ERC FUNDED PROJECTS

"The origin of life is not well understood, and is one of the great remaining questions in science. Autocatalytic chemical reactions have been extensively studied with the aim of providing insight into the principles underlying living systems. In biology, organisms can be thought of as imperfect self-replicators, which produce closely related species, allowing for selection and evolution. Autocatalysis is also an important part of many other biological processes. This project aims to develop new autocatalytic reactions where two simple chemical building blocks come together to give a more complex product, and then the product aggregates to give primitive cell-like structures or "protocells" such as micelles or vesicles. The protocells allow the starting materials to mix more efficiently, speeding up the reaction in time and giving rise to complex behaviour of the protocells. These reactions will serve as models that I hope will contribute to understanding how cell-like systems can emerge from simpler chemicals and be relevant to how life started on earth. This project will give the opportunity to study chemical systems that may be able to evolve in time, allow development of useful chemical models of important biological processes, and provide ‘bottom-up’ approaches to synthetic biology. This research will potential allow the study evolution in a new ways, develop technology useful to a number of scientific fields, and potentially shed light on the processes that allowed chemistry to become biology on the primitive Earth."

2 278 073 €

Start date: 2016-05-01, End date: 2021-04-30

The use of bioinorganic nanohybrids (nanoscaled systems based on an inorganic and a biological component) has already resulted in several innovative medical breakthroughs for drug delivery, therapeutics, imaging, diagnosis and biocompatibility. However, researchers still know relatively little about the structure, function and mechanism of these nanodevices. Theoretical investigations of bioinorganic interfaces are mostly limited to force-field approaches which cannot grasp the details of the physicochemical mechanisms. The BIOINOHYB project proposes to capitalize on recent massively parallelized codes to investigate bioinorganic nanohybrids by advanced quantum chemical methods. This approach will allow to master the chemical and electronic interplay between the bio and the inorganic components in the first part of the project, and the interaction of the hybrid systems with light in the second part. The ultimate goal is to provide the design principles for novel, unconventional assemblies with unprecedented functionalities and strong impact potential in nanomedicine. More specifically, in this project the traditional metallic nanoparticle will be substituted by emerging semiconducting metal oxide nanostructures with photocatalytic or magnetic properties capable of opening totally new horizons in nanomedicine (e.g. photocatalytic therapy, a new class of contrast agents, magnetically guided drug delivery). Potentially efficient linkers will be screened regarding their ability both to anchor surfaces and to bind biomolecules. Different kinds of biomolecules (from oligopeptides and oligonucleotides to small drugs) will be tethered to the activated surface according to the desired functionality. The key computational challenge, requiring the recourse to more sophisticated methods, will be the investigation of the photo-response to light of the assembled bioinorganic systems, also with specific reference to their labelling with fluorescent markers and contrast agents.

1 748 125 €

Start date: 2016-02-01, End date: 2021-01-31

Hydrogels cross-linked through supramolecular interactions are highly dependant on the dynamic charac- teristics of the physical cross-links. Few fundamental studies have been undertaken to quantitatively de- scribe structure-property relationships for these types of systems. Hydrogels formed from CB[8]-mediated supramolecular physical cross-linking mechanisms have gained significant interest on account of their excel- lent physical and mechanical properties such as self-healing and shear-thinning. This supramolecular motif has been further exploited to introduce and compatibilise a wide variety of different materials into hydrogel networks without phase separation, forming hybrid composite hydrogels attributed with unique and emergent properties. This proposal aims to pioneer the combination of several state-of-the-art characterisation tech- niques into an unique experimental setup (CAM-RIG), which will combine super-resolution and confocal microscopy imaging modalities with simultaneous strain-controlled rheological measurements to investigate fundamental structure-property relationships of these systems. For the first time it will be possible to decon- volute the molecular-level dynamics of the supramolecular physical cross-links from chain entanglement of the polymeric networks and understand their relative contributions on the resultant properties of the hydrogels. Using the fundamental insight gained, a set of key parameters will be determined to maximise the potential of supramolecular biocompatible hydrogels, driving paradigm shifts in sustainable science and biomaterial applications through the precise tuning of physical properties.

