Guest-guided anchoring patterns of cyclodextrin supramolecular microcrystals on droplet surfaces.

The growth of cyclodextrin inclusion complexes (ICs) on oil/water interfaces represents a beautiful example of spontaneous pattern formation in nature. How the supramolecules evolve remains a challenge because surface confinement can frustrate microcrystal growth and give rise to unusual phase transitions. Here we investigate the self-assembly of ICs on droplet surfaces using microfluidics, which allows directly visualizing packing, wetting and ordering of the microcrystals anchored on the surface. The oil guests of distinct molecular structures can direct the assembly of the ICs and largely affect anchoring dynamics of the ICs microcrystals, leading to a range of behaviors including orientating, slipping, buckling, jamming, or merging. We discuss the behaviors observed in terms of the flexibility of the building blocks, which offers a new degree of freedom through which to tailor their properties and gives rise to a striking feature of anchoring patterns that have no counterpart in normal colloidal crystals.

Jamming to unjamming: Phase transition in cyclodextrin-based emulsions mediated by sodium casein.

HYPOTHESIS: Cyclodextrin (CD) can spontaneously build up the solid particle membrane with CD-oil inclusion complexes (ICs) by a self-assembly process. Sodium casein (SC) is expected to preferentially adsorb at the interface to transform the type of interfacial film. The high-pressure homogenization can increase interfacial contact opportunities of the components, which promote the phase transition of the interfacial film. EXPERIMENTS: We added SC by sequential and simultaneous orders to mediate the assembly model of the CD-based films, examined the patterns in which the films adopt phase transitions to retard emulsion flocculation, and studied the physic-chemical properties of the emulsions and films from the structural arrest, interface tension, interfacial rheology, linear rheology, and nonlinear viscoelasticities through Fourier transform (FT)-rheology and Lissajous-Bowditch plots. FINDINGS: The interfacial and large amplitude oscillatory shear (LAOS) rheological results showed that the films changed from jammed to unjammed. We divide the unjammed films into two types: one is SC dominated liquid-like film, which is fragile and related to droplet coalescence; the other is cohesive SC-CD film, which helps droplet rearrangement and retards droplet flocculation. Our results highlight the potential of mediating phase transformation of interfacial films to improve emulsion stability.

The Simultaneous Production of Two Distinct Types of Cellulose Nanocrystals.

We develop a route to prepare two types of cellulose nanocrystals (CNCs, CNC1 and CNC2) from a unique biomass resource, the fruit shell of Camellia oleifera Abel (SCOA), by integrating sulfuric acid hydrolysis and high-pressure homogenization and examine the effects of hydrolysis time on characteristics of the CNCs during the process. The CNCs exhibit different evolutions in size, morphology, surface charge, and crystallinity with increasing hydrolysis time. While both the CNCs have high crystallinity, CNC1 is of rod-like character with a relatively low aspect ratio, and CNC2 exhibits a hairy appearance with a high aspect ratio. We highlight that controlled acid hydrolysis contributes to the formation of weak spots with an increased susceptibility for homogenizing cellulosic solid residues into hairy CNCs. This is a good step toward tailoring CNC properties in a conventional and scalable approach to maximize their potential applications.

Droplet Dispersion States of Cyclodextrin-Based Emulsions from Nonlinear Rheological Properties.

Polymers are desirable to improve emulsion stability by stuffing them into the continuous phase. How to get information on the droplet dispersion states of the emulsions remains a challenge, as the emulsion characteristics are dictated by two intertwining components, the polymer matrix and the droplets. Herein, we use an amphiphilic polymer, gum arabic (GA), to mediate the droplet flocculation of cyclodextrin (CD)-based emulsions and compare them with our previous studies on the stabilization of CD-based emulsions by a nonamphiphilic polymer, methylcellulose (MC). We characterize the emulsions by using optical microscopy, confocal laser scanning microscopy, and laser particle analysis, explore their rheological behavior through large-amplitude oscillatory shear experiments, and analyze the nonlinear viscoelasticities through Fourier transform (FT)-rheology and Lissajous-Bowditch plots. There is a great difference between GA and MC in the viscosity effect and the arrangement around emulsion droplets. GA is not an effective flocculation inhibitor due to a bridging flocculation mechanism rather than a direct viscosity effect. Our analysis highlights the role of the intrinsic nonlinearity parameter (Q0) extracted by FT analysis in reflecting the droplet dispersion states of the emulsions by decoupling structural contributions from the polymers and the emulsion droplets.

Stress buffering in cyclodextrin-based membranes coated on emulsion droplet surfaces.

