| 1. |
- Al-Tikriti, Yassir, et al.
(författare)
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Drug-Induced Phase Separation in Polyelectrolyte Microgels
- 2022
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Ingår i: Gels. - : MDPI AG. - 2310-2861. ; 8:1
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Tidskriftsartikel (refereegranskat)abstract
- Polyelectrolyte microgels may undergo volume phase transition upon loading and the release of amphiphilic molecules, a process important in drug delivery. The new phase is "born" in the outermost gel layers, whereby it grows inward as a shell with a sharp boundary to the "mother" phase (core). The swelling and collapse transitions have previously been studied with microgels in large solution volumes, where they go to completion. Our hypothesis is that the boundary between core and shell is stabilized by thermodynamic factors, and thus that collapsed and swollen phases should be able to also coexist at equilibrium. We investigated the interaction between sodium polyacrylate (PA) microgel networks (diameter: 400-850 mu m) and the amphiphilic drug amitriptyline hydrochloride (AMT) in the presence of NaCl/phosphate buffer of ionic strength (I) 10 and 155 mM. We used a specially constructed microscopy cell and micromanipulators to study the size and internal morphology of single microgels equilibrated in small liquid volumes of AMT solution. To probe the distribution of AMT micelles we used the fluorescent probe rhodamine B. The amount of AMT in the microgel was determined by a spectrophotometric technique. In separate experiments we studied the binding of AMT and the distribution between different microgels in a suspension. We found that collapsed, AMT-rich, and swollen AMT-lean phases coexisted in equilibrium or as long-lived metastable states at intermediate drug loading levels. In single microgels at I = 10 mM, the collapsed phase formed after loading deviated from the core-shell configuration by forming either discrete domains near the gel boundary or a calotte shaped domain. At I = 155 mM, single microgels, initially fully collapsed, displayed a swollen shell and a collapsed core after partial release of the AMT load. Suspensions displayed a bimodal distribution of swollen and collapsed microgels. The results support the hypothesis that the boundary between collapsed and swollen phases in the same microgel is stabilized by thermodynamic factors.
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| 2. |
- Alves, Luis, et al.
(författare)
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New Insights on the Role of Urea on the Dissolution and Thermally-Induced Gelation of Cellulose in Aqueous Alkali
- 2018
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Ingår i: GELS. - : MDPI AG. - 2310-2861. ; 4:4
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Tidskriftsartikel (refereegranskat)abstract
- The gelation of cellulose in alkali solutions is quite relevant, but still a poorly understood process. Moreover, the role of certain additives, such as urea, is not consensual among the community. Therefore, in this work, an unusual set of characterization methods for cellulose solutions, such as cryo-transmission electronic microscopy (cryo-TEM), polarization transfer solid-state nuclear magnetic resonance (PTssNMR) and diffusion wave spectroscopy (DWS) were employed to study the role of urea on the dissolution and gelation processes of cellulose in aqueous alkali. Cryo-TEM reveals that the addition of urea generally reduces the presence of undissolved cellulose fibrils in solution. These results are consistent with PTssNMR data, which show the reduction and in some cases the absence of crystalline portions of cellulose in solution, suggesting a pronounced positive effect of the urea on the dissolution efficiency of cellulose. Both conventional mechanical macrorheology and microrheology (DWS) indicate a significant delay of gelation induced by urea, being absent until ca. 60 degrees C for a system containing 5wt % cellulose, while a system without urea gels at a lower temperature. For higher cellulose concentrations, the samples containing urea form gels even at room temperature. It is argued that since urea facilitates cellulose dissolution, the high entanglement of the cellulose chains in solution (above the critical concentration, C*) results in a strong three-dimensional network.
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| 3. |
- Andersson, Martin, et al.
(författare)
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Binding of Lysozyme to Spherical Poly(styrenesulfonate) Gels
- 2018
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Ingår i: Gels. - : MDPI AG. - 2310-2861. ; 4:1
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Tidskriftsartikel (refereegranskat)abstract
- Polyelectrolyte gels are useful as carriers of proteins and other biomacromolecules in, e.g., drug delivery. The rational design of such systems requires knowledge about how the binding and release are affected by electrostatic and hydrophobic interactions between the components. To this end we have investigated the uptake of lysozyme by weakly crosslinked spherical poly(styrenesulfonate) (PSS) microgels and macrogels by means of micromanipulator assisted light microscopy and small angle X-ray scattering (SAXS) in an aqueous environment. The results show that the binding process is an order of magnitude slower than for cytochrome c and for lysozyme binding to sodium polyacrylate gels under the same conditions. This is attributed to the formation of very dense protein-rich shells in the outer layers of the microgels with low permeability to the protein. The shells in macrogels contain 60 wt % water and nearly charge stoichiometric amounts of lysozyme and PSS in the form of dense complexes of radius 8 nm comprising 30–60 lysozyme molecules. With support from kinetic modelling results we propose that the rate of protein binding and the relaxation rate of the microgel are controlled by the protein mass transport through the shell, which is strongly affected by hydrophobic and electrostatic interactions. The mechanism explains, in turn, an observed dependence of the diffusion rate on the apparent degree of crosslinking of the networks.
