Thermoreversible Behavior Research Articles

Gelatins derived from aronia-supplemented fish diets: Structural effect and molecular simulation.

Fish gelatin, a sustainable substitute for mammalian gelatin, frequently exhibits weaker gel strength and thermal stability, limiting its industrial uses. This study investigated an in vivo method to improve functional characteristics by supplementing Nile tilapia diets with Aronia extract. The control diet (A0) contained no Aronia extract, while the remaining four diets consisted of commercial pelleted feed enriched with 250mg/kg (A250), 500mg/kg (A500), 750mg/kg (A750), and 1000mg/kg (A1000) of Aronia extract. The gelatin samples revealed thermo-reversible behavior with increasing temperature. A250 exhibited the highest melting temperature of 29.65°C, compared to 27.43°C for A0. The gelation temperature for A250 was 17.56°C, indicating a relatively stable gelatin structure. The elastic modulus (G') was the highest in A250, suggesting an improved gel network compared to the other samples. The gelation rate constant (kgel) was highest in A250 (540.67Pa), followed by A750 (447.32Pa), A500 (393.85Pa), and A1000 (370.97Pa), compared to 391.15Pa for A0. The gel strength was improved, with A250 showing the highest value at 133.9g, followed by A750, A1000, and A500, while A0 was 102.1g. The glass transition temperatures (Tg) for A250, fish gelatin (FG), bovine gelatin (BG), and A0 were 76.72°C, 74.31°C, 70.71°C, and 73.52°C, respectively. Molecular docking studies revealed strong binding interactions between A250 and phenolic compounds, which contributed to the observed structural enhancements. These findings suggest that supplementing fish diets with Aronia extract can substantially enhance gelatin quality, offering a promising alternative to traditional gelatin sources.

α-Substituted ketones as reagent for Passerini modification of carboxymethyl cellulose: Toward dually functionalized derivatives and thermo-sensitive chemical hydrogels

The present works describes the Passerini modification of carboxymethyl cellulose (CMC) by using a library of nine α-substituted ketones derivatives, differing in their hydrophobicity and reactivity, conjointly with cyclohexyl isocyanide. The Passerini ligation, achieved in aqueous and mild conditions, was shown to be successful, leading to a large panel of dually functionalized CMC derivatives, in an eco-friendly manner. A particular attention was dedicated to the influence of the experimental parameters such as the stoichiometry, the nature of a co-solvent or the temperature, which allowed to tune the extent of modification. The reactivity of the ketone was proven to be governed by its i) compatibility with water, ii) sterical accessibility, and by iii) the presence of neighboring electron-withdrawing group. The resulting Passerini CMC products modified by methacrylate moieties (CMC-MA) were used as reactive macromonomer under a “grafting through” approach. The copolymerization of CMC-MA with oligoethylene glycol methacrylate (OEGMA) and diethylene glycol methacrylate (DEGMA) upon thermal radical reaction conditions enabled to generate tightly cross-linked chemical hydrogels, with a thermo-sensitive and thermo-reversible behavior, reflected by a macroscopical shrinkage/swelling response, and confirmed by SAXS analysis. Such chemical strategy paves the way toward multifunctional polysaccharide-based networks with potential utilizations as drug delivery devices, dye removals or actuators.

Designing New Sustainable Polyurethane Adhesives: Influence of the Nature and Content of Diels-Alder Adducts on Their Thermoreversible Behavior.

With a view to the development of new sustainable and functional adhesives, two Diels–Alder (DA) adducts are incorporated as a third component into the curing process of solvent-based and solvent-free polyurethanes in this study. The influence of the nature and content of the DA molecules on the retro-DA (rDA) reaction and its reversibility and cyclability is investigated. It is demonstrated that the bonding/debonding properties of the adhesives are mainly controlled by the concentration of the DA adducts, with a minimum thermoreversible bond (TB) content required that depends on the system and the total ratio between all the diols in the formulation. For the solvent-based system, rDA/DA reversibility can be repeated up to ~20 times without deterioration, in contrast to the solvent-free system where a gradual loss in the DA network reconstruction efficiency is observed. Despite this limitation, the solvent-free system presents clear advantages from an environmental point of view. The changes observed in the physical properties of these new thermoreversible adhesives are of great relevance for recycling strategies and, in particular, their potential for separating multilayered film packaging materials in order to recycle the individual polymer films involved.

