Effect of Chemical Composition of Metal-Organic Crosslinker on the Properties of Fracturing Fluid in High-Temperature Reservoir.

To investigate the effect of the chemical composition of a metal-organic crosslinker on the performances of fracturing fluid in high-temperature conditions, four zirconium (Zr) crosslinkers and one aluminum-zirconium (Al-Zr) crosslinker with a polyacrylamide were used. The crosslinkers possessed the same Zr concentration, but they differed in component amounts and the order of the addition of the crosslinker components, leading to different chemical compositions in the crosslinkers. The fracturing fluids prepared by different tested crosslinkers were compared in terms of properties of rheological behavior, sand-carrying ability, microstructure, and gel breaking characteristics. The results showed that the fracturing fluids prepared by zirconium lactic acid, ethanediamine, and sorbitol crosslinkers offered the slowest viscosity development and highest final viscosity compared to the zirconium lactic acid crosslinker and the zirconium lactic acid and ethanediamine crosslinker. The zirconium sorbitol, lactic acid, and ethanediamine crosslinker exhibited a faster crosslinking rate and a higher final viscosity than the zirconium lactic acid, ethanediamine, and sorbitol crosslinker; the crosslinker showed crosslinking density and crosslinking reactivity, resulting in more crosslinking sites and a higher strength in the fracturing fluid. The Al-Zr-based crosslinker possessed better properties in temperature and shear resistance, viscoelasticity, shear recovery, and sand-carrying ability than the Zr-based crosslinker due to the synergistic crosslinking effect of aluminum and zirconium ions. The tertiary release gelation mechanism of the Al-Zr-based fracturing fluid achieved a temperature resistance performance in the form of continuous crosslinking, avoiding the excessive crosslinking dehydration and reducing viscosity loss caused by early shear damage. These results indicated that the chemical compositions of metal-organic crosslinkers were important factors in determining the properties of fracturing fluids. Therefore, the appropriate type of crosslinker could save costs without adding the additional components required for high-temperature reservoirs.

Gel performance of surimi induced by various thermal technologies: A review.

Heating is a vital step in the gelation of surimi. Conventional water bath heating (WB) has the advantages of easy operation and low equipment requirements. However, the slow heat penetration during WB may lead to poor gel formation or gels prone to deterioration, especially with one-step heating. The two-step WB is time-consuming, and a large amount of water used tends to cause environmental problems. This review focuses on key factors affecting the quality of surimi gels in various heating technologies, such as surimi protein structure, chemical forces, or the activity of endogenous enzymes. In addition, the relationships between these factors and the gel performance of surimi under various heating modes are discussed by analyzing the heating temperature and heating rate. Compared with WB, the gel performance can be improved by controlling the heating conditions of microwave heating and ohmic heating, which are mainly achieved by changing the molecular structure of myofibrillar proteins or the activity of endogenous enzymes in surimi. Nevertheless, the novel thermal technologies still face several limitations and further research is needed to realize large-scale industrial production. This review provides ideas and directions for developing heat-induced surimi products with excellent gel properties.

Fabrication and Characterization of Konjac Glucomannan/Oat ß-Glucan Composite Hydrogel: Microstructure, Physicochemical Properties and Gelation Mechanism Studies.

The aim of this study was to evaluate the effect of oat ß-glucan on the formation mechanism, microstructure and physicochemical properties of konjac glucomannan (KGM) composite hydrogel. The dynamic rheology results suggested that the addition of oat ß-glucan increased the viscoelastic modulus of the composite hydrogel, which was conducive to the formation of a stronger gel network. Gelling force experiments showed that hydrogen bonds and hydrophobic interactions participated in the formation of the gel network. Textural profile analysis results found that the amount of oat ß-glucan was positively correlated with the elasticity, cohesiveness and chewiness of the composite hydrogel. The water-holding capacity of the composite hydrogel was enhanced significantly after the addition of oat ß-glucan (p < 0.05), which was 18.3 times that of the KGM gel. The thermal stability of KGM gel was enhanced after the addition of oat ß-glucan with the increase in Tmax being approximately 30 °C. Consequently, a composite hydrogel based on KGM and oat ß-glucan was a strategy to overcome pure KGM gel shortcomings.

