RESUMEN
Water-in-water (W/W) emulsions, also called aqueous two-phase systems, are formed by mixing two incompatible polymers in water that phase separate into two distinct phases. They can be stabilized by addition of colloidal particles. Droplets of the dispersed phase can be used to compartmentalize ingredients and induce localized reactions. By mixing more types of incompatible polymers, emulsions containing droplets of different phases can be formed that can potentially capture different ingredients. Here the interaction between dispersed droplets of different types was studied by gently mixing a W/W emulsion containing droplets rich in dextran (DEX) dispersed in a continuous phase rich in polyethylene oxide with an emulsion containing droplets rich in fish gelatin (GEL) dispersed in the same continuous medium. Bis-hydrophilic microgels (MG) consisting of DEX grafted with poly(N-isopropylacrylamide) were added and their effect on the stability of each binary emulsion was investigated. Interestingly, when two very stable emulsions were gently mixed, droplets of different types were observed with confocal scanning laser microscopy to coalesce immediately upon contact. In this manner, Janus-type droplets were formed containing a DEX and a GEL compartment with no MG at the GEL/DEX interface that further associated into strings of alternating droplets. Contact angles between the different phases in emulsions with and without MG were compared and used to determine the effect of the microgels on the interfacial tension between the phases.
RESUMEN
Nanocomposite hydrogels were elaborated that consisted of a physical network formed by an amphiphilic polymer in which C60 fullerene nanoplatelets were embedded. Characterization showed that the nanoplatelets within the polymer network were aggregated. The presence of these nanoplatelets led to an increase of the shear modulus of the hydrogels, that cannot be explained by a filler effect alone. The nanocomposite gels displayed similar rheological behavior, both in linear and non-linear domains, as neat hydrogels at higher polymer concentrations. We suggest that the particles reinforced the gels by forming additional connections between the polymer chains.
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The degradation of (micro)gels and fractal aggregates based on self-assembled amphiphilic triblock copolymers has been investigated in water by confocal microscopy and light scattering respectively. The triblock copolymer consisted of a central hydrophilic poly(acrylic acid) (pAA) block and two hydrophobic end blocks that contained an equal amount of randomly distributed n-butyl acrylate (nBA) and AA units. These latter units helped at tempering the hydrophobic end blocks resulting in the control and the fine tuning of the dynamics of the self-assembled triblock through the pH. Starting from a pH where the dynamics is frozen, the rate of breakup of the macroscopic gels, microgels and of fractal aggregates was measured after increasing the pH to different values. The mechanism of the breakup was found to be independent of the pH, but its rate increased exponentially with increasing pH. The degradation proceeded through the release of the polymers from the bulk into the surrounding aqueous phase.
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Macroporous hydrogels have great potential for biomedical applications. Liquid or gel-like pores were created in a photopolymerizable hydrogel by forming water-in-water emulsions upon mixing aqueous solutions of gelatin and a poly(ethylene oxide) (PEO)-based triblock copolymer. The copolymer constituted the continuous matrix, which dominated the mechanical properties of the hydrogel once photopolymerized. The gelatin constituted the dispersed phase, which created macropores in the hydrogel. The microstructures of the porous hydrogel were determined by the volume fraction of the gelatin phase. When volume fractions were close to 50 v%, free-standing hydrogels with interpenetrated morphology can be obtained thanks to the addition of a small amount of xanthan. The hydrogels displayed Young's moduli ranging from 5 to 30 kPa. They have been found to be non-swellable and non-degradable in physiological conditions. Preliminary viability tests with hepatic progenitor cells embedded in monophasic PEO-based hydrogels showed rapid mortality of the cells, whereas encouraging viability was observed in PEO-based triblock copolymer/gelatin macroporous hydrogels. The latter has the potential to be used in cell therapy.
Asunto(s)
Gelatina , Hidrogeles , Hidrogeles/química , Gelatina/química , Óxido de Etileno , Encapsulación Celular , Polietilenglicoles/química , Polímeros , Células Madre , AguaRESUMEN
Polymerization-induced self-assembly (PISA) has established itself as a powerful and straightforward method to produce polymeric nano-objects of various morphologies in (aqueous) solution. Generally, spheres are formed in the early stages of polymerization that may evolve to higher order morphologies (worms or vesicles), as the solvophobic block grows during polymerization. Hitherto, the mechanisms involved in these morphological transitions during PISA are still not well understood. Combining a systematic study of a representative PISA system with rheological measurements, we demonstrate that-unexpectedly-unimer exchange is not necessary to form higher order morphologies during radical RAFT-mediated PISA. Instead, in the investigated aqueous PISA, the monomer present in the polymerization medium is responsible for the morphological transitions, even though it slows down unimer exchange.
