on organoclays. https://pubs.rsc.org/en/Content/ArticleLanding/2015/RA/c5ra05998d Adsorption of phosphate and cadmium on iron (oxyhydr)oxides: A comparative study on ferrihydrite, goethite, and hematite. https://www.sciencedirect.com/science/article/pii/S0016706120325544

Self-funding applicants are welcome. In addition to tuition fees, bench fees of between £3-£15,000 per annum are required depending on the nature of the project.

Our standard University deadlines apply. Please see our Deadlines for Applications page to find out more

• Dr Marco Molinari
• Professor Paul Humphreys

Biomedical materials engineering develops biomaterials that are manufactured to be suitable for use as medical devices. Nanomaterials of oxides, metals, carbon-based materials (i.e. graphene, nanotubes, etc.), and polymers make up the vast majority of biomaterials. For practical uses (sensors, biosensors, nanozymes etc.) nanomaterials are usually chemically modified at the surface forming composite materials. Unlike, the bulk properties of these materials which are generally well known, the properties arising at the nanoscale from surfaces and interfaces in contact to the biological environment are peculiar to the system. The chemistry of surfaces and interfaces and their characterization are therefore key to a quantitative understanding of the materials properties. Controlling such properties is imperative to allow for the prediction of the materials behaviour when immerse in the biological environment. This will not only affect biomedical processes at the materials interfaces but also any industrial and technological applications that see such systems at the heart of their approaches. The PhD student will undertake novel research using multiscale computational approaches capable of gaining nanoscale and microscale insights into the chemistry, structure and processes at the surfaces and interfaces of biomedically relevant materials. The details of the project will be discussed with the candidate and the project will be tailored based on the candidate’s research interest. All research outputs: https://scholar.google.co.uk/citations?user=jAUrSBQAAAAJ&hl=en Examples of research outputs for this PhD are listed below: Computer-Aided Design of Nanoceria Structures as Enzyme Mimetic Agents: The Role of Bodily Electrolytes on Maximising Their Activity. https://pubs.acs.org/doi/10.1021/acsabm.8b00709 Strongly Bound Surface Water Affects the Shape Evolution of Cerium Oxide Nanoparticles https://pubs.acs.org/doi/full/10.1021/acs.jpcc.9b09046 Thermodynamic Evolution of Cerium Oxide Nanoparticle Morphology Using Carbon Dioxide https://pubs.acs.org/doi/10.1021/acs.jpcc.0c07437

Self-funding applicants are welcome. In addition to tuition fees, bench fees of between £3-£15,000 per annum are required depending on the nature of the project.

Our standard University deadlines apply. Please see our Deadlines for Applications page to find out more

• Dr Marco Molinari
• Professor Roger Phillips

Since the discovery of cisplatin, a metal complex based anticancer drug, there has been enormous interest in inorganic chemistry for the development of novel complexes as next generation drugs for the treatment of cancer and in combatting the rise of antimicrobial resistant bacteria. Many transition metal complexes also exhibit light-induced photochemical reactivity which can make them amenable for application in photodynamic therapy and photoactivated chemotherapy, offering excellent spatiotemporal control of light-activated therapeutic activity. Projects are available for supervision by Prof Paul Elliott, and in collaboration with pharmacologists and biologists, for the exploration and development of novel metal complexes as light-activated therapeutic agents against cancer and antibiotic resistant bacteria. See publications from our group at https://www.hud.ac.uk/ourstaff/profile/index.php?staffid=222

There is currently no funding for this project and we encourage interested self-funding students to apply. In addition to tuition fees, bench fees of £5,000 per annum are required.

