Simple Method to Assess Foam Structure and Stability using Hydrophobin and BSA as Model Systems.

The properties and arrangement of surface-active molecules at air-water interfaces influence foam stability and bubble shape. Such multiscale-relationships necessitate a well-conducted analysis of mesoscopic foam properties. We introduce a novel automated and precise method to characterize bubble growth, size distribution and shape based on image analysis and using the machine learning algorithm Cellpose. Studying the temporal evolution of bubble size and shape facilitates conclusions on foam stability. The addition of two sets of masks, for tiny bubbles and large bubbles, provides for a high precision of analysis. A python script for analysis of the evolution of bubble diameter, circularity and dispersity is provided in the Supporting Information. Using foams stabilized by bovine serum albumin (BSA), hydrophobin (HP), and blends thereof, we show how this technique can be used to precisely characterize foam structures. Foams stabilized by HP show a significantly increased foam stability and rounder bubble shape than BSA-stabilized foams. These differences are induced by the different molecular structure of the two proteins. Our study shows that the proposed method provides an efficient way to analyze relevant foam properties in detail and at low cost, with higher precision than conventional methods of image analysis.

Structural characterization of solvent-based food preparation of jellyfish.

Jellyfish as a potential sustainable food material has recently gained increasing interest. However, with their soft gel-like texture and easy spoilage, it remains challenging to achieve desirable edible structures from jellyfish. The culinary preparation of jellyfish is a complex process and extends beyond conventional cooking methods. In this study, we investigate the transformation of jellyfish into crispy-like structures by manipulating their microstructural and mechanical properties through a solvent-based preparation. The study focuses on the use of "poor solvents", namely ethanol and acetone, and employs rheology measurements and quantitative microscopy techniques to analyze the effects of these solvents on the mechanical properties and microstructure of jellyfish. Our findings reveal that both ethanol and acetone lead to a significant increase in jellyfish hardness and deswelling. Notably, a micro-scale network is formed within the jellyfish matrix, and this network is then mechanically reinforced before a crispy-like texture can be obtained. Our study points to solvent polarity as also being a crucial factor for creating these effects and determines an upper polarity limit in the range of 12.2-12.9 MPa1/2 for added solvents, corresponding to approximately 60% of added ethanol or 70% of added acetone. Our study highlights that solvent-based preparation serves as a "reverse cooking" technique, where mechanical modification rather than traditional softening mechanisms are employed to stabilize and strengthen the microstructures and fibers of jellyfish. By elucidating the underlying mechanisms of solvent-induced stabilization, our findings may facilitate the development of innovative and sustainable culinary practices, paving the way for broader applications of jellyfish and other soft edible materials in the gastronomic landscape.

Soft matter food physics--the physics of food and cooking.

This review discusses the (soft matter) physics of food. Although food is generally not considered as a typical model system for fundamental (soft matter) physics, a number of basic principles can be found in the interplay between the basic components of foods, water, oil/fat, proteins and carbohydrates. The review starts with the introduction and behavior of food-relevant molecules and discusses food-relevant properties and applications from their fundamental (multiscale) behavior. Typical food aspects from 'hard matter systems', such as chocolates or crystalline fats, to 'soft matter' in emulsions, dough, pasta and meat are covered and can be explained on a molecular basis. An important conclusion is the point that the macroscopic properties and the perception are defined by the molecular interplay on all length and time scales.

Force spectroscopy of polymer desorption: theory and molecular dynamics simulations.

Forced detachment of a single polymer chain, strongly adsorbed on a solid substrate, is investigated by two complementary methods: a coarse-grained analytical dynamical model, based on the Onsager stochastic equation, and Molecular Dynamics (MD) simulations with a Langevin thermostat. The suggested approach makes it possible to go beyond the limitations of the conventional Bell-Evans model. We observe a series of characteristic force spikes when the pulling force is measured against the cantilever displacement during detachment at constant velocity vc (displacement control mode) and find that the average magnitude of this force increases as vc increases. The probability distributions of the pulling force and the end-monomer distance from the surface at the moment of the final detachment are investigated for different adsorption energies ε and pulling velocities vc. Our extensive MD simulations validate and support the main theoretical findings. Moreover, the simulations reveal a novel behavior: for a strong-friction and massive cantilever the force spike pattern is smeared out at large vc. As a challenging task for experimental bio-polymer sequencing in future we suggest the fabrication of a stiff, super-light, nanometer-sized AFM probe.

Structure and dynamics of polymer melt confined between two solid surfaces: A molecular dynamics study.

