ERC FUNDED PROJECTS

This proposal aims to develop a combination of a chirped-pulse (sub)mm-wave rotational spectrometer with uniform supersonic flows generated by expansion of gases through Laval nozzles and apply it to problems at the frontiers of reaction kinetics. The CRESU (Reaction Kinetics in Uniform Supersonic Flow) technique, combined with laser photochemical methods, has been applied with great success to perform research in gas-phase chemical kinetics at low temperatures, of particular interest for astrochemistry and cold planetary atmospheres. Recently, the PI has been involved in the development of a new combination of the revolutionary chirped pulse broadband rotational spectroscopy technique invented by B. Pate and co-workers with a novel pulsed CRESU, which we have called Chirped Pulse in Uniform Flow (CPUF). Rotational cooling by frequent collisions with cold buffer gas in the CRESU flow at ca. 20 K drastically increases the sensitivity of the technique, making broadband rotational spectroscopy suitable for detecting a wide range of transient species, such as photodissociation or reaction products. We propose to exploit the exceptional quality of the Rennes CRESU flows to build an improved CPUF instrument (only the second worldwide), and use it for the quantitative determination of product branching ratios in elementary chemical reactions over a wide temperature range (data which are sorely lacking as input to models of gas-phase chemical environments), as well as the detection of reactive intermediates and the testing of modern reaction kinetics theory. Low temperature reactions will be initially targeted; as it is here that there is the greatest need for data. A challenging development of the technique towards the study of high temperature reactions is also proposed, exploiting existing expertise in high enthalpy sources.

2 100 230 €

Start date: 2016-09-01, End date: 2021-08-31

The aim of the work proposed here is to develop a completely new method to electronically dope assemblies of semiconductor nanocrystals (a.k.a quantum dots, QDs), and porous semiconductors in general. External dopants are added on demand in the form of electrolyte ions in the voids between QDs. These ions will be introduced via electrochemical charge injection, and will subsequently be immobilized by (1) freezing the electrolyte solvent at room temperature or (2) chemically linking the ions to ligands on the QD surface, or by a combination of both. Encapsulating doped QD films using atomic layer deposition will provide further stability. This will result in stable doped nanocrystal assemblies with a constant Fermi level that is controlled by the potential set during electrochemical charging. QDs are small semiconductor crystals with size-tunable electronic properties that are considered promising materials for a range of opto-electronic applications. Electronic doping of QDs remains a big challenge even after two decades of research into this area. At the same time it is highly desired to dope QDs in a controlled way for applications such as LEDs, FETs and solar cells. This research project will provide unprecedented control over the doping level in QD films and will provided a major step in the optimization of optoelectronic devices based on QDs. The “Doping-on-Demand” approach will be exploited to develop degenerately doped, low-threshold QD lasers that can be operated under continuous wave excitation, and QD laser diodes that use electrical injection of charge carriers. The precise control of the Fermi-level will further be used to optimize pin junction QD solar cells and to develop, for the first time, QD pn junction solar cells with precise control over the Fermi levels.

1 497 842 €

Start date: 2016-01-01, End date: 2020-12-31

Over the last decades European societies have become more ethnically diverse. However, a more comprehensive understanding of the life course and population dynamics in migrant families is still lacking. Ignoring a large share of the population in studies on family and population dynamics is exclusive and does not reflect reality. My project is first of all innovative in providing a more comprehensive overview of individual life courses of migrants: events in different life domains are linked and full life trajectories are analysed and explained. I will focus not only on the causes but also study the consequences of life course decisions. The second project goal is to explain the effect of migration on intergenerational solidarity and family ties. The analyses will link different phases in the life course as well as different generations. Families of different migrant and native origin will be compared in these parts. Third, I will make unique comparisons between the life course trajectories in the countries of origin and settlement of migrants. Bringing in the perspective of the sending country is original and crucial for understanding to what extent life course choices are related to the integration process in the host society, or to a trend that also occurs in the country of origin. A final major novelty of this project is that different recent data sources are linked within each of the components of the project. The combination of data from the Gender and Generations Survey (GGS), The Integration of the Second Generation (TIES) survey, the PAIRFAM survey, the European Social Survey, the Demographic and Health Surveys and the census, allow for a more complete understanding of the life courses of migrants and population dynamics in migrant families.

