Phase separation in aqueous mixtures of hydrophobically modified cellulose derivatives with their nonmodified analogues

Polyelectrolyte complexes (PECs) offer enormous material tunability and desirable functionalities, and consequently have found broad utility in biomedical and materials industries. Poly(acrylic acid) (PAA) and poly(allylamine hydrochloride) (PAH) are one of the most commonly used pairings to form PECs. However, various aspects of the phase behavior of PAA-PAH complexes have not been sufficiently quantified. We present a comprehensive experimental study depicting the binodal phase boundaries for the PAA-PAH complexes prepared in acidic, neutral and basic conditions using thermogravimetric analysis, turbidimetry and optical microscopy. In neutral and basic conditions, phase behaviors of the complexes were largely similar to each other and followed general expectations of PEC phase behavior, except for unusually high salt resistance with stable complexes observed up to 4 M NaCl concentrations. In acidic conditions, a remarkably different phase behavior of the PAA-PAH complexes was observed. The polymer content in the complex phase increased initially followed by an expected decrease as salt was added to the complexes. This behavior may result from a combination of associative phase separation of PAA and PAH chains, influenced by electrostatic interactions, and segregative phase separation which can be ascribed to the influence of a combination of the hydrophobic interactions of the aliphatic polymer backbone and the interpolymer hydrogen bonding of un- ionized acrylic monomer units. Our systematic investigations detailing these discrepancies in the PAA-PAH phase behavior are expected to clarify the inconsistencies among the reports in the literature and inform the materials design strategies for practical use of the PAA-PAH complexes and multilayer assemblies.

Polyelectrolyte complexes (PECs) offer enormous material tunability and desirable functionalities, and consequently have found broad utility in biomedical and material industries. While poly(acrylic acid) (PAA) and poly(allylamine hydrochloride) (PAH) are a commonly used pairing, various aspects of the phase behavior of PAA–PAH complexes have not been sufficiently quantified. We present a comprehensive experimental study depicting the binodal phase boundaries for the PAA–PAH complexes prepared under acidic, neutral, and basic conditions using thermogravimetric analysis, turbidimetry, and optical microscopy. Under neutral and basic conditions, phase behaviors of the complexes were largely similar to one another and followed general expectations of PEC phase behavior, except for unusually high resistance to disruption of the complex with added salt. Stable complexes are observed up to 4 M NaCl concentrations. Under acidic conditions, strikingly different phase behaviors of the PAA–PAH complexes were observed. The polymer content in the complex phase increased initially, followed by an expected decrease as salt was added to the complexes. This behavior may result from a combination of associative phase separation of PAA and PAH chains, influenced by electrostatic interactions, and segregative phase separation, which can be ascribed to the influence of a combination of the hydrophobic interactions of the aliphatic polymer backbone and the interpolymer hydrogen bonding of un-ionized acrylic monomer units. Our systematic investigations over a range of pH detailing these discrepancies in the PAA–PAH phase behavior are expected to clarify the inconsistencies among the reports in the literature and provide the material design strategies for practical use of the PAA–PAH complexes and multilayer assemblies.

Chemical Structure Analysis of Starch and Cellulose Derivatives

The nature and kinetics of phase separation processes of solutions of cellulose acetate (degree of substitution, 2.5) in mixtures of dioxane and water are studied by differential scanning calorimetry (DSC). The thermograms on heating show small endothermic effects, detectable only after prolonged aging below the phase separation temperature. Experiments in two regions of the ternary diagram are of interest for the description of the formation mechanism of asymmetric membranes viz., (1) at high polymer and high concentrations and low concentrations of nonsolvent (gelation); (2) at lower polymer concentrations of nonsolvent (liquid–liquid separation followed by gelation). Endothermic effects after prolonged aging are found at high polymer concentrations (≥40%). These results demonstrate that gelation is very slow in these systems. At lower concentrations of polymer and high concentrations of nonsolvent (up to 40%) a more rapid type of phase separation can be observed visually on cooling. The temperature where turbidity sets in (the cloud point) is independent of the rate of cooling. In DSC experiments no exothermic effect is found on cooling. Again, after aging an endothermic effect is present. The endothermic peak, which is situated below the cloud point, is probably a result of melting of the gelled concentrated phase.

