Supramolecular functional assemblies with photo or chemical addressability

Supramolecular self-assembly represents a key technology for the spontaneous construction of nanoarchitectures and for the fabrication of materials with enhanced physical and chemical properties. In addition, a significant asset of supramolecular self-assemblies rests on their reversible formation, thanks to the kinetic lability of their non-covalent interactions. This dynamic nature can be exploited for the development of “self-healing” and “smart” materials towards the tuning of their functional properties upon various external factors. One particular intriguing objective in the field is to reach a high level of control over the shape and size of the supramolecular architectures, in order to produce well-defined functional nanostructures by rational design. In this direction, many investigations have been pursued toward the construction of self-assembled objects from numerous low-molecular weight scaffolds, for instance by exploiting multiple directional hydrogen-bonding interactions. In particular, nucleobases have been used as supramolecular synthons as a result of their efficiency to code for non-covalent interaction motifs. Among nucleobases, guanine represents the most versatile one, because of its different H-bond donor and acceptor sites which display self-complementary patterns of interactions. Interestingly, and depending on the environmental conditions, guanosine derivatives can form various types of structures. Most of the supramolecular architectures reported in this Thesis from guanosine derivatives require the presence of a cation which stabilizes, via dipole-ion interactions, the macrocyclic G-quartet that can, in turn, stack in columnar G-quadruplex arrangements. In addition, in absence of cations, guanosine can polymerize via hydrogen bonding to give a variety of supramolecular networks including linear ribbons. This complex supramolecular behavior confers to the guanine-guanine interactions their upper interest among all the homonucleobases studied. They have been subjected to intense investigations in various areas ranging from structural biology and medicinal chemistry – guanine-rich sequences are abundant in telomeric ends of chromosomes and promoter regions of DNA, and are capable of forming G-quartet based structures– to material science and nanotechnology. This Thesis, organized into five Chapters, describes mainly some recent advances in the form and function provided by self-assembly of guanine based systems. More generally, Chapter 4 will focus on the construction of supramolecular self-assemblies whose self-assembling process and self-assembled architectures can be controlled by light as external stimulus. Chapter 1 will describe some of the many recent studies of G-quartets in the general area of nanoscience. Natural G- quadruplexes can be useful motifs to build new structures and biomaterials such as self-assembled nanomachines, biosensors, therapeutic aptamer and catalysts. In Chapters 2-4 it is pointed out the core concept held in this PhD Thesis, i.e. the supramolecular organization of lipophilic guanosine derivatives with photo or chemical addressability. Chapter 2 will mainly focus on the use of cation-templated guanosine derivatives as a potential scaffold for designing functional materials with tailored physical properties, showing a new way to control the bottom-up realization of well-defined nanoarchitectures. In section 2.6.7, the self-assembly properties of compound 28a may be considered an example of open-shell moieties ordered by a supramolecular guanosine architecture showing a new (magnetic) property. Chapter 3 will report on ribbon-like structures, supramolecular architectures formed by guanosine derivatives that may be of interest for the fabrication of molecular nanowires within the framework of future molecular electronic applications. In section 3.4 we investigate the supramolecular polymerizations of derivatives dG 1 and G 30 by light scattering technique and TEM experiments. The obtained data reveal the presence of several levels of organization due to the hierarchical self-assembly of the guanosine units in ribbons that in turn aggregate in fibrillar or lamellar soft structures. The elucidation of these structures furnishes an explanation to the physical behaviour of guanosine units which display organogelator properties. Chapter 4 will describe photoresponsive self-assembling systems. Numerous research examples have demonstrated that the use of photochromic molecules in supramolecular self-assemblies is the most reasonable method to noninvasively manipulate their degree of aggregation and supramolecular architectures. In section 4.4 we report on the photocontrolled self-assembly of modified guanosine nucleobase E-42: by the introduction of a photoactive moiety at C8 it is possible to operate a photocontrol over the self-assembly of the molecule, where the existence of G-quartets can be alternately switched on and off. In section 4.5 we focus on the use of cyclodextrins as photoresponsive host-guest assemblies: αCD–azobenzene conjugates 47-48 (section 4.5.3) are synthesized in order to obtain a photoresponsive system exhibiting a fine photocontrollable degree of aggregation and self-assembled architecture. Finally, Chapter 5 contains the experimental protocols used for the research described in Chapters 2-4.