Staggered Herringbone Microfluid Device for the Manufacturing of Chitosan/TPP Nanoparticles: Systematic Optimization and Preliminary Biological Evaluation.

Chitosan nanoparticles (CS NPs) showed promising results in drug, vaccine and gene delivery for the treatment of various diseases. The considerable attention towards CS was owning to its outstanding biological properties, however, the main challenge in the application of CS NPs was faced during their size-controlled synthesis. Herein, ionic gelation reaction between CS and sodium tripolyphosphate (TPP), a widely used and safe CS cross-linker for biomedical application, was exploited by a microfluidic approach based on a staggered herringbone micromixer (SHM) for the synthesis of TPP cross-linked CS NPs (CS/TPP NPs). Screening design of experiments was applied to systematically evaluate the main process and formulative factors affecting CS/TPP NPs physical properties (mean size and size distribution). Effectiveness of the SHM-assisted manufacturing process was confirmed by the preliminary evaluation of the biological performance of the optimized CS/TPP NPs that were internalized in the cytosol of human mesenchymal stem cells through clathrin-mediated mechanism. Curcumin, selected as a challenging model drug, was successfully loaded into CS/TPP NPs (EE% > 70%) and slowly released up to 48 h via the diffusion mechanism. Finally, the comparison with the conventional bulk mixing method corroborated the efficacy of the microfluidics-assisted method due to the precise control of mixing at microscales.

Effect of sanxan as novel natural gel modifier on the physicochemical and structural properties of microbial transglutaminase-induced mung bean protein isolate gels.

Mung bean protein isolate (MBPI) has attracted much attention as an emerging plant protein. However, its application was limited by the poor gelling characteristics. Thus, the effect of sanxan (SAN) on the gelling behavior of MBPI under microbial transglutaminase (MTG)-induced condition were explored in this study. The results demonstrated that SAN remarkably enhanced the storage modulus, water-holding capacity and mechanical strength. Furthermore, SAN changed the microstructure of MBPI gels to become more dense and ordered. The results of zeta potential indicated the electrostatic interactions existed between SAN and MBPI. The incorporation of SAN altered the secondary structure and molecular conformation of MBPI, and hydrophobic interactions and hydrogen bonding were necessary to maintain the network structure. Additionally, in vitro digestion simulation results exhibited that SAN remarkably improved the capability of MBPI gels to deliver bioactive substances. These findings provided a practical strategy to use natural SAN to improve legume protein gels.

Inorganic Hydrogel Based on Low-Dimensional Nanomaterials.

Composed of three-dimensional (3D) nanoscale inorganic bones and up to 99% water, inorganic hydrogels have attracted much attention and undergone significant growth in recent years. The basic units of inorganic hydrogels could be metal nanoparticles, metal nanowires, SiO2 nanowires, graphene nanosheets, and MXene nanosheets, which are then assembled into the special porous structures by the sol-gel process or gelation via either covalent or noncovalent interactions. The high electrical and thermal conductivity, resistance to corrosion, stability across various temperatures, and high surface area make them promising candidates for diverse applications, such as energy storage, catalysis, adsorption, sensing, and solar steam generation. Besides, some interesting derivatives, such as inorganic aerogels and xerogels, can be produced through further processing, diversifying their functionalities and application domains greatly. In this context, we primarily provide a comprehensive overview of the current status of inorganic hydrogels and their derivatives, including the structures of inorganic hydrogels with various compositions, their gelation mechanisms, and their exceptional practical performance in fields related to energy and environmental applications.

Comparison and analysis of mechanism of ß-lactoglobulin self-assembled gel carriers formed by different gelation methods.

