Critical Gelation Research Articles

Non-Stoichiometric Effects on Viscoelasticity in DGEBA-EDA Systems: Insights from Brillouin Light Scattering.

The initial and final stages of the isothermal curing reaction between diglycidyl ether of bisphenol A and ethylenediamine were investigated by using Brillouin light scattering spectroscopy. High-frequency acoustic parameters were measured for these stages as a function of the diamine molar fraction, ranging from the pure prepolymer to the pure cross-linker. Significant differences in the concentration dependencies of the mechanical parameters are interpreted in relation to changes in the system's viscoelastic properties. At the final stage of the reaction, the concentration dependencies exhibit notable changes at two characteristic nonstoichiometric compositions─one corresponding to amine excess and the other to epoxy excess. While these concentrations align well with Flory's critical gel points, experimental evidence suggests they should instead be interpreted as vitrification points.

Improving gel properties of low-salt silver carp surimi through single-mode microwave-assisted processing

Surimi, a product derived from low-value fish, is widely used to produce high-value items such as imitation crabsticks and fish balls. However, surimi from freshwater fish like silver carp generally exhibits inferior gel properties compared to marine fish. This study investigated the effects of 915 MHz single-mode microwave-assisted processing on the gel properties of low-salt silver carp surimi. Traditional water bath processing served as the control for comparison. Gel strength, texture, water-holding capacity (WHC), whiteness, protein secondary structure, and microstructure, along with thermal processing efficiency for microbial inactivation were evaluated. The results demonstrated that single-mode microwave processing significantly improved gel properties compared to water bath processing. Compared with the optimal water bath treatment, the gel strength of microwave processed samples increased significantly from 479.32 g·cm to 821.74 g·cm, while WHC increased from 0.77 to 0.87. The microwave processed surimi exhibited a more uniform microstructure. Because it enhanced the dissolution and cross-linking of myofibrillar proteins, leading to superior gel formation characterized by a lower α-helix content (10.31%) and higher β-sheet content (61.70%). Furthermore, microwave processing achieved faster heating rates, reducing the time spent in the critical gel deterioration temperature range, thereby improving overall gel quality. Single-mode microwave-assisted gelation also provided better thermal processing uniformity and efficiency, achieving pasteurization standards. The study highlights the potential of 915 MHz single-mode microwave processing to produce high-quality, low-salt surimi products, meeting contemporary health and convenience demands. These findings offer valuable insights for the industrial application of single-mode microwave technology in surimi production, promoting the development of innovative processing techniques to enhance the quality of surimi-based food products.

Exosome Loaded Protein Hydrogel for Enhanced Gelation Kinetics and Wound Healing.

Exosomes are being increasingly explored in biomedical research for wound healing applications. Exosomes can improve blood circulation and endocrine signaling, resulting in enhanced cell regeneration. However, exosome treatments suffer from low retention and bioavailability of exosomes at the wound site. Hydrogels are a popular tool for drug delivery due to their ability to encapsulate drugs in their network and allow for targeted release. Recently, hydrogels have proven to be an effective method to provide increased rates of wound healing when combined with exosomes that can be applied noninvasively. We have designed a series of single-domain protein-based hydrogels capable of physical cross-linking and upper critical solution temperature (UCST) behavior. Hydrogel variant Q5, previously designed with improved UCST behavior and a significantly enhanced gelation rate, is selected as a candidate for encapsulation release of exosomes dubbed Q5Exo. Q5Exo exhibits low critical gelation times and significant decreases in wound healing times in a diabetic mouse wound model showing promise as an exosome-based drug delivery tool and for future hybrid, noninvasive protein-exosome design.

Effect of Micellar Morphology on the Temperature-Induced Structural Evolution of ABC Polypeptoid Triblock Terpolymers into Two-Compartment Hydrogel Network.

