Intramolecular conflict : conformation and self-assembly of architecturally complex macromolecules in solution

The solution behavior of linear polymer chains is well understood, having been the subject of intense study throughout the previous century. As plastics have become ubiquitous in everyday life, polymer science has grown into a major field of study. The conformation of a polymer in solution depends on the molecular architecture and its interactions with the surroundings. Developments in synthetic techniques have led to the creation of precision-tailored polymeric materials with varied topologies and functionalities. In order to design materials with the desired properties, it is imperative to understand the relationships between polymer architecture and their conformation and behavior. To meet that need, this thesis investigates the conformation and self-assembly of three architecturally complex macromolecular systems with rich and varied behaviors driven by the resolution of intramolecular conflicts. First we describe the development of a robust and facile synthetic approach to reproducible bottlebrush polymers (Chapter 2). The method was used to produce homologous series of bottlebrush polymers with polynorbornene backbones, which revealed the effect of side-chain and backbone length on the overall conformation in both good and theta solvent conditions (Chapter 3). The side-chain conformation was obtained from a series of SANS experiments and determined to be indistinguishable from the behavior of free linear polymer chains. Using deuterium-labeled bottlebrushes, we were able for the first time to directly observe the backbone conformation of a bottlebrush polymer which showed self-avoiding walk behavior. Secondly, a series of SANS experiments was conducted on a homologous series of Side Group Liquid Crystalline Polymers (SGLCPs) in a perdeuterated small molecule liquid crystal (5CB). Monodomain, aligned, dilute samples of SGLCP-b-PS block copolymers were seen to self-assemble into complex micellar structures with mutually orthogonally oriented anisotropies at different length scales (Chapter 4). Finally, we present the results from the first scattering experiments on a set of fuel-soluble, associating telechelic polymers. We observed the formation of supramolecular aggregates in dilute (≤0.5wt%) solutions of telechelic polymers and determined that the choice of solvent has a significant effect on the strength of association and the size of the supramolecules (Chapter 5). A method was developed for the direct estimation of supramolecular aggregation number from SANS data. The insight into structure-property relationships obtained from this work will enable the more targeted development of these molecular architectures for their respective applications.

Nematic ordering pattern formation in the process of self-organization of microtubules in a gravitational field

Papaseit et al. (Proc. Nati. Acad. Sci. U.S.A. 97, 8364, 2000) showed the decisive role of gravity in the formation of patterns by assemblies of microtubules in vitro. By virtue of a functional scaling, the free energy for MT systems in a gravitational field was constructed. The influence of the gravitational field on MT's self-organization process, that can lead to the isotropic to nematic phase transition, is the focus of this paper. A coupling of a concentration gradient with orientational order characteristic of nernatic ordering pattern formation is the new feature emerging in the presence of gravity. The concentration range corresponding to a phase coexistence region increases with increasing g or NIT concentration. Gravity facilitates the isotropic to nernatic phase transition leading to a significantly broader transition region. The phase transition represents the interplay between the growth in the isotropic phase and the precipitation into the nematic phase. We also present and discuss the numerical results obtained for local NIT concentration change with the height of the vessel, order parameter and phase transition properties.

Self-assembly of brush polymers

The unique structure and properties of brush polymers have led to increased interest in them within the scientific community. This thesis describes studies on the self-assembly of these brush polymers.

Chapter 2 describes a study on the rapid self-assembly of brush block copolymers into nanostructures with photonic bandgaps spanning the entire visible spectrum, from ultraviolet to near infrared. Linear relationships are observed between the peak wavelengths of reflection and polymer molecular weights. This work enables "bottom-up" fabrication of photonic crystals with application-tailored bandgaps, through synthetic control of the polymer molecular weight and the method of self-assembly.

Chapter 3 details the analysis of the self-assembly of symmetrical brush block copolymers in bulk and thin films. Highly ordered lamellae with domain spacing ranging from 20 to 240 nm are obtained by varying molecular weight of the backbone. The relationship between degree of polymerization and the domain spacing is reported, and evidence is provided for how rapidly the brush block copolymers self-assemble and achieve thermodynamic equilibrium.

Chapter 4 describes investigations into where morphology transitions take place as the volume fraction of each block is varied in asymmetrical brush block copolymers. Imaging techniques are used to observe a transition from lamellar to a cylindrical morphology as the volume fraction of one of the blocks exceeds 70%. It is also shown that the asymmetric brush block copolymers can be kinetically trapped into undulating lamellar structures by drop casting the samples.