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Aqueous multiphase systems (AMPS) were formed by mixtures of three or more incompatible water-soluble macromolecules. Droplets formed by different phases in the water-in-water emulsions were found to associate and their morphology was studied using confocal laser scanning microscopy. By analyzing the angles between different associated phases it was possible to determine the relative interfacial tensions between phases with respect to each other. In this manner, the relative interfacial tension of 15 different pairs of polymers solutions was determined. The effect of the total polymer concentration on the relative interfacial tensions was found to be small as long as mixing of the polymers in the phases was small. The effect of adding protein microgels was studied for systems where they adsorb at the interface between the phases. It is shown that protein microgels can in some cases stabilize associated droplets in suspension.
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The effect of adding a small quantity of linear polymers on the stability of water-in-water (W/W) emulsions was studied for emulsions of dextran-rich droplets in a continuous poly(ethylene oxide) (PEO) phase (D/P) and vice versa (P/D). It was found that out of 16 different polymers that were tested, three had a significant effect: chitosan (Chit), diethyl aminoethyl dextran (DEAED), and propylene glycol alginate (PGA). In the presence of Chit or PGA, P/D emulsions were much less stable than D/P emulsions, but DEAED stabilized both types of emulsion. Interactions of these polymers with PEO or dextran were investigated with light scattering, and the microstructure of the emulsions was studied with confocal laser scanning microscopy. The effect of pH, polymer concentration, interfacial tension, and ionic strength on the stability was investigated and was found to be different for the three polymer types. The results suggest that stabilization of W/W emulsions by linear polymers requires that they contain both charged and hydrophobic units.
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Protein aggregates were generated by thermal denaturation of whey protein isolates. Depending on the heating conditions, fractal aggregates of various sizes or microgels were obtained. The osmotic compressibility and correlation length of mixtures of fractal aggregates of different sizes were found to be close to the weighted averages of the individual components at the same concentration. The viscosity of these mixtures can be described by a logarithmic mixing law using the weight fraction and the viscosity of the individual components. The same mixing law describes the behavior of mixtures of fractal aggregates and microgels. The effect of the type of protein was investigated by mixing fractal aggregates formed by whey and soy protein isolates. It is suggested that the viscosity of the mixtures is determined by the cooperative movement over length scales much larger than the size of the aggregates.
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Agregado de Proteínas , Proteínas de Soja/química , Proteína de Suero de Leche/química , ViscosidadRESUMEN
Protein particles were complexed with polysaccharides, and the effect on their capacity to stabilize water-in-water (W/W) emulsions was investigated. Protein microgels were formed by heating aqueous solutions of whey protein isolate. The microgels were subsequently mixed with anionic or cationic polysaccharides: κ-carrageenan (κ-car) or chitosan, respectively. The molar mass and radius of the complexes formed in dilute microgel suspensions (40 mg/L) were characterized by light scattering techniques as a function of the pH and the composition. The structure and stability of complexes formed at a higher microgel concentration (3 g/L) were studied by confocal laser scanning microscopy. It was found that small stable complexes can be formed with κ-car between pH 4.3 and pH 5.5 and with chitosan between pH 4.1 and pH 6.5, that is, both below and above the isoionic point of the microgels (pI = 5.0). Complexation with polysaccharides stabilized aqueous suspensions of microgels in the pH range where they flocculated in the absence of polysaccharides (4.3-5.5). W/W emulsions were produced by mixing dextran and poly(ethylene oxide) solutions. Microgels added to these emulsions spontaneously form a layer around the dispersed droplets, which inhibits coalescence to different extents depending on the conditions. The effect of complexation on the structure of the emulsions was investigated as a function of the pH. It is shown that stable liquid-like emulsions can be obtained in the pH range where emulsions containing only microgels flocculate.
