Bulk and Interfacial Behavior of Potato Protein-Based Microgels.

This study aims to understand the bulk and interfacial performance of potato protein microgels. Potato protein (PoP) was used to produce microgels of submicrometer diameter via a top-down approach of thermal cross-linking followed by high-shear homogenization of the bulk gel. Bulk "parent" gels were formed at protein concentrations [PoP] = 5-18 wt %, which subsequently varied in their bulk shear elastic modulus (G') by several orders of magnitude (1-100 kPa), G' increasing with increasing [PoP]. The PoP microgels (PoPM) formed from these parent gels had diameters varying between 100 and 300 nm (size increasing with increasing G' and [PoP]), as observed via dynamic light scattering and atomic force microscopy (AFM) of PoPM adsorbed onto silicon. Interfacial rheology (interfacial shear storage and loss moduli, Gi' and Gi″) and interfacial tension (γ) of adsorbed films of PoP (i.e., nonheated PoP) and PoPM (both at tetradecane-water interfaces) were also studied, as well as the bulk rheology of the PoPM dispersions. The results showed that PoPM dispersions (at 50 vol %) had significantly higher bulk viscosity and shear thinning properties compared to the nonmicrogelled PoP at the same overall [PoP], but the bulk rheological behavior was in sharp contrast to the interfacial rheological performance, where Gi' and Gi″ of PoP were higher than for any of the PoPM. This suggests that the deformability and size of the microgels were key in determining the interfacial rheology of the PoPM. These findings may be attributed to the limited capacity for "unfolding" and lateral interactions of the larger PoPM at the interface, which are presumed to be stiffer due to their production from the strongest PoP gels. Our study further confirmed that heating and cooling the adsorbed films of PoPM after their adsorption showed little change, highlighting that hydrogen bonding was limited between the microgel particles.

Demulsification of Pickering emulsions: advances in understanding mechanisms to applications.

Pickering emulsions are ultra-stable dispersions of two immiscible fluids stabilized by solid or microgel particles rather than molecular surfactants. Although their ultra-stability is a signature performance indicator, often such high stability hinders their demulsification, i.e., prevents the droplet coalescence that is needed for phase separation on demand, or release of the active ingredients encapsulated within droplets and/or to recover the particles themselves, which may be catalysts, for example. This review aims to provide theoretical and experimental insights on demulsification of Pickering emulsions, in particular identifying the mechanisms of particle dislodgment from the interface in biological and non-biological applications. Even though the adhesion of particles to the interface can appear irreversible, it is possible to detach particles via (1) alteration of particle wettability, and/or (2) particle dissolution, affecting the particle radius by introducing a range of physical conditions: pH, temperature, heat, shear, or magnetic fields; or via treatment with chemical/biochemical additives, including surfactants, enzymes, salts, or bacteria. Many of these changes ultimately influence the interfacial rheology of the particle-laden interface, which is sometimes underestimated. There is increasing momentum to create responsive Pickering particles such that they offer switchable wettability (demulsification and re-emulsification) when these conditions are changed. Demulsification via wettability alteration seems like the modus operandi whilst particle dissolution remains only partially explored, largely dominated by food digestion-related studies where Pickering particles are digested using gastrointestinal enzymes. Overall, this review aims to stimulate new thinking about the control of demulsification of Pickering emulsions for release of active ingredients associated with these ultra-stable emulsions.

γ-Cyclodextrin Metal-Organic Frameworks: Do Solvents Make a Difference?

Conventionally, methanol is the solvent of choice in the synthesis of gamma-cyclodextrin metal-organic frameworks (γ-CD-MOFs), but using ethanol as a replacement could allow for a more food-grade synthesis condition. Therefore, the aim of the study was to compare the γ-CD-MOFs synthesised with both methanol and ethanol. The γ-CD-MOFs were characterised by scanning electron microscopy (SEM), surface area and pore measurement, Fourier transform infrared spectroscopy (FTIR) and powder X-ray diffraction (PXRD). The encapsulation efficiency (EE) and loading capacity (LC) of the γ-CD-MOFs were also determined for curcumin, using methanol, ethanol and a mixture of the two as encapsulation solvent. It was found that γ-CD-MOFs synthesised by methanol and ethanol do not differ greatly, the most significant difference being the larger crystal size of γ-CD-MOFs crystallised from ethanol. However, the change in solvent significantly influenced the EE and LC of the crystals. The higher solubility of curcumin in ethanol reduced interactions with the γ-CD-MOFs and resulted in lowered EE and LC. This suggests that different solvents should be used to deliberately manipulate the EE and LC of target compounds for better use of γ-CD-MOFs as their encapsulating and delivery agents.

