University of St Andrews

UKRI Gateway to Research · FY 2024 · 2024-08

The selective formation of carbon halogen bonds (C-Cl, C-Br, C-I, referred to here as a C-X bond) is of great importance to the pharmaceutical and agrochemical industries. The introduction of a halogen into a molecule can be used to modulate bioactivity, bioavailability and metabolic stability. Even more significantly, the carbon halogen bond provides a chemically orthogonal and reactive handle for molecule building. For these reasons, analyses of the top 200 pharmaceuticals reveals that over 90% rely upon chlorine chemistry1 and C-Cl/Br/I formation is estimated as being worth $250B per annum2 A significant manufacturing challenge is that synthetic chemical approaches to halogenation employ highly reactive and toxic reagents: chlorine gas and bromine liquid. Elemental Cl2 are predominantly prepared through high energy processes in China, India, US and Germany 3 while leading Br2 producers are Israel, Jordan and China 4 The halides and often reactive halogenated chemical building blocks are not only hard to handle but subject to fragile and geopolitically challenged supply chains, there would be significant benefit to the UK from an alternative, more robust supply. Furthermore, the use of elemental halides for halogenation of aromatic compounds lacks regioselectivity, mixtures of compounds are generated that require challenging separations. Conversely, biosynthetic (enzymatic) halogenation is mild, highly selective and utilises readily available salts such as NaCl or NH4Br as the source of halide. Here we will work toward demonstrating enzymatic halogenation in flow in an industry relevant manner.

UKRI Gateway to Research · FY 2024 · 2024-08

The origin, survival, and early evolution of life on the Earth, and if exists, on Enceladus must require transition metals (e.g., Ni, Mo, Cu etc.). Weathering of continental crust followed by riverine transport, which is the main source of metals in the present Earth, was/is limited on the Early earth/present-day Enceladus. Instead, hydrothermal vents (HTVs) and/or weathering of the sub-oceanic rocks are proposed to be the main source of metal on these planetary bodies, however, the metal concentrations in these vents are highly speculative and unconstrained. Furthermore, the existing models that tried to quantify the metal contents in the early ocean on Earth and Enceladus are theoretical and lack the consideration of critical parameters (e.g., organic ligands) that influence metal solubility. The proposed research aims to quantify the metal contents in HTVs and in the ocean on the early earth and Enceladus by performing hydrothermal experiments followed by thermodynamic and mass-balance (Box) modelling. Together these methods would replicate the interaction between early Earth Crust/Enceladus core with corresponding ocean water at various pressures (P) and temperatures (T) and the mixing of HTV fluids with ocean water. Experiments will be performed using novel set-up comprising hydrothermal reactor and syringe pump, which will allow performing multiple experiments in controlled T, P, and redox conditions. The modelling will be done using computer-based software. The proposed research will finally be able to constrain if obtained metal concentrations (in vents and ocean) are sufficient to trigger biologic pathways required for the origin and early evolution of life in these planetary bodies. The results are therefore critical for future space exploration targeting the existence of extra-terrestrial life. With the expertise of the researcher and the host, available facilities at the host institution, the project can be finished within proposed time (24 months).

UKRI Gateway to Research · FY 2024 · 2024-08

Doctoral Training Partnerships: a range of postgraduate training is funded by the Research Councils. For information on current funding routes, see the common terminology at https://www.ukri.org/apply-for-funding/how-we-fund-studentships/. Training grants may be to one organisation or to a consortia of research organisations. This portal will show the lead organisation only.

