Heat- and shear-reversible networks in food: A review.

While nature behaves like an irreversible network with respect to entropy and time, certain systems in nature exist that are, to some extent, reversible. The property of reversibility imparts unique benefits to systems that possess them, making them suitable for designing self-healing, stimuli-responsive, and smart materials that can be used in widely divergent fields. Reversible networks are currently being exploited for applications in tissue engineering, drug delivery, and soft robotics. They are also being utilized as low-calorie fat mimetics with melt-in-your-mouth textures, as well as being explored as potential scaffolds for three-dimensional (3D) printable food, among other applications. This review aims to gather representative examples of heat- and shear-reversible networks in the food science literature from the last 30 or so years, in other words, reversible food gels made either from linear biopolymers or from colloidal, particulate dispersions, including those that have been modified specifically to induce reversibility. An overview of the network mechanisms involved that impart reversibility, including a discussion of the strength and range of forces involved, will be highlighted. A model that explains why certain networks are thermoreversible while others are shear-reversible, and why others are both, will also be proposed. A fundamental understanding of these mechanisms will prove invaluable when designing reversible networks in the future, making possible the precise control of their properties, thus fostering innovative applications within the food industry and beyond.

Microfluidic Fabrication of Colloidal Nanomaterials-Encapsulated Microcapsules for Biomolecular Sensing.

Implantable sensors that detect biomarkers in vivo are critical for early disease diagnostics. Although many colloidal nanomaterials have been developed into optical sensors to detect biomolecules in vitro, their application in vivo as implantable sensors is hindered by potential migration or clearance from the implantation site. One potential solution is incorporating colloidal nanosensors in hydrogel scaffold prior to implantation. However, direct contact between the nanosensors and hydrogel matrix has the potential to disrupt sensor performance. Here, we develop a hollow-microcapsule-based sensing platform that protects colloidal nanosensors from direct contact with hydrogel matrix. Using microfluidics, colloidal nanosensors were encapsulated in polyethylene glycol microcapsules with liquid cores. The microcapsules selectively trap the nanosensors within the core while allowing free diffusion of smaller molecules such as glucose and heparin. Glucose-responsive quantum dots or gold nanorods or heparin-responsive gold nanorods were each encapsulated. Microcapsules loaded with these sensors showed responsive optical signals in the presence of target biomolecules (glucose or heparin). Furthermore, these microcapsules can be immobilized into biocompatible hydrogel as implantable devices for biomolecular sensing. This technique offers new opportunities to extend the utility of colloidal nanosensors from solution-based detection to implantable device-based detection.

Quantification of diffusion coefficients of commonly used high-intensity sweeteners through mucin.

Low- and no-calorie sweeteners reduce the amount of carbohydrates in foods and beverages. However, concerns about taste perception surrounding the role of non-nutritive sweeteners in the oral cavity remain unanswered. One of the parameters that influences taste perception is the diffusion coefficient of the sweetener molecules inside the mucin layer lining the mouth. This study investigated the impact of diffusion coefficients of common high-intensity sweeteners on taste perception focusing on the sweeteners' diffusion through mucin. Transwell Permeable Support well plates were used to measure diffusion coefficients of samples that were collected at specific intervals to estimate the coefficients based on concentration measurements. The diffusion coefficients of acesulfame-K, aspartame, rebaudioside M, sucralose, and sucrose with and without NaCl were compared. We found that different sweeteners show different diffusion behavior through mucin and that the presence of salt enhances the diffusion. These findings contribute insights into the diffusion of high-intensity sweeteners, offer a way to evaluate diffusion coefficients in real-time, and inform the development of products with improved taste profiles.

Polymer microcapsules with programmable active release.