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Emulsiones/química , Geles/química , Polisacáridos/química , Agua/química , Carragenina/química , Quitosano/química , Dextranos/química , Concentración de Iones de Hidrógeno , Peso Molecular , Tamaño de la Partícula , Polietilenglicoles/química , Proteína de Suero de Leche/químicaRESUMEN
Particle-stabilized water-in-water emulsions were prepared by mixing dextran and poly(ethylene oxide) (PEO) in water and adding cellulose nanocrystals (CNC). The CNC formed a layer at the surface of the dispersed droplets formed by the PEO-rich phase. Excess CNC partitioned to the continuous dextran phase. Aggregation of CNC at different rates was induced by adding NaCl between 10 and 100 mM. In the presence of more than 2 g/L CNC, fast aggregation led to the formation of an emulsion gel showing no signs of creaming. Confocal laser scanning microscopy showed that the emulgels were formed by a continuous network of CNC in which the randomly distributed droplets were embedded. The gel stiffness was measured with oscillatory shear rheology and found to increase strongly with increasing CNC concentration ( C). The dispersed droplets were elastically active and increased the gel stiffness at low C. However, up to C = 10 g/L, the yield stress was too small to inhibit the flow when the gels were tilted. At C < 2 g/L, creaming was observed until the network of connected droplets became sufficiently dense to be strong enough to resist buoyancy.
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Self-assembly of native glycinin at room temperature was investigated as a function of the pH and the NaCl concentration. Microphase separation leading to the formation of dense protein microdomains was observed by confocal laser scanning microscopy. Depending on the conditions, the microdomains coalesced into a continuous protein rich phase or associated into large clusters. Addition of ß-conglycinin inhibited phase separation and reduced the pH range in which it occurred. Microdomains of glycinin that were formed in the presence of 0.1 M NaCl transformed into hollow stable cross-linked microcapsules when heated above 60 °C with diameters between 3 and 30 µm depending on the protein concentration and a shell thickness between 1.0 and 1.4 µm. The microcapsules were stable to dilution in salt free water, whereas microdomains formed at room temperature redispersed. Microdomains formed in mixtures with ß-conglycinin did not transform into microcapsules, but they became stable cross-linked homogeneous microgels.
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Cápsulas , Globulinas/química , Cloruro de Sodio/química , Proteínas de Soja/química , Cápsulas/síntesis química , Cápsulas/química , Tamaño de la PartículaRESUMEN
The phase diagram of mixtures of xyloglucan (XG) and amylopectin (AMP) in aqueous solution is presented. Water-in-water emulsions prepared from mixtures in the two-phase regime were studied in detail, and the interfacial tension was determined. It is shown that the emulsions can be stabilized by addition of ß-lactoglobulin microgels (ßLGm), but only at pH ≤ 5.0. Excess ßLGm preferentially entered the AMP phase at pH > 5.0 and the XG phase at lower pH. The inversion was caused by adsorption of XG onto ßLGm that started below pH 5.5. It is shown that modification of the surface of particles by coating with polysaccharides is a potential lever to control stabilization of water-in-water emulsions.
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Amilopectina/química , Glucanos/química , Lactoglobulinas/química , Xilanos/química , Emulsiones , Fluoresceína-5-Isotiocianato , Geles , Concentración de Iones de Hidrógeno , Rodaminas , Tensión Superficial , Agua/químicaRESUMEN
Protein fibrils, microgels, and fractal aggregates were produced by heating solutions of ß-lactoglobulin (ß-lg) under different conditions. The effect of the protein particle morphology on the stability and the structure of water-in-water (W/W) emulsions was studied for mixtures of poly(ethylene oxide) (PEO) and dextran. The protein particles partition to the dextran phase at pH 7.0 where they have a net negative charge, but they prefer the PEO phase at pH 3.0 where they have a net positive charge. The effect of partitioning on the stability and the structure of water-in-water (W/W) emulsions was studied by comparing emulsions at pH 3.0 with those at pH 7.0. The protein particle morphology and preference for one phase or the other are shown to have important consequences for the stability and the structure of the emulsions. Fibrils were found to be the most effective stabilizers at pH 7.0, whereas fractals were most effective at pH 3.0. The average droplet size obtained from confocal scanning laser microscopy was for most systems between 10 and 5 µm but was notably smaller for emulsions with fractals at pH 3.0.