Improved Antioxidant and Mechanical Properties of Food Packaging Films Based on Chitosan/Deep Eutectic Solvent, Containing Açaí-Filled Microcapsules.

The development of biobased antioxidant active packaging has been valued by the food industry for complying with environmental and food waste concerns. In this work, physicochemical properties for chitosan composite films as a potential active food packaging were investigated. Chitosan films were prepared by solution casting, plasticized with a 1:2 choline chloride: glycerol mixture as a deep eutectic solvent (DES) and incorporated with 0-10% of optimized açaí oil polyelectrolyte complexes (PECs). Scanning electron microscopy and confocal laser scanning microscopy revealed that the chitosan composite films were continuous and contained well-dispersed PECs. The increased PECs content had significant influence on the thickness, water vapor permeability, crystallinity (CrD) and mechanical and dynamic behavior of the films, as well as their antioxidant properties. The tensile strength was reduced in the following order: 11.0 MPa (control film) > 0.74 MPa (5% DES) > 0.63 MPa (5% DES and 5% PECs). Films containing 2% of PECs had an increased CrD, ~6%, and the highest elongation at break, ~104%. Films with 1% of PECs displayed the highest antioxidant properties against the ABTS and DPPH radicals, ~6 and ~17 mg TE g-1, respectively, and highest equivalent polyphenols content (>0.5 mg GAE g-1). Films with 2% of particles were not significantly different. These results suggested that the chitosan films that incorporated 1-2% of microparticles had the best combined mechanical and antioxidant properties as a potential material for food packaging.

Synergistic Interactions of Plant Protein Microgels and Cellulose Nanocrystals at the Interface and Their Inhibition of the Gastric Digestion of Pickering Emulsions.

It is possible that Pickering emulsions can optimize the transport of nutraceuticals, pharmaceuticals, and other bioactive compounds in human physiology. So-called ultrastable Pickering emulsions are often destabilized in the gastric digestion regime if the particles are proteinaceous in nature. The present study seeks to test how the interfacial structure can be engineered via synergistic particle-particle interactions to impact the gastric coalescence of Pickering emulsions. In this study, we designed plant-based protein-particle-stabilized oil-in-water emulsions (PPM-E, with 20 wt % sunflower oil) via pea protein microgels (PPM at 1 wt %). The PPM hydrodynamic diameter is ∼250 nm. In vitro gastric digestion of PPM-E confirmed droplet coalescence within 30 min of pepsin addition. Supposedly surface-active cellulose nanocrystals (CNCs, 1-3 wt %) were added to PPM-E at pH 3.0 to determine if they could act as a barrier to interfacial pepsinolysis due to the CNC and PPM being oppositely charged at this gastric pH value. A combination of confocal microscopy, zeta potential, and Langmuir trough measurements suggested that CNCs and PPMs might form a combined layer at the O/W interface, owing to the electrostatic attraction between them. CNCs at >2 wt % inhibited the pepsinolyis of the adsorbed PPM film and thus droplet coalescence. However, increasing concentrations of CNC also increased the bulk viscosity of the PPM-E and eventually caused gelation of the emulsions, which would also delay their gastric breakdown. In conclusion, tuning the bulk and interfacial structure of Pickering emulsions via synergistic interactions between two types of particles could be an effective strategy to modify the enzymatic breakdown of such emulsions, which would have important applications in pharmaceuticals, foods, and other soft-matter applications.

On the Origin of Seemingly Nonsurface-Active Particles Partitioning between Phase-Separated Solutions of Incompatible Nonadsorbing Polymers and Their Adsorption at the Phase Boundary.