We present a new type of microcapsule programmed with a tunable active release mechanism. The capsules are triggered by a plasticizing stimulus that induces a phase change transition of the polymeric membrane from a solid to a fluidized form; thereafter, the cargo is actively driven out of the capsule through a defect at the capsule wall with controllable release kinetics. Tuning the degree of membrane fluidity by tailoring the amount of plasticizing stimulus present allows us to obtain temporal variation of the release kinetics from a subsecond abrupt burst release to a slow sustained release of encapsulant over many minutes. Moreover, we demonstrate tuning of the collective capsule triggering response by adjusting stimulus content, polymer molecular weight, and capsule membrane thickness. For this model system, we use a microfluidic approach to fabricate polystyrene capsules triggered by a toluene stimulus. However, this active release approach is general and is applicable to diverse polymeric capsule systems; this versatility is demonstrated by extension of our trigger-release scheme to capsules fabricated from a rubberlike block copolymer. The utility of our technique further enhances the potential of these active release capsules for practical application.

Mechanism and kinetics of enzymatic degradation of polyester microparticles using a shrinking particle-shrinking core model.

Generalized shrinking particle (SPM) and shrinking core (SCM) models were developed to the kinetics of heterogenous enzymatic degradation of polymer microparticles in a continuous microflow system. This enzymatic degradation was performed in a microfluidic device designed to both physically separate and immobilize the microparticles. Then time-resolved measurements were made using image processing of the physical changes of the particles during degradation. The kinetics of enzyme-polymer intermediate formation, enzymatic bond cleavage, and enzyme diffusion through the layer of degraded substrate (SCM only) were mathematically derived to predict the time-resolved degradation of the substrate. The proposed models were tested against the degradation of 15-25 µm particles of polycaprolactone (PCL) and poly (butylene adipate-co-terephthalate) (PBAT) by cutinase enzyme from Humicola insolens. Degradation of PCL microparticles followed the SPM model and its kinetics were found to be zero-order, while the SCM model applied to PBAT microparticles showed first-order kinetics. Further, the degradation of polybutylene succinate (PBS), and poly butylene-sebacate-co-terephthalate (PBSeT) microparticles demonstrated wide applicability of the method. The use of image processing simplifies the required analysis by eliminating the need to remove aliquots or concentrate effluent for additional analytical characterization.

Protein expression, aggregation, and triggered release from polymersomes as artificial cell-like structures.

Bringing droplets to life: A cytoskeletal protein (red dots, see scheme) is expressed in artificial cells composed of biocompatible polymersomes, which encapsulate expression machinery and amino acid building blocks. Release of the expressed proteins can be triggered by a negative osmotic shock.

Improved pH stability, heat stability, and functionality of phycocyanin after PEGylation.

Phycocyanin (PC), a spirulina-derived protein-chromophore complex, suffers from poor techno-functional properties and is highly susceptible to aggregation and color changes upon heating and pH fluctuations. We tackled these issues by modifying PC via PEGylation. Electrophoresis and Fourier transform infrared spectroscopy proved successful conjugation of methoxy PEG (mPEG) chains on PC after PEGylation. Circular dichroism indicated highly ordered folding states adopted by PEGylated PC, which we attributed to the mPEG chains on the protein surface that sterically stabilized the protein structure. Consequently, the mPEG-PC conjugates exhibited high blue color intensity and improved thermodynamic stability. Further, benefit from an electrostatic shielding effect of mPEG chains, surface charges of PEGylated PC were neutralized over pH 2-9 and the blue hue of PC was stabilized against pH variations. Additionally, the flexible and hydrophilic mPEG polymers on the PC surface promoted protein-protein and protein-water interactions. PEGylated PC thus gained increased protein solubility, techno-functionality (emulsifying, foaming, and gelling performance), and antioxidant activities, when compared to unmodified PC. Heat-induced gels formed by mPEG-PC conjugates exhibited increased stiffness, higher water retention, and weak gel-type rheological properties. After PEGylation, the improved functional properties, bioactivity, and color stability against heat and pH fluctuations will facilitate food and pharmaceutical applications of PC.

Alterations in Intestinal Brush Border Membrane Functionality and Bacterial Populations Following Intra-Amniotic Administration (Gallus gallus) of Catechin and Its Derivatives.