Based on the findings of our previous studies, a comprehensive comparative investigation of the quality and formation mechanism of gels obtained from protein self-assemblies induced by different methods is necessary. Self-assembled heat-induced gels had higher gel mechanical strength, and hydrophobic interactions played a greater role. Whether or not heat treatment was used to induce gel formation may play a more important role than the effect of divalent cations on gel formation. Hydrogen bonds played an important role in all gels formed using different gelation methods. Furthermore, Self-assembled cold-induced gels were considered to can load bioactive substances with different hydrophilicity properties due to the high water-holding capacity and the smooth, dense microstructure. Therefore, ß-lactoglobulin fibrous and worm-like self-assembled cold-induced gels as a delivery material for hydrophilic bioactive substances (epigallocatechin gallate, vitamin B2) and amphiphilic bioactive substance (naringenin), with good encapsulation efficiency (91.92 %, 97.08 %, 96.72 %, 96.52 %, 98.94 %, 97.41 %, respectively) and slow-release performance.

Universal Behavior of Fractal Water Structures Observed in Various Gelation Mechanisms of Polymer Gels, Supramolecular Gels, and Cement Gels.

So far, it has been difficult to directly compare diverse characteristic gelation mechanisms over different length and time scales. This paper presents a universal water structure analysis of several gels with different structures and gelation mechanisms including polymer gels, supramolecular gels composed of surfactant micelles, and cement gels. The spatial distribution of water molecules was analyzed at molecular level from a diagram of the relaxation times and their distribution parameters (τ-ß diagrams) with our database of the 10 GHz process for a variety of aqueous systems. Polymer gels with volume phase transition showed a small decrease in the fractal dimension of the hydrogen bond network (HBN) with gelation. In supramolecular gels with rod micelle precursor with amphipathic molecules, both the elongation of the micelles and their cross-linking caused a reduction in the fractal dimension. Such a reduction was also found in cement gels. These results suggest that the HBN inevitably breaks at each length scale with relative increase in steric hindrance due to cross-linking, resulting in the fragmentation of collective structures of water molecules. The universal analysis using τ-ß diagrams presented here has broad applicability as a method to characterize diverse gel structures and evaluate gelation processes.

Development and Gelation Mechanism of Ultra-High-Temperature-Resistant Polymer Gel.

To expand the applicability of gel fracturing fluids in ultra-high-temperature reservoirs, a temperature-resistant polymer was synthesized using the solution polymerization method. Subsequently, an ultra-high-temperature-resistant polymer gel was formulated by incorporating an organic zirconium crosslinking agent. A comprehensive investigation was carried out to systematically study and evaluate the steady shear property, dynamic viscoelasticity, and temperature and shear resistance performance, as well as the core damage characteristics of the polymer gel. The obtained results demonstrate that the viscosity remained at 147 mPa·s at a temperature of 200 °C with a shear rate of 170 s-1. Compared with the significant 30.9% average core damage rate observed in the guanidine gum fracturing fluid, the core damage attributed to the polymer gel was substantially mitigated, measuring only 16.6%. Finally, the gelation mechanism of the polymer gel was scrutinized in conjunction with microscopic morphology analysis. We expect that this study will not only contribute to the effective development of deep and ultradeep oil and gas reservoirs but also furnish a theoretical foundation for practical field applications.

A review of sodium silicate solutions: Structure, gelation, and syneresis.

Sodium silicate solutions, also known as waterglass, have been found to have remarkable utility in a variety of applications. The cumulative weight of evidence from 70 years of varied analysis indicates that silicate solutions consist of a wide range of species, from monomers through oligomers, up to colloids. Moreover, the structure and distribution of these species are greatly dependent upon many parameters, such as solute concentrations, silica to alkali ratio, pH, and temperature. The most interesting and characteristic property of silicate solutions is their ability to form silica gels. Overall, despite extensive research using different spectroscopic and scattering techniques, many questions related to sodium silicate's dynamic structure, stability, polymerization, and gelation remain difficult to answer. The multitude of simultaneous reactions which restructure the silicate species at the atomic scale in response to variation in solution and environmental parameters, makes it difficult to investigate the individual events using only experimental data. Molecular modelling provides an alternative way to study the unknown areas in the aqueous silicate and silica gel systems, generating key insights into the chemical reactions at microscopic length scales. However, sufficient sampling remains a challenge for the practical use of molecular simulation for these systems. Based on both experimental and modelling studies, this review provides a detailed discussion over the structure and speciation of sodium silicate solutions, their gelation mechanism and kinetics, and the syneresis phenomenon. The goal is not only to review the current level of understanding of sodium silicate solutions, silica gels and characterization techniques suitable for studying them, but also to identify the gaps in the literature and open up opportunities for advancing knowledge about these complex systems. We believe that the future direction of research should be toward correlating atomistic, molecular, and meso-scale level details of interactions and reactions in silicate solution and establishing a fundamental understanding of its gelation mechanism and kinetics. We believe that this knowledge could eliminate the "trial and error" approach in manufacturing, and improve structural control in the synthesis of important materials derived from these solutions, such as silica gels and zeolites.

