Gamma Radiation- and Ultraviolet-Induced Polymerization of Bis(amino acid)fumaramide Gel Assemblies

Controlling the polymerization of supramolecular self-assembly through external stimuli holds great potential for the development of responsive soft materials and manipulation at the nanoscale. Vinyl esters of bis(leu or val)fumaramide (1a and 2a) have been found to be gelators of various organic solvents and were applied in this investigation of the influence of organogelators’ self-assembly on solid-state polymerization induced by gamma and ultraviolet irradiation. Here, we report our investigation into the influences of self-assemblies of bis(amino acid vinyl ester)fumaramides on gamma-ray- and ultraviolet-induced polymerization. The gelator molecules self-assembled by non-covalent interactions, mainly through hydrogen bonds between the amide group (CONH) and the carboxyl group (COO), thus forming a gel network. NMR and FTIR spectroscopy were used to investigate and characterize supramolecular gels. TEM and SEM microscopy were used to investigate the morphology of gels and polymers. Morphology studies showed that the gels contained a filamentous structure of nanometer dimensions that was exhaustive in a three-dimensional network. The prepared derivatives contained reactive alkyl groups suitable for carrying out the polymerization reaction initiated by gamma or ultraviolet radiation in the supramolecular aggregates of selected gels. It was found that the polymerization reaction occurred only in the network of the gel and was dependent on the structure of aggregates or the proximity and orientation of double bonds in the gel network. Polymers were formed by the gels exposure to gamma and ultraviolet radiation in toluene, and water/DMF gels with transcripts of their gel structure into polymers. The polymeric material was able to immobilize various solvents by swelling. Furthermore, methyl esters of bis(leu and val)fumaramide (1b and 2b) were synthesized; these compounds showed no gelling properties, and the crystal structure of the valine derivative 2b was determined.

Fabrication and Characterization of Gel Beads of Whey Isolate Protein–Pectin Complex for Loading Quercetin and Their Digestion Release

In this study, emulsion gel beads for loading quercetin were prepared through an emulsification/gelation process using whey protein isolate (WPI) and pectin. Emulsion gel beads’ properties were investigated by different pectin content. Additionally, the physicochemical properties, morphology and quercetin release properties from beads were explored. Firstly, electrical characteristics and the rheology of bead-forming solutions were measured, revealing that all systems had strong negative charge and exhibited shear-thinning behavior. The textural results demonstrated that the properties of emulsion gel beads were improved with increasing the content of pectin. It was also confirmed that crosslinking was formed between WPI emulsion and pectin by Fourier Transform Infrared (FTIR) analysis and thermogravimetric analysis (TGA). In addition, the shape of the beads was spherical or ellipses with smooth surfaces and they had a tight gel network of internal structures, which was visualized by using electron microscopy (SEM). Finally, the amount of quercetin released in vitro was gradually decreased with increasing pectin content; it was as low as 0.59%. These results revealed that WPI emulsion–pectin gel beads might be an effective delivery system for quercetin as a colon target and are worth exploring further.

Effect of Sand-Frying-Triggered Puffing on the Multi-Scale Structure and Physicochemical Properties of Cassava Starch in Dry Gel

This study revealed the underlying mechanisms involved in the puffing process of dried cassava starch gel by exploring the development of the puffed structure of gel upon sand-frying, chiefly focused on the changes in the multi-scale structure and the physicochemical properties of starch. The results suggested that the sand-frying-induced puffing proceeded very fast, completed in about twenty seconds, which could be described as a two-phase pattern including the warming up (0~6 s) and puffing (7~18 s) stages. In the first stage, no significant changes occurred to the structure or appearance of the starch gel. In the second stage, the cells in the gel network structure were expanded until burst, which brought about a decrease in moisture content, bulk density, and hardness, as well as the increase in porosity and crispness when the surface temperature of gel reached glass transition temperature of 125.28 °C. Upon sand-frying puffing, the crystalline melting and molecular degradation of starch happened simultaneously, of which the latter mainly occurred in the first stage. Along with the increase of puffing time, the thermal stability, peak viscosity, and final viscosity of starch gradually decreased, while the water solubility index increased. Knowing the underlying mechanisms of this process might help manufacturers produce a better quality of starch-based puffed products.

