The industrial mass production of machines and devices relies on the assembly of different components in a specific order in the most rapid and efficient way. However what is routine at everyday length scales is infinitely more difficult and time consuming when we consider linking components to create nano-devices. This is particularly the case when one wishes to create a specific molecule-nanostructure construct. The individual component molecules and complex nanostructure architectures can be mass produced using tools of synthetic chemistry and nanofabrication techniques (e.g. nano-imprint and injection moulding). However, established technologies for combining these individual elements in a specific way are slow (e.g. dip pen nanolithography takes tens of hours to functionalise cm2 samples) and hence low throughput (i.e. incompatible with mass production). Therfore, creating relative complex hybrid molecular-nanofabricated materials is comparable to handcrafting a Bentley rather than the assembly line mass production of Volkswagen Golfs. We propose an innovative approach for nanoscale spatial control of chemical functionalisation of (plasmonic) nanostructures which has both nanoscale resolution ca. 20 nm and is simple and rapid. The concept, which we call "Meta-chemistry", involves using a pulsed laser to locally heat the solvent in specific regions surrounding a nanostructure. These nanoscale thermal gradients can then be exploited to drive chemistry in a spatially selective manner. In the proposal we will develop a fundamental understanding of how heat is generated and transported in a liquid surrounding a nanostructure, thus providing the foundation for optimal spatial control. Also crucially, we will synthesise thermally responsive polymers which will be transformed in the locally heated solvent, creating nano-domains which can be subsequently chemically functionalised. Using the meta-chemistry concept cm2 of a nanostructured substrate can be both spatially and selectively chemically modified, in preparation for subsequent chemical functionalisation, in less than 60 seconds. The proposal is at the cusp of chemistry physics and engineering, it will discover novel fundamental science which in the longer term could be the foundation of a powerful flexible technology for the nanoscience toolbox.

Ferroics are a class of materials that, below a certain ordering temperature, display either a long range ordering of microscopic +/- dipoles or of magnetic north-south (N/S) poles. These orderings on the microscopic atomic length scale give rise to macroscopic measurable physical properties. The +/- dipoles or N/S poles can be read and manipulated on the nanoscale by applying electronic and magnetic stimuli. In this manner existing technologies use materials like this in data storage devices where the "storage bits", the 1's and 0's correspond to the different state of either +/- or N/S. However, for next generation storage devices to improve energy consumption, increase speeds and data density, it will be desirable to have a new class of "multiferroic materials" in which these two phenomena of +/- charge dipoles and N/S magnetic state, not only coexist with one another, but are strongly coupled and depend on each other. This has significant advantages in that the data written by applying an electric field to switch a +/- state can now be read back quickly and non-destructively using a magnetic field to sense the flipping of the N/S pole. However, as yet it is still a substantial challenge to identify new materials that display this desired coupling between these two ferroic properties at or near room temperature, which would make such a device possible. The present work uses a novel approach to enumerate the possible types of materials exhibiting these properties, leading to a systematic strategy for attempting to make and test these materials for the desired physical properties. The work will contribute both new fundamental mechanistic insight into how multiferroic materials work, and can be rationally designed, as well as providing new materials that may be tested for application in next generation storage technologies.