Stellar Relics of the hierarchical assembly of the Galaxy

This PhD Thesis is part of a long-term wide research project, carried out by the "Osservatorio Astronomico di Bologna (INAF-OABO)", that has as primary goal the comprehension and reconstruction of formation mechanism of galaxies and their evolution history. There is now substantial evidence, both from theoretical and observational point of view, in favor of the hypothesis that the halo of our Galaxy has been at least partially, built up by the progressive accretion of small fragments, similar in nature to the present day dwarf galaxies of the Local Group. In this context, the photometric and spectroscopic study of systems which populate the halo of our Galaxy (i.e. dwarf spheroidal galaxy, tidal streams, massive globular cluster, etc) permits to discover, not only the origin and behaviour of these systems, but also the structure of our Galactic halo, combined with its formation history. In fact, the study of the population of these objects and also of their chemical compositions, age, metallicities and velocity dispersion, permit us not only an improvement in the understanding of the mechanisms that govern the Galactic formation, but also a valid indirect test for cosmological model itself. Specifically, in this Thesis we provided a complete characterization of the tidal Stream of the Sagittarius dwarf spheroidal galaxy, that is the most striking example of the process of tidal disruption and accretion of a dwarf satellite in to our Galaxy. Using Red Clump stars, extracted from the catalogue of the Sloan Digital Sky Survey (SDSS) we obtained an estimate of the distance, the depth along the line of sight and of the number density for each detected portion of the Stream (and more in general for each detected structure along our line of sight). Moreover comparing the relative number (i.e. the ratio) of Blue Horizontal Branch stars and Red Clump stars (the two features are tracers of different age/different metallicity populations) in the main body of the galaxy and in the Stream, in order to verify the presence of an age-metallicity gradient along the Stream. We also report the detection of a population of Red Clump stars probably associated with the recently discovered Bootes III stellar system. Finally, we also present the results of a survey of radial velocities over a wide region, extending from r ~ 10' out to r ~ 80' within the massive star cluster Omega Centauri. The survey was performed with FLAMES@VLT, to study the velocity dispersion profile in the outer regions of this stellar system. All the results presented in this Thesis, have already been published in refeered journals.

Control of the long-range self-organization of polycyclic aromatic hydrocarbons for device applications

Electronic devices based on organic semiconductors have gained increased attention in nanotechnology, especially applicable to the field of field-effect transistors and photovoltaic. A promising class of materials in this reseach field are polycyclic aromatic hydrocarbons (PAHs). Alkyl substitution of these graphenes results in the selforganization into one-dimensional columnar superstructures and provides solubility and processibility. The nano-phase separation between the π-stacking aromatic cores and the disordered peripheral alkyl chains leads to the formation of thermotropic mesophases. Hexa-peri-hexabenzocoronenes (HBC), as an example for a PAH, exhibits some of the highest values for the charge carrier mobility for mesogens, which makes them promising candidates for electronic devices. Prerequisites for efficient charge carrier transport between electrodes are a high purity of the material to reduce possible trapping sites for charge carriers and a pronounced and defect-free, long-range order. Appropriate processing techniques are required to induce a high degree of aligned structures in the discotic material over macroscopic dimensions. Highly-ordered supramolecular structures of different discotics, in particular, of HBC derivatives have been obtained by solution processing using the zone-casting technique, zone-melting or simple extrusion. Simplicity and fabrication of highly oriented columnar structures over long-range are the most essential advantages of these zone-processing methods. A close relation between the molecular design, self-aggregation and the processing conditions has been revealed. The long-range order achieved by the zone-casting proved to be suitable for field effect transistors (FET).