Protein microparticles visualize the contact network and rigidity onset in the gelation of model proteins

Protein aggregation into gel networks is of immense importance in diverse areas from food science to medical research; however, it remains a grand challenge as the underlying molecular interactions are complex, difficult to access experimentally, and to model computationally. Early stages of gelation often involve protein aggregation into protein clusters that later on aggregate into a gel network. Recently synthesized protein microparticles allow direct control of these early stages of aggregation, decoupling them from the subsequent gelation stages. Here, by following the gelation of protein microparticles directly at the particle scale, we elucidate in detail the emergence of a percolating structure and the onset of rigidity as measured by microrheology. We find that the largest particle cluster, correlation length, and degree of polymerization all diverge with power laws, while the particles bind irreversibly indicating a nonequilibrium percolation process, in agreement with recent results on weakly attractive colloids. Concomitantly, the elastic modulus increases in a power-law fashion as determined by microrheology. These results give a consistent microscopic picture of the emergence of rigidity in a nonequilibrium percolation process that likely underlies the gelation in many more systems such as proteins, and other strongly interacting structures originating from (bio)molecules.

New Hydrogel Network Based on Alginate and a Spiroacetal Copolymer

This study reports a strategy for developing a biohybrid complex based on a natural/synthetic polymer conjugate as a gel-type structure. Coupling synthetic polymers with natural compounds represents an important approach to generating gels with superior properties and with potential for biomedical applications. The study presents the preparation of hybrid gels with tunable characteristics by using a spiroacetal polymer and alginate as co-partners in different ratios. The new network formation was tested, and the structure was confirmed by FTIR and SEM techniques. The physical properties of the new gels, namely their thermal stability and swelling behavior, were investigated. The study showed that the increase in alginate content caused a smooth increase in thermal stability due to the additional crosslinking bridges that appeared. Moreover, increasing the content of the synthetic polymer in the structure of the gel network ensures a slower release of carvacrol, the encapsulated bioactive compound.

Differences in Eating Quality Attributes between Japonica Rice from the Northeast Region and Semiglutinous Japonica Rice from the Yangtze River Delta of China

Differences in cooked rice and starch and protein physicochemical properties of three japonica rice were compared systematically. Cultivars of japonica rice, Daohuaxiang2, from Northeast China (NR) and two semiglutinous japonica rice (SGJR), Nangeng46 and Nangeng2728, from the Yangtze River Delta (YRD) were investigated. Both Daohuaxiang2 and Nangeng46 achieved high taste values, but there were great differences in starch and protein physicochemical properties. Daohuaxiang2 showed higher apparent amylose content (AAC), lower protein content (PC), and longer amylopectin (especially fb2 and fb3) and amylose chain lengths, resulting in thicker starch lamellae and larger starch granule size. Its cooked rice absorbed more water and expanded to larger sizes. All of these differences created a more compact gel network and harder but more elastic cooked rice for Daohuaxiang2. Nangeng46 produced a lower AAC, a higher PC, shorter amylopectin and amylose chain lengths, thinner starch lamellae, and smaller starch granule sizes, creating a looser gel network and softer cooked rice. The two SGJR, Nangeng46 and Nangeng2728, had similar low AACs but great differences in taste values. The better-tasting Nangeng46 had a lower PC (especially glutelin content) and higher proportion of amylopectin fa chains, which likely reduced the hardness, improved the appearance, and increased the adhesiveness of its cooked rice. Overall, both types of japonica rice from the NR and YRD could potentially have good eating qualities where Nangeng46’s cooked rice was comparable to that of Daohuaxiang2 because of its lower AC. Moreover, its lower PC and higher proportion of amylopectin fa chains likely improved its eating quality over the inferior-tasting SGJR, Nangeng2728. This research lays a foundation for the improvement of the taste of japonica rice in rice breeding.

Carboxylated Cellulose Nanocrystals as Environmental-Friendly and Multi-Functional Additives for Bentonite Water-Based Drilling Fluids Under High-temperature Conditions

During the oil and gas drilling engineering, the selection of drilling fluids must take account of the technical and environmental factors. This study investigated the effectiveness of carboxylated cellulose nanocrystals (denoted as CNCs) as environmentally friendly additives in improving the rheological, filtration, and inhibitive performances of bentonite (BT) water-based drilling fluids (WBDFs). CNCs used in this study were modified by carboxylation reaction, displaying small size, negative surface charge, good colloidal stability, and prominent shear thinning behavior. The experimental results indicated that BT/CNC suspensions had superior rheological properties, low fluid loss volumes, and effective inhibition, even at 140 °C. Microstructure analysis demonstrated that CNCs could attach to the surface of BT via hydrogen bond and ionic bond. CNCs, BT, and vicinal water molecules could form a stiff gel network, which had a strong resistance to flow under shear force, leading to a significant improvement in the rheological properties. Moreover, under the differential pressure, BT/CNC suspensions formed thin and less hydrophilic filter cakes with compact layered structure, thereby efficiently decreasing the fluid loss volume. Finally, due to the gel network and filtration ability, BT/CNC suspensions performed low water activity, which was beneficial for preventing the penetration of free water into the shales and borehole well. Thus CNCs also exerted satisfactory inhibition on hydration and dispersion of BT and shales. As a result, CNCs showed great potential to be used as efficient, multi-functional, and environmentally friendly additives in WBDFs.