We investigated the temperature-dependent structural evolution of thermoreversible triblock terpolypeptoid hydrogels, namely poly(N-allyl glycine)-b-poly(N-methyl glycine)-b-poly(N-decyl glycine) (AMD), using small-angle neutron scattering (SANS) with contrast matching in conjunction with X-ray scattering and cryogenic transmission electron microscopy (cryo-TEM) techniques. At room temperature, A100M101D10 triblock terpolypeptoids self-assemble into core-corona-type spherical micelles in aqueous solution. Upon heating above the critical gelation temperature (T gel), SANS analysis revealed the formation of a two-compartment hydrogel network comprising distinct micellar cores composed of dehydrated A blocks and hydrophobic D blocks. At T ≳ T gel, the temperature-dependent dehydration of A block further leads to the gradual rearrangement of both A and D domains, forming well-ordered micellar network at higher temperatures. For AMD polymers with either longer D block or shorter A block, such as A101M111D21 and A43M92D9, elongated nonspherical micelles with a crystalline D core were observed at T < T gel. Although these enlarged crystalline micelles still undergo a sharp sol-to-gel transition upon heating, the higher aggregation number of chains results in the immediate association of the micelles into ordered aggregates at the initial stage, followed by a disruption of the spatial ordering as the temperature further increases. On the other hand, fiber-like structures were also observed for AMD with longer A block, such as A153M127D10, due to the crystallization of A domains. This also influences the assembly pathway of the two-compartment network. Our findings emphasize the critical impact of initial micellar morphology on the structural evolution of AMD hydrogels during the sol-to-gel transition, providing valuable insights for the rational design of thermoresponsive hydrogels with tunable network structures at the nanometer scale.

Optimizing Seaweed Capsule Shell Formula with Multiple Disintegrants to Accelerate Disintegration Time

Abstract Seaweed-based capsule shells are gaining popularity due to their animal-free sourcing and guaranteed quality. However, these shells often suffer from prolonged disintegration. Various studies have explored formulations with additional disintegrants like polyvinylpyrrolidone (PVP) K-30, yet results have fallen short of pharmacopeia standards. In this research, multiple disintegrants and formulations were tested to develop seaweed capsule shells with rapid disintegration times. The variation in composition of disintegrants was determined using Simplex Lattice Design (SLD) in Design Expert® 13.0.12. By altering the variables in the form of concentrations of PVP K-30, Avicel PH 101, Primogel, Amylum Manihot, Carrageenan, Tween 80, and Aquadest. Primary targets were to identify disintegrants that can significantly reduce disintegration time while maintaining adherence to pharmacopeia standards. Using primogel can fully produce a capsule shell with a promising disintegration time of around 17 minutes, thereby achieving the objective of expediting the disintegration process. Primogel also reduces the critical gel point to 48.23°C when completely replacing PVP K-30. However, balancing desirability proved challenging, as reducing PVP K-30 led to increased disintegration time. Other disintegrants, like Avicel PH 101 or amylum manihot, had no significant impact on disintegration time or gel point. These findings contribute to understanding the complex relationship between disintegrants and their effects on seaweed capsule shell properties, advancing the objectives in optimizing formulation for improved pharmaceutical applications.

Synthesis and end-group control of soluble, high-molecular-weight hyperbranched poly(phenylene thienylene)s by non-stoichiometric A2 + B3 Suzuki-Miyaura polycondensation without gelation