Chapter 5 explores the capability of macromolecules to interdigitate into densely grafted molecular brush copolymers using stereocomplex formation as a driving force. The stereocomplex formation between complementary linear polymers and brush copolymers is demonstrated, while the stereocomplex formation between complementary brush copolymers is shown to be restricted.

Effects of self energy of the ions on the double layer structure and properties at the dielectric interface

Although numerous theoretical efforts have been put forth, a systematic, unified and predictive theoretical framework that is able to capture all the essential physics of the interfacial behaviors of ions, such as the Hofmeister series effect, Jones-Ray effect and the salt effect on the bubble coalescence remain an outstanding challenge. The most common approach to treating electrostatic interactions in the presence of salt ions is the Poisson-Boltzmann (PB) theory. However, there are many systems for which the PB theory fails to offer even a qualitative explanation of the behavior, especially for ions distributed in the vicinity of an interface with dielectric contrast between the two media (like the water-vapor/oil interface). A key factor missing in the PB theory is the self energy of the ion.

In this thesis, we develop a self-consistent theory that treats the electrostatic self energy (including both the short-range Born solvation energy and the long-range image charge interactions), the nonelectrostatic contribution of the self energy, the ion-ion correlation and the screening effect systematically in a single framework. By assuming a finite charge spread of the ion instead of using the point-charge model, the self energy obtained by our theory is free of the divergence problems and gives a continuous self energy across the interface. This continuous feature allows ions on the water side and the vapor/oil side of the interface to be treated in a unified framework. The theory involves a minimum set of parameters of the ion, such as the valency, radius, polarizability of the ions, and the dielectric constants of the medium, that are both intrinsic and readily available. The general theory is first applied to study the thermodynamic property of the bulk electrolyte solution, which shows good agreement with the experiment result for predicting the activity coefficient and osmotic coefficient.

Next, we address the effect of local Born solvation energy on the bulk thermodynamics and interfacial properties of electrolyte solution mixtures. We show that difference in the solvation energy between the cations and anions naturally gives rise to local charge separation near the interface, and a finite Galvani potential between two coexisting solutions. The miscibility of the mixture can either increases or decreases depending on the competition between the solvation energy and translation entropy of the ions. The interfacial tension shows a non-monotonic dependence on the salt concentration: it increases linearly with the salt concentration at higher concentrations, and decreases approximately as the square root of the salt concentration for dilute solutions, which is in agreement with the Jones-Ray effect observed in experiment.

Next, we investigate the image effects on the double layer structure and interfacial properties near a single charged plate. We show that the image charge repulsion creates a depletion boundary layer that cannot be captured by a regular perturbation approach. The correct weak-coupling theory must include the self-energy of the ion due to the image charge interaction. The image force qualitatively alters the double layer structure and properties, and gives rise to many non-PB effects, such as nonmonotonic dependence of the surface energy on concentration and charge inversion. The image charge effect is then studied for electrolyte solutions between two plates. For two neutral plates, we show that depletion of the salt ions by the image charge repulsion results in short-range attractive and long-range repulsive forces. If cations and anions are of different valency, the asymmetric depletion leads to the formation of an induced electrical double layer. For two charged plates, the competition between the surface charge and the image charge effect can give rise to like- charge attraction.

Then, we study the inhomogeneous screening effect near the dielectric interface due to the anisotropic and nonuniform ion distribution. We show that the double layer structure and interfacial properties is drastically affected by the inhomogeneous screening if the bulk Debye screening length is comparable or smaller than the Bjerrum length. The width of the depletion layer is characterized by the Bjerrum length, independent of the salt concentration. We predict that the negative adsorption of ions at the interface increases linearly with the salt concentration, which cannot be captured by either the bulk screening approximation or the WKB approximation. For asymmetric salt, the inhomogeneous screening enhances the charge separation in the induced double layer and significantly increases the value of the surface potential.

Finally, to account for the ion specificity, we study the self energy of a single ion across the dielectric interface. The ion is considered to be polarizable: its charge distribution can be self-adjusted to the local dielectric environment to minimize the self energy. Using intrinsic parameters of the ions, such as the valency, radius, and polarizability, we predict the specific ion effect on the interfacial affinity of halogen anions at the water/air interface, and the strong adsorption of hydrophobic ions at the water/oil interface, in agreement with experiments and atomistic simulations.

The theory developed in this work represents the most systematic theoretical technique for weak-coupling electrolytes. We expect the theory to be more useful for studying a wide range of structural and dynamic properties in physicochemical, colloidal, soft-matter and biophysical systems.