Essays in industrial organization

The thesis consists in three papers that investigate two debated topics in industrial organization (in particular in competition policy) through formal models based on game-theory. The first paper deals with potential effects of conglomerate mergers among leading brands in facilitating foreclosure of new suppliers through the retailing channel. The two remaining papers analyze antitrust policy with respect to monopolization of markets of spare parts and aftermarkets by monopolistic equipment manufacturers.

Three essays in industrial organization

This dissertation comprises three essays on the topic of industrial organization. The first essay considers how different intellectual property systems can affect the incentives to invest in R&D when innovation is cumulative. I introduce a distinction between plain and sophisticated technological knowledge, which plays a crucial role in determining how different appropriability rules affect the incentives to innovate. I argue that the positive effect of weak intellectual property regimes on the sharing of intermediate technological knowledge vanishes when technological knowledge is sophisticated, as is likely to be the case in many high tech industries. The second essay analyzes a two-sided market for news where advertisers may pay a media outlet to conceal negative information on the quality of their own product (paying positive to avoid negative) and/or to disclose negative information on the quality of their competitors products (paying positive to go negative). It is shown that whether advertisers have negative consequences on the accuracy of media reports or not, ultimately depends on the extent of correlation among advertisers products. The third essay considers the role of social learning in the diffusion of a new technology. A population of agents can choose between two risky technologies: an old one for which they know the expected outcome, and a new one for which they have only a prior. Different environments are confronted. In the benchmark case agents are isolated and can perform costly experiments to infer the quality of the new technology. In the other cases agents are settled in a network and can observe the outcomes of neighbors. We observe that in expectations the quality of the new technology may be overestimated when there is a network spread of information.

C 3-symmetric discotic liquid crystalline materials for molecular electronics: versatile synthesis and self-organization

This thesis presents the versatile synthesis and self-organization of C3-symmetric discotic nanographene molecules as well as their potential applications as materials in molecular electronics. The details can be described as follows: 1) A novel synthetic strategy towards properly designed C3 symmetric 1,3,5-tris-2’arylbenzene precursors has been developed. After the final planarization by treatment with FeCl3 under mild conditions, for the first time, it became possible to access a variety of new C3-symmetric hexa-peri-hexabenzocoronenes (HBCs) and a series of triangle-shaped nanographenes. D3 symmetric HBC with three alkyl substituents and C2 symmetric HBC with two alkyl substituents were synthesized and found to show the surprising decrease of isotropic points., the self-assembly at the liquid-solid interface displayed a unique zigzag and flower patterns. 2) Triangle-shaped discotics revealed a unique self-assembly behavior in solution, solid state as well as at the solution-substrate interface. A mesophase stability over the broad temperature range with helical supramoelcular arrangement were observed in the bulk state. The honeycomb pattern as the result of novel self-assembly was presented. Triangle-shaped discotics with swallow alkyl tails were fabricated into photovoltaic devices, the supramolecular arrangement upon thermal treatment was found to play a key role in the improvement of solar efficiency. 3) A novel class of C3 symmetric HBCs with alternating polar/apolar substituents was synthesized. Their peculiar self-assembly in solution, in the bulk and on the surface were investigated by NMR techniques, X-ray diffraction as well as different electron microscope techniques. 4) A novel concept for manipulating the intracolumnar stacking of discotics and thus for controlling the helical pitch was presented. A unique staggered stacking in the column was achieved for the first time. Theoretical simulations confirmed this self-organization and predicted that this packing should show the highest charge carrier mobility for all discotics.

