The overall objective of the project is to develop a novel, unconventional and cost efficient type of multipurpose high temperature coating systems on the basis of property tailoring by particle size processing of metallic source materials. It shall possess multi-functionality that will comprise thermal barrier effect, oxidation and corrosion protection, lotus effect, electrical insulation at elevated temperatures and fire protection. The concept of the novel approach to protection of surfaces is a coating consisting in its initial state of nano- and/or micro-scaled metal particles with a defined size, deposited by spraying, brushing, dipping or sol-gel. During the heat treatment, the binder is expelled, bonding to the substrate surface achieved, the metallic particles sinter and oxidise completely resulting in hollow oxide spheres that form a quasi-foam structure. Simultaneously, a diffusion layer is formed below the coating serving as a corrosion protection layer and as a bond coat for the top layer. The structure of the coating system shall be adjusted by parameters like selection of source metal/alloy, particle size, substrate, binder and a defined heat treatment. For fire protection the formation of hollow oxide spheres will be processed in a separate step before deposition. The flexibility of the new coatings integrates a wide field of application areas, such as gas and steam turbines in electric power generation and aero-engines, combustion chambers, boilers, steam generators and super-heaters, waste incineration, fire protection of composite materials in construction as well as reactors in chemical and petrochemical industry. A broad impact will thus be ensured increasing safety and the durability of components by an economic, multifunctional and flexible protection of their surfaces. The novelty will provide a real step change in the understanding of materials degradation mechanisms in extreme environments.

An unprecedented development in particle synthesis is providing methods to generate high yield quantities of nano- and micro-particles of different shapes, compositions, patterns and functionalities and an unprecedented diverse spectrum of particle patchiness, significantly extending the naturally available choices. These methods draw from the diverse fields of chemistry, physics, biology, engineering and materials science, and, in combination, provide a powerful arsenal for the fabrication of new particulate building blocks, the molecules of tomorrow materials, self-assembling into molecular-mimetic and unique structures, fluids, and gels made possible solely by their design. The new particles offer the possibility to go beyond the spherical interaction case, to move from the colloidal atom to the colloidal molecule --- providing valence to colloids --- and to further strength the analogies between colloids and globular proteins. The present theoretical and computational project aims at providing new ideas for developing effective methodologies of bottom-up manufacturing, at providing the scientific community with the background necessary to fully control the self-assembly of these new building blocks as well as solutions to relevant condensed-matter physics problems. The project also aims at developing realistic models of DNA-functionalized nano and micro particles, presently the most promising and versatile building block of bio-colloid materials. Understanding the assembly of patchy particles will offer fine control over the three-dimensional organization of materials, as well as the combination of different materials over several length scales, making it possible to design a spectrum of crystal polymorphs and self-assembled ordered and disordered structures unprecedented in colloid science.

The major goal of the proposed project is to facilitate the applicant's reintegration to his home institute after a successful Marie Curie training period at the Surface Chemistry, Dept. of Chemistry, KTH, Stockholm. To reach this goal the host (Eötvös Lorand University, Budapest) offers a permanent position for him and provides the infrastructure necessary to implement the proposed research project. The proposed research project consists of two independent work packages. The first work package aims at developing and applying a nanoprobe technique to determine the optimal structure of DNA-polyelectrolyte complexes, which is an important step required to increase the efficiency of current non-viral gene delivery systems. The second work package will map the effect of multivalent ions on the interaction of a flexible polyelectrolyte and an oppositely charged surfactant, which will provide information how the strong ion-ion correlations, introduced by the multivalent ions, affect surfactant/polyelectrolyte self-assembly. Finally, the reintegration grant will allow the researcher to transfer his new competences (related to modern surface characterization techniques, e.g. DPI, AFM, QCM-D, ellipsometry) to the host institution of the reintegration period and to the wider audience of its students.

Colloidal quantum dots (CQDs) have recently attracted significant attention as a candidate material for optoelectronic devices, and in particular photodetectors and solar cells. These materials can be manufactured in the solution phase and spin-cast onto a variety of substrates, significantly reducing the cost of device fabrication. Additionally, the bandgap of CQD films can be tuned to allow absorption of specific wavelength regions by varying the diameter of the CQDs, due to the quantum confinement size effect. To maintain efficient charge extraction in these devices, the thickness of the CQD layer is restricted, resulting in devices that are limited by non-complete absorption. To improve efficiencies it is necessary to decouple the optical thickness from the electrical thickness by employing novel light-trapping schemes. Plasmonics offers the opportunity to confine light in sub-wavelength volumes, increasing the absorption in thin films. Discrete metal particles can be fabricated on a glass substrate, by simple self assembly or by nano-fabrication techniques, before the CQD are spin cast thus allowing plasmonic scattering structures to be incorporated into the cells without significantly increasing the complexity or cost of cell fabrication. By integrating plasmonic light trapping based on sub wavelength scattering structures with CQD devices, we will aim to dramatically increase the absorption, while maintaining good electrical characteristics, and hence achieve gains in overall performance and efficiency. Additionally, we will study the physical mechanisms behind plasmonic enhancement by employing FDTD simulations to investigate the scattering behaviour of single particles and periodic arrays embedded in CQD films, and combine this with simple conceptual models to design optimal scattering structures. These will be fabricated on CQD devices with the aim of providing the maximal absorption enhancement possible with plasmonic structures.

