Gels

The objective of this article is to introduce the readers to the field of polyelectrolyte gels. These materials are common in living systems and have great importance in many biomedical and industrial applications. In the first part of this paper, we briefly review some characteristic properties of polymer gels with an emphasis on the unique features of this type of soft material. Unsolved problems and possible future research directions are highlighted. In the second part, we focus on the typical behavior of polyelectrolyte gels. Many biological materials (e.g., tissues) are charged (mainly anionic) polyelectrolyte gels. Examples are shown to illustrate the effect of counter-ions on the osmotic swelling behavior and the kinetics of the swelling of model polyelectrolyte gels. These systems exhibit a volume transition as the concentration of higher valence counter-ions is gradually increased in the equilibrium bath. A hierarchy is established in the interaction strength between the cations and charged polymer molecules according to the chemical group to which the ions belong. The swelling kinetics of sodium polyacrylate hydrogels is investigated in NaCl solutions and in solutions containing both NaCl and CaCl₂. In the presence of higher valence counter-ions, the swelling/shrinking behavior of these gels is governed by the diffusion of free ions in the swollen network, the ion exchange process and the coexistence of swollen and collapsed states. Full article

Cell encapsulating scaffolds are necessary for the study of cellular mechanosensing of cultured cells. However, conventional scaffolds used for loading cells in bulk generally fail at low compressive strain, while hydrogels designed for high toughness and strain resistance are generally unsuitable for cell encapsulation. Here we describe an alginate/gelatin methacryloyl interpenetrating network with multiple crosslinking modes that is robust to compressive strains greater than 70%, highly biocompatible, enzymatically degradable and able to effectively transfer strain to encapsulated cells. In future studies, this gel formula may allow researchers to probe cellular mechanosensing in bulk at levels of compressive strain previously difficult to investigate. Full article

With the increased incidence of bone defects following trauma or diseases in recent years, three-dimensional porous scaffolds fabricated using bioprinting technologies have been widely explored as effective alternatives to conventional bone grafts, which provide cell-friendly microenvironments promoting bone repair and regeneration. However, the limited use of biomaterials poses a significant challenge to the robust and accurate fabrication of bioprinted bone scaffolds that enable effective regeneration of the target tissues. Although bioceramic/polymer composites can provide tunable biomimetic conditions, their effects on the bioprinting process are unclear. Thus, in this study, we fabricated hydroxyapatite (HA)/gelatin composite scaffolds containing large weight fractions of HA using extrusion-based bioprinting, with the aim to provide an adequate biomimetic environment for bone tissue regeneration with compositional and mechanical similarity to the natural bone matrix. The overall features of the bioprinted HA/gelatin composite scaffolds, including rheological, morphological, physicochemical, mechanical, and biological properties, were quantitatively assessed to determine the optimal conditions for both fabrication and therapeutic efficiency. The present results show that the bioprinted bioceramic/hydrogel scaffolds possess excellent shape fidelity; mechanical strength comparable to that of native bone; and enhanced bioactivity in terms of cell proliferation, attachment, and osteogenic differentiation. This study provides a suitable alternative direction for the fabrication of bioceramic/hydrogel-based scaffolds for bone repair based on bioprinting. Full article

This study aims to understand the fundamental mechanical relationship between polypropylene (PP)-gels and solid PPs without solvent through mechanical and thermal analyses, by which the mechanical similarities between molten PPs and PP gels were found, leading to the reliable estimate of the mechanical properties of semi-crystalline gels. The gelation of syndiotactic and isotactic polypropylenes (sPP and iPP) was found when PPs were dissolved in 1,2,3,4-tetrahydronaphthalene (tetralin). Interestingly, it was found that the storage modulus of sPP-gel became higher than that of iPP-gel at low PP concentration (<~40 wt%). The result was distinctly different from the result of neat solid PPs (without solvent), where the modulus of solid sPP is generally significantly lower than that of solid iPP. Such inversion behavior in the mechanical property of semi-crystalline gels had not been reported and discussed before. By further investigation of the storage moduli of neat sPP and iPP, it was found that the storage modulus of sPP became higher than that of iPP above the melting points of PP, which was similar to the behavior of the storage moduli observed in the diluted PP-gels. Such similarity between PP-gels and PP melts was also observed within iPP samples with different molecular weights. Full article