2 038 120 €

Start date: 2017-05-01, End date: 2022-04-30

Genome sequencing projects have provided unique insights into the cellular inventory of genes and their corresponding protein products. Despite this success, a large fraction of cellular proteins remains functionally uncharacterized. Their annotation represents a major challenge for contemporary research, reaching beyond the power of bioinformatic sequence similarity searches. Thus multidisciplinary strategies consolidating chemical and biological methods are required to close this gap. We here approach the challenge by two chemical proteomic platforms that focus on disease relevant sub-fractions of the uncharacterized proteome. The first platform utilizes functionalized cofactors that exploit cognate cellular uptake systems and report specific binding of large enzyme families. The molecules will be applied to mine cellular proteomes for unknown family members with crucial roles in diseases and assign their function. The second platform exploits phosphoaspartate as an important disease-related post-translational modification. Due to low stability, this transient modification currently escapes detection by established proteomic procedures. Moreover, little is known about the enzymes that catalyze aspartate phosphorylation. We here use specific nucleophilic traps that convert phosphoaspartate into stable modifications suitable for analytic detection. In addition, the complement of currently unknown phosphodonor proteins will be identified with customized tools. With these platforms we aim to functionally annotate sub-fractions of the uncharacterized proteome and utilize our tools for the identification of new drug targets by comparative analysis of healthy and diseased cells. Finally, we apply the camouflaged molecular design strategy in the synthesis of compound libraries to screen for candidate inhibitors against selected, disease-modulating targets. The previous record of my group in chemical proteomics provides a strong basis to achieve these challenging goals.

1 936 250 €

Start date: 2017-03-01, End date: 2022-02-28

Nature has evolved astonishingly diverse structures where the nanoscale assembly of components is key to their functionality. Such nanostructures self-assemble at massive scales and at spatial resolutions surpassing top-down production techniques. The leaves of a single tree, e.g., can cover the area of 10.000 m^2 while every mm^2 contains more than 10^8 highly efficient light-harvesting complexes. For future photovoltaic devices, light-managing surfaces and photonic devices it will thus be beneficial to adopt principles of self-assembly. Advances in design and low-cost production of DNA nanostructures allow us to challenge nature. By combining the assembly power of bottom-up DNA origami with top-down lithography it will be possible to fabricate functional nanostructured materials designed on the molecular level while reaching macroscopic dimensions. With the goal to boost energy conversion rates, I will design DNA structures that grow from pre-patterned surfaces and assemble into interpenetrating 3D networks that exhibit the highest possible contact area for electron donor and acceptor molecules in organic photovoltaic devices. Spectral tuning through carefully designed dye arrangements will complement these efforts. Custom-tailored photonic crystals built from lattices of DNA origami structures will control the flow of light. By incorporating dynamic DNA reconfigurability and colloidal nanoparticles at freely chosen positions, intelligent materials that respond to external cues such as light or heat are projected. Positioning accuracy of 1 nm renders possible the emergence of so-called “Dirac plasmons” in DNA-assembled particle lattices. Such topologically protected states are sought after for the coherent and loss-less propagation of energy and information in next-generation all-optical circuits. These approaches have the potential to reduce production costs and increase efficiencies of light-harvesting devices, intelligent surfaces and future computing devices.

1 997 500 €

Start date: 2019-04-01, End date: 2024-03-31

This high-impact, challenging CoG Proposal integrates multiple novel ideas in boron and zinc chemistry into an overarching project to open up new horizons across synthesis and catalysis. The Applicant’s successful ERC StG has opened up new avenues of pioneering research in main group element mediated transformations that were not conceivable before the work was done. Components of this proposal extend out from the StG into new, exciting research areas that are completely different. Developing low toxicity earth abundant catalysts for important transformations is vital to the EU with the focus herein being on; (i) the Suzuki-Miyaura (S-M) cross coupling reaction which is ubiquitous in industry and academia, and (ii) the formation of organoboranes that are essential synthetic intermediates. Both of these are currently dominated by toxic, expensive and low abundance precious metal catalysts (e.g. Pd, Ir). This project will deliver innovation through utilising combinations of main group Lewis acids and nucleophilic anions that do not react with each other, i.e. are frustrated pairs. This “frustration” enables the two species to concertedly transform substrates to achieve: (i) Precious metal-free S-M cross coupling reactions of sp3C electrophiles catalysed by zinc and boron compounds, including stereospecific couplings and one pot two step cross electrophile couplings. (ii) Trans-elementoboration of alkynes, including the unprecedented fluoroboration of alkynes. Other new approaches will be developed to access novel (hetero)arylboronic acid derivatives using only simple boranes and without requiring noble metal catalysts, specifically: (i) boron directed C-H borylation and (ii) directed ortho borylation to enable subsequent meta selective SEAr C-H functionalisation. This CoG will afford the freedom and impetus via consolidated funding to undertake fundamental research to deliver high impact results, including developing a new area of cross coupling catalysis research.

