The proposal is built on the core idea to use an ensemble of multiple level self-organization processes to create a next generation photocatalytic platform that provides unprecedented property and reactivity control. As a main output, the project will yield a novel highly precise combined catalyst/photocatalyst assembly to: 1) provide a massive step ahead in photocatalytic applications such as direct solar hydrogen generation, pollution degradation (incl. CO2 decomposition), N2 fixation, or photocatalytic organic synthesis. It will drastically enhance efficiency and selectivity of photocatalytic reactions, and enable a high number of organic synthetic reactions to be carried out economically (and ecologically) via combined catalytic/photocatalytic pathways. Even more, it will establish an entirely new generation of '100% depoisoning', anti-aggregation catalysts with substantially enhanced catalyst life-time. For this, a series of self-assembly processes on the mesoscale will be used to create highly uniform arrays of single-catalyst-particle-in-a-single-TiO2-cavity; target is a 100% reliable placement of a single <10 nm particle in a 10 nm cavity. Thus catalytic features of, for example Pt nanoparticles, can ideally interact with the photocatalytic properties of a TiO2 cavity. The cavity will be optimized for optical and electronic properties by doping and band-gap engineering; the geometry will be tuned to the range of a few nm.. This nanoscopic design yields to a radical change in the controllability of length and time-scales (reactant, charge carrier and ionic transport in the substrate) in combined photocatalytic/catalytic reactions. It is of key importance that all nanoscale assembly principles used in this work are scalable and allow to create square meters of nanoscopically ordered catalyst surfaces. We target to demonstrate the feasibility of the implementation of the nanoscale principles in a prototype macroscopic reactor.

There is great need for radically new paradigms that significantly push forward the complexity, multiscale control, and functionality of novel materials. Molecular self-assembling strategies are continuously being explored for developing ever more precise and organized materials. The development of adaptive materials that can be morphed into complex shapes of hierarchical structure through bottom-up mechanisms that mimic those found in tissue development is a fascinating possibility. This proposal (BIOMORPH) aims to develop a novel dynamic self-assembling material fabrication platform that combines the benefits of molecular self-assembly, bioengineering, nanotechnology, and tissue engineering. The system integrates simple peptide and protein building-blocks with multiple cells types to create complex hierarchical, biomimetic, hybrid structures that exhibit remarkable properties such as self-healing and the capacity to undergo morphogenesis. The work would represent a major step-change by developing a dynamic strategy based on emerging physico-chemical mechanisms that generate and dissipate stresses, and maintain a controlled non-equilibrium state that together is reminiscent of elements found in tissue morphogenesis. The work is divided in four work packages that expand from building block design and synthesis to biomechanical and in vitro assessment of the generated materials. The proposed fabrication platform may find applications in a variety of tissue engineering applications. However, as a first stage, the work proposes to grow tubes and tubular networks that recreate vascular tissue.

BENGRAS is a Marie Curie IIF project that focuses on multidisciplinary transfer of knowledge from a promising Australian early career researcher to KU Leuven towards the design and synthesis of novel functional nano-materials and the development of advanced analytical techniques for material analysis. The project will study bandgap engineering in graphene induced by physi- and chemi- sorption of self-assembled molecular monolayers, which is an interdisciplinary research topic centered at the interface between materials science, supramolecular chemistry, nanoscience and physics. Graphene, a material consisting of flat one-atom-thick sheets of carbon atoms has enormous potential for the use in electronic transistors because of the unique electronic properties and the reduced dimensionality. Graphene is a ‘zero-gap’ semiconductor and to unlock its electronic properties two basic requirements must be satisfied. Firstly, precise control over electronic band structure (bandgap) is needed. This can be achieved by adsorbing atoms and molecules (e.g. H, OH, K, NH3) on its surface thus generating local mid-gap states. Secondly, the means to control the degree of ordering and periodicity of modified graphene layers are to be derived. In other words, the regions where bandgap can be locally tuned have to be extended to a micron scale for practical applications. At present, this issue remains largely unexplored. This project will investigate the electronic structure of graphene the surface of which has been nano-patterned by physisorped (i.e. weak surface interactions) and covalent (i.e. strong surface interactions) molecular monolayers. Through BENGRAS the fellow will contribute extensive expertise in carbonaceous materials and spectroscopy towards controlled modification of electronic properties of graphene and, designing appropriate analytical methods for the study of low-dimensional materials using optical spectroscopy methods at the nanoscale.

