ERC FUNDED PROJECTS

"Amines and their acylated derivatives – amides – are among the most common chemical functional groups found in modern pharmaceuticals. Despite this there are few methods for their efficient, environmentally sustainable production in enantiomerically pure form. This proposal seeks to provide new catalytic chemical methods including 1) the catalytic, enantioselective synthesis of peptides and 2) catalytic methods for the preparation of enantiopure nitrogen-containing heterocycles. The proposed work features innovative chemistry including novel reaction mechanism and catalysts. These methods have far reaching applications for the sustainable production of valuable compounds as well as fundamental science."

1 500 000 €

Start date: 2012-12-01, End date: 2017-11-30

Amines are crucially important classes of chemicals, widely present in pharmaceuticals, agrochemicals and surfactants. Yet, surprisingly, a systematic approach to obtaining this essential class of compounds from renewables has not been realized to date. The aim of this proposal is to enable chemical pathways for the production of amines through alcohols from renewable resources, preferably lignocellulose waste. Two key scientific challenges will be addressed: The development of efficient cleavage reactions of complex renewable resources by novel heterogeneous catalysts; and finding new homogeneous catalyst based on earth-abundant metals for the atom-economic coupling of the derived alcohol building blocks directly with ammonia as well as possible further functionalization reactions. The program is divided into 3 interrelated but not mutually dependent work packages, each research addressing a key challenge in their respective fields, these are: WP1: Lignin conversion to aromatics; WP2: Cellulose-derived platform chemicals to aromatic and aliphatic diols and solvents. WP3: New iron-based homogeneous catalysts for the direct, atom-economic C-O to C-N transformations. The approach taken will embrace the inherent complexity present in the renewable feedstock. A unique balance between cleavage and coupling pathways will allow to access chemical diversity in products that is necessary to achieve economic competitiveness with current fossil fuel-based pathways and will permit rapid conversion to higher value products such as functionalized amines that can enter the chemical supply chain at a much later stage than bulk chemicals derived from petroleum. The proposed high risk-high gain research will push the frontiers of sustainable and green chemistry and reach well beyond state of the art in this area. This universal, flexible and iterative approach is anticipated to give rise to a variety of similar systems targeting diverse product outcomes starting from renewables.

1 500 000 €

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

Nonlinear optics is present in our daily life with applications, e.g. light sources for microsurgery or green laser pointer. All of them use bulk materials such as glass fibers or crystals. Generating nonlinear effects from materials at the nanoscale would expand the applications to biology as imaging markers or optoelectronic integrated devices. However, nonlinear signals scale with the volume of a material. Therefore finding materials with high nonlinearities to avoid using high power and large interaction length is challenging. Many studies focus on third order nonlinearities (described by a χ(3) tensor) present in every material (silicon, graphene…) or on metals for enhancing nonlinearities with plasmonics. My approach is to explore second-order χ(2) nanomaterials, since they show higher nonlinearities than χ(3) ones, additional properties such as birefringence, wide band gap for transparency, high refractive index (n>2), and no ohmic losses. Typical χ(2) materials are oxides (BaTiO3, LiNbO3…) with a non-centrosymmetric crystal used for wavelength conversion like in second-harmonic generation (SHG). The key idea is to demonstrate original strategies to enhance SHG of χ(2) nano-oxides with the material itself and without involving any hybrid effects from other materials such as plasmonic resonances of metals. First, I propose to use multiple Mie resonances from BaTiO3 nanoparticles to boost SHG in the UV to NIR range. Up to now, Mie effects at the nanoscale have been measured in materials with no χ(2) nonlinearities (silicon spheres). Second, since χ(2) oxides are difficult to etch, I will overcome this fabrication issue by demonstrating solution processed imprint lithography to form high-quality photonic crystal cavities from nanoparticles. Third, I will use facet processing of single LiNbO3 nanowire to obtain directionality effects for spectroscopy on-a-chip. This work fosters applications and commercial devices offering a sustainable future to this field.

1 500 000 €

Start date: 2017-02-01, End date: 2022-01-31

Synthesizing organic molecules in high purity with designed properties is of utmost importance for pharmaceutical applications and material- and polymer sciences including the efficient production of enantiopure compounds and the compliance with ecological concerns and sustainability. The efficiency of all reaction classes has improved over the past decades. However, the basic principle and execution did not change: The target molecule is disconnected into donor and acceptor synthons and appropriate functional groups need to be introduced and adjusted to carry out the envisioned coupling. These additional steps decrease the yield and efficiency, are costly in time, resources and produce waste. The introduction of new functionalities by direct C-H or C-C bond activation is a unique and highly appealing strategy. The range of substrates is virtually unlimited, including hydrocarbons, small molecules and polymers. Such dream reactions avoid any pre-functionalization, shorten synthetic routes, make unsought disconnections possible and allow for a more efficient usage of our dwindling resources. Despite recent progress in the activations of inert bonds, narrow scopes, poor reactivities and harsh conditions hamper most general practical applications. Especially, enantioselective activations are a longstanding challenge. The outlined project seeks to address these issues by the development and exploitation of new catalytic enantioselective C-H and C-C functionalizations of broadly available organic substrates, using chiral Rh- and Pd- catalysts, additionally supported by automated screening and computational techniques. These reactions will be then applied in the streamlined synthesis of pharmaceutically relevant scaffolds and of compounds for organic electronics.

1 499 500 €

Start date: 2011-02-01, End date: 2016-01-31