Non-stoichiometric Suzuki-Miyaura polycondensation of tribromo monomer 1, containing a thienylene group, with diboronic acid (ester) monomer 7 in the presence of tBuPPd catalyst, which has a propensity for intramolecular catalyst transfer on a π-electron face, was investigated. We anticipated that the presence of thienylene groups in the obtained hyperbranched polymer would increase the detection sensitivity in matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometry and enable the analysis of the polymer end groups up to the high-molecular-weight region. We first conducted Suzuki-Miyaura reaction of several kinds of 1 with phenylboronic acid 2 in the presence of tBuPPd precatalyst 3. The reaction of tris(5-bromo-4-hexylthien-2-yl)benzene 1c with 2 afforded exclusively tri-substituted product 4c, indicating that the tBuPPd catalyst undergoes intramolecular catalyst transfer on 1c after the first and second substitutions of 1c with 2. The polycondensation of equimolar 1c and pinacol phenylenediboronate 7a (reaction site ratio of Br:BPin = 1.5:1.0 (BPin = pinacol boronate)) was then carried out in the presence of 3 for 3 h, affording hyperbranched polymer with Mn = 37500 without gelation. The product was purified by precipitation. The degree of polymerization (DP) was calculated from the absolute molecular weight, determined by multi-angle light scattering (MALLS) analysis, to be 200, which is a far higher than would be predicted from the Flory-Stockmayer theory at the critical gel point (DP = 6.6). Furthermore, the MALDI-TOF mass spectra showed two series of peaks due to polymer with boronate ends and boronate ends along with one cyclic unit up to m/z of about 7500, as we had expected. The absence of peaks due to polymer with Br ends indicates that the degree of branching (DB) of this hyperbranched polymer is 100 %.

A New Concept for Interpretation of the Viscoelastic Behavior of Aqueous Sodium Carboxymethyl Cellulose Systems.

Viscoelastic behaviors of aqueous systems of commercially available sodium carboxymethyl cellulose (NaCMC) samples with the degrees of substitution (DS) of approximately 0.68 and 1.3, and the weight-average molar masses (Mw) higher than 200 kg mol-1 dissolved in pure water and aqueous sodium chloride solutions were investigated over a wide concentration (c) range of NaCMC samples. The dependencies of the specific viscosity (ηsp), the average relaxation time (τw), and the reciprocal of the steady-state compliance (Je-1) on c were discussed. The relationships ηsp ∝ c3, τw ∝ c2, and Je-1 ∝ c, characteristic of the rod particle suspensions, were clearly observed in a range lower than the c where the critical gel behavior was observed. Thus, a new concept based on the rheology of rod particle suspensions was employed to interpret the viscoelastic behaviors obtained in the c range. In this context, NaCMC polymer molecules are assumed to behave as extended rod particles with length (L) and diameter (d), including effective electrostatic repulsive distances, due to the dissociation of Na+ in aqueous systems. Thus, the number density of polymer molecules is given to be ν = c/Mw, and viscoelastic parameters such as ηsp, τw, and Je-1 are calculated using the theoretical model for rod particle suspensions proposed by Doi and Edwards. This concept reasonably described not only the viscoelastic data obtained in this study but also those from other groups using NaCMC samples with different DS and Mw values.

Influence of PEG-PPG-PEG Block Copolymer Concentration and Coagulation Bath Temperature on the Structure Formation of Polyphenylsulfone Membranes.