Sponge-like Cryogels from Liquid-Liquid Phase Separation: Structure, Porosity, and Diffusional Gel Properties.

Macroporous gels find application in several scientific fields, ranging from art restoration to wastewater filtration or cell entrapment. In this work, two-component sponge-like cryogels are challenged to assess their cleaning performances and to investigate how pores size and connectivity affect physico-chemical properties. The gels were obtained through a freeze-thaw process, exploiting a spontaneous polymer-polymer phase-separation occurring in the pre-gel solution. During the freezing step, a highly hydrolyzed polyvinyl alcohol (H-PVA) forms the hydrogel walls. The secondary components, namely a partially hydrolyzed polyvinyl alcohol (L-PVA) or polyvinyl pyrrolidone (PVP), act as modular porogens, being partially extracted during gel washing. H-PVA/L-PVA and H-PVA/PVP mixtures were studied by confocal laser scanning microscopy to unveil sols and gels morphology at the micron-scale, while small angle X-ray scattering was used to get insights about characteristic dimensions at the nanoscale. The gelation mechanism was investigated through rheology measurements, and the characteristic exponents were compared to De Gennes' scaling laws gathered from percolation. In the field of art conservation, these sponge-like gels are ideal systems for the cleaning of artistic painted surfaces. Their interconnected pores allow the diffusion of cleaning fluids at the painted interface, facilitating dirt uptake and/or detachment. This study uncovered a direct relationship linking a gel's cleaning performance to its apparent tortuosity. These findings can pave the way to fine-tuning systems with enhanced cleaning abilities, not restricted to the restoration of irreplaceable priceless works of art, but with possible application in diverse research fields.

On the gelation of Premna microphylla turcz extracts: The effects of supernatant and precipitate of plant ash suspension.

In order to elucidate the gelling mechanism of Premna microphylla turcz (PMT) induced by plant ash (PA), PA was fractionated into supernatant (PA-S) and precipitation (PA-P) and added to the PMT suspension, respectively. The effects of different concentrations (1-9%) and fractions (PA, PA-S, PA-P) of PA suspension on the gel properties were studied. Results showed that the electrical conductivity, content of monovalent cations, pH were higher in PA-S than PA-P. Both the PA-S and PA-P fractions induced the gelation of PMT (except for the low concentration at 1% for PA-S), and the PA-P-PMT gels showed much higher gel strength and hardness than PA-S-PMT gels. With increased concentration, the gel strength increased in PA-P-PMT, but decreased in PA-S-PMT. A hypothesis for the gelation of PMT induced by PA was proposed: the divalent cations in PA bind to carboxyl group in pectin and form gels; when higher content of PA is added, a higher pH leads to extensive dissociation of carboxyl groups thereby increases the electrostatic repulsion between pectin chains, which ultimately weakens the gelling forces. This study can provide theoretical support for further optimization of the traditional processing of PMT gels.

Recent advances on small molecular gels: formation mechanism and their application in pharmaceutical fields.

INTRODUCTION: As an essential complement to chemically cross-linked macromolecular gels, drug delivery systems based on small molecular gels formed under the driving forces of non-covalent interactions are attracting considerable research interest due to their potential advantages of high structural functionality, lower biological toxicity, reversible stimulus-response, and so on. AREA COVERED: The present review summarizes recent advances in small molecular gels and provides their updates as a comprehensive overview in terms of gelation mechanism, gel properties, and physicochemical characterizations. In particular, this manuscript reviews the effects of drug-based small molecular gels on the drug development and their potential applications in the pharmaceutical fields. EXPERT OPINION: Small molecular-based gel systems, constructed by inactive compounds or active pharmaceutical ingredients, have been extensively studied as carriers for drug delivery in pharmaceutical field, such as oral formulations, injectable formulations, and transdermal formulations. However, the construction of such gel systems yet faces several challenges such as rational and efficient design of functional gelators and the great occasionality of drug-based gel formation. Thus, a deeper understanding of the gelation mechanism and its relationship with gel properties will be conducive to the construction of small molecular gels systems and their future application.