We have computed the free energy per unit area (i.e., interfacial tension) between a solid surface and two coexisting polymer solutions, where there is no specific interaction between the particles and either polymer, via self-consistent field calculations. Several different systems have been studied, including those where the two polymers differ in molecular weight (Mw) by a factor of ∼2 or where the polymers have the same Mw, but one set of chains is branched with the other linear. In the absence of any enthalpic contribution resulting from adsorption on the solid particle surface, the differences in the free energy per unit area resulting from the polymer-depleted regions around the particles in the two coexisting phases are found to be ∼1 µN m-1. Although this value may seem rather small, this difference is more than capable of inducing the partitioning of particles of 100 nm in size (or larger) into the phase with the lower interfacial free energy at the solid surface. By examining the density profile variation of the polymers close to the surface, we can also infer information about the wettability and contact angle (θ) of solid particles at the interface between the two coexisting phases. This leads to the conclusion that for all systems of this type, when the incompatibility between the two polymers is sufficiently large, θ will be close to 90°.

Water-in-Oil Pickering Emulsions Stabilized by Synergistic Particle-Particle Interactions.

Here, we report a novel "double Pickering stabilization" of water-in-oil (W/O) emulsions, where complex formation at the interface between Pickering polyphenol particles adsorbing from the oil side and whey protein microgel (WPM) particles coadsorbing from the aqueous side of the interface is investigated. The interfacial complex formation was strongly dependent on the concentration of WPM particles. At low WPM concentrations, both polyphenol crystals and WPM particles are present at the interface and the water droplets were stabilized through their synergistic action, while at higher concentrations, the WPM particles acted as "colloidal glue" between the water droplets and polyphenol crystals, enhancing the water droplet stability for more than 90 days and prevented coalescence. Via this mechanism, the addition of WPM up to 1 wt % gave a significant improvement in the stability of the W/O emulsions, allowing an increase to a 20 wt % water droplet fraction. The evidence suggests that the complex was probably formed due to electrostatic attraction between oppositely charged polyphenol Pickering particles on the oil side of the interface and WPM Pickering particles mainly on the aqueous side of the interface. Interfacial shear viscosity measurements and monolayer (Langmuir trough) experiments at the air-water interface provided further evidence of this strengthening of the film due to the synergistic particle-particle complex formation at the interface.

Water-In-Oil Pickering Emulsions Stabilized by Water-Insoluble Polyphenol Crystals.

In recent years, there has been a resurgence of interest in Pickering emulsions because of the recognition of the unique high steric stabilization provided by particles at interfaces. This interest is particularly keen for water-in-oil (W/O) emulsions because of the limited range of suitable Pickering stabilizers available. We demonstrate for the first time that W/O emulsions can be stabilized by using crystals from naturally occurring polyphenols (curcumin and quercetin particles). These particles were assessed based on their size, microstructure, contact angle, interfacial tension, and ζ-potential measurements in an attempt to predict the way that they act as Pickering stabilizers. Static light-scattering results and microstructural analysis at various length scales [optical microscopy, confocal laser scanning microscopy (CLSM), and scanning electron microscopy (SEM)] confirmed that the quercetin particles has a nearly perfect crystalline rod shape with a high aspect ratio; that is, the ratio of length to diameter ( L/ D) was ca. 2.5:1-7:1. On the other hand, the curcumin particles ( d3,2 = 0.2 µm) had a polyhedral shape. Droplet sizing and CLSM revealed that there was an optimum concentration (0.14 and 0.25 wt % for quercetin and curcumin, respectively) where smaller water droplets were formed ( d3,2 ≈ 6 µm). Interfacial shear viscosity (η i) measurements confirmed that a stronger film was formed at the interface with quercetin particles (η i ≈ 25 N s m-1) rather than with curcumin particles (η i ≈ 1.2 N s m-1) possibly because of the difference in the shape and size of the two crystals. This study provides new insights into the creation of Pickering W/O emulsions with polyphenol crystals and may lead to various soft matter applications where Pickering stabilization using biocompatible particles is a necessity.

Comparison of blueberry powder produced via foam-mat freeze-drying versus spray-drying: evaluation of foam and powder properties.