Role of chain architecture in the solution phase assembly and thermoreversibility of aqueous PNIPAM/silyl methacrylate copolymers.

Stimuli-responsive polymers functionalized with reactive inorganic groups enable creation of macromolecular structures such as hydrogels, micelles, and coatings that demonstrate smart behavior. Prior studies using poly(N-isopropyl acrylamide-co-3-(trimethoxysilyl)propyl methacrylate) (P(NIPAM-co-TMA)) have stabilized micelles and produced functional nanoscale coatings; however, such systems show limited responsiveness over multiple thermal cycles. Here, polymer architecture and TMA content are connected to the aqueous self-assembly, optical response, and thermo-reversibility of two distinct types of PNIPAM/TMA copolymers: random P(NIPAM-co-TMA), and a 'blocky-functionalized' copolymer where TMA is localized to one portion of the chain, P(NIPAM-b-NIPAM-co-TMA). Aqueous solution behavior characterized via cloud point testing (CPT), dynamic light scattering (DLS), and variable-temperature nuclear magnetic resonance spectroscopy (NMR) demonstrates that thermoresponsiveness and thermoreversibility over multiple cycles is a strong function of polymer configuration and TMA content. Despite low TMA content (≤2% mol), blocky-functionalized copolymers assemble into small, well-ordered structures above the cloud point that lead to distinct transmittance behaviors and stimuli-responsiveness over multiple cycles. Conversely, random copolymers form disordered aggregates at elevated temperatures, and only exhibit thermoreversibility at negligible TMA fractions (0.5% mol); higher TMA content leads to irreversible structure formation. This understanding of the architectural and assembly effects on the thermal cyclability of aqueous PNIPAM-co-TMA can be used to improve the scalability of responsive polymer applications requiring thermoreversible behavior, including sensing, separations, and functional coatings.

Enhanced Transdermal Delivery of Pranoprofen Using a Thermo-Reversible Hydrogel Loaded with Lipid Nanocarriers for the Treatment of Local Inflammation.

A biocompatible topical thermo-reversible hydrogel containing Pranoprofen (PF)-loaded nanostructured lipid carriers (NLCs) was studied as an innovative strategy for the topical treatment of skin inflammatory diseases. The PF-NLCs-F127 hydrogel was characterized physiochemically and short-time stability tests were carried out over 60 days. In vitro release and ex vivo human skin permeation studies were carried out in Franz diffusion cells. In addition, a cytotoxicity assay was studied using the HaCat cell line and in vivo tolerance study was performed in humans by evaluating the biomechanical properties. The anti-inflammatory effect of the PF-NLCs-F127 was evaluated in adult male Sprague Daw-ley® rats using a model of inflammation induced by the topical application of xylol for 1 h. The developed PF-NLCs-F127 exhibited a heterogeneous structure with spherical PF-NLCs in the hydrogel. Furthermore, a thermo-reversible behaviour was determined with a gelling temperature of 32.5 °C, being close to human cutaneous temperature and thus favouring the retention of PF. Furthermore, in the ex vivo study, the amount of PF retained and detected in human skin was high and no systemic effects were observed. The hydrogel was found to be non-cytotoxic, showing cell viability of around 95%. The PF-NLCs-F127 is shown to be well tolerated and no signs of irritancy or alterations of the skin’s biophysical properties were detected. The topical application of PF-NLCs-F127 hydrogel was shown to be efficient in an inflammatory animal model, preventing the loss of stratum corneum and reducing the presence of leukocyte infiltration. The results from this study confirm that the developed hydrogel is a suitable drug delivery carrier for the transdermal delivery of PF, improving its dermal retention, opening the possibility of using it as a promising candidate and safer alternative to topical treatment for local skin inflammation and indicating that it could be useful in the clinical environment.