Different ionic liquids containing the cation such as 1-N-butyl-3-methylimida-zolium (Bmim+) are able to efficiently dissolve cellulose. The ability of ionic liquids to truly dissolve cellulose is significant when cellulose derivatization is attempted. A series of experiments on etherification (carboxymethylation) of cellulose was performed, using both the conventional suspension approach (slurry) with 2-propanol as the principal reaction media and a totally homogenous reaction approach utilizing ionic liquids as a reaction media capable of dissolving cellulose. It was observed that a pre-treatment with the ionic liquid 1-N-butyl-3-methylimidazolium iodide ([Bmim][I]) seems to promote substitution in line with the conventional, heterogeneous suspension process. Under carefully chosen reaction conditions, a higher degree of substitution was obtained when wetting the cellulose with [Bmim][I] prior to classical derivatization than without this pre-treatment. It was also observed that the substitution pattern was changing upon use of the ionic liquid [Bmim][I]. Upon a totally homogenous etherification, it was found that the ionic liquid 1-N-butyl-3-methylimidazolium acetate ([Bmim][oAc]) gave the highest degree of substitution. The product obtained was water-soluble and had a DS (degree of substitution) of 0.59. The substitution pattern of the products obtained from the homogenous reactions follow the same substitution pattern as the products obtained from the conventional suspension process. This indicates that the properties of the products are in line with products prepared via the conventional reaction route.

Cellulose derivatives have attracted attention as environmentally friendly materials that can exhibit a cholesteric liquid crystal (CLC) phase with visible light reflection. Previous reports have shown that the chemical structures and the degrees of substitution of cellulose derivatives have significant influence on their reflection properties. Although many studies have been reported on CLC using ethyl cellulose (EC) derivatives in which the hydroxy groups are esterified, there have been no studies on EC derivatives with etherified side chains. In this article, we optimized the Williamson ether synthesis to introduce pentyl ether groups in the EC side chain. The degree of substitution with pentyl ether group (DSPe), confirmed via 1H-NMR spectroscopic measurements, was controlled using the solvent and the base concentration in this synthesis. All the etherified EC derivatives were soluble in methacrylic acid (MAA), allowing for the preparation of lyotropic CLCs with visible reflection. Although the reflection peak of lyotropic CLCs generally varies with temperature, the reflection peak of lyotropic CLCs of completely etherified EC derivatives with MAA could almost be preserved in the temperature range from 30 to 110 °C even without the aid of any crosslinking. Such thermal stability of the reflection peak of CLCs may be greatly advantageous for fabricating new photonic devices with eco-friendliness.

The pH-triggered transitional phase behaviour of Pickering emulsions stabilised by hydrophobised bacterial cellulose (BC) is reported in this work. Neat BC was esterified with acetic (C2–), hexanoic (C6–) and dodecanoic (C12–) acids, respectively. We observed that C6– and C12–BC stabilised emulsions exhibited a pH-triggered reversible transitional phase separation. Water-in-toluene emulsions containing of 60vol.% dispersed phase stabilised by C6– and C12–BC were produced at pH 5. Lowering the pH of the aqueous phase to 1 did not affect the emulsion type. Increasing the pH to 14, however, caused the emulsions to phase separate. This phase separation was caused by electrostatic repulsion between modified BC due to dissociable acidic surface groups at high pH, which lowered the surface coverage of the water droplets by modified BC. When the pH was re-adjusted to 1 again, w/o emulsions re-formed for C6– and C12–BC stabilised emulsions. C2–BC stabilised emulsions, on the other hand, underwent an irreversible pH-triggered transitional phase separation and inversion. This difference in phase behaviour between C2–BC and C6–/C12–BC was attributed to the hydrolysis of the ester bonds of C2–BC at high pH. This hypothesis is in good agreement with the measured degree of surface substitution (DSS) of modified BC after the pH-triggered experiments. The DSS of C2–BC decreased by 20% whilst the DSS remained constant for C6– and C12–BC.