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Dextranos/química , Lactoglobulinas/química , Polietilenglicoles/química , Agua/química , Emulsiones , Concentración de Iones de HidrógenoRESUMEN
Cellulose nanocrystals (CNC) are rod-like biosourced nanoparticles that are widely used in a range of applications. Charged CNC was obtained by acid extraction from cotton and dispersed in aqueous solution using ultrasound and characterized by light scattering. Aggregation and gelation of CNC induced by addition of NaCl was investigated by light scattering as a function of the NaCl concentration (30-70 mM), the CNC concentration (0.5-5 g/L), and the temperature (10-60 °C). Formation of fractal aggregates was observed that grow with time until they percolate and form a weak system spanning network. The aggregation rate and gel time were found to decrease very steeply with increasing NaCl concentration and more weakly with increasing CNC concentration. A decrease of the gel time was also observed with increasing temperature for T > 20 °C. The structure of the CNC networks was studied using confocal laser scanning microscopy and light scattering. The local structure of the networks was fractal and reflected that of the constituting aggregates. The gels were homogeneous on length scales larger than the correlation length, which decreased with increasing CNC concentration. The CNC gels flowed when tilted for C < 12 g/L and sedimentation was observed macroscopically for C < 4 g/L due to the collapse of the CNC network under gravity. The speed and extent of sedimentation was investigated as a function of the ionic strength and the CNC concentration. Gelled CNC could be completely redispersed by applying ultrasound.
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Celulosa/química , Geles/química , Nanopartículas/química , Soluciones/química , Celulosa/síntesis química , Celulosa/ultraestructura , Dispersión Dinámica de Luz , Geles/síntesis química , Cinética , Nanopartículas/ultraestructura , Concentración Osmolar , Temperatura , Agua/químicaRESUMEN
Heat-induced aggregation and gelation of aqueous solutions of whey protein isolate (WPI) in the presence of sodium caseinate (SC) and CaCl2 was studied at pH 6.6. The effect of adding SC (0-100 g/L) on the structure of the aggregates and the gels was investigated by light scattering and confocal laser scanning microscopy at different CaCl2 concentration ([CaCl2] = 0-30 mM). The gelation process was studied by oscillatory shear rheology. At the whey protein concentrations studied here (34 and 60 g/L), no gels were formed in the absence of CaCl2 and SC. However, WPI solutions gelled above a critical CaCl2 concentration that increased with increasing SC concentration. In the absence of CaCl2, WPI gels were formed only above a critical SC concentration. The critical SC concentration needed to induce WPI gelation decreased weakly when CaCl2 was added. In an intermediate range of CaCl2 concentrations, gels were formed both at low and high SC concentrations, but not at intermediate SC concentrations. Finally, at high CaCl2 concentrations gels were formed at all SC concentrations. The gelation rate and the gel structure of the gels formed at low and high casein concentrations were very different. The effect of SC on the thermal gelation of WPI was interpreted by competition for Ca2+, a chaperon effect, and microphase separation.
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Calcio/química , Reología , Proteína de Suero de Leche/química , Caseínas/química , Caseínas/farmacología , Geles/química , Calor , Concentración de Iones de Hidrógeno , Soluciones/química , Proteína de Suero de Leche/antagonistas & inhibidoresRESUMEN
Solutions of the globular whey protein ß-lactoglobulin (ß-lg) were heated at different protein concentrations leading to the formation of polydisperse fractal aggregates with different average sizes. The structure of the solutions was analyzed with light scattering as a function of the protein concentration. The osmotic compressibility and the dynamic correlation length decreased with increasing concentration and became independent of the aggregate size in dense suspensions. The results obtained for different aggregate sizes could be superimposed after normalizing the concentration with the overlap concentration. Dense suspensions of fractal protein aggregates are strongly interpenetrated and can be visualized as an ensemble of fractal 'blobs'. The viscosity of the heated ß-lg solutions increased extremely sharply above 80 g L(-1) and diverged at 98 g L(-1), mainly due to the sharply increasing aggregate size. At a fixed aggregate size, the viscosity increased initially exponentially with increasing concentration and then diverged. The increase was stronger when the aggregates were larger, but the dependence of the viscosity on the aggregate size was weaker than that of the osmotic compressibility and the dynamic correlation length. The concentration dependence of the viscosity of solutions of fractal ß-lg aggregates is much stronger than that of homogeneous ß-lg microgels. The behavior of fractal aggregates formed by whey protein isolates was similar.