Surface instability of membranes not only plays a critical role in the morphological evolution observed in natural and biological systems, but also underpins a promising way for the bottom-up fabrication of novel functional materials. There is an urgent need for the design of novel building blocks into membranes, and the understanding of the abilities of the membranes to cope with mechanical stress is therefore of considerable importance. Here, we design membranes built with cyclodextrin-oil inclusion complexes, which are formed spontaneously at the oil/water interface by a self-assembly process. We select the oil phases of distinct molecular structures, namely, branched triglyceride oil and straight-chain n-dodecane, and examine the patterns in which the membranes adopt morphological transitions to buffer stress. We discuss two possible buffering scenarios for the behaviors observed in view of structural arrest and interfacial rheology, which are most closely linked to the rigidity of the membranes. The membranes represent fascinating models and shed some light on the origin of arrested stress relaxation.

Bulk and Interfacial Contributions to Stabilization of Cyclodextrin-Based Emulsions Mediated by Bacterial Cellulose.

Cyclodextrin (CD)-based emulsions have a characteristic of rapid droplet flocculation, which limits their application as functional material templates, so it is very important to improve the stability of CD-based emulsions. In this study, we select bacterial cellulose (BC) as a nonadsorbing inhibitor to prevent flocculation of CD-based emulsions. We map a phase diagram of the aqueous dispersions of CD inclusion complexes (ICs) and BC from morphological observations and investigate the effects of BC on properties of the IC-laden films. We further explore the effects of BC concentration on the stability of the CD-based emulsions and investigate rheological behavior of the emulsions through large-amplitude oscillatory shear experiments. It shows that BC can effectively suppress the flocculation of CD-based emulsion droplets even at a concentration as low as 0.01 wt %. We propose that BC has dual effects from bulk and interfacial contributions on increasing emulsion stability. At low concentrations, BC mainly results in higher packing density of ICs on the emulsion droplet surface through excluded volume repulsion, and at high concentrations, BC creates a network structure that confines the motion of emulsion droplets and retards flocculation.

Microstructure and physiochemical properties of meat sausages based on nanocellulose-stabilized emulsions.

Here we prepared some meat sausages using soybean oil in pure liquid form or pre-emulsified form stabilized with nanocelluloses (NCs) to partially replace pork back-fat and investigated the effects of NC types (sisal cellulose nanofiber, cotton cellulose nanofiber, and cotton cellulose nanocrystal) on the physicochemical properties and microstructure of the sausages. The physicochemical properties, including cooking loss, water holding capacity (WHC), textural properties, and rheological behavior, were evaluated. The results show that the sausages with pre-emulsified oil exhibited much-improved water and fat binding capacities, with significantly increased hardness, springiness, and chewiness. Additionally, pre-emulsifying soybean oil provided a more compact structure with smaller cavities. The sausages with different NCs had no significant difference in textural and microstructural properties, whereas they presented different water and fat binding capacities. From the results, it is concluded that NC-based emulsions are a viable fat replacer for meat sausages by providing similar stability and textural attributes.

Droplet clustering in cyclodextrin-based emulsions mediated by methylcellulose.

Rapid droplet aggregation in cyclodextrin (CD)-stabilized emulsions limits their practical use as material templates. Herein, we formulate mixtures of submicron CD-based emulsion droplets suspended in aqueous solutions of methylcellulose (MC) with various concentrations and molecular weights. We evaluate the effects of MC on the microstructure and stability of the emulsions using different techniques including optical microscopy, laser particle analysis, confocal laser scanning microscopy and multiple light scattering, explore the rheological behavior of the emulsions through large amplitude oscillatory shear experiments, and study the viscoelastic nonlinearities of the emulsions as a function of strain and strain-rate space through nondimensional elastic and viscous Lissajous-Bowditch plots. It is demonstrated that the emulsion droplets are present in the form of small clusters and their size is almost independent of MC concentration and molecular weight. The clustering pattern is also supported by the changes in viscoelastic properties of the emulsions and the intracycle nonlinear behavior of the Lissajous-Bowditch plots. We propose for the first time that glass-like dynamic arrest takes place with the formation of small equilibrium droplet clusters in the situation where the CD-based emulsion droplets are forced by depletion flocculation and kinetic trapping simultaneously exerted by MC.

Driving Forces for Accumulation of Cellulose Nanofibrils at the Oil/Water Interface.

Understanding the adsorption and organization of nanocelluloses at oil/water interfaces is crucial to develop a promising route to fabricate functional materials from the bottom-up. Here, we prepare acetylated cellulose nanofibrils (CNFs) with 2 degrees of substitution and investigate their assembly behavior at the oil/water interface. We study the adsorption process by tracking the dynamic interfacial tension using pendant drop tensiometry and further characterize the viscoelasticity of the CNF interfacial films as a function of ionic strength. The results show that the adsorption of the CNFs at the interface is dominated by energy barriers associated with electrostatic repulsion. With the addition of NaCl, the fibrils are rapidly accumulated at the oil/water interface and jammed into a solidlike film. The overall accumulation of the fibrils is related to the competition between van der Waals attractive forces and electrostatic repulsive forces according to the Derjaguin-Landau-Verwey-Overbeek theory. By screening on the fibril-fibril and fibril-interface electrostatic repulsive forces, the salt addition facilitates the formation of packed fibril clusters and the development of the clusters into a solidlike film. Moreover, the salt addition is assumed to trigger an abrupt density fluctuation in the vicinity of the interface (the formation of locally dense clusters and voids), leading to an increase in brittleness of the film.