1 012 800 €

Start date: 2011-02-01, End date: 2016-08-31

Green Paradoxes are defined as the phenomenon that climate change policies can have counterproductive effects. For example, a subsidy on clean energy from renewable resources (solar, wind) will decrease the price at which this energy is supplied. But if the price still exceeds the cost of fossil fuel extraction and given that available stocks will be depleted, the price decrease will speed up the extraction from non-renewable resources, such as oil, that cause CO2 emissions. Hence, instead of delaying extraction the policy enhances initial extraction and emissions. In the design of environmental policy this effect is insufficiently taken into account, because the supply side of the market for fossil fuels is largely neglected. The principal aim of this research proposal is to critically investigate Green Paradoxes and to come up with sound policy recommendations, taking into account the demand as well as the supply dimension of fossil fuels. Particular attention is paid to a broad and dynamic welfare analysis, allowing for concerns regarding sustainability. Especially relevant for tackling the research question is to provide a closer examination of imperfect competition on the oil market and to distinguish between dirty and clean alternatives for fossil fuel. In addition the proposal is to study the political economy of climate change policy to come up with proposals that not only muster global support but also address the adverse distributional aspects of climate change itself on developing economies and on the poorest of advanced economies who get hardest hit by green taxes. This requires not only the tools of modern political economy, but also the realms of second-best economics and the latest developments in public finance.

2 743 548 €

Start date: 2011-05-01, End date: 2016-04-30

This project centers around the investigation of molecular mobility in solid layers by a truly multidisciplinary approach: combining the expertise from crystal growth, astrophysics, and chemistry. We aim to answer long standing questions in the context of two cross-disciplinary applications: the formation and evolution of interstellar ices and the solid state transition from one crystal structure — polymorph — to another. The first is important for fundamental questions dealing with the origin of life, specifically concerning the delivery of molecules—like H2O, CO2 and organic molecules—to habitable planets. The second application is of great interest to the pharmaceutical industry where polymorph control is crucial. The polymorphic form controls the solubility of the compound and is therefore key in dose determination. The goal of the investigation is to obtain an understanding of mobility in molecular layers on the molecular level in order to (i) understand the processes in interstellar ices leading to the meeting of two reactive species, (ii) identify the trapping mechanisms in interstellar ices, (iii) predict which molecules can survive in ices in the harsh environment of star and planet forming regions, (iv) determine which processes are fundamental to polymorphic conversion, and (v) design a way to inhibit or promote polymorphic conversion. I propose to study the mobility in molecular layers This project centers around the investigation of molecular mobility in solid layers by a truly multidisciplinary approach: combining the expertise from crystal growth, astrophysics, and chemistry. We aim to answer long standing questions in the context of two cross-disciplinary applications: the formation and evolution of interstellar ices and the solid state transition from one crystal structure - polymorph -to another. The first is important for fundamental questions dealing with the origin of life, specifically concerning the delivery of molecules -like H2O, CO2 and organic molecules - to habitable planets. The second application is of great interest to the pharmaceutical industry where polymorph control is crucial. The polymorphic form controls the solubility of the compound and is therefore key in dose determination. The goal of the investigation is to obtain an understanding of mobility in molecular layers on the molecular level in order to (i) understand the processes in interstellar ices leading to the meeting of two reactive species, (ii) identify the trapping mechanisms in interstellar ices, (iii) predict which molecules can survive in ices in the harsh environment of star and planet forming regions, (iv) determine which processes are fundamental to polymorphic conversion, and (v) design a way to inhibit or promote polymorphic conversion. I propose to study the mobility in molecular layers using a combination of simulation techniques. The fundamental difficulty is to cover processes that take place over a large range of timescales: from picoseconds to years. Advances in numerical simulations have only recently made this research possible. Using Molecular Dynamics and Monte Carlo simulations we will study the interactions and processes in molecular layers on different lengthscales and covering a timescale range of roughly 20 orders of magnitude. This ambitious research project will be carried out in the Institute for Molecules and Materials at the Radboud University in Nijmegen, but will also benefit from existing and new collaborations with local, national and international colleagues.

1 500 000 €

Start date: 2011-02-01, End date: 2016-01-31

Is it possible to really 'see' individual molecules in action as they are involved in a chemical reaction at a surface? And can we, in this way, get a complete understanding of reaction mechanisms, at the resolution of atoms? The importance of studying chemical reactions at surfaces has recently been highlighted by Gerhard Ertl being awarded the Nobel Prize in chemistry in 2007, for elucidating mechanisms of chemical processes on heterogeneous catalysts at the single molecule level with Scanning Tunneling Microscopy (STM). Although ground-breaking, these studies were carried out in ultra-high vacuum, which is, however, an unrealistic condition for conventional chemical or biological reactions which usually occur in a liquid medium. The aim of this ERC proposal is to establish a research area at the interface of chemistry and physics which has so far been nearly completely unexplored: the investigation of chemical reactions at solid-liquid interfaces at the highest detail possible, by visualizing molecules with STM while they are involved in a reaction. By doing so, unique information about reaction mechanisms can be obtained by looking at individual molecules, instead of ensembles where the behaviour of many molecules is averaged. Towards this goal I propose to use a newly developed catalysis-STM setup, which is equipped with a liquid-cell and a bell-jar, and in which the conditions that are commonly applied in chemical laboratory processes (e.g. addition and withdrawal of chemicals, working under different atmospheres) can be closely resembled. In this setup I intend to carry out chemical reactions at a surface and monitor the behaviour of individual adsorbed catalysts, while they are in action. More specifically, it is my aim to investigate in detail the relation between structure and reactivity at the nanoscale

