Sol-gel Transition Research Articles

Gelation melioration with synergistic interaction between κ-carrageenan and senna tora gum mixed gel

This study aimed to explore the synergistic effect between κ-carrageenan (KC) and senna tora gum (STG). Firstly, we found that the texture parameters, freeze-thaw stability and viscosity of KC-STG mixed gel were obviously improved compared with KC and STG. After that, the Fourier transform infrared spectroscopy (FT-IR) and X-ray diffraction (XRD) results showed that KC's structure is the main one in the KC-STG mixed gel, and the hydrogen bonding force between KC and STG molecules was enhanced. The results of thermal analysis showed a high gel-sol transition temperature in the KC-STG mixed gel. A reduction in the mobility of water molecules and a more uniform distribution of water in the KC-STG mixed gel could be observed in the low-field nuclear magnetic resonance (LF-NMR) consequences. Finally, the microstructure of the gel was observed by scanning electron microscopy (SEM) and confocal laser scanning microscopy (CLSM), in which the STG network acted as a scaffold to fill in between the multilayered sheets of KC. The above results suggested an obvious synergistic effect between KC and STG.

Engineering an injectable gellan gum-based hydrogel with osteogenesis and angiogenesis for bone regeneration

Injectable hydrogels are currently a topic of great interest in bone tissue engineering, which could fill irregular bone defects in a short time and avoid traditional major surgery. Herein, we developed an injectable gellan gum (GG)-based hydrogel for bone defect repair by blending nano-hydroxyapatite (nHA) and magnesium sulfate (MgSO4). In order to acquire an injectable GG-based hydrogel with superior osteogenesis, nHA were blended into GG solution with an optimized proportion. For the aim of endowing this hydrogel capable of angiogenesis, MgSO4 was also incorporated. Physicochemical evaluation revealed that GG-based hydrogel containing 5% nHA (w/v) and 2.5 mM MgSO4 (GG/5%nHA/MgSO4) had appropriate sol-gel transition time, showed a porosity-like structure, and could release magnesium ions for at least 14 days. Rheological studies showed that the GG/5%nHA/MgSO4 hydrogel had a stable structure and repeatable self-healing properties. In-vitro results determined that GG/5%nHA/MgSO4 hydrogel presented superior ability on stimulating bone marrow mesenchymal stem cells (BMSCs) to differentiate into osteogenic linage and human umbilical vein endothelial cells (HUVECs) to generate vascularization. In-vivo, GG/5%nHA/MgSO4 hydrogel was evaluated via a rat cranial defect model, as shown by better new bone formation and more neovascularization invasion. Therefore, the study demonstrated that the new injectable hydrogel, is a favorable bioactive GG-based hydrogel, and provides potential strategies for robust therapeutic interventions to improve the repair of bone defect.

Efficient Electromagnetic Wave Absorption and Thermal Infrared Stealth in PVTMS@MWCNT Nano-Aerogel via Abundant Nano-Sized Cavities and Attenuation Interfaces

HighlightsPVTMS@MWCNT nano-aerogel with nano-pore size and abundant heterogeneous interface was fabricated via radical polymerization, sol–gel transition and CO2 drying.The nano-aerogel shows superior electromagnetic wave absorption property (RLmin = −36.1 dB and cover all Ku-band) and thermal infrared stealth property (ΔT reached 60.7 °C).Layered nano-aerogel/graphene film with high EMI shielding and absorption properties was obtained;

Aerogel-glass fiber composite filter media for effective separation of emulsified water droplets from diesel fuel

This work evaluates several mechanisms of separation of surfactant-stabilized emulsified water droplets from diesel fuel using high surface area (50–370 m2/g) and high porosity (>90 %) filter media fabricated by combining aerogels and glass fiber mats. Specifically, high surface area, porous gels of syndiotactic polystyrene (sPS) and silica are developed inside glass fiber mats via dip coating in corresponding sol followed by sol–gel transition. The resultant materials are supercritically dried to obtain aerogel-coated separation media. The abundant meso- and macropores of the aerogel network and the different surface energy of sPS and silica produce cooperative functioning of the mechanisms of size exclusion, coalescence filtration, surfactant adsorption, and volumetric water absorption for removal of emulsified water droplets from ultralow sulfur diesel fuel under continuous flow conditions. The role of each separation mechanism is elucidated in this paper. The results reveal high water separation efficiency of ∼92 % compared to ∼30 % for the glass fiber mats.

