This proposal aims to identify novel strategies for preparing better single-molecule magnets. Single-molecule magnets are molecules that show stable magnetisation of purely molecular origin, due to their magnetic anisotropy. They are promising candidates for a bottom-up approach to magnetic data storage materials. One of the advantages is that all the molecules are the same and there is no distribution in the size of the particles. However, the blocking temperature of the magnetisation is still too low. Here we propose to study three classes of single molecule magnets that may show higher blocking temperatures: First of all, those composed of high-anisotropy ions, secondly, those containing ions with an orbital moment, and finally those containing lanthanide ions. We will study these systems using a combination of magnetometry and frequency domain magnetic resonance spectroscopy. The latter is a method that is new to the UK.

In state-of-the-art laboratories worldwide, gases of atoms are being cooled down to temperatures less than a millionth of a degree above absolute zero. At this extreme coldness, quantum mechanics takes over; the atoms lose their individual identities and become smeared out into a giant wave of matter. This quantum gas hosts a range of bizarre behaviours, from its capacity to undergo wave-like interference to its embodiment of a superfluid, a fluid with no resistance to motion. The quantum gas is far from just a scientific curiosity. It represents a clean and pure exemplar of a many-particle quantum system, giving rich insight into the quantum world. Atomic physics techniques empower experimentalists to precisely tune its physical properties and manipulate it in time and space. Due to these facets, quantum gases are being exploited as "emulators" to recreate and understand complicated physical phenomena, from superconductors and turbulence to black holes and the Big Bang. The quantum gas also holds exciting technological prospects. Their exceptional sensitivity to being disturbed is driving their development as ultra-precise sensors, e.g. of gravity, for which they are touted to lead to major advancement in oil and mineral exploration. Meanwhile, their unprecedented quantum control makes these gases candidates for performing quantum gate operations, the basis of the much-lauded quantum computer. Recent experiments in quantum gases have created a "quantum ferrofluid". Being both a superfluid and a ferrofluid, this novel state lies at the interface of two of our most bizarre fluids. Ferrofluids are liquids dispersed with tiny magnetic iron particles. Just like bar magnets, the particles interact over long-range, prefer to lie with north and south poles being adjacent, and become aligned in an imposed magnetic field. This leads to peculiar patterns and instabilities in the fluid, but, more importantly, enables the flow and physical properties to be controlled via magnetic fields, as exploited in ferrofluid technologies in medicine, information display and sealants. The quantum sibling of the ferrofluid, the quantum ferrofluid, has been formed from an ultracold quantum gas of magnetic atoms. This gas is being hotly researched to probe its novel properties and potential exploitation. Its magnetic nature extends the above-mentioned capabilities of the quantum gas into new territories, e.g., providing a testbed of quantum magnetism, emulation of systems with long-range interactions, and a sensitivity to magnetic fields which can be exploited in a new generation of magnetic sensors, with potential applications from geological exploration to military detection. Meanwhile, the long-range magnetic interaction between atoms is particularly attractive for quantum computation since it allows the computational operations to be performed at a distance. The fundamental nature of superfluidity in the quantum ferrofluid remains uncharted, and uncovering it is the core aim of this project. With superfluidity underpinning the transport properties of the system, we will reveal how the quantum ferrofluid moves and flows, swirls and gyrates, and responds to agitation. This is of fundamental interest to our understanding of superfluidity in general, but, more specifically, is of great practical benefit for future manipulation and exploitation of the quantum ferrofluid. The distinctive behaviour of conventional ferrofluids and their virtuous control via magnetic fields is suggestive of a rich plethora of novel superfluid behaviour and a new dimension of control over the superfluid state. The quantum ferrofluid may in turn provide insight into the conventional ferrofluid; being superfluid, with an absence of viscosity, the quantum ferrofluid embodies a simplified version of the ferrofluid from which outstanding problems in ferrofluids can be tackled afresh.

Biocatalysis is the application of enzymes and microorganisms to the production of chemicals for the pharmaceutical, agrochemical and bulk chemical industries. As part of the wider field of 'Industrial Biotechnology' (IB) that is making an increasing contribution to the production of essential chemicals. Biocatalysis is an attractive alternative to traditional methods of chemical synthesis in some applications as it provides processes that are environmentally benign and highly selective, in a way that many conventional catalysts are not. One example of this is the ability of biocatalysts to generate single optical isomers, or 'enantiomers' of otherwise identical chemical products, where the properties of different isomers can have vastly different effects in a biological context, such as in a drug. Researchers in the chemical industry are always looking for new biocatalysts to replace established chemical processes, and these new enzymes are often discovered in microbes. Hydratase enzymes are biocatalysts that are capable of turning one form of abundant petrochemically-derived hydrocarbons, known as alkenes, into synthetically valuable alcohols, in single isomer form, which can act as precursors for the pharmaceutical and flavour/fragrance industries. These new enzymes offer great promise, but being only recently discovered, little is known about what they look like or how they work, and further knowledge of these aspects is essential if the enzymes are to be engineered for improved activity and process suitability. In this project, we will study a new class of hydratase enzymes that not only catalyse the production of alcohols from alkenes, but are also able to take naturally occurring alcohols, and, in the reverse reaction, turn them into non-natural alkenes such as isoprene for the production of polymers including rubber. We will determine the structures of the enzymes using X-ray crystallography, and use the information to study how the enzymes work, and to inform protein engineering studies that will help us change and improve the enzymes for different applications. Finally we will, with the assistance of commercial partners, apply the improved enzymes to the transformation of useful molecules, with a view to providing new selective and sustainable methods of chemistry for industrial processes.