Chitosan/β-glycerophosphate in situ forming thermo-sensitive hydrogel for improved ocular delivery of moxifloxacin hydrochloride

The aim of the current work is to develop a thermo-sensitive hydrogel system of moxifloxacin hydrochloride (MOX) for improved ocular delivery. Fifteen formulations were prepared at different concentrations of β-glycerophosphate disodium salt (β-GP) 12–20% (w/v) and chitosan (CS) 1.7–1.9% (w/v). The optimized MOX loaded thermo-sensitive hydrogel system (F8), consisting of CS (1.8%, w/v) and β-GP (16%, w/v), showed optimum gelation temperature (35 °C) and gelation time (2 min), thus was selected for further investigations. It showed a significant decrease (p < 0.05) in the zeta potential value compared to CS solution with a favorable pH value (7.1) and confirmed thermoreversible behavior. MOX loaded F8 displayed a porous structure under scanning electron microscopy. Rheological investigation of MOX loaded F8 revealed the presence of a strong hydrogel network with high elasticity along with a small loss factor of 0.08 indicating a great ease of gel formation. The release of MOX from F8 was found to be governed by a combined mechanism of diffusion and relaxation. Biological assessment of two concentrations of MOX loaded F8 (0.25 and 0.5%) was conducted using healthy and infected male albino New Zealand rabbits, where an improved and prolonged antibacterial activity against Staphylococcus aureus compared to plain MOX (0.5%), marketed MOX eye drops (0.5%), was shown. Moreover, histopathological examination of ocular tissues confirmed the antibacterial efficacy of the optimized formulation eight days post topical therapy. Consequently, the developed CS/β-GP thermo-sensitive hydrogel system (F8) reveals a promising potential for enhancing the ocular delivery of MOX for treatment of bacterial infections.

Self‐Healable Hydrophobic Material Based on Anthracenyl Functionalized Fluorous Block Copolymers via Reversible Addition‐Fragmentation Chain Transfer Polymerization and Rapid Diels–Alder Reaction

AbstractRecently, among the available approaches to develop self‐healable materials, 1,2,4‐triazoline‐3,5‐dione (TAD)‐based Diels–Alder (DA) chemistry has gained tremendous attention, becuase this DA reaction is very rapid under ambient conditions. This study delineates developing a self‐healing hydrophobic fluorinated polymer utilizing dynamic and rapid TAD‐DA chemistry. For this purpose, block copolymers of 2‐hydroxyethyl methacrylate (HEMA) and 2,2,2‐trifluoroethylmethacrylate (TFEMA) are prepared via reversible addition‐fragmentation chain transfer polymerization. Subsequently, the pendant hydroxyl groups of the HEMA repeat units are modified with anthracenyl functionality via esterification with 9‐anthracenecarboxylic acid. The tailor‐made polymer‐bearing anthracenyl pendants are subsequently crosslinked via a rapid DA reaction using a bifunctional TAD derivative at room temperature (r.t.). Differential scanning calorimetry (DSC) analysis is performed to interpret the thermoreversible behavior of the TAD‐derived DA polymer. The self‐healing characteristics of this TAD‐derived DA conjugate are studied by monitoring the healing of a notched surface via AFM analysis. Interestingly, the TAD conjugated fluoropolymers are hydrophobic, as evidenced by the water contact angle analysis. Such TAD‐derived DA fluoropolymer conjugates with remarkable hydrophobic characteristics and excellent self‐healing features can pave a new direction in the potential materials for specialty paints, coatings, and adhesives.

Self-healing polymers synthesized by ring opening metathesis polymerization (ROMP) of bio-derived furanic molecules

Novel bio-derivable tricyclic oxanorbornene polymers, based upon secondary furfurylamine and maleic anhydride derived monomers, prepared via ring opening metathesis polymerization (ROMP) are reported. The tricyclic oxanorbornenes with fused lactam ring are exo Diels–Alder adducts. DFT calculations support the cycloaddition is the first step, followed by lactamization. The polymerizations are rapid and deliver polymers with targeted molar mass and low dispersity (Đ). The prepared polymers with furanyl pendant groups have reactivity towards maleimide-bearing compounds to form thermally induced crosslinked networks through thermoreversible Diels–Alder reactions. The thermoreversible (self-healing) behavior is confirmed by sol gel transition. This new class of bio-derived polymer could be further modified with different active moieties as pendant groups and hence be tailored for more applications in the future.Graphical abstract

Techniques to characterize dynamics in biomaterials microenvironments: XPCS and microrheology of alginate/PEO-PPO-PEO hydrogels.