The effect of amphiphilic block copolymer polyethylene glycol (PEG)-polypropylene glycol (PPG)-PEG concentration in the polyphenylsulfone (PPSU) casting solution and coagulation bath temperature (CBT) on the structure, separation, and antifouling performance of PPSU ultrafiltration membranes was studied for the first time. According to the phase diagram obtained, PPSU/PEG-PPG-PEG/N-methyl-2-pyrrolidone (NMP) systems are characterized by a narrow miscibility gap. It was found that 20 wt.% PPSU solutions in NMP with the addition of 5-15 wt.% of PEG-PPG-PEG block copolymer feature upper critical solution temperature, gel point, and lower critical solution temperature. Membrane composition and structure were studied by Fourier-transform infrared spectroscopy, scanning electron and atomic force microscopies, and water contact angle measurements. The addition of PEG-PPG-PPG to the PPSU casting solution was found to increase the hydrophilicity of the membrane surface (water contact angle decreased from 78° for the reference PPSU membrane down to 50° for 20 wt.%PPSU/15 wt.% PEG-PPG-PEG membrane). It was revealed that the pure water flux increased with the rise of CBT from 18-20 L·m-2·h-1 for the reference PPSU membrane up to 38-140 L·m-2·h-1 for 20 wt.% PPSU/10-15 wt.% PEG-PPG-PEG membranes. However, the opposite trend was observed for 20 wt.% PPSU/5-7 wt.% PEG-PPG-PEG membranes: pure water flux decreased with an increase in CBT. This is due to the differences in the mechanism of phase separation (non-solvent-induced phase separation (NIPS) or a combination of NIPS and temperature-induced phase separation (TIPS)). It was shown that 20 wt.% PPSU/10 wt.% PEG-PPG-PEG membranes were characterized by significantly higher antifouling performance (FRR-81-89%, DRr-26-32%, DRir-10-20%, DT-33-45%) during the ultrafiltration of bovine serum albumin solutions compared to the reference PPSU membrane prepared at different CBTs (FRR-29-38%, DRr-6-14%, DRir-74-89%, DT-88-94%).

Rheo-SAXS study of a shear-thinning hydrogel containing clay nanoplatelets

Shear-induced orientation of clay nanoplatelets within a physically cross-linked hydrogel based on ionenes, positively charged polyelectrolytes, is studied here. Small angle X-ray scattering measurements (SAXS) are performed under shear within a Couette cell cylinder (rheo-SAXS). As the SAXS signal is dominated by that of the clay component, we follow the evolution of the orientational distribution of the clay nanoplatelets within the hydrogel as a function of shear. We investigate the effect of the clay volume fraction, polyelectrolyte concentration, clay charge location and clay charge density by screening three different types of clay: Wyoming and Arizona montmorillonites and Idaho beidellite. The orientational field of clay nanoplatelets in the gel is shown to strongly depend on the clay charge location and shear rate, whereas it is independent of the clay volume fraction. Approaching the critical gelation concentration of the polyelectrolyte system, these features change drastically.

Composition-antifreeze property relationships of gelatin and the corresponding mechanisms

The inherent functional fractions (gelation and ice-affinitive fractions) of gelatin enable it as a promising cryoprotectant alternative. However, the composition-antifreeze property relationships of gelatin remain to be investigated. In this study, the HW-PSG and LW-PSG fractions of gelatin from fish scales were obtained, according to the critical gelation conditions and ice-binding measurements, respectively. Thermal hysteresis (THA) value, associated with ice nucleation, of LW-PSG was higher than that of HW-PSG. Besides, the relatively low-sized ice crystals (210–550 μm2) indicated that HW-PSG showed strong ice recrystallization inhibition (IRI) ability, compared to other groups. These results suggested that LW-PSG inhibited ice nucleation, while HW-PSG displayed the strong IRI ability. Furthermore, the antifreeze mechanisms were clarified through IRI measurements and molecular dynamics simulation. The minimum size of ice crystals was found for HW-PSG gels with dense microstructure, suggesting the HW-PSG retarded the growth of ice crystals by restricting the migration and phase transformation of water molecules. The hydrogen bond interactions between the ice crystal surface and ASN1294 and PRO1433 residues of LW-PSG, and hydrophobic interactions contributed to inhibiting the nucleation of ice crystals. This study provided some references to further enhance antifreeze performance of gelatin by modulating fragment composition.

Evaluating models that predict epoxy conversion using rheological properties.

Simultaneous rheology and conversion measurements of neat and composite epoxy resins reveal that conventional models neither accurately nor fully describe the relationship between rheology and conversion. We find that models predicting thermoset conversion based on mixing rules of rheological properties are quantitatively inaccurate and do not account for chemical gelation. Models based on percolation theory and the divergence of the viscosity at the gel point are more accurate but only valid before the gel point. Here, we propose the use of the generalized effective medium (GEM) model, which incorporates the divergence of rheological properties on both sides of the critical gel point. We show that the GEM model works well for both neat resins and filled systems, and the resulting parameters estimate the gel point and scaling behavior on either side of the sol-gel transition.