Polymeric Sol-Gel Transition with the Diverging Correlation Length Verified by Small-Angle X-ray Scattering.

Sol-gel transitions of polymers are pivotal phenomena in material science, yet the critical phenomenon of structure during gelation has remained unclear. Here, we investigated the sol-gel transition of a fluorous polymer, poly(vinylidene fluoride-co-hexafluoropropylene), in a blend of two ionic liquids. This system features a quite high amount of cross-linker and binding sites with ion-dipole interactions between the cation and C-F dipoles, thereby facilitating easy exchange of the cross-links. Changing the mixing ratio of the two ionic liquids enabled tuning the ion-dipole interactions and inducing sol-gel transition. Notably, the correlation length and molar mass, obtained by small-angle X-ray scattering, diverged at the gelation point. Moreover, the derived critical exponents (ν = 0.85 ± 0.05) aligns remarkably well with the prediction from percolation theory (ν = 0.88). To our knowledge, this is the first report on the evident divergence during polymeric gelation by small-angle scattering and the verification of the critical exponents of the percolation theory.

Microrheological characterisation of Cyanoflan in human blood plasma

Naturally occurring polysaccharidic biopolymers released by marine cyanobacteria are of great interest for numerous biomedical applications, such as wound healing and drug delivery. Such polymers generally exhibit high molecular weight and an entangled structure that impact the rheology of biological fluids. However, biocompatibility tests focus not so much on rheological properties as on immune response. In the present study, the rheological behaviour of native blood plasma as a function of the concentration of a cyanobacterium biopolymer is investigated via multiple particle tracking microrheology, which measures the Brownian motion of probes embedded in a sample, and cryogenic scanning electron microscope microstructural characterisation. We use Cyanoflan as the biopolymer of choice, and profit from our knowledge of its chemical structure and its exciting potential for biotechnological applications. A sol–gel transition is identified using time-concentration superposition and the power-law behaviour of the incipient network's viscoelastic response is observed in a variety of microrheological data. Our results point to rheology-based principles for blood compatibility tests by facilitating the assignment of quantitative values to specific properties, as opposed to more heuristic approaches.

Temperature sensitive nanogel-stabilized pickering emulsion of fluoroalkane for ultrasound guiding vascular embolization therapy

Various X-ray imaging technologies like computed tomography (CT) and digital subtraction angiography (DSA) are widely used in transcatheter arterial embolization (TAE) therapy for treating hepatocellular cancer (HCC) patients. Although they display high-contrast imaging, they have a few disadvantages, such as complex operation and exposure to ionizing radiation. Thus, ultrasound (US) imaging plays an important role in medical diagnosis because of its advantages, like simple and fast operation, no ionizing radiation exposure, and accurate real-time imaging. Subsequently, Poly N-isopropylacrylamide-co-2,2,3,4,4,4-Hexafluorobutyl methacrylate (PNF) nanogels were synthesized for stabilizing TGFPE, the Pickering emulsions of 2H, 3H-decafluoropentane (HDFP). These emulsions displayed dual abilities of thermosensitive sol–gel transition and long-term US imaging in vitro. Thus, it was concluded that these emulsions could achieve vascular embolization and long-term US imaging in vivo as per the TAE animal model results. The emulsion droplets’ flow and accumulation were visualized under the US imaging guidance. In summary, the Pickering emulsions have the potential to be used as US-guided embolization material for mediating TAE surgeries.