Many recent studies have highlighted the timescale for stress relaxation of biomaterials on the microscale as an important factor in regulating a number of cell-material interactions, including cell spreading, proliferation, and differentiation. Relevant timescales on the order of 0.1-100 s have been suggested by several studies. While such timescales are accessible through conventional mechanical rheology, several biomaterials have heterogeneous structures, and stress relaxation mechanisms of the bulk material may not correspond to that experienced in the cellular microenvironment. Here we employ X-ray photon correlation spectroscopy (XPCS) to explore the temperature-dependent dynamics, relaxation time, and microrheology of multicomponent hydrogels comprising of commercial poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) triblock copolymer F127 and alginate. Previous studies on this system have shown thermoreversible behavior in the bulk oscillatory shear rheology. At physiological temperatures, bulk rheology of these samples shows behavior characteristic of a soft solid, with G' > G'' and no crossover between G' and G'' over the measurable frequency range, indicating a relaxation time >125 s. By contrast, XPCS-based microrheology shows viscoelastic behavior at low frequencies, and XPCS-derived correlation functions show relaxation times ranging from 10-45 s on smaller length scales. Thus, we are able to use XPCS to effectively probe the viscoelasticity and relaxation behavior within the material microenvironments.

Impact of octenyl succinic anhydride (OSA) modified starch on the particle size distribution and rheological properties of xanthan gum in aqueous solutions

Abstract Effects of addition of octenyl succinate anhydride (OSA) starch on the structural, rheological and thermo-rheological properties of aqueous solutions of 0.5 (w/v %) xanthan gum were evaluated. Analysis by dynamic light scattering revealed the absence of complex formation in the mixed solution. However, it was noticed that an increase in the concentration of OSA starch (COSA) leads simultaneously to an increase of the number of micelles and their self-assembly within the network formed by the xanthan macromolecules. This same mechanism was observed during the evaluation of the rheological properties. For systems containing 0.5 (w/v %) of xanthan and for which COSA ≤ 4 (w/v %), a thermoreversible behavior was found similar to that of xanthan in solution. Furthermore, for COSA ≥ 5 (w/v %), the rheological behavior remained indifferent to the increase in temperature but, scored a spectacular rise in storage modulus when the cooling temperature begins near 70 °C.

Hierarchical microfibrillar gels from evaporation-induced anisotropic self-assembly of in situ-generated nanocrystals

Whilst nanocrystal gels may be formed via destabilization of pre-functionalized nanocrystal dispersions, gelation via assembly of unfunctionalized nanocrystals into fibrillar networks remains a significant challenge. Here, we show that gels with hierarchical microfibrillar networks are formed from anisotropic self-assembly of in situ-generated mesolamellar nanocrystals upon evaporation of ZnO nanofluids. The obtained gels display the thermo-reversible behavior characteristic of a non-covalent physical gel. We elucidate a three-stage gelation mechanism. In the pre-nucleation stage, the cloudy ZnO nanofluid transforms into a transparent stable suspension, comprising multi-branched networks of aggregates self-assembled from in situ-generated layered zinc hydroxide (LZH) nanocrystals upon solvent evaporation. In the subsequent nucleation and anisotropic 1D fibre growth stage, further evaporation triggers nucleation and growth of 1D nanofibers through reorganization of the nanocrystal aggregates, before rapid nanofibre bundling leading to microfibrillar networks in the ultimate gelation stage. Our results provide mechanistic insights for hierarchical self-assembly of nanocrystals into fibrillar gels and open up facile fabrication routes using reactive transition metal-oxide nanofluids for new functional fibres and gels.