Catechin is a flavonoid naturally present in numerous dietary products and fruits (e.g., apples, berries, grape seeds, kiwis, green tea, red wine, etc.) and has previously been shown to be an antioxidant and beneficial for the gut microbiome. To further enhance the health benefits, bioavailability, and stability of catechin, we synthesized and characterized catechin pentaacetate and catechin pentabutanoate as two new ester derivatives of catechin. Catechin and its derivatives were assessed in vivo via intra-amniotic administration (Gallus gallus), with the following treatment groups: (1) non-injected (control); (2) deionized H2O (control); (3) Tween (0.004 mg/mL dose); (4) inulin (50 mg/mL dose); (5) Catechin (6.2 mg/mL dose); (6) Catechin pentaacetate (10 mg/mL dose); and (7) Catechin pentabutanoate (12.8 mg/mL dose). The effects on physiological markers associated with brush border membrane morphology, intestinal bacterial populations, and duodenal gene expression of key proteins were investigated. Compared to the controls, our results demonstrated a significant (p < 0.05) decrease in Clostridium genera and E. coli species density with catechin and its synthetic derivative exposure. Furthermore, catechin and its derivatives decreased iron and zinc transporter (Ferroportin and ZnT1, respectively) gene expression in the duodenum compared to the controls. In conclusion, catechin and its synthetic derivatives have the potential to improve intestinal morphology and functionality and positively modulate the microbiome.

Development and characterization of probiotic mucilage based edible films for the preservation of fruits and vegetables.

There is growing interest among the public and scientific community toward the use of probiotics to potentially restore the composition of the gut microbiome. With the aim of preparing eco-friendly probiotic edible films, we explored the addition of probiotics to the seed mucilage films of quince, flax, and basil. These mucilages are natural and compatible blends of different polysaccharides that have demonstrated medical benefits. All three seed mucilage films exhibited high moisture retention regardless of the presence of probiotics, which is needed to help preserve the moisture/freshness of food. Films from flax and quince mucilage were found to be more thermally stable and mechanically robust with higher elastic moduli and elongation at break than basil mucilage films. These films effectively protected fruits against UV light, maintaining the probiotics viability and inactivation rate during storage. Coated fruits and vegetables retained their freshness longer than uncoated produce, while quince-based probiotic films showed the best mechanical, physical, morphological and bacterial viability. This is the first report of the development, characterization and production of 100% natural mucilage-based probiotic edible coatings with enhanced barrier properties for food preservation applications containing probiotics.

Covalent polybenzimidazole-based triazine frameworks: A robust carrier for non-steroidal anti-inflammatory drugs.

Covalent triazine-based polymers (CTPs) are a new class of porous materials that can be used for the intercalation of therapeutic agents. The main purposes of designing new drug carriers include protecting them from degradation, enhancing their poor aqueous solubility, and investigating their controlled release properties. In this context, a novel polybenzimidazole-based CTP (BZ-CTP) was prepared by a solvothermal reaction between 4,4',4″-((1,3,5-triazine-2,4,6-triyl) tris(azanediyl)) tribenzoic acid (TCA) and 3,3'-diaminobenzidine. Piroxicam (PRX) and mefenamic acid (MFA) were loaded thoroughly into the CTP by using ultrasonication to form MFA-loaded CTP (MFA@BZ-CTP) and PRX-loaded CTP (PRX@BZ-CTP) with drug loading efficiencies of 49% and 53%, respectively. We attribute the increased loading efficiencies to the formation of π-π stacking forces between the aromatic rings present in the CTP structure and drugs. The in vitro release experiments were assessed in simulated physiological conditions using the dialysis method. Moreover, the release mechanisms were evaluated by Korsmeyer-Peppas kinetic studies and the obtained results showed excellent sustained releases of 81% after 96 h and 87% after 24 h for the PRX@BZ-CTP and MFA@BZ-CTP hybrids, respectively.

Preparation and characterization of polylactic-co-glycolic acid/insulin nanoparticles encapsulated in methacrylate coated gelatin with sustained release for specific medical applications.