UKRI Gateway to Research · FY 2024 · 2024-07

Electron paramagnetic resonance (EPR) spectroscopy detects the magnetism arising from the "spin", a quantum mechanical property, of unpaired electrons. In most molecules and materials electrons are paired, quenching their magnetism. However, in radicals and paramagnetic metal ions unpaired electrons persist and EPR is exclusively and exquisitely sensitive to these species. This can be exploited, e.g., in structural biology, where persistent radicals are linked to biomacromolecules, and their surroundings investigated, or distances between pairs of radicals can be measured on the nanometre scale. This approach has become a highly valuable complementary tool to explore the shapes and motion of biomacromolecules and their complexes as they function. Combined with recent advances in deep-learning, this has become a powerful tool to predict and validate structure-function relationships of biological systems. Investing in technology that can experimentally validate computational structures with very modest sample requirements will be strategically important for the UK. St Andrews has a strong track record in biological pulse EPR methodology. The current workhorse pulse EPR equipment is based on a 20-year-old instrument that has had repeated downtime due to critical repairs. While this existing Q-band equipment housed in Physics is of world-leading sensitivity, expanding capacity and enabling higher throughput that will facilitate new research are a clear priority for the University and aligned with the strategic objectives of the BBSRC. To achieve this capability, we propose to upgrade the pulse EPR spectrometer installed in 2011 in the School of Chemistry and embedded in the Biomedical Sciences Research Complex (BSRC) from X-band to Q-band giving a twenty-fold sensitivity improvement over its current capability. Addition of a small sample access probe head will increase absolute sensitivity, compared to the existing Q-band, by four-fold. This will provide a significant boost to research, facilitating high quality data for samples available in only limited quantities, provide critical contingency in the case of instrument outage for maintenance or repairs, while simultaneously extending capacity that will allow higher throughput and widen access to other users. Of specific interest, recent developments in EPR technology allow measuring distances between fluorine atoms and spin-labels for structural restraints or the use of laser excitation for light-induced spin centres. Both innovations have generated significant interest in the EPR community and are starting to become more widely applied. However, in St Andrews the requirement of additional downtime for reconfiguration and testing means that only the expanded capacity of the upgraded instrument would allow exploring these new opportunities more widely. With this proposal, we therefore seek: (i) Funds to support procurement and installation of a Q-band upgrade to the pulse EPR spectrometer in the BSRC and (ii) To use this upgraded facility to provide training of existing and new users, and exploration of new frontier bioscience research opportunities. The upgrade will enable research that spans four academic schools in St Andrews and a wide network of local, national, and international collaborations including bioscience for health, exploring fundamental biological mechanisms, novel imaging materials, chemical biology, and sustainable feedstocks.

UKRI Gateway to Research · FY 2024 · 2024-07

Abstracts are not currently available in GtR for all funded research. This is normally because the abstract was not required at the time of proposal submission, but may be because it included sensitive information such as personal details.

UKRI Gateway to Research · FY 2024 · 2024-07

Organic light-emitting diodes (OLEDs) have become a dominant technology in the display industry and hold great promise for a variety of applications in the fields of lighting, visible communication, sensing and healthcare. Current research efforts focus on the development of thermally-activated delayed fluorescent (TADF) emitters that promise highly efficient and long-lifetime performance without the use of any heavy metals. These materials show a small energy gap between their singlet and triplet energy levels allowing the up-conversion of non-emissive triplets to light-emitting singlets at room temperature via the reverse intersystem crossing process. Although efficient triplet harvesting can take place in TADF OLEDs, the dynamics involved in the TADF mechanism need to be faster to substantially reduce the accumulation of long-lived triplet excitons during the device operation and improve their overall performance. This project addresses this research challenge by proposing an innovative approach based on the integration of sub-wavelength photonic nanostructures into TADF OLEDs. Via their effects on the local photonic density and the dielectric permittivity of the effective media, the photonic nanostructures will be engineered to accelerate both radiative decay and reverse intersystem crossing rates. This will improve the efficiency of OLEDs, especially at high brightness and increase their lifetime. The successful outcome of the project is expected to lead to an improvement of the TADF OLED technology and will be highly relevant for a range of other applications in fields as diverse as organic optoelectronics, sensing and photochemistry.