Hybrid microstructure of smectite clay gels revealed using neutron and synchrotron X-ray scattering

Aqueous suspensions of swelling clays display a nematic sol-gel transition at very low solid concentrations. The underlying microstructure of the gel has remained a point of contention since the time of Irving Langmuir and has been a major obstacle to fully realizing the potential of clays for practical applications. Here, we comprehensively probe the microstructure of a smectite clay suspension using ultra-small angle neutron/X-ray scattering and find that the nematic gel is structurally ordered and contains entities that are at least an order of magnitude larger than the individual particles. Complementary cryo-electron microscopy shows the presence of domains having particle-particle ordering responsible for nematic texture and regions of particle-particle aggregation responsible for gel-like behavior. We find that the smectic clay gels have a hybrid microstructure with co-existing repulsive nematic domains and attractive disordered domains.

Ophthalmic Bimatoprost-Loaded Niosomal In Situ Gel: Preparation, Optimization, and In Vivo Pharmacodynamics Study.

This study aimed at formulating the antiglaucoma agent, Bimatoprost (BMT), into niosomal in situ gel (BMT-ISG) for ocular delivery. Niosomes containing cholesterol/span 60 entrapping BMT were fabricated using a thin-film hydration method. The fabricated niosomes were optimized and characterized for entrapment efficiency (%EE) and size. The optimized BMT-loaded niosomal formulation prepared at a cholesterol/span 60 ratio of 1:2 exhibited the highest entrapment (81.2 ± 1.2%) and a small particle size (167.3 ± 9.1 nm), and they were selected for incorporation into in situ gelling systems (BMT-ISGs) based on Pluronic F127/Pluronic F68. Finally, the in vivo efficiency of the BMT-ISG formulation, in terms of lowering the intraocular pressure (IOP) in normotensive male albino rabbits following ocular administration, was assessed and compared to that of BMT ophthalmic solution. All the formulated BMT-ISGs showed sol-gel transition temperatures ranging from 28.1 °C to 40.5 ± 1.6 °C. In addition, the BMT-ISG formulation sustained in vitro BMT release for up to 24 h. Interestingly, in vivo experiments depicted that topical ocular administration of optimized BMT-ISG formulation elicited a significant decline in IOP, with maximum mean decreases in IOP of 9.7 ± 0.6 mm Hg, compared to BMT aqueous solution (5.8 ± 0.6 mm Hg). Most importantly, no signs of irritation to the rabbit's eye were observed following topical ocular administration of the optimized BMT-ISG formulation. Collectively, our results suggested that niosomal in situ gels might be a feasible delivery vehicle for topical ocular administration of anti-glaucoma agents, particularly those with poor ocular bioavailability.

Carboxymethyl cellulose-based supramolecular hydrogel with thermo-responsive gel-sol transition for temporary plugging of oil pipeline in hot work

Temporary plugging of the pipeline is necessary for safety in the hot work process of a flame-cutting pipeline. Chemical hydrogel plugging materials may block valves or sensors in the pipeline due to incomplete breakage. Herein, we prepared a carboxymethyl cellulose-based supramolecular hydrogel with thermo-responsive gel-sol transition, crosslinked by hydrogen bonding and π-π stacking between melamine (MEL) and 6-aminouracil modified carboxymethyl cellulose (AUCMC). The supramolecular hydrogel exhibits tunable mechanical properties and good self-recovery. Furthermore, the result of rheo-kinetics suggests a rapid gel-sol transition of the hydrogel with thermal stimulus due to the hydrogen bonding. The pressure resistance test indicates that the hydrogel has a good plugging effect in the simulated pipeline, and the great flame retardancy of the hydrogel can ensure the safety of operation. The residual hydrogel was completely broken and the simulated pipeline with the plugging length of 10 cm was dredged within 21 min by flushing hot water above 70 °C. The supramolecular hydrogel, as the plugging materials for hot work of oil pipeline, exhibits obvious advantages such as ensuring the safety of hot work, simplifying the operation process, and avoiding secondary damage to the pipeline, which further widens the application field of CMC.