This study aimed to examine the possibility of using insulin orally with gelatin encapsulation to enhance the usefulness of the drug and increase the lifespan of insulin in the body using polylactic-co-glycolic acid (PLGA) nanoparticles alongside gelatin encapsulation. In this regard, PLGA was synthesized via ring opening polymerization, and PLGA/insulin nanoparticles were prepared by a modified emulsification-diffusion process. The resulting nanoparticles with various amounts of insulin were fully characterized using FTIR, DSC, DLS, zeta potential, SEM, and glucose uptake methods, with results indicating the interaction between the insulin and PLGA. The process efficiency of encapsulation was higher than 92%, while the encapsulation efficiency of nanoparticles, based on an insulin content of 20 to 40%, was optimized at 93%. According to the thermal studies, the PLGA encapsulation increases the thermal stability of the insulin. The morphological studies showed the fine dispersion of insulin in the PLGA matrix, which we further confirmed by the Kjeldahl method. According to the release studies and kinetics, in-vitro degradation, and particle size analysis, the sample loaded with 30% insulin showed optimum overall properties, and thus it was encapsulated with gelatin followed by coating with aqueous methacrylate coating. Release studies at pH values of 3 and 7.4, alongside the Kjeldahl method and standard dissolution test at pH 5.5, and glucose uptake assay tests clearly showed the capsules featured 3-4 h biodegradation resistance at a lower pH along with the sustained release, making these gelatin-encapsulated nanoparticles promising alternatives for oral applications.[Figure: see text].

Fabrication of chitosan/polyvinylpyrrolidone hydrogel scaffolds containing PLGA microparticles loaded with dexamethasone for biomedical applications.

One of the most effective approaches for treatment of chronic rhinosinusitis is the use of hydrogel scaffolds with the sustained release of a given required drug. With this in mind, first, we synthesized and characterized poly (lactide-co-glycolide) (PLGA) micro and nano particles loaded with dexamethasone (DEX). We observed a 7-day release of DEX from nanoparticles, while the microparticles showed a 22-day release profile. Due to their slower rate of release, the PLGA microparticles loaded with DEX (PLGADEX microparticles) were specifically chosen for this study. As a second step, chitosan/polyvinylpyrrolidone (PVP) based hydrogels were prepared in various weight ratios and the PLGADEX microparticles were optimized in their structure based on variable gelation times. The morphological studies showed PLGADEX microparticles homogenously dispersed in the hydrogels. Moreover, the effect of weight ratio in the presence and absence of optimum percentage of PLGADEX microparticles was studied. The resultant hydrogels demonstrated a range of advantages, including good mechanical strength, porous morphology, amorphous structure, high swelling ratio, controlled biodegradability rate, and antibacterial activity. Additionally, a cytotoxicity analysis confirmed that the hydrogel scaffolds do not have adverse effects on the cells; our release studies in the hydrogel with the highest PVP content also showed 80% release after 30 days. Based on these results we were able to predict and control some of the mechanical properties, including the microstructure of the scaffolds, as well as the drug release, by optimizing the polymers - microparticle concentration, plus their resulting interactions. This optimized hydrogel can become part of a suitable alternative for treatment of allergic rhinitis and chronic sinusitis.

Microencapsulation of vitamin D using gelatin and cress seed mucilage: Production, characterization and in vivo study.

Vitamin D plays a significant role in human health and preventing diseases such as heart, immune system, and infectious problems. In this study encapsulation of vitamin D by complex coacervation with a carbohydrate (cress seed mucilage, CSM) and a protein (gelatin) was investigated. Production conditions were optimized based on ratio of core to shell, pH and CSM to gelatin volume ratio. The results showed that both the ratio of core to shell and the mucilage to gelatin ratio had significant effects (p < 0.05) on encapsulation efficiency and load. The optimum microcapsules had efficiency and loading capacity of 67.93 and 50.9%, respectively. The microcapsules were generally non-spherical and had rough surfaces. The average size of this particle was 137.22 ±â€¯3.21 µm. The FTIR result confirmed presence of vitamin D in microparticle. TGA results indicated that main weight loss of vitamin loaded microcapsules were in the temperature range of 270 to 500 °C whereas weight loss of pure vitamin started from 185 °C and completely decomposed at 300 °C. About 28 and 70% of vitamin release were occurred in simulated gastric and intestinal media, respectively. In vivo test was also performed on male rats to investigate the efficiency of microencapsulated vitamin on blood vitamin D, calcium and glucose as well as body height and weight and the data revealed its functionality.

