This thesis studies the synthesis of diverse architectures of polymers via the reversible addition fragmentation chain transfer (RAFT) polymerisation process that is one of the most novel and versatile controlled polymerisation techniques. Star polymers, comb polymers, amphiphilic block copolymers, and random copolymers were utilised to fabricate porous films with hexagonal arrangement via a ???bottom-up??? engineering approach, namely a ???breath figure??? technique. The quality (i.e. pore regularity and pore size) of the films was optimised by controlling casting variables including humidity, airflow, concentration of polymer solution, polymer architecture, molecular weight of polymer, substrate, and casting volume. Porous membranes were chemically crosslinked to improve their mechanical strength if required. Furthermore, chemical surface modification of porous films was performed by grafting desired polymer (i.e. PNIPAAm or PAGA) via RAFT polymerisation. The RAFT groups present in the films play a role as anchoring sites for polymerisation, thus the complex initiator immobilising can be avoided in our system. The desired polymer grafting is able to enhance wettability and provide binding sites for adhesion and proliferation of cells. The topography of ungrafted and grafted films was analysed using optical microscopy, scanning electron microscopy, atomic force microscopy, confocal microscopy, ATR-FTIR, and XPS.

O presente estudo demonstrou que a formação de cavidades (breath figures) em filmes de CA, CAPh, CAB e CMCAB preparados por spin-coating de soluções em tetrahidrofurano (THF) foi dependente das características moleculares dos polímeros quando preparados em ambiente com umidade relativa baixa (UR 35%), enquanto que em UR mais elevadas (55% e 75%) o balanço entre a energia superficial da água, THF e energia interfacial entre água e THF foi determinante. Por outro lado, a rápida exposição (de 3 a 6 min) desses filmes ao vapor de solvente teve um efeito plastificante tornando os filmes de CAB, CAPh e CMCAB completamente lisos, enquanto que para filmes de CA foi observado o efeito dewetting. Surfactantes biocompatíveis à base de sorbitano (Tween®) foram usados como plastificantes para filmes de ésteres de celulose obtidos por evaporação de solvente. O comportamento térmico dos filmes foi dependente do tamanho da cauda hidrofóbica do surfactante, do tipo do grupo lateral dos polímeros e da composição da mistura. Tween 20 e 40 mostraram agir como um excelente plastificante para os ésteres de celulose, exceto para o CA, no qual foi imiscível. Teores baixos de Tween favoreceram a flexibilidade das cadeias de polímeros ao passo que quantidades maiores aumentaram a mobilidade molecular dos ésteres de celulose levando a variações de Tg de até 200 °C. Filmes de nanocompósitos de CAB reforçados com nanocristais de celulose (CNC) modificados com diferentes grupos funcionais (acetato e metiladipoíla) foram preparados a partir de dispersões em acetato de etila (AE), THF e N,N-dimetilformamida (DMF). A melhor estabilidade coloidal foi verificada em DMF, devido sua alta polaridade. Suspensões em AE e THF de CNC modificados foram mais estáveis do que CNC por conta das interações entre grupos substituintes e solventes. As propriedades mecânicas dos nanocompósitos, resultantes da dispersibilidade de nanocristais na matriz de CAB mostraram forte relação com a estabilidade coloidal das dispersões. Beads de celulose foram obtidos utilizando polpa pré-tratada de eucalipto, oxidados e utilizados como suporte para incorporação de um agente bactericida QPVP-C5. Bactérias de Micrococcus luteus adsorveram sobre beads oxidados e nos beads contendo baixa quantidade de QPVP-C5 adsorvido e foi observada propriedade biocida nos beads com elevada quantidade de QPVP-C5 adsorvido. Os resultados mostram o preparo de materiais celulósicos multifuncionais de baixo custo e simples preparação para aplicações em meios aquosos com a finalidade de imobilização e ação biocida frente a bactérias Gram-positivas. / The present study demonstrated that the breath figures formation in CA, CAPh, CAB and CMCAB films spin-coated from solutions in tetrahydrofuran (THF) was dependent on the polymers molecular characteristics when prepared under low relative humidity (RH 35%), whereas under higher RH (55% and 75%), the balance among water and THF surface energy and interfacial energy between water and THF was determinant. On the other hand, the short solvent vapor exposure had a plasticizer effect, making CAB, CAPh and CMCAB films completely smooth (from 3 up to 6 min), while dewetting phenomena was observed for CA films. Biocompatible sorbitan-based surfactants (Tween®) were used as plasticizer for CA, CAPh, CAB and CMCAB casted films. The thermal behavior of films was dependent on the size of surfactant hydrophobic tail, type of polymer side group and the mixture composition. Tween 20 and 40 showed act as an excellent plasticizer for cellulose esters, except for CA, which was immiscible. Low Tween content favored polymeric chains flexibility while higher content increased the cellulose esters molecular mobility leading to Tg variations up to 200 °C. CAB-based nanocomposites casted films reinforced with cellulose nanocrystals (CNC) modified with different functional groups (acetate and methyl adipoil) were prepared from dispersions in ethyl acetate (EA), THF and N,N-dimethylformamide (DMF). The best colloidal stability was verified in DMF, due its high polarity. Suspensions in EA and THF of modified CNC where more stable than unmodified CNC, regarding the interactions among substituents groups and solvents. The mechanical properties of nanocomposites stemming from nanocrystals dispersibility in the CAB matrix showed strong relationship with the colloidal stability. Cellulose beads were obtained by using pretreated Eucalyptus pulp, oxidized and used as a support for the incorporation of a biocide agent. Micrococcus luteus bacteria adsorbed onto oxidized beads and on the beads with low content of adsorbed QPVP-C5. It was observed biocide property for the beads with high QPVP-C5 content. The results show the simple preparation of low cost multifunctional cellulosic materials for applications in aqueous media for the purpose of immobilization and biocide action against Gram-positive bacteria.

