ERC FUNDED PROJECTS

Microporous materials are an important class of solid; the two main members of this family are zeolites and metal-organic frameworks (MOFs). Zeolites are industrial solids whose applications range from catalysis, through ion exchange and adsorption technologies to medicine. MOFs are some of the most exciting new materials to have been developed over the last two decades, and they are just beginning to be applied commercially. Over recent years the applicant’s group has developed new synthetic strategies to prepare microporous materials, called the Assembly-Disassembly-Organisation-Reassembly (ADOR) process. In significant preliminary work the ADOR process has shown to be an extremely important new synthetic methodology that differs fundamentally from traditional solvothermal methods. In this project I will look to overturn the conventional thinking in materials science by developing methodologies that can target both zeolites and MOF materials that are difficult to prepare using traditional methods – the so-called ‘unfeasible’ materials. The importance of such a new methodology is that it will open up routes to materials that have different properties (both chemical and topological) to those we currently have. Since zeolites and MOFs have so many actual and potential uses, the preparation of materials with different properties has a high chance of leading to new technologies in the medium/long term. To complete the major objective I will look to complete four closely linked activities covering the development of design strategies for zeolites and MOFs (activities 1 & 2), mechanistic studies to understand the process at the molecular level using in situ characterisation techniques (activity 3) and an exploration of potential applied science for the prepared materials (activity 4).

2 489 220 €

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

Amine containing compounds are ubiquitous in everyday life and find applications ranging from polymers to pharmaceuticals. The vast majority of amines are synthetic and manufactured on large scale which creates waste as well as requiring high temperatures and pressures. The increasing availability of biocatalysts, together with an understanding of how they can be used in organic synthesis (biocatalytic retrosynthesis), has stimulated chemists to consider new ways of making target molecules. In this context, the iterative construction of C-N bonds via biocatalytic hydrogen borrowing represents a powerful and unexplored way to synthesise a wide range of target amine molecules in an efficient manner. Hydrogen borrowing involves telescoping redox neutral reactions together using only catalytic amounts of hydrogen. In this project we will engineer the three key target biocatalysts (reductive aminase, amine dehydrogenase, alcohol dehydrogenase) required for biocatalytic hydrogen borrowing such that they possess the required regio-, chemo- and stereo-selectivity for practical application. Recently discovered reductive aminases (RedAms) and amine dehydrogenases (AmDHs) will be engineered for enantioselective coupling of alcohols (1o, 2o) with ammonia/amines (1o, 2o, 3o) under redox neutral conditions. Alcohol dehydrogenases will be engineered for low enantioselectivity. Hydrogen borrowing requires mutually compatible cofactors shared by two enzymes and in some cases will require redesign of cofactor specificity. Thereafter we shall develop conditions for the combined use of these biocatalysts under hydrogen borrowing conditions (catalytic NADH, NADPH), to enable the conversion of simple and sustainable feedstocks (alcohols) into amines using ammonia as the nitrogen source. The main deliverables of BIO-H-BORROW will be a set of novel engineered biocatalysts together with redox neutral cascades for the synthesis of amine products from inexpensive and renewable precursors.

2 337 548 €

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

Despite that C–H functionalization represents a paradigm shift from the standard logic of organic synthesis, the selective activation of non-functionalized alkanes has puzzled chemists for centuries and is always referred to one of the remaining major challenges in chemical sciences. Alkanes are inert compounds representing the major constituents of natural gas and petroleum. Converting these cheap and widely available hydrocarbon feedstocks into added-value intermediates would tremendously affect the field of chemistry. For long saturated hydrocarbons, one must distinguish between non-equivalent but chemically very similar alkane substrate C−H bonds, and for functionalization at the terminus position, one must favor activation of the stronger, primary C−H bonds at the expense of weaker and numerous secondary C-H bonds. The goal of this work is to develop a general principle in organic synthesis for the preparation of a wide variety of more complex molecular architectures from saturated hydrocarbons. In our approach, the alkane will first be transformed into an alkene that will subsequently be engaged in a metal-catalyzed hydrometalation/migration sequence. The first step of the sequence, ideally represented by the removal of two hydrogen atoms, will be performed by the use of a mutated strain of Rhodococcus. The position and geometry of the formed double bond has no effect on the second step of the reaction as the metal-catalyzed hydrometalation/migration will isomerize the double bond along the carbon skeleton to selectively produce the primary organometallic species. Trapping the resulting organometallic derivatives with a large variety of electrophiles will provide the desired functionalized alkane. This work will lead to the invention of new, selective and efficient processes for the utilization of simple hydrocarbons and valorize the synthetic potential of raw hydrocarbon feedstock for the environmentally benign production of new compounds and new materials.

2 499 375 €

Start date: 2018-11-01, End date: 2023-10-31

The fundamental objective of the research described in this proposal is to lay the foundations for understanding how structural complexity can give rise to materials properties inaccessible to structurally-simple states. The long-term vision is a paradigm shift in the way we as chemists design materials—the “Complexity Revolution”—where we move to thinking beyond the unit cell and harness unconventional order to generate emergent states with entirely novel behaviour. The key methodologies of the project are (i) exploitation of the rich structural information accessible using 3D-PDF / diffuse scattering techniques, (ii) exploration of the phase behaviour of unconventional ordered states using computational methods, and (iii) experimental/computational studies of a broad range of materials in which complexity arises from a large variety of different phenemona. In this way, the project will establish how we might controllably introduce complexity into materials by varying chemical composition and synthesis, how we might then characterise these complex states, and how we might exploit this complexity when designing next-generation materials with unprecedented electronic, catalytic, photonic, information storage, dielectric, topological, and magnetic properties.

3 362 635 €

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