Synthesis, characterization and properties of self-healable ionomeric carboxylated styrene–butadiene polymer

The paper describes synthesis and properties of carboxylated styrene–butadiene rubber (XSBR) and its ionomer using the reaction between carboxyl groups of XSBR and zinc stearate. The self-aggregation of Zn2+ ion pairs resulted in the formation of an ionic cross-linked network, which gave excellent properties to XSBR. The transitions due to the self-association of the ionic cross-links in the ionomers in addition to the glass transition were observed in the dynamic mechanical analysis. The cross-linked XSBR with 1 and 3 wt% of zinc stearate showed a tensile strength value of 4.2 and 5.2 MPa, which were much higher than that (2.5 MPa) of pristine XSBR. Self-healing test was done for the ionomer, where a tensile strength value of 5.2 MPa (before healing) and a value of 3.5 MPa (after healing) were observed, which indicated that the ionic cross-links could heal the interphase. The ionic network polymers also displayed excellent self-healing ability, triggered by heating at 100 °C for 3 h via atomic force microscopy. The healing efficiency of the XSBR/Zn stearate compound was calculated as 68%. Thermoreversible behaviour of the polymer via ionic cross-links showed regular reversal of storage modulus (E’) with varying temperature at constant frequency and strain. This study thus opens up a route for developing the self-healable ionic cross-linked XSBR with considerable mechanical properties for various engineering applications.

Temperature-dependent structure and compressive mechanical behavior of alginate/polyethylene oxide-poly(propylene oxide)-poly(ethylene oxide) hydrogels.

We report the structural and mechanical behavior of multicomponent hydrogels comprising the commercial poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) block copolymer F127 and alginate. Previous studies on this system have shown thermoreversible behavior in shear rheology. Here we explore the properties of these materials under compression and large deformations, relevant to applications such as wound dressings that require mechanical robustness. For gels with lower F127 concentration, we find that the stiffness of the gels can be ascribed to the alginate network, and that the Young's modulus and fracture stress do not strongly depend on temperatures. However, for gels with an F127 concentration of 30 wt %, the Young's modulus is enhanced at higher temperatures. Under large deformations, the fracture stress and fracture strain of the materials can be independently varied using the alginate and F127 concentrations, respectively; without the trade-off in these properties that is often observed in rigid polymer networks. Small-angle X-ray scattering shows a power-law dependence scattering intensity on q arising from the alginate network and scattering peaks consistent with rearranging micelles. For gels with lower F127 concentrations, we find a disordered-body-centered cubic (BCC)-face-centered cubic (FCC) progression of states with temperature, and a BCC/FCC mixture for gels with higher F127 concentrations.

Homogeneous, monodispersed furan-melamine particles performing reversible binding and forming networks

Homogeneous and monodispersed furan-functionalised melamine-formaldehyde particles were produced. As a precursor, 2-chloro-1,3,5-triazine-2,4-diamine (Mel) was selectively substituted with 2-aminomethyl furan (Fu) units in a convenient one step reaction. The pure reaction product Fu-Mel, which was used without further purification, was reacted with formaldehyde by conventional sol-gel condensation in aqueous medium to yield chemically homogenous, spherically shaped and monodispersed particles. The particles were analysed using ATR-FT-IR, Raman, 1H and 13C NMR spectroscopy, TGA, SEM and DSC measurements. The reactivity of the furan groups located at the particle surface was studied by performing a thermoreversible Diels-Alder cycloaddition reaction with bis-maleimide coupling agents. The formed networks showed thermoreversible behaviour, which was characterised by dynamic IR and DSC measurements.