Essays in Industrial Organization

This dissertation comprises four essays on the topic of industrial organization and environmental economics. The first essay investigates the profitability of horizontal mergers of firms with price adjustments. We take a differential game approach and both the open-loop as well as the closed-loop equlibria are considered. In the second essay, using the same approach as the first one, we study the profitability of horizontal merger of firms where the demand function is nonlinear. We take into consideration the open-loop equilibrium. The third essay studies the profitability of exogenous output constraint in a differential game model with price dynamics under the feedback strategies. The fourth essay investigates a second-best trade agreement between two countries when pollution spillovers are asymmetric to examine the strategic behavior of governments in using pollution taxes and tariffs under trade liberalization.

Structure, organization and dynamics of functional supramolecular materials studied by solid-state NMR

Functional materials have great importance due to their many important applications. The characterization of supramolecular architectures which are held together by non-covalent interactions is of most importance to understand their properties. Solid-state NMR methods have recently been proven to be able to unravel such structure-property relations with the help of fast magic-angle spinning and advanced pulse sequences. The aim of the current work is to understand the structure and dynamics of functional supramolecular materials which are potentially important for fuel-cell (proton conducting membrane materials) and solar-cell or plastic-electronic applications (photo-reactive aromatic materials). In particular, hydrogen-bonding networks, local proton mobility, molecular packing arrangements, and local dynamics will be studied by the use of advanced solid-state NMR methods. The first class of materials studied in this work is proton conducting polymers which also form hydrogen-bonding network. Different materials, which are prepared for high 1H conduction by different approaches are studied: PAA-P4VP, PVPA-ABPBI, Tz5Si, and Triazole-functional systems. The materials are examples of the following major groups; - Homopolymers with specific functional groups (Triazole functional polysiloxanes). - Acid-base polymer blends approach (PAA-P4VP, PVPA-ABPBI). - Acid-base copolymer approach (Triazole-PVPA). - Acid doped polymers (Triazole functional polymer doped with H3PO4). Perylenebisimide (PBI) derivatives, a second type of important functional supramolecular materials with potent applications in plastic electronics, were also investigated by means of solid-state NMR. The preparation of conducting nanoscopic fibers based on the self-assembling functional units is an appealing aim as they may be incorporated in molecular electronic devices. In this category, perylene derivatives have attracted great attention due to their high charge carrier mobility. A detailed knowledge about their supramolecular structure and molecular dynamics is crucial for the understanding of their electronic properties. The aim is to understand the structure, dynamics and packing arrangements which lead to high electron conductivity in PBI derivatives.

Molecular organization of n-cyanobiphenyl liquid crystals on a molybdenite surface

The alignement and anchoring of liquid crystals on solid surfaces is a key problem for modern device technology that until now has been treated empirically, but that can now be tackled by atomistic computer simulations. Molecular dynamics (MD) simulations were used in this thesis work to study two films of 7 and 8 n-alkyl-4’cyanobiphenyl (7CB and 8CB) liquid crystals , with a thickness of 15 nm, confined between two (001) surfaces of MoS2 (molybdenite). The isotropic and nematic phases of both liquid crystals were simulated, and the resulting structures characterized structurally. A new force field was designed to model the interactions between the liquid crystal (LC) molecules and the surface of molybdenite, while an accurate force field developed previously was used to model the 7CB and 8CB molecules. The results show that the (001) molybdenite surface induces a planar orientation in both the liquid crystals. For the nematic phase of 8CB, one of the two solid/LC interfaces is composed of a first layer of molecules aligned parallel to the surface, followed by a second layer of molecules aligned perpendicular to the surface (also called, homeotropic). The effect of the surface appears to be local in nature as it is confined to the first 15 Angström of the LC film. Conversely, for the nematic phase of 7CB, a planar ordering is established into the LC film. The LC molecules at the interface with the molybdenite appear to align preferentially their alkyl chains toward the solid substrate. The resulting tilt angle of molecules was found to be in good agreement with experimental measurements available in literature. Despite the fact that the MD simulations spanned a time range of more than 100 ns, the nematic phases of both 7CB and 8CB were found not to be completely formed. In order to confirm the findings presented in this thesis, we propose to extend the current study.

