Project acronym HIGH-GEAR
Project High-valent protein-coordinated catalytic metal sites: Geometric and Electronic ARchitecture
Researcher (PI) Martin Ivar HÖGBOM
Host Institution (HI) STOCKHOLMS UNIVERSITET
Call Details Consolidator Grant (CoG), PE4, ERC-2016-COG
Summary It is estimated that almost half of all enzymes utilize metal cofactors for their function, for example the respiratory complexes and the oxygen-evolving photosystem II, the most fundamental requirements for aerobic life as we know it. If we could mimic nature’s use of metals for harvesting sunlight, energy conversion and chemical synthesis it would eliminate the need for fossil fuels and greatly increase the possibilities of chemical industry while reducing the environmental impact. Achieving this type of chemistry is an outstanding testament to evolution and understanding it is a glaring challenge to mankind.
These types of reactions are based on very challenging redox chemistry (involving one or several electrons). The key catalytic species are generally high-valent metal clusters with a varying ligand environment, provided by the protein and other bound molecules, that directly controls the reactivity of the inorganic core. To be able to understand and mimic this chemistry it is of central importance to know the geometric and electronic structures of the metal core as well as the entire ligand environment for these usually short-lived and very reactive intermediates. It has, for a number of reasons, proven extremely challenging to obtain these for protein-coordinated catalysts.
The central goal of this project is to determine true and accurate geometric and electronic structures of high-valent di-nuclear Fe/Fe and Mn/Fe metal sites coordinated in protein matrices known to direct these for varied and important chemistry. By combining new X-ray diffraction based techniques with advanced spectroscopy we aim to define how the protein controls the entatic state as well as reactivity and mechanism for some of the most potent catalysts in nature. The results will serve as a basis for design of oxygen-activating catalysts with novel properties.
Summary
It is estimated that almost half of all enzymes utilize metal cofactors for their function, for example the respiratory complexes and the oxygen-evolving photosystem II, the most fundamental requirements for aerobic life as we know it. If we could mimic nature’s use of metals for harvesting sunlight, energy conversion and chemical synthesis it would eliminate the need for fossil fuels and greatly increase the possibilities of chemical industry while reducing the environmental impact. Achieving this type of chemistry is an outstanding testament to evolution and understanding it is a glaring challenge to mankind.
These types of reactions are based on very challenging redox chemistry (involving one or several electrons). The key catalytic species are generally high-valent metal clusters with a varying ligand environment, provided by the protein and other bound molecules, that directly controls the reactivity of the inorganic core. To be able to understand and mimic this chemistry it is of central importance to know the geometric and electronic structures of the metal core as well as the entire ligand environment for these usually short-lived and very reactive intermediates. It has, for a number of reasons, proven extremely challenging to obtain these for protein-coordinated catalysts.
The central goal of this project is to determine true and accurate geometric and electronic structures of high-valent di-nuclear Fe/Fe and Mn/Fe metal sites coordinated in protein matrices known to direct these for varied and important chemistry. By combining new X-ray diffraction based techniques with advanced spectroscopy we aim to define how the protein controls the entatic state as well as reactivity and mechanism for some of the most potent catalysts in nature. The results will serve as a basis for design of oxygen-activating catalysts with novel properties.
Max ERC Funding
1 968 375 €
Duration
Start date: 2017-06-01, End date: 2022-05-31
Project acronym MolStrucDyn
Project Ultrafast Molecular Structural Dynamics
Researcher (PI) Sebastian Westenhoff
Host Institution (HI) GOETEBORGS UNIVERSITET
Call Details Consolidator Grant (CoG), PE4, ERC-2016-COG
Summary Chemical reactions in solution are strongly influenced by femtosecond solvent-solute dynamics. Likewise, proteins provide specific environments to control the outcome of substrate reactions. The molecular understanding of these effect are currently poorly developed.
I propose to fill this knowledge gap by ‘filming’ elementary chemical reactions in solution and in proteins. I will pioneer new time-resolved scattering and diffraction experiments using X-ray Free Electron Lasers (XFELs).
Using femtosecond time-resolved X-ray scattering, I plan to decipher the structural dynamics of bond breaking and bond formation in iodine containing compounds in solution. I will pioneer time-resolved fluctuation correlation X-ray scattering to recover full electron density maps of the reaction trajectories at an atomic resolution. I will visualize the as yet unknown structures of reaction intermediates and the solvent response.
Furthermore, I propose to investigate the molecular photoresponse of phytochrome photoconversion with femtosecond time-resolved serial microcrystallography. Phytochromes are ubiquitous photosensory proteins in plants and are essential to all vegetation on earth. I will resolve how the chromophore and the protein react collectively to photoexcitation and how this leads to conformational changes.
Combined, this interdisciplinary project will yield microscopic understanding on how the surrounding of reactants guides the outcome of elementary (bio)chemical reactions.
This program builds on my strengths in structural biology of phytochromes (Takala et al., Nature, 2014), time-resolved X-ray scattering (Westenhoff et al., Nature Methods 2010), and femtosecond spectroscopy (21 papers in PRL, JACS, Nature Methods 2006-2012 & 2016).
The new XFEL-based methods will have wide-ranging applications in chemistry and biology. My work will open new horizons in physical chemistry and structural biology.