Home/EU -June 30th/October 31st and Overseas May 31st/September 30th

• Dr Paul Elliott
• Mr Paul Scattergood

There are important key factors that have to be considered when studying nuclear materials. (1) An important challenge is the modelling of transport properties in polycrystalline materials, and hence at their interfaces and grain boundaries. Most interfaces are not pristine and dopants and fission products are likely to segregate, thus impacting the transport properties at the grain boundary. In this PhD, we will use atomistic simulations to model the effect of grain boundaries on the transport properties of actinide oxides. (2) Important challenges when studying the corrosion of actinides oxides is the effect of the environment on the surfaces of the materials. Indeed, radiolytic corrosion of actinide materials represent an issue for the long-term storage and disposal of nuclear materials. To be able to understand how surface composition affect the rate of radiolysis and corrosion, we will be using molecular modelling to predict surface composition at relevant conditions of temperature and pressure. By mapping the energetics of the interactions, we can calculate temperature of desorption and predict nanoparticle morphology of actinides oxides. The PhD student will undertake novel research using multiscale computational approaches capable of gaining nanoscale and microscale insights into the chemistry, structure and processes at the surfaces and interfaces of materials for nuclear applications. The details of the project will be discussed with the candidate and the project will be tailored based on the candidate’s research interest. All research outputs: https://scholar.google.co.uk/citations?user=jAUrSBQAAAAJ&hl=en Examples of research outputs for this PhD are listed below: The energetics of carbonated PuO2 surfaces affects nanoparticle morphology: a DFT+U study. https://pubs.rsc.org/en/content/articlelanding/2020/cp/d0cp00021c Defect segregation facilitates oxygen transport at fluorite UO2 grain boundaries. https://royalsocietypublishing.org/doi/10.1098/rsta.2019.0026 The critical role of hydrogen on the stability of oxy-hydroxyl defect clusters in uranium oxide. https://pubs.rsc.org/en/content/articlelanding/2018/TA/C8TA02817F Computer simulation of defect clusters in UO2 and their dependence on composition. https://www.sciencedirect.com/science/article/pii/S0022311514006849

Self-funding applicants are welcome. In addition to tuition fees, bench fees of between £3-£15,000 per annum are required depending on the nature of the project.

Our standard University deadlines apply. Please see our Deadlines for Applications page to find out more

• Dr Marco Molinari
• Dr Lisa Gillie

A civil engineer cannot design architectural structures without knowing the mechanical properties of the building materials being used. Similarly, scientists and engineers require access to physical properties of chemicals to design and validate experiments and industrial processes. Physical properties depend on the nature of molecules of the substance. The ultimate generalisation of physical properties requires a complete understanding of molecular behaviour, which we do not have yet. Reliable physical property data estimation is important for a range of applications. These include the design of industrial processes, computer-aided molecular design, prediction of physicochemical properties for regulatory purposes, toxicity prediction, and determining the properties of substances for which direct measurement is difficult or impossible. There are a number of approaches to property estimation and prediction, including using the law of corresponding states, empirical data fitting, first order approximations using group contributions, quantitative structure-property relationships (QSPRs), statistical mechanics, and molecular modelling. However, many existing approaches fall down on a number of counts. Weaknesses include: replying on data collected under varying conditions or with different protocols; undefined ranges of applicability; use of imprecise data; repetition of data from the same compound within the training and/or validation dataset; inadequate or misinterpretation of statistics; inadequate and/or undisclosed dataset; and failure to validate correctly. This project will combine the power of experimental measurements with data analysis and computation modelling. It is expected that the triangulation and cross-validation of these approaches will allow us to greatly advance physical property estimation and prediction methodologies.

Self-funding applicants are welcome. In addition to tuition fees, bench fees of £5,000 per annum are required.

Home/EU -June 30th/October 31st and Overseas May 31st/September 30th

• Dr Daniel Belton
• Dr David Cooke

The purification of systems that exhibit azeotropic behaviour is a key challenge for many industrial processes. Various approaches to solving this challenge have been explored since the late 1920s. One such approach is pressure swing distillation (PSD). This method utilizes the pressure sensitivity of some binary azeotropes to shift the azeotropic composition of the mixture. Another, more common method that has been used since the 1920s is extractive distillation (ED). This method involves adding a third component called an entrainer to a binary mixture creating a ternary mixture. This method is becoming increasingly unpopular due to the restriction of solvent uses by environmental health and safety commissions world-wide, and it may continue to become more unpopular due to increase in global demand for reduced energy usage and CO2 emissions. As such it is imperative to better understand both approaches, to examine how they can be improved and to explore alternative solutions. For example, various PSD studies exist, however, these only scratched the surface of PSD development; this might be due in part to a lack of interest from industry or the prevalence of previous work into ED systems. These works, along with others have shown that PSD can have numerous benefits over more contemporary methods if built and utilized to full optimization. PSD could become more widely used, however, further work is needed to unlock the full potential of this methodology. Furthermore, the identification and study of greener solvents for use as entrainers in ED is a very underdeveloped area. In addition, alternative/novel methods for azeotrope purification are lacking and the reasons for an absence of innovation in this area is unclear. This project will utilise process simulation in order to examine the optimisation of existing approaches to azeotropic distillation, to identify and test more environmentally friendly entrainers for ED and to explore the feasibility of novel methods for azeotrope purification.