Demonstration of laser-produced neutron diagnostic by radiative capture gamma-rays.

We report a new scenario of the time-of-flight technique in which fast neutrons and delayed gamma-ray signals were both recorded in a millisecond time window in harsh environments induced by high-intensity lasers. The delayed gamma signals, arriving far later than the original fast neutron and often being ignored previously, were identified to be the results of radiative captures of thermalized neutrons. The linear correlation between the gamma photon number and the fast neutron yield shows that these delayed gamma events can be employed for neutron diagnosis. This method can reduce the detecting efficiency dropping problem caused by prompt high-flux gamma radiation and provides a new way for neutron diagnosing in high-intensity laser-target interaction experiments.

Laboratory Study on Disconnection Events in Comets.

When comets interacting with solar wind, straight and narrow plasma tails will be often formed. The most remarkable phenomenon of the plasma tails is the disconnection event, in which a plasma tail is uprooted from the comet's head and moves away from the comet. In this paper, the interaction process between a comet and solar wind is simulated by using a laser-driven plasma cloud to hit a cylinder obstacle. A disconnected plasma tail is observed behind the obstacle by optical shadowgraphy and interferometry. Our particle-in-cell simulations show that the difference in thermal velocity between ions and electrons induces an electrostatic field behind the obstacle. This field can lead to the convergence of ions to the central region, resulting in a disconnected plasma tail. This electrostatic-field-induced model may be a possible explanation for the disconnection events of cometary tails.

Decoupling Arrest Origins in Hydrogels of Cellulose Nanofibrils.

Colloidal gels with various architectures and different types of interactions provide a unique opportunity to shed light on the interplay between microscopic structures and mechanical properties of soft glassy materials. Here, we prepare acetylated cellulose nanofibrils with 2 degrees of substitution and make a structural and rheological characterization of their hydrogels. Two-step yielding processes are observed in the shear experiments, which allow us to deduce more precise knowledge regarding localized structural changes of the fibrils. We separate the viscoelastic response into two contributions: the establishment of cross-linked clusters on a fibril level and the arrested phase separation on a cluster level. We hypothesize that with the addition of salt, the hydrogels exhibit different arrested states that are identified as unable to access the thermodynamic equilibrium. Our results highlight that the coexistence of gelation and glass transitions are experimentally recognized in the hydrogels, with a global gelation driven by a local glasslike arrest during spinodal decomposition.

Effects of cellulose derivative hydrocolloids on pasting, viscoelastic, and morphological characteristics of rice starch gel.

Effects of sodium carboxymethyl cellulose (CMC) and hydroxypropyl methyl cellulose (HPMC) on the pasting, viscoelastic, and morphological properties of rice starch gel were studied. The addition of CMC increased the peak and trough viscosities, while decreased the final and setback viscosities of rice starch. The peak and trough viscosities of rice starch gel were only little affected by the addition of HPMC. The dynamic viscoelastic result showed that the addition of CMC significantly increased the values of storage modulus (G') and loss modulus (G″), while reduced the value of tanδ as compared to the control sample. Only a small increase in values of G' and G″ was observed in the case of HPMC. The rice starch gel with CMC addition exhibited higher resistances to the stress and produced a stronger gel network. The creep recovery data were well fitted by a four-element Burger's model. Furthermore, the morphological characteristics were in agreement with the finding of rheological results. It was concluded that the addition of CMC and HPMC modified the rheology of rice starch gel in different ways and interacted under different models based on their molecular structures. PRACTICAL APPLICATIONS: Gluten-free foods such as rice cake are essential for people who suffer from celiac disease which is a digestive disorder caused by the consumption of grains containing gluten. The use of CMC and HPMC represents the most widespread approach used to mimic gluten in the manufacture of gluten-free breads based on rice starch, due to their structure-building and water-binding properties. Therefore, it is necessary and crucial to investigate the physical-chemical properties such as pasting and rheological properties of the rice starch with these hydrocolloids. In addition, a better understanding of the interactions of CMC and HPMC on the rice starch could provide additional tools for selection of gluten free recipes with improved rheological and textural properties.

Shear-Induced Breakup of Cellulose Nanocrystal Aggregates.