2 070 093 €

Start date: 2018-05-01, End date: 2023-04-30

The astonishing properties of the f-elements have been exploited in numerous consumer technologies, despite their fundamental chemistry being poorly developed. It is now crucial to address this issue to provide the necessary insights to develop future applications. Design criteria exist to build f-element complexes with maximised physical attributes. This adventurous proposal targets the synthesis and thorough analysis of two complementary molecular f-element architectures that 1) optimise magnetic properties and 2) stabilise unusual oxidation states. In Part 1, we target highly axial f-element complexes that lack equatorial ligand interactions. These molecules can exhibit maximised single-molecule magnet properties, including magnetic hysteresis, a memory effect and as a prerequisite of data storage, at liquid nitrogen temperatures. This is the necessary first step towards achieving high-density molecular data storage without expensive liquid helium cooling and future commercial applications. In Part 2, we target trigonal f-element complexes that lack axial ligand interactions. These are optimal ligand fields for the stabilisation of low oxidation states, thus we aim for rare lanthanide/actinide(II) and unprecedented lanthanide/actinide(I) complexes. These compounds are ideal candidates for unique measurements of covalency by pulsed electron paramagnetic resonance spectroscopy, which will provide textbook data that can be transferable to nuclear fuel cycles. An ERC CoG will provide the necessary resources to build a world-leading research team that will deliver landmark synthetic results and fresh insights into f-element electronic structure, whilst opening up new chemical space for future exploitation. These findings will underpin current technologies and will facilitate the discovery of future applications, supporting key Horizon 2020 priority areas including the Flagship on Quantum Technologies, and enhancing the scientific reputation and economy of the EU.

1 990 801 €

Start date: 2019-09-01, End date: 2024-08-31

The aerobic conditions on our planet enable the accumulation of oxidized matter whereas reduced chemicals are the most valuable energy carriers. Future shortages of energy-rich resources make efficient reductive transformations one of the greatest scientific challenges. To address this societal, economic and environmental demand, we propose new approaches to the design and application of stabilized iron catalysts. Our endeavour exploits the higher reducing power of Fe (vs. noble metals) in challenging reductive transformations and capitalizes on the high sustainability of Fe catalysis over noble metal technologies. The use of low-valent Fe catalysts, the realization of new catalytic reactions and their mechanistic understanding will only be possible through the controlled generation and effective stabilization of reduced Fe species and active nanoparticles. Major emphasis will be placed on coordinative ligand/solvent systems which accommodate electron-rich Fe centers (olefins, arenes, Lewis acids, redox-ligands, ionic liquids). We address new approaches to the synthesis of low-valent Fe complexes and bottom-up/top-down preparations of Fe(0) nanoparticles. Catalytic reactions of high relevance to the manufacture of chemicals and materials will be studied (reduction, cross-coupling, hydrogenation, defunctionalization) with special emphasis on cheap abundant substrates. Mechanistic studies aim at understanding Fe-centered reductive bond activations and ligand co-operation. The proposed use of the most abundant transition metal for challenging reductive processes under practical conditions extends beyond the realm of synthesis, catalysis, and materials into spectroscopy, solvent technologies and reaction processing with direct relevance to sustainable chemicals and energy production. Our multidisciplinary program will provide new sets of active iron catalysts for reductive processes and is a major puzzle piece toward a greener chemical synthesis.

1 995 400 €

Start date: 2016-10-01, End date: 2021-09-30

Chemical transformations comprise the polarization of the reacting species. As a consequence, partially or fully charged reagents and intermediates are omnipresent in chemistry. Although anion-binding processes are well-known for their crucial role in molecular recognition, this type of phenomenon has only recently been utilized for catalysis. Since catalytic reactions are of utmost relevance to construct valuable chemicals and materials, this mode of catalytic chemical activation might be the key for the future design of original and more efficient synthetic transformations. However, the effects of anions in catalytic processes are still largely unknown. Aiming at providing a novel general synthetic toolbox, in this project I propose several anion-binding activation concepts to solve current challenging catalytic synthetic problems. To achieve this goal, structurally different chiral anion-binding catalysts will be developed and incorporated into the existing limited palette of catalyst library. Furthermore, I propose a significant expansion of the application scope of anion-binding catalysis based on the activation and modulation of anionic nucleophiles and oxidants to develop organocatalytic reactions such as halogenations and oxidations, including the asymmetric functionalization of C-H bonds. In addition, anion-binding processes will be used to facilitate key steps in cross-coupling reactions such as the transmetallation, as well as the photoactivity modulation of readily available photosensitizers and the introduction of asymmetric photocatalysis involving radical-anions. The proposed groundbreaking approaches will revolutionize not only anion-binding catalysis but also all the scientific areas relying on catalytic synthetic methods. Thus, the results derived from this project will have a tremendous impact in diverse fields such as catalysis, organic synthesis and material sciences, as well as in economical, environmental and industrial issues.