Supramolecular assemblies -formed by the self-assembly of hundreds of protein subunits -are part of bacterial nanomachines involved in key cellular processes. Important examples in pathogenic bacteria are pili and type 3 secretion systems (T3SS) that mediate adhesion to host cells and injection of virulence proteins. Structure determination at atomic resolution of such assemblies by standard techniques such as X-ray crystallography or solution NMR is severely limited: Intact T3SSs or pili cannot be crystallized and are also inherently insoluble. Cryo-electron microscopy techniques have recently made it possible to obtain low- and medium-resolution models, but atomic details have not been accessible at the resolution obtained in these studies, leading sometimes to inaccurate models. I propose to use solid-state NMR (ssNMR) to fill this knowledge-gap. I could recently show that ssNMR on in vitro preparations of Salmonella T3SS needles constitutes a powerful approach to study the structure of this virulence factor. Our integrated approach also included results from electron microscopy and modeling as well as in vivo assays (Loquet et al., Nature 2012). This is the foundation of this application. I propose to extend ssNMR methodology to tackle the structures of even larger or more complex homo-oligomeric assemblies with up to 200 residues per monomeric subunit. We will apply such techniques to address the currently unknown 3D structures of type I pili and cytoskeletal bactofilin filaments. Furthermore, I want to develop strategies to directly study assemblies in a native-like setting. As a first application, I will study the 3D structure of T3SS needles when they are complemented with intact T3SSs purified from Salmonella or Shigella. The ultimate goal of this proposal is to establish ssNMR as a generally applicable method that allows solving the currently unknown structures of bacterial supramolecular assemblies at atomic resolution.

One-atom thin two-dimensional nanomaterials possess unique properties different from their bulk counterparts. Initiated by the discovery of graphene, many stable one atom-thick layers such as boron nitride, molybdenum disulphide, tungsten disulphide etc., have been isolated and characterized. However, the individual properties of such 2D-atomic crystals (except graphene) were modest. The combination of isolated single atomic layers into designer structures, named as 2D-heterostrcutures, is predicted to give synergetic properties. In order to harness the interesting properties the combination of various 2D-atomic crystals have to offer, a method to assemble them in a simple and scalable way is required. Currently, the only method known is manual placing of the 2D-atomic crystal layers sequentially which limits the scope of the study of such structures. The objective of the proposal is to assemble layered (each layer is one atom thick) stacks of graphene superlattices and heterostructures with other 2D-atomic crystals such as BN, MoS2, WS2 etc., by deoxyribonucleic acid (DNA)-mediated assembly. DNA mediated assembly is highly programmable by chemically specific interaction between nucleotides, length of the DNA, strength of the interactions in addition to the symmetry control of the assembled structures. Top-down lithography will be combined with bottom-up DNA assembly to fabricate seed layers of DNA for the guided assembly which lead to patterned heterostructures. This approach is targeted toward combinatorial screening of exotic properties of varied architectures of heterostructures with control over the composition of 2D-atomic crystals and spacing between the layers (controlled by DNA). The anticipated structures would be vertical atomic scale Legos of 2D-atomic crystal layers with DNA spacers.

Recent advances made in the field of crystallization-driven self-assembly (CDSA) of block copolymers (BCPs) with a crystallisable core-forming block in selective solvents have opened up exciting opportunities in the creation of well-defined nanostructures such as monodisperse cylinders with precisely controlled length. Herein, we propose to study linear-dendritic BCPs and to obtain new, well-defined materials with the dimensional precision provided by CDSA and also higher orders of complexity arising from surface functionalization with dendrimers. The overall objectives of this proposal are two-fold. First, to combine well-defined dendrons with crystallizable linear blocks such as metal-containing polyferrocenylsilane (PFS) and crystalline biodegradable organic blocks such as polycaprolactone (PCL) and polylactide (PLA) to yield linear-dendritic BCPs to further advance fundamental knowledge by studying their self-assembly behavior. Second, by combining CDSA and dendrimer science we intend to take a significant step toward the creation of precisely surface-engineered materials for potential applications in nanomedicine. The proposed research objectives will be accomplished by bringing a highly talented researcher, Dr. Nazemi, from Canada with his extensive experience in dendrimer synthesis and bionanomaterials to stay for 2 years in one of Europe's highest ranked research laboratories, that of Professor Ian Manners at Bristol. This group is recognised as being among the world leaders in the fields of metallopolymers, BCP self-assembly, and in particular the use of CDSA. At the end of the 2 year stay Dr. Nazemi wishes to return to Canada to take up an academic position at a research-intensive University.