The flow properties of two kinds of cellulose nanocrystal (CNC) rods with different aspect ratios and similar zeta potentials in aqueous suspensions have been investigated. The aqueous CNC suspensions undergo a direct transition from dilute solution to colloidal glass instead of phase separation with the increasing CNC concentration. The viscosity profile shows a single shear-thinning behavior over the whole range of shear rates investigated. The shear-thinning behavior becomes stronger with the increasing CNC concentration. The viscosity is much higher for the unsonicated suspension when compared with the sonicated suspensions. The CNC rods appear arrested without alignment with an increasing shear rate from the small-angle light scattering patterns. The arrested glass state results from electric double layers surrounding the CNC rods, which give rise to long-ranged repulsive interactions. For the first time, we demonstrate that, within a narrow range of CNC concentrations, a shear-induced breakup process of the CNC aggregates exists when the shear rate is over a critical value and that the process is reversible in the sense that the aggregates can be reformed. We discuss the competition between the shear-induced breakup and the concentration-driven aggregation based on the experimental observations. The generated aggregate structure during the breakup process is characterized by a fractal dimension of 2.41. Furthermore, we determine two important variables-the breakup rate and the characteristic aggregate size-and derive analytical expressions for their evolution during the breakup process. The model predictions are in quantitative agreement with the experimental results.

Effect of sucrose fatty acid esters with different hydrophilic-lipophilic balance values on pasting and rheological properties of waxy rice flour.

Effects of sucrose fatty acid esters (SEs) with hydrophilic-lipophilic balance (HLB) values of 5 (S-570), 9 (S-970), and 15 (S-1570) on the pasting and rheological properties of waxy rice flour (WRF) were investigated. Rapid Visco Analyzer (RVA) showed that addition of SEs affected the pasting properties of WRF. Rheological experiment includes the steady shear flow characteristics, and dynamic viscoelastic properties were also determined using a controlled-stress rheometer. The steady shear tests demonstrated that the viscosity data fitted well with the power law model (R 2≥0.976) and all WRF pastes exhibited typical pseudoplastic and shear-thinning properties. Dynamic rheological measurements revealed that the addition of S-970 and S-1570 significantly increased the values of G' and G″ of samples, whereas the addition of S-570 decreased these values. The addition of S-1570 reduced the value of tanδ, whereas S-570 and S-970 increased it.

Blocking and Blending: Different Assembly Models of Cyclodextrin and Sodium Caseinate at the Oil/Water Interface.

The stability of cyclodextrin (CD)-based emulsions is attributed to the formation of a solid film of oil-CD complexes at the oil/water interface. However, competitive interactions between CDs and other components at the interface still need to be understood. Here we develop two different routes that allow the incorporation of a model protein (sodium caseinate, SC) into emulsions based on ß-CD. One route is the components adsorbed simultaneously from a mixed solution to the oil/water interface (route I), and the other is SC was added to a previously established CD-stabilized interface (route II). The adsorption mechanism of ß-CD modified by SC at the oil/water interface is investigated by rheological and optical methods. Strong sensitivity of the rheological behavior to the routes is indicated by both steady-state and small-deformation oscillatory experiments. Possible ß-CD/SC interaction models at the interface are proposed. In route I, the protein, due to its higher affinity for the interface, adsorbs strongly at the interface with blocking of the adsorption of ß-CD and formation of oil-CD complexes. In route II, the protein penetrates and blends into the preadsorbed layer of oil-CD complexes already formed at the interface. The revelation of interfacial assembly is expected to help better understand CD-based emulsions in natural systems and improve their designs in engineering applications.

Salting-out and salting-in: competitive effects of salt on the aggregation behavior of soy protein particles and their emulsifying properties.

Emulsions stabilized by protein particles have gained increasing research attention due to their combined advantages of biocompatibility and superior stability. In this study, colloidal particles consisting of soy protein isolates (SPIs) prepared through a heat-treatment procedure are used to make oil-in-water emulsions at a protein concentration of 10 g L(-1) and a pH of 5.91. We investigate parallelly the effects of NaCl on the stability and rheological properties of the particle suspensions and their stabilized emulsions at salt concentrations of 0, 100 and 400 mM. The aggregation behavior of the particles is strongly dependent on the NaCl concentration, showing signs of sedimentation at low NaCl concentration (100 mM) but redispersion again at high NaCl concentration (400 mM). The extensive particle aggregation is beneficial to the formation of a continuous interfacial film for the emulsions, and hence results in a remarkable increase of creaming stability and interfacial viscoelastic moduli. The results can be explained in terms of two competitive effects of NaCl: salting-out and salting-in, which are attributed to complex electrostatic interactions between the particles as a function of NaCl concentration. The delicate balance between salting-out and salting-in provides an interesting insight into the nature of underlying protein particle interactions in aqueous suspensions and a possible mechanism for tailoring their emulsifying properties via salt effects.