From dendrimers to fractal polymers and beyond

O advento da química dendrítica tem facilitado a pesquisa de materiais por permitir o controle preciso do posicionamento do componente funcional na arquitetura macromolecular. Os protocolos sintéticos iterativos usados para construção dos dendrímeros foram desenvolvidos baseados no desejo de elaborar moléculas extremamente ramificadas, com alta massa molecular, massa exata e funcionalidade planejada. Arborols, inspirados em árvores e precursores de macromoléculas utilitárias, conhecidas hoje como dendrímeros, foram os primeiros exemplos a empregar blocos de construção de ramificação-C 1→3; Características físicas dos Arborols, incluindo a sua forma globular, excelente solubilidade, e agregação, combinam-se para revelar o potencial supramolecular inerente (isto é, a micela unimolecular) destas espécies únicas. A arquitetura que é característica dos materiais dendríticos também exibe qualidades fractais com base em estruturas repetitivas, ramificadas e auto-similares. Assim, o design fractal e os aspectos supramoleculares destas construções são sugestivas de um campo maior de materiais fractais que incorporam geometrias repetidas. O uso de terpiridina-M2+-terpiridina (onde, M = Ru, Zn, Fe, etc) em conjunto com algoritmos matemáticos tais como as formas da base do Triângulo de Seirpinski, tem permitido o início da exploração da construção de materiais fractais. A propensão da auto-criação de moléculas fractais para arquiteturas de ordem superior adiciona outra dimensão para essa nova arena de materiais e construção de compostos.The advent of dendritic chemistry has facilitated materials research by allowing precise control of functional component placement in macromolecular architecture. The iterative synthetic protocols used for dendrimer construction were developed based on the desire to craft highly branched, high molecular weight, molecules with exact mass and tailored functionality. Arborols, inspired by trees and precursors of the utilitarian macromolecules known as dendrimers today, were the first examples to employ predesigned, 1 → 3 C-branched, building blocks; physical characteristics of the arborols, including their globular shapes, excellent solubilities, and demonstrated aggregation, combined to reveal the inherent supramolecular potential (e.g., the unimolecular micelle) of these unique species. The architecture that is a characteristic of dendritic materials also exhibits fractal qualities based on self-similar, repetitive, branched frameworks. Thus, the fractal design and supramolecular aspects of these constructs are suggestive of a larger field of fractal materials that incorporates repeating geometries and are derived by complementary building block recognition and assembly. Use of terpyridine-M2+-terpyridine (where, M = Ru, Zn, Fe, etc) connectivity in concert with mathematical algorithms, such as forms the basis for the Seirpinski gasket, has allowed the beginning exploration of fractal materials construction. The propensity of the fractal molecules to self-assemble into higher order architectures adds another dimension to this new arena of materials and composite construction