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| 4. |
- Carmona, Pierre, 1995, et al.
(författare)
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Glyceraldehyde as an efficient chemical crosslinker agent for the formation of chitosan hydrogels
- 2021
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Ingår i: Gels. - : MDPI AG. - 2310-2861. ; 7:4
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Tidskriftsartikel (refereegranskat)abstract
- The rheological changes that occur during the chemical gelation of semidilute solutions of chitosan in the presence of the low‐toxicity agent glyceraldehyde (GCA) are presented and discussed in detail. The entanglement concentration for chitosan solutions was found to be approximately 0.2 wt.% and the rheological experiments were carried out on 1 wt.% chitosan solutions with various amounts of GCA at different temperatures (25 °C and 40 °C) and pH values (4.8 and 5.8). High crosslinker concentration, as well as elevated temperature and pH close to the pKa value (pH ≈ 6.3–7) of chitosan are three parameters that all accelerate the gelation process. These conditions also promote a faster solid‐like response of the gel‐network in the post‐gel region after long curing times. The mesh size of the gel‐network after a very long (18 h) curing time was found to contract with increasing level of crosslinker addition and elevated temperature. The gelation of chitosan in the presence of other chemical crosslinker agents (glutaraldehyde and genipin) is discussed and a comparison with GCA is made. Small angle neutron scattering (SANS) results reveal structural changes between chitosan solutions, incipient gels, and mature gels.
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| 5. |
- Çimen, Duygu, et al.
(författare)
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Injectable cryogels in biomedicine
- 2021
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Ingår i: Gels. - : MDPI AG. - 2310-2861. ; 7:2
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Forskningsöversikt (refereegranskat)abstract
- Cryogels are interconnected macroporous materials that are synthesized from a monomer solution at sub-zero temperatures. Cryogels, which are used in various applications in many research areas, are frequently used in biomedicine applications due to their excellent properties, such as biocompatibility, physical resistance and sensitivity. Cryogels can also be prepared in powder, column, bead, sphere, membrane, monolithic, and injectable forms. In this review, various examples of recent developments in biomedical applications of injectable cryogels, which are currently scarce in the literature, made from synthetic and natural polymers are discussed. In the present review, several biomedical applications of injectable cryogels, such as tissue engineering, drug delivery, therapeutic, therapy, cell transplantation, and immunotherapy, are emphasized. Moreover, it aims to provide a different perspective on the studies to be conducted on injectable cryogels, which are newly emerging trend.
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| 6. |
- Hansson, Per
(författare)
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Volume Transition and Phase Coexistence in Polyelectrolyte Gels Interacting with Amphiphiles and Proteins
- 2020
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Ingår i: Gels. - : MDPI AG. - 2310-2861. ; 6:3
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Forskningsöversikt (refereegranskat)abstract
- Polyelectrolyte gels have the capacity to absorb large amounts of multivalent species of opposite charge from aqueous solutions of low ionic strength, and release them at elevated ionic strengths. The reversibility offers the possibility to switch between "storage" and "release" modes, useful in applications such as drug delivery. The review focuses on systems where so-called volume phase transitions (VPT) of the gel network take place upon the absorption and release of proteins and self-assembling amphiphiles. We discuss the background in terms of thermodynamic driving forces behind complex formation in oppositely charged mixtures, the role played by cross-links in covalent gels, and general aspects of phase coexistence in networks in relation to Gibbs' phase rule. We also briefly discuss a gel model frequently used in papers covered by the review. After that, we review papers dealing with collapse and swelling transitions of gels in contact with solution reservoirs of macroions and surfactants. Here we describe recent progress in our understanding of the conditions required for VPT, competing mechanisms, and hysteresis effects. We then review papers addressing equilibrium aspects of core-shell phase coexistence in gels in equilibrium. Here we first discuss early observations of phase separated gels and results showing how the phases affect each other. Then follows a review of recent theoretical and experimental studies providing evidence of thermodynamically stable core-shell phase separated states, and detailed analyses of the conditions under which they exist. Finally, we describe the results from investigations of mechanisms and kinetics of the collapse/swelling transitions induced by the loading/release of proteins, surfactants, and amphiphilic drug molecules.
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| 7. |
- Lopez-Sanchez, Patricia, 1977, et al.