Using large scale molecular dynamics simulations we investigate the static and dynamic properties of a linear polymer melt confined between two solid surfaces. One of the walls is repulsive and the other is attractive wall. The bottom attractive wall is characterized by different degrees of roughness which is tuned by an array of short perpendicular rigid pillars with variable grafting density. We demonstrate that the conformations of polymers at the interfaces do not depend on substrate-polymer interactions, rather they show similar conformations of a single end-grafted chain under critical adsorption condition, consistent with the Silberberg's hypothesis. This observation is found to be in a good agreement with the analysis of the size distributions of trains, loops, and tails of melt chains at the walls known from the theoretical prediction of the end-grafted single chains at critical adsorption. Furthermore, we find that the pressure of the melt PN decreases as PN - P∞ ∝ N-1 with growing length of the chains N (where P∞ is the extrapolated pressure for N → ∞). Moreover, the surface tension γ near both walls is found to follow γN∝N(-2/3). Eventually, the lateral dynamics near rough surface drops suddenly when the separation between the neighboring pillars becomes smaller than 2Rg, where Rg is the bulk radius of gyration.

Effect of heat treatment on.wheat dough rheology and wheat protein solubility.

In the present study, the influence of moisture content, temperature and time during heat treatment of wheat flour was investigated. Heat treatment was carried out on laboratory scale in a water bath at 50-90 degrees C for times up to 3 h. Flour functionality was evaluated by analysing protein solubility in acetic acid as well as by the formation of bread-like doughs, which were then analysed with dynamic oscillatory and rotational rheometry. Effects during heat treatment were explained on a molecular level using a simplified physical model describing wheat dough as a continuous gluten matrix with starch as filler particles. Heat treatment causes the formation of gluten aggregates resulting in decreased protein solubility and lower network strength of dough. Rheological data also indicate the formation of starch aggregates and modified interactions between gluten and starch. The effects were more pronounced in heat-treated flours with increased moisture content due to a higher mobility of the molecules.

Influence of nongelling hydrocolloids on the gelation of agarose.

The combination of different gelling and nongelling hydrocolloids is known to yield complex systems with a wide range of mechanical properties. Here, the influence of the nongelling hydrocolloids sodium-alginate and xanthan on the gelation of agarose is investigated. The two polyelectrolytes differ significantly in their flexibility, leading to opposing effects on the thermomechanical properties of the resulting composite gels. The network structure of the agarose as well as viscoelasticity, gelling temperature, and thermal stability of the gels are altered. These properties are investigated by strain and temperature dependent oscillatory rheological measurements as well as confocal laser scanning microscopy. A phenomenological model to describe the network formation of agarose in the presence of alginate or xanthan respectively is presented.

Dynamic behavior of acrylic acid clusters as quasi-mobile nodes in a model of hydrogel network.

Using a molecular dynamics simulation, we study the thermo-mechanical behavior of a model hydrogel subject to deformation and change in temperature. The model is found to describe qualitatively poly-lactide-glycolide hydrogels in which acrylic acid (AA)-groups are believed to play the role of quasi-mobile nodes in the formation of a network. From our extensive analysis of the structure, formation, and disintegration of the AA-groups, we are able to elucidate the relationship between structure and viscous-elastic behavior of the model hydrogel. Thus, in qualitative agreement with observations, we find a softening of the mechanical response at large deformations, which is enhanced by growing temperature. Several observables as the non-affinity parameter A and the network rearrangement parameter V indicate the existence of a (temperature-dependent) threshold degree of deformation beyond which the quasi-elastic response of the model system turns over into plastic (ductile) one. The critical stretching when the affinity of the deformation is lost can be clearly located in terms of A and V as well as by analysis of the energy density of the system. The observed stress-strain relationship matches that of known experimental systems.

Molecular behavior of fluid gels - the crucial role of edges and particle surface in macroscopic properties.

Fluid gels exhibit unique properties during oral processing and thus are well known in gastronomy as well as for use in dysphagia patients. Agarose fluid gels, which are produced by gelation under shear, in particular, show elastic solid-like behavior at rest but a fluid-like behavior once critical stress is exceeded. In a previous study this special behavior is addressed to the "hairy" structure of the microgel particles - dangling gel parts and chains on the particle surface - which plays a crucial role in the rheological, mechanical and tribological properties of the gels. In this paper, atomic force microscopy (AFM) was used to investigate the underlying microscopic structures and develop a consistent physical model, which relates the irregular particle structures and their heterogonous shape to the experimental observation of the previous studies. One crucial point is the inner structure of the gel particles, which show a dense area in the center, whereas towards the periphery the network and thus the elastic properties change. Agarose gels by forming helices and meshes, which defines the basic length scale for their elastic response in bulk. These properties in turn depend on the concentration and preparation conditions. The present study is meant to address the still prevalent lack of understanding regarding a direct structure-property relationship of these novel fluid gels. Controlling the properties of such fluid gels may play a crucial role in the texture modification of foods and beverages for dysphagia.