HIGH VOLTAGE ELECTROPHORETIC DEPOSITION FOR ELECTROCHEMICAL ENERGY STORAGE AND OTHER APPLICATIONS

High voltage electrophoretic deposition (HVEPD) has been developed as a novel technique to obtain vertically aligned forests of one-dimensional nanomaterials for efficient energy storage. The ability to control and manipulate nanomaterials is critical for their effective usage in a variety of applications. Oriented structures of one-dimensional nanomaterials provide a unique opportunity to take full advantage of their excellent mechanical and electrochemical properties. However, it is still a significant challenge to obtain such oriented structures with great process flexibility, ease of processing under mild conditions and the capability to scale up, especially in context of efficient device fabrication and system packaging. This work presents HVEPD as a simple, versatile and generic technique to obtain vertically aligned forests of different one-dimensional nanomaterials on flexible, transparent and scalable substrates. Improvements on material chemistry and reduction of contact resistance have enabled the fabrication of high power supercapacitor electrodes using the HVEPD method. The investigations have also paved the way for further enhancements of performance by employing hybrid material systems and AC/DC pulsed deposition. Multi-walled carbon nanotubes (MWCNTs) were used as the starting material to demonstrate the HVEPD technique. A comprehensive study of the key parameters was conducted to better understand the working mechanism of the HVEPD process. It has been confirmed that HVEPD was enabled by three key factors: high deposition voltage for alignment, low dispersion concentration to avoid aggregation and simultaneous formation of holding layer by electrodeposition for reinforcement of nanoforests. A set of suitable parameters were found to obtain vertically aligned forests of MWCNTs. Compared with their randomly oriented counterparts, the aligned MWCNT forests showed better electrochemical performance, lower electrical resistance and a capability to achieve superhydrophpbicity, indicating their potential in a broad range of applications. The versatile and generic nature of the HVEPD process has been demonstrated by achieving deposition on flexible and transparent substrates, as well as aligned forests of manganese dioxide (MnO2) nanorods. A continuous roll-printing HVEPD approach was then developed to obtain aligned MWCNT forest with low contact resistance on large, flexible substrates. Such large-scale electrodes showed no deterioration in electrochemical performance and paved the way for practical device fabrication. The effect of a holding layer on the contact resistance between aligned MWCNT forests and the substrate was studied to improve electrochemical performance of such electrodes. It was found that a suitable precursor salt like nickel chloride could be used to achieve a conductive holding layer which helped to significantly reduce the contact resistance. This in turn enhanced the electrochemical performance of the electrodes. High-power scalable redox capacitors were then prepared using HVEPD. Very high power/energy densities and excellent cyclability have been achieved by synergistically combining hydrothermally synthesized, highly crystalline α-MnO2 nanorods, vertically aligned forests and reduced contact resistance. To further improve the performance, hybrid electrodes have been prepared in the form of vertically aligned forest of MWCNTs with branches of α-MnO2 nanorods on them. Large- scale electrodes with such hybrid structures were manufactured using continuous HVEPD and characterized, showing further improved power and energy densities. The alignment quality and density of MWCNT forests were also improved by using an AC/DC pulsed deposition technique. In this case, AC voltage was first used to align the MWCNTs, followed by immediate DC voltage to deposit the aligned MWCNTs along with the conductive holding layer. Decoupling of alignment from deposition was proven to result in better alignment quality and higher electrochemical performance

Unraveling complex relations between forest-cover change and conflicts through spatial and relational analyses

Unidad de excelencia María de Maeztu MdM-2015-0552Despite the increasing prevalence of forest-cover change and conflicts, most studies have been unable to unravel the complex relations between the two processes. We attribute this failure to methodological limitations. We put forward an alternative approach that combines different datasets (remote sensing, GIS, local narratives, official censuses, newspaper articles), methods (spatial and relational analyses), and scales (subregions, economic sectors, land-based activities) to create a robust explanation of the relations between different intensities of forest-cover change and conflict in the Meseta Purépecha region, central Mexico. This is an important forest region, inhabited by indigenous and mestizo peasants; it has a worldwide reputation for community forestry and is also the epicenter of international avocado production. Forest-cover change is intense and there are recurrent episodes of conflict. We clustered communities in three subregions according to their patterns of forest-cover change. We analyzed the spatial patterns of forest-cover change and conflicts and we characterized the structure and function of the different economic sectors to unravel the nonlinear, interdependent (and sometimes contradictory) relations among these processes. We found that avocado production has differentially shaped the composition and working of society within each subregion, leading to three diverging patterns. Avocado production has provoked conflicts over landownership and over illegal logging in nearby areas. In some areas, a low incidence of conflicts over forest clearance might be explained by high profits, coercion, and violence. We suggest that, by combining spatial and relational analyses, we can integrate and check the congruence of nonequivalent representations from quantitative sources and observant participation at different scales and explain the heterogeneity that processes display across space. Our methodological approach can thus improve our understanding of similar and other complex and uncertain environmental problems elsewhere, especially when accurate or appropriate data are missing

Cuts and flows of cell complexes

We study the vector spaces and integer lattices of cuts and flows associated with an arbitrary finite CW complex, and their relationships to group invariants including the critical group of a complex. Our results extend to higher dimension the theory of cuts and flows in graphs, most notably the work of Bacher, de la Harpe and Nagnibeda. We construct explicit bases for the cut and flow spaces, interpret their coefficients topologically, and give sufficient conditions for them to be integral bases of the cut and flow lattices. Second, we determine the precise relationships between the discriminant groups of the cut and flow lattices and the higher critical and cocritical groups with error terms corresponding to torsion (co)homology. As an application, we generalize a result of Kotani and Sunada to give bounds for the complexity, girth, and connectivity of a complex in terms of Hermite's constant.Comment: 30 pages. Final version, to appear in Journal of Algebraic Combinatoric

