Gels — Open Access Physical and Chemical Gels Journal

We investigated the mechanical, swelling, and structural properties of mechanically tough clay/sodium polyacrylate (PAAS) hydrogels prepared by simple mixing. The gels had large swelling ratios, reflecting the characteristics of the constituent polymer. The swelling ratios initially increased with the increase of the swelling time, and then attained maximum values. Afterwards, they decreased with an increase of the swelling time and finally became constant. An increase in the clay concentration lead to a decrease in the swelling ratios, whereas an increase in the PAAS concentration lead to an increase in the swelling ratios. Tensile measurements indicated that the toughness for clay/PAAS (M_w = 3.50 × 10⁶) gels was several hundred times larger than that of clay/PAAS (M_w = 5.07 × 10⁵) gels, i.e., the use of ultra-high molecular weight PAAS is essential for fabricating mechanically tough clay/PAAS blend hydrogels. Synchrotron small-angle X-ray scattering (SAXS) results showed that the SAXS intensity measured at small scattering angles decreased with an increase in the clay concentration, indicating that the interparticle interactions were more repulsive at higher concentrations. The decrease of the scattering intensity at high clay concentrations was larger for the clay/PAAS (M_w = 5.07 × 10⁵) gel system than for the clay/PAAS (M_w = 3.50 × 10⁶) gel system. Full article

Chiral and helical polymers possess special helical structures and optical property, and may find applications in chiral catalysis and optical devices. This work presents the preparation and formation process of helical phenolic resins through a sol-gel transcription method. A pair of bola-type chiral low-molecular-weight gelators (LMWGs) derived from valine are used as templates, while 2,4-dihydroxybenzoic acid and formaldehyde are used as precursors. The electron microscopy images show that the phenolic resins are single-handed helical bundles comprised of helical ultrafine nanofibers. The diffused reflection circular dichroism spectra indicate that the helical phenolic resins exhibit optical activity. A possible formation mechanism is proposed, which shows the co-assembly of the LMWGs and the precursors. Full article

Mesoporous silica nanoparticles (MSNs) with ordered pore structure have been synthesized and used as carriers for the anticancer drug curcumin. MSNs were functionalized with amine groups and further attached with carboxymethyl cellulose (CMC) using 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide (EDC) coupling chemistry, which increased the hydrophilicity and biocompatibility of MSNs. The functionalized MSNs (MSN-NH₂ and MSN-CMC) were characterized using Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), Dynamic Light Scattering (DLS), N₂ adsorption, X-Ray Diffraction (XRD), Thermo Gravimetric Analysis (TGA) and Fourier Transform Infrared Spectroscopy (FT-IR). The in vitro release of curcumin from the –NH₂ and CMC functionalized MSNs (MSN-cur-NH₂ and MSN-cur-CMC) was performed in 0.5% aqueous solution of sodium lauryl sulphate (SLS). The effect of CMC functionalization of MSNs towards cellular uptake was studied in the human breast cancer cell line MDA-MB-231 and was compared with that of MSN-NH₂ and free curcumin (cur). Both MSN-NH₂ and MSN-CMC showed good biocompatibility with the breast cancer cell line. The MTT assay study revealed that curcumin-loaded MSN-cur-CMC showed better uptake as compared to curcumin-loaded MSN-cur-NH₂. Free curcumin was used as a control and was shown to have much less internalization as compared to the curcumin-loaded functionalized MSNs due to poor bioavailability. Fluorescence microscopy was used to localize the fluorescent drug curcumin inside the cells. The work demonstrates that CMC-functionalized MSNs can be used as potential carriers for loading and release of hydrophobic drugs that otherwise cannot be used effectively in their free form for cancer therapy. Full article

The result of polymeric nanogels and lipid vesicles interaction—lipobeads—can be considered as multipurpose containers for future therapeutic applications, such as targeted anticancer chemotherapy with superior tumor response and minimum side effects. In this work, micrometer sized lipobeads were synthesized by two methods: (i) mixing separately prepared microgels made of poly(N-isopropylacrylamide) (PNIPA) and phospholipid vesicles of micrometer or nanometer size and (ii) polymerization within the lipid vesicles. For the first time, a high vacuum scanning electron microscopy was shown to be suitable for a quick validation of the structural organization of wet lipobeads and their constituents without special sample preparation. In particular, the structural difference of microgels prepared by thermal and UV-polymerization in different solvents was revealed and three types of giant liposomes were recognized under high vacuum in conjunction with their size, composition, and method of preparation. Importantly, the substructure of the hydrogel core and multi- and unilamellar constructions of the peripheral lipid part were explicitly distinguished on the SEM images of lipobeads, justifying the spontaneous formation of a lipid bilayer on the surface of microgels and evidencing an energetically favorable structural organization of the hydrogel/lipid bilayer assembly. This key property can facilitate lipobeads’ preparation and decrease technological expenses on their scaled production. The comparison of the SEM imaging with the scanning confocal and atomic force microscopies data are also presented in the discussion. Full article