Self-funding applicants are welcome. In addition to tuition fees, bench fees of £3.000 per annum are required.

Home/EU -June 30th/October 31st and Overseas May 31st/September 30th

• Dr Daniel Belton

There are important key factors that have to be considered when studying energy materials. (1) An important challenge is the modelling of transport properties in polycrystalline materials, and hence at their interfaces and grain boundaries. Most interfaces are not pristine and dopants are likely to segregate, thus impacting the transport properties at the grain boundary. In fluorite-based materials as dopants accumulate at the grain boundaries so do oxygen vacancies, which blocks transport of oxygen across the interface. This is known as the “grain boundary blocking effect” in the space charge theory. However, as the segregation behaviour is highly dependent on the grain boundary there is scope to control the transport properties at the interface. In this PhD, we will use atomistic simulations to model the effect of grain boundaries on the transport properties of energy oxide materials. (2) Surface morphology is known to affect catalytic activity. Here one of the key challenges is to identify strategies to enhance the expression of such surfaces and also to prevent their disappearance over time. To understand how surface composition affect the surface catalysis, we will be using molecular modelling to predict surface composition at relevant conditions of temperature and pressure. By mapping the energetics of the interactions, we can calculate temperature of desorption and predict nanoparticle morphology of catalytically relevant oxides. The PhD student will undertake novel research using multiscale computational approaches capable of gaining nanoscale and microscale insights into the chemistry, structure and processes at the surfaces and interfaces of materials for energy generation and catalysis. The details of the project will be discussed with the candidate and the project will be tailored based on the candidate’s research interest. All research outputs: https://scholar.google.co.uk/citations?user=jAUrSBQAAAAJ&hl=en Examples of research outputs for this PhD are listed below: Controlling the {111}/{110} surface Ratio of Cuboidal Ceria Nanoparticles. https://pubs.acs.org/doi/10.1021/acsami.8b21667 The role of dopant segregation on the oxygen vacancy distribution and oxygen diffusion in CeO2 grain boundaries. https://iopscience.iop.org/article/10.1088/2515-7655/ab28b5 Thermodynamic Evolution of Cerium Oxide Nanoparticle Morphology Using Carbon Dioxide https://pubs.acs.org/doi/10.1021/acs.jpcc.0c07437 Concurrent La and A-Site Vacancy Doping Modulates the Thermoelectric Response of SrTiO3: Experimental and Computational Evidence. https://pubs.acs.org/doi/10.1021/acsami.7b14231 Structural, Electronic, and Transport Properties of Hybrid SrTiO3-Graphene and Carbon Nanoribbon Interfaces. https://pubs.acs.org/doi/10.1021/acs.chemmater.7b02253 Structural, electronic and thermoelectric behaviour of CaMnO3 and CaMnO(3− δ). https://pubs.rsc.org/en/content/articlelanding/2014/ta/c4ta01514b

Self-funding applicants are welcome. In addition to tuition fees, bench fees of between £3-£15,000 per annum are required depending on the nature of the project.