1 997 763 €

Start date: 2017-06-01, End date: 2022-05-31

Organophosphorus compounds are an important and industrially relevant class of molecules with numerous uses, e.g. as reagents in organic synthesis, ligands in catalytically active metal complexes, and in pest control. State-of-the-art synthesis methods for all these valuable and useful compounds rely on an atom inefficient and hazardous multi-step procedure involving the oxidation of white phosphorus (P4) with toxic chlorine gas. Less wasteful and more environmentally benign methods are highly desirable, but transformations of white phosphorus directly into organophosphorus compounds are hardly developed. This project explores new methods for the activation and functionalization of white phosphorus. The metal-mediated stepwise transformation of P4 into organophosphorus compounds is a key objective. Novel transition metal compounds are designed and synthesized, which can generate reactive phosphorus units. The concept of heterobimetallic P4 activation, where two electronically different metal complexes interact with P4 cooperatively, is introduced for this purpose. Reactions of the phosphorus fragments in these new, reactive complexes with electrophiles will produce novel, fundamentally interesting organophosphorus compounds avoiding chlorinated intermediates. Catalytic methods for P4 functionalization are currently unknown, and developing such methods using transition metal and photoredox catalysts is an additional objective of this proposal. By providing novel synthetically useful and even catalytic procedures for converting P4 into organophosphorus compounds, this project will significantly contribute to the development of phosphorus chemistry and more sustainable synthesis methods.

1 955 846 €

Start date: 2018-09-01, End date: 2023-08-31

"We aim to consolidate a trans-disciplinary research programme in which synthetic biology is harnessed to enable synthetic chemistry. We will utilise this approach to expeditiously access series of previously intractable natural product analogues. There is an urgent need for the discovery and development of new drugs and in particular new antibiotics. More than 13 million lives worldwide are currently claimed each year due to infectious diseases. Natural products provide an unparalleled starting point for drug discovery, with over 60% of anticancer agents and over 70% of antibiotics entering clinical trials in the last three decades being based on such compounds. In order to gain a full understanding as to how a drug works and in order to be able to generate compounds with improved biological activity and physicochemical properties the generation of analogues is essential. In recent years pharmaceutical industries have shied away from natural products due to the perceived synthetic intractability of libraries of natural product analogues and the misperception that it is not possible to carry out thorough structure activity relationship (SAR) assessment on such compounds. As a result of largely abandoning natural products, industries’ drug discovery pipelines are beginning to run dry; this is a particular concern when faced with the need to combat the ever-increasing problem of drug resistance and infectious disease. We aim to challenge the misperception that natural products are not “med chemable” We are developing a new approach to natural product analogue synthesis. By introducing a gene from a foreign organism to complement existing natural product biosynthetic machinery we are able to introduce a chemically orthogonal, reactive and selectably chemically functionalisable handle into the natural product (the antithesis of a protecting group) - this reactive handle will enable us to carry out chemical modifications only at the site at which it is located."

1 981 272 €

Start date: 2014-06-01, End date: 2019-05-31

This proposal aims to understand and control glycosylation reactions. In a glycosylation reaction a “donor” glycoside and an “acceptor” (the nucleophile) are united to form an oligosaccharide. Although it is the central reaction in carbohydrate chemistry, our understanding of this reaction, in terms of stereoselectivity and productivity is still limited. The structural variation in the building blocks leads to a complex continuum of SN2-SN1 mechanisms that operates and it is currently impossible to predict where in the continuum the reaction exactly takes place. This proposal provides fundamental insight into the outcome of glycosylations by studying both the activated donor glycoside and the acceptor nucleophile. Activation of a donor glycoside leads to different reactive intermediates, covalent anomeric species (most often triflates) and oxocarbenium ion-like species. The relative reactivity of these species is quantified to generate novel reactivity charts. The covalent species are studied by innovative competition experiments, kinetic studies and NMR spectroscopy. The (fleeting) oxocarbenium ion-like intermediates are probed by a computational approach and by “super-acid NMR” studies in which stable glycosyl cations are generated and studied in super-acid media. The reactivity of glycosyl acceptors is systematically studied in a set of SN2 or SN1-type glycosylations. Using kinetic studies and competition reactions charts of acceptor nucleophilicity are compiled. The reactivity of the donors and acceptors is matched using a family of tailor made “reactivity modulators”, spanning a broad reactivity window bridging the reactivity gap between the building blocks leading to predictable glycosylations. The developed methodology is employed in automated solid phase syntheses of libraries of oligosaccharides featuring multiple cis-glycosidic linkages. The proposal is a major step forward in the development of a general glycosylation procedure.