Application of various polysaccharide gums to improve gelation and rheological properties of hydroxypropyl starch hydrocolloids

This work aims to develop starch-based low-cost vegetarian soft capsules used for medicine and health products through compounding with different polysaccharide gums. In this work, the phase diagrams, gelation behaviors, rheological properties, and microstructures of hydroxypropyl starch (HPS) blending with various polysaccharide gums, including ι and κ-carrageen (LC and KC), curdlan (CL) and agar (AG) have been investigated. The materials in both solution and hydrogel were systematically characterized in the review of practical processing and application based on the requirements of fabricating soft capsules. The phase diagram was firstly drawn based on critical gel concentration at 30–60 °C; the rheological behaviors of various blending systems were investigated under both oscillatory and dynamical conditions; and the gel microstructures were studied by SEM. The phase diagrams showed that HPS-AG has the lowest critical gel concentration while HPS-CL has the highest one since AG itself has shown the lowest critical gel concentration. The order of both critical gel concentration and viscosity of the HPS-based suspensions is HPS-CL > HPS-KC > HPS-LC > HPS-AG. In contrast, the gel strengths of HPS-based hydrogels are almost opposite to the order of viscosity HPS-AG > HPS-KC > HPS-LC > HPS-CL. Some of the blending systems (HPS-KC and HPS-CL) showed higher viscosity then the summary of the individual material, indicating some polymeric chain intergradation. All the compounding systems showed the porous structure of typical hydrogel, and cell size generally decreased after adding various gums. The hydroxyl bound and network between HPS and gums (carrageen and curdlan) results in higher gel strength of the blending system than that of any single substance. The relationships among the phase diagrams, microstructures, and rheological properties were compared and discussed. The results provide a guideline to design and develop capsules using multi-gums systems based on exploring their individual behaviors.

Phenanthrothiophene-Triazine Star-Shaped Discotic Liquid Crystals: Synthesis, Self-Assembly, and Stimuli-Responsive Fluorescence Properties.

Lipophilic biphenylthiophene- and phenanthrothiophene-triazine compounds, BPTTn and CPTTn, respectively, were prepared by a tandem procedure involving successive Suzuki-Miyaura coupling and Scholl cyclodehydrogenation reactions. These compounds display photoluminescence in solution and in thin film state, solvatochromism with increasing solvent's polarity, as well as acidochromism and metal ion recognition stimuli-responsive fluorescence. Protonation of BPTT10 and CPTT10 by trifluoroacetic acid results in fluorescence quenching, which is reversibly restored once treated with triethylamine (ON-OFF switch). DFT computational studies show that intramolecular charge transfer (ICT) phenomena occurs for both molecules, and reveal that protonation enhances the electron-withdrawing ability of the triazine core and reduces the band gap. This acidochromic behavior was applied to a prototype fluorescent anti-counterfeiting device. They also specifically recognize Fe3+ through coordination, and the recognition mechanism is closely related to the photoinduced electron transfer between Fe3+ and BPTT10/CPTT10. CPTTn self-assemble into columnar rectangular (Colrec) mesophase, which can be modulated by oleic acid via the formation of a hydrogen-bonded supramolecular liquid crystal hexagonal Colhex mesophase. Finally, CPTTn also form organic gels in alkanes at low critical gel concentration (3.0 mg/mL). Therefore, these star-shaped triazine molecules possess many interesting features and thus hold great promises for information processing, liquid crystal semiconductors and organogelators.

Critical Conditions Regulating the Gelation in Macroionic Cluster Solutions.