Polysaccharide hydrogels: Functionalization, construction and served as scaffold for tissue engineering.

Polysaccharide hydrogels have been widely utilized in tissue engineering. They interact with the organismal environments, modulating the cargos release and realizing of long-term survival and activations of living cells. In this review, the potential strategies for modification of polysaccharides were introduced firstly. It is not only used to functionalize the polysaccharides for the consequent formation of hydrogels, but also used to introduce versatile side groups for the regulation of cell behavior. Then, techniques and underlying mechanisms in inducing the formation of hydrogels by polysaccharides or their derivatives are briefly summarized. Finally, the applications of polysaccharide hydrogels in vivo, mainly focus on the performance for alleviation of foreign-body response (FBR) and as cell scaffolds for tissue regeneration, are exemplified. In addition, the perspectives and challenges for further research are addressed. It aims to provide a comprehensive framework about the potentials and challenges that the polysaccharide hydrogels confronting in tissue engineering.

Ultralight Magnetic and Dielectric Aerogels Achieved by Metal-Organic Framework Initiated Gelation of Graphene Oxide for Enhanced Microwave Absorption.

HIGHLIGHTS: Metal-organic frameworks (MOFs) are used to directly initiate the gelation of graphene oxide (GO), producing MOF/rGO aerogels. The ultralight magnetic and dielectric aerogels show remarkable microwave absorption performance with ultralow filling contents. The development of a convenient methodology for synthesizing the hierarchically porous aerogels comprising metal-organic frameworks (MOFs) and graphene oxide (GO) building blocks that exhibit an ultralow density and uniformly distributed MOFs on GO sheets is important for various applications. Herein, we report a facile route for synthesizing MOF/reduced GO (rGO) aerogels based on the gelation of GO, which is directly initiated using MOF crystals. Free metal ions exposed on the surface of MIL-88A nanorods act as linkers that bind GO nanosheets to a three-dimensional porous network via metal-oxygen covalent or electrostatic interactions. The MOF/rGO-derived magnetic and dielectric aerogels Fe3O4@C/rGO and Ni-doped Fe3O4@C/rGO show notable microwave absorption (MA) performance, simultaneously achieving strong absorption and broad bandwidth at low thickness of 2.5 (- 58.1 dB and 6.48 GHz) and 2.8 mm (- 46.2 dB and 7.92 GHz) with ultralow filling contents of 0.7 and 0.6 wt%, respectively. The microwave attenuation ability of the prepared aerogels is further confirmed via a radar cross-sectional simulation, which is attributed to the synergistic effects of their hierarchically porous structures and heterointerface engineering. This work provides an effective pathway for fabricating hierarchically porous MOF/rGO hybrid aerogels and offers magnetic and dielectric aerogels for ultralight MA.

Revealing the enhanced structural recovery and gelation mechanisms of cation-induced cellulose nanofibrils composite hydrogels.

In this study, we fabricate physically dual-crosslinked cellulose-based hydrogels by varying coordination bonding effects with the addition of either divalent or trivalent metal cations. The first crosslinked network is created by metal-carboxylate coordination bonds between the cellulose nanofibrils that have abundant carboxyl groups and the metal cations. The second crosslinked network is formed by the reaction of tetra-functional borate ion complex and the hydroxyl groups in polyvinyl alcohol. These physically dual-crosslinked networks are strongly interwoven by non-sacrificial hydrogen bonds, this dual-crosslinked network leads to enhanced recovery characteristics in the resulting hydrogels. We use three interval thixotropic testing to investigate the deformation and recovery behaviors of the hydrogels and plot their structural deformation parameters in phase diagrams to understand the underlying complexity of energy dissipation and viscoelastic dynamics of the dual-crosslinked hydrogels.

Investigations into the role of non-bond interaction on gelation mechanism of silk fibroin hydrogel.