New approach to electron microscopy imaging of gel nanocomposites in situ

Characterization of Au-nanocomposites is routinely done with scattering techniques where the structure and ordering of nanoparticles can be analyzed. Imaging of Poloxamer gel-based Au-nanocomposites is usually limited to cryo-TEM imaging of cryo-microtomed thin sections of the specimen. While this approach is applicable for imaging of the individual nanoparticles and gauging their size distribution, it requires altering the state of the specimen and is prone to artifacts associated with preparation protocols. Use of Scanning Transmission Electron Microscopy (S/TEM) with fluid cell in situ provides an opportunity to analysis of these complex materials in their hydrated state with nanometer resolution, yet dispensing dense gel-based samples onto electron-transparent substrates remains challenging. We show that Poloxamer gel-based Au nanocomposites exhibiting thermoreversible behavior can be imaged in a fully hydrated state using a commercially available fluid cell holder, and we describe a specimen preparation method for depositing femtoliter amounts of gel-based nanocomposites directly onto the 50 nm-thick SiN window membranes. Ultimately, fluid cell S/TEM in situ imaging approach offers a pathway to visualization of individual nanoparticles within a thick gel media while maintaining the hydrated state of the carrier polymeric matrix.

Self-suspended starch fluids for simultaneously optimized toughness, electrical conductivity, and thermal conductivity of polylactic acid composite

It is challenging to fabricate a starch derivative with a plasticizing effect and good dispersion in a poly(lactic acid) matrix to achieve desirable performance. In this study, self-suspended starch fluids composed of modified granules as the core and polyethylene glycol-substituted tertiary amines as the shell were first fabricated via a combined carboxymethylation and acylation reaction. The as-prepared starch fluids exhibited liquid-like behavior and had semiconductor electric conductivity (4.91 × 10−5 S/cm) at room temperature without a solvent. The modulus of starch fluids was clearly reduced under the heating process and exhibited its initial flow properties upon cooling, displaying thermo-reversible behavior. The resultant fluids were then incorporated into a poly(lactic acid) matrix to produce fully biodegradable composites with desirable performance. At a loading level of 10 wt%, starch fluids exhibited simultaneous enhancements in elongation at break (increase of 164.7%) and thermal conductivity (increase of 119%) of PLA composites compared to pure PLA, attributable to the good dispersion and heat-transfer properties of starch fluids. In addition, PLA composites with 10 wt% loading of starch fluids demonstrated excellent antistatic performance (3.08 × 10−4 S/cm), suggesting that polar groups of the PLA structure and PEG groups of starch fluids contributed synergistically to the electrical conductivities of composites. These results indicate that starch fluids are promising antistatic agents and plasticizers for potential applications in biodegradable materials.

Critical Dependence of Molecular Weight on Thermoresponsive Behavior of Diblock Copolymer Worm Gels in Aqueous Solution.

Reversible addition–fragmentation chain transfer (RAFT) aqueous dispersion polymerization of 2-hydroxypropyl methacrylate was used to prepare three poly(glycerol monomethacrylate)x–poly(2-hydroxypropyl methacrylate)y (denoted Gx-Hy or PGMA-PHPMA) diblock copolymers, namely G37-H80, G54-H140, and G71-H200. A master phase diagram was used to select each copolymer composition to ensure that a pure worm phase was obtained in each case, as confirmed by transmission electron microscopy (TEM) and small-angle x-ray scattering (SAXS) studies. The latter technique indicated a mean worm cross-sectional diameter (or worm width) ranging from 11 to 20 nm as the mean degree of polymerization (DP) of the hydrophobic PHPMA block was increased from 80 to 200. These copolymer worms form soft hydrogels at 20 °C that undergo degelation on cooling. This thermoresponsive behavior was examined using variable temperature DLS, oscillatory rheology, and SAXS. A 10% w/w G37-H80 worm dispersion dissociated to afford an aqueous solution of molecularly dissolved copolymer chains at 2 °C; on returning to ambient temperature, these chains aggregated to form first spheres and then worms, with the original gel strength being recovered. In contrast, the G54-H140 and G71-H200 worms each only formed spheres on cooling to 2 °C, with thermoreversible (de)gelation being observed in the former case. The sphere-to-worm transition for G54-H140 was monitored by variable temperature SAXS: these experiments indicated the gradual formation of longer worms at higher temperature, with a concomitant reduction in the number of spheres, suggesting worm growth via multiple 1D sphere–sphere fusion events. DLS studies indicated that a 0.1% w/w aqueous dispersion of G71-H200 worms underwent an irreversible worm-to-sphere transition on cooling to 2 °C. Furthermore, irreversible degelation over the time scale of the experiment was also observed during rheological studies of a 10% w/w G71-H200 worm dispersion. Shear-induced polarized light imaging (SIPLI) studies revealed qualitatively different thermoreversible behavior for these three copolymer worm dispersions, although worm alignment was observed at a shear rate of 10 s–1 in each case. Subsequently conducting this technique at a lower shear rate of 1 s–1 combined with ultra small-angle x-ray scattering (USAXS) also indicated that worm branching occurred at a certain critical temperature since an upturn in viscosity, distortion in the birefringence, and a characteristic feature in the USAXS pattern were observed. Finally, SIPLI studies indicated that the characteristic relaxation times required for loss of worm alignment after cessation of shear depended markedly on the copolymer molecular weight.