1 500 000 €

Start date: 2010-09-01, End date: 2015-08-31

In recent years water near surfaces and solutes has been observed to be differently structured and to show slower reorientation and hydrogen-bond dynamics than in bulk. Aqueous proton transfer is a process that strongly relies on the structure and dynamics of the hydrogen-bond network of liquid water and that often occurs near surfaces. Examples are thylakoid and mitochondrial membranes and the nanochannels of transmembrane proteins and fuel cells. An important but experimentally largely unexplored area of research is how the rate and mechanism of aqueous proton transfer change due to the surface-induced structuring of the water medium. Theoretical work showed that the structuring and nano-confinement of water can have a strong effect on the proton mobility. Recently, experimental techniques have been developed that are capable of probing the structural dynamics of water molecules and proton-hydration structures near surfaces. These techniques include heterodyne detected sum-frequency generation (HD-SFG) and two-dimensional HD-SFG (2D-HD-VSFG). I propose to use these and other advanced spectroscopic techniques to study the rate and molecular mechanisms of proton transfer through structured aqueous media. These systems include aqueous solutions of different solutes, water near extended surfaces like graphene and electrically switchable monolayers, and the aqueous nanochannels of metal-organic frameworks. These studies will provide a fundamental understanding of the molecular mechanisms of aqueous proton transfer in natural and man-made (bio)molecular systems, and can lead to the development of new proton-conducting membranes and nanochannels with applications in fuel cells. The obtained knowledge can also lead to new strategies to control proton mobility, e.g. by electrical switching of the properties of the water network at surfaces and in nanochannels, i.e. to field-effect proton transistors.

2 495 000 €

Start date: 2016-10-01, End date: 2021-09-30

Extremely high separation powers are required to fully characterize complex mixtures that are of crucial importance in many fields, such as life science (including systems biology), food science, renewable energy sources and feedstocks, and high-tech materials. The STAMP project is aimed at obtaining a peak capacity of one million in liquid-phase analytical separations. Spatial three-dimensional liquid chromatography will be used to achieve this goal. The major advantage of this technique is that all second-dimension separations and – in a next step – all third-dimension separations are performed in parallel. This allows high-resolution separations to be performed in each dimension, while the total analysis time remains reasonable. Optical and mass-spectrometric imaging techniques are envisaged as detection methods after printing (STAMPing) the effluent from the 3D separation body on a suitable substrate. The STAMP project also has a number of sub-targets that will bring additional significant benefits to all the above application fields. The target and the sub-targets of the STAMP project may be summarized as follows. • Separations with a peak capacity of 1,000,000 (through the use of spatial 3D-LC) • Fast and efficient spatial 2D-LC separations • Devices for spatial 2D-LC and 3D-LC • Detection principles for spatial 2D-LC and 3D-LC • Suitable stationary-phase materials and mechanisms for orthogonal 2D and 3D separations • Relevant applications of all of the above in various fields of science.

2 499 780 €

Start date: 2016-09-01, End date: 2021-08-31

The proteins from thermophilic organisms are the objects of the present study. Here it is specifically proposed a study on the microscopic origin of proteins thermostability using a multi-computational approach. The multi-methodological strategy is a powerful tool for exploring this issue since it allows an investigation at many different levels of molecular details. Neutron Scattering experiments will complement the in silico investigation. The present study will tackle the issue of thermostability under a new light by explicitly focusing on the role of hydration water and by carefully selecting homologues proteins from mesophilic, thermophilic and hyperthermophilic organisms as cases of study. I will investigate how the chemical composition of a protein surface, the distribution of charged, polar and hydrophobic amino acids, could be tuned in order to increase/reduce thermal resistance of the hydration layer and of the protein matrix. I will examine whether thermostability correlates to the flexibility or the rigidity of the protein matrix and/or of its hydration skin. I will study in details how the catalytic activity of enzymes is affected by the dynamics of the protein at extreme temperatures. The theoretical study will be supported by Neutron Scattering experiments gaining key knowledge on the structure and dynamics of hydration water and on the dynamics of proteins in the nanosecond time scale. Nowadays the possibility to design functional thermostable proteins is strategic for expanding the use of enzymes in industrial processes and in biotechnology. The study of the coupling between hydration water and protein surface could pave the way for the computer-aided engineering of thermostable proteins.

1 225 000 €

Start date: 2011-05-01, End date: 2016-04-30