O presente estudo demonstrou que a formação de cavidades (breath figures) em filmes de CA, CAPh, CAB e CMCAB preparados por spin-coating de soluções em tetrahidrofurano (THF) foi dependente das características moleculares dos polímeros quando preparados em ambiente com umidade relativa baixa (UR 35%), enquanto que em UR mais elevadas (55% e 75%) o balanço entre a energia superficial da água, THF e energia interfacial entre água e THF foi determinante. Por outro lado, a rápida exposição (de 3 a 6 min) desses filmes ao vapor de solvente teve um efeito plastificante tornando os filmes de CAB, CAPh e CMCAB completamente lisos, enquanto que para filmes de CA foi observado o efeito dewetting. Surfactantes biocompatíveis à base de sorbitano (Tween®) foram usados como plastificantes para filmes de ésteres de celulose obtidos por evaporação de solvente. O comportamento térmico dos filmes foi dependente do tamanho da cauda hidrofóbica do surfactante, do tipo do grupo lateral dos polímeros e da composição da mistura. Tween 20 e 40 mostraram agir como um excelente plastificante para os ésteres de celulose, exceto para o CA, no qual foi imiscível. Teores baixos de Tween favoreceram a flexibilidade das cadeias de polímeros ao passo que quantidades maiores aumentaram a mobilidade molecular dos ésteres de celulose levando a variações de Tg de até 200 °C. Filmes de nanocompósitos de CAB reforçados com nanocristais de celulose (CNC) modificados com diferentes grupos funcionais (acetato e metiladipoíla) foram preparados a partir de dispersões em acetato de etila (AE), THF e N,N-dimetilformamida (DMF). A melhor estabilidade coloidal foi verificada em DMF, devido sua alta polaridade. Suspensões em AE e THF de CNC modificados foram mais estáveis do que CNC por conta das interações entre grupos substituintes e solventes. As propriedades mecânicas dos nanocompósitos, resultantes da dispersibilidade de nanocristais na matriz de CAB mostraram forte relação com a estabilidade coloidal das dispersões. Beads de celulose foram obtidos utilizando polpa pré-tratada de eucalipto, oxidados e utilizados como suporte para incorporação de um agente bactericida QPVP-C5. Bactérias de Micrococcus luteus adsorveram sobre beads oxidados e nos beads contendo baixa quantidade de QPVP-C5 adsorvido e foi observada propriedade biocida nos beads com elevada quantidade de QPVP-C5 adsorvido. Os resultados mostram o preparo de materiais celulósicos multifuncionais de baixo custo e simples preparação para aplicações em meios aquosos com a finalidade de imobilização e ação biocida frente a bactérias Gram-positivas. / The present study demonstrated that the breath figures formation in CA, CAPh, CAB and CMCAB films spin-coated from solutions in tetrahydrofuran (THF) was dependent on the polymers molecular characteristics when prepared under low relative humidity (RH 35%), whereas under higher RH (55% and 75%), the balance among water and THF surface energy and interfacial energy between water and THF was determinant. On the other hand, the short solvent vapor exposure had a plasticizer effect, making CAB, CAPh and CMCAB films completely smooth (from 3 up to 6 min), while dewetting phenomena was observed for CA films. Biocompatible sorbitan-based surfactants (Tween®) were used as plasticizer for CA, CAPh, CAB and CMCAB casted films. The thermal behavior of films was dependent on the size of surfactant hydrophobic tail, type of polymer side group and the mixture composition. Tween 20 and 40 showed act as an excellent plasticizer for cellulose esters, except for CA, which was immiscible. Low Tween content favored polymeric chains flexibility while higher content increased the cellulose esters molecular mobility leading to Tg variations up to 200 °C. CAB-based nanocomposites casted films reinforced with cellulose nanocrystals (CNC) modified with different functional groups (acetate and methyl adipoil) were prepared from dispersions in ethyl acetate (EA), THF and N,N-dimethylformamide (DMF). The best colloidal stability was verified in DMF, due its high polarity. Suspensions in EA and THF of modified CNC where more stable than unmodified CNC, regarding the interactions among substituents groups and solvents. The mechanical properties of nanocomposites stemming from nanocrystals dispersibility in the CAB matrix showed strong relationship with the colloidal stability. Cellulose beads were obtained by using pretreated Eucalyptus pulp, oxidized and used as a support for the incorporation of a biocide agent. Micrococcus luteus bacteria adsorbed onto oxidized beads and on the beads with low content of adsorbed QPVP-C5. It was observed biocide property for the beads with high QPVP-C5 content. The results show the simple preparation of low cost multifunctional cellulosic materials for applications in aqueous media for the purpose of immobilization and biocide action against Gram-positive bacteria.