Hydrogels are attractive materials not only for their tremendous applications but also for theoretical studies as they provide macroscopic monitoring of the conformation change of polymer chains. The pioneering theoretical work of Dusek predicting the discontinuous volume phase transition in gels followed by the experimental observation of Tanaka opened up a new area, called smart hydrogels, in the gel science. Many ionic hydrogels exhibit a discontinuous volume phase transition due to the change of the polymer–solvent interaction parameter χ depending on the external stimuli such as temperature, pH, composition of the solvent, etc. The observation of a discontinuous volume phase transition in nonionic hydrogels or organogels is still a challenging task as it requires a polymer–solvent system with a strong polymer concentration dependent χ parameter. Such an observation may open up the use of organogels as smart and hydrophobic soft materials. The re-entrant phenomenon first observed by Tanaka is another characteristic of stimuli responsive hydrogels in which they are frustrated between the swollen and collapsed states in a given solvent mixture. Thus, the hydrogel first collapses and then reswells if an environmental parameter is continuously increased. The re-entrant phenomenon of hydrogels in water–cosolvent mixtures is due to the competitive hydrogen-bonding and hydrophobic interactions leading to flow-in and flow-out of the cosolvent molecules through the hydrogel moving boundary as the composition of the solvent mixture is varied. The experimental results reviewed here show that a re-entrant conformation transition in hydrogels requires a hydrophobically modified hydrophilic network, and a moderate hydrogen-bonding cosolvent having competitive attractions with water and polymer. The re-entrant phenomenon may widen the applications of the hydrogels in mechanochemical transducers, switches, memories, and sensors. Full article

1,3:2,4-Dibenzylidene-D-sorbitol (DBS) and 12-hydroxystearic acid (12-HSA) are well-known as low-molecular-weight organogelators (LMOGs) capable of gelling an organic liquid phase. Considering their unique chemical and physical properties, we assessed their potential effects in new lipstick formulations by discrimination testing; in vitro measurements of the sun protection factor (SPF); and thermal, mechanical and texture analyzes. DBS and 12-HSA were used to formulate four types of lipsticks: L1 (1% DBS), L2 (10% 12-HSA), L3 (1.5% DBS) and L4 (control, no LMOGs). The lipsticks were tested for sensory perception with an untrained panel of 16 consumers. LMOG formulations exhibited higher UVA protection factor (UVA-PF) and in vitro SPF, particularly in the 12-HSA-based lipstick. Regarding thermal properties, the 12-HSA-based lipstick and those without LMOGs were more heat-amenable compared to thermoresistant DBS-based lipsticks. The results also showed the viscoelastic and thermally reversible properties of LMOGs and their effect of increasing pay-off values. In general, the texture analysis indicated that 12-HSA-based lipstick was significantly harder to bend compared to control, while the other formulations became softer and easier to bend throughout the stability study. This work suggests the potential use of LMOGs as a structuring agent for lipsticks, paving the way towards more photoprotective and sustainable alternatives. Full article

(1) Introduction: in recent decades, interdisciplinary research on the utilization of natural products as “active moiety carriers” was focused on due to their superior safety profile, biodegradability, biocompatibility and the ability for sustained or controlled release activity. The nano-based neuroprotective strategy is explored as an imperative treatment for diabetic neuropathy (DN). Avanafil (AV), that selectively inhibits the degradation of cGMP-specific phosphodiesterase, thereby increasing the levels of cGMP, makes a decisive mediator for cytoprotection. (2) Methods: AVnanocomplex formulations were prepared by a modified anti-solvent precipitation method and the method was optimized by Box–Behnken design. An optimized formulation was characterized and evaluated for various in vitro parameters; (3) results:based on the desirability approach, the formulation containing 2.176 g of chitosan, 7.984 g of zein and 90% v/v ethanol concentration can fulfill the prerequisites of optimum formulation (OB-AV-NC).OB-AV-NC was characterized and evaluated for various parameters. The neuroprotective mechanism of AV was evaluated by pretreatment of PC12 cells with plain AV, avanafil nanocomplex (NC) without antioxidants (AV-NC) and with antioxidants (α-Lipoic acid LP; Ellagic Acid EA), AV-LP-EA-Nanocomplex has also shown considerable attenuation in intracellular reactive oxygen species (ROS) and lipid peroxidation with a significant increase in the PC 12 viability under HG conditions in comparison to pure AV; (4) conclusion: the nanocomplex of AV prepared to utilize natural polymers and antioxidants aided for high solubility of AV and exhibited desired neuroprotective activity.This can be one of the promisingstrategy to translate the AV nanocomplex with safety and efficacy in treating DN. Full article