The mid-infrared band of the electromagnetic spectrum has huge potential in healthcare technologies. Many biological molecules exhibit very strong absorption of radiation (light) in this region. This absorption depends strongly on matching the wavelength (colour) of the light to the stretching of the molecular bonds, unique to each molecule. For example, water absorbs radiation at a mid-infrared wavelength of 2.94 um nearly 100,000 times more strongly than a near-infrared wavelength of 1 um. A laser is an intense, highly directional, and monochromatic beam of radiation. The potential of mid-infrared lasers at 2.94 um as medical tools was recognised early on, due to the high-water content of biological tissue (>70%). Focussing a 2.94 um laser on tissue results in highly efficient absorption of the radiation in a very localised area. The subsequent rapid heating in this area causes the tissue to vaporise into a gas (ablation), resulting in an ultra-precise method of removing tissue, e.g. for use as laser scalpels or biopsy replacements. There are, however, a lack of ultrafast mid-infrared lasers with pulse durations shorter than 1 nanosecond (a billionth of a second) suitable for tissue ablation. Existing ultrafast mid-infrared commercial lasers do not have enough energy to initiate ablation, are often too large and complex to be deployed outside of specialist laser laboratories, or have poor beam qualities leading to large beam sizes on the sample (poor spatial resolution). As a result, the standard approach to 2.94 um tissue ablation is to use more widely available lasers (Er:YAG/Nd:YAG OPO) with longer pulses. However, the effect of these longer pulses on tissue can be highly problematic, causing tissue carbonisation (burning) and necrosis (cell-death) in surrounding cells, which can be avoided when using picosecond (ultrafast) pulses. In this project, I will create a compact, robust, fibre-integrated picosecond mid-infrared laser (fPIRL) platform. The platform will be based on a novel cascaded nonlinear wavelength conversion scheme, employing a combination of advanced fibre optic technology and new mid-infrared materials to create a completely fibre-integrated source suitable for wide deployment in non-specialist laboratories and clinics. The fPIRL platform will be employed as an ultra-precise laser scalpel, removing minute volumes of tissue for subsequent analysis with mass spectrometry. The tool will be much less destructive and much more precise than existing techniques. The team assembled crosses industry and academia, including materials scientists, laser physicists, analytical chemists, and systems medicine specialists. Together, we will enable significant advances in various biomolecular analysis techniques. The proposed single-cell resolution molecular mapping setup will help drive improvements in cancer tumour removal surgeries. Our fibre-delivered source will underpin future robotic surgical interventions in hard-to-reach surgical sites. With our long-wavelength source (6 um) we aim to reveal different biological fingerprints, improving diagnoses for certain diseases, than with existing ablation techniques. This project will create a new photonics-based healthcare technologies tool. The tool will enable significant advances in disease diagnosis and intervention, through advances in biomolecular analysis techniques suitable for both research and in-vivo applications. These advances will ultimately improve patient outcomes in the UK for the NHS, leading to a healthier, happier, and more productive society. Beyond this project, the fPIRL could be used for any precision surgical intervention, cultural preservation in ancient art, and polymer processing for biological implants.

Complex multicellular life first appeared on Earth some 800 million years ago and subsequently diversified through a bewilderingly complex pattern of species originations/extinctions. However, this was not a steady and uninterrupted process. On at least five occasions the biota of the planet was devastated by a catastrophe that eliminated a considerable proportion of total biodiversity--including entire groups of organisms (higher taxa). These so-called 'mass extinctions' fundamentally changed the nature of life on Earth by steering evolution into a completely different trajectory. Of the 'Big Five' mass extinctions by far the least understood is the Devonian mass extinction that occurred ca.370 million years ago. There is widespread debate regarding both the timing and nature of this event, which has led to a complete lack of consensus regarding its causes. This proposal seeks to investigate the Devonian mass extinction from a fresh perspective focussing on changes in carbon-cycling. The Earth currently has two carbon-cycles of similar magnitude: a marine one based on photosynthetic plankton and a terrestrial one based on photosynthetic land plants. Fundamental changes in carbon-cycling took place during the Devonian due to dramatic changes in the nature of terrestrial vegetation. At the start of the Devonian land plants were centimetres tall, rooted in very shallow soils and covered a limited area of the continents. By the end of the Devonian vast swathes of the continents were shrouded in forests of trees tens of metres tall that deep-rooted into mature soils. These major vegetation changes caused profound changes in the terrestrial carbon-cycle (due to carbon sequestration from chemical weathering and biomass burial). We hypothesise that it was dramatic changes to the terrestrial carbon-cycle that disrupted the Earth system and caused the Devonian mass extinction. However, we believe that it was not a single