Summary
Chemical reactions in solution are strongly influenced by femtosecond solvent-solute dynamics. Likewise, proteins provide specific environments to control the outcome of substrate reactions. The molecular understanding of these effect are currently poorly developed.
I propose to fill this knowledge gap by ‘filming’ elementary chemical reactions in solution and in proteins. I will pioneer new time-resolved scattering and diffraction experiments using X-ray Free Electron Lasers (XFELs).
Using femtosecond time-resolved X-ray scattering, I plan to decipher the structural dynamics of bond breaking and bond formation in iodine containing compounds in solution. I will pioneer time-resolved fluctuation correlation X-ray scattering to recover full electron density maps of the reaction trajectories at an atomic resolution. I will visualize the as yet unknown structures of reaction intermediates and the solvent response.
Furthermore, I propose to investigate the molecular photoresponse of phytochrome photoconversion with femtosecond time-resolved serial microcrystallography. Phytochromes are ubiquitous photosensory proteins in plants and are essential to all vegetation on earth. I will resolve how the chromophore and the protein react collectively to photoexcitation and how this leads to conformational changes.
Combined, this interdisciplinary project will yield microscopic understanding on how the surrounding of reactants guides the outcome of elementary (bio)chemical reactions.
This program builds on my strengths in structural biology of phytochromes (Takala et al., Nature, 2014), time-resolved X-ray scattering (Westenhoff et al., Nature Methods 2010), and femtosecond spectroscopy (21 papers in PRL, JACS, Nature Methods 2006-2012 & 2016).
The new XFEL-based methods will have wide-ranging applications in chemistry and biology. My work will open new horizons in physical chemistry and structural biology.
Max ERC Funding
2 000 000 €
Duration
Start date: 2017-06-01, End date: 2022-05-31
Project acronym No-LIMIT
Project Boosting Photovoltaic Performance by the Synergistic Interaction of Halide Perovskites and Semiconductor Quantum Dots
Researcher (PI) Iván MORA SERÓ
Host Institution (HI) UNIVERSITAT JAUME I DE CASTELLON
Call Details Consolidator Grant (CoG), PE4, ERC-2016-COG
Summary Photovoltaic conversion has the extraordinary property of transforming the solar energy directly into electric power. However, the available electrical power is known to be severely limited by the so-called Shockley-Queisser (SQ) photoconversion limit. The maximum efficiency for a single absorber is limited as photons with energy lower than the bandgap (BG) cannot be absorbed, and just an energy equivalent to the BG can be used for photons with higher energy than the BG, due to thermalization. Tandem cells have overcome this SQ limit upon exploiting complex and expensive configurations. Alternative approaches, even with higher potentiality, as Intermediate Bandgap Solar Cells (IBSCs) have not reached the expected performance mainly due to the limitations introduced by the monocrystalline matrix. The incorporation of quantum dots (QD) to create the IB produces layer strain and defects that limit the cell performance. No-LIMIT proposes to revamp IBSCs concept, using polycrystalline halide perovskites (HP) host matrix in order to take benefit from the strain relaxation at polycrystalline materials and from HP benign defect physics. HPs show an outstanding performance even when they are grown in a porous structure, indicating that their excellent transport and recombination properties are preserved with embedded materials. No-LIMIT will exploit this potentiality by using the states of embedded QD as IB in IBSC with HP matrix. The project will focus on the preparation of HPs-QD systems with enhanced light collection efficiency preserving charge transport, recombination and stability. No-LIMIT will study the properties and interactions of the HP and QD materials developed, as well as injection, recombination and transport properties in the coupled system. The combination of these strategies will build a ground-breaking synergistic system able to break the SQ limit. The achievements of IBSC, together with the intermediate steps, will have a colossal impact on photovoltaics
Summary
Photovoltaic conversion has the extraordinary property of transforming the solar energy directly into electric power. However, the available electrical power is known to be severely limited by the so-called Shockley-Queisser (SQ) photoconversion limit. The maximum efficiency for a single absorber is limited as photons with energy lower than the bandgap (BG) cannot be absorbed, and just an energy equivalent to the BG can be used for photons with higher energy than the BG, due to thermalization. Tandem cells have overcome this SQ limit upon exploiting complex and expensive configurations. Alternative approaches, even with higher potentiality, as Intermediate Bandgap Solar Cells (IBSCs) have not reached the expected performance mainly due to the limitations introduced by the monocrystalline matrix. The incorporation of quantum dots (QD) to create the IB produces layer strain and defects that limit the cell performance. No-LIMIT proposes to revamp IBSCs concept, using polycrystalline halide perovskites (HP) host matrix in order to take benefit from the strain relaxation at polycrystalline materials and from HP benign defect physics. HPs show an outstanding performance even when they are grown in a porous structure, indicating that their excellent transport and recombination properties are preserved with embedded materials. No-LIMIT will exploit this potentiality by using the states of embedded QD as IB in IBSC with HP matrix. The project will focus on the preparation of HPs-QD systems with enhanced light collection efficiency preserving charge transport, recombination and stability. No-LIMIT will study the properties and interactions of the HP and QD materials developed, as well as injection, recombination and transport properties in the coupled system. The combination of these strategies will build a ground-breaking synergistic system able to break the SQ limit. The achievements of IBSC, together with the intermediate steps, will have a colossal impact on photovoltaics
Max ERC Funding
1 999 072 €
Duration
Start date: 2017-09-01, End date: 2022-08-31