Developing Synthetic Methods to Prepare Discrete Metal-Organic Nanotubes

Metal-organic nanotubes (MONTs) are an emerging class of discrete materials that are the 1D variant of metal-organic frameworks (MOFs). MONTs have potential to become an alternative 1D material to carbon nanotubes, metal oxide nanotubes, and boron nitride nanotubes because they possess an organic ligand that can be functionalized and tuned for specific applications. Despite this potential, only a handful of structures have been reported and only two examples of discrete MONTs exist in the literature. It is thus imperative to develop general methods to prepare and characterize discrete MONTs to bring them to the forefront of the scientific literature. Efforts were directed to design ligands that will readily facilitate MONT dispersion post-synthetically, or by hindering their crystal packing as they form from solution. Our group has previously reported 5 MONT structures that employ semi-rigid, di-triazole ligands, and by employing isoreticular synthesis, our goal was to determine which structural characteristics will direct MONTs to form discrete nanotubes or small bundles. A collaboration with the Dadmun group here at UTK was established to employ smallangle scattering methods to study their kinetics and growth, information that will be useful to guide future efforts to prepare discrete MONTs

Iterative restricted space search : a solving approach based on hybridization

Face à la complexité qui caractérise les problèmes d'optimisation de grande taille l'exploration complète de l'espace des solutions devient rapidement un objectif inaccessible. En effet, à mesure que la taille des problèmes augmente, des méthodes de solution de plus en plus sophistiquées sont exigées afin d'assurer un certain niveau d 'efficacité. Ceci a amené une grande partie de la communauté scientifique vers le développement d'outils spécifiques pour la résolution de problèmes de grande taille tels que les méthodes hybrides. Cependant, malgré les efforts consentis dans le développement d'approches hybrides, la majorité des travaux se sont concentrés sur l'adaptation de deux ou plusieurs méthodes spécifiques, en compensant les points faibles des unes par les points forts des autres ou bien en les adaptant afin de collaborer ensemble. Au meilleur de notre connaissance, aucun travail à date n'à été effectué pour développer un cadre conceptuel pour la résolution efficace de problèmes d'optimisation de grande taille, qui soit à la fois flexible, basé sur l'échange d'information et indépendant des méthodes qui le composent. L'objectif de cette thèse est d'explorer cette avenue de recherche en proposant un cadre conceptuel pour les méthodes hybrides, intitulé la recherche itérative de l'espace restreint, ±Iterative Restricted Space Search (IRSS)>>, dont, la principale idée est la définition et l'exploration successives de régions restreintes de l'espace de solutions. Ces régions, qui contiennent de bonnes solutions et qui sont assez petites pour être complètement explorées, sont appelées espaces restreints "Restricted Spaces (RS)". Ainsi, l'IRSS est une approche de solution générique, basée sur l'interaction de deux phases algorithmiques ayant des objectifs complémentaires. La première phase consiste à identifier une région restreinte intéressante et la deuxième phase consiste à l'explorer. Le schéma hybride de l'approche de solution permet d'alterner entre les deux phases pour un nombre fixe d'itérations ou jusqu'à l'atteinte d'une certaine limite de temps. Les concepts clés associées au développement de ce cadre conceptuel et leur validation seront introduits et validés graduellement dans cette thèse. Ils sont présentés de manière à permettre au lecteur de comprendre les problèmes que nous avons rencontrés en cours de développement et comment les solutions ont été conçues et implémentées. À cette fin, la thèse a été divisée en quatre parties. La première est consacrée à la synthèse de l'état de l'art dans le domaine de recherche sur les méthodes hybrides. Elle présente les principales approches hybrides développées et leurs applications. Une brève description des approches utilisant le concept de restriction d'espace est aussi présentée dans cette partie. La deuxième partie présente les concepts clés de ce cadre conceptuel. Il s'agit du processus d'identification des régions restreintes et des deux phases de recherche. Ces concepts sont mis en oeuvre dans un schéma hybride heuristique et méthode exacte. L'approche a été appliquée à un problème d'ordonnancement avec deux niveaux de décision, relié au contexte des pâtes et papier: "Pulp Production Scheduling Problem". La troisième partie a permit d'approfondir les concepts développés et ajuster les limitations identifiées dans la deuxième partie, en proposant une recherche itérative appliquée pour l'exploration de RS de grande taille et une structure en arbre binaire pour l'exploration de plusieurs RS. Cette structure a l'avantage d'éviter l'exploration d 'un espace déjà exploré précédemment tout en assurant une diversification naturelle à la méthode. Cette extension de la méthode a été testée sur un problème de localisation et d'allocation en utilisant un schéma d'hybridation heuristique-exact de manière itérative. La quatrième partie généralise les concepts préalablement développés et conçoit un cadre général qui est flexible, indépendant des méthodes utilisées et basé sur un échange d'informations entre les phases. Ce cadre a l'avantage d'être général et pourrait être appliqué à une large gamme de problèmes