Innovative Homogeneous and Heterogeneous Systems for Electrochemically Generated Luminescence Investigations: Towards One-Dimensional ECL

My research PhD work is focused on the Electrochemically Generated Luminescence (ECL) investigation of several different homogeneous and heterogeneous systems. ECL is a redox induced emission, a process whereby species, generated at electrodes, undergo a high-energy electron transfer reaction to form excited states that emit light. Since its first application, the ECL technique has become a very powerful analytical tool and has widely been used in biosensor transduction. ECL presents an intrinsically low noise and high sensitivity; moreover, the electrochemical generation of the excited state prevents scattering of the light source: for all these characteristics, it is an elective technique for ultrasensitive immunoassay detection. The majority of ECL systems involve species in solution where the emission occurs in the diffusion layer near to the electrode surface. However, over the past few years, an intense research has been focused on the ECL generated from species constrained on the electrode surface. The aim of my work is to study the behavior of ECL-generating molecular systems upon the progressive increase of their spatial constraints, that is, passing from isolated species in solution, to fluorophores embedded within a polymeric film and, finally, to patterned surfaces bearing “one-dimensional” emitting spots. In order to describe these trends, I use different “dimensions” to indicate the different classes of compounds. My thesis was mostly developed in the electrochemistry group of Bologna with the supervision of Prof Francesco Paolucci and Dr Massimo Marcaccio. With their help and also thanks to their long experience in the molecular and supramolecular ECL fields and in the surface investigations using scanning probe microscopy techniques, I was able to obtain the results herein described. Moreover, during my research work, I have established a new collaboration with the group of Nanobiotechnology of Prof. Robert Forster (Dublin City University) where I spent a research period. Prof. Forster has a broad experience in the biomedical field, especially he focuses his research on film surfaces biosensor based on the ECL transduction. This thesis can be divided into three sections described as follows: (i) in the fist section, homogeneous molecular and supramolecular ECL-active systems, either organic or inorganic species (i.e., corannulene, dendrimers and iridium metal complex), are described. Driving force for this kind of studies includes the search for new luminophores that display on one hand higher ECL efficiencies and on the other simple mechanisms for modulating intensity and energy of their emission in view of their effective use in bioconjugation applications. (ii) in the second section, the investigation of some heterogeneous ECL systems is reported. Redox polymers comprising inorganic luminophores were described. In such a context, a new conducting platform, based on carbon nanotubes, was developed aimed to accomplish both the binding of a biological molecule and its electronic wiring to the electrode. This is an essential step for the ECL application in the field of biosensors. (iii) in the third section, different patterns were produced on the electrode surface using a Scanning Electrochemical Microscopy. I developed a new methods for locally functionalizing an inert surface and reacting this surface with a luminescent probe. In this way, I successfully obtained a locally ECL active platform for multi-array application.

Memory hierarchy and data communication in heterogeneous reconfigurable SoCs

The miniaturization race in the hardware industry aiming at continuous increasing of transistor density on a die does not bring respective application performance improvements any more. One of the most promising alternatives is to exploit a heterogeneous nature of common applications in hardware. Supported by reconfigurable computation, which has already proved its efficiency in accelerating data intensive applications, this concept promises a breakthrough in contemporary technology development. Memory organization in such heterogeneous reconfigurable architectures becomes very critical. Two primary aspects introduce a sophisticated trade-off. On the one hand, a memory subsystem should provide well organized distributed data structure and guarantee the required data bandwidth. On the other hand, it should hide the heterogeneous hardware structure from the end-user, in order to support feasible high-level programmability of the system. This thesis work explores the heterogeneous reconfigurable hardware architectures and presents possible solutions to cope the problem of memory organization and data structure. By the example of the MORPHEUS heterogeneous platform, the discussion follows the complete design cycle, starting from decision making and justification, until hardware realization. Particular emphasis is made on the methods to support high system performance, meet application requirements, and provide a user-friendly programmer interface. As a result, the research introduces a complete heterogeneous platform enhanced with a hierarchical memory organization, which copes with its task by means of separating computation from communication, providing reconfigurable engines with computation and configuration data, and unification of heterogeneous computational devices using local storage buffers. It is distinguished from the related solutions by distributed data-flow organization, specifically engineered mechanisms to operate with data on local domains, particular communication infrastructure based on Network-on-Chip, and thorough methods to prevent computation and communication stalls. In addition, a novel advanced technique to accelerate memory access was developed and implemented.