UKRI Gateway to Research · FY 2024 · 2024-07

Large scale social data have become vital for the governance and operation of society, and we live in an era of an abundance of data. Most of these data - be they from surveys, commercial sources, administrative records or from internet and mobile devices – include only a selection of any given population. Thus emerges a challenge for data producers, analysts and users: How to we ensure that ‘hard to reach’ populations are included? How do we know whether ‘hard to reach’ populations are adequately included? For those with an interest in social equality, these questions are particularly pertinent because ‘hard to reach’ populations are very often those who are marginalised and disadvantaged, bringing the risk that they become invisible (or misrepresented) in social data. This project will provide recommendations for delivering inclusive social surveys in terms of representation, robustness and financial feasibility. The project is timely given falling response rates in traditional surveys, the general unsatisfactory representation of small and hard-to-survey groups and places, and the recognition of the potential of non-traditional approaches. The aims of the project will be achieved via in-depth analysis of the methodological implementation and resulting data in the Evidence for Equality National Survey (EVENS), conducted by the project team (2020-2023) to document the lives of ethnic and religious minority people during the Covid-19 pandemic. EVENS was successful in delivering a robust dataset of 14,200 participants using pioneering non-traditional (non-probability) online survey methods. This project will maximise the learning from EVENS by providing a deep interrogation of its methodological innovations and an understanding of the limitations. The project is structured around 3 workstreams: recruitment methods for improved representation; innovations in survey adjustments and estimation; and, mitigating illegitimate participation in online surveys. The project will use a combination of quantitative and qualitative approaches to interrogate: How successful were the various community-led, partnership based, media-focused recruitment approaches of EVENS in achieving representativeness, and what can be learnt for future (non probability) surveys? How can robustness in data be ensured by accounting for selection bias and mitigating illegitimate survey participation? How financially and operationally feasible are non-traditional survey approaches, such as used in EVENS?   The team constitutes a highly skilled, specialised and complementary collaboration of leading scholars in their field. They bring interdisciplinarity, all with expertise in social survey research, and with mixed-methods experience. The successful working dynamics of the applicant team are demonstrated through their collaboration in the EVENS project, the ESRC Centre on the Dynamics of Ethnicity and the ESRC Centre for Population Change. The collaboration is also mindful of capacity building, being constituted of senior academics, mid career scholars and early career colleagues. The outcomes of the project will be relevant to social data producers, analysts and users in research, policy, advocacy and commercial sectors. It will progress work on equitable statistics by advancing inclusive survey recruitment methods, delivering methodological innovation in bias accounting, building methods for data integrity (mitigating illegitimate participation in online surveys), and reviewing financial feasibility of online, non-probability approaches. The findings can be directly applied to non-probability and probability-based surveys, including via integration to existing UK Data Infrastructure. They are also of relevance to the broader data transformation landscape in which multi-source data and data linkage are at the fore, and questions of representation will continue to be salient.

UKRI Gateway to Research · FY 2024 · 2024-06

In July 2020, the Khabarovsk region emerged as a new center of political protest in Putin's Russia. The arrest of the popularly elected local governor Sergei Furgal on murder charges associated with the deaths of two businessmen triggered unprecedentedly large demonstrations against the Kremlin's intervention in local affairs. My project explores the massive legitimacy crisis the federal government faces in the region through an ethnography of grassroots social movements in Komsomolsk-na-Amure, the largest military-industrial base in the Russian Far East. While there is a rich literature documenting the cultural practices of indigenous groups of the Far East as well as forms of economic transborder exchange with Korea, China, and Japan, the urban and political life of this region remains critically understudied. Drawing on archival research, discourse analysis, and fieldwork with Komsomolsk's citizens engaged in different forms of community organizing, I analyse the legacy of Soviet industrialization in Eastern Russia and ways in which it continues to shape the regional identities of local residents. Specifically, I focus on how the socialist ethics of the Soviet period intertwine with the informal ethics of the Gulag's criminal subculture, in structuring the political imaginaries of Komsomolsk's activists as well as their attitudes towards the federal center. My project offers a novel take on the consequences of the post-Soviet culture of informality by showing that it can provide a powerful basis for political mobilization in contexts where an unwritten social contract is violated by state actors. In addition to theorizing the political dimension of the ethics of informality, my project makes a contribution to the emerging literature on forms of popular protest in contemporary Russia by destabilizing the stereotype of the "silent" provinces as the base of President Putin's support and showing the key role regional mobilization plays in challenging the Kremlin.

Other NSERC · FY 2024

group theory, permutation groups, computational algebra, computational group theory

Other NSERC · FY 2024

measure theory, fractal geometry, dynamical systems, iterated function system, multifractal analysis, self-similar, self-affine