Our standard University deadlines apply. Please see our Deadlines for Applications page to find out more

• Dr Marco Molinari
• Dr Lisa Gillie

Photoactive metal complexes of first row transition metal ions is currently a hot topic in contemporary chemical science. Transition metal complexes have attracted enormous interest for their photophysical and photochemical properties which make them amenable for a range of applications including photovoltaics, artificial photosynthesis and solar fuels, photocatalysis, electronic display and artificial lighting and in biomedical areas such photodynamic therapy. Metal complexes explored for these applications predominantly incorporate heavy metallic elements such as iridium, ruthenium, platinium, etc. Whilst the properties of complexes of these metals are well suited for these applications these represent the rarest elements in the Earth’s crust. There is therefore an imperative to develop photofunctional metal complexes based on far more abundant and lighter first row transition metal elements such as iron, chromium, cobalt, etc. Development of new photofunctional complexes based on lighter first row metals as replacements for those of heavier transition metal elements presents a significant challenge, requiring chemists to explore entirely new conceptual approaches to metal complex photophysics. Several possible projects are available for supervision by Professor Paul Elliott and Dr Paul Scattergood in this exciting and rapidly developing area. See publications from our group at https://www.hud.ac.uk/ourstaff/profile/index.php?staffid=222

There is currently no funding for this project and we encourage interested self-funding students to apply. In addition to tuition fees, bench fees of £5,000 per annum are also required.

• Dr Paul Elliott
• Mr Paul Scattergood

Graphene has been heralded as a “wonder material” and is among a number of recently discovered carbon allotropes that demonstrate outstanding and versatile properties. Chemical vapour deposition (CVD) is a powerful and flexible technique for creating single- and multilayer-graphene and carbon nanotubes. These new materials exhibit a variety of unique and tuneable optical, electronic, mechanical, structural, thermal and chemical properties, offering the prospect of applications in photovoltaics, nanoelectronics, sensors, display technology, nanocomposites, simulated photosynthesis, batteries and supercapacitors. The aim of this project is to understand and optimise the CVD synthesis and graphene transfer/utilisation conditions on the final properties of graphene materials produced. This will involve examining the effect of substrate properties and processing conditions on the graphene material morphological and physical properties. The optimisation of these properties and parameters will lead to new materials with “super”-properties, making them suitable to fulfil a range of unmet industrial needs. Potential applications include super-strong fibres, supercapacitors and superconductors.

Self-funding applicants are welcome. In addition to tuition fees, bench fees of £5,000 per annum are required.

Home/EU -June 30th/October 31st and Overseas May 31st/September 30th

• Dr Daniel Belton

This research will be in the area of synthetic organic chemistry and will focus specifically on the synthesis of heterocyclic natural products. The targets of this project are the indolizidine and pyrrolizidine alkaloids. These systems are of interest in the possible treatment of various diseases such as cancer, diabetes and viral infections such as AIDS, and some of them have the potential to function as potent analgesics or as potential treatments for Alzheimer’s disease and other neurological disorders. Examples of such compounds include the well-known "poison frog alkaloids".

Self-funding applicants are welcome. In addition to tuition fees, bench fees of £6,000 per annum are required.

Home/EU -June 30th/October 31st and Overseas May 31st/September 30th

• Dr Karl Hemming

This topic is in the area of synthetic organic chemistry used to target heterocyclic products with medicinal applications. The heterocyclic targets include pyrrolo-fused natural products such as the pyrrolobenzodiazepines and their sulfur analogues, beta-sultams, homotropanes, isoflavones, oxadiazoles and aza-sugars. The biological activities that we are interested in include anti-tumour compounds, antibiotics and anti-inflammatory compounds that target diseases such as Alzheimer's.

Self-funding applicants are welcome. In addition to tuition fees, bench fees of between £3-£15,000 per annum are required depending on the nature of the project.

Home/EU – for September- June 30th, for January-October 31st and Overseas for September- May 31st, for January- September 30th

• Dr Karl Hemming

We are involved in research programmes with cancer biologists that require the preparation of novel molecules for testing. This includes the development of synthetic methodology to prepare potential drugs containing fluorescent tags and antibody conjugates.

Self-funding applicants are welcome. In addition to tuition fees, bench fees of £xx per annum are required.

Home/EU -June 30th/October 31st and Overseas May 31st/September 30th

• Dr Wesley Moran

Silicon is the second most abundant element on Earth however its synthetic chemistry has been little studied compared to its close neighbour carbon. The aim of this project is to develop new synthetic methods to access silicon heterocycles. These types of compounds are becoming of increasing interest in drug discovery.

Self-funding applicants are welcome. In addition to tuition fees, bench fees of £6,000 per annum are required.

Home/EU -June 30th/October 31st and Overseas May 31st/September 30th

• Dr Wesley Moran