Physics of agarose fluid gels: Rheological properties and microstructure.

Agarose, a strongly gelling polysaccharide, is a common ingredient used to optimize the viscoelastic properties of a multitude of food products. Through aggregation of double helices via hydrogen bonds while cooling under quiescent conditions it forms firm and brittle gels. However, this behavior can be altered by manipulating the processing conditions viz shear. For example, gelation under shear leads to microgel particles with large surface area, which in turn leads to completely different rheological properties and texture. Such fluid gels are shown to play an important role in texture modification of foods and beverages for dysphagia patients. In this study, different concentration of agarose fluid gel (0.5 % wt, 1 % wt and 2 % wt) were considered. Rheological measurements of the microgel particles showed an increase of storage and loss modulus with increasing concentration. However, 1 % wt fluid gel exhibited the lowest viscosity in the low shear range and the shortest LVE range. Furthermore, the effect on the microstructure and size of gel particles were also investigated by using light microscopy and particle size analysis. It was observed that as the concentration of agarose increased the particle size and unordered chains present at the particle surface decreases. Based on our results, we propose specific models suggesting the impact of the particle size, the concentration and the "hairy" projections on the rheological and tribological properties that could help in understanding the differences in characteristics of fluid gels.

Effect of different derivatives of paraffin waxes on crystallization of eutectic mixture of cocoa butter-coconut oil.

Paraffin wax is a mixture of numerous unbranched hydrocarbons used frequently for various purposes: to improve the shelf life of products containing lipid system and develop more shiny products. However, because of its complex nature, the effect of such molecular structure on the solid phase behavior of lipids is hardly unstated. Hence in our study, we focus on understanding the impact of derivatives of paraffin wax on the lipid system. In the current work, three unbranched derivatives of paraffin wax: Eicosane C (20), Pentacosane C (25) and Triacontane C (30) were selected as additives. These n-alkanes are specifically added to the eutectic mixture of cocoa butter (CB) and coconut oil (CO) (ECB-CO) to observe the effect on thermal, morphological, rheological properties and crystallization kinetics with respect to the carbon chain length. Results from our study illustrate that melting and crystallization temperature, storage modulus and solid fat content (SFC) increases after the addition of 1 wt% of C (20), C (25). In contrast, there is a phase separation for 1 wt% C (30). Further similar study with addition of n-alkanes to pure CB and CO reveals that the interaction of n-alkanes with ECB-CO is dominated by the interaction of n-alkanes with CO instead of CB. Therefore, our findings provide insight into the effect of addition of n-alkanes having different carbon chain length and their respective concentration on crystallization process of CB and CO. This will definitely help to design the processes for products containing such model systems.

Comparative Study on Mixing Behavior of Binary Mixtures of Cocoa Butter/Tristearin (CB/TS) and Cocoa Butter/Coconut Oil (CB/CO).

The comparative study between the mixing behavior of two binary mixtures of cocoa butter (CB)/tristearin (TS) and cocoa butter (CB)/coconut oil (CO) was investigated by using differential scanning calorimetry (DSC). The DSC profile for CB/TS blends resulted in a monotectic temperature-concentration (T-X) phase diagram, whereas a phase diagram of eutectic type was observed for CB/CO blends at 65 wt % of CO and 35 wt % CB; this suggests that the eutectic crystal can be formed when the saturated fat (blue = CO) is smaller in size compared to monounsaturated fat (orange = CB), whereas, for similar and larger size (red = TS) to CB, phase separation under crystallization is likely to occur (as shown in the graphical abstract). In order to understand the interaction between the binary systems, the profile of the phase diagram was fitted with Bragg-Williams approximation for estimation of the nonideality mixing parameter. Moreover, the morphology of the two different systems by polarized light microscopy (PLM) also depicted the variations in phase behavior by showing a significant change in CB morphology from spherulitic, grainy to granular and needlelike after the addition of TS and CO, respectively. Our findings emphasize the fundamental understanding of the interaction of bulk fat/fat and fat/oil system.

