Gels, Volume 3, Issue 3 (September 2017) – 11 articles

Core-shell microgels were synthesized via a free radical emulsion polymerization of thermoresponsive poly-(N-isopropyl acrylamide), pNipam, on the surface of silica nanoparticles. Pure pNipam microgels have a lower critical solution temperature (LCST) of about 32 °C. The LCST varies slightly with the crosslinker density used to stabilize the gel network. Including a silica core enhances the mechanical robustness. Here we show that by varying the concentration gradient of the crosslinker, the thermoresponsive behaviour of the core-shell microgels can be tuned. Three different temperature scenarios have been detected. First, the usual behaviour with a decrease in microgel size with increasing temperature exhibiting an LCST; second, an increase in microgel size with increasing temperature that resembles an upper critical solution temperature (UCST), and; third, a decrease with a subsequent increase of size reminiscent of the presence of both an LCST, and a UCST. However, since the chemical structure has not been changed, the LCST should only change slightly. Therefore we demonstrate how to tune the particle size independently of the LCST. Full article

The interest in using colloidal dispersions of gelled lipid nanoparticles (GLN) for different fields of application has increased in recent years, notably in cosmetic, dermatology, and/or pharmaceutics due to their capacity to immobilize compounds with poor water solubility. The pharmaceutical field desires to achieve lipophilic drug formulations which are able to conserve their stability, although it is well-known that emulsions and solid lipid nanoparticles (SLN) present a lack of stability over time, leading to system destabilization. Furthermore, stable colloidal dispersions of gelled oil particles do not affect the properties of the molecule to be delivered, and they result as an alternative for the previously appointed systems. This review is an attempt to present the reader with an overview of colloidal dispersions of GLN, their concept, formulation methods, as well as the techniques used for their characterization. Moreover, various application fields of organogel dispersions have been illustrated to demonstrate the potential application range of these recent materials. Full article

Hydrophilic fumed silica (FS) and precipitated silica (PS) powders were suspended in mineral oil; increasing the silica volume fraction (φ in the suspension led to the formation of sol, pre-gel, and gel states. Gelation took place at lower φ values in the FS than the PS suspension because of the lower silanol density on the FS surface. The shear stresses and dynamic moduli of the FS and PS suspensions were measured as a function of φ. Plots of the apparent shear viscosity against shear rate depended on φ and the silica powder. The FS suspensions in the gel state exhibited shear thinning, followed by a weak shear thickening or by constant viscosity with an increasing shear rate. In contrast, the PS suspensions in the gel state showed shear thinning, irrespective of φ. The dynamic moduli of the pre-gel and gel states were dependent on the surface silanol density: at a fixed φ, the storage modulus G′ in the linear viscoelasticity region was larger for the FS than for the PS suspension. Beyond the linear region, the G′ of the PS suspensions showed strain hardening and the loss modulus G″ of the FS and PS suspensions exhibited weak strain overshoot. Full article

Adhesive processes in aqueous media play a crucial role in nature and are important for many technological processes. However, direct quantification of adhesion still requires expensive instrumentation while their sample throughput is rather small. Here we present a fast, and easily applicable method on quantifying adhesion energy in water based on interferometric measurement of polymer microgel contact areas with functionalized glass slides and evaluation via the Johnson–Kendall–Roberts (JKR) model. The advantage of the method is that the microgel matrix can be easily adapted to reconstruct various biological or technological adhesion processes. Here we study the suitability of the new adhesion method with two relevant examples: (1) antibody detection and (2) soil release polymers. The measurement of adhesion energy provides direct insights on the presence of antibodies showing that the method can be generally used for biomolecule detection. As a relevant example of adhesion in technology, the antiadhesive properties of soil release polymers used in today’s laundry products are investigated. Here the measurement of adhesion energy provides direct insights into the relation between polymer composition and soil release activity. Overall, the work shows that polymer hydrogel particles can be used as versatile adhesion sensors to investigate a broad range of adhesion processes in aqueous media. Full article

Gelation in water-based systems can be achieved in many different ways. This review focusses on ways that are based on self-assembly, i.e., a bottom-up approach. Self-assembly naturally requires amphiphilic molecules and accordingly the systems described here are based on surfactants and to some extent also on amphiphilic copolymers. In this review we are interested in cases of low and moderate concentrations of amphiphilic material employed to form hydrogels. Self-assembly allows for various approaches to achieve gelation. One of them is via increasing the effective volume fraction by encapsulating solvent, as in vesicles. Vesicles can be constructed in various morphologies and the different cases are discussed here. However, also the formation of very elongated worm-like micelles can lead to gelation, provided the structural relaxation times of these systems is long enough. Alternatively, one may employ amphiphilic copolymers of hydrophobically modified water soluble polymers that allow for network formation in solution by self-assembly due to having several hydrophobic modifications per polymer. Finally, one may combine such polymers with surfactant self-assemblies and thereby produce interconnected hybrid network systems with corresponding gel-like properties. As seen here there is a number of conceptually different approaches to achieve gelation by self-assembly and they may even become combined for further variation of the properties. These different approaches are described in this review to yield a comprehensive overview regarding the options for achieving gel formation by self-assembly. Full article