This study aimed to prepare and evaluate virgin olive oil (VOO) oleogels enriched with thyme and cumin spices with sunflower wax (SW) organogelator. Common physico-chemical, structural, thermal, and rheological analyses were completed. Furthermore, aromatic volatiles composition, sensory descriptive analysis, and consumer tests were provided. Results indicated that spice addition does not interfere with gel formation, stability, and gelation time. The oleogels’ color values were affected by the color of the VOO and the spices. The free fatty acidity and peroxide values were within the acceptable limits for virgin olive oils. There were β’ crystal polymorphs, and melting peak temperatures were around 62 °C. Rheological analyses proved that the oleogels were fairly stable under moderate frequencies, maintained their gelled state until around 52 °C, and recovered their shear induced structural loss after force cessation. There were 22 aromatic volatiles quantified in the samples, which originated from the VOO and spices used as ingredients. A trained panel defined the samples using 13 sensory descriptors. Consumer tests proved that the new oleogels were liked by consumers. Overall, this study provided information and the possibility of spice-enriched and spreadable VOO oleogels to enhance per capita consumption of olive oils with new consumption habits. Full article

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. Full article

The phase diagrams of organogels are necessary for applications and fundamental aspects, for instance to understand their thermodynamics. Differential scanning calorimetry is one of the techniques implemented to map these diagrams. The thermograms of organogels upon heating show broad endotherms, increasing gradually to a maximum, at a temperature $T_{\max }$, and decreasing back to the baseline, sometimes 10 °C above. This broadening can lead to uncertainty in determining the molar enthalpies and the melting temperatures $T_{\mathrm{m}}$ of the gels. Herein, we have measured the thermograms of the 12-hydroxystearic acid/nitrobenzene gels for weight fractions ranging from 0.0015 to 0.04. Compared with transition temperatures measured by other techniques, the inflection points of the thermograms provide a measurement of $T_{\mathrm{m}}$ with less bias than $T_{\max }$. The phase diagram explains why the molar melting enthalpies derived from the thermograms for samples of low concentration are lower than expected. The shapes of the heat flows below the peak correlate quantitatively with the diagrams: after suitable correction and normalization, the integral curves superimpose with the phase diagram in their ascending branch and reach a plateau when the gel is fully melted. The shape of the thermograms upon cooling is also qualitatively explained within the frame of the diagrams. Full article

Three-dimensional (3D) printing is a promising technology for solving a wide range of problems: regenerative medicine, tissue engineering, chemistry, etc. One of the potential applications of additive technologies is the production of highly porous structures with complex geometries, while printing is carried out using gel-like materials. However, the implementation of precise gel printing is a difficult task due to the high requirements for “ink”. In this paper, we propose the use of gel-like materials based on sodium alginate as “ink” for the implementation of the developed technology of extrusion-based 3D printing. Rheological studies were carried out for the developed alginate ink compositions. The optimal rheological properties are gel-like materials based on 2 wt% sodium alginate and 0.2 wt% calcium chloride. The 3D-printed structures with complex geometry were successfully dried using supercritical drying. The resulting aerogels have a high specific surface area (from 350 to 422 m²/g) and a high pore volume (from 3 to 3.78 cm³/g). Full article

Slide-ring (SR) gels cross-linked by ring molecules are characterized by softness (low Young’s modulus), elasticity (low hysteresis loss), and toughness (large fracture energy). In this article, the mechanical and fracture properties of SR gels are reviewed to clarify the physical understanding of the relationship between the molecular-level sliding dynamics of the slide-ring cross-links and macroscopic properties of SR gels. The low Young’s modulus and large fracture energy of SR gels are expressed by simple equations as a function of the degree of sliding movement. The dynamic fracture behaviors of SR gels gives us the time scale of the sliding dynamics of the cross-links, which is at the micro-sec scale. The fast sliding motion of the cross-links leads to the elasticity of the SR gels. The SR concept can be applied to solvent-free elastomers and composite materials. Full article

The control of the three-dimensional (3D) polymer network structure is important for permselective materials when specific biomolecule detection is needed. Here we investigate conditions to obtain a tailored hydrogel network that combines both molecular filtering and molecular capture capabilities for biosensing applications. Along this line, short oligonucleotide detection in a displacement assay is set within PEGDA hydrogels synthetized by UV radical photopolymerization. To provide insights on the molecular filter capability, diffusion studies of several probes (sulforhodamine G and dextrans) with different hydrodynamic radii were carried out using NMR technique. Moreover, fluorometric analyses of hybridization of DNA oligonucleotides inside PEGDA hydrogels shed light on the mechanisms of recognition in 3D, highlighting that mesh size and crowding effect greatly impact the hybridization mechanism on a polymer network. Finally, we found the best probe density and diffusion transport conditions to allow the specific oligonucleotide capture and detection inside PEGDA hydrogels for oligonucleotide detection and the filtering out of higher molecular weight molecules. Full article

