<p>The polyelectrolyte titration method has been developed overthe years in order to determine the surface charge ofcellulosic fibers. The conditions have been varied depending onthe author. This work has been aimed at resolving theappropriate conditions for measuring the charge, such aselectrolyte concentration and molecular mass of thepolyelectrolyte. The charge ratio of variously treated pulpswas also investigated.</p><p>The polyelectrolyte titration technique is based on a 1:1adsorption stoichiometry between fiber and polyelectrolytecharges. Adsorption of polydiallyldimethylammonium chloride(poly-DADMAC) was first performed at various electrolyteconcentrations and then with various molecular masses. ESCA(Electron Spectroscopy for Chemical Analysis) was used toindependently validate the polyelectrolyte titrationmethod.</p><p>Results showed that stoichiometry prevailsat lowelectrolyte concentrations. Increasing the electrolyteconcentration screens the fiber charges, initially enhancingthe adsorption and causing a deviation from stoichiometry.Further increases in electrolyte concentration eventuallydecrease the adsorption. Deviation from stoichiometry occurredat higher electrolyte concentrations for higher charge densitypulps. ESCA-measurements showed that high and low molecularmass cationic polyelectrolyte adsorb to the same extent on thefiber surface, confirming stoichiometry. There was a goodagreement between the two techniques, hence, thepolyelectrolyte titration technique is a good method to measuresurface charges. Comparing the charge ratio between differentkind of pulps and treatments, it was found that mechanicalpulps have a higher surface charge than chemical pulps. Thecharge ratio of chemical pulps was, however, practicallyunchanged when comparing different types of wood and bleachingsequences.</p><p><b>KEYWORDS:</b>Adsorption, electrolyte, polyelectrolyte,polyelectrolyte titration, charge stoichiometry, charge ratio,diffuse electric double layer, Debye length, poly-DADMAC,cellulosic fibers, ESCA.</p>

Encapsulation is a wide spread industrial technique. The use of biopolymers to form capsules has an obvious advantage for food, biomedical or personal care applications, as they can be made of food grade and biodegradable materials. Polyelectrolyte complexes (PEC) have been widely used to form capsules by the multilayer technique, usually coating a solid core with a layer by layer deposition technique involving various steps of deposition of polyelectrolyte of opposite charge. In this thesis we focused on capsules made with a one step technique where a liquid drop containing a concentrated solution of the polycation is dropped into a dilute solution of the polyanionic solution. Chitosan was the natural polycation used, due to its interesting properties such as biodegradability, biocompatibility or muco-adhesion, and because it is one of the rare cationic polysaccharides which is safe to be used in food applications. The simple one step technique used to form these capsules brings an advantage in terms of manufacturing. The drop deformation due to the impact of droplets at the surface of a liquid bath was studied and the conditions for these droplets to detach from the surface and disperse into the solution were examined. It was found that a balance between the kinetic energy and the absorbed viscous energy of the drop during impact is necessary for the formation of capsules by this technique. Initial work was performed on capsules made with chitosan and polyanionic biopolymers such as alginate or pectins. However, these biopolymers are usually provided with a polydispersed molecular weight distribution and impurities. Polyacrylic acid was thus chosen to study the effect of molecular weight, charge density, and pH on the microstructure, mechanical, swelling and release behaviour of these capsules. The microstructure of the capsules was observed by cryo-scanning electron microscopy, and the effect of molecular weight charge density of the polyelectrolytes on the shell thickness were shown and related to the mechanical and release properties of the capsules. It was shown that the molecular weight has an important role as it determines the thickness of the shell. The charge density of the polyelectrolytes, which can be controlled by the pH and ionic strength of the solution, dictates the density of the shell. The study of the release properties of these capsules showed that they could be completely impermeable to molecules with a molecular weight higher than 2000 g/mol, and surprisingly, the capsules could withstand a wide range of pH extending beyond the pH where electrostatic interactions occur, as they only dissolved at extreme pHs of 2 and 12. Chitosan was also used to make swellable hydrogels microparticles, by cross-linking with glutaraldehyde. The swelling behaviour in gastro-intestinal environment was studied in vitro and in vivo using Magnetic Resonance Imaging techniques.