Supramolecular hydrogels offer interesting opportunities for co-assembly with drugs towards sustained release over time, which could be achieved given that the drug participates in the hydrogel nanostructure, and it is not simply physically entrapped within the gel matrix. ^dLeu-Phe-Phe is an attractive building block of biomaterials in light of the peptide’s inherent biocompatibility and biodegradability. This study evaluates the assembly of the tripeptide in the presence of either of the anti-inflammatory drugs ketoprofen or naproxen at levels analogous to commercial gel formulations. Fourier-transformed infrared (FT-IR), circular dichroism, Thioflavin T fluorescence, transmission electron microscopy (TEM), and oscillatory rheometry are used. Drug release over time is monitored by means of reverse-phase high performance liquid chromatography, and shows different kinetics for the two drugs. Full article

Hydrogels based on polysaccharide and protein natural polymers are of great interest in biomedical applications and more specifically for tissue regeneration and drug delivery. Cellulose, chitosan (a chitin derivative), and collagen are probably the most important components since they are the most abundant natural polymers on earth (cellulose and chitin) and in the human body (collagen). Peptides also merit attention because their self-assembling properties mimic the proteins that are present in the extracellular matrix. The present review is mainly focused on explaining the recent advances on hydrogels derived from the indicated polymers or their combinations. Attention has also been paid to the development of hydrogels for innovative biomedical uses. Therefore, smart materials displaying stimuli responsiveness and having shape memory properties are considered. The use of micro- and nanogels for drug delivery applications is also discussed, as well as the high potential of protein-based hydrogels in the production of bioactive matrices with recognition ability (molecular imprinting). Finally, mention is also given to the development of 3D bioprinting technologies. Full article

Glioblastoma (GBM) is one of most aggressive forms of brain cancer, with a median survival time of 14.6 months following diagnosis. This low survival rate could in part be attributed to the lack of model systems of this type of cancer that faithfully recapitulate the tumor architecture and microenvironment seen in vivo in humans. Therapeutic studies would provide results that could be translated to the clinic efficiently. Here, we assess the role of the tumor microenvironment physical parameters on the tumor, and its potential use as a biomarker using a hyaluronic acid hydrogel system capable of elastic modulus tuning and dynamic elastic moduli changes. Experiments were conducted to assess the sensitivity of glioblastoma cell populations with different mutations to varying elastic moduli. Cells with aberrant epithelial growth factor receptor (EGFR) expression have a predilection for a stiffer environment, sensing these parameters through focal adhesion kinase (FAK). Importantly, the inhibition of FAK or EGFR generally resulted in reversed elastic modulus preference. Lastly, we explore the concept of therapeutically targeting the elastic modulus and dynamically reducing it via chemical or enzymatic degradation, both showing the capability to reduce or stunt proliferation rates of these GBM populations. Full article

In this study, a hybrid system consisting of 3D printed polycaprolactone (PCL) filled with hydrogel was developed as an application for reconstruction of long bone defects, which are innately difficult to repair due to large missing segments of bone. A 3D printed gyroid scaffold of PCL allowed a larger amount of hydrogel to be loaded within the scaffolds as compared to 3D printed mesh and honeycomb scaffolds of similar volumes and strut thicknesses. The hydrogel was a mixture of alginate, gelatin, and nano-hydroxyapatite, infiltrated with human mesenchymal stem cells (hMSC) to enhance the osteoconductivity and biocompatibility of the system. Adhesion and viability of hMSC in the PCL/hydrogel system confirmed its cytocompatibility. Biomineralization tests in simulated body fluid (SBF) showed the nucleation and growth of apatite crystals, which confirmed the bioactivity of the PCL/hydrogel system. Moreover, dissolution studies, in SBF revealed a sustained dissolution of the hydrogel with time. Overall, the present study provides a new approach in bone tissue engineering to repair bone defects with a bioactive hybrid system consisting of a polymeric scaffold, hydrogel, and hMSC. Full article

Hydrogels have become key players in the field of drug delivery owing to their great versatility in terms of composition and adjustability to various administration routes, from parenteral (e.g., intravenous) to non-parenteral (e.g., oral, topical) ones. In addition, based on the envisioned application, the design of bioadhesive or mucoadhesive hydrogels with prolonged residence time in the administration site may be beneficial. For example, hydrogels are used as wound dressings and patches for local and systemic therapy. In a similar way, they can be applied in the vaginal tract for local treatment or in the nasal cavity for a similar goal or, conversely, to target the central nervous system by the nose-to-brain pathway. Overall, hydrogels have demonstrated outstanding capabilities to ensure patient compliance, while achieving long-term therapeutic effects. The present work overviews the most relevant and recent applications of hydrogels in drug delivery with special emphasis on mucosal routes. Full article

Titanium dioxide (TiO₂) nanotube and its hybrid nanotubes (with various metal oxides such as Ta₂O₅, Nb₂O₅, ZrO_2, and SiO₂) were fabricated by the sol-gel polymerization in the ethanol gels formed by simple l-lysine-based organogelator. The self-assembled nanofibers (gel fibers) formed by the gelator functioned as a template. The different calcination temperatures gave TiO₂ nanotubes with various crystalline structures; e.g., anatase TiO₂ nanotube was obtained by calcination at 600 °C, and rutile TiO₂ nanotube was fabricated at a calcination temperature of 750 °C. In the metal oxide/TiO₂ hybrid nanotubes, the metal oxide species were uniformly dispersed in the TiO₂ nanotube, and the percent content of metal oxide species was found to correspond closely to the feed ratio of the raw materials. This result indicated that the composition ratio of hybrid nanotubes was controllable by the feed ratio of the raw materials. It was found that the metal oxide species inhibited the crystalline phase transition of TiO₂ from anatase to rutile. Furthermore, the success of the hybridization of other metal oxides (except for TiO₂) indicated the usefulness of the organogel route as one of the fabrication methods of metal oxide nanotubes. Full article