Complex tracer mobilities in polymer networks revealed by fluorescence correlation spectroscopy

Gels are elastic porous polymer networks that are accompanied by pronounced mechanical properties. Due to their biocompatibility, ‘responsive hydrogels’ (HG) have many biomedical applications ranging from biosensors and drug delivery to tissue engineering. They respond to external stimuli such as temperature and salt by changing their dimensions. Of paramount importance is the ability to engineer penetrability and diffusion of interacting molecules in the crowded HG environment, as this would enable one to optimize a specific functionality. Even though the conditions under which biomedical devices operate are rather complex, a bottom-up approach could reduce the complexity of mutually coupled parameters influencing tracer mobility. The present thesis focuses on the interaction-induced tracer diffusion in polymer solutions and their homologous gels, probed by means of Fluorescence Correlation Spectroscopy (FCS). This is a single-molecule-sensitive technique having the advantage of optimal performance under ultralow tracer concentrations, typically employed in biosensors. Two different types of hydrogels have been investigated, a conventional one with broad polydispersity in the distance between crosslink points and a so-called ‘ideal’, with uniform mesh size distribution. The former is based on a thermoresponsive polymer, exhibiting phase separation in water at temperatures close to the human body temperature. The latter represents an optimal platform to study tracer diffusion. Mobilities of different tracers have been investigated in each network, varying in size, geometry and in terms of tracer-polymer attractive strength, as perturbed by different stimuli. The thesis constitutes a systematic effort towards elucidating the role of the strength and nature of different tracer-polymer interactions, on tracer mobilities; it outlines that interactions can still be very important even in the simplified case of dilute polymer solutions; it also demonstrates that the presence of permanent crosslinks exerts distinct tracer slowdown, depending on the tracer type and the nature of the tracer-polymer interactions, expressed differently by each tracer with regard to the selected stimulus. In aqueous polymer solutions, the tracer slowdown is found to be system-dependent and no universal trend seems to hold, in contrast to predictions from scaling theory for non-interacting nanoparticle mobility and empirical relations concerning the mesh size in polymer solutions. Complex tracer dynamics in polymer networks may be distinctly expressed by FCS, depending on the specific synergy among-at least some of - the following parameters: nature of interactions, external stimuli employed, tracer size and type, crosslink density and swelling ratio.

Modeling the molecular weight distribution of block copolymer formation in a reversible addition-fragmentation chain transfer mediated living radical polymerization

Block copolymers have become an integral part of the preparation of complex architectures through self-assembly. The use of reversible addition-fragmentation chain transfer (RAFT) allows blocks ranging from functional to nonfunctional polymers to be made with predictable molecular weight distributions. This article models block formation by varying many of the kinetic parameters. The simulations provide insight into the overall polydispersities (PDIs) that will be obtained when the chain-transfer constants in the main equilibrium steps are varied from 100 to 0.5. When the first dormant block [polymer-S-C(Z)=S] has a PDI of 1 and the second propagating radical has a low reactivity to the RAFT moiety, the overall PDI will be greater than 1 and dependent on the weight fraction of each block. When the first block has a PDI of 2 and the second propagating radical has a low reactivity to the RAFT moiety, the PDI will decrease to around 1.5 because of random coupling of two broad distributions. It is also shown how we can in principle use only one RAFT agent to obtain block copolymers with any desired molecular weight distribution. We can accomplish this by maintaining the monomer concentration at a constant level in the reactor over the course of the reaction. (c) 2005 Wiley Periodicals, Inc.

Uma revisão sobre o efeito Toms: o fenômeno onde macromoléculas atenuam a turbulência em um líquido

It is very well known that the addition of polymers to a liquid increases the shear viscosity of the solution. In other words, the polymer increases the dissipation of the flow energy. Contrarily, in turbulent flow, some particular macromolecules in very low concentration are able to produce large attenuation in the turbulence and thus, decreasing the dissipation of the energy. This article present a brief revision about macroscopic and molecular models used to explain this dynamic effect. Some of the experimental techniques used to quantify the attenuation of the turbulence and the main active substances are also discussed.