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The polyelectrolyte titration method has been developed overthe years in order to determine the surface charge ofcellulosic fibers. The conditions have been varied depending onthe author. This work has been aimed at resolving theappropriate conditions for measuring the charge, such aselectrolyte concentration and molecular mass of thepolyelectrolyte. The charge ratio of variously treated pulpswas also investigated. The polyelectrolyte titration technique is based on a 1:1adsorption stoichiometry between fiber and polyelectrolytecharges. Adsorption of polydiallyldimethylammonium chloride(poly-DADMAC) was first performed at various electrolyteconcentrations and then with various molecular masses. ESCA(Electron Spectroscopy for Chemical Analysis) was used toindependently validate the polyelectrolyte titrationmethod. Results showed that stoichiometry prevailsat lowelectrolyte concentrations. Increasing the electrolyteconcentration screens the fiber charges, initially enhancingthe adsorption and causing a deviation from stoichiometry.Further increases in electrolyte concentration eventuallydecrease the adsorption. Deviation from stoichiometry occurredat higher electrolyte concentrations for higher charge densitypulps. ESCA-measurements showed that high and low molecularmass cationic polyelectrolyte adsorb to the same extent on thefiber surface, confirming stoichiometry. There was a goodagreement between the two techniques, hence, thepolyelectrolyte titration technique is a good method to measuresurface charges. Comparing the charge ratio between differentkind of pulps and treatments, it was found that mechanicalpulps have a higher surface charge than chemical pulps. Thecharge ratio of chemical pulps was, however, practicallyunchanged when comparing different types of wood and bleachingsequences. <b>KEYWORDS:</b>Adsorption, electrolyte, polyelectrolyte,polyelectrolyte titration, charge stoichiometry, charge ratio,diffuse electric double layer, Debye length, poly-DADMAC,cellulosic fibers, ESCA. / NR 20140805

No description available.

Colloidal macroions are known to interact very strongly with oppositely charged polyionic hydrogels. Sometimes this results in a non-uniform distribution of the macroions within the gel, a phenomenon that is not fully understood. This thesis is a summary of four papers on the development of a theory of the thermodynamics of macroions interacting with hydrogels, aimed at explaining the phenomenon of core/shell separation in spherical gels. It is the first theory of such interactions to use a rigorous approach to whole-gel mechanics, in which the elastic interplay between different parts of the gel is treated explicitly. The thesis shows that conventional theories of elasticity, earlier used on gels in pure solvent, can be generalised to apply also to gels in complex fluids, and that the general features of the phase behaviour are the same if mapped to corresponding system variables. It is found that the emergence of shells is due to attractions between macroions in the gel, mediated by polyions. Since the shell state is unfavourable from the perspective of the shell itself, being deformed from its preferred state, there will be a hysteresis between the uptake and the release of the macroion, like already known to occur with the uptake and release of pure solvent. Due to the elastic interplay, growth of the shell makes further growth progressively more favourable. Thus, unless there is a limited amount of macroions available the system will not reach equilibrium until complete phase transition has taken place. If the amount is limited the core/shell separation can be in equilibrium, so the volume of the solution that the gel is in contact with plays a very important part in determining the thermodynamic resting point of the system. The ability of a macroion/hydrogel to phase separate thus depends on the molecular properties whereas the ultimate fate of such a separation depends on the proportions in number between the ingoing components.

This project aims to discover a new means of overcoming the drawbacks of traditional layer-by-layer dip coating through the use of polyelectrolyte complexes (PECs) and electrophoretic deposition. The layer-by-layer process, by which oppositely charged polyelectrolytes or other charged particle are alternately adsorbed onto a substrate to produce a thin film of precisely controllable thickness, is versatile and simple to implement but suffers from requiring numerous, long deposition steps to produce uniform micron thick films. PECs are small associations of oppositely charged polyelectrolytes that, when mixed in non-stoichiometric ratios, can form charged water- soluble particles. There is much still to be determined about the phase behavior of PECs. However, it has been shown that they can exist over a range of conditions. Electrophoretic deposition is a technique used in many commercial applications for the deposition of charged particles onto a conducting substrate. It has even been shown to enhance the deposition of polyelectrolyte single layers and multilayers. This study examines the phase behavior of PECs made of linear poly(ethyleneimine) (LPEI) and poly(acrylic acid) (PAA). PEC behavior is studied over a pH range of 4.0 to 6.0, with no salt added to the system. This study also reports the results of tests examining how soluble PECs responded to changes in pH and whether solid PECs could be made to dissolve through the addition of different salts. Light scattering is used to examine the particle size distribution and effective diameter of PECs in solution. This information is then used to electrophoretically deposit PECs with 10%, 30%, 70%, and 90% excess LPEI. Stylus profilometry is used to assess the thickness of deposited films. The results showing that PEC layers deposited under an applied voltage were 40% to 400% thicker than PECs deposited with no applied potential.

