The construction of nanostructured objects of well-defined size is of outmost importance for nanotechnology to surmount claims for potential applications and exploit improved chemical, physical or biological properties of a functional nanofeatured material. Biomedical imaging is one particular field of interest for water-compatible chemical self-assembly of nanosized objects. The outlined project aims to develop a methodology for the preparation of nanostructured objects in aqueous media with the emphasis lying on the precise control over the size, shape and degree of functionalisation of the features. The goal is to build upon supramolecular helical scaffolds for the development of self-assembled functional structures in the nanoscopic range, which are to be used in magnetic resonance imaging (MRI) applications. MRI has made a significant impact to the area of diagnostic medicine, predominantly due to advances in the development of contrast agents (e.g. paramagnetic Gd(III)-complexes). We believe that a supramolecular approach based on self-assembled Gd(III) chelating molecular units can combine the benefits from both low and high molecular weight derivatives: high contrast agent efficiency or contrast enhancement on one hand, and an improved control over the pharmacokinetics on the other hand, because of the non-covalent dynamic nature that holds the objects together. Furthermore, challenges in the field of MRI contrast agents will be met by the development of multivalent target-specific structures. Advantages include the accumulation of MRI signals in a region of interest, and the combination of 1H MRI contrast enhancement with a second imaging label. 19F MRI is a highly promising probe because of the high sensitivity of the 19F nuclide and the absence of any background interference in living systems.

Cell-cell and cell-extracellular matrix (ECM) adhesion are complex, highly regulated processes that play a crucial role in most fundamental cellular functions including motility, proliferation, differentiation and apoptosis. Focal adhesions are major cellular sites responsible for cell-ECM attachment and adhesion-mediated signalling. These complex multimolecular assemblies consist of transmembrane integrin receptors that are linked to the actin cytoskeleton via cytoplasmic anchor proteins, such as vinculin, paxillin and focal adhesion kinase. To study the function behind molecular arrangement of single integrins in cell adhesion, we will design rigid template of cell adhesive gold nano-dots coated with cyclic RGDfK peptide by lithographic means of diblock copolymer self-assembly. The diameter of the adhesive dots is smaller 8 nm, which allows the binding of only up to one integrin per dot. These dots are positioned with high precision on a molecular scale at a controllable separation distance between 10-150 nm in different but defined pattern geometries. Because the dots may only be occupied by up to one integrin the dot pattern also resembles the integrin pattern in focal adhesions. We will study how the chemical nanoadhesive template effects cell spreading and shape, adhesion forces and expression of Fibronectin and Collagen.

HESPERUS aims at enabling cross-disciplinary training and research at the interface between Electrical Engineering, Supramolecular Chemistry, Materials- and Nano-Science and Physics. The overall goal of HESPERUS is to generate new scientific and technological knowledge by combining supramolecularly engineered nanostructures (SENs), mostly based on organic semiconductors, with tailor-made interfaces to textured solid substrates and electrodes, for fabricating prototypes of two-terminal devices (supramolecular wires) and three-terminal devices (field-effect transistors). The training and research objectives of HESPERUS are: 1. Surface texturing: derivatization of electrically conductive solid substrates and metallic nanostructures to achieve a full control over the surface work-function, wettability and adhesion, thus ultimately to be able to tune the self-assembly of electroactive molecules at surfaces into pre-programmed supramolecular assemblies. 2. Hierarchical self-organization on textured surface of multifunctional SENs based on electrically/optically active functionalized carbon-based (I) 2D nano-objects such as n- and p-type discotics (perylenediimide and hexabenzocoronene derivatives) and (II) polymeric multichromophoric architectures at surfaces on the functionalized substrates. 3. Nanochemistry and nanoprobes: Scanning probes (AFM, STM, KPFM, C-AFM) quantitative time and space resolved characterization of various physico chemical properties of SENs, in particular correlation between structural and electronic properties. 4. Fabrication of supramolecular wires and transistors: Measurement of charge mobility in SENs two- and three-terminal devices varying systematically the wire’s (1) chemical composition, (2) conformation, (3) length and (4) doping.