BACKGROUND: Blueberry juice powder was developed via foam-mat freeze-drying (FMFD) and spray-drying (SD) via addition of maltodextrin (MD) and whey protein isolate (WPI) at weight ratios of MD/WPI = 0.4 to 3.2 (with a fixed solids content of 5 wt% for FMFD and 10 wt% for SD). Feed rates of 180 and 360 mL h-1 were tested in SD. The objective was to evaluate the effect of the drying methods and carrier agents on the physical properties of the corresponding blueberry powders and reconstituted products. RESULTS: Ratios of MD/WPI = 0.4, 1.0 and 1.6 produced highly stable foams most suitable for FMFD. FMFD gave high yields and low bulk density powders with flake-like particles of large size that were also dark purple with high red values. SD gave low powder recoveries. The powders had higher bulk density and faster rehydration times, consisting of smooth, spherical and smaller particles than in FMFD powders. The SD powders were bright purple but less red than FMFD powders. Solubility was greater than 95% for both FMFD and SD powders. CONCLUSION: The FMFD method is a feasible method of producing blueberry juice powder and gives products retaining more characteristics of the original juice than SD. © 2017 Society of Chemical Industry.

Aqueous Lubrication, Structure and Rheological Properties of Whey Protein Microgel Particles.

Aqueous lubrication has emerged as an active research area in recent years due to its prevalence in nature in biotribological contacts and its enormous technological soft-matter applications. In this study, we designed aqueous dispersions of biocompatible whey-protein microgel particles (WPM) (10-80 vol %) cross-linked via disulfide bonding and focused on understanding their rheological, structural and biotribological properties (smooth polydimethylsiloxane (PDMS) contacts, Ra < 50 nm, ball-on-disk set up). The WPM particles (Dh = 380 nm) displayed shear-thinning behavior and good lubricating performance in the plateau boundary as well as the mixed lubrication regimes. The WPM particles facilitated lubrication between bare hydrophobic PDMS surfaces (water contact angle 108°), leading to a 10-fold reduction in boundary friction force with increased volume fraction (ϕ ≥ 65%), largely attributed to the close packing-mediated layer of particles between the asperity contacts acting as "true surface-separators", hydrophobic moieties of WPM binding to the nonpolar surfaces, and particles employing a rolling mechanism analogous to "ball bearings", the latter supported by negligible change in size and microstructure of the WPM particles after tribology. An ultralow boundary friction coefficient, µ ≤ 0.03 was achieved using WPM between O2 plasma-treated hydrophilic PDMS contacts coated with bovine submaxillary mucin (water contact angle 47°), and electron micrographs revealed that the WPM particles spread effectively as a layer of particles even at low ϕ∼ 10%, forming a lubricating load-bearing film that prevented the two surfaces from true adhesive contact. However, above an optimum volume fraction, µ increased in HL+BSM surfaces due to the interpenetration of particles that possibly impeded effective rolling, explaining the slight increase in friction. These effects are reflected in the highly shear thinning nature of the WPM dispersions themselves plus the tendency for the apparent viscosity to fall as dispersions are forced to very high volume fractions. The present work demonstrates a novel approach for providing ultralow friction in soft polymeric surfaces using proteinaceous microgel particles that satisfy both load bearing and kinematic requirements. These findings hold great potential for designing biocompatible particles for aqueous lubrication in numerous soft matter applications.

Experimental Modeling of Flavonoid-Biomembrane Interactions.

Nonspecific interactions of flavonoids with lipids can alter the membrane's features (e.g., thickness and fluctuations) as well as influence their therapeutic potentials. However, relatively little is known about the details of how flavonoids interact with lipid components. Structure-dependent interactions of a variety of flavonoids with phospholipid monolayers on a mercury (Hg) film electrode were established by rapid cyclic voltammetry (RCV). The data revealed that flavonoids adopting a planar configuration altered the membrane properties more significantly than nonplanar flavonoids. Quercetin, rutin, and tiliroside were selected for follow-up experiments with Langmuir monolayers, Brewster angle microscopy (BAM), and small-angle X-ray scattering (SAXS). Relaxation phenomena in DOPC monolayers and visualization of the surface with BAM revealed a pronounced monolayer stabilization effect with both quercetin and tiliroside, whereas rutin disrupted the monolayer structure rendering the surface entirely smooth. SAXS showed a monotonous membrane thinning for all compounds studied associated with an increase in the mean fluctuations of the membrane. Rutin, quercetin, and tiliroside decreased the bilayer thickness of DOPC by ∼0.45, 0.8, and 1.1 Šat 6 mol %, respectively. In addition to the novelty of using lipid monolayers to systematically characterize the structure-activity relationship (SAR) of a variety of flavonoids, this is the first report investigating the effect of tiliroside with biomimetic membrane models. All the flavonoids studied are believed to be localized in the lipid/water interface region. Both this localization and the membrane perturbations have implications for their therapeutic activity.