Injectable thermogel incorporating reactive oxygen species scavenger and nitric oxide donor to accelerate the healing process of diabetic wounds

The healing of diabetic wounds is challenging due to redox imbalances. Herein, the thermogelling system AR-ACP hydrogel, with encapsulated biosafe nitric oxide (NO) donor L-arginine and resveratrol as an ROS scavenger, is established for sustainable wound therapy in the diabetic state. The innovated AR-ACP hydrogel dressings shows the sol–gel transition at 34 °C, allowing the hydrogel to fully cover wounds. The combination of L-arginine and resveratrol showed a prominent effect on anti-oxidative activity. The elimination of superoxide anions from the activated immune cells/oxidative cells by resveratrol maintained the NO-proangiogenic factors generated from L-arginine. Furthermore, the AR-ACP hydrogel endowed outstanding features such as haemocompatibility, non-skin irradiation as well as antibacterial activity. In the in vivo diabetic mice model, complete epidermal regeneration comparable to undamaged skin was observed with AR-ACP hydrogel. The synergy between L-arginine and resveratrol in the ACP hydrogel facilitated neovascularisation in the early stage, resulting in the higher balance in cellularity growth and collagen deposition in the dermal layer compared to control groups. Taken together, our findings demonstrate that the use of a customised ACP-based hydrogel, with the additional L-arginine and resveratrol, resulted in significant skin regeneration in the diabetic state.

A suture-free, shape self-adaptive and bioactive PEG-Lysozyme implant for Corneal stroma defect repair and rapid vision restoration.

Corneal transplantation is a prevailing treatment to repair injured cornea and restore vision but faces the limitation of donor tissue shortage clinically. In addition, suturing-needed transplantation potentially causes postoperative complications. Herein, we design a PEG-Lysozyme injective hydrogel as a suture-free, shape self-adaptive, bioactive implant for corneal stroma defect repair. This implant experiences a sol-gel phase transition via an in situ amidation reaction between 4-arm-PEG-NHS and lysozyme. The physicochemical properties of PEG-Lysozyme can be tuned by the components ratio, which confers the implant mimetic corneal modulus and provides tissue adhesion to endure increased intraocular pressure. In vitro tests prove that the implant is beneficial to Human corneal epithelial cells growth and migration due to the bioactivity of lysozyme. Rabbit lamellar keratoplasty experiment demonstrates that the hydrogel can be filled into defect to form a shape-adaptive implant adhered to native stroma. The implant promotes epithelialization and stroma integrity, recovering the topology of injured cornea to normal. A newly established animal forging behavior test prove a rapid visual restoration of rabbits when use implant in a suture free manner. In general, this work provides a promising preclinical practice by applicating a self-curing, shape self-adaptive and bioactive PEG-Lysozyme implant for suture-free stroma repair.

Influence of chain topology on gel formation and direct ink printing of model linear and star block copolymers with poly(ethylene oxide) and poly(ε-caprolactone) semi-crystalline blocks

In this work, a set of well-defined linear triblock copolymers and star block copolymers (3 and 4-arms) with semi-crystalline blocks consisting of poly(ethylene oxide) (PEO) and poly(ε-caprolactone) (PCL), synthesized by combining ring-opening polymerization and organic catalyst switch strategy, were studied as thermosensitive gel-forming biomaterials for applications in 3D extrusion printing. The hydrogels derived from linear copolymers underwent a temperature-dependent sol–gel–sol transition, behaving as a flowing sol at room temperature and transforming into a non-flowing gel upon heating. On the other hand, the hydrogels derived from 4-arm star block copolymers experienced a gel-sol transition and did not flow at room temperature. This behavior allowed them to be used as 3D printing inks at room temperature. 3D printing results revealed that the semi-crystalline hydrogels of the 4-arm star block copolymers could not only be extruded and printed with high shape fidelity, but they also exhibited a favorable dissolution profile for their use as sacrificial biomaterial inks. Additionally, we thoroughly investigated the crystalline organization of the PCL and the PEO blocks within the hydrogels through comparison with the results obtained in bulk. The results demonstrated evident structural ordering in the hydrogels associated with the crystallization of the PCL blocks. Unexpectedly, DSC results combined with SAXS experiments revealed the presence of PEO block crystals within the 30 % w/v hydrogels from 4-arm star block copolymers, in addition to the PCL block crystals. Hence, remarkable double crystalline hydrogels have been obtained for the first time.

Fabrication of Low-Temperature Fast Gelation β-Cyclodextrin-Based Hydrogel-Loaded Medicine for Wound Dressings.