Enhanced compatibility of starch with poly(lactic acid) and poly(ɛ-caprolactone) by incorporation of POSS nanoparticles: Study on thermal properties.

In this work, we explore the ability of polyhedral oligomeric silsesquioxane (POSS) nanoparticles to increase the compatibility of hydrophilic starch with hydrophobic poly(lactic acid) (PLA) and poly(ɛ-caprolactone) (PCL). Morphological analysis demonstrated that lower contents of POSS (0.5 and 1 wt%) enhances the compatibility of the system. However, higher inclusion of POSS results in the formation of aggregates and thus a lower level of compatibility. Transmission electron microscopy revealed that PCL acts as an intermediate between PLA and starch, and that POSS is primarily localized within the PLA and PCL phases. Based on differential scanning calorimetry, PLA's crystallinity increases from 22.9% to 31.6% upon adding a very low content of POSS (0.5 wt%). However, the PCL's crystallinity is slightly hampered due to formation of these PLA crystallites. In contrast with the crystallization behavior and based on the thermal degradation kinetics, we found the composite's thermal stability is greatly increased when moderate to high contents (3 and 5 wt%) of POSS are utilized. Dynamic mechanical analysis results also confirmed good POSS dispersion within the matrix, especially at lower contents. In conclusion, POSS serves as an efficient compatibilizer for PLA/starch/PCL systems with improved thermal properties.

Controlling the Release from Enzyme-Responsive Microcapsules with a Smart Natural Shell.

We design a natural and simple core-shell-structured microcapsule, which releases its cargo only when exposed to lipase. The cargo is entrapped inside a gel matrix, which is surrounded by a double-layer shell containing an inner solid lipid layer and an outer polymer layer. This outer polymer layer can be designed according to the intended biological system and is responsible for protecting the microcapsule architecture and transporting the cargo to the desired site of action. The lipid layer contains natural ester bonds, which are digested by lipase, controlling the release of cargo from the microcapsule core. To demonstrate the feasibility of this approach, our model system includes a colorant bixin entrapped inside a κ-carrageenan gel matrix. This core is surrounded by an inner beeswax-palmitic acid layer and an outer casein-poloxamer 338 layer. These fabricated microcapsules are then applied into Cheddar cheese, where they selectively color the cheese matrix.

Formation of shelf stable Pickering high internal phase emulsions (HIPE) through the inclusion of whey protein microgels.

High internal phase emulsions (HIPE) prepared using whey protein microgels (WPMs) as a surfactant were demonstrated to have substantially higher stability than HIPEs prepared using similar loadings of non-gelled whey protein isolate (WPI) or Tween 20. Microgel colloids were prepared from WPI solutions by heat treatment at 85 °C in a narrow pH range (5.8-6.0) to particle sizes of approximately 90, 160 and 350 nm in diameter. ζ-potentials of the WPM increased in negativity with decreasing particle size from -7.4 ± 2.5 down to -21.1 ± 0.9 at 90 nm. All WPMs conferred high stability to corn oil based HIPE when used as an emulsifier. Light microscopy and cryo-scanning electron microscopy showed that both increasing WPM concentration and decreasing WPM particle size produced increasingly smaller and more hexagonally shaped corn oil emulsion droplets; WPI and Tween 20 based HIPE droplets were generally smaller and spherical in shape. The HIPE (75% w/w corn oil) produced with 1% (w/w) WPM as an emulsifier showed stability through 6 months storage at 4 °C at all WPM sizes tested, while the HIPE prepared with 1% (w/w) WPI or Tween 20 exhibited significant creaming. WPM and WPI based HIPE both showed thermal stability at 70 °C and 95 °C while the heating of Tween 20 based HIPE resulted in droplet coalescence and oil-phase separation. HIPE production with WPMs significantly improved the viscoelastic properties of the HIPE, imparting drastic increases in yield stress, critical stress, complex modulus and elastic modulus over HIPE prepared with WPI or Tween 20. The more rigid rheology of the WPM HIPE indicated by these data is likely the primary mechanism driving the improved stability of these emulsions.