Encapsulation of short-chain bioactive peptides (BAPs) for gastrointestinal delivery: a review.

The majority of known peptides with high bioactivity (BAPs) such as antihypertensive, antidiabetic, antioxidant, hypocholesterolemic, anti-inflammatory and antimicrobial actions, are short-chain sequences of less than ten amino acids. These short-chain BAPs of varying natural and synthetic origin must be bioaccessible to be capable of being adsorbed systemically upon oral administration to show their full range of bioactivity. However, in general, in vitro and in vivo studies have shown that gastrointestinal digestion reduces BAPs bioactivity unless they are protected from degradation by encapsulation. This review gives a critical analysis of short-chain BAP encapsulation and performance with regard to the oral delivery route. In particular, it focuses on short-chain BAPs with antihypertensive and antidiabetic activity and encapsulation methods via nanoparticles and microparticles. Also addressed are the different wall materials used to form these particles and their associated payloads and release kinetics, along with the current challenges and a perspective of the future applications of these systems.

Effect of oil droplets and their solid/liquid composition on the phase separation of protein-polysaccharide mixtures.

The phase separation of a model system consisting of sodium caseinate + xanthan ± a low fraction (up to 3 wt %) of an oil-in-water emulsion was studied at room temperature (20-25 °C). The composition of the oil phase was either 100 wt % n-tetradecane (TD); 50% TD + 50% eicosane (EC) or 100% EC. The droplets in these three "emulsions" were therefore totally liquid, partially solid, and totally solid, respectively. In the presence of 22 mM CaCl2, the mixed TD+EC droplets were most effective at inhibiting phase separation, while the EC emulsions could not prevent phase separation at all. At 32 mM CaCl2 the emulsions tended to promote phase separation, possibly due to enhanced calcium ion-induced droplet aggregation. The apparent interfacial viscosity (ηi) between two macroscopically separated phases was also measured. In the presence of the semisolid mixed droplets ηi = 25 mN s m(-1), significantly higher than ηi with the pure (liquid) TD droplets (15 mN s m(-1)) or with the pure solid EC droplets (12 mN s m(-1)) or in the absence of droplets (<3 mN s m(-1)). Confocal microscopy showed that the microstructure of the phase separating regions also depended upon the composition of the oil droplets, and it is tentatively suggested that the more marked effects of the mixed emulsion droplets were due to them forming a stronger network at the interface via partial coalescence. Control of the extent of interfacial aggregation of droplets is therefore possibly one way to influence the course of phase separation in biopolymer mixtures.

Surface adsorption properties of peptides produced by non-optimum pH pepsinolysis of proteins: A combined experimental and self-consistent-field calculation study.

HYPOTHESIS: Partial hydrolysis of large molecular weight (Mw), highly aggregated plant proteins is frequently used to improve their solubility. However, if this hydrolysis is extensive, random or nonselective, it is unlikely to improve functional properties such as surface activity, emulsion, or foam-stabilising capacity. EXPERIMENTS AND SIMULATION: Soy protein isolate (SPI) was hydrolysed by pepsin under optimal (pH 2.1) and non-optimal (pH 4.7) conditions. The surface activity and emulsion stabilising capacity of the resultant peptides were measured and compared. The colloidal interactions between a pair of emulsion droplets were modelled via Self-Consistent-Field Calculations (SCFC). FINDINGS: Hydrolysis at pH 2.1 and 4.7 resulted in a considerable increase in measured surface activity compared to the native (non-hydrolysed) SPI, but the hydrolysate from pH 2.1 was not as good an emulsion stabiliser as the hydrolysate (particularly the fraction Mw > 10 kDa) at pH 4.7. Furthermore, peptide analysis of the latter suggested it was dominated by a fragment of one of the major soy proteins ß-conglycinin, with Mw ≈ 25 kDa. SCFC calculations confirmed that interactions mediated by adsorbed layers of this peptide point to it being an excellent emulsion stabiliser.