The critical gelation conditions observed in dilute aqueous solutions of multiple nanoscale uranyl peroxide molecular clusters are reported, in the presence of multivalent cations. This gelation is dominantly driven by counterion-mediated attraction. The gelation areas in the corresponding phase diagrams all appear in similar locations, with a characteristic triangle shape outlining three critical boundary conditions, corresponding to the critical cluster concentration, cation/cluster ratio, and the degree of counterion association with increasing cluster concentration. These interesting phrasal observations reveal general conditions for gelation driven by electrostatic interactions in hydrophilic macroionic solutions.

Preparation and sustained-release mechanism of hydroxybutyl chitosan/graphene oxide temperature-sensitive hypoglycaemic subcutaneous implants

The current situation of diabetes prevention and control is extremely severe. For instance, glimepiride (GLM), a third-generation sulfonylurea, demonstrates suboptimal clinical efficacy in oral dosage forms, which underscores the pressing need for the development of a new dosage form. Recently, in situ gel subcutaneous implants have garnered considerable attention. Hydroxybutyl chitosan (HBC) can spontaneously crosslink to form a thermosensitive hydrogel and has good biocompatibility. However, its application is hindered by its limited mechanical properties. Graphene oxide (GO), known for its stable dispersion in water, can load GLM through π–π stacking interactions. When combined with HBC, GO enhances the mechanical properties and stability of the hydrogel. Therefore, an HBC–GO@GLM hydrogel was prepared. Rheological analysis revealed that the incorporation of GO increased the critical gelation temperature of the 5 wt% HBC hydrogel from 19.1°C to 27.2°C, considerably enhancing the mechanical properties of the hydrogel. Using encapsulation efficiency as an evaluation index, the optimal encapsulation efficiency of GO@GLM was determined to be 73.53% ± 0.45% with a drug loading capacity of 27.39 ± 0.17% using the Box–Behnken design model. Computer simulation technology validated the interaction between the materials and the drug release mechanism. Pharmacokinetic results showed that compared to the HBC@GLM group, the half-life (t1/2), mean residence time and the area under the curve for the HBC–GO@GLM group were approximately 3 times those of the HBC@GLM group. Subcutaneous implantation of the HBC–GO@GLM hydrogel for drug delivery considerably extended the drug’s action time in the body, thereby maintaining blood sugar levels within a normal and stable range for an extended period.

Self-compliant ionic skin by leveraging hierarchical hydrogen bond association

Robust interfacial compliance is essential for long-term physiological monitoring via skin-mountable ionic materials. Unfortunately, existing epidermal ionic skins are not compliant and durable enough to accommodate the time-varying deformations of convoluted skin surface, due to an imbalance in viscosity and elasticity. Here we introduce a self-compliant ionic skin that consistently works at the critical gel point state with almost equal viscosity and elasticity over a super-wide frequency range. The material is designed by leveraging hierarchical hydrogen bond association, allowing for the continuous release of polymer strands to create topological entanglements as complementary crosslinks. By embodying properties of rapid stress relaxation, softness, ionic conductivity, self-healability, flaw-insensitivity, self-adhesion, and water-resistance, this ionic skin fosters excellent interfacial compliance with cyclically deforming substrates, and facilitates the acquisition of high-fidelity electrophysiological signals with alleviated motion artifacts. The presented strategy is generalizable and could expand the applicability of epidermal ionic skins to more complex service conditions.