β-Cyclodextrin (β-CD) is often used as a drug carrier for biomedical materials due to its unique cavity structure. Herein, β-CD was modified by acryloyl chloride and further copolymerized with N-isopropylacrylamide (NIPAM) and acrylic acid (AA) to obtain PNIPAM-co-β-CD-AC. The results showed that the critical phase transition temperature of PNIPAM/β-CD-AC could be controlled at 19 °C, and the fast sol-gel phase transition was realized in 2-10 s. The hydrophobic drug carried in this hydrogel can constantly be released for more than 6 days at pH values (pH 5.5-8), and the duration may match the recovery of the wound. As a dressing hydrogel, its rapid gel formation and inversion as well as shear-thinning behavior prevent secondary wound damage. The β-CD-based hydrogel also has good biocompatibility and antioxidant properties, which provide a good potential choice for wound dressings, especially for exposed wounds in winter.

NMR Self-Diffusion and Transverse Relaxation Time in Bitumen: The Effect of Aging.

In this investigation the dynamics of two types of bitumens with different penetration grade were tested by using dynamic shear rheometry (DSR) and Nuclear Magnetic Resonance (NMR) at unaged conditions, and upon both short- and long-term artificial aging. The gel-sol transition temperature was found to increase with increasing the time of aging treatment. Arrhenius parameters of the viscosity were found, unexpectedly, to be correlated with those of simple liquids, suggesting that the two kinds of systems, although chemically and physically quite different, share the same basic process at the molecular level. The molecular dynamics has been then investigated by NMR Pulsed Field Gradient Stimulated-Echo (PFGSE) and relaxometry (Carr-Purcell-Meiboom-Gill, CPMG, spin-echo pulse sequence) to capture the effect of aging upon dynamics variables such as self-diffusion coefficients D and transverse relaxation times T2 . The translational diffusion at T> of the light molecular components of both types of bitumens was characterized by broad distributions of D which were found independent of the experimental time scale up to 0.2 s. Similarly, T2 data could be described as a continuous unimodal distributions of relaxation times determined both at T< and T> .

Riboflavin mediated UV crosslinking of chitosan-gelatin cryogels for loading of hydrophobic bioactive compounds

Chitosan-gelatin cryogels with good loading capacity of hydrophobic compounds were successfully obtained by UV-induced crosslinking. Using riboflavin as photoinitiator was a suitable alternative to classical carbodiimide crosslinking in obtaining carrier matrices for bioactive hydrophobic compounds. Chitosan had a double role, acting both as a base polymer for the hydrogel network and as co-initiator in riboflavin photo-crosslinking. This co-initiator role of chitosan is due to its electron donor capacity, being well known as a Lewis base type macromolecule. The rheological behaviour of the chitosan-gelatin hydrogel precursor solutions was greatly influenced by riboflavin addition as well as by UV irradiation. As a consequence, the temperature of the sol-gel transition during cooling decreased to 25.5 °C. Compared with classical carbodiimide crosslinking, UV irradiation lead to gels with increased network stability, enhanced elastic behaviour, higher structural strength and almost total stress recovery yield (99 %), the latter indicating self-healing capacity. The cryogels manifested pH responsive swelling, this being highest at close to neutral pH of 7.4. Although hydrophilic in nature, the chitosan-gelatin cryogels crosslinked under the combined effect of riboflavin and UV exposure possess the necessary chemical functionality and morphology that allowed successful embedding of hydrophobic clove essential oil. This was loaded by immersion or fumigation and imparted antioxidant activity to the polymeric matrix.

Biomimetic Hemostatic Powder Derived from Coacervate-Immobilized Thermogelling Copolymers.