The breath figure method is a versatile and facile approach of generating ordered micro and nanoporous structures in polymeric materials. When a polymer solution (dissolved in a high vapor pressure organic solvent) is evaporated out in the presence of a moist air stream, the evaporative cooling effect causes the condensation and nucleation of water droplets onto the polymer solution surface. This leads to the formation of an imprinted porous structure upon removal of the residual solvent and water. The facile removal of the water droplet template leaving its structural imprint is a specifically appealing aspect of the breath figure film technology. The first part of the dissertation work involves the fabrication of drug loaded breath figure thin films and its utilization as a controlled drug release carrier and biomaterial scaffold. In a single fabrication step, single layer/multilayer porous thin films were designed and developed by combining the breath figure process and a modified spin or dip coating technique. Using biodegradable polymers such as poly (lactic-co-glycolic acid) (PLGA) and poly (ethylene glycol) (PEG), drug loaded films were fabricated onto FDA approved medical devices (the Glaucoma drainage device and the Surgical hernia mesh). The porosity of the films is in the range of 2-4 µm as characterized by scanning electron microscope. The drug coated medical implants were characterized for their surface and bulk morphology, the degradation rate of the film, drug release rate and cell cytotoxicity. The results suggest that the use of breath figure morphologies in biodegradable polymer films adds an additional level of control to drug release. In comparison to non-porous films, the breath figure films showed an increased degradation and enhanced drug release. Furthermore, the porous nature of the film was investigated as a biomaterial scaffold to construct three dimensional in vitro tissue model systems. The breath figure film with interconnected pores facilitates cell infiltration and tissue remodelling in vitro, suggesting its high potential in regenerative medicine and tissue engineering applications. In the second part of the dissertation, the versatility of breath figure polymers was explored as a reverse template to create micropatterned soft materials. Unlike traditional lithographic masters, the breath figure assembly is a simple and cost-effective approach to create micro/nano sized “bead†like uniform patterns on the surface of hydrogels and biopolymers. By incorporating iron nanoparticles into the pores, this technique was extended to form hydrogels decorated with nanoparticles specifically in the pattern. The morphology features and the functional characteristics were demonstrated through scanning electron microscopy. The potential applications of these micro-fabricated materials in biosensors and cell culture substrates are outlined. / acase@tulane.edu

In this study, we investigate and fabricate two-dimensional ordered lattice structure by breath figures method. The breath figures pattern was prepared with the solution of carbon disulfide (CS2) doped with 1% weight concentration of polystyrene. The temperature and the humidity were controlled at ~23¢J and ~60 %, respectively. The breath figures pattern began to expand while CS2 is under evaporation. We explored the relationship between self-assemble of the water droplet and ordered structure via the solution height, the temperature evolution, and the dynamical optical images in the formation process of breath figures pattern. It was found that the radius of the water droplets varying with time follows the power law, £l ~ t £go; £g0=0.76. The fast Fourier transformation and Voronoi Diagram were used to conform that the formation of the breath figures pattern varied form a disordered state to an ordered state with the evaporation of CS2. The understanding of the breath figures pattern provides us to fabricate the photonics with size from nano- to micro-scale and to improve the application of nano device.