In the ERC-StG-project CoCooN, we investigate the surface modification of nanoparticles by Atomic Layer Deposition (ALD). To enable this research, a rotary ALD reactor was developed. The number of possible applications for nanoparticles has strongly increased in the last decade. For many applications, such as catalysis, batteries, solid-state lighting, but also drug development and biotech, nanoparticles with different surface properties are necessary. Today, and with the help of the ERC- project CoCooN, ALD has proven to be a reliable method for depositing ultrathin and conformal coatings, even on large quantities of (nano)particles. We have designed and built a prototype rotary ALD reactor that enables both thermal and plasma-enhanced ALD surface modification of (nano)particles. In PaNaCo, we will push this rotary ALD reactor to a pre-commercial level.

The project aims at exploring the use of nanovoids and nanodots prepared as plasmonic structures to enhance the efficiency of Si single-crystalline photovoltaic (PV) devices. Fabrication and experimental investigation of plasmonic structures in strained Si/SiGe multilayered structures will be carried to enhance light harvesting in solar cells due to both near-field and far-field effects. The main idea behind the production of nanovoids and nanodots is based on the ability of compressively strained thin SiGe alloy layers, incorporated in a Si matrix during epitaxial growth, to collect small-sized molecules (H, He, C) or vacancies, induced by irradiation. Further, thermal treatment results in the formation of nano-voids which are strictly assembled within the strained SiGe layers. The following key processes will be used: Molecular beam epitaxy of strained Si/SiGe/Si structures followed by irradiation with light ions (hydrogen, carbon) and rapid thermal treatment. This structure will then be additionally used as a template for segregation and self-assembling of metallic or carbon nanodots. The fundamental investigations of the structural, optical and electronic properties of the strained Si/SiGe layers will be carried out with a range of available methods for structural, electronical and optical characterization. By placing the nanovoids and nanodots in a highly doped emitter layer close enough to the p-n-junction that the near-fields will extend into the depletion layer, the effects of near-fields will be obtained. This will give a contribution to the electron-hole pair generation, and this will be additional to the far field effects. Being formed periodically, strained layers with self-assembled nanovoids or nanodots will display fundamentally unusual electronic and optical properties. These effects have not previously been experimentally studied in a solar cell configuration. The present system offers a unique configuration for such investigation.

A novel light trapping approach will be developed to enhance the absorption of thin film silicon (Si) solar cells using periodic arrangements of resonant dielectric micro-particles (DMPs) with dimensions on the other of the illuminating wavelengths. The main goal is to construct prototype cells that show enhanced sunlight-to-electricity conversion efficiency due to the action of DMP arrays incorporated on their transparent top contact. The strategy investigated here deals with advanced optical concepts that allow the manipulation and concentration of light in ways that can greatly surpass conventional geometrical optics or sub-wavelength plasmonics, by employing wavelength-sized dielectric scatterers. Therefore, the results of this work should not only broaden the understanding of the scientific community in the field of physical optics, but also foster the interest of the photovoltaics community towards light trapping with DMPs, a topic that is currently still under germination. The project will involve computational and experimental work executed in parallel in the Portuguese host institution CENIMAT-I3N, a world-renowned nanotechnology center in the area of functional materials. The computational studies will be performed using a finite-elements-method software (COMSOL) to optimize the physical parameters of the DMPs that allow maximum photocurrent enhancement in the Si cell material. The DMP structures will be then fabricated in laboratory using colloidal self-assembly combined with lithographic processes, and implemented in solar cells grown by plasmon-enhanced chemical vapor deposition. The work will be performed in close collaboration with the Italian institute IMM-CNR, a top microelectronics center where the candidate is currently working as a Marie Curie ITN Experienced Researcher. Therefore, the project shall nourish a new partnership between CENIMAT and IMM which is likely to be extended to other research and industrial partners in the European Union.