Electrochemistry of carbon based engineered structures

The main aims of my PhD research work have been the investigation of the redox, photophysical and electronic properties of carbon nanotubes (CNT) and their possible uses as functional substrates for the (electro)catalytic production of oxygen and as molecular connectors for Quantum-dot Molecular Automata. While for CNT many and diverse applications in electronics, in sensors and biosensors field, as a structural reinforcing in composite materials have long been proposed, the study of their properties as individual species has been for long a challenging task. CNT are in fact virtually insoluble in any solvent and, for years, most of the studies has been carried out on bulk samples (bundles). In Chapter 2 an appropriate description of carbon nanotubes is reported, about their production methods and the functionalization strategies for their solubilization. In Chapter 3 an extensive voltammetric and vis-NIR spectroelectrochemical investigation of true solutions of unfunctionalized individual single wall CNT (SWNT) is reported that permitted to determine for the first time the standard electrochemical potentials of reduction and oxidation as a function of the tube diameter of a large number of semiconducting SWNTs. We also established the Fermi energy and the exciton binding energy for individual tubes in solution and, from the linear correlation found between the potentials and the optical transition energies, one to calculate the redox potentials of SWNTs that are insufficiently abundant or absent in the samples. In Chapter 4 we report on very efficient and stable nano-structured, oxygen-evolving anodes (OEA) that were obtained by the assembly of an oxygen evolving polyoxometalate cluster, (a totally inorganic ruthenium catalyst) with a conducting bed of multiwalled carbon nanotubes (MWCNT). Here, MWCNT were effectively used as carrier of the polyoxometallate for the electrocatalytic production of oxygen and turned out to greatly increase both the efficiency and stability of the device avoiding the release of the catalysts. Our bioinspired electrode addresses the major challenge of artificial photosynthesis, i.e. efficient water oxidation, taking us closer to when we might power the planet with carbon-free fuels. In Chapter 5 a study on surface-active chiral bis-ferrocenes conveniently designed in order to act as prototypical units for molecular computing devices is reported. Preliminary electrochemical studies in liquid environment demonstrated the capability of such molecules to enter three indistinguishable oxidation states. Side chains introduction allowed to organize them in the form of self-assembled monolayers (SAM) onto a surface and to study the molecular and redox properties on solid substrates. Electrochemical studies on SAMs of these molecules confirmed their attitude to undergo fast (Nernstian) electron transfer processes generating, in the positive potential region, either the full oxidized Fc+-Fc+ or the partly oxidized Fc+-Fc species. Finally, in Chapter 6 we report on a preliminary electrochemical study of graphene solutions prepared according to an original procedure recently described in the literature. Graphene is the newly-born of carbon nanomaterials and is certainly bound to be among the most promising materials for the next nanoelectronic generation.