Thermodiffusion in a multicomponent lyotropic mixture in the vicinity of the critical micellar concentration by using the Z-scan technique

Thermodiffusion in a lyotropic mixture of water and potassium laurate is investigated by means of an optical technique (Z scan) distinguishing the index variations due to the temperature gradient and the mass gradients. A phenomenological framework allowing for coupled diffusion is developed in order to analyze thermodiffusion in multicomponent systems. An observable parameter relating to the mass gradients is found to exhibit a sharp change around the critical micellar concentration, and thus may be used to detect it. The change in the slope is due to the markedly different values of the Soret coefficients of the surfactant and the micelles. The difference in the Soret coefficients is due to the fact that the micellization process reduces the energy of interaction of the ball of amphiphilic molecules with the solvent.

Viscoelasticity of radiation-formed PVA/PVP hydrogel

The dynamic theological behaviour of gamma-irradiated 12.8 wt% poly(vinyl alcohol) (PVA), 12.8 wt% poly(vinyl pyrrolidone) (PVP), and a blend of 8 wt% PVA and 4.8 wt% PVP aqueous solutions have been studied pre- and post-gelation. The non-irradiated solutions displayed theological behaviour typical of dilute to semi-dilute polymer solutions, with the complex viscosity being independent of the frequency and shear rate (i.e. Newtonian behaviour) over the range of frequencies tested and the loss modulus G(omega) and storage modulus G(omega) being nearly proportional to omega and omega(2) respectively. After a set of doses of gamma-radiation, the magnitudes of the dynamic moduli G'(omega) and G(omega) increased as the absorbed dose increased, with notable differences between the two homopolymers and the blend. The stages of gelation were effectively monitored by means of dynamic theological measurements, allowing the possible mechanisms of network formation to be elucidated. The doses required for gelation of the PVA, PVP, and blend samples, determined on the basis of the Winter and Chambon criteria for gelation, were found to be 12 kGy for the 12.8 wt% PVA, 4 kGy for the 12.8 wt% PVP, and 5 kGy for the 8 wt% PVA/4.8 wt% PVP solutions. The unexpected lower gelation dose demonstrated by the blend sample, compared with predictions based on the blend composition, and the associated gelation mechanism are also discussed.

Structural Color and Iridescence in Transparent Sheared Cellulosic Films

Shear transparent cellulose free-standing thin films can develop iridescence similar to that found in petals of the tulip Queen of the Night. The iridescence of the film arises from the modulation of the surface into bands periodically spread perpendicular to the shear direction. Small amounts of nanocrystalline cellulose (NCC) rods in the precursor liquid-crystalline solutions do not disturb the optical properties of the solutions but enhance the mechanical characteristics of the films and affects their iridescence. Smaller bands periodicity, not affected by the NCC rods, slightly deviated from the shear direction is also observed. NCCs are crucial to tune and understand the film's surface features formation. Our findings could lead to new materials for application in soft reflective screens and devices.

Friction losses of Newtonian and non-Newtonian fluids flowing in laminar regime in a helical coil

This study aimed to carry out experimental work to determine, for Newtonian and non-Newtonian fluids, the friction factor (fc) with simultaneous heat transfer, at constant wall temperature as boundary condition, in fully developed laminar flow inside a vertical helical coil. The Newtonian fluids studied were aqueous solutions of glycerol, 25%, 36%, 43%, 59% and 78% (w/w). The non-Newtonian fluids were aqueous solutions of carboxymethylcellulose (CMC), a polymer, with concentrations of 0.2%, 0.3%, 0.4% and 0.6% (w/w) and aqueous solutions of xanthan gum (XG), another polymer, with concentrations of 0.1% and 0.2% (w/w). According to the rheological study done, the polymer solutions had shear-thinning behavior and different values of viscoelasticity. The helical coil used has an internal diameter, curvature ratio, length and pitch, respectively: 0.00483 m, 0.0263, 5.0 m and 11.34 mm. It was concluded that the friction factors, with simultaneous heat transfer, for Newtonian fluids can be calculated using expressions from literature for isothermal flows. The friction factors for CMC and XG solutions are similar to those for Newtonian fluids when the Dean number, based in a generalized Reynolds number, is less than 80. For Dean numbers higher than 80, the friction factors of the CMC solutions are lower those of the XG solutions and of the Newtonian fluids. In this range the friction factors decrease with the increase of the viscometric component of the solution and increase for increasing elastic component. The change of behavior at Dean number 80, for Newtonian and non-Newtonian fluids, is in accordance with the study of Ali [4]. There is a change of behavior at Dean number 80, for Newtonian and non-Newtonian fluids, which is in according to previous studies. The data also showed that the use of the bulk temperature or of the film temperature to calculate the physical properties of the fluid has a residual effect in the friction factor values.