2 000 000 €

Start date: 2017-05-01, End date: 2022-04-30

"Nanowires are a powerful and versatile platform for a broad range of applications. Among all semiconductors, the heavy-elements materials exhibit the highest electron mobilities, strongest spin-orbit coupling and best thermoelectric properties. Nonetheless, heavy-element nanowires have been unexplored. With this proposal we unite the unique advantages of design freedom of nanowires with the special properties of heavy-element semiconductors. We specifically reveal the potential of heavy-element nanowires in the areas of thermoelectrics, and topological insulators. Using our strong track record in this area, we will pioneer the synthesis of this new class of materials and study their intrinsic materials properties. Starting point are nanowires of InSb and PbTe grown using the vapor-liquid-solid mechanism. Our aims are 1) to obtain highest-possible electron mobilities for these bottom-up fabricated materials by investigating new materials combinations of different semiconductor classes to effectively passivate the nanowire surface and we will eliminate impurities; 2) to investigate and optimize thermoelectric properties by developing advanced superlattice and core/shell nanowire structures where electronic and phononic transport is decoupled; and 3) to fabricate high-quality planar nanowire networks, which enable four-point electronic transport measurements and allow precisely determining carrier concentration and mobility. Besides the fundamentally interesting materials science, the heavy-element nanowires will have major impact on the fields of renewable energy, new (quasi) particles and quantum information processing. Recently, the first signatures of Majorana fermions have been observed in our InSb nanowires. With the proposed nanowire networks the special properties of this recently discovered particle can be tested for the first time."

2 698 447 €

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

In the physics and chemistry of materials science, an intense focus of forefront research is the search for ever-smaller and ever-faster building blocks for information and communication technology (ICT) applications. The realization of next-generation devices, in ICT fields such as spintronics, spin-orbitronics and plasmonics, will depend decisively on our ability to generate new functionalities that can be actively controlled on the shortest length and time scales. The groundbreaking idea of hyControl is to develop a conceptually new class of active ICT nano-scale materials by building functionality into the nano-scale object that naturally forms when an organic molecule is hybridized on a metallic surface: a nano-scale hybrid unit (NHyU). NHyUs will be realized by depositing selected organic molecules onto three classes of inorganic systems: transition metals; spin-textured materials such as Rashba systems and topological insulators; and magneto-plasmonic nano-structures. By tuning optical excitation to specific resonances, we will control the hybridization strength with ultrashort laser pulses, and thereby induce a coherent response in the spin, orbit, and/or electron degrees of freedom of the NHyU. Thereby we will achieve coherent control - at the molecular scale - of technologically important parameters, such as magnetization, plasmonic resonances, and spin texture. This hyControl concept will be implemented using a novel experimental method, spin- and phase-resolved orbital mapping, that is capable of resolving the transient spin-dependent electronic structure of precisely those valence band electrons which mediate the hybridization in a single NHyU. While inspired by the latest achievements in molecular spintronics, hyControl will open the way to new technologies in various ICT applications, three of which - spintronics, spin-orbitronics, and plasmonics - have been selected to demonstrate the ability and versatility of optically controlled NHyUs.

1 994 791 €

Start date: 2017-09-01, End date: 2022-08-31

RNAs are linear biopolymers that consist of only four types of building blocks, but can fold into complex three-dimensional structures that are endowed with selective, high-affinity ligand-binding abilities known as aptamers, and catalytic activities known as ribozymes. Genome projects have brought the surprising insight that a large part of the human genome is transcribed into RNAs, but only a very small fraction is translated into proteins. The actual number of noncoding RNAs with specific functions is currently unknown, but many are considered as prominent regulators of cellular functions. Posttranscriptional modifications of RNA add an extra layer of complexity, but their regulatory roles in RNA metabolism are only poorly understood. Despite the relative simplicity in molecular composition, the available methodological repertoire for manipulation, interrogation and visualization of RNA is rather limited. This project aims to solve the challenge of RNA labeling in both fixed and living cells, using aptamers and ribozymes for RNA imaging and functional characterization. We introduce the term illumizymes for novel tools that attach bio-orthogonal tags and fluorophores to specific RNA sequences, in vitro and in vivo. Ribozymes and aptamers for small, stable, and specific labels will be identified by in vitro selection and systematic evolution of ligands by exponential enrichment (SELEX) to activate the fluorescence of latent chromophores by restricting their conformational flexibility and/or formation of covalent bonds by new bio-orthogonal reactions. Using naturally inspired, cell-permeable and non-toxic ligands, we will specifically select for increased brightness and photostability, and evolve illumizymes into color-switching probes for RNA microscopy. The new genetically encodable RNA devices will find widespread applications in diverse disciplines to enlighten our understanding of cellular RNA functions in health and disease.