Study of Ordered Macroporous Polymer Films by Templating Breath Figures Lulu Song 193 pages Directed by Dr. Mohan Srinivasarao Macroporous films with highly ordered pore patterns have many potential applications. Some examples include microstructured electrode surfaces, photonic band gap materials and filters for cell sorting and bio-interfaces. In this dissertation we discuss a moist-casting method to prepare hexagonally-ordered macroporous films with pore sizes in the range of sub-micron to several microns, where condensed water droplets (breath figures) work as templates. Compared with other templating methods, this one is fast and simple. Well-ordered porous films can be obtained in tens of seconds and the pore size can be easily tailored and dynamically controlled by adjusting the casting conditions. More importantly, there is no need to remove the templates; water droplets just evaporate when the casting processes are finished. This study was carried out with the intention of characterizing the structures, understanding film-formation processes and exploring special properties and possible applications. For the structural characterization, film morphology was studied in detail by normal optical microscopy and laser scanning confocal microscopy (LSCM). Several interesting features have been revealed. Meanwhile, the degree of the order of the porous structures were characterized both in real space via Voronoi diagram and bond-orientational correlation function, and in reciprocal space via Fraunhofer diffraction pattern. To further understand the mechanism, the evaporation of the polymer solutions during the film formation was studied by monitoring their mass over time. Besides, the evolution of breath figures formed on the evaporating polymer solutions was in-situ recorded via a high-speed camera coupled to an optical microscope. Combined with the information on the film structures obtained via LSCM, explanations for some detailed features have been attempted. Wetting property of these films was studied in some detail. The films exhibited lotus effect, mimicking natural non-wetting surfaces. To improve the solvent stability and mechanical properties of the macroporous films for possible applications, crosslinking of the polymer matrix was tried by heating. Crosslinked structures with hexagonal arrays of cone-like air holes were obtained, which might find use as micron-sized beakers for small-quantity analysis.

The ring opening polymerization of D,L-lactide (DLLA) using multifunctional hydroxyl-terminated initiators and catalyst/coinitiator systems based on Sn(Oct)2 afforded the preparation of star-shaped, poly(D,L-lactide)s (PDLLA)s of controlled molar mass, narrow molar mass distributions, and well-defined chain end functionality. Various modifications of star-shaped PDLLA resulted in macromolecules with tailored functionalities for biomedical applications. Star-shaped PDLLAs were modified to contain photoreactive methacrylate end groups and subsequent photo-crosslinking was performed. Photo-crosslinked networks based on methacrylated star-shaped PDLLAs exhibited thermal properties and mechanical performance that were superior to current approved clinical adhesives. In addition, the thermal and mechanical properties of the networks were strongly dependent on the composition and molar mass of the star-shaped PDLLA precursors. Tensile strengths in the range of 8-21 MPa were obtained while the Young's modulus increased from 12 to 354 MPa and were higher for networks based on urethane containing polymers. Star-shaped PDLLAs bearing complementary adenine and thymine terminal units were also prepared. The hydrogen bonding associations between complementary PDLLA macromolecules depended strongly on molar mass and hence, the concentration of multiple hydrogen bonding units. 1H NMR spectroscopy confirmed the formation of hydrogen-bonded complexes with a 1:1 optimal stoichiometry and an association constant of 84 M-1. The hydrogen-bonded complexes also exhibited significantly higher solution viscosities than non-blended polymer solutions of similar molar mass and concentration. Thermoreversible associations of PDLLA-based complementary polymers were observed in the melt phase and the melt viscosity of a blended complex was consistently an order of magnitude higher than non-functionalized star-shaped PDLLA of similar molar mass. Furthermore, melt electrospinning of the hydrogen-bonded complexes successfully resulted in fibers of significantly larger diameter (9.8 ± 2.0 µm) compared to the individual precursors (PDLLA-A = 4.0 ± 0.6 µm and PDLLA-T = 4.4 ± 1.0 µm). These results suggested that thermoreversibility, as well as the strength of the hydrogen bonding interactions between the end groups of the tailored star-shaped PDLLA-based supramolecular polymers controlled the fiber diameter in the melt electrospinning process. Highly ordered microporous honeycomb structures were developed on photo-functional star-shaped PDLLA surfaces. The pore dimensions were dependent on polymer solution concentration, polymer molar mass and relative humidity. The combination of self-organizing and cross-linking techniques resulted in free-standing, PDLLA membranes with high chemical stability as well as higher mechanical strength for further material patterning. Amikacin, an antibiotic commonly used for treating infections was successfully encapsulated in star-shaped PDLLA fibers that were electrospun from solution. Preliminary results suggested that molecular architecture influenced the encapsulation of the antibiotic and subsequent drug release profile. / Ph. D.

