Influence of Sonication on the Molecular Characteristics of Carbopol® and Its Rheological Behavior in Microgels.

In this work, the effect of sonication on the molecular characteristics of polyacrylic acid (Carbopol® Ultrez 10), as well as on its rheological behavior in aqueous dispersions and microgels, was analyzed for the first time by rheometry, weight-average molecular weight (Mw) measurements via static light scattering (SLS), Fourier transform infrared (FTIR) spectroscopy and confocal microscopy. For this, the precursor dispersion and the microgels containing 0.25 wt.% of Ultrez 10 were sonicated in a commercial ultrasound bath at constant power and at different times. The main rheological properties of the microgel, namely, shear modulus, yield stress and viscosity, all decreased with increasing sonication time, while the microgel's Herschel-Bulkley (H-B) behavior, without thixotropy, was preserved. Also, Mw of Ultrez 10 decreased up to almost one-third (109,212 g/mol) of its original value (300,860 g/mol) after 180 min of sonication. These results evidence a softening of the gel microstructure, which results from the reduction in the Mw of polyacrylic acid with sonication time. Separately, FTIR measurements show that sonication produces scission in the C-C links of the Carbopol® backbone, which results in chains with the same chemistry but lower molecular weight. Finally, confocal microscopy observations revealed a diminution of the size of the microsponge domains and more free solvent with sonication time, which is reflected in a less compact and softer microstructure. The present results indicate that both the microstructure and the rheological behavior of Carbopol® microgels, in particular, and complex fluids, in general, may be manipulated or tailored by systematic high-power ultrasonication.

Whey Protein Isolate Microgel Properties Tuned by Crosslinking with Organic Acids to Achieve Stabilization of Pickering Emulsions.

Whey protein isolate (WPI) can be used effectively to produce food-grade particles for stabilizing Pickering emulsions. In the present study, crosslinking of WPI microgels using organic acids (tannic and citric acids) is proposed to improve their functionality in emulsions containing roasted coffee oil. It was demonstrated that crosslinking of WPI by organic acids reduces the microgels' size from ≈1850 nm to 185 nm and increases their contact angle compared to conventional WPI microgels, achieving values as high as 60°. This led to the higher physical stability of Pickering emulsions: the higher contact angle and smaller particle size of acid-crosslinked microgels contribute to the formation of a thinner layer of particles on the oil/water (O/W) interface that is located mostly in the water phase, thus forming an effective barrier against droplet coalescence. Particularly, emulsions stabilized by tannic acid-crosslinked WPI microgels presented neither creaming nor sedimentation up to 7 days of storage. The present work demonstrates that the functionality of these crosslinked WPI microgels can be tweaked considerably, which is an asset compared to other food-grade particles that mostly need to be used as such to comply with the clean-label policy. In addition, the applications of these particles for an emulsion are much more diverse as of the starting material.

A self-consistent Ornstein-Zernike jellium for highly charged colloids (microgels) in suspensions with added salt.

This work discusses a jellium scheme, built within the framework of the multicomponent Ornstein-Zernike (OZ) equation, which is capable of describing the collective structure of suspensions of highly charged colloids with added salt, even in the presence of finite-size multivalent microions. This approach uses a suitable approximation to decouple the microion-microion correlations from the macroion-microion profiles, which in combination with the methodology from the dressed ion theory (DIT) gives a full account of the electrostatic effective potential among the colloids. The main advantages of the present contribution reside in its ability to manage the short-range potentials and non-linear correlations among the microions, as well as its realistic characterization of the ionic clouds surrounding each macroion. The structure factors predicted by this jellium scheme are contrasted with previously reported experimental results for microgel suspensions with monovalent salts (2019Phys. Rev. E100032602), thus validating its high accuracy in these situations. The present theoretical analysis is then extended to microgel suspensions with multivalent salts, which reveals the prominent influence of the counterion valence on the makeup of the effective potentials. Although the induced differences may be difficult to identify through the mesoscopic structure, our results suggest that the microgel collapsing transition may be used to enhance these distinct effects, thus giving a feasible experimental probe for these phenomena.

Microfluidic encapsulation of nanoparticles in alginate microgels gelled via competitive ligand exchange crosslinking.

Efficient delivery of nanometric vectors complexed with nanoparticles at a target tissue without spreading to other tissues is one of the main challenges in gene therapy. One means to overcome this problem is to confine such vectors within microgels that can be placed in a target tissue to be released slowly and locally. Herein, a conventional optical microscope coupled to a common smartphone was employed to monitor the microfluidic production of monodisperse alginate microgels containing nanoparticles as a model for the encapsulation of vectors. Alginate microgels (1.2%) exhibited an average diameter of 125 ± 3 µm, which decreased to 106 ± 5 µm after encapsulating 30 nm fluorescent nanoparticles. The encapsulation efficiency was 70.9 ± 18.9%. In a 0.1 M NaCl solution, 55 ± 5% and 92 ± 4.7% of nanoparticles were released in 30 minutes and 48 hours, respectively. Microgel topography assessment by atomic force microscopy revealed that incorporation of nanoparticles into the alginate matrix changes the scaffold's interfacial morphology and induces crystallization with the appearance of oriented domains. The high encapsulation rate of nanoparticles, alongside their continuous release of nanoparticles over time, makes these microgels and the production unit a valuable system for vector encapsulation for gene therapy research.

