Supratim Ghosh

Intermolecular Interactions during Complex Coacervation of Pea Protein Isolate and Gum Arabic

The nature of intermolecular interactions during complexation between pea protein isolate (PPI) and gum arabic (GA) was investigated as a function of pH (4.30-2.40) by turbidimetric analysis and confocal scanning microscopy in the presence of destabilizing agents (100 mM NaCl or 100 mM urea) and at different temperatures (6-60 degrees C). Complex formation followed two pH-dependent structure-forming events associated with the formation of soluble and insoluble complexes and involved interactions between GA and PPI aggregates. Complex formation was driven by electrostatic attractive forces between complementary charged biopolymers, with secondary stabilization by hydrogen bonding. Hydrophobic interactions were found to enhance complex stability at lower pH (pH 3.10), but not with its formation.

Comparison of Pickering and Network Stabilization in Water-in-Oil Emulsions

We compared the efficacy of Pickering crystals, a continuous phase crystal network, and a combination thereof against sedimentation and dispersed phase coalescence in water-in-oil (W/O) emulsions. Using 20 wt % water-in-canola oil emulsions as our model, glycerol monostearate (GMS) permitted Pickering-type stabilization, whereas simultaneous usage of hydrogenated canola oil (HCO) and glycerol monooleate (GMO) primarily led to network-stabilized emulsions. A minimum of 4 wt % GMS or 10 wt % HCO was required for long-term sedimentation stability. Although there were no significant differences between the two in mean droplet size with time, the free water content of the network-stabilized emulsions was higher than Pickering-stabilized emulsions, suggesting higher instability. Microscopy revealed the presence of crystal shells around the dispersed phase in the GMS-stabilized emulsions, whereas in the HCO-stabilized emulsion, spherulitic growth in the continuous phase and on the droplet surface occurred. The displacement energy (E(disp)) to detach crystals from the oil-water interface was ∼10(4) kT, and was highest for GMS crystals. Thermal cycling to induce dispersed phase coalescence of the emulsions resulted in desorption of both GMS and GMO from the interface, which we ascribed to solute-solvent hydrogen bonding between the emulsifier molecules and the solvent oil, based on IR spectra. Overall, Pickering crystals were more effective than network crystals for emulsion stabilization. However, the thermal stability of all emulsions was hampered by the diffusion of the molten emulsifiers from the interface.

Freeze-thaw stability of water-in-oil emulsions

Factors influencing water-in-oil emulsion stability during freeze/thaw-cycling, namely interfacial crystallization vs. network crystallization and the sequence of crystallization events (i.e., dispersed vs. continuous phase or vice versa), are assessed. We show that destabilization is most apparent with a liquid-state emulsifier and a continuous oil phase that solidifies prior to the dispersed phase. Emulsions stable to F/T-cycling are obtained when the emulsifier crystallizes at the oil-water interface or in emulsions where the continuous phase crystallizes after the dispersed aqueous phase. The materials used are two food-grade oil-soluble emulsifiers - polyglycerol polyricinoleate (PGPR) and glycerol monostearin (GMS) and two continuous oil phases with differing crystallization temperatures - canola oil and coconut oil. Emulsion stability is assessed with pulsed field gradient NMR droplet size analysis, sedimentation, microscopy and differential scanning calorimetry. This study demonstrates the sequence of crystallization events and the physical state of the surfactant at the oil-water interface strongly impact the freeze-thaw stability of water-in-oil emulsions.

Baclofen, raclopride, and naltrexone differentially reduce solid fat emulsion intake under limited access conditions

Previous work in rats has demonstrated that an Intermittent (Monday, Wednesday, Friday) schedule of access promotes binge-type consumption of 100% vegetable shortening during a 1-h period of availability. The present study used novel shortening-derived stable solid emulsions of various fat concentrations. These emulsions were the consistency of pudding and did not demonstrate oil and water phase separation previously reported with oil-based liquid emulsions. Male Sprague-Dawley rats were grouped according to schedule of access (Daily or Intermittent) to one of three concentrations (18%, 32%, 56%) of solid fat emulsion. There were no significant Intermittent vs. Daily differences in amount consumed, due to high intakes in all groups. This indicated the acceptability of the emulsions. Baclofen (GABA(B) agonist) and raclopride (D2-like antagonist) both significantly reduced emulsion intake in all Daily groups, but only in the 56% fat Intermittent group. Naltrexone (opioid antagonist), in contrast, significantly reduced 32% and 56% fat emulsion intake in the Intermittent, as well as the Daily groups. These results indicate that the fat intake-reducing effects of GABA(B) activation and D(2) blockade depend upon fat concentration and schedule of fat access, while the fat intake-reducing effects of opioid blockade depend upon fat concentration but not schedule of access.

Comparison of the Dispersed Phase Coalescence Mechanisms in Different Tablespreads

Temperature-induced destabilization of the dispersed phase in butter and margarine was compared by following changes in droplet size (d(3,3)), solid fat content (SFC), and fat crystal spatial organization in the 28-34 degrees C range. At 28 degrees C, both butter and margarine were stable, with similar d(3,3) values (approximately 6 microm) and droplet size distributions. As the storage temperature was raised above 30 degrees C, notable droplet coalescence was observed (for example, at 32 degrees C d(3,3) values of approximately 10 microm for butter and approximately 12 microm for margarine were obtained). Dispersed phase coalescence in butter was dominated by coagulation, with the fat crystal network-limiting droplet-droplet contact until a minimum SFC was reached (approximately 2.5%). In margarine, the rate-limiting step for coalescence was the melting of Pickering crystals present around the dispersed aqueous droplets. Unlike butter, there was no sharp change in stability at a particular temperature or critical SFC. With these differences, coalescence in butter could be modeled as a 2nd-order process and as a 1st-order process in margarine. Overall, these results demonstrated that the kinetic stability of the dispersed aqueous phase in butter and margarine depends on SFC and the spatial distribution of fat crystals within the spreads.