Hydrogels are hydrophilic, three-dimensional networks that are able to absorb large quantities of water or biological fluids, and thus have the potential to be used as prime candidates for biosensors, drug delivery vectors, and carriers or matrices for cells in tissue engineering. In this critical review article, advantages of the hydrogels that overcome the limitations from other types of biomaterials will be discussed. Hydrogels, depending on their chemical composition, are responsive to various stimuli including heating, pH, light, and chemicals. Two swelling mechanisms will be discussed to give a detailed understanding of how the structure parameters affect swelling properties, followed by the gelation mechanism and mesh size calculation. Hydrogels prepared from natural materials such as polysaccharides and polypeptides, along with different types of synthetic hydrogels from the recent reported literature, will be discussed in detail. Finally, attention will be given to biomedical applications of different kinds of hydrogels including cell culture, self-healing, and drug delivery. Full article

Thermoresponsive gelling materials constructed from natural and synthetic polymers can be used to provide triggered action and therefore customised products such as drug delivery and regenerative medicine types as well as for other industries. Some materials give Arrhenius-type viscosity changes based on coil to globule transitions. Others produce more counterintuitive responses to temperature change because of agglomeration induced by enthalpic or entropic drivers. Extensive covalent crosslinking superimposes complexity of response and the upper and lower critical solution temperatures can translate to critical volume temperatures for these swellable but insoluble gels. Their structure and volume response confer advantages for actuation though they lack robustness. Dynamic covalent bonding has created an intermediate category where shape moulding and self-healing variants are useful for several platforms. Developing synthesis methodology—for example, Reversible Addition Fragmentation chain Transfer (RAFT) and Atomic Transfer Radical Polymerisation (ATRP)—provides an almost infinite range of materials that can be used for many of these gelling systems. For those that self-assemble into micelle systems that can gel, the upper and lower critical solution temperatures (UCST and LCST) are analogous to those for simpler dispersible polymers. However, the tuned hydrophobic-hydrophilic balance plus the introduction of additional pH-sensitivity and, for instance, thermochromic response, open the potential for coupled mechanisms to create complex drug targeting effects at the cellular level. Full article

Supramolecular polysaccharide-based hydrogels have attracted considerable research interest recently due to their high structural functionality, low toxicity, and potential applications in foods, cosmetics, catalysis, drug delivery, tissue engineering and the environment. Modulation of the stability of hydrogels is of paramount importance, especially in the case of stimuli-responsive systems. This review will update the recent progress related to the rational design of supramolecular hydrogels with the objective of understanding the gelation process and improving their physical gelation properties for tailored applications. Emphasis will be given to supramolecular host–guest systems with reference to conventional gels in describing general aspects of gel formation. A brief account of the structural characterization of various supramolecular hydrogels is also provided in order to gain a better understanding of the design of such materials relevant to the nature of the intermolecular interactions, thermodynamic properties of the gelation process, and the critical concentration values of the precursors and the solvent components. This mini-review contributes to greater knowledge of the rational design of supramolecular hydrogels with tailored applications in diverse fields ranging from the environment to biomedicine. Full article

Chiral low-molecular-weight gelators (LMWGs) derived from amino acids can self-assemble into helical fibers and twisted/coiled nanoribbons by H-bonding and π–π interaction. Silica nanotubes with single-handed helices have been prepared using chiral LMWGs through sol–gel transcription. Molecular-scale chirality exists at the inner surfaces. Here, we discuss single-handed helical aromatic ring-bridged polybissilsesquioxane nanotubes and mesoporous nanofibers prepared using chiral LMWGs. This review aims at describing the formation mechanisms of the helical nanostructures, the origination of optical activity, and the applications for other helical nanomaterial preparation, mainly based on our group’s results. The morphology and handedness can be controlled by changing the chirality and kinds of LMWGs and tuning the reaction conditions. The aromatic rings arrange in a partially crystalline structure. The optical activity of the polybissilsesquioxane nanotubes and mesoporous nanofibers originates from chiral defects, including stacking and twisting of aromatic groups, on the inner surfaces. They can be used as the starting materials for preparation of silica, silicon, carbonaceous, silica/carbon, and silicon carbide nanotubes. Full article

