Search Results (13)

In ophthalmology, developing effective drug delivery systems is crucial to overcome anatomical and physiological barriers, such as rapid tear turnover and blinking, which limit the efficacy of conventional formulations like eye drops. Poloxamers, especially the derivatives 407 (P407) and 188, are amphiphilic triblock copolymers characterized by an intriguing thermo-reversible behavior, making them ideal candidates for the development of in situ hydrogels for ocular applications. Various thermo-sensitive poloxamer-based hydrogels were designed to be easily instilled as liquids at room temperature, gelling promptly upon contact with the corneal surface. These systems promoted a controlled release of active compounds, significantly improving their adhesion to the ocular surface. This review discusses the most relevant scientific literature on the topic, with particular attention to studies published in recent years. The results demonstrated that poloxamer formulations are capable of overcoming typical ocular barriers, thereby increasing drug bioavailability. The intrinsic biocompatibility of poloxamers contributes to the safety and tolerability of the system. Furthermore, P407 showed additional wound healing features. The combination of biocompatibility and thermo-reversible behavior makes poloxamer-based hydrogels a promising platform for the development of innovative ocular drug delivery systems able to enhance therapeutic efficacy and patient comfort. Full article

In this study, a strategy was adopted to promote the formation of NiAl precipitates with the aim of enhancing strength by incorporating a 0.2 wt.% Al into a traditional ultra-low carbon bainitic (ULCB) steel alloy. By integrating thermo-mechanical control processing (TMCP) and a tailored tempering process, a new-generation steel with an outstanding combination of properties has been successfully developed for shipbuilding and marine engineering equipment. It features a yield strength of 880 MPa, a yield ratio of 0.84, and an impact toughness of 175 J. The precipitation characteristics of nanoscale particles in this steel, including NiAl intermetallics and carbides, were systematically investigated. The results show that the alloy with low Al addition formed NiAl precipitates during tempering. The high-density distributions of NiAl, (Mo, V)C, and (Ti, V, Nb)C precipitates, which exhibit slow coarsening kinetics, played a dominant role in enhancing the strength of the tempered steel. In addition to precipitation, the microstructure before and after tempering was also analyzed. It was observed that a granular bainite morphology was favorable for decreasing the yield ratio. Additionally, the formation of reverse-transformed austenite during tempering was critical for retaining toughness despite substantial strength gains. Finally, theoretical modeling was employed to quantitatively assess the contributions of these microstructural modifications to yield strength enhancement of thermo-mechanical controlled processing (TMCP) and tempered steel. This study establishes a fundamental basis for subsequent industrial-scale development and practical engineering applications of novel products. Full article

Anionic thermo- and pH-responsive copolymers were synthesized by photoiniferter reversible addition–fragmentation chain transfer polymerization (PI-RAFT). The thermo-responsive properties were provided by oligo(ethylene glycol)-based macromonomer units containing hydrophilic and hydrophobic moieties. The pH-responsive properties were enabled by the addition of 5–20 mol% of strong (2-acrylamido-2-methylpropanesulfonic) and weak (methacrylic) acids. Upon initiation by visible light at 470 nm and in the absence of radical initiators, yields from the ternary copolymers reached 94% in 2.5 h when the process was carried out in continuous flow mode using 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoic acid as a light-sensitive RAFT agent. The polymers were characterized using size exclusion chromatography, IR and NMR spectroscopy, and differential scanning calorimetry. The copolymers featured a sufficiently high molecular weight (93–146 kDa) consistent with theoretical values and satisfactory dispersities in the range of 1.18–1.45. The pH-responsive properties were studied in deionized water, saline, and buffer solutions. Dramatic differences in LCST behavior were observed in strong and weak acid-based polyelectrolytes. The introduction of sulfonic acid units, even in very small amounts, completely suppressed the LCST transition in deionized water while maintaining it in the saline and buffer solutions, with a negligible LCST dependence on the pH. In contrast, the incorporation of weak methacrylic acid demonstrated a pronounced pH dependence. The peculiarities of micelle formation in aqueous solutions were investigated and critical micelle concentrations and their ability to retain pyrene, a hydrophobic drug model, were determined. It was observed that anionic molecular brushes formed small micelles with aggregation numbers of 1–2 at concentrations in the order of 10⁻⁴ mg/mL. These micelles have a high ability to entrap pyrene, which makes them a promising tool for targeted drug delivery. Full article

Supramolecular gels were developed by taking advantage of an assembly of small dipeptides containing pyrrolo-pyrazole scaffolds. The dipeptides were prepared through a robust and ecofriendly synthetic approach from the commercially available starting materials of diazoalkanes and maleimides. By playing with the functionalization of the scaffold, the choice of the natural amino acid, and the stereochemistry, we were able to obtain phase-selective gels. In particular, one peptidomimetic showed gelation ability and thermoreversibility in aromatic solvents at very low concentrations. Rheology tests showed a typical viscoelastic solid profile, indicating the formation of strong gels that were stable under high mechanical deformation. NMR studies were performed, allowing us to determine the conformational and stereochemical features at the base of the supramolecular interactions. Full article

When it comes to seawater desalination in the small- to medium-electricity ranges, the organic Rankine cycle (ORC) powered by solar energy stands out as the most energy-efficient technology currently available. Various solar techniques have been developed to capture and absorb solar energy. Among them, the parabolic trough collector (PTC) has gained recognition as a low-cost solar thermal collector with a long operating life. This study investigates the thermodynamic performance and economic parameters of a PTC-powered ORC using Dowtherm A and toluene as working fluids for the solar cycle and ORC cycle, respectively. Thermo-economic multi-objective optimization and decision-making techniques are applied to assess the system’s performance. Four key parameters are analyzed for their impact on exergy efficiency and total hourly cost. Using TOPSIS decision-making, the best solution from the Pareto frontier is identified, featuring an ORC exergy efficiency of 30.39% and a total hourly cost of 39.38 US$/h. The system parameters include a mass flow rate of fresh water at 137.7 m³/h, a total output net power of 577.9 kJ/kg, and a district heating supply of 1074 kJ/kg. The cost analysis reveals that the solar collector represents approximately 68% of the total hourly cost at 26.77 US$/h, followed by the turbine, thermoelectric generator, and reverse osmosis (RO) unit. Full article

Membranes are used in desalination or water treatment to separate pollutants from water based on characteristics such as size or charge. Nanofiltration (NF), ultrafiltration (UF), microfiltration (MF), and reverse osmosis (RO) are typical membrane techniques. However, traditional membranes have a number of disadvantages, including fouling both on surfaces and in internal structures, uncontrollable pore size, and membrane features. Smart membranes, also known as stimuli-responsive membranes, have recently attracted attention due to their selectivity, tunable permeability, and tunable and/or reversible attributes. This new generation of smart membranes is created by integrating various stimuli-responsive materials into membrane substrates. These multi-functional smart membranes can self-adjust their physical and chemical features in response to environmental signals such as temperature, pH, light, and other stimuli. Thermo-responsive membranes, pH