Encapsulation of Gold Nanostructures and Oil-in-Water Nanocarriers in Microgels with Biomedical Potential.

Here we report the incorporation of gold nanostructures (nanospheres or nanorods, functionalized with carboxylate-end PEG) and curcumin oil-in-water (O/W) nanoemulsions (CurNem) into alginate microgels using the dripping technique. While gold nanostructures are promising nanomaterials for photothermal therapy applications, CurNem possess important pharmacological activities as reported here. In this sense, we evaluated the effect of CurNem on cell viability of both cancerous and non-cancerous cell lines (AGS and HEK293T, respectively), demonstrating preferential toxicity in cancer cells and safety for the non-cancerous cells. After incorporating gold nanostructures and CurNem together into the microgels, microstructures with diameters of 220 and 540 µm were obtained. When stimulating microgels with a laser, the plasmon effect promoted a significant rise in the temperature of the medium; the temperature increase was higher for those containing gold nanorods (11⁻12 °C) than nanospheres (1⁻2 °C). Interestingly, the incorporation of both nanosystems in the microgels maintains the photothermal properties of the gold nanostructures unmodified and retains with high efficiency the curcumin nanocarriers. We conclude that these results will be of interest to design hydrogel formulations with therapeutic applications.

Self-Assembly of Ionic Microgels Driven by an Alternating Electric Field: Theory, Simulations, and Experiments.

The structural properties of a system of ionic microgels under the influence of an alternating electric field are investigated both theoretically and experimentally. This combined investigation aims to shed light on the structural transitions that can be induced by changing either the driving frequency or the strength of the applied field, which range from string-like formation along the field to crystal-like structures across the orthogonal plane. In order to highlight the physical mechanisms responsible for the observed particle self-assembly, we develop a coarse-grained description, in which effective interactions among the charged microgels are induced by both equilibrium ionic distributions and their time-averaged hydrodynamic responses to the applied field. These contributions are modeled by the buildup of an effective dipole moment at the microgels backbones, which is partially screened by their ionic double layer. We show that this description is able to capture the structural properties of this system, allowing for very good agreement with the experimental results. The model coarse-graining parameters are indirectly obtained via the measured pair distribution functions and then further assigned with a clear physical interpretation, allowing us to highlight the main physical mechanisms accounting for the observed self-assembly behavior.

Properties of microparticles from a whey protein isolate/alginate emulsion gel.

Designing soft, palatable and nutritious texture-modified foods for the elderly is a challenge for food technologists. The aim of this work was to produce and characterize emulsion-gelled microparticles (EGM) made from whey protein isolate (WPI) and sodium alginate (NaAlg) that may be used to modify the rheology of liquid foods and as carriers of lipids and lipophilic nutrients and bioactives. Olive oil microdroplets became embedded in the WPI/NaAlg gel matrix in the form of an emulsion produced by ultrasound (US) or high-speed blending (HSB). Oil microdroplets were obtained by US and HSB, with an average equivalent diameter varying between 2.0-3.2 µm and 4.5-6.7 µm, respectively. Oil incorporation increased compression stress of bulk emulsion gels at small deformations compared to the no-oil microgel, but this effect was reversed at high strains. EGM were prepared by shear-induced size reduction. Rheological tests at 20 ℃ and 40 ℃ showed that US-EGM and HSB-EGM exhibited a predominant elastic behavior, with G' > G″ throughout the frequency range. However, when HSB-EGM were heated at 60 ℃ their rheological behavior changed to a more fluid-like condition, but not that of US-EGM. Consequently, EGM have the properties needed to improve food texture for people with masticatory/swallowing dysfunctions or needing special nutrition.

Oil-in-microgel strategy for enzymatic-triggered release of hydrophobic drugs.

Polymer microgels have received considerable attention due to their great potential in the biomedical field as drug delivery systems. Hyaluronic acid (HA) is a naturally occurring glycosaminoglycan composed of N-acetyl-d-glucosamine and d-glucuronic acid. This polymer is biodegradable, nontoxic, and can be chemically modified. In this work, a co-flow microfluidic strategy for the preparation of biodegradable HA microgels encapsulating hydrophobic drugs is presented. The approach relies on: (i) generation of a primary oil-in-water (O/W) nanoemulsion by the ultrasonication method, (ii) formation of a double oil-in-water-in-oil emulsion (O/W/O) using microfluidics, and (iii) cross-linking of microgels by photopolymerization of HA precursors modified with methacrylate groups (HA-MA) present in the aqueous phase of the droplets. The procedure is used for the encapsulation and controlled release of progesterone. Degradability and encapsulation/release studies in PBS buffer at 37°C in presence of different concentrations of hyaluronidase are performed. It is demonstrated that enzymatic degradation can be used to trigger the release of progesterone from microgels. This method provides precise control of the release system and can be applied for the encapsulation and controlled release of different types of hydrophobic drugs.