(författare)
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Impact of Glucose on the Nanostructure and Mechanical Properties of Calcium-Alginate Hydrogels
- 2022
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Ingår i: Gels. - : MDPI AG. - 2310-2861. ; 8:2
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Tidskriftsartikel (refereegranskat)abstract
- Alginate is a polysaccharide obtained from brown seaweed that is widely used in food, pharmaceutical, and biotechnological applications due to its versatility as a viscosifier and gelling agent. Here, we investigated the influence of the addition of glucose on the structure and mechanical properties of alginate solutions and calcium-alginate hydrogels produced by internal gelation through crosslinking with Ca2+ . Using1H low-field nuclear magnetic resonance (NMR) and small angle neutron scattering (SANS), we showed that alginate solutions at 1 wt % present structural hetero-geneities at local scale whose size increases with glucose concentration (15–45 wt %). Remarkably, the molecular conformation of alginate in the gels obtained from internal gelation by Ca2+ crosslinking is similar to that found in solution. The mechanical properties of the gels evidence an increase in gel strength and elasticity upon the addition of glucose. The fitting of mechanical properties to a poroelastic model shows that structural changes within solutions prior to gelation and the increase in solvent viscosity contribute to the gel strength. The nanostructure of the gels (at local scale, i.e., up to few hundreds of Å) remains unaltered by the presence of glucose up to 30 wt %. At 45 wt %, the permeability obtained by the poroelastic model decreases, and the Young’s modulus increases. We suggest that macro (rather than micro) structural changes lead to this behavior due to the creation of a network of denser zones of chains at 45 wt % glucose. Our study paves the way for the design of calcium-alginate hydrogels with controlled structure for food and pharmaceutical applications in which interactions with glucose are of relevance.
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| 8. |
- Orellana, Mónica V., et al.
(författare)
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Marine Polymer-Gels' Relevance in the Atmosphere as Aerosols and CCN
- 2021
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Ingår i: Gels. - : MDPI AG. - 2310-2861. ; 7:4
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Tidskriftsartikel (refereegranskat)abstract
- Marine polymer gels play a critical role in regulating ocean basin scale biogeochemical dynamics. This brief review introduces the crucial role of marine gels as a source of aerosol particles and cloud condensation nuclei (CCN) in cloud formation processes, emphasizing Arctic marine microgels. We review the gel's composition and relation to aerosols, their emergent properties, and physico-chemical processes that explain their change in size spectra, specifically in relation to aerosols and CCN. Understanding organic aerosols and CCN in this context provides clear benefits to quantifying the role of marine nanogel/microgel in microphysical processes leading to cloud formation. This review emphasizes the DOC-marine gel/aerosolized gel-cloud link, critical to developing accurate climate models.
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| 9. |
- Alakpa, Enateri V., et al.
(författare)
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Bioprinted schwann and mesenchymal stem cell co-cultures for enhanced spatial control of neurite outgrowth
- 2023
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Ingår i: Gels. - : MDPI. - 2310-2861. ; 9:3
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Tidskriftsartikel (refereegranskat)abstract
- Bioprinting nerve conduits supplemented with glial or stem cells is a promising approach to promote axonal regeneration in the injured nervous system. In this study, we examined the effects of different compositions of bioprinted fibrin hydrogels supplemented with Schwann cells and mesenchymal stem cells (MSCs) on cell viability, production of neurotrophic factors, and neurite outgrowth from adult sensory neurons. To reduce cell damage during bioprinting, we analyzed and optimized the shear stress magnitude and exposure time. The results demonstrated that fibrin hydrogel made from 9 mg/mL of fibrinogen and 50IE/mL of thrombin maintained the gel’s highest stability and cell viability. Gene transcription levels for neurotrophic factors were significantly higher in cultures containing Schwann cells. However, the amount of the secreted neurotrophic factors was similar in all co-cultures with the different ratios of Schwann cells and MSCs. By testing various co-culture combinations, we found that the number of Schwann cells can feasibly be reduced by half and still stimulate guided neurite outgrowth in a 3D-printed fibrin matrix. This study demonstrates that bioprinting can be used to develop nerve conduits with optimized cell compositions to guide axonal regeneration.
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| 10. |
- Cretella, Margherita, et al.
(författare)
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Determination of Density of Starch Hydrogel Microspheres from Sedimentation Experiments Using Non-Stokes Drag Coefficient
- 2024
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Ingår i: Gels. - 2310-2861. ; 10:4
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Tidskriftsartikel (refereegranskat)abstract
- Sedimentation is an important property of colloidal systems that should be considered when designing pharmaceutical formulations. In pharmaceutical applications, sedimentation is normally described using Stokes' law, which assumes laminar flow of fluid. In this work we studied swelling and hydration of spherical cross-linked amorphous starch microspheres in pure water, solutions of sodium chloride, and in pH-adjusted aqueous solutions. We demonstrated that Reynolds numbers obtained in these experiments correspond to the transition regime between the laminar flow and the turbulent flow and, hence, expressions based on the non-Stokes drag coefficient should be used for calculations of sedimentation velocity from known density or for assessment of density from observed sedimentation velocity. The density of starch microparticles hydrated in water was about 1050 kg/m3, while densities obtained from experiment with other liquids were dependent on the liquids' densities. The data indicate that the swelling of the cross-linked starch microparticles as characterized by their densities is not sensitive to pH and salt concentration in the studied range of these parameters.
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