catastrophic event (such as the bolide impact that caused the end Cretaceous mass extinction) but rather it occurred sequentially as discrete morphological/anatomical innovations led to changes in plant size and coverage causing step-changes in the terrestrial carbon-cycle. The research project will focus on the Devonian sequences of northern Spain. These are ideal because they: (i) are remarkably complete and incorporate known extinction events at the Frasnian-Famennian and Devonian-Carboniferous boundaries; (ii) accumulated in isolation on a large microcontinent and as such are not influence by species immigration/emigration and habitat tracking; (iii) contain an excellent fossil record of both marine plankton (acritarchs and chitinozoans) and terrestrial vegetation (plant spores/pollen). We will study the evolutionary dynamics of both the marine plankton and terrestrial vegetation through a study of species origination/extinction patterns. This biodiversity profile will be integrated with geochemical analyses that will identify perturbations in the Earth's carbon-cycle (in addition to nutrient cycling, redox conditions and volcanic activity). These data will be fed into an Earth Systems model for the Devonian carbon-cycle that we generate using inverse modelling techniques. The model will also incorporate data on the appearance of major plant groups and novelties (e.g. first forests). Together these data will shed light on the nature and timing of Devonian extinction events among primary producers and link them to changes in the carbon-cycle. Our research will clarify many aspects of the Devonian mass extinction (nature and timing) and link it to the monumental changes in carbon-cycling brought about by the dramatic evolution of terrestrial vegetation. This will also serve as a warning for the present day regarding consequences of human induced changes to the Earth's carbon-cycle bought about by deforestation, soil erosion and other detrimental activities.

The theory of plate tectonics revolutionised the Earth sciences and had impacts across society, by providing a framework to understand the motion of Earth's surface. However, plate tectonic theory does not tell us about the processes deeper in the Earth that drive plate motions, nor does it explain some of the most dramatic events in Earth history: the breakup of plates and outpouring of huge volumes of lava. The next required breakthrough is to make this leap, from a 2D description of plates to understanding the truly 4D nature of Earth's interior processes. Motion of the Earth's interior, its circulation, involves both upwelling and downwelling. The upwelling flow in the Earth remains enigmatic, occurring in the present-day as both hot focused plumes, which are only just observable through modern seismic imaging techniques, and a hypothesised diffuse flow, which has evaded detection entirely. A third mode of mantle upwelling is currently dormant, making its mantle flow signature unknown. However, this dormant mode of flow drives massive outpourings of lava, and has been associated with continental breakup and mass extinction events. Our project's overall goal is to constrain how mantle upwellings operate within the Earth. We will investigate how plate tectonics is linked to mantle circulation, by combining the history of plate movements across Earth's surface with observations drawn from across the geosciences, and use these to constrain state-of-the-art 4D computational models of mantle flow. These advances are made possible by recent progress in disciplines from across the Earth sciences, expertise we bring together here in geodynamics, seismology, geomagnetism, geochemistry, petrology, and thermodynamics. We will constrain present mantle flow by gathering new seismic imaging data of the Earth's deep interior. We will constrain past mantle flow using newly collected data on the mantle's composition, past magnetic field, and the history of Earth's surface uplift. We will use these multidisciplinary approaches to generate the most spatially and temporally complete set of observational constraints on mantle circulation yet assembled. These observations will be used to constrain and improve models that calculate mantle circulation in an Earth-like 3D geometry, driven by plate motion histories (mantle circulation models, MCMs). This is a timely development capitalising on the only recently available record of plate motion over 1 billion years of Earth History. The MCMs predict the mantle's temperature, density, and velocity through time, providing a 4D model of the Earth. Uncertain inputs in these models such as mantle viscosity and composition will be investigated within the bounds provided by the project's geochemical and thermodynamic work packages that will develop new models of Earth's high pressure mineralogy and physical properties. We will test the present-day predictions of the MCMs by converting model outputs to predict density and material properties within the Earth, using our developments on mineral physics modelling. With these inputs and constraints, we will create the first accurate computational models of mantle circulation over the last 1 billion years, which will provide dynamical insight into what drives the diversity of upwellings in the Earth. This tightly integrated multidisciplinary project is absolutely essential to achieve the best constrained MCMs and advance our understanding of Earth's interior processes. The result will be a coherent mantle circulation record of one quarter of Earth's history, and a major advance in our understanding of how mantle upwellings have impacted planetary evolution over this period.