ERC FUNDED PROJECTS

Optical bioimaging is limited by visible light penetration depth and stability of fluorescent dyes over extended periods of time. Surface enhanced Raman scattering (SERS) offers the possibility to overcome these drawbacks, through SERS-encoded nanoparticle tags, which can be excited with near-IR light (within the biological transparency window), providing high intensity, stable, multiplexed signals. SERS can also be used to monitor relevant bioanalytes within cells and tissues, during the development of diseases, such as tumours. In 4DBIOSERS we shall combine both capabilities of SERS, to go well beyond the current state of the art, by building three-dimensional scaffolds that support tissue (tumour) growth within a controlled environment, so that not only the fate of each (SERS-labelled) cell within the tumour can be monitored in real time (thus adding a fourth dimension to SERS bioimaging), but also recording the release of tumour metabolites and other indicators of cellular activity. Although 4DBIOSERS can be applied to a variety of diseases, we shall focus on cancer, melanoma and breast cancer in particular, as these are readily accessible by optical methods. We aim at acquiring a better understanding of tumour growth and dynamics, while avoiding animal experimentation. 3D printing will be used to generate hybrid scaffolds where tumour and healthy cells will be co-incubated to simulate a more realistic environment, thus going well beyond the potential of 2D cell cultures. Each cell type will be encoded with ultra-bright SERS tags, so that real-time monitoring can be achieved by confocal SERS microscopy. Tumour development will be correlated with simultaneous detection of various cancer biomarkers, during standard conditions and upon addition of selected drugs. The scope of 4DBIOSERS is multidisciplinary, as it involves the design of high-end nanocomposites, development of 3D cell culture models and optimization of emerging SERS tomography methods.

2 410 771 €

Start date: 2018-10-01, End date: 2023-09-30

The selective functionalization of C-H and C=C bonds remains a formidable unsolved problem, owing to their inert nature. Novel alkane and alkene oxidation reactions exhibiting good and/or unprecedented selectivities will have a big impact on bulk and fine chemistry by opening novel methodologies that will allow removal of protection-deprotection sequences, thus streamlining synthetic strategies. These goals are targeted in this project via design of iron and manganese catalysts inspired by structural elements of the active site of non-heme enzymes of the Rieske Dioxygenase family. Selectivity is pursued via rational design of catalysts that will exploit substrate recognition-exclusion phenomena, and control over proton and electron affinity of the active species. Moreover, these catalysts will employ H2O2 as oxidant, and will operate under mild conditions (pressure and temperature). The fundamental mechanistic aspects of the catalytic reactions, and the species implicated in C-H and C=C oxidation events will also be studied with the aim of building on the necessary knowledge to design future generations of catalysts, and provide models to understand the chemistry taking place in non-heme iron and manganese-dependent oxygenases.

1 299 998 €

Start date: 2009-11-01, End date: 2015-10-31

Visible light photocatalysis and metal-free organocatalytic processes are powerful strategies of modern chemical research with extraordinary potential for the sustainable preparation of organic molecules. However, these environmentally respectful approaches have to date remained largely unrelated. The proposed research seeks to merge these fields of molecule activation to redefine their synthetic potential. Light-driven processes considerably enrich the modern synthetic repertoire, offering a potent way to build complex organic frameworks. In contrast, it is extremely challenging to develop asymmetric catalytic photoreactions that can create chiral molecules with a well-defined three-dimensional arrangement. By developing innovative methodologies to effectively address this issue, I will provide a novel reactivity framework for conceiving light-driven enantioselective organocatalytic processes. I will translate the effective tools governing the success of ground state asymmetric organocatalysis into the realm of photochemical reactivity, exploiting the potential of key organocatalytic intermediates to directly participate in the photoexcitation of substrates. At the same time, the chiral organocatalyst will ensure effective stereochemical control. This single catalyst system, where stereoinduction and photoactivation merge in a sole organocatalyst, will serve for developing novel enantioselective photoreactions. In a complementary dual catalytic approach, the synergistic activities of an organocatalyst and a metal-free photosensitiser will combine to realise asymmetric variants of venerable photochemical processes, which have never before succumbed to a stereocontrolled approach. This proposal challenges the current perception that photochemistry is too unselective to parallel the impressive levels of efficiency reached by the asymmetric catalysis of thermal reactions, expanding the way chemists think about making chiral molecules

2 000 000 €

Start date: 2016-11-01, End date: 2021-10-31

Metal-Organic-Frameworks (MOFs) offer appealing advantages over classical solids from combination of high surface areas with the crystallinity of inorganic materials and the synthetic versatility (unlimited combination of metals and linkers for fine tuning of properties) and processability of organic materials. Provided chemical stability, I expect combination of porosity with manipulable electrical and optical properties to open a new world of possibilities, with MOFs playing an emerging role in fields of key environmental value like photovoltaics, photocatalysis or electrocatalysis. The conventional insulating character of MOFs and their poor chemical stability (only a minimum fraction are hydrolytically stable) are arguably the two key limitations hindering further development in this context. With chem-fs-MOF I expect to deliver: 1. New synthetic routes specifically designed for producing new, hydrolytically stable Fe(III) and Ti(IV)-MOFs (new synthetic platforms for new materials). 2. More advanced crystalline materials to feature tunable function by chemical manipulation of MOF’s optical/electrical properties and pore activity (function-led chemical engineering). 3. High-quality ultrathin films, reliant on the transfer of single-layers, alongside establishing the techniques required for evaluating their electric properties (key to device integration). Recent works on graphene and layered dichalcogenides anticipate the benefits of nanostructuration for more efficient optoelectronic devices. Notwithstanding great potential, this possibility remains still unexplored for MOFs. Overall, I seek to exploit MOFs’ unparalleled chemical/structural flexibility to produce advanced crystalline materials that combine hydrolytical stability and tunable performance to be used in environmentally relevant applications like visible light photocatalysis. This is an emerging research front that holds great potential for influencing future R&D in Chemistry and Materials Science.

1 527 351 €

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