Synthetic and biopolymeric microgels: Review of similarities and difference in behaviour in bulk phases and at interfaces.

This review discusses the current knowledge of interfacial and bulk interactions of biopolymeric microgels in relation to the well-established properties of synthetic microgels for applications as viscosity modifiers and Pickering stabilisers. We present a timeline showing the key milestones in designing microgels and their bulk/ interfacial performance. Poly(N-isopropylacrylamide) (pNIPAM) microgels have remained as the protagonist in the synthetic microgel domain whilst proteins or polysaccharides have been primarily used to fabricate biopolymeric microgels. Bulk properties of microgel dispersions are dominated by the volume fraction (ϕ) of the microgel particles, but ϕ is difficult to pinpoint, as addressed by many theoretical models. By evaluating recent experimental studies over the last five years, we find an increasing focus on the analysis of microgel elasticity as a key parameter in modulating their packing at the interfaces, within the provinces of both synthetic and biopolymeric systems. Production methods and physiochemical factors shown to influence microgel swelling in the aqueous phase can have a significant impact on their bulk as well as interfacial performance. Compared to synthetic microgels, biopolymer microgels show a greater tendency for polydispersity and aggregation and do not appear to have a core-corona structure. Comprehensive studies of biopolymeric microgels are still lacking, for example, to accurately determine their inter- and intra- particle interactions, whilst a wider variety of techniques need to be applied in order to allow comparisons to real systems of practical usage.

Structure and oxidative stability of oil in water emulsions as affected by rutin and homogenization procedure.

The structural properties of oil-in-water (O/W) emulsions, as well as their oxidative stability upon storage at 50 °C, were studied. Eight different formulations were prepared, with the aim of studying the effect of three variables: the composition of the oil phase, the presence of the flavonoid rutin and the homogenization procedure on the structure and the oxidative stability. It was found that high pressure homogenization, through droplet size reduction, stabilized the emulsions both against creaming and oil oxidation. The interfacial protein was also partially replaced by rutin, further improving the stability of the emulsions, whereas purification of the oil phase had hardly any effect. Thus, the structural and oxidative stability of emulsions was controlled by the size of the droplets and improved by the addition of rutin.

Effect of Oil on Cellulose Dissolution in the Ionic Liquid 1-Butyl-3-methyl Imidazolium Acetate.

While ionic liquids (ILs) are well known to be excellent solvents for cellulose, the exact mechanism of dissolution has been a much disputed topic in recent years and is still not completely clear. In this work, we add to the current understanding and highlight the importance of hydrophobic interactions, through studying cellulose dissolution in mixtures of 1-butyl-3-methyl imidazolium acetate (BmimAc) and medium-chain triglyceride (MCT) oil. We demonstrate that the order in which constituents are mixed together plays a key role, through nuclear magnetic resonance (NMR) spectroscopic analysis. When small quantities of MCT oil (0.25-1 wt %) were introduced to BmimAc before cellulose, the effect on BmimAc chemical shift values was much more significant compared to when the cellulose was dissolved first, followed by oil addition. Rheological analysis also showed small differences in the viscosities of oil-cellulose-BmimAc solutions, depending on the order the constituents were added. On the other hand, no such order effect on the NMR results was observed when cellulose was replaced with cellobiose, suggesting that this observation is unique to the macromolecule. We propose that a cellulose-oil interaction develops but only when the cellulose structure has a sufficient degree of order and not when the cellulose is molecularly dispersed, since the hydrophobic cellulose plane is no longer intact. In all cases, cellulose-BmimAc-oil solutions were stable for at least 4 months. To our knowledge, this is the first work that investigates the effect of oil addition on the dissolving capacity of BmimAc and highlights the need for further re-evaluation of accepted mechanisms for cellulose dissolution in ILs.

Pectin-based microgels for rheological modification in the dilute to concentrated regimes.