Analysis of the carbon-13 n.m.r. spectrum of hydrolyzed O-(carboxymethyl)cellulose: monomer composition and substitution patterns

The confinement of colloidal particles at liquid interfaces offers many opportunities for materials design. Adsorption is driven by a reduction of the total free energy as the contact area between the two liquids is partially replaced by the particle. From an application point of view, particle-stabilized interfaces form emulsions and foams with superior stability. Liquid interfaces also effectively confine colloidal particles in two dimensions and therefore provide ideal model systems to fundamentally study particle interactions, dynamics, and self-assembly. With progress in the synthesis of nanomaterials, more and more complex and functional particles are available for such studies. In this Account, we focus on poly(N-isopropylacrylamide) nanogels and microgels. These are cross-linked polymeric particles that swell and soften by uptaking large amounts of water. The incorporated water can be partially expelled, causing a volume phase transition into a collapsed state when the temperature is increased above approximately 32 °C. Soft microgels adsorbed to liquid interfaces significantly deform under the influence of interfacial tension and assume cross sections exceeding their bulk dimensions. In particular, a pronounced corona forms around the microgel core, consisting of dangling chains at the microgel periphery. These polymer chains expand at the interface and strongly affect the interparticle interactions. The particle deformability therefore leads to a significantly more complex interfacial phase behavior that provides a rich playground to explore structure formation processes. We first discuss the characteristic "fried-egg" or core-corona morphology of individual microgels adsorbed to a liquid interface and comment on the dependence of this interfacial morphology on their physicochemical properties. We introduce different theoretical models to describe their interfacial morphology. In a second part, we introduce how ensembles of microgels interact and self-assemble at liquid interfaces. The core-corona morphology and the possibility to force these elements into overlap upon compression results in a complex phase behavior with a phase transition between microgels with extended and collapsed coronae. We discuss the influence of the internal particle architecture, also including core-shell microgels with rigid cores, on the phase behavior. Finally, we present new routes for the realization of more complex structures, resulting from multiple deposition protocols and from engineering the interaction potential of the individual particles.

Aromatic rings are a common feature of biological and synthetic polymers that form polyelectrolyte complexes and coacervates. These functional groups can engage in cation-π interactions; however, the impact of such interactions on the physical properties of polyelectrolyte complex materials is not well understood. Here, we investigate the effect of cation-π interactions on the phase behavior and viscoelasticity of polyelectrolyte complexes of poly-(styrenesulfonate) (PSS) and poly-(diallyldimethylammonium), which contain aromatic functional groups on every repeat unit of the PSS polyanion. We prepare samples with matched polymer and/or salt concentrations using salts with different cation-π interaction strengths. Characterization by turbidity, thermogravimetric analysis, and rheology reveals that salts that engage in stronger cation-π interactions destabilize coacervation and speed up the viscoelastic relaxation of the materials. By contrast, removing the aromatic ring by replacing PSS with poly-(2-acrylamido-2-methylpropanesulfonate removes the sensitivity of the phase behavior and viscoelasticity of the complexes to the cation-π interaction strength of the salt. These results reveal that cation-π interactions play a significant role in determining the phase behavior and viscoelasticity of polyelectrolyte complexes and coacervates made from polymers with aromatic functional groups and suggest that cation-π interactions may be a useful molecular handle for tuning coacervate properties.

Electrochemical Oscillation in Li-Ion Batteries

Performance of cellulose derivatives in deep-fried battered snacks: Oil barrier and crispy properties

Esters of cellulose with trifluoroethoxy acetic acid (TFAA) were prepared in homogeneous phase using a mixed anhydride with p-toluenesulfonic acid. Esters with low degree of substitution (DS), and with DS rising from 0 to 3, had hydrophobic character that prevented the usual association with moisture, which is otherwise typical of cellulose esters with low DS. Cellulose trifluoroethoxy acetate (CT) had Tg's declining by about 40 °C per DS-unit (from 160 to 41 °C) as DS rose from 1 to 3. Mixed esters, cellulose derivatives with acetate and trifluoroethoxy acetate substituents (CAT), exhibited glass-to-rubber and melting transitions by DSC. A linear relationship between both Tg and Tm with respect to DS was recorded with the Tg and Tm separated by 30° to 40 °C. This is consistent with cellulose esters described elsewhere. Surprisingly, the Tg's of CT and CAT were found to be identical when the DS was equivalent to the DS of the fluoro substituents (DSF). © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 486–494, 2000

Influence of the guests, the type and degree of substitution on inclusion complex formation of substituted β-cyclodextrins

Partitioning and phase equilibria of PEGylated excipients in fluorinated liquids