Open accessJournal Article

# Kinetics of Network Formation and Heterogeneous Dynamics of an Egg White Gel Revealed by Coherent X-Ray Scattering.

02 Mar 2021-Physical Review Letters (American Physical Society)-Vol. 126, Iss: 9, pp 098001
Abstract: The kinetics of heat-induced gelation and the microscopic dynamics of a hen egg white gel are probed using x-ray photon correlation spectroscopy along with ultrasmall-angle x-ray scattering. The kinetics of structural growth reveals a reaction-limited aggregation process with a gel fractal dimension of ≈2 and an average network mesh size of ca. 400 nm. The dynamics probed at these length scales reveals an exponential growth of the characteristic relaxation times followed by an intriguing steady state in combination with a compressed exponential correlation function and a temporal heterogeneity. The degree of heterogeneity increases with decreasing length scale. We discuss our results in the broader context of experiments and models describing attractive colloidal gels.

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Open accessJournal Article
Abstract: While the interplay between liquid-liquid phase separation (LLPS) and glass formation in biological systems is highly relevant for their structure formation and thus function, the exact underlying mechanisms are not well known. The kinetic arrest originates from the slowdown at the molecular level, but how this propagates to the dynamics of microscopic phase domains is not clear. Since with diffusion, viscoelasticity, and hydrodynamics, distinctly different mechanisms are at play, the dynamics needs to be monitored on the relevant time and length scales and compared to theories of phase separation. Using x-ray photon correlation spectroscopy, we determine the LLPS dynamics of a model protein solution upon low temperature quenches and find distinctly different dynamical regimes. We observe that the early stage LLPS is driven by the curvature of the free energy and speeds up upon increasing quench depth. In contrast, the late stage dynamics slows down with increasing quench depth, fingerprinting a nearby glass transition. The dynamics observed shows a ballistic type of motion, implying that viscoelasticity plays an important role during LLPS. We explore possible explanations based on the Cahn-Hilliard theory with nontrivial mobility parameters and find that these can only partially explain our findings.

Topics: Phase transition (52%), Phase (matter) (50%)

7 Citations

Open accessJournal Article
02 Jul 2021-Applied Sciences
Abstract: X-ray photon correlation spectroscopy (XPCS) enables the study of sample dynamics between micrometer and atomic length scales. As a coherent scattering technique, it benefits from the increased brilliance of the next-generation synchrotron radiation and Free-Electron Laser (FEL) sources. In this article, we will introduce the XPCS concepts and review the latest developments of XPCS with special attention on the extension of accessible time scales to sub-μs and the application of XPCS at FELs. Furthermore, we will discuss future opportunities of XPCS and the related technique X-ray speckle visibility spectroscopy (XSVS) at new X-ray sources. Due to its particular signal-to-noise ratio, the time scales accessible by XPCS scale with the square of the coherent flux, allowing to dramatically extend its applications. This will soon enable studies over more than 18 orders of magnitude in time by XPCS and XSVS.

7 Citations

Open accessPosted Content
Abstract: Employing X-ray photon correlation spectroscopy we measure the kinetics and dynamics of a pressure-induced liquid-liquid phase separation (LLPS) in a water-lysozyme solution. Scattering invariants and kinetic information provide evidence that the system reaches the phase boundary upon pressure-induced LLPS with no sign of arrest. The coarsening slows down with increasing quench depths. The $g_2$-functions display a two-step decay with a gradually increasing non-ergodicity parameter typical for gelation. We observe fast superdiffusive ($\gamma \geq 3/2$) and slow subdiffusive ($\gamma < 0.6$) motion associated with fast viscoelastic fluctuations of the network and a slow viscous coarsening process, respectively. The dynamics age linear with time $\tau \propto t_\mathrm{w}$ and we observe the onset of viscoelastic relaxation for deeper quenches. Our results suggest that the protein solution gels upon reaching the phase boundary.

2 Citations

Open accessJournal Article
17 May 2021-Scientific Reports
Abstract: Epoxy resin is indispensable for modern industry because of its excellent mechanical properties, chemical resistance, and excellent moldability. To date, various methods have been used to investigate the physical properties of the cured product and the kinetics of the curing process, but its microscopic dynamics have been insufficiently studied. In this study, the microscopic dynamics in the curing process of a catalytic epoxy resin were investigated under different temperature conditions utilizing X-ray photon correlation spectroscopy. Our results revealed that the temperature conditions greatly affected the dynamical heterogeneity and cross-linking density of the cured materials. An overview of the microscopic mechanism of the curing process was clearly presented through comparison with the measurement results of other methods, such as 1H-pulse nuclear magnetic resonance spectroscopy. The quantification of such heterogeneous dynamics is particularly useful for optimizing the curing conditions of various materials to improve their physical properties.

Topics: Curing (chemistry) (60%), Epoxy (56%)

1 Citations

Open accessJournal Article
02 Mar 2021-Physics
Abstract: An x-ray scattering technique reveals how egg whites gel on a range of length and timescales.

