Inspired by the possibility to create an artificial electronic band structure through the interplay of a molecular nanoporous network with the surface state electrons of a metallic substrate (recently reported by us), the utilization of this new concept for controlling the electronic surface properties of a material as well as establishing understanding of the underlying principles for the observed behavior is the overall aim of this project. The modification of the electronic surface properties also affects the material properties in general, such as conductivity, surface catalysis properties and reflectivity. Thus, the proposed concept has great potential for materials research and will ultimately result in the development of new materials with adjustable electronic properties. Such materials will find applications in e. g. (nano)electronic devices or sensors.

The unique properties of nucleic acids have made them the material of choice for complex nanofabrication. High fidelity formation of duplexes via non-covalent interactions between complementary sequences provides a straightforward approach to molecular programming of multicomponent self-assembly processes. The structure of the nucleic acid backbone and bases can be changed without destroying these properties, suggesting that there are all kinds of unexplored polymeric structures that will also show sequence selective duplex formation. This proposal investigates this rich new area at the interface of supramolecular, biological and polymer chemistry. The appeal of nucleic acids is that we can dial up any desired sequence via chemical solid phase synthesis or via biological template synthesis. With recent advances in polymerisation processes, which proceed under mild conditions compatible with non-covalent chemistry, we are now in a position to develop comparable processes for synthetic polymers. This proposal explores a ground-breaking approach to the synthesis of polymeric systems equipped with defined sequences of recognition sites. The aim is to establish protocols for routine solid phase synthesis of one class of oligomer, which can be used to template the synthesis of different classes of oligomer. This template chemistry will provide tools for polymerisation of conventional monomers using templates to determine the sequence of recognition sites and hence incorporate the selective recognition properties of nucleic acids into bulk polymers like polystyrene. The ability to program polymers with recognition information will open the way to new materials of unprecedented complexity and functionality with applications in all areas of nanotechnology where precise control over macromolecular structure and supramolecular organisation will be used to program mechanical, photochemical and electronic properties into sophisticated assemblies that rival biology.

The pressing need for a more sustainable society has sparked intensive research efforts in search for novel materials with controlled structure, porosity and functionalities. Such porous materials may combine high catalytic activity and selectivity with a long-term stability in the conversion of renewable (e.g. biomass) and non-renewable feedstock when producing future transportation fuels and chemicals. Rational design and optimization of the catalytic properties of these materials is one of the keys for the transition from a fossil fuels based society to a sustainable society.

Graphene is a new class of promising material with exceptional properties and thus warrants a plethora of potential applications in various domains of science and technology. However, due to intrinsic zero bandgap and inherently low solubility, a prerequisite for the use of graphene in several applications is its controlled and reproducible functionalization in a nanostructured fashion. Being a ‘surface-only’ nanomaterial, its properties are extremely sensitive not only to chemical modification but also to noncovalent interactions with simple organic molecules. A systematic knowledge base for targeted functionalization of graphene still eludes the scientific community. The present experimental protocols suffer from important shortcomings. Firstly, graphene functionalization occurs randomly in solution based methods and there is scarcity of methods that can exert precise control over how and where the reactions/interactions occur. Secondly, due to random functionalization, producing reproducible samples of structurally uniform graphene and graphitic materials remains a major challenge. Lastly, a molecular level understanding of the functionalization process is still lacking which precludes systematic strategies for manipulation of graphene and graphitic materials.

In view of current developments in the fields of porous materials and discrete nano-sized molecules and aggregates the lack of organometallic-based compounds acting as nodes together with functionalized organic linkers in such materials and as linkers and building blocks for nano-sized spheres and aggregates is obvious. By using organometallic polyphosphorus compounds it was possible to synthesize unprecedented prototypes of such materials and molecular nano-sized superspheres. These ground-breaking discoveries will be subsequently further developed to excess a qualitatively novel level of research by using polypnictogen starting materials. Key targets will be the generation of rigid 3D organometallic-based materials, discrete supramolecular nano-sized aggregates (charged moiety approach) and novel fullerene-like supramolecules as nano-spheres, nano-capsules and nano-wheels (neutral moiety approach). Especially the latter approach will generate unprecedented spheres and molecules which are extreme in size and function as there are multifunctional binding sites; multi-magnetic properties; tuning templates in size; generating, encapsulating and releasing highly reactive intermediates and reaction components. Finally, the work will move beyond our knowledge of known structurally characterized fullerenes by the development of non-carbon based alternatives within and beyond the fullerene topology.