This project aims to evaluate the effect of phosphonic acid adsorption on metal surfaces. Much is known about the adsorption of these molecules on oxide surfaces but very little is known about their behaviour on metals. The first primary aim is to determine adsorption and phase behaviour quantitatively as a function of surface charge, which will be controlled by varying applied electrical potential. A strategic combination of classical electrochemical and modern surface analytical probes will be employed, including atomic force microscopy and the recently developed in situ infrared technique, PM-IRRAS (Polarisation Modulation Infrared Reflection Absorption Spectroscopy). These results will be combined together with computational simulations, a combination of density functional theory and molecular dynamics simulations, to form a complete picture of the surface aggregation phenomena of these molecules. The strategy will be to evaluate the phosphonic acid behaviour first on single crystal substrates and then on nanoparticle surfaces, which will be prepared on carbon substrate by electrodeposition. The second primary aim of the proposal project is to evaluate the effect of adsorption of these molecules on the electrochemical reduction of oxygen (ORR), a reaction of immense technological importance. Phosphonates have previously received very limited study for fuel cell and battery applications. We aim to determine whether phosphonic acid adsorption can be used as a tool to direct the selectivity of the ORR toward a specific product. If the reaction can be steered toward peroxide formation rather than water, this would open up possibilities for the commercial production of hydrogen peroxide (using existing fuel cell technology) and Li-air batteries, where the peroxo product is preferred to permit the re-charging of the battery.

Metal nanoparticles (NPs) have been studied intensely in the last decade due to their novel optical, catalytic and electronic properties. Because of the nanoscopic size of NPs, self-assembly has been by far the most important means of generating higher-order architectures. Light is a particularly attractive means to self-assemble of NPs because it can be delivered instantaneously and into a precise location. In order to render NPs photoactive, their surfaces need to be functionalized with photoresponsive ligands. As an incoming Independent Researcher at the Weizmann Institute of Science, the Applicant wishes to develop new nanomaterials resulting from this marriage of nanoscience and organic chemistry. The Applicant has extensive experience in the fields of nanoscience and organic chemistry, acquired during the last several years at Northwestern University, USA. In the proposed project, he would like to develop a NP-based system, in which catalysis is regulated by light. This system takes advantage of his previous research, which has shown that NPs can be reversibly assembled and disassembled using light (PNAS 2007, 104, 10305; Science 2007, 316, 261). For NPs decorated with mixed monolayers comprising photoswitches and molecular catalysts, disassembly of such aggregates will result in a drastic increase of a catalytic surface area exposed to the solvent, and therefore in effective catalysis of a model reaction. As a result, self-assembly process will be transduced into catalytic activity. The system will then be extended to include various types of NPs functionalized with mixtures of different photoswitches and catalysts. These NPs will assemble / disassemble when exposed to different wavelengths of light. The ultimate goal of the project is to demonstrate that in a complex mixture of mutually incompatible chemicals, reactions can be turned 'on' and 'off' using light of different wavelengths, in a way similar to enzymatic regulation of reactions in living cells.

We have demonstrated the presence of attractive interactions arising in low ionic strength solution between charged soft-matter objects and highly curved regions of like-charged confining surfaces. These unexpected interactions result in stretching of DNA and trapping of colloidal particles in solution in a nanofluidic slit. This proposal seeks to further understand the attractive interactions arising between colloidal objects and like-charged confining walls in low-ionic-strength solution, in order to better control the underlying self-assembly process. The controlled self-assembly of arrays or arbitrary arrangements of discrete charged metal or dielectric nano-objects will permit the investigation of plasmonic and photonic phenomena in two dimensions, e.g., plasmonic coupling of resonantly excited metal nanoparticles, modification of fluorescence emission of single emitters diffusing in solution very close to discrete metal nano-objects, realization of novel ordered and disordered arrangements of nano-objects (e.g. dielectric particles like TiO2) for studying light scattering phenomena in two dimensions. One of the chief advantages of the self-assembly technique described here over conventional fabrication techniques is that the substrate surface structure which directs self-assembly of the optically active element acts as a 'rewritable surface' enabling the investigation of the plasmonic and photonic properties of ensembles of particles of similar surface charge but variable dielectric properties.