HYPOTHESIS: A novel range of microgel particles of different internal cross-linking densities can be created by covalently cross-linking sugar beet pectin (SBP) with the enzyme laccase and mechanically breaking down the subsequent parent hydrogels to sugar beet pectin microgels (SBPMG) via shearing. The bulk rheological properties of suspensions of the different SBPMG are expected to depend on the microgel morphology, elasticity (crosslinking density) and volume fraction respectively. EXPERIMENTS: The rheology of both dilute and concentrated dispersions of SBPMG were studied in detail via capillary viscometry and shear rheometry, supplemented by information on particle size and shape from static light scattering, confocal microscopy and electron microscopy. FINDINGS: For dilute suspensions of SBPMG, data for viscosity versus effective volume fraction (ɸeff) falls on a 'master' curve for all 3 types of SBPMG. In the more concentrated regime, the softer microgels allow greater packing and interpenetration and give lower viscosities at the same ɸeff, but all 3 types of microgel give much higher viscosities than the equivalent concentration of 'non-microgelled' pectin. The firmer microgels can be concentrated to achieve elasticities equivalent to the original parent hydrogel. All SBPMG suspensions were extremely shear thinning but showed virtually no time-dependence.

Rheology and tribology of starch + κ-carrageenan mixtures.

In this study, we investigated the rheological and tribological properties of biopolymer mixtures of gelatinized corn starches (0.5 - 10.0 wt%) and κ-carrageenan (κC) (0.05 - 1.0 wt%). Two different starch samples were used. The first starch (CS1), despite extensive heating and shearing contained "ghost" granules, while the second starch (CS2) had no visible ghost granules after the same gelatinization process as CS1. Apparent viscosity measurements demonstrated that κC + CS1 mixtures were shear thinning liquids, with viscosity values being lower than the corresponding weight average of the values of the individual equilibrium phases at shear rates < 50 s-1 . Tribological results revealed that κC ≥ 0.5 wt% was required to observe any decrease in friction coefficients in the mixed lubrication regime. Starch (CS1) showed an unusual behavior at ≥ 5 wt%, where the friction coefficient decreased not only in the mixed regime but also in the boundary regime, probably due to the presence of the "ghost" granules, as the latter became entrained in the contact region. The CS1 + κC mixtures showed significantly lower friction coefficients than that of pure CS1 and κC in the mixed regime. However, the CS2 + κC mixture (i.e., containing no ghost granules) showed similar behavior to pure κC in the mixed regime, while lower friction coefficients than that of the pure CS2 and κC in the boundary regime. These findings illustrate new opportunities for designing biopolymer mixtures with tunable lubrication performance, via optimizing the concentrations of the individual biopolymers and the gelatinization state of the starch.

Rheological and NMR Studies of Cellulose Dissolution in the Ionic Liquid BmimAc.

Solutions of two types of cellulose in the ionic liquid 1-butyl-3-methyl-imidazolium acetate (BmimAc) have been analyzed using rheology and fast-field cycling nuclear magnetic resonance (NMR) spectroscopy, in order to analyze the macroscopic (bulk) and microscopic environments, respectively. The degree of polymerization (DP) was observed to have a significant effect on both the overlap (c*) and entanglement (ce) concentrations and the intrinsic viscosity ([η]). For microcrystalline cellulose (MCC)/BmimAc solutions, [η] = 116 mL g-1, which is comparable to that of MCC/1-ethyl-3-methyl-imidazolium acetate (EmimAc) solutions, while [η] = 350 mL g-1 for the commercial cellulose (higher DP). Self-diffusion coefficients (D) obtained via the model-independent approach were found to decrease with cellulose concentration and increase with temperature, which can in part be explained by the changes in viscosity; however, ion interactions on a local level are also important. Both Stokes-Einstein and Stokes-Einstein-Debye analyses were carried out to directly compare rheological and relaxometry analyses. It was found that polymer entanglements affect the microscopic environment to a much lesser extent than for the macroscopic environment. Finally, the temperature dependencies of η, D, and relaxation time (T1) could be well described by Arrhenius relationships, and thus, activation energies (Ea) for flow, diffusion, and relaxation were determined. We demonstrate that temperature and cellulose concentration have different effects on short- and long-range interactions.