Heat transfer coefficients from Newtonian and non-Newtonian fluids flowing in laminar regime in a helical coil

This study aimed to carry out experimental work to obtain, for Newtonian and non-Newtonian fluids, heat transfer coefficients, at constant wall temperature as boundary condition, in fully developed laminar flow inside a helical coil. The Newtonian fluids studied were aqueous solutions of glycerol, 25%, 36%, 43%, 59% and 78% (w/w) and the non-Newtonian fluids aqueous solutions of carboxymethylcellulose (CMC), a polymer, with concentrations 0.1%, 0.2%, 0.3%, 0.4% and 0.6% (w/w) and aqueous solutions of xanthan gum (XG), another polymer, with concentrations 0.1% and 0.2% (w/w). According to the rheological study performed, the polymer solutions had shear thinning behavior and different values of elasticity. The helical coil used has internal diameter, curvature ratio, length and pitch, respectively: 0.004575 m, 0.0263, 5.0 m and 11.34 mm. The Nusselt numbers for the CMC solutions are, on average, slightly higher than those for Newtonian fluids, for identical Prandtl and generalized Dean numbers. As outcome, the viscous component of the shear thinning polymer tends to potentiate the mixing effect of the Dean cells. The Nusselt numbers of the XG solutions are significant lower than those of the Newtonian solutions, for identical Prandtl and generalized Dean numbers. Therefore, the elastic component of the polymer tends to diminish the mixing effect of the Dean cells. A global correlation, for Nusselt number as a function of Péclet, generalized Dean and Weissenberg numbers for all Newtonian and non-Newtonian solutions studied, is presented.

Development of 2-oxazoline-based hydrogels and porous polyester microparticles in scCO2

Thesis submitted to Faculdade de Ciências e Tecnologia from Universidade Nova de Lisboa in partial fulfillment of the requirements for the obtention of the degree of Master of Science in Biotechnology

Development of biomimetic microengineered hydrogel fibers for tendon regeneration

Musculoskeletal diseases are one of the leading causes of disability worldwide. Tendon injuries are responsible for substantial morbidity, pain and disability. Tissue engineering strategies aim at translating tendon structure into biomimetic materials. The main goal of the present study is to develop microengineered hydrogel fibers through the combination of microfabrication and chemical interactions between oppositely charged polyelectrolytes. For this, methacrylated hyaluronic acid (MeHA) and chondroitin sulfate (MeCS) were combined with chitosan (CHT). Hydrogel fibers were obtained by injecting polymer solutions (either MeHA or MeHA/MeCS and CHT) in separate microchannels that join at a y-junction, with the materials interacting upon contact at the interface. To evaluate cell behavior, human tendon derived cells (hTDCs) were isolated from tendon surplus samples during orthopedic surgeries and seeded on top of the fibers. hTDCs adhered to the surface of the fibers, remaining viable, and were found to be expressing CD44, the receptor for hyaluronic acid. The synthesis of hydrogel fibers crosslinkable through both physical and chemical mechanisms combined with microfabrication technology allows the development of biomimetic structures with parallel fibers being formed towards the replication of tendon tissue architecture.