Hyaluronic acid (HA) of different molar masses (respectively 38,000, 140,000 and 1,200,000 g.mol⁻¹) have been functionalized with a commercial poly(etheramine), Jeffamine^® M2005, in order to devise physical thermo-responsive hydrogels. Two routes have been studied, involving the use of either water for the first one or of N,N′-Dimethylformamide (DMF), a polar aprotic solvent, for the second one. In the case of the water route, the reaction was performed using a mixture of N-(3-Dimethylaminopropyl)-N′-ethylcarbodiimide (EDC) and N-hydroxysuccinimide (NHS) as coupling reagents. The reaction was optimized while making sure no free M2005 remained in the final material, leading to M2005 grafting degrees of about 4%, which enabled the formation of hydrogels by increasing the temperature. In the case of the organic solvent route, propylphosphonic anhydride T3P^® was used as a coupling reagent in DMF, resulting in a M2005 grafting degree of around 8% with better thermo-responsive properties of HA-g-M2005 compared to those obtained when the reaction was performed in water. However, the reaction systematically led to covalent cross-linking in the case of the HA, with the highest starting molar masses resulting in a very different rheological behaviour and with higher gel strength retaining thermo-responsive behaviour but being only poorly soluble in water. Full article

Supramolecular gels form a class of soft materials that has been heavily explored by the chemical community in the past 20 years. While a multitude of experimental techniques has demonstrated its usefulness when characterizing these materials, the potential value of computational techniques has received much less attention. This review aims to provide a complete overview of studies that employ computational tools to obtain a better fundamental understanding of the self-assembly behavior of supramolecular gels or to accelerate their development by means of prediction. As such, we hope to stimulate researchers to consider using computational tools when investigating these intriguing materials. In the concluding remarks, we address future challenges faced by the field and formulate our vision on how computational methods could help overcoming them. Full article

Oleogels are semi-solid materials containing a large fraction of liquid oil entrapped in a network of structuring molecules. In the food industry, these formulations can be used to mimic fats and to deliver bioactive compounds. In the last decade, there has been increasing interest in these structures, not only from a scientific point of view, i.e., studying new molecules, methodologies for gelification, and new structures, but also from a technological point of view, with researchers and companies exploring these structures as a way to overcome certain challenges and/or create new and innovative products. One of the exciting applications of oleogels is the delivery of functional molecules, where the incorporation of oil-soluble functional compounds can be explored not only at the macroscale but also at micro- and nanoscales, resulting in different release behaviors and also different applications. This review presents and discusses the most recent works on the development, production, characterization, and applications of oleogels and other oleogel-based systems to deliver functional molecules in foods. Full article

Metal-ligand interactions have emerged as an important tool to trigger and modulate self-assembly, and to tune the properties of the final supramolecular materials. Herein, we report the metal-cation induced self-assembly of a pyrene–peptide conjugate to form hydrogels. The peptide has been rationally designed to favor the formation of β-sheet 1D assemblies and metal coordination through the Glu side chains. We studied in detail the self-assembly process in the presence of H⁺, Li⁺, Na⁺, K⁺, Ca²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺, Co²⁺, Fe³⁺, and Cr³⁺ and found that the morphology and mechanical properties of the hydrogels are ion-dependent. Moreover, thanks to the presence of the metal, new applications could be explored. Cu²⁺ metallogels could be used for amine sensing and meat freshness monitoring, while Zn²⁺ metallogels showed good selectivity for cationic dye adsorption and separation. Full article

A series of star and linear polymers based on a poly(ethylene oxide) core and poly(diethylene glycol ethyl ether acrylate) outer arms were synthesised by atom-transfer radical polymerization. The polydispersity of the polymers were low, showing good control of initiation and growth. They all showed lower critical solution (LCST) behaviour, and at 30% concentration most gelled at or below room temperature. The behaviour depended on the number and length of the arms, with the polymers with longer arms gelling at a lower temperature and producing stiffer gels. The shear modulus of the gels varied between 1 and 48 kPa, with the gelling temperature varying between 16 and 23 °C. Attempted cell cultures with the polymers proved unsuccessful, which was determined to be due to the high concentration of polymers needed for gelling. Full article