Annatto-entrapped casein-chitosan complexes improve whey color quality after acid coagulation of milk.

A fraction of annatto is often transferred to the whey fluid during Cheddar cheese processing, which negatively impacts the visual and sensory attributes of the resultant whey powder. Alternatives to reduce the color in the powder are still needed. In this study, casein-chitosan complexes were prepared to deliver annatto preferentially to the curd and reduce the amount of carryover colorant in whey powder. These complexes were relatively spherical, with a mean complex diameter of 8.3 ±â€¯1.9 µm, zeta-potential of +39.4 ±â€¯1.3 mV, and entrapment efficiency of 38.2 ±â€¯3.1%. FT-IR spectroscopy confirmed the electrostatic interaction between casein and chitosan. Complexes and commercial annatto powder were incorporated into homogenized, reduced-fat, and fat-free milk, and subjected to acid coagulation. Whey powder produced from casein-chitosan-complex-treated samples exhibited better color quality than that prepared with annatto powder, indicating that the approach considered in this study was efficient in preventing the migration of colorant to the whey.

GBR membrane of novel poly (butylene succinate-co-glycolate) co-polyester co-polymer for periodontal application.

In periodontics, osteoconductive biodegradable guided bone regeneration (GBR) membranes with acceptable physico-mechanical properties are required to fix alveolar bone defects. The objectives of the present study were to produce and characterize a novel co-polyester-poly (butylene succinate-co-glycolate) (PBSGL), and fabricate a PBSGL membrane by electrospinning. We then aimed to evaluate the in vitro effect of the glycolate ratio on the biocompatibility and osteogenic differentiation of mesenchymal stem cells (MSCs), and evaluate in vivo bone regeneration using these membranes in rabbit calvarial defects by histology. Increasing the glycolate ratio of electrospun PBSGL membranes resulted in better cell attachment, greater cell metabolic activity, and enhanced osteogenic potential at both transcriptional and translational levels. Histologic and histomorphometric evaluations revealed further that bone defects covered with fibers of higher glycolate ratios showed more bone formation, with no adverse inflammatory response. These results suggest that novel PBSGL electrospun nanofibers show great promise as GBR membranes for bone regeneration.

Microfluidic-Based Cell-Embedded Microgels Using Nonfluorinated Oil as a Model for the Gastrointestinal Niche.

Microfluidic-based cell encapsulation has promising potential in therapeutic applications. It also provides a unique approach for studying cellular dynamics and interactions, though this concept has not yet been fully explored. No in vitro model currently exists that allows us to study the interaction between crypt cells and Peyer's patch immune cells because of the difficulty in recreating, with sufficient control, the two different microenvironments in the intestine in which these cell types belong. However, we demonstrate that a microfluidic technique is able to provide such precise control and that these cells can proliferate inside microgels. Current microfluidic-based cell microencapsulation techniques primarily use fluorinated oils. Herein, we study the feasibility and biocompatibility of different nonfluorinated oils for application in gastrointestinal cell encapsulation and further introduce a model for studying intercellular chemical interactions with this approach. Our results demonstrate that cell viability is more affected by the solidification and purification processes that occur after droplet formation rather than the oil type used for the carrier phase. Specifically, a shorter polymer cross-linking time and consequently lower cell exposure to the harsh environment (e.g., acidic pH) results in a high cell viability of over 90% within the protected microgels. Using nonfluorinated oils, we propose a model system demonstrating the interplay between crypt and Peyer's patch cells using this microfluidic approach to separately encapsulate the cells inside distinct alginate/gelatin microgels, which allow for intercellular chemical communication. We observed that the coculture of crypt cells alongside Peyer's patch immune cells improves the growth of healthy organoids inside these microgels, which contain both differentiated and undifferentiated cells over 21 days of coculture. These results indicate the possibility of using droplet-based microfluidics for culturing organoids to expand their applicability in clinical research.