Milk Emulsions: Structure and Stability.

The main aim of this research is to investigate the characteristics of milk and milk proteins as natural emulsifiers. It is still largely unclear how the two main fractions of the milk proteins behave as emulsifier in highly concentrated emulsions. The surface-active effect of these is determined experimentally for emulsions with a high oil content (φ > 0.7), in this case fully refined rapeseed oil. Recent publications have not yet sufficiently investigated how proteins from native milk behave in emulsions in which a jamming transition is observed. In addition, scientific measurements comparing fresh milk emulsions and emulsions of dried milk protein powders based on rheological and thermal properties are pending and unexamined. The emulsions, prepared with a rotor-stator disperser, are investigated by their particle size and analysed by microscopy, characterised by their rheological properties. The behaviour under shear is directly observed by rheo-optical methods, which enables the direct observation of the dynamic behaviour of the oil droplets undergoing a size selective jamming transition. For a better understanding of the contributions of the different emulsifying proteins, oil-in-water emulsions have been prepared by using whey protein isolates and sodium casinates. Their different role (and function) on the interface activity can be assigned to the droplet sizes and mechanical behaviour during increasing shear deformation. In addition, solid (gelled) emulsions are prepared by heating. It is shown that the cysteine-containing whey proteins are mainly responsible for the sol-gel transition in the continuous water phase and the formation of soft solids.

Effect of cysteine addition and heat treatment on the properties and microstructure of a calcium-induced whey protein cold-set gel.

A model gel of whey protein isolate (WPI) was prepared by cold gelation with calcium. This system was modified by the addition of free cysteine residues (Cys) at different steps of the process. The WPI cold-set gels obtained were then subjected to heat treatment at 90°C. First, the effect of Cys addition on the heat-induced aggregation of WPI was studied through Atomic Force Microscopy (AFM) and infrared spectroscopy (ATR-FTIR), while Cys' effect on cold gelation was observed by AFM, Confocal Laser Scanning Microscopy (CLSM) and oscillatory rheology (amplitude sweeps). The impact of heating on the microstructure and the viscoelastic properties of the WPI cold-set gels were finally investigated through several techniques, including DSC, ATR-FTIR, CLSM, cryo-SEM, and rheological measurements (temperature sweeps). When added during the first step of cold gelation, Cys modified heat-induced aggregation of WPI, resulting in the formation of a denser gel network with a fractal dimension (Df) of 2.8. However, the addition of Cys during the second step of cold gelation led to the formation of highly branched clusters of WPI and a looser gel network was observed (Df = 2.4). In this regard, the use and limitations of oscillatory rheology and the "Kraus model" to determine the Df of WPI cold-set gels was discussed. The viscoelastic properties and the microstructure of the WPI cold-set gels were irreversibly modified by heating. Gels were stiffer, more brittle, and coarser after heat treatment. New disulfide bonds and calcium bridges formed, as well as H-bonded ß-sheets, all contributing to the formation of the final gel network structure.

Enhanced orientational ordering of water dipoles in uniaxially stretched hydrogels.

The electrostatics and density correlations of dipolar solvent molecules in weakly charged polyelectrolyte solutions and charged gels are studied using a field-theoretical approach. For miscible dipolar solvent mixtures, an exact expression for the effective dielectric permittivity is obtained on the mean-field level, which depends upon the individual volume of each solvent species before mixing and the final volume of the mixture. If the effect of volume change is small during mixing, the dielectric permittivity is approximately equal to the volume-averaged dielectric permittivity of the individual components of the dipolar solvent mixture. It is found that the electrostatic interaction between the dipolar solvent molecules or any charged species in the polyelectrolyte solution is screened by both counterions (and co-ions if salt is added) and polyions, and there exists a total screening length for any charged species in the system which contains the contribution from the polyions. The screening from the polyions is as important as that from the counterions on the length scale of the polymer coil size. For uniaxially stretched charged gels, it is shown that there is an enhanced orientational ordering of the dipolar solvent molecules along the stretching direction, and the correlation length (r(cor)) of this enhanced orientational ordering is about the product of the total screening length (xi(-1)) due to the counterions and polyions times the square root of the dielectric constant of the medium, that is, r(cor)approximately equal to (epsilon(r)xi(-1))1/2.

Path-integral approach to the dynamics of a random chain with rigid constraints.