Making and Breaking of Gels: Stimuli-Responsive Properties of Bis(Pyridyl-N-oxide Urea) Gelators

The structural modification of existing supramolecular architecture is an efficient strategy to design and synthesize supramolecular gels with tunable and predictable properties. In this work, we have modified bis(pyridyl urea) compounds with different linkers, namely hexylene and butylene, to their corresponding bis(pyridyl-N-oxide urea). The gelation properties of both the parent and the modified compounds were studied, and the results indicated that modification of the 3-pyridyl moieties to the corresponding 3-pyridyl-N-oxides induced hydrogelation. The stability of the parent and modified compounds were evaluated by sol-gel transition temperature (Tgel) and rheological measurements, and single-crystal X-ray diffraction was used to analyze the solid-state interactions of the gelators. The morphologies of the dried gels were analyzed by scanning electron microscopy (SEM), which revealed that the structural modification did not induce any prominent effect on the gel morphology. The stimuli-responsive behavior of these gels in the presence of salts in DMSO/water was evaluated by rheological experiments, which indicated that the modified compounds displayed enhanced gel strength in most cases. However, the gel network collapsed in the presence of the chloride salts of aluminum(III), zinc(II), copper(II), and cadmium(II). The mechanical strength of the parent gels decreased in the presence of salts, indicating that the structural modification resulted in robust gels in most cases. The modified compounds formed gels below minimum gel concentration in the presence of various salts, indicating salt-induced gelation. These results show the making and breaking ability of the gel network in the presence of external stimuli (salts), which explains the potential of using LMWGs based on N-oxide moieties as stimuli-responsive materials.

More natural more better: triple natural anti-oxidant puerarin/ferulic acid/polydopamine incorporated hydrogel for wound healing

Background During wound healing, the overproduction of reactive oxygen species (ROS) can break the cellular oxidant/antioxidant balance, which prolongs healing. The wound dressings targeting the mitigation of ROS will be of great advantages for the wound healing. puerarin (PUE) and ferulic acid (FA) are natural compounds derived from herbs that exhibit multiple pharmacological activities, such as antioxidant and anti-inflammatory effects. Polydopamine (PDA) is made from natural dopamine and shows excellent antioxidant function. Therefore, the combination of natural antioxidants into hydrogel dressing is a promising therapy for wound healing. Results Hydrogel wound dressings have been developed by incorporating PUE or FA via PDA nanoparticles (NPs) into polyethylene glycol diacrylate (PEG-DA) hydrogel. This hydrogel can load natural antioxidant drugs and retain the drug in the gel network for a long period due to the presence of PDA NPs. Under oxidative stress, this hydrogel can improve the activity of superoxide dismutase and glutathione peroxidase and reduce the levels of ROS and malondialdehyde, thus preventing oxidative damage to cells, and then promoting wound healing, tissue regeneration, and collagen accumulation. Conclusion Overall, this triple antioxidant hydrogel accelerates wound healing by alleviating oxidative injury. Our study thus provides a new way about co-delivery of multiple antioxidant natural molecules from herbs via antioxidant nanoparticles for wound healing and skin regeneration. Graphic Abstract

Competition between Osmotic Squeezing versus Friction-Driven Swelling of Gels

Some types of hydro-gels have almost the same equilibrium swelling volume in water and in ethylene glycol (EG), a highly viscous liquid completely miscible with water. Experiments showed that when a gel fully swollen with EG is immersed into a large amount of water, it temporarily swells up and then relaxes to the equilibrium volume in water. The temporary swelling is explained by the friction force exerted on the gel network from the outward EG flux In this paper, we experimentally show that the temporary swelling is suppressed by adding linear PEG (polyethylene glycol) in the outer water. Although the suppression seems to be explained by the osmotic pressure (i.e., by the same mechanism as the conventional osmotic squeezing), our theoretical analysis reveals that the effect of PEG is much stronger than that expected from the equilibrium osmotic pressure, implying that the PEG chains are condensed on the gel surface.