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Geles/química , Lactoglobulinas/química , Agregado de Proteínas , Animales , Calor , Reología , Viscosidad , Proteína de Suero de Leche/químicaRESUMEN
Interpenetrated gels of biocompatible polysaccharides alginate and silanized hydroxypropyl methyl cellulose (Si-HPMC) have been studied in order to assess their potential as scaffolds for the regeneration of human tissues. Si-HPMC networks were formed by reduction of the pH to neutral and alginate networks were formed by progressive in situ release of Ca(2+). Linear and non-linear mechanical properties of the mixed gels at different polymer and calcium concentrations were compared with those of the corresponding single gels. The alginate/Si-HPMC gels were found to be stiffer than pure Si-HPMC gels, but weaker and more deformable than pure alginate gels. No significant difference was found for the maximum stress at rupture measured during compression for all these gels. The degrees of swelling or contraction in excess water at pH 7 as well as the release of Ca(2+) was measured as a function of time. Pure alginate gels contracted by as much as 50 % and showed syneresis, which was much reduced or even eliminated for mixed gels. The important release of Ca(2+) upon ageing for pure alginate gels was much reduced for the mixed gels. Furthermore, results of cytocompatibility assays indicated that there was no cytotoxicity of Si-HPMC/alginate hydrogels in 2D and 3D culture of human SW1353 cells. The results show that using interpenetrated Si-HPMC/alginate gels has clear advantages over the use of single gels for application in tissue regeneration.
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Alginatos/química , Regeneración Tisular Dirigida/métodos , Hidrogeles/química , Andamios del Tejido/química , Materiales Biocompatibles , Línea Celular , Supervivencia Celular , Ácido Glucurónico/química , Ácidos Hexurónicos/química , Humanos , Derivados de la Hipromelosa/química , Ensayo de Materiales , Silanos/química , Factores de Tiempo , AguaRESUMEN
The structure and stability of water-in-water emulsions was investigated in the presence of spherical, pH-sensitive microgels. The emulsions were formed by mixing aqueous solutions of dextran and PEO. The microgels consisted of cross-linked, synthetic polymers with a radius that steeply increased from 60 to 220 nm with increasing pH within a narrow range around 7.0. At all pH values between 5.0 and 7.5, the microgels were preferentially situated at the interface, but only in a narrow range between pH 7.0 and 7.5, the emulsions were stable for at least 1 week. The droplet size was visualized with confocal laser scanning microscopy and was found to be smallest in the stable pH range. Emulsions could be stabilized or destabilized by small changes of the pH. Addition of small amounts of salt led to a shift of the pH range where the emulsions were stable. The effects of varying the microgel concentration and the polymer composition were investigated.
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Dynamic mechanical properties of aqueous solutions of hydroxypropyl methyl cellulose (HPMC) were investigated using oscillatory shear measurements. The structure was investigated with light scattering. A systematic investigation of the frequency dependence of the shear moduli showed that HPMC forms two distinct interpenetrating networks. A transient network is formed above about 0.3 wt % by reversible cross-linking of the chains. The elastic modulus of this network is independent of the temperature, but increases linearly with the concentration. An independent permanent network is formed involving a small fraction of the polymers and has an elastic modulus that increases with increasing temperature. Its elastic modulus is history dependent and evolves slowly with time. The transient network collapses at a critical temperature where micro phase separation occurs, but the permanent network is not influenced by this phenomenon. Light scattering showed that the pore size of the transient network is less than 40 nm, while probe diffusion measurements showed that the pore size of the permanent network is larger than 1 µm.
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Metilcelulosa/análogos & derivados , Derivados de la Hipromelosa , Metilcelulosa/análisis , Metilcelulosa/química , Resistencia al CorteRESUMEN
The effect of dynamic arm exchange on the crystallization and the jamming of multiarm starlike polymers was studied using small angle x-ray scattering and rheology. Poly(ethylene oxide) end capped with a small hydrophobic chain formed spherical micelles in water. Dynamic arm exchange allowed rapid crystallization and caused a discontinuous liquid-solid transition in dense suspensions after cooling. It is shown here that this is caused by spontaneous fine-tuning of the number of arms per micelle (f). Elimination of arm exchange by in situ photo-cross-linking of the core did not influence the behavior when f was at the optimum value. However, suboptimal values of f inhibited crystallization and the liquid-solid transition.