2 061 250 €

Start date: 2016-07-01, End date: 2021-06-30

Ions are nearly omnipresent in chemistry and biochemistry. By providing the highest intermolecular interaction energies, ionic interactions have an extreme impact on molecular structures, which are the key to molecular functions. Experimentally determined structures of small contact ion pairs in solution are very rare and sometimes lacking in complete research fields. In addition, despite the amazing progress in theoretical and supramolecular chemistry, the subtle interplay of interactions in small organic ion pairs remains largely unknown. As a result design principles for small organic ion pairs in solution are not available. To solve this general problem there is an urgent and actual need of the synthetic community, because ion-pairing catalysis is the actual hot topic in asymmetric catalysis. There, new catalysts have to be screened with high effort in a black box mode and reviews state that structural and mechanistic studies will be an essential part of the further progress in the field. In previous projects spread over the fields of organometallic, bioorganic, supramolecular and medicinal chemistry as well as transition metal catalysis and organocatalysis, we gained special NMR expertise in the structure elucidation of ion pairs and reaction intermediates as well as the assessment of intermolecular interactions. Now in this project, nearly all of these various techniques and approaches will be combined in a new and so far unprecedented way and complemented by techniques used for protein ligand interactions and extreme low temperature measurements. With this unique combination, NMR approaches will be developed and applied to elucidate the structures of catalytically active ion pairs and their intermediates in solution and to dissect their intermolecular interactions. The resulting detailed design concept for small ion pairs in solution will revolutionize not only ion-pairing catalysis but all scientific fields working with organic ion pairs in solution.

1 994 685 €

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

Research in 2D materials has increased dramatically since the first isolation of graphene in 2004, with diverse interdisciplinary studies. In the last few years, 2D material research expanded beyond graphene by the development of other 2D materials, such as monolayered transition metal dichalcogenides, black phosphorous, and Boron Nitride. There are hundreds of possible 2D crystals that can be isolated, with properties ranging from metallic, semi-metallic, semiconducting to insulating, depending on the material composition. Semiconducting 2D materials have attracting interest in next-generation electronics/opto-electronics such as transistors, photo-gated transistors, photo-detectors, solar cells, and light emitting devices (LEDs), molecular sensors and optical imaging sensors. The unique structural form of 2D materials provides several benefits over other existing materials: ultrathin, flexible, highly transparent, large surface to volume ratio, and 2D quantum confinement. High transparency LEDs are required for applications in transparent displays on glass panels. Many 2D based opto-electronic devices have used mechanical exfoliation from bulk crystals, but this is limited to small areas. Recent work on chemical vapour deposition (CVD) to grow wafer-scale 2D materials has opened up exciting opportunities for commercial exploitation and has accelerated the intensity of research in this field towards real applications. The vision of this proposal is to realize a new class of ultra-thin, flexible, large-area, transparent, high-sensitivity opto-electronic device arrays based on all 2D materials, with a focus on imaging sensors and LEDs. This will involve wafer-scale CVD synthesis of 2D materials including novel blue and green 2D semiconductors, optical spectroscopy to probe the interlayer interactions, atomic level structure-property correlations using advanced electron microscopy, and the nanoscale fabrication and testing of high efficiency devices.

1 999 318 €

Start date: 2017-04-01, End date: 2022-03-31

"Living organisms are sophisticated self-assembled structures that exist and operate far from thermodynamic equilibrium and, as such, represent the ultimate example of dissipative self-assembly. They remain stable at highly organized (low-entropy) states owing to the continuous consumption of energy stored in ""chemical fuels"", which they convert into low-energy waste. Dissipative self-assembly is ubiquitous in nature, where it gives rise to complex structures and properties such as self-healing, homeostasis, and camouflage. In sharp contrast, nearly all man-made materials are static: they are designed to serve a given purpose rather than to exhibit different properties dependent on external conditions. Developing the means to rationally design dissipative self-assembly constructs will greatly impact a range of industries, including the pharmaceutical and energy sectors. The goal of the proposed research program is to develop novel principles for designing dissipative self-assembly systems and to fabricate a range of dissipative materials based on these principles. To achieve this goal, we will employ novel, unconventional approaches based predominantly on integrating organic and colloidal-inorganic building blocks. Specifically, we will (WP1) drive dissipative self-assembly using chemical reactions such as polymerization, oxidation of sugars, and CO2-to-methanol conversion, (WP2) develop new modes of intrinsically dissipative self-assembly, whereby the activated building blocks are inherently unstable, and (WP3&4) conceive systems whereby self-assembly is spontaneously followed by disassembly. The proposed studies will lead to new classes of ""driven"" materials with features such as tunable lifetimes, time-dependent electrical conductivity, and dynamic exchange of building blocks. Overall, this project will lay the foundations for developing new synthetic dissipative materials, bringing us closer to the rich and varied functionality of materials found in nature."