The present review article highlights a specific class of responsive polymer-based hydrogels which are formed through association of oppositely charged polyion segments. The underpinning temporary three-dimensional network is constituted of hydrophilic chains (either ionic or neutral) physically crosslinked by ion pair formation arising from intermolecular polyionic complexation of oppositely charged repeating units (polyacid/polybase ionic interactions). Two types of hydrogels are presented: (i) hydrogels formed by triblock copolymers bearing oppositely charged blocks (block copolyampholytes), forming self-assembled networks; and (ii) hydrogels formed by co-assembly of oppositely charged polyelectrolyte segments belonging to different macromolecules (either block copolymers or homopolyelectrolytes). Due to the weak nature of the involved polyions, these hydrogels respond to pH and are sensitive to the presence of salts. Discussing and evaluating their solution, rheological and structural properties in dependence on pH and ionic strength, it comes out that the hydrogel properties are tunable towards potential applications. Full article

Poly(N-isopropylacrylamide) (PNIPAM) hydrogels containing carboxymethylcellulose (CMC) and CMC/Fe₃O₄ nanoparticles were prepared. Free-radical polymerization with BIS as cross-linker was used to synthesize the hydrogels. The morphology at the microscopic scale of these materials was investigated using field emission scanning electron microscopy (FESEM). The images show that CMC in the PNIPAM hydrogels induces the formation of a honeycomb structure. This surface morphology was not observed for pure PNIPAM hydrogels prepared under similar conditions. The equilibrium swelling degree of the PNIPAM/CMC hydrogels (5200%) is much larger than that of the pure PNIPAM hydrogels (2500%). The water retention of PNIPAM/CMC hydrogels above the volume phase transition temperature is strongly reduced compared to that of pure PNIPAM hydrogel. Both PNIPAM/Fe₃O₄ and PNIPAM/CMC/Fe₃O₄ hydrogels exhibit a superparamagnetic behavior, but the blocking temperature (104 K) of the former is higher than that of the latter (83 K). Full article

Recently-developed photo-crosslinkable PMMA (polymethylmethacrylate) colloidal spheres are a highly promising system for fundamental studies in colloidal physics and may have a wide range of future technological applications. We synthesize these colloids and characterize their size distribution. Their swelling in a density- and index- matching organic solvent system is demonstrated and we employ dynamic light scattering (DLS), as also the recently-developed confocal differential dynamic microscopy (ConDDM), to characterize the structure and the dynamics of a fluid bulk suspension of such colloids at different particle densities, detecting significant particle charging effects. We stretch these photo-crosslinkable spheres into ellipsoids. The fact that the ellipsoids are cross-linked allows them to be fluorescently stained, permitting a dense suspension of ellipsoids, a simple model of fluid matter, to be imaged by direct confocal microscopy. Full article

Disease, trauma, and aging account for a significant number of clinical disorders. Regenerative medicine is emerging as a very promising therapeutic option. The design and development of new cell-customised biomaterials able to mimic extracellular matrix (ECM) functionalities represents one of the major strategies to control the cell fate and stimulate tissue regeneration. Recently, hydrogels have received a considerable interest for their use in the modulation and control of cell fate during the regeneration processes. Several synthetic bioresponsive hydrogels are being developed in order to facilitate cell-matrix and cell-cell interactions. In this review, new strategies and future perspectives of such synthetic cell microenvironments will be highlighted. Full article

Hydrogels are of intense recent interest in connection with biomedical applications ranging from 3-D cell cultures and stem cell differentiation to regenerative medicine, controlled drug delivery, and tissue engineering. This prototypical form of soft matter has many emerging material science applications outside the medical field. The physical processes underlying this type of solidification are incompletely understood, and this limits design efforts aimed at optimizing these materials for applications. We address this general problem by applying multiple techniques (e.g., NMR, dynamic light scattering, small angle neutron scattering, rheological measurements) to the case of a peptide derivative hydrogelator (molecule 1, NapFFKYp) over a broad range of concentration and temperature to characterize both the formation of individual nanofibers and the fiber network. We believe that a better understanding of the hierarchical self-assembly process and control over the final morphology of this kind of material should have broad significance for biological and medicinal applications utilizing hydrogels. Full article