There have been major advances in the efficiency and efficacy of flexible electronic devices such as Organic Photovoltaics (OPV's) and Organic Light Emitting Diodes (OLEDS). Premature failure of the devices will occur through ingress of moisture and oxygen. Today there is however no simple, low cost process to create a 'barrier' to such ingress and extend device lifetimes. This project will investigate the structure–barrier property relationships in inorganic-organic hybrid coatings. The structures will be formed through the controlled self-assembly of nano-scale inorganic building-blocks synthesized through adaption of sol-gel chemistry. A variety of characterization methodologies including NMR, GPC, LC-MASS, DSC (Differential Scanning Calorimetry), WAXD (wide-angle X-ray diffraction), SAXS (small-angle X-ray scattering) will be used to assess the structures formed. Focus will be directed toward regimes of hybrid composition where the inorganic self-assembles as lamellae. Such structures offer the prospects of coatings which give both the high 'barrier' and the high optical transparency required in targeted applications. Cytec Surface Specialties, a chemical company, is the world leader in the supply of radiation curing resins for coatings and has the capabilities to formulate, apply, cure and test these hybrid coatings. The prospective fellow, Dr D Kogelnig, will have ample potential to expand his chemical skills from his previous work on the P/O/C based inorganic chemistry of ionic liquids to Si/O/C based chemistry required here and broaden his technical competences in polymer chemistry. His geographic transfer (Austria to Belgium) and from academia to industry is an example of genuine mobility. The training available would help him establish a career in Industry, but should he return to academia his experience will make his potential contribution from an academic environment all the more valued by industrial partners.

Integration of magnetic functionalities into electronic circuits requires the use of low cost, scalable methods focusing on the manipulation of magnetic moments by electric fields, as opposed to external magnetic fields. Spin polarized carriers can exert a torque to control the magnetization orientation. These carriers can be injected from ferromagnets (FM). They can also originate from the spin-orbit interaction, by using the Rashba, Dresselhaus and spin Hall effects. Ultimately, one may take advantage of the spin-textured states at the surface of topological insulators (TIs), a recently discovered new state of matter. The later 'spin-orbit torques' (SOTs) were recently observed in heavy-metal/FM and semiconducting structures. However, the mechanisms in play are under fierce debate, which is hindering technological progress.

Diamond and graphite, the two well-known allotropes of carbon, were familiar from the ancient times. Fullerenes, the third form of carbon, were discovered in 1985 and carbon nanotubes in 1991. Thus three dimensional (3D) (diamond and graphite), 1D (nanotubes) and 0D (fullerenes) allotropes were known. Since the breakthrough in 2004 that two dimensional allotropes of carbon, graphene has been reported. It can be used in molecular electronics applications, such as field-effect transistors, research into this novel material has exploded. Graphene, a single sheet of graphite, consists of a hexagonal array of sp2-hybridised carbon atoms. The material has excellent electrical properties, is cheap to make and requires no helicity control, giving it a definitive advantage over other carbon-based materials such as nanotubes. In addition, the electronic properties of graphene sheets can be influenced by introducing atomic defects, using programmed self-assembly, and by changing the charge carrier concentration in bilayer graphene. Unfortunately though, the conductivity as of yet cannot be switched off, which impedes its incorporation into switchable systems. Recently, the poor material properties of the graphene were improved considerably by dispersing the single carbon sheets inside a polymer matrix, providing a path to a broad class of conductive composite graphene-based materials. The construction of small graphene sheets by chemical synthesis has recently been reported by Müllen. This bottom-up chemical synthesis of such large, unsaturated polycyclic aromatic hydrocarbon surfaces, however, has proven very laborious and time consuming, requiring a huge synthetic effort. Therefore, the aim of this proposal is the construction and physical characterisation of a novel class of materials which closely resemble graphene, by facile chemical synthesis, which can be synthetically tailored and post-processed to tune the material properties: clickgraphene.