Intrinsic hemostasis is an innate body response to prevent bleeding based on the sol-gel transition of blood. However, it is often inadequate for exceptional situations, such as acute injury and coagulation disorders, which typically require immediate medical intervention. Herein, we report the preparation of an efficient hemostatic powder, composed of tannic acid (TA), poly(ethylene glycol) (PEG), and poly(d,l-lactide-co-glycolide)-b-poly(ethylene glycol)-b-poly(d,l-lactide-co-glycolide) triblock copolymer (TB), for biomimetic hemostasis at the bleeding sites. TA has a high affinity for biomolecules and cells and can form coacervates with PEG driven by hydrogen bonding. TB enhances the mechanical strength and provides thermoresponsiveness. The hemostatic powder can rapidly transit into a physical and biodegradable seal on wet substrates under physiological conditions, demonstrating its promise for the generation of instant artificial clots. Importantly, this process is independent of the innate blood clotting process, which could benefit those with blood clotting disorders. This biomimetic hemostatic powder is an adaptive topical sealing agent for noncompressible and irregular wounds, which is promising for biomedical applications.

Elaborating Spatiotemporal Hierarchical Structure of Carrageenan Gels and Their Mixtures during Sol–Gel Transition

Elaborating Spatiotemporal Hierarchical Structure of Carrageenan Gels and Their Mixtures during Sol–Gel Transition

Thermoreversible Gelation with Supramolecularly Polymerized Cross-Link Junctions.

Structure and reversibility of cross-link junctions play pivotal roles in determining the nature of thermoreversible gelation and dynamic mechanical properties of the produced polymer networks. We attempt to theoretically explore new types of sol-gel transitions with mechanical sharpness by allowing cross-links to grow without upper bound. We consider thermoreversible gelation of the primary molecules R{Af} carrying the number f of low molecular weight functional groups (gelators) A. Gelators A are assumed to form supramolecular assemblies. Some examples are: telechelic polymers (f=2) carrying π-π stacking benzene derivatives at their both ends, and trifunctional star molecules (f=3) bearing multiple hydrogen-bonding gelators. The sol-gel transition of the primary molecules becomes sharper with the cooperativity parameter of the stepwise linear growth of the cross-links. There is a polymerization transition (crossover without singularity) of the junctions in the postgel region after the gel point is passed. If the gelator A tends to form supramolecular rings competitively with linear chains, there is another phase transition in the deep postgel region where the average molecular weight of the rings becomes infinite (Bose-Einstein condensation of rings). As a typical example of binary cross-links where gelators A and B form mixed junctions, we specifically consider metal-coordinated binding of ligands A by metal ions B. Two types of multi-nuclear supramolecular complexes are studied: (i) linear stacking (ladder) of the sandwich A2B units, and (ii) linear train of egg-box A4B units. To find the strategy towards experimental realization of supramolecular cross-links, the average molecular weight, the gel fraction, the average length of the cross-link junctions are numerically calculated for all of these models as functions of the functionality f, the concentration of the solute molecules, and the temperature. Potential candidates for the realization of these new types of thermoreversible gelation are discussed.

Recycling polycarbonate wastes to prepare hydrophobic and super mechanically robust aerogels with excellent oil–water and emulsion separation performance

With the development of our society, plastic pollution is becoming more and more prominent. It is attractive and challenging to recycle plastic wastes to prepare valuable products at low cost. In this study, we report a unique strategy to obtain hydrophobic and super robust aerogels from polycarbonate wastes: (1) 4,4-diaminodibenzomethane is used to decompose polycarbonate (PC) waste, (2) the degradation product is compounded with organically modified montmorillonite (OMMT) to gel up through sol–gel transition, (3) solvent exchange and ambient-drying are performed to obtain the final aerogel samples. The addition of OMMT not only promotes the ring opening of the oxazine rings in the polymer matrix and the gelation rate of the system, but also strengthen the prepared aerogels due to the formation of stronger honeycomb network structure as a result of hydrogen bonding between OMMT and polymer matrix. The resulting aerogels can withstand up to 46,000 times its own weight and exhibits superb hydrophobic properties with contact angle up to 146.2°, as well as being suitable for use in a wide range of pH values. Besides, the aerogels possess good capacity for continuous oil–water separation, whose oil absorption performance does not deteriorate perceptibly after 50 cycles of oil absorption and degreasing. The aerogel obtained by this simple method not only has superb mechanical properties, hydrophobic properties, and oil–water emulsion separation, but also has many potential industrial applications and, most importantly, solves the waste disposal dilemma.