Influence of emulsifier concentration on nanoemulsion gelation.

Nanoemulsion gels are a new class of soft materials that manifest stronger elasticity even at lower dispersed phase volume fraction. In this work, gelation in 40 wt % canola oil-in-water nanoemulsions was investigated as a function of emulsifier type (anionic sodium dodecyl sulfate (SDS) or nonionic Tween 20) and concentration. It was observed that the liquid nanoemulsions transformed into viscoelastic gels at a specific concentration range of SDS, whereas no gelation was observed for Tween 20. The apparent viscosity, yield stress, and storage modulus of the nanogels increased with SDS concentration until 15 times critical micelle concentration (CMC), thereafter decreased steadily as the gelation weakened beginning 20 CMC. Three regimes of colloidal interactions in the presence of emulsifier were proposed. (1) Repulsive gelation: at low SDS concentration (0.5-2 times CMC) the repulsive charge cloud around the nanodroplets acted as interfacial shell layer that significantly increased the effective volume fraction of the dispersed phase (ϕ(eff)). When ϕ(eff) became comparable to the volume fraction required for maximal random jamming, nanoemulsions formed elastic gels. (2) Attractive gelation: as the SDS concentration increased to 5-15 times CMC, ϕ(eff) dropped due to charge screening by more counterions from SDS, but depletion attractions generated by micelles in the continuous phase led to extensive droplet aggregation which immobilized the continuous phase leading to stronger gel formation. (3) Decline in gelation due to oscillatory structural forces (OSF): at very high SDS concentration (20-30 time CMC), structural forces were manifested due to the layered-structuring of excess micelles in the interdroplet regions resulting in loss of droplet aggregation. Tween 20 nanoemulsions, on the other hand, did not show repulsive gelation due to lack of charge cloud, while weak depletion attraction and early commencement of OSF regime leading to liquid-like behavior at all concentrations. The nanogels possess great potential for use in low-fat foods, pharmaceuticals and cosmetic products.

Equivalent conditions for uniform asymptotic consensus among distributed agents

A set of conditions equivalent to uniform asymptotic consensus for distributed agents involving switched stability theory, linear matrix inequalities, and graph-theoretic notions has been established. These conditions are presented for both leaderless and leader-follower situations and extend previous results to wider classes of multi-agent systems. In particular, the uniformity requirement imposed on the convergence rate of mixed matrix products not only plays a crucial role in theoretical developments, but it also meets the practical needs of reaching consensus robustly against disturbances.

Emulsion breakdown in foods and beverages.

Abstract: This chapter focuses on the effect of emulsion breakdown on food quality. The mechanisms of emulsion destabilization are described and ways to control them discussed. The factors (composition, heating, freezing and processing conditions) that influence emulsion destabilization are described, and a brief section on the methods used to characterize emulsion stability is presented. Future trends in the area of emulsion (de)stabilization are outlined.

Long-term stability of crystal-stabilized water-in-oil emulsions

The impact of cooling rate and mixing on the long-term kinetic stability of wax-stabilized water-in-oil emulsions was investigated. Four cooling/mixing protocols were investigated: cooling from 45°C to either 25°C or 4°C with/without stirring and two cooling rates - slow (1°C/min) and fast (5°C/min). The sedimentation behaviour of the emulsions was significantly affected by cooling protocol. Stirring was critical to the stability of all emulsions, with statically-cooled (no stirring) emulsions suffering from extensive aqueous phase separation. Emulsions stirred while cooling showed sedimentation of a waxy emulsion layer leaving a clear oil layer at the top, with a smaller separation and droplet size distribution at 4°C compared to 25°C, indicating the importance of the amount of crystallized wax on emulsion stability. Light microscopy revealed that crystallized wax appeared both on the droplet surface and in the continuous phase, suggesting that stirring ensured dispersibility of the water droplets during cooling as the wax was crystallizing. Wax crystallization on the droplet surface provided stability against droplet coalescence while continuous phase wax crystals minimized inter-droplet collisions. The key novel aspect of this research is in the simplicity to tailor the spatial distribution of wax crystals, i.e., either at the droplet surface or in the continuous phase via use of a surfactant and judicious stirring and/or cooling. Knowledge gained from this research can be applied to develop strategies for long-term storage stability of crystal-stabilized W/O emulsions.

Optimal distributed consensus on unknown undirected graphs

For multi-agent networks described by fixed undirected connectivity graphs, the problem of optimal controller synthesis for distributed consensus is addressed without assuming prior knowledge about the global network topology. Under the proposed control scheme, the agents maintain a Nash equilibrium by updating their beliefs about the network topology over time and by computing their decisions via online optimization. This equilibrium attains finite-time consensus in minimum time while optimizing a quadratic transient performance index on the way to consensus.