Silk fibroin hydrogel not only has biocompatibility, but also has environmental response ability. It plays an important role in the development of material. The gelation mechanism of silk fibroin hydrogel is very important to textile and medicine fields. The molecular dynamics simulation was used to discuss the structure and non-bond interaction of silk fibroin hydrogel. The results show that the non-bond interactions between silk fibroin molecules and water molecules have certain influence on the formation of silk fibroin hydrogel. According to the hydrogen bond analysis, the hydrogen bonds are mainly formed between random coil peptide fragments at the two ends of silk fibroin molecules and residues 252-254 are the key residues. The electrostatic and polar solvation interactions between silk fibroin molecules plays a major role in cross-linking of the coil segments of two silk fibroin molecules.

Effects of calcium ion on gel properties and gelation of tilapia (Oreochromis niloticus) protein isolates processed with pH shift method.

The effect and mechanisms of calcium chloride and citric acid addition on the acid method of processing tilapia protein isolates and surimi gels were studied. The alkaline method shows better gel quality than the acid method with lower yield and high lipid content. The addition of calcium chloride increased the breaking force to 494.56 g and citric acid helped reducing the lipid content by 85.85%, resulting in a higher yield of 75.36%. Gels with calcium maintained low levels of expressible moisture (2.30%), indicating a well-organised gel matrix. The decrease in -SH content and increase in ionic bonds content suggested increased formation of disulphide bonds and ionic bonds. Oscillatory dynamic measurement indicated that more heat resistant bonds were formed. The morphology of myofibril proteins studied by atomic force microscopy (AFM) showed that the height of the proteins in the calcium-added gels decreased 79.4%, which suggested that the protein structure was "suppressed".

Rheo-Kinetic Study of Sol-Gel Phase Transition of Chitosan Colloidal Systems.

Chitosan colloidal systems, created by dispersing in aqueous solutions of hydrochloric acid, with and without the addition of disodium ß-glycerophosphate (ß-NaGP), were prepared for the investigation of forming mechanisms of chitosan hydrogels. Three types of chitosan were used in varying molecular weights. The impacts of the charge and shape of the macromolecules on the phase transition process were assessed. The chitosan system without the addition of ß-NaGP was characterized by stiff and entangled molecules, in contrast to the chitosan system with the addition of ß-NaGP, wherein the molecules adopt a more flexible and disentangled form. Differences in molecules shapes were confirmed using the Zeta potential and thixotropy experiments. The chitosan system without ß-NaGP revealed a rapid nature of phase transition-consistent with diffusion-limited aggregation (DLA). The chitosan system with ß-NaGP revealed a two-step nature of phase transition, wherein the first step was consistent with reaction-limited aggregation (RLA), while the second step complied with diffusion-limited aggregation (DLA).

Design of polygalacturonate hydrogels using iron(II) as cross-linkers: A promising route to protect bioavailable iron against oxidation.

We designed stable and highly reproducible hydrogels by external unidirectional diffusion of Fe2+ ions into aqueous solutions of polygalacturonate (polyGal) chains. The Fe2+ ions act as cross-linkers between the Gal units in such a way that both the molar ratio R ([Fe2+]/[Gal units] = 0.25) and the mesh size of the polyGal network at the local scale (ξ = 75 ±â€¯5 Å) have constant values within the whole gel, as respectively determined by titration and Small Angle Neutron Scattering. From macroscopic point of view, there is a progressive decrease of polyGal concentration from the part of the gel formed in the early stages of the gelation process, which is homogeneous, transparent and whose Young modulus has a high value of ∼105 Pa, up to the part of the gel formed in the late stages, which is heterogeneous, highly turbid and has a much lower Young modulus of ∼103 Pa. Since the local organization of the polyGal chains remains identical all along the hydrogels, this macroscopic concentration gradient originates from the formation of heterogeneities at a mesoscopic length scale during the gelation process. In addition, X-ray Absorption Spectroscopy measurements remarkably reveal that Fe2+ ions keep their +II oxidation state in the whole gels once they have cross-linked the Gal units. These polyGal hydrogels thus protect iron against oxidation and could be used for iron fortification.