Heterogeneous multicore systems for signal processing

This thesis explores the capabilities of heterogeneous multi-core systems, based on multiple Graphics Processing Units (GPUs) in a standard desktop framework. Multi-GPU accelerated desk side computers are an appealing alternative to other high performance computing (HPC) systems: being composed of commodity hardware components fabricated in large quantities, their price-performance ratio is unparalleled in the world of high performance computing. Essentially bringing “supercomputing to the masses”, this opens up new possibilities for application fields where investing in HPC resources had been considered unfeasible before. One of these is the field of bioelectrical imaging, a class of medical imaging technologies that occupy a low-cost niche next to million-dollar systems like functional Magnetic Resonance Imaging (fMRI). In the scope of this work, several computational challenges encountered in bioelectrical imaging are tackled with this new kind of computing resource, striving to help these methods approach their true potential. Specifically, the following main contributions were made: Firstly, a novel dual-GPU implementation of parallel triangular matrix inversion (TMI) is presented, addressing an crucial kernel in computation of multi-mesh head models of encephalographic (EEG) source localization. This includes not only a highly efficient implementation of the routine itself achieving excellent speedups versus an optimized CPU implementation, but also a novel GPU-friendly compressed storage scheme for triangular matrices. Secondly, a scalable multi-GPU solver for non-hermitian linear systems was implemented. It is integrated into a simulation environment for electrical impedance tomography (EIT) that requires frequent solution of complex systems with millions of unknowns, a task that this solution can perform within seconds. In terms of computational throughput, it outperforms not only an highly optimized multi-CPU reference, but related GPU-based work as well. Finally, a GPU-accelerated graphical EEG real-time source localization software was implemented. Thanks to acceleration, it can meet real-time requirements in unpreceeded anatomical detail running more complex localization algorithms. Additionally, a novel implementation to extract anatomical priors from static Magnetic Resonance (MR) scansions has been included.

Numerical models of trench migration for lateral heterogeneous subducting plates

The aim of this Thesis is to investigate the effect of heterogeneities within the subducting plate on the dynamics of subduction. In particular, I study the motion of the trench for oceanic and continental subduction, first, separately, and, then, together in the same system to understand how they interact. The understanding of these features is fundamental to reconstruct the evolution of complex subduction zones, such as the Central Mediterranean. For this purpose, I developed 2D and 3D numerical models of oceanic and continental subduction where the rheological, geometrical and compositional properties of the plates are varied. In these models, the trench and the overriding plate move self-consistently as a function of the dynamics of the system. The effect of continental subduction on trench migration is largely investigated. Results from a parametric study showed that despite different rheological properties of the plates, all models with a uniform continental crust share the same kinematic behaviour: the trench starts to advance once the continent arrives at the subduction zone. Hence, the advancing mode in continental collision scenarios is at least partly driven by an intrinsic feature of the system. Moreover, the presence of a weak lower crust within the continental plate can lead to the occurrence of delamination. Indeed, by changing the viscosity of the lower crust, both delamination and slab detachment can occur. Delamination is favoured by a low viscosity value of the lower crust, because this makes the mechanical decoupling easier between crust and lithospheric mantle. These features are observed both in 2D and 3D models, but the numerical results of the 3D models also showed that the rheology of the continental crust has a very strong effect on the dynamics of the whole system, since it influences not only the continental part of plate but also the oceanic sides.

Investigation of heterogeneous catalysts for the synthesis of fine chemicals

In order to match the more stringent environmental regulations, heterogenization of traditional homogeneous processes is one of the main challenges of the modern chemical industry. Great results have been achieved in the fields of petrochemicals and base chemicals, whereas in fine chemical industry most of the synthetic procedures are based on multistep processes catalyzed by homogeneous catalysts mainly used in stoichiometric amounts. In the fine chemicals manufacture not so much efforts have been devoted to the investigation of suitable solid catalysts for the development of greener processes, then this sector represent a very attractive field of research. In this context, the present work deals with the extensive investigation of the possibility to heterogenize existing processes, in particular two different classes of reactions have been studied: alkylation of aromatic and heteroaromatic compounds and selective oxidation of aromatic alcohols. Traditional solid acid catalysts, such as zeolites, clays and alumina have been tested in the gas phase alkylation of 1,2-methylendioxybenzene, core building block of many drugs, pesticides and fragrances. The observed reactivity were clarified through a deep FTIR investigation complemented by ab initio calculation. The same catalysts were tested in the gas phase isopropylation of thiophene with the aim of clearly attribute the role of the reaction parameters in the reaction proceeding and verify the possibility to enhance the selectivity of one of the two possible isomers. Finally various Au/CeO2 catalysts were tested in the synthesis of benzaldehyde and piperonal, two aldehydes largely employed in the manufacture of fine chemical products, through liquid phase oxidation of the corresponding alcohols in very mild conditions.