Responsive Properties of Bis-urea-based Supramolecular Hydrogels

Physical hydrogels exhibit sol-gel reversibility, which is affected by external stimuli such as variations in pH and temperature. One class of hydrogelators, known as the low-molecular- weight gelators, can form fibrillar networks through noncovalent self-assembly, resulting in the formation of physical gels. This study aims to investigate the pH-responsive properties of bis-urea-based supramolecular hydrogelators. A series of bis-urea compounds containing an aromatic linker and various end groups were synthesized via a one-pot condensation reaction. Gelation of the compounds in water was conducted at pH 2–13, whereby the inversion technique was used to confirm the hydrogel formation. The compound bearing an m-picolyl end group effectively forms gels within the pH 3–12 range. The gelator also exhibits decreasing critical gel concentration with increasing pH, presumably due to the ionizability of the pyridyl groups. Rheological analysis of the gels determined the storage modulus (G’) to be greater than the loss modulus (G”), which indicated the expected solid-like behavior of the hydrogel at low strain. The morphology of the gel obtained by scanning electron microscopy revealed a fibrous aggregated structure. Results obtained from this study may suggest the applicability of bis-urea compounds as pH-sensitive physical hydrogelators.

Ultralight aerogels via supramolecular polymerization of a new chiral perfluoropyridine-based sulfonimidamide organogelator.

Chiral and enantiopure perfluorinated sulfonimidamides act as low-molecular weight gelators at low critical gelation concentration (<1 mg mL-1) via supramolecular polymerization in nonpolar organic solvents and more heterogenic mixtures, such as biodiesel and oil. Freeze-drying of the organogel leads to ultralight aerogel with extremely low density (1 mg mL-1). The gelation is driven by hydrogen bonding resulting in a helical molecular ordering and unique fibre assemblies as confirmed by scanning electron microscopy, CD spectroscopy, and computational modeling of the supramolecular structure.

Aluminosilicate colloidal gels: from the early age to the precipitation of zeolites.

Aluminosilicate hydrogels are often considered to be precursors for the crystallisation of zeolites carried out under hydrothermal conditions. The preparation of mechanically homogeneous aluminosilicate gels enables the study of these materials through bulk rheology and observation of the aging dynamics until the precipitation of crystalline zeolites. The first part of this study deals with the establishment of ternary state diagrams, in order to identify the range of chemical formulations that enable preparation of single-phase homogeneous gels. Then, by studying the viscoelastic moduli during the gelation reaction, and by yielding the gel under large deformation, we propose an empirical law considering the partial order of reaction on each chemical element, to predict the gelation time according to the chemical formulation. The scaling behavior of the elastic properties of this colloidal gel shows a transition from a strong link behavior to a weak link regime. Long term aging results in the shrinkage of the gel, accompanied by syneresis of interstitial liquid at the surface. Zeolites precipitate through crystallisation by a particle attachment mechanism, when thermodynamic equilibrium is reached. The stoichiometry of the precipitated zeolites is not only consistent with the concentration of the remaining species in the supernatant but, surprisingly, it is also very close to the partial order of the reaction of the chemical elements involved in the determination of the critical gel point. This indicates a strong correlation between the morphology of the soft amorphous gel network that is formed at an early age and those of the final solid precipitated crystals.

Mechanically tunable organogels from highly charged polyoxometalate clusters loaded with fluorescent dyes

Inorganic nanowires-based organogel, a class of emerging organogel with convenient preparation, recyclability, and excellent mechanical properties, is in its infancy. Solidifying and functionalizing nanowires-based organogels by designing the gelator structure remains challenging. Here, we fabricate Ca2-P2W16 and Ca2-P2W15M nanowires utilizing highly charged [Ca2P2W16O60]10− and [Ca2P2W15MO60]14−/13− cluster units, respectively, which are then employed for preparing organogels. The mechanical performance and stability of prepared organogels are improved due to the enhanced interactions between nanowires and locked organic molecules. Compressive stress and tensile stress of Ca2-P2W16 nanowires-based organogel reach 34.5 and 29.0 kPa, respectively. The critical gel concentration of Ca2-P2W16 nanowires is as low as 0.28%. Single-molecule force spectroscopy confirms that the connections between cluster units and linkers can regulate the flexibility of nanowires. Furthermore, the incorporation of fluorophores into the organogels adds fluorescence properties. This work reveals the relationships between the microstructures of inorganic gelators and the properties of organogels, guiding the synthesis of high-performance and functional organogels.