Made available in DSpace on 2014-06-11T19:35:07Z (GMT). No. of bitstreams: 0 Previous issue date: 2003-08-20Bitstream added on 2014-06-13T20:26:03Z : No. of bitstreams: 1 pereira_fc_dr_araiq.pdf: 4196917 bytes, checksum: 11491725a43d3f472d5e3e7ea3e850fe (MD5) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / A formação de filmes do poliaminoácido poli-l-lisina, (PLL), foi investigada sobre eletrodo de carbono de duas formas distintas: pela sua imobilização direta na superfície do eletrodo obtido pela deposição de 10 μL de uma alíquota seguido de secagem a 80oC em estufa e com a utilização do agente de ligação cruzada Glutaraldeído. Filmes de PLL sobre eletrodo de carbono pirolítico apresentaram-se suficientemente estáveis para pré-concentração do fármaco antiasmático cromoglicato disódico com máxima interação em valor de pH 4,0. Utilizando-se filmes do poliaminoácido obtido com soluções a 1,0% m/v de PLL foi possível estabelecer uma curva analítica para monitoramento do composto em valores de concentração entre 2,18x10-7 mol L-1 a 3,29x10-6 mol L-1 e limite de detecção de 2,1x10-8 mol L-1. A aplicação do procedimento proposto foi realizada para a determinação da droga em urina humana segundo o método de adições-padrão apresentando índices de recuperação de 99,8%, compatível com valores obtidos em procedimentos espectrofotométricos. O nitroprussiato de sódio pode ser monitorado voltametricamente com filmes de PLL imobilizados na superfície do eletrodo de carbono vítreo com auxílio do agente de ligação cruzada Glutaraldeído. O fármaco é pré-concentrado na superfície modificada e exibe maior amplificação de corrente em valor de pH 4,0. Utilizando as melhores condições analíticas, uma curva de calibração foi obtida no intervalo de concentração de 1,21x10-6 a 2,06x10-5 mol L-1 e limite de determinação igual a 4,62x10-7 mol L-1. A aplicação da metodologia foi conduzida para a determinação de NIPRIDE® em plasma e urina humana apresentando índices de recuperação de 95,0% e 96,2%, concordante com resultados obtidos por ensaios espectrofotométricos. A investigação sobre o comportamento voltamétrico do iodeto de potássio com... / The formation of polyelectrolyte film, poly-l-lysina (PLL), was investigated using carbon electrode in two distinct manners: by direct surface immobilization of the electrode obtained by depositing 10 μL of aliquot followed by heating at 80ºC; and with the use of a cross linking agent, glutaraldehyde. PLL films subjected to pirolitic carbon electrode presented themselves as sufficiently stable for the pre-concentrated anti-asthmatic pharmaceutical disodium cromoglicate with a maximum interaction value of pH 4.0. Using polyelectrolyte films, obtained with solutions of PLL 1.00 %m/v it was possible to establish an analytic curve for monitoring the composition in varying levels of concentration, between 2.18x10-7 mol L-1 – 3.29x10-6 mol L-1 and a detection limit of 2.1x10-8 mol L- 1. The proposed application procedure was realized for drug determination in human urine followed by the method of standard additions presenting indexes of recovery, 99.8%, compatible with values obtained by spectrophotometric procedures. The sodium nitroprusside can be monitored voltammetrically with PLL films, immobilized on the surface of a glassy carbon electrode with the assistance of the bonding agent glutaraldheyde. The pharmaceutical is pre-concentrated on the modified surface and exhibited larger current amplification at pH 4.0. Using the best analytic conditions, the calibration curve was obtained at the concentration interval of 1,21x10-6 to 2,06x10-5 mol L-1, and a determination limit equal to 4,62x10-7 mol L-1. The application of this methodology was used to determine NIPRIDE® in plasma and human urine presenting levels of recovery of 95.0% and 96.2%, which agree with the results achieved by spectrophotometric tests...(Complete abstract, click electronic access below)