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53 results found

Open accessJournal ArticleDOI: 10.1039/B204495A
Luca Cipelletti1, Laurence Ramos1, Suliana Manley2, Estelle Pitard1  +3 moreInstitutions (3)
Abstract: We use conventional and multispeckle dynamic light scattering to investigate the dynamics of a wide variety of jammed soft materials, including colloidal gels, concentrated emulsions, and concentrated surfactant phases. For all systems, the dynamic structure factor f(q,t) exhibits a two-step decay. The initial decay is due to the thermally activated diffusive motion of the scatterers, as indicated by the q−2 dependence of the characteristic relaxation time, where q is the scattering vector. However, due to the constrained motion of the scatterers in jammed systems, the dynamics are arrested and the initial decay terminates in a plateau. Surprisingly, we find that a final, ultraslow decay leads to the complete relaxation of f(q,t), indicative of rearrangements on length scales as large as several microns or tens of microns. Remarkably, for all systems the same very peculiar form is found for the final relaxation of the dynamic structure factor: f(q,t) ∼ exp[−(t/τs)p], with p ≈ 1.5 and τs ∼ q−1, thus suggesting the generality of this behavior. Additionally, for all samples the final relaxation slows down with age, although the aging behavior is found to be sample dependent. We propose that the unusual ultraslow dynamics are due to the relaxation of internal stresses, built into the sample at the jamming transition, and present simple scaling arguments that support this hypothesis.

Topics: Relaxation (NMR) (54%), , Soft matter (50%)

224 Citations

Journal Article
23 Sep 1999-Langmuir
Abstract: The effects of ionic strength on fractal structures in heat-induced gels prepared from globular proteins were investigated in the framework of a fractal aggregation of colloidal particles. All gels formed at 90 °C exhibited power law relationships between the storage shear modulus (G‘) and protein concentration. At 25 mM NaCl, the fractal dimension, d (∼2.2), calculated based on the value of the power law exponent agreed with those for reaction-limited cluster−cluster aggregation. Further addition of NaCl (50, 80, 500, 1000 mM) decreased the values of d (∼1.8), which agreed with d for diffusion-limited cluster−cluster aggregation. These results suggest that the predominant effect of an increase in ionic strength on globular protein gelation is ascribed to shielding charges on the surface of the proteins, thereby increasing the reaction probability of protein aggregation. The effective structure-determining rheological properties of heat-induced protein gels are characterized by fractal dimensions deduced ...

Topics: Globular protein (55%), Fractal dimension (55%), Fractal (51%) ... show more

185 Citations

Open accessJournal Article
21 Sep 2010-Soft Matter
Abstract: Covalently cross-linked whey protein microgels (WPM) were produced without the use of a chemical cross-linking agent. The hierarchical structure of WPM is formed by a complex interplay of heat denaturation, aggregation, electrostatic repulsion, and formation of disulfide bonds. Therefore, well-defined spherical particles with a diameter of several hundreds of nanometers and with relatively low polydispersity are formed in a narrow pH regime (5.8–6.2) only. WPM production was carried out on large scale by heating a protein solution in a plate-plate heat exchanger. Thereafter, the microgels were concentrated by microfiltration and spray dried into a powder. The spherical structure of the WPM was conserved in the powder. After re-dispersion, the microgel dispersions fully recovered their initial structure and size distribution. Due to the formation of disulfide bonds the particles were internally covalently cross-linked and were remarkably stable in a large pH range. Because of the pH dependent charge of the constituents the particles underwent significant size changes upon shifting the pH. Small angle X-ray scattering experiments were used to reveal their internal structure, and we report on the pH-induced structural changes occurring on different length scale. Our experiments showed that close analogies could be drawn to internally cross-linked and pH-responsive microgels based on weak polyelectrolytes. WPM also exhibited a pronounced swelling at pH values below the isoelectric point (IEP), and a collapse at the IEP. However, in contrast to classical microgels, WPM are not build up by simple polymer chains but possess a complex hierarchical structure consisting of strands formed by clusters of aggregated denatured proteins that act as primary building blocks. They were flexible enough to respond to changes of the environment, and were stable enough to tolerate pH values where the proteins were highly charged and the strands were stretched.

Topics: Isoelectric point (52%), Polyelectrolyte (50%)

173 Citations

Journal Article
Abstract: The heat-induced aggragation of egg white protein and conformational change of heat-denatured protein at a high pH value were investigated. The flexibility, surface hydrophobicity, and changes in sulfhydryl groups were determined.

Topics: Egg white (69%),

170 Citations

Journal Article
Kai Yu1, Tao Xie2, Jinsong Leng3, Yifu Ding1  +1 moreInstitutions (3)
28 May 2012-Soft Matter
Abstract: Shape memory polymers have attracted increasing research interest due to their capability of fixing a temporary shape and associated deformation energy then releasing them later on demand. Recently, it has been reported that polymers with a broad thermomechanical transition temperature range can demonstrate a multi-shape memory effect (m-SME), where shape recovery and energy release occur in a stepped manner during free recovery. This paper investigated the underlying physical mechanisms for these observed shape memory behaviors and the associated energy storage and release by using a theoretical modeling approach. A multibranch model, which is similar to the generalized standard linear solid model of viscoelasticity, was used for a quantitative analysis. In this model, individual nonequilibrium branches represent different relaxation modes of polymer chains with different relaxation times. As the temperature was increased in a staged manner, for a given temperature, different numbers of branches (or relaxation modes) became shape memory active or inactive, leading to the observed m-SME. For energy release during free recovery, under a tensile deformation of the SMP, stored energy in individual nonequilibrium branches was first transferred into a compressive deformation energy, then gradually declined to zero. Energy release during recovery was a complicated process due to the involvement of multiple relaxation modes.