ERC FUNDED PROJECTS

Many significant global challenges in catalysis for energy and sustainable chemistry have already been solved in nature. Metalloenzymes within microorganisms catalyse the transformation of carbon dioxide into simple carbon building blocks or fuels, the reduction of dinitrogen to ammonia under ambient conditions and the production and utilisation of dihydrogen. Catalytic sites for these reactions are necessarily based on metals that are abundant in the environment, including iron, nickel and molybdenum. However, attempts to generate biomimetic catalysts have largely failed to reproduce the high activity, stability and selectivity of enzymes. Proton and electron transfer and substrate binding are all finely choreographed, and we do not yet understand how this is achieved. This project develops a suite of new experimental infrared (IR) spectroscopy tools to probe and understand mechanisms of redox metalloenzymes in situ during electrochemically-controlled steady state turnover, and during electron-transfer-triggered transient studies. The ability of IR spectroscopy to report on the nature and strength of chemical bonds makes it ideally suited to follow the activation and transformation of small molecule reactants at metalloenzyme catalytic sites, binding of inhibitors, and protonation of specific sites. By extending to the far-IR, or introducing mid-IR-active probe amino acids, redox and structural changes in biological electron relay chains also become accessible. Taking as models the enzymes nitrogenase, hydrogenase, carbon monoxide dehydrogenase and formate dehydrogenase, the project sets out to establish a unified understanding of central concepts in small molecule activation in biology. It will reveal precise ways in which chemical events are coordinated inside complex multicentre metalloenzymes, propelling a new generation of bio-inspired catalysts and uncovering new chemistry of enzymes.

1 997 286 €

Start date: 2019-03-01, End date: 2024-02-29

"The main objective of COMOTION is to enable novel experiments for the investigation of the intrinsic properties of large molecules, including biological samples like proteins, viruses, and small cells -X-ray free-electron lasers have enabled the observation of near-atomic-resolution structures in diffraction- before-destruction experiments, for instance, of isolated mimiviruses and of proteins from microscopic crystals. The goal to record molecular movies with spatial and temporal atomic-resolution (femtoseconds and picometers) of individual molecules is near. -The investigation of ultrafast, sub-femtosecond electron dynamics in small molecules is providing first results. Its extension to large molecules promises the unraveling of charge migration and energy transport in complex (bio)molecules. -Matter-wave experiments of large molecules, with currently up to some hundred atoms, are testing the limits of quantum mechanics, particle-wave duality, and coherence. These metrology experiments also allow the precise measurement of molecular properties. The principal obstacle for these and similar experiments in molecular sciences is the controlled production of samples of identical molecules in the gas phase. We will develop novel concepts and technologies for the manipulation of complex molecules, ranging from amino acids to proteins, viruses, nano-objects, and small cells: We will implement new methods to inject complex molecules into vacuum, to rapidly cool them, and to manipulate the motion of these cold gas-phase samples using combinations of external electric and electromagnetic fields. These external-field handles enable the spatial separation of molecules according to size, shape, and isomer. The generated controlled samples are ideally suited for the envisioned precision experiments. We will exploit them to record atomic-resolution molecular movies using the European XFEL, as well as to investigate the limits of quantum mechanics using matter-wave interferometry."

1 982 500 €

Start date: 2014-09-01, End date: 2019-08-31

Galaxy Surveys are a key resource for observational cosmology, with the potential to provide the answers to many fundamental questions in modern physics. The Darksurvey project will use the Dark Energy Survey (DES) and extended-Baryon Oscillation Spectroscopic Survey (eBOSS) within which Will Percival has key leadership positions, and future projects including MS-DESI to measure the cosmological expansion rate between redshifts 0.5 and 2, testing Dark Energy. Complimentary structure growth measurements will test Einstein's theory of Gravity on the largest scales possible. The large-scale clustering of galaxies will be used to constrain primordial non-Gaussianity, testing and constraining models of inflation. The scale-dependence of the clustering signal will be used to measure the masses of neutrinos through their early Universe effects, and to set constraints on the evolution of galaxies and structure over cosmological time-scales. Parallel development of innovative tests and measurement methods will be undertaken to enable and enhance these results, while joint analysis with CMB and weak-lensing data will be used to perform additional tests, and to break degeneracies present when cosmological models are tested. This grant will consolidate the world-leading position of the group initiated by Will Percival at the University of Portsmouth, and developed over the last 4 years. Furthermore, it will train and develop a group of scientists within Europe with the key experimental skills required for the ESA Euclid mission.

2 151 192 €

Start date: 2014-06-01, End date: 2020-05-31

The coherent dynamics of excitons in systems of biological interest and in organic materials can now be studied with advanced experimental techniques, including two dimensional electronic spectroscopy, with time resolution of few femtoseconds. The theory of open quantum systems, that should support the interpretation of these new experiments, has been developed in different contexts over the past 60 years but seems now very inadequate for the problems of current interest. First of all, the systems under investigation are extremely complex and the most common approach, based on the development of phenomenological models, is often not very informative. Many different models yield results in agreement with the experiments and there is no systematic way to derive these models or to select the best model among many. Secondly, the quantum dynamics of excitons is so fast that one cannot assume that the dynamics of environment is much faster than the dynamics of the system, an assumption crucial for most theories. A remedy to the current limitation is proposed here through the following research objectives. (1) A general and automatic protocol will be developed to generate simple treatable models of the system from an accurate atomistic description of the same system based on computational chemistry methods. (2) A professionally-written software will be developed to study the quantum dynamics of model Hamiltonians for excitons in molecular aggregates. This software will incorporate different methodologies and will be designed to be usable also by non-specialists in the theory of quantum open systems (e.g. spectroscopists, computational chemists). (3) A broad number of problems will be studied with this methodology including (i) exciton dynamics in light harvesting complexes and artificial proteins and (ii) exciton dynamics in molecular aggregates of relevance for organic electronics devices.

1 512 873 €

Start date: 2014-04-01, End date: 2019-03-31