Avaliação do potencial económico de implementação da construção em BTC

Dissertação de mestrado integrado em Engenharia Civil

High performance screen printable lithium-ion battery cathode ink based on C-LiFePO4

Lithium-ion battery cathodes have been fabricated by screen-printing through the development of CLiFePO4 inks. It is shown that shear thinning polymer solutions in N-methyl-2-pyrrolidone (NMP) with Newtonian viscosity above 0.4 Pa s are the best binders for formulating a cathode paste with satisfactory film forming properties. The paste shows an elasticity of the order of 500 Pa and, after shear yielding, shows an apparent viscosity of the order of 3 Pa s for shear rates corresponding to those used during screen-printing. The screen-printed cathode produced with a thickness of 26 mm shows a homogeneous distribution of the active material, conductive additive and polymer binder. The total resistance and diffusion coefficient of the cathode are 450 V and 2.5 10 16cm2 s 1, respectively. The developed cathodes show an initial discharge capacity of 48.2 mAh g 1 at 5C and a discharge value of 39.8 mAh g 1 after 50 cycles. The capacity retention of 83% represents 23% of the theoretical value (charge and/or discharge process in twenty minutes), demonstrating the good performance of the battery. Thus, the developed C-LiFePO4 based inks allow to fabricate screen-printed cathodes suitable for printed lithium-ion batteries

Ion-exchange resins as stationary phase in reactive chromatography

Dynamic behavior of bothisothermal and non-isothermal single-column chromatographic reactors with an ion-exchange resin as the stationary phase was investigated. The reactor performance was interpreted by using results obtained when studying the effect of the resin properties on the equilibrium and kinetic phenomena occurring simultaneously in the reactor. Mathematical models were derived for each phenomenon and combined to simulate the chromatographic reactor. The phenomena studied includes phase equilibria in multicomponent liquid mixture¿ion-exchange resin systems, chemicalequilibrium in the presence of a resin catalyst, diffusion of liquids in gel-type and macroporous resins, and chemical reaction kinetics. Above all, attention was paid to the swelling behavior of the resins and how it affects the kinetic phenomena. Several poly(styrene-co-divinylbenzene) resins with different cross-link densities and internal porosities were used. Esterification of acetic acid with ethanol to produce ethyl acetate and water was used as a model reaction system. Choosing an ion-exchange resin with a low cross-link density is beneficial inthe case of the present reaction system: the amount of ethyl acetate as well the ethyl acetate to water mole ratio in the effluent stream increase with decreasing cross-link density. The enhanced performance of the reactor is mainly attributed to increasing reaction rate, which in turn originates from the phase equilibrium behavior of the system. Also mass transfer considerations favor the use ofresins with low cross-link density. The diffusion coefficients of liquids in the gel-type ion-exchange resins were found to fall rapidly when the extent of swelling became low. Glass transition of the polymer was not found to significantlyretard the diffusion in sulfonated PS¿DVB ion-exchange resins. It was also shown that non-isothermal operation of a chromatographic reactor could be used to significantly enhance the reactor performance. In the case of the exothermic modelreaction system and a near-adiabatic column, a positive thermal wave (higher temperature than in the initial state) was found to travel together with the reactive front. This further increased the conversion of the reactants. Diffusion-induced volume changes of the ion-exchange resins were studied in a flow-through cell. It was shown that describing the swelling and shrinking kinetics of the particles calls for a mass transfer model that explicitly includes the limited expansibility of the polymer network. A good description of the process was obtained by combining the generalized Maxwell-Stefan approach and an activity model that was derived from the thermodynamics of polymer solutions and gels. The swelling pressure in the resin phase was evaluated by using a non-Gaussian expression forthe polymer chain length distribution. Dimensional changes of the resin particles necessitate the use of non-standard mathematical tools for dynamic simulations. A transformed coordinate system, where the mass of the polymer was used as a spatial variable, was applied when simulating the chromatographic reactor columns as well as the swelling and shrinking kinetics of the resin particles. Shrinking of the particles in a column leads to formation of dead volume on top of the resin bed. In ordinary Eulerian coordinates, this results in a moving discontinuity that in turn causes numerical difficulties in the solution of the PDE system. The motion of the discontinuity was eliminated by spanning two calculation grids in the column that overlapped at the top of the resin bed. The reactive and non-reactive phase equilibrium data were correlated with a model derived from thethermodynamics of polymer solution and gels. The thermodynamic approach used inthis work is best suited at high degrees of swelling because the polymer matrixmay be in the glassy state when the extent of swelling is low.