Production of aerogels starts with solution chemistry and may end with supercritical carbon dioxide drying, which both require a specialized system. Here we present a complete aerogel production system that was developed and used in our laboratory over the last nine years. Our aim was to develop a supercritical dryer and a protocol, whereby the CO₂ pump can be left out, and the entire flow system is operated by the pressure of the CO₂ cylinder. Drying pressure and temperature are controlled by the combination of the filling and heating temperatures. A continuous-mode solvent exchange system has also been developed, in which the solvent consumption during the process can be reduced to one-third of the batch method. In the new medium temperature 1.5 L volume supercritical dryer, the temperature is set to a constant 80–82 °C, and the pressure can be in the 90–200 bar range, depending on the conditions. We have performed approximately 200 dryings thus far, and prepared a wide range of monolithic aerogels, from pristine silica aerogels to polysaccharides and collagen. In this paper, we have summarized not only the technical details, but also the work experiences, as well as advantages and disadvantages of the systems. Full article

A new bolaamphiphile analog featuring carbamate moieties was synthesized in six steps starting from thymidine. The amphiphile structure exhibits nucleoside-sugar polar heads attached to a hydrophobic spacer via carbamate (urethane) functions. This molecular structure, which possesses additional H-bonding capabilities, induces the stabilization of low-molecular-weight gels (LMWGs) in water. The rheological studies revealed that the new bolaamphiphile 7 stabilizes thixotropic hydrogels with a high elastic modulus (G′ > 50 kPa). Full article

Some vinyl hydrogels containing α-amino acid residues (l-phenylalanine, l-valine) were used as polyelectrolyte platforms for the evaluation of the controlled release of two antidepressants (paroxetine and duloxetine). The closer acidity constant (pKa) values of the two drugs show a closer release profile in physiological phosphate buffered saline (PBS) buffer (pH 7.40) and for long periods of time. The great electrostatic interaction forces between the COO⁻ group of the hydrogel and the protonated secondary amino nitrogen of the drug are the main factor improving the release kinetics; this release was found to be slower compared to that of two structurally related drugs bearing the tertiary amino nitrogen atom (citalopram and trazodone). Moreover, at the lower value of pH 4.60, paroxetine showed a flatter release profile from the hydrogel containing the l-phenylalanine residues that, after six days, is half of that shown by duloxetine. Further effects due to steric and hydrophobic interactions may contribute to the different release profile. A further stimulation with alternating magnetic fields (AMF) of low frequency (20 kHz/50 W) enhanced the release of the drug at pH 7.40 from the hydrogel containing magnetic nanoparticles. Both AMF and PBS solution at pH 7.40 were used to trigger the ‘on-demand’ pulsatile paroxetine release from the nanocomposite hydrogel. Full article

The aim of this work was to study the effect of xanthan gum (XG) on the gelation process of bovine sodium caseinate (NaCAS) induced by acidification with glucono-δ-lactone (GDL) and on the mixed acid gel microstructure. Before GDL addition, segregative phase separation was observed in all the NaCAS-XG mixtures evaluated. The gelation process was analyzed by using a fractional factorial experimental design. The images of the microstructure of the mixed acid gels were obtained by conventional optical microscopy and the mean diameter of the interstices was determined. Both the elastic character and the microstructure of the gels depended on the concentrations of XG added. As XG concentration increased, the kinetics of the gelation process was modified and the degree of compactness and elasticity component of the gel network increased. The microstructure of gels depends on the balance among thermodynamic incompatibility, protein gelation and NaCAS-XG interactions. Full article

Emulsion-filled gels are classified as soft solid materials and are complex colloids formed by matrices of polymeric gels into which emulsion droplets are incorporated. Several structural aspects of these gels have been studied in the past few years, including their applications in food, which is the focus of this review. Knowledge of the rheological behavior of emulsion-filled gels is extremely important because it can measure interferences promoted by droplets or particle inclusion on the textural properties of the gelled systems. Dynamic oscillatory tests, more specifically, small amplitude oscillatory shear, creep-recovery tests, and large deformation experiments, are discussed in this review as techniques present in the literature to characterize rheological behavior of emulsion-filled gels. Moreover, the correlation of mechanical properties with sensory aspects of emulsion-filled gels appearing in recent studies is discussed, demonstrating the applicability of these parameters in understanding mastication processes. Full article