Semiconductor materials form the basis of modern electronics, communication, data storage and computing technologies. One of today’s major challenges for the development of future technologies is the realization of devices that control not only the electron charge, as in present electronics, but also its spin, setting the basis for future spintronics. Spintronics represents the concept of the synergetic and multifunctional use of charge and spin dynamics of electrons, aiming to go beyond the traditional dichotomy of semiconductor electronics and magnetic storage technology. The most direct method to induce spin-polarized electrons into a semiconductor is by introducing appropriate transition metal dopants producing a dilute magnetic semiconductor (DMS). The seamless integration of future spintronic architectures into nanodevices would require the fabrication 1-D DMS nanostructures in well defined architectures. In this project we propose to use a simple low-cost, low-temperature electrodeposition process to not only synthesise and characterise ZnO based bipolar DMS nanowire heterostructures but, even more importantly, fabricate an array of p-n and n-p-n junctions which could lead to novel nano-spintronic devices within ordered pre-defined nano-architectures. We will study the structural and functional properties of these heterostructures, which could have applications such as spin polarised LED and spin polarised bipolar junction transistor. By fully exploring the parameters controlling the growth and functionality of these materials we will try to gain a holistic understanding of the processing/structure/property relationships for this system. The ultimate goal of this project is to be able to design and fabricate specific nanowire heterostructures with tuneable magnetic and electrical properties which could lead to practical spintronic applications. Moreover this approach is inherently clean and scalable and easily integrated within current industrial practice.

The aim of the project is a rational design of complex molecular self-assembled surface nanostructures the properties of which could be externally switched or their self-assembly process could be externally controlled. The project covers the research on the self-organization processes of molecules on metallic surfaces with ultra thin insulating layers and graphene substrates. Using the intermolecular bonds with graded strength the complex hierarchical architectures should be realized. The incorporation of switchable molecules gives the structures specific functional properties. The main idea lies in the preparation of nanopores which can be opened or closed through switching the molecules by light induced cis/trans isomeration which will be controlled by a proper choice of the used light wavelength. The detailed study of intermolecular interactions on insulating layers as well as understanding the light-induced switching processes in the nanostructures will be in centre of interest. Next, the influence of adjustable electronic density of graphene substrates or external electric fields on molecular self-assembly processes will be also studied.

The project 'Superantibodies' encompasses an interdisciplinary approach to accomplish the first instance of a biohybrid, yet fully synthetic three dimensional recognition element by converging the benefits of natural biorecognition with those of a synthetic approach. The bio-inspired concept is modelled on the antibody binding site whose binding capacity is the result of a defined three-dimensional structure in which loops of polypeptides cooperatively interact with the antigen through specific biomolecular interactions. The project implements a combination of modern biomolecular and bioanalytical techniques to identify peptides within these structures that are pivotal for the interaction with the antigen, and to use organic chemistry to synthetically mimic these peptides whilst maintaining their biological function. Affinity driven self-assembly between these peptides and their specific antigen is used to produce templates for a subsequent molecular imprinting process, resulting in a site-specific integration of peptides into the structural backbone of a molecularly imprinted polymer. It is hypothesised that it will be possible to rationally engineer recognition elements with tailored affinities by changing the number and the type of the embedded peptides to rationally create structures whose affinity can outperform that of naturally derived antibodies. This proposal is built on the expertises and scientific strengths of Dr Heiko Andresen while taking him in new directions. The multidisciplinary group of Dr Molly Stevens provides a fertile environment for the scientific and professional development of the applicant, and Imperial's infrastructures and dedication to high-quality professional and personal career development strongly support Dr Andresen in reaching a position of professional maturity. The project proposal is in line with aims and policy objectives of the FP7, with particular high relevance for the theme-crossing FP7 initiative 'NanoMedicine'.

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.