Self-assembly of metallated TPP porphyrin by external dipyridyl ligands

Póster presentado en: XXII International Congress and General Assembly of the International Union of Crystallography (UICr), 22–30 Agosto 2011. Madrid, España

Self-assembly of metalloporphyrins: first TPP-bipy coordination polymer with CoII (TPP=meso-tetraphenylporphyrin and bipy=4,4´-bipyridine)

Póster presentado en: 11th International Symposium on Applied Bioinorganic Chemistry. 2-5 Diciembre 2011. Barcelona, España (ISABC 2011)

Self-formation of quasiperiodic void structure in CaF2 induced by femtosecond laser irradiation

We report the self-formation of quasiperiodic void structure with the length of several hundred micrometers inside the CaF2 crystal. The quasiperiodical voids along the propagation direction of the laser beam were formed spontaneously after the irradiation of a single femtosecond laser beam which was focused at a fixed point inside the crystal sample. The length of the void array varied with the focal depth beneath the sample surface. The possible mechanism of the self-formed void structure was discussed. (c) 2007 American Institute of Physics.

Self-assembly of iron TCPP (meso-tetra(4-carboxyphenyl)porphyrin) into a chiral 2D coordination polymer

Artículo Polyhedron 2011

A Social and Economic Characterization of the U.S. Gulf of Mexico Recreational Shark Fishery

A mail survey of tournament shark anglers and party boat shark anglers was completed to examine their fishing activity, attitudes, trip expenditures, and consumer surplus. A sample of 700 shark anglers was selected from tournaments in the Gulf of Mexico during 1990, and a sample of party boat shark anglers was drawn from Port Aransas, Tex., party boat anglers during the summer of 1991. A response rate of 58% (excluding nondeliverables) was obtained from tournament anglers. The sample of party boat shark anglers was too small to provide useful results. Tournament shark anglers reported fishing an average of 58 days per year and targeted sharks and other large marine species. Tournaments occupy a small portion of their fishing effort. If this group of anglers were not able to fish for sharks, one-third indicated no other species would be an acceptable substitute, while others were willing to substitute other large marine species. Shark trip expenditures averaged $197 per trip with a consumer surplus of $111 per trip. Based on MRFSS estimates of the number of shark fishing trips, we estimate a total of $43,355,000 was spent by shark anglers in the Gulf of Mexico with a consumer surplus of $23,865,000 for a total gross value of the shark fishery of $66,220,000. MRFSS estimates of the number of sharks landed indicate an equivalent use value of $183 per shark.

Serviço social e educação: o exercício profissional dos assistentes sociais em escolas públicas de favelas

A proposta deste estudo inserido na linha de pesquisa Questão Social e Democracia, do Programa de Pós-Graduação em Serviço Social da Universidade do Estado do Rio de Janeiro (UERJ), articulada com o Centro de Estudos Octavio Ianni e com o Núcleo de Estudos e Pesquisas sobre Espaços Populares da REDES da Maré - realiza uma análise do exercício profissional de 42 assistentes sociais que atuam nas escolas públicas de Ensino Fundamental da rede pública da Prefeitura da Cidade do Rio de Janeiro. Considerando que escolas das favelas, distintas das demais escolas públicas do asfalto, possuem características que, incorporando os estigmas e estereótipos que marcam esses territórios, demandam novas necessidades, novas formas de compreensão e intervenção dos sujeitos sociais no âmbito da escola pública, o estudo se propõe também a analisar conceitualmente as favelas e a suas representações sociais. Para tanto, são analisados os atuais contornos da Educação Básica, sobretudo o Ensino Fundamental, onde se inserem os assistentes sociais que atuam na Secretaria Municipal de Educação. Ressaltando a construção histórica da inserção profissional dos assistentes sociais brasileiros no universo escolar, é problematizada a expansão desta requisição nos marcos da primeira década do século XXI. As múltiplas contradições que marcam espaços sócio-ocupacionais das escolas impõem ao assistente social sua inserção qualificada, sua legitimidade, o repensar a escola pública e a construção de projetos de intervenção que avancem na realização dos atendimentos individuais aos educandos e suas famílias. Considerando a dimensão pedagógica intrínseca na prática profissional, a construção desses espaços se torna uma atribuição a ser desenvolvida pelo assistente social que requer re-pensar a forma como ocorre o exercício profissional nesses espaços. Para tanto, foi realizado uma coleta de dados com 42 profissionais onde, para atingir os objetivos propostos foi pesquisado o perfil destes profissionais; sua formação acadêmica, local e condições de trabalho, experiência profissional, questões sobre o exercício profissional, sobre as dimensões do trabalho profissional, sobre a escola, sobre a relação com a comunidade e o entorno, e sobre a participação dos assistentes sociais em espaços de organização política.