An unprecedented comprehensive study of ammonium and phosphonium polyelectrolytes probed and examined structure-property relationships with a focus on different macromolecular properties. Conventional free radical polymerization readily generated a large library of ammonium- and phosphonium-containing polyelectrolytes. Along with the two different cationic atoms, the alkyl substituent lengths and counterions were varied to generate a thorough structure-property relationship analysis. Phosphonium macromolecules displayed improved thermal stabilities and improved ionic conductivities compared to ammonium analogs. Longer alkyl substituent lengths systematically decreased the glass transition temperatures of all polyelectrolytes; the larger, bulkier counterions also resulted in lower glass transition temperatures. Counterion also impacted the thermal stability of the polymerized ionic liquids with less basic counterions leading to improved thermal stability. For the first time, the efficacy of phosphonium macromolecules for nonviral nucleic acid delivery was examined. Phosphonium macromolecules more efficiently complexed nucleic acids than ammonium analogs and butyl-containing phosphonium macromolecules delivered nucleic acids more effectively than the ammonium analog. Controlled radical polymerization generated unprecedented phosphonium-containing diblock copolymers and these diblock copolymers displayed enhanced colloidal stability and lower cytotoxicity compared to the phosphonium homopolymer for nucleic acid delivery. Step-growth polymerization techniques enabled the synthesis of well-defined, high molecular weight phosphonium ionenes for the first time. Phosphonium ionenes exhibited higher thermal stability and alkaline stability compared to ammonium ionenes. Due to their high thermal stability and relatively low glass transition temperatures, unprecedented melt rheology studies on polyelectrolytes probed the melt flow characteristics of phosphonium ionenes. Novel phosphonium gemini surfactants displayed interesting solution properties in aqueous and chloroform solutions. Electrospinning of the phosphonium gemini surfactants created uniform fibers. The synthesis and characterization of sulfonium polyelectrolytes enabled the first examination of sulfonium macromolecules for nonviral nucleic acid delivery. Sulfonium polyelectrolytes successfully bound nucleic acids and delivered them in vitro. Controlled radical polymerization generated innovative AB diblock and ABA triblock copolymers that displayed salt- and temperature-responsive properties suitable for biological applications such as drug delivery vehicles and hydrogels. Finally, adenine-containing polyelectrolytes were synthesized and they were successfully electrospun to generate adenine-decorated nanofibers appropriate for filtration and nonwoven applications. / Ph. D.

Microbial infections are a global problem. Due to the over and misuse of antibiotics, drug-resistant pathogens are becoming more common. It is imperative to explore broad spectrum antimicrobial approaches. In this work, we modified collagen/hyaluronic acid polyelectrolyte multilayers (PEMs) with the natural antimicrobial peptide, LL-37 to study hepatic infections. LL-37 was physisorbed and covalently linked to the surface of the PEMs. Escherichia coli DH10B were cultured in the presence of LL-37modified PEMs in bacterial adhesion and contact killing models. Physisorbed LL-37 PEMs prevented bacterial adhesion and could also kill pathogens in the surrounding environment due to the release of LL-37 from the film. Immobilized LL-37 PEMs resulted in less bacterial adhesion on the surface due to the presence of the peptide. Films were then placed in contact with primary rat hepatocytes as well as in hepatocyte/bacteria co-cultures. LL-37 input concentrations up to of 16μM did not exhibit cytotoxic effects on hepatocytes. The LL-37 modified PEMs exhibited a hepatoprotective effect on albumin and urea secretion functions in co-cultures. The hepatoprotective effects were dependent on the ratio of hepatocytes and bacteria as well as the concentration of LL-37. These findings are encouraging and demonstrate that LL-37 modified PEMs can be used to investigate hepatic infections caused by bacteria. / Master of Science