1 999 572 €

Start date: 2019-01-01, End date: 2023-12-31

Molecular chirality is a central theme in chemistry; in 2015 approximately 13% of publications in J. Am. Chem. Soc. and 12% in Angew. Chem. concerned chirality. All previously studied forms of molecular asymmetry (central, axial, planar and helical chirality) have found applications throughout the sub-disciplines of chemistry including as catalysts, materials and sensors. Mechanically chiral rotaxanes are molecules in which the mechanical bond between a macrocycle and dumbbell-shaped component is the source of asymmetry rather than the covalent structure of the components themselves. These unusual molecules represent a novel and unexplored chiral supramolecular environment as the lack of a scalable synthetic approach for their isolation in enantiopure form has prevented all but the most cursory investigation of their properties. Thus, mechanical chirality remains an unexplored frontier of molecular asymmetry with the potential to deliver novel functions and impact across a range of chemical disciplines from materials chemistry to the synthesis of pharmaceutically active compounds. The Goldup Group has recently demonstrated the first practical method for the synthesis of enantiopure mechanically chiral rotaxanes using a flexible active template methodology and thus the stage is finally set for the study and exploitation of this novel form of supramolecular asymmetry. Within the period of this ERC Consolidator Grant the PI will lead a team to investigate the synthesis, properties and applications of these intriguing mechanically chiral molecules.

1 998 928 €

Start date: 2017-04-01, End date: 2022-03-31

A fundamental difference between man-made and living matter is metabolism: the ability to dissipate chemical energy to drive many different chemical processes out of equilibrium. Metabolism endows chemical systems within living organisms with properties that are standard in biology but odd in chemistry: the capability to process information, to move and to react to the external world. My goal is to endow soft materials with dynamic life-like properties. I have chosen four: molecular computation, movement, self-construction and the capacity to entertain complex chemical conversations with living cells. To do so I will embed stimuli-responsive materials with a biocompatible synthetic metabolism capable of sustaining autonomous chemical feedback loops that process information and perform autonomous macroscopic actions. My approach combines concepts from systems chemistry, synthetic biology and DNA molecular programming with soft materials and uses a biochemical system that I have contributed to pioneer: DNA/enzyme active solutions that remain out of equilibrium by consuming a chemical fuel with non-trivial reaction kinetics. This system has three unique properties: programmability, biocompatibility and a long-term metabolic autonomy. Metabolic matter will be assembled in two stages: i) enabling metabolic materials with dynamic chemical, biological and mechanical responses, and ii) creating metabolic materials with unprecedented properties, in particular, the capacity of self-construction, which I will seek by emulating embryogenesis, and the ability to autonomously pattern a community of living cells. By doing this I will create for the first time chemical matter that is both dynamically and structurally complex, thus bringing into the realm of synthetic chemistry behaviors that so far only existed in biological systems. In the long term, metabolic matter could provide revolutionary solutions for soft robotics and tissue engineering.

1 899 333 €

Start date: 2018-06-01, End date: 2023-05-31

Organometallic redox-catalysts of energy relevance, i.e. water and hydrogen oxidation, and proton and carbon dioxide reduction catalysts, will be incorporated into metal-organic frameworks (MOFs). Immobilization and spatial organization of the molecular catalysts will stabilize their molecular integrity and ensure longevity and recyclability of the resulting MOFcats. The organized environment provided by the MOF will enable the control of conformational flexibility, diffusion, charge transport, and higher coordination sphere effects that play crucial roles in enzymes, but cannot be addressed in homogenous solution and are thus largely unexplored. The effect that the MOF environment has on catalysis will be directly probed electrochemically in MOFcats that are immobilized or grown on electrode surfaces. In combination with spectroscopic techniques in spectroelectrochemical cells, intermediates in the catalytic cycles will be detected and characterized. Kinetic information of the individual steps in the catalytic cycles will be obtained in MOFs that contain both a molecular photosensitizer (PS) and a molecular catalyst (PS-MOFcats). The envisaged systems will allow light-induced electron transfer processes to generate reduced or oxidized catalyst states the reactivity of which will be studied with high time resolution by transient UV/Vis and IR spectroscopy. The acquired fundamental mechanistic knowledge is far beyond the current state-of-the-art in MOF chemistry and catalysis, and will be used to prepare MOFcat-based electrodes that function at highest possible rates and lowest overpotentials. PS-MOFcats will be grown on flat semiconductor surfaces, and explored as a novel concept to photoanode and -cathode designs for dye-sensitized solar fuel devices (DSSFDs). The design is particularly appealing as it accommodates high PS concentrations for efficient light-harvesting, while providing potent catalysts close to the solvent interface.