Fluorescence energy transfer from poly(9,9-dioctylfluorene) to polymeric energy acceptors that include head-to-tail regioregular poly(3-hexylthiophene or P3HT) and poly(2-methoxy-5(2 -ethylhexyloxy)-1,4-phenylenevinylene) or MEH-PPV and monomeric acceptor meso-tetraphenylporphyrin or TPP was studied and correlated with the underlying morphology when the donor-acceptor blends were prepared as drop-coated films or breath-figure structures. It was found that the phase-separate morphology in films and breath figures was influenced by a number of factors, including material transport dynamics, solubility of the blend components in a solvent, interaction of the solvent with the substrate, and the diffusion rate of the blend components.

Water drops that nucleate and grow over an evaporating polymer solution exposed to a current of moist air remain noncoalescent and self-assemble into close packed arrays. The hexagonally close packed, nearly monodisperse drops, eventually evaporate away, leaving a polymer film, with ordered array of pores. Meanwhile, typical breath figures or dew that form when moist air contacts cold surfaces involve coalescence-assisted growth of highly polydisperse, disordered array of water drops. This dissertation provides the first quantitative attempt aimed at the elucidation of the mechanism of the breath figure templated assembly of the ordered arrays of pores in polymer films. The creation and evolution of a population of close packed drops occur in response to the heat and mass fluxes involved in water droplet condensation and solvent evaporation. The dynamics of drop nucleation, growth, noncoalescence and self-assembly are modeled by accounting for various transport and thermodynamic processes. The theoretical results for the rate and extent of evaporative cooling and growth are compared with experiments. Further, the dissertation describes a rich array of experimental observations about water droplet growth, noncoalescence, assembly and drying that have not been reported in the published literature so far. The theoretical framework developed in this study allows one to rationalize and predict the structure and size of pores formed in different polymer-solvent systems under given air flow conditions. While the ordered arrays of water drops present an example of dynamics, growth and assembly of spherical particles, the study on colloidal gold nanorods focuses on the behavior of rodlike particles. A comprehensive set of theoretical arguments based on the shape dependent hydrodynamics of rods were developed and used for centrifugation-assisted separation of rodlike particles from nanospheres that are typical byproducts of seed mediated growth of nanorods. Since the efficiency of shape separation is assessed using UV-Vis-NIR spectroscopy and transmission electron microscopy (TEM), the present dissertation elucidates the shape dependent parameters that affect the optical response and phase behavior of colloidal gold nanorods. The drying of a drop of colloidal gold nanorods on glass slides creates coffee ring like deposits near the contact line, which is preceded by the formation of a liquid crystalline phase. The assemblies of rods on TEM grids are shown to be the result of equilibrium and non-equilibrium processes, and the ordered phases are compared with two dimensional liquid crystals. The methodology of pattern characterization developed in this dissertation is then used to analyze the structure of the exocuticle of iridescent beetle Chrysina gloriosa. The patterns were characterized using Voronoi analysis and the effect of curvature on the fractions on hexagonal order of tiles was determined. Further, these patterns were found to be analogous to the focal conic domains formed spontaneously on the free surface of a cholesteric liquid crystal. In summary, the dissertation provides the crucial understanding required for the widespread use of breath figure templated assembly as a method for manufacturing porous films, that requires only a drop of polymer solution (dilute) and a whiff of breath! Further, the dissertation establishes the physical basis and methodology for separating and characterizing colloidal gold nanorods. The dissertation also suggests the basis for the formation and structure of tiles that decorate the exoskeleton of an iridescent beetle Chrysina gloriosa.

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