When the Practice of Theorizing Meets the Theorizing of Practice. Social Knowledge Making in Organization Science Academia and Managerial Communities

The aim of the present work is to contribute to a better understanding of the relation between organization theory and management practice. It is organized as a collection of two papers, a theoretical and conceptual contribution and an ethnographic study. The first paper is concerned with systematizing different literatures inside and outside the field of organization studies that deal with the theory-practice relation. After identifying a series of positions to the theory-practice debate and unfolding some of their implicit assumptions and limitations, a new position called entwinement is developed in order to overcome status quo through reconciliation and integration. Accordingly, the paper proposes to reconceptualize theory and practice as a circular iterative process of action and cognition, science and common-sense enacted in the real world both by organization scholars and practitioners according to purposes at hand. The second paper is the ethnographic study of an encounter between two groups of expert academics and practitioners occasioned by a one-year executive business master in an international business school. The research articulates a process view of the knowledge exchange between management academics and practitioners in particular and between individuals belonging to different communities of practice, in general, and emphasizes its dynamic, relational and transformative mechanisms. Findings show that when they are given the chance to interact, academics and practitioners set up local provisional relations that enable them to act as change intermediaries vis-a-vis each other’s worlds, without tying themselves irremediably to each other and to the scenarios they conjointly projected during the master’s experience. Finally, the study shows that provisional relations were accompanied by a recursive shift in knowledge modes. While interacting, academics passed from theory to practical theorizing, practitioners passed from an involved practical mode to a reflexive and quasi-theoretical one, and then, as exchanges proceeded, the other way around.

Export Supply Chain Organization and Food Safety and Quality Standards: a case study of the Moroccan Fruit and Vegetable Sector

Agri-food supply chains extend beyond national boundaries, partially facilitated by a policy environment that encourages more liberal international trade. Rising concentration within the downstream sector has driven a shift towards “buyer-driven” global value chains (GVCs) extending internationally with global sourcing and the emergence of multinational key economic players that compete with increase emphasis on product quality attributes. Agri-food systems are thus increasingly governed by a range of inter-related public and private standards, both of which are becoming a priori mandatory, especially in supply chains for high-value and quality-differentiated agri-food products and tend to strongly affect upstream agricultural practices, firms’ internal organization and strategic behaviour and to shape the food chain organization. Notably, increasing attention has been given to the impact of SPS measures on agri-food trade and notably on developing countries’ export performance. Food and agricultural trade is the vital link in the mutual dependency of the global trade system and developing countries. Hence, developing countries derive a substantial portion of their income from food and agricultural trade. In Morocco, fruit and vegetable (especially fresh) are the primary agricultural export. Because of the labor intensity, this sector (especially citrus and tomato) is particularly important in terms of income and employment generation, especially for the female laborers hired in the farms and packing houses. Hence, the emergence of agricultural and agrifood product safety issues and the subsequent tightening of market requirements have challenged mutual gains due to the lack of technical and financial capacities of most developing countries.

Essays in Industrial Organization and Information Technology

Chapter 1 studies how consumers’ switching costs affect the pricing and profits of firms competing in two-sided markets such as Apple and Google in the smartphone market. When two-sided markets are dynamic – rather than merely static – I show that switching costs lower the first-period price if network externalities are strong, which is in contrast to what has been found in one-sided markets. By contrast, switching costs soften price competition in the initial period if network externalities are weak and consumers are more patient than the platforms. Moreover, an increase in switching costs on one side decreases the first-period price on the other side. Chapter 2 examines firms’ incentives to invest in local and flexible resources when demand is uncertain and correlated. I find that market power of the monopolist providing flexible resources distorts investment incentives, while competition mitigates them. The extent of improvement depends critically on demand correlation and the cost of capacity: under social optimum and monopoly, if the flexible resource is cheap, the relationship between investment and correlation is positive, and if it is costly, the relationship becomes negative; under duopoly, the relationship is positive. The analysis also sheds light on some policy discussions in markets such as cloud computing. Chapter 3 develops a theory of sequential investments in cybersecurity. The regulator can use safety standards and liability rules to increase security. I show that the joint use of an optimal standard and a full liability rule leads to underinvestment ex ante and overinvestment ex post. Instead, switching to a partial liability rule can correct the inefficiencies. This suggests that to improve security, the regulator should encourage not only firms, but also consumers to invest in security.