Uma revisão sobre o efeito Toms: o fenômeno onde macromoléculas atenuam a turbulência em um líquido

It is very well known that the addition of polymers to a liquid increases the shear viscosity of the solution. In other words, the polymer increases the dissipation of the flow energy. Contrarily, in turbulent flow, some particular macromolecules in very low concentration are able to produce large attenuation in the turbulence and thus, decreasing the dissipation of the energy. This article present a brief revision about macroscopic and molecular models used to explain this dynamic effect. Some of the experimental techniques used to quantify the attenuation of the turbulence and the main active substances are also discussed.

Une nouvelle méthode smoothed particle hydrodynamics : simulation des interfaces immergées et de la dynamique Brownienne des molécules avec des interactions hydrodynamiques

Dans cette thèse, nous présentons une nouvelle méthode smoothed particle hydrodynamics (SPH) pour la résolution des équations de Navier-Stokes incompressibles, même en présence des forces singulières. Les termes de sources singulières sont traités d'une manière similaire à celle que l'on retrouve dans la méthode Immersed Boundary (IB) de Peskin (2002) ou de la méthode régularisée de Stokeslets (Cortez, 2001). Dans notre schéma numérique, nous mettons en oeuvre une méthode de projection sans pression de second ordre inspirée de Kim et Moin (1985). Ce schéma évite complètement les difficultés qui peuvent être rencontrées avec la prescription des conditions aux frontières de Neumann sur la pression. Nous présentons deux variantes de cette approche: l'une, Lagrangienne, qui est communément utilisée et l'autre, Eulerienne, car nous considérons simplement que les particules SPH sont des points de quadrature où les propriétés du fluide sont calculées, donc, ces points peuvent être laissés fixes dans le temps. Notre méthode SPH est d'abord testée à la résolution du problème de Poiseuille bidimensionnel entre deux plaques infinies et nous effectuons une analyse détaillée de l'erreur des calculs. Pour ce problème, les résultats sont similaires autant lorsque les particules SPH sont libres de se déplacer que lorsqu'elles sont fixes. Nous traitons, par ailleurs, du problème de la dynamique d'une membrane immergée dans un fluide visqueux et incompressible avec notre méthode SPH. La membrane est représentée par une spline cubique le long de laquelle la tension présente dans la membrane est calculée et transmise au fluide environnant. Les équations de Navier-Stokes, avec une force singulière issue de la membrane sont ensuite résolues pour déterminer la vitesse du fluide dans lequel est immergée la membrane. La vitesse du fluide, ainsi obtenue, est interpolée sur l'interface, afin de déterminer son déplacement. Nous discutons des avantages à maintenir les particules SPH fixes au lieu de les laisser libres de se déplacer. Nous appliquons ensuite notre méthode SPH à la simulation des écoulements confinés des solutions de polymères non dilués avec une interaction hydrodynamique et des forces d'exclusion de volume. Le point de départ de l'algorithme est le système couplé des équations de Langevin pour les polymères et le solvant (CLEPS) (voir par exemple Oono et Freed (1981) et Öttinger et Rabin (1989)) décrivant, dans le cas présent, les dynamiques microscopiques d'une solution de polymère en écoulement avec une représentation bille-ressort des macromolécules. Des tests numériques de certains écoulements dans des canaux bidimensionnels révèlent que l'utilisation de la méthode de projection d'ordre deux couplée à des points de quadrature SPH fixes conduit à un ordre de convergence de la vitesse qui est de deux et à une convergence d'ordre sensiblement égale à deux pour la pression, pourvu que la solution soit suffisamment lisse. Dans le cas des calculs à grandes échelles pour les altères et pour les chaînes de bille-ressort, un choix approprié du nombre de particules SPH en fonction du nombre des billes N permet, en l'absence des forces d'exclusion de volume, de montrer que le coût de notre algorithme est d'ordre O(N). Enfin, nous amorçons des calculs tridimensionnels avec notre modèle SPH. Dans cette optique, nous résolvons le problème de l'écoulement de Poiseuille tridimensionnel entre deux plaques parallèles infinies et le problème de l'écoulement de Poiseuille dans une conduite rectangulaire infiniment longue. De plus, nous simulons en dimension trois des écoulements confinés entre deux plaques infinies des solutions de polymères non diluées avec une interaction hydrodynamique et des forces d'exclusion de volume.