In this work the dynamics of a chain consisting of a set of beads attached to the ends of segments of fixed lengths is investigated. The chain fluctuates at constant temperature in a viscous medium. For simplicity, all interactions among the beads have been switched off and the number of spatial dimensions has been limited to two. In the limit in which the chain becomes a continuous system, its behavior may be described by a path integral, in which the rigid constraints coming from the infinitesimally small segments are imposed by means of a functional delta function. In this way a model of the dynamics of the chain is obtained, which closely resembles a two-dimensional nonlinear sigma model. The partition function of this generalized nonlinear sigma model is computed explicitly for a ring-shaped chain in the semiclassical approximation. The behavior of the chain at both long and short scales of time and distances is investigated. The connection between the generalized nonlinear sigma model presented here and the Rouse model is discussed.

Soybean oleosomes studied by small angle neutron scattering (SANS).

HYPOTHESIS: Oleosomes are stabilized by a complex outer phospholipid-protein-layer. To improve understanding of its structure and stabilization mechanism, this shell has to be studied in extracellular native conditions. This should be possible by SANS using contrast variation. Oleosomes are expected to be highly temperature stable, with molecular changes occurring first in the protein shell. Direct measurements of changes in the shell structure are also important for processing methods, e.g. encapsulation. EXPERIMENTS: Extracted soybean oleosomes were studied directly and after encapsulation with pectin by SANS using contrast variation. In order to determine structure and size, a shell model of oleosomes was developed. The method was tested against a simple phospholipid-stabilized emulsion. The oleosomes' temperature stability was investigated by performing SANS at elevated temperatures. FINDINGS: Size (Rg = 1380 Å) and shell thickness of native and encapsulated oleosomes have been determined. This is the first report measuring the shell thickness of oleosomes directly. For native oleosomes, a shell of 9 nm thickness surrounds the oil core, corresponding to a layer of phospholipids and proteins. Up to 90 °C, no structural change was observed, confirming the oleosomes' high temperature stability. Successful coavervation of oleosomes was shown by an increase in shell thickness of 10 nm after electrostatic deposition of pectin.

Label-free in situ imaging of oil body dynamics and chemistry in germination.

Plant oleosomes are uniquely emulsified lipid reservoirs that serve as the primary energy source during seed germination. These oil bodies undergo significant changes regarding their size, composition and structure during normal seedling development; however, a detailed characterization of these oil body dynamics, which critically affect oil body extractability and nutritional value, has remained challenging because of a limited ability to monitor oil body location and composition during germination in situ Here, we demonstrate via in situ, label-free imaging that oil bodies are highly dynamic intracellular organelles that are morphologically and biochemically remodelled extensively during germination. Label-free, coherent Raman microscopy (CRM) combined with bulk biochemical measurements revealed the temporal and spatial regulation of oil bodies in native soya bean cotyledons during the first eight days of germination. Oil bodies undergo a cycle of growth and shrinkage that is paralleled by lipid and protein compositional changes. Specifically, the total protein concentration associated with oil bodies increases in the first phase of germination and subsequently decreases. Lipids contained within the oil bodies change in saturation and chain length during germination. Our results show that CRM is a well-suited platform to monitor in situ lipid dynamics and local chemistry and that oil bodies are actively remodelled during germination. This underscores the dynamic role of lipid reservoirs in plant development.

Constrained dynamics of a polymer ring enclosing a constant area.

The dynamics of an ideal polymer ring enclosing a constant algebraic area is studied. The constraint of a constant area is found to couple the dynamics of the two Cartesian components of the position vector of the polymer ring through the Lagrange multiplier function which is time dependent. The time dependence of the Lagrange multiplier is evaluated in a closed form both at short and long times. At long times, the time dependence is weak, and is mainly governed by the inverse of the first mode of the area. The presence of the constraint changes the nature of the relaxation of the internal modes. The time correlation of the position vectors of the ring is found to be dominated by the first Rouse mode which does not relax even at very long times. The mean square displacement of the radius vector is found to be diffusive, which is associated with the rotational diffusion of the ring.

Directed polymers with constrained winding angle.

In this paper we study from a nonperturbative point of view the entanglement of two directed polymers subjected to repulsive interactions given by a Dirac delta-function potential. An exact formula of the so-called second moment of the winding angle is derived. This result is used to provide a thorough analysis of entanglement phenomena in the classical system of two polymers subjected to repulsive interactions and related problems. No approximation is made in treating the constraint on the winding angle and the repulsive forces. In particular, we investigate how repulsive forces influence the entanglement degree of the two-polymer system. In the limit of ideal polymers, in which the interactions are switched off, we show that our results are in agreement with those of previous works.