The project aims to create new fundamental knowledge and advanced numerical tools regarding the atomisation, heating and evaporation characteristics of liquefied gases, in order to significantly advance the technology required to efficiently control cryogenic injection. Liquid gases such as air, nitrogen or natural gas can serve as cost-effective energy vectors within power production units as well as transport "fuels" with zero emissions. For example, energy coming from renewables can be used in order to "cool" air or nitrogen, up to the point that they become liquids. Follow up injection of these liquids to a higher temperature environment causes rapid re-gasification and a 700-fold expansion in volume, which can drive a turbine or piston engine even without combustion. Most importantly, because of the low boiling point of cryogenic liquids, low-grade or ambient heat can be used as a heat source, which otherwise is wasted. A better understanding and control of the injection dynamics of the cryogenic fluids could boost the efficiency of hybrid combustion systems to 60% (Ricardo's Cryopowder split-cycle engine), and achieve zero emissions when used for work generation through isothermal expansion without the need of combustion (Dearman Engine and Libertine Free Piston Engine). Recently, there has been an increased interest towards cryogenic technologies, however this has been focused mostly on the liquefaction processes (such as the £6m EPSRC grant to the Birmingham Centre for Cryogenic Energy Storage). Within the suggested project the attention is shifted towords the injection process of the cryogenics in real life industrial applications. Dr Vogiatzaki with the support from two leading UK companies in the field of innovative energy system solutions (Ricardo Ltd and Libertine Ltd) aspires to provide new knowledge and robust modelling tools to unlock the dynamics of cryogenic energy carrier's atomisation and heat transfer dynamics.

Metal-ligand multiple-bonds represent fundamental aspects of chemistry and underpin chemical structure, bonding, reactivity, and catalysis. Indeed, transition metal-carbon multiple bonds are the basis for the 2005 Nobel Chemistry Prize and transition metal-nitrogen triple bonds are well established and important intermediates in biological processes (nitrogenases) and ammonia synthesis. For uranium, the heaviest naturally occurring element, double bonds to oxygen, exemplified by the ubiquitous linear uranyl dication, and nitrogen are well known, and the area of uranium-carbon double bonds is burgeoning. A molecular uranium-nitrogen triple bond, known as a uranium nitride, was for decades the ultimate target in synthetic actinide chemistry; however it eluded all attempts to prepare it. Very recently, we made a landmark advance and prepared the first example of a molecular uranium-nitride triple bond (Science, 2012, 337, 717). Our breakthrough method utilises a very bulky ligand which generates a pocket at uranium in which to install the nitride, coupled to stabilisation during synthesis using a sodium cation, followed by gentle removal of the sodium to furnish the terminal nitride linkage. This project aims to exploit our advance in order to develop this exciting area so that we may map out the intrinsic structure and reactivity of the uranium-nitride triple bond. We will expand the range of uranium-nitride triple bonds with our proven method to generate a family of compounds so that meaningful comparisons can be made. Surprisingly, the 1909 Haber-Bosch patent for ammonia synthesis, where nitrides are implicated, clearly references uranium as the best catalyst. We therefore seek to assess the role of uranium-nitrides in ammonia synthesis to answer long-standing questions regarding the role of uranium. Furthermore, we will assess the potential of uranium-nitrides in atom-efficient N-atom transfer reactions which may straightforwardly be 15N-isotopically labelled. We will establish the intrinsic reactivity character of the uranium-nitride linkage and will test the hypothesis that our nitrides represent a hitherto unavailable entry point to long-targeted, high value uranium-carbon triple and heteroatom-free double bonds that have no precedent. We also seek to extend this chemistry to heavier analogues where the nitride nitrogen is replaced by a phosphorus or arsenic atom which will afford an opportunity to compare trends within a chemical group. We will combine synthetic and structural studies with interdisciplinary magnetometric, computational, and spectroscopic studies (EPSRC EPR National Service at Manchester University, far-IR at Stuttgart University, and XANES at Canberra University) to give a comprehensive understanding of uranium-nitrogen bonding. Our uranium-nitride linkage provides a unique opportunity to probe the nature and extent of covalency in uranium-ligand bonding. The issue of covalency in uranium chemical bonding is long-running, still hotly debated, and important because of the nuclear waste legacy which the UK already has. Spent nuclear fuel is ~96% uranium and the official Nuclear Decommissioning Authority figure for nuclear waste clean-up bill is 70 billion pounds. If we can better understand the chemistry of uranium this higher platform of knowledge may in the future contribute to ameliorating the UK's nuclear waste legacy.