Large-area alginate/PEO-PPO-PEO hydrogels with thermoreversible rheology at physiological temperatures

Alginate hydrogels have shown great promise for applications in wound dressings, drug delivery, and tissue engineering. This report details the fabrication and rheological properties of a multicomponent hydrogel consisting of alginate and poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) triblock copolymers, and the achievement of thick, castable gels with tunable, thermoreversible behavior at physiological temperatures. PEO-PPO-PEO triblock copolymers can form temperature-sensitive hydrogels that exist as liquids at low temperatures and soft solids at high temperatures. In this work, we have employed PEO-PPO-PEO triblock copolymers to impart thermoresponsive properties to alginate hydrogels in the form of a multicomponent hydrogel. These systems can transition between a weak gel and a stiff gel, with a corresponding increase in the viscoelastic moduli of approximately two orders of magnitude as temperature is increased. The temperatures corresponding to the upper and lower boundaries of the stiff gel region, as well as the storage modulus at physiological temperatures (e.g., 36–40 °C), can be controlled through the PEO-PPO-PEO concentration. Optically clear gels that are homogeneous on the microscale can be fabricated in a scalable manner to create flat, large-area thick films, making these systems favorable for applications in wound healing, soft tissue repair, and biomedical device coatings.

Thermoreversible (Ionic-Liquid-Based) Aqueous Biphasic Systems.

The ability to induce reversible phase transitions between homogeneous solutions and biphasic liquid-liquid systems, at pre-defined and suitable operating temperatures, is of crucial relevance in the design of separation processes. Ionic-liquid-based aqueous biphasic systems (IL-based ABS) have demonstrated superior performance as alternative extraction platforms, and their thermoreversible behaviour is here disclosed by the use of protic ILs. The applicability of the temperature-induced phase switching is further demonstrated with the complete extraction of two value-added proteins, achieved in a single-step. It is shown that these temperature-induced mono(bi)phasic systems are significantly more versatile than classical liquid-liquid systems which are constrained by their critical temperatures. IL-based ABS allow to work in a wide range of temperatures and compositions which can be tailored to fit the requirements of a given separation process.

Preparation and thermo-reversible gelling properties of protein isolate from defatted Antarctic krill (Euphausia superba) byproducts

Protein isolate was prepared from defatted Antarctic krill (Euphausia superba) byproducts by 0.1M NaOH extraction. Maximum yield of krill protein isolate reached 28.66% by precipitation at pH 4.6. Krill protein isolate demonstrated its excellent nutritional values through amino acid composition and in vitro digestibility. Thermal transition of krill protein isolate was determined by differential scanning calorimetry measurement. Extrapolated values of glass transition temperature (Tg) and denaturation temperature (Td) of krill protein isolate were 33.8°C and 80.3°C when the heating rate was 2°C/min. Dispersions of krill protein isolate generated self-supported gels at concentrations above 100g/L without the addition of salt or other additives. A noticeable enhancement of gel strength was induced through cooling. Gels with krill protein isolate displayed a thermo-reversible behavior under repeating heating/cooling cycles, which was primarily due to the formation and disruption of hydrogen bonds. Network strength of protein gels was strongly dependent on protein concentrations.