The PHOTOSURF project will investigate self-assembled networks of photo-sensitive molecules formed at semiconductor and dielectric surfaces. The interaction between light and photo-sensitive dye molecules adsorbed on semiconductors plays a pivotal role in several renewable energy technologies: dye sensitised solar cells (DSSC) and the photo-catalytic production of solar fuels. In both of these applications the configuration of dyes with respect to each other and the underlying surface is a key factor in determining how efficiently solar energy is converted to either electricity or to green fuel sources. Knowledge of how the nanoscale organisation of molecules influences the operation of solar energy devices, coupled with an increased ability to control that organisation, will help to maximise the efficiency of such devices. Self-assembly is a process by which individual molecules can organise themselves into ordered and complex structures through simple intermolecular interactions. In recent years the formation of ordered molecular networks on surfaces using 2D self-assembly has been an area of intense research. PHOTOSURF will use concepts from the field of 2D molecular self-assembly to control the structural arrangement of photo-sensitive dye and catalyst molecules on semiconductor and dielectric surfaces. These molecular structures will then be investigated using a range of techniques including scanning tunnelling microscopy (STM) and scanning microwave microscopy (SMM). Such experiments will allow the project to study charge transfer, photo-catalysis and light harvesting effects at the level of individual dye molecules. From these studies we will gain a deeper fundamental understanding of how molecular orientation, bonding and arrangement influences these physical and optical processes. This knowledge will be vital to the future development of cost effective solar energy technologies.

This project will develop novel, bio-inspired routes to the synthesis of porous inorganic nanoparticles with sponge-like internal structures, using nanostructured polymer capsules as templates. The application of these structures in targeted drug delivery and controlled release will then be investigated. Biominerals provide a unique inspiration for the design and synthesis of new materials. While showing remarkable structures and properties, these amazing materials form in aqueous environments under ambient conditions and organic molecules -either as soluble additives or insoluble matrices -are used to control crystal growth. We will here employ a bio-inspired strategy to generate porous calcium carbonate and calcium phosphate nanoparticles with sponge-like structures. A novel class of polymer capsules with bicontinuous internal structures, which are formed by the self-assembly of comb-like block copolymers in water will be used as templates. This system will also provide a unique opportunity for studying the effect of confinement on crystal nucleation and growth. Crystallisation in confinement is widespread in Nature, the environment and technology, and the research will therefore impact on fundamental research and technology across many disciplines. The synthesised porous nanoparticles will then be used to build targeted drug delivery systems (DDSs) by encapsulating anti-cancer drugs for the treatment of bone cancer. While mesoporous silica nanoparticles have been investigated quite extensively, little work has to-date been performed on alternative nanoporous crystalline inorganic nanoparticles. As compared with mesoporous silica, the calcium phosphate and calcium carbonate nanoparticles will show superior biocompatibility and biodegradation, and will also offer acid-responsive solubility and therefore will give the pH-responsive release of the encapsulated drugs from the drug delivery system in the acidic environment of tumors.

The efficient, reproducible synthesis of bespoke organic nanoparticles of controlled size, morphology and surface functionality in concentrated solution is widely regarded to be a formidable technical challenge. However, recent advances by the Principal Investigator (PI) suggest that this important problem can be addressed by polymerisation-induced self-assembly (PISA) directly in aqueous solution to form a range of diblock copolymer 'nano-objects'. The proposal combines three synergistic themes within the PI's group: (i) controlled-structure water-soluble polymers, (ii) living radical polymerisation and (iii) novel polymer colloids. More specifically, the PI will work closely with four post-doctoral scientists and a PhD student to design a series of diblock copolymer nanoparticles with either spherical, worm-like or vesicular morphologies under dispersion polymerisation conditions in either water, alcohol or n-alkanes. This exciting and timely fundamental research programme will produce world-leading scientific innovation. Moreover, the targeted nanoparticles will be evaluated for various potential applications, such as (i) intracellular delivery of various biomolecules (e.g. DNA, proteins, antibodies), (ii) readily sterilisable biocompatible hydrogels, (iii) bespoke Pickering emulsiifiers and foam stabilisers, (iv) tough nanocomposite monoliths, (v) new components for next-generation paints, (vi) novel boundary lubricants for high performance engine oils. Informal collaborations with four academic partners and four industrial companies will ensure that maximum scientific value and economic impact is extracted from this ambitious work programme. All research findings will be published in top-quality scientific journals and the PI will provide appropriate mentoring to inspire his research team to become the next generation of creative, productive scientists for the EC.