1 968 750 €

Start date: 2017-01-01, End date: 2021-12-31

The goal of the MULTIPROSMM project is to design systems able to present magnetic bistabilities under different stimuli (temperature, magnetic field or light) on an unprecedented large temperature range, i.e. very low temperature with Single Molecule Magnet (SMM) behaviour, intermediate temperature with Light Induced Excited State Trapping (LIESST) and high temperature with SpinCrossOver (SCO). On one hand, as a photography of the energy-splitting of the spectroscopic states, the lanthanide luminescence will be used as a key tool for the understanding of the magnetic properties of lanthanide ions. On the other hand, Circularly Polarized Luminescence (CPL) combines the sensitivity of the luminescence with crucial information on the chiral environment. A step by step synthetic strategy will be used to elaborate molecular systems in which the coexistence of i) SMM and SCO; ii) SMM and CPL and iii) SMM, SCO and CPL are operating. The enhancement of the magnetic properties is needed to step forward towards applications. To reach such optimizations, the quantum regime of the SMM and the internal magnetic field must be vanished playing with the hyperfine coupling and magnetic dilutions. Both isotopic enrichment and shaping (i.e. decoration of both mesoporous silica and nanoparticle surfaces) of the designed systems could allow high magnetic performance in multiple properties SMM. The final result could be a system suitable for very high density data storage on a wide temperature range (from cryogenic to room temperature).

1 505 000 €

Start date: 2017-08-01, End date: 2022-07-31

Great successes have been achieved in nanoscience where the development of functional properties and the assembly of nanostructures into nanomaterials have become increasingly important. In general, both the tuning of the chemical and physical properties and the self-assembly of nanocrystals into 2D or 3D superstructures take place in a liquid environment. When analysing the structural properties of nanocrystals using Transmission Electron Microscopy (TEM), this liquid environment is contained between membranes to keep it in the high vacuum. At present, the thickness of the liquid is not controlled, which renders standard imaging at atomic resolution impossible. Here I propose to integrate micro-electromechanical actuator functionalities in the Liquid Cell chips to overcome this problem so that real-time atomic resolution imaging and chemical analysis on nanoparticles in solution becomes a reality. This new in-situ technology will elucidate what really happens during chemical reactions, and will thereby enable the development of new nanomaterials for optoelectronics, lighting, and catalysis. Oriented attachment processes and self-assembly of nanoparticles, which are key to the large-scale production of 2D and 3D nanomaterials, can also be followed in the Liquid Cell. Furthermore, the hydration of nanoscale model systems of earth materials such as magnesia, alumina, and calcium oxide is of major importance in the geosciences. In the field of enhanced oil recovery, for example, the huge volumetric expansion that comes with the hydration of these minerals could facilitate access to reservoirs. My research group has extensive experience in in-situ TEM and recently has achieved significant successes in Liquid Cell studies. We are in an ideal position to develop this new technology and open up these new research areas, which will have a major impact on science, industry, and society.

1 996 250 €

Start date: 2016-09-01, End date: 2021-08-31

In Naturale CG I propose transformative bioengineering approaches that will overcome severe limitations in current materials in two main areas, namely 1) Biosensing and 2) Regenerative Medicine. A key focus is on understanding and engineering the biomaterial interface using innovative designs and state of the art materials characterisation methods. Firstly I aim to transform the way that we can currently detect disease through innovations in the design and development of nanomaterials-based biosensors that could be used to detect a number of diseases with global implications, such as cancer, malaria, heart failure and tuberculosis. These innovations in biosensor design will involve both building on our existing highly successful work on plasmonic biosensors and also involve the design and development of completely new polymersome and fluorescent based biosensors. Another key aim of Naturale CG is to design first in kind biosensors for the facile detection of microRNAs. Secondly, the goal of regenerating failing organs before the body as a whole is ready to surrender, is now timelier than ever and one in which the design of new bio-inspired materials can play an important role. In Naturale CG I will build on my previous research in the design of 3-dimensional tissue engineering scaffolds and address an important new direction in the engineering of new bio-inspired conducting polymers as tissue engineering materials to promote cardiac tissue regeneration. First-in-field biomaterials-based innovations generated from this programme could enable far more effective regeneration of functional myocardial tissue which has been notoriously difficult to achieve thus far. Whilst I will lead this grant and the research within it, the proposed innovations are truly multidisciplinary in nature and will be accelerated towards clinical translation through the numerous clinical, scientific and industrial collaborations that I have established.

1 999 460 €

Start date: 2014-07-01, End date: 2019-06-30