Learning Methods and Algorithms for Semantic Text Classification across Multiple Domains

Information is nowadays a key resource: machine learning and data mining techniques have been developed to extract high-level information from great amounts of data. As most data comes in form of unstructured text in natural languages, research on text mining is currently very active and dealing with practical problems. Among these, text categorization deals with the automatic organization of large quantities of documents in priorly defined taxonomies of topic categories, possibly arranged in large hierarchies. In commonly proposed machine learning approaches, classifiers are automatically trained from pre-labeled documents: they can perform very accurate classification, but often require a consistent training set and notable computational effort. Methods for cross-domain text categorization have been proposed, allowing to leverage a set of labeled documents of one domain to classify those of another one. Most methods use advanced statistical techniques, usually involving tuning of parameters. A first contribution presented here is a method based on nearest centroid classification, where profiles of categories are generated from the known domain and then iteratively adapted to the unknown one. Despite being conceptually simple and having easily tuned parameters, this method achieves state-of-the-art accuracy in most benchmark datasets with fast running times. A second, deeper contribution involves the design of a domain-independent model to distinguish the degree and type of relatedness between arbitrary documents and topics, inferred from the different types of semantic relationships between respective representative words, identified by specific search algorithms. The application of this model is tested on both flat and hierarchical text categorization, where it potentially allows the efficient addition of new categories during classification. Results show that classification accuracy still requires improvements, but models generated from one domain are shown to be effectively able to be reused in a different one.

Deep learning for computer vision: a comparison between convolutional neural networks and hierarchical temporal memories on object recognition tasks

In recent years, Deep Learning techniques have shown to perform well on a large variety of problems both in Computer Vision and Natural Language Processing, reaching and often surpassing the state of the art on many tasks. The rise of deep learning is also revolutionizing the entire field of Machine Learning and Pattern Recognition pushing forward the concepts of automatic feature extraction and unsupervised learning in general. However, despite the strong success both in science and business, deep learning has its own limitations. It is often questioned if such techniques are only some kind of brute-force statistical approaches and if they can only work in the context of High Performance Computing with tons of data. Another important question is whether they are really biologically inspired, as claimed in certain cases, and if they can scale well in terms of "intelligence". The dissertation is focused on trying to answer these key questions in the context of Computer Vision and, in particular, Object Recognition, a task that has been heavily revolutionized by recent advances in the field. Practically speaking, these answers are based on an exhaustive comparison between two, very different, deep learning techniques on the aforementioned task: Convolutional Neural Network (CNN) and Hierarchical Temporal memory (HTM). They stand for two different approaches and points of view within the big hat of deep learning and are the best choices to understand and point out strengths and weaknesses of each of them. CNN is considered one of the most classic and powerful supervised methods used today in machine learning and pattern recognition, especially in object recognition. CNNs are well received and accepted by the scientific community and are already deployed in large corporation like Google and Facebook for solving face recognition and image auto-tagging problems. HTM, on the other hand, is known as a new emerging paradigm and a new meanly-unsupervised method, that is more biologically inspired. It tries to gain more insights from the computational neuroscience community in order to incorporate concepts like time, context and attention during the learning process which are typical of the human brain. In the end, the thesis is supposed to prove that in certain cases, with a lower quantity of data, HTM can outperform CNN.