Oxygen: problems and solutions in electrochemistry

Different aspects of the electrochemistry of oxygen are examined through four experimental examples: corrosion, passivation via organic thin films, oxygen reduction and water oxidation catalysis are outlined in order to outline the very different ways and circumstances in which oxygen plays a major role in electrochemistry.

Sustainable processes using heterogeneous acid catalysts. Some examples of industrial interest.

In recent years the need for the design of more sustainable processes and the development of alternative reaction routes to reduce the environmental impact of the chemical industry has gained vital importance. Main objectives especially regard the use of renewable raw materials, the exploitation of alternative energy sources, the design of inherently safe processes and of integrated reaction/separation technologies (e.g. microreactors and membranes), the process intensification, the reduction of waste and the development of new catalytic pathways. The present PhD thesis reports results derived during a three years research period at the School of Chemical Sciences of Alma Mater Studiorum-University of Bologna, Dept. of Industrial Chemistry and Materials (now Dept. of Industrial Chemistry “Toso Montanari”), under the supervision of Prof. Fabrizio Cavani (Catalytic Processes Development Group). Three research projects in the field of heterogeneous acid catalysis focused on potential industrial applications were carried out. The main project, regarding the conversion of lignocellulosic materials to produce monosaccharides (important intermediates for production of biofuels and bioplatform molecules) was financed and carried out in collaboration with the Italian oil company eni S.p.A. (Istituto eni Donegani-Research Center for non-Conventional Energies, Novara, Italy) The second and third academic projects dealt with the development of green chemical processes for fine chemicals manufacturing. In particular, (a) the condensation reaction between acetone and ammonia to give triacetoneamine (TAA), and (b) the Friedel-Crafts acylation of phenol with benzoic acid were investigated.

Temperature Variation Aware Energy Optimization in Heterogeneous MPSoCs

Thermal effects are rapidly gaining importance in nanometer heterogeneous integrated systems. Increased power density, coupled with spatio-temporal variability of chip workload, cause lateral and vertical temperature non-uniformities (variations) in the chip structure. The assumption of an uniform temperature for a large circuit leads to inaccurate determination of key design parameters. To improve design quality, we need precise estimation of temperature at detailed spatial resolution which is very computationally intensive. Consequently, thermal analysis of the designs needs to be done at multiple levels of granularity. To further investigate the flow of chip/package thermal analysis we exploit the Intel Single Chip Cloud Computer (SCC) and propose a methodology for calibration of SCC on-die temperature sensors. We also develop an infrastructure for online monitoring of SCC temperature sensor readings and SCC power consumption. Having the thermal simulation tool in hand, we propose MiMAPT, an approach for analyzing delay, power and temperature in digital integrated circuits. MiMAPT integrates seamlessly into industrial Front-end and Back-end chip design flows. It accounts for temperature non-uniformities and self-heating while performing analysis. Furthermore, we extend the temperature variation aware analysis of designs to 3D MPSoCs with Wide-I/O DRAM. We improve the DRAM refresh power by considering the lateral and vertical temperature variations in the 3D structure and adapting the per-DRAM-bank refresh period accordingly. We develop an advanced virtual platform which models the performance, power, and thermal behavior of a 3D-integrated MPSoC with Wide-I/O DRAMs in detail. Moving towards real-world multi-core heterogeneous SoC designs, a reconfigurable heterogeneous platform (ZYNQ) is exploited to further study the performance and energy efficiency of various CPU-accelerator data sharing methods in heterogeneous hardware architectures. A complete hardware accelerator featuring clusters of OpenRISC CPUs, with dynamic address remapping capability is built and verified on a real hardware.