Self-assembly is the key construction principle that nature uses so successfully to fabricate its molecular machinery and highly elaborate structures. In this project we will follow nature’s strategies and make a concerted experimental and theoretical effort to study, understand and control self-assembly for a new generation of colloidal building blocks. Starting point will be recent advances in colloid synthesis strategies that have led to a spectacular array of colloids of different shapes, compositions, patterns and functionalities. These allow us to investigate the influence of anisotropy in shape and interactions on aggregation and self-assembly in colloidal suspensions and mixtures. Using responsive particles we will implement colloidal lock-and-key mechanisms and then assemble a library of “colloidal molecules” with well-defined and externally tunable binding sites using microfluidics-based and externally controlled fabrication and sorting principles. We will use them to explore the equilibrium phase behavior of particle systems interacting through a finite number of binding sites. In parallel, we will exploit them and investigate colloid self-assembly into well-defined nanostructures. Here we aim at achieving much more refined control than currently possible by implementing a protein-inspired approach to controlled self-assembly. We combine molecule-like colloidal building blocks that possess directional interactions and externally triggerable specific recognition sites with directed self-assembly where external fields not only facilitate assembly, but also allow fabricating novel structures. We will use the tunable combination of different contributions to the interaction potential between the colloidal building blocks and the ability to create chirality in the assembly to establish the requirements for the controlled formation of tubular shells and thus create a colloid-based minimal model of synthetic virus capsid proteins.

Inspired by the diverse functionalities of complex molecular building blocks evidenced in manifold life processes as transport of respiratory gases, metabolism or light harvesting, we aim for a comprehensive characterization and control of molecular properties in surface-based model systems. To fully exploit and tune molecular functionality on substrates, a paradigm shift away from conventional metal supports, which might drastically affect adsorbates, is mandatory. We propose to apply nanostructured boron nitride (BN) monolayers and sp2-heterostructures as templates for molecular units and architectures. As indicated by the fascinating nanomesh interface and the electronically corrugated atomically thin BN sheet on Cu we recently reported, inert, temperature stable and insulating BN has a huge potential as advanced substrate supporting molecular functionality, self-ordering and intercalation.

Control of matter via light has always fascinated humankind; not surprisingly, laser patterning of materials is as old as the history of the laser. However, this approach has suffered to date from a stubborn lack of long-range order. We have recently discovered a method for regulating self-organised formation of metal-oxide nanostructures at high speed via non-local feedback, thereby achieving unprecedented levels of uniformity over indefinitely large areas by simply scanning the laser beam over the surface.

The precipitation of alkaline-earth carbonates in silica-rich alkaline solutions yields nanocrystalline aggregates that develop non-crystallographic morphologies. These purely inorganic hierarchical materials, discovered by the IP of this project, form under geochemically plausible conditions and closely resemble typical biologically induced mineral textures and shapes, thus the name ‘biomorphs’. The existence of silica biomorphs has questioned the use morphology as an unambiguous criterion for detection of primitive life remnants. Beyond applications, the study of silica biomorphs has revealed a totally new morphogenetic mechanism capable of creating crystalline materials with positive or negative constant curvature and biomineral-like textures which lead to the design of new pathways towards concerted morphogenesis and bottom-up self-assembly created by a self-triggered chemical coupling mechanism. The potential interest of these fascinating structures in Earth Sciences has never been explored mostly because of their complexity and multidisciplinary nature. PROMETHEUS proposes an in depth investigation of the nature of mineral structures such as silica biomorphs and chemical gardens, and the role of mineral self-organization in extreme alkaline geological environments. The results will impact current understanding of the early geological and biological history of Earth by pushing forward the unexplored field of inorganic biomimetic pattern formation. PROMETHEUS will provide this discipline with much needed theoretical and experimental foundations for its quantitative application to Earth Sciences. The ambitious research program in PROMETHEUS will require the development of high-end methods and instruments for the non-intrusive in-situ characterization of geochemically important variables, including pH mapping with microscopic resolution, time resolved imaging of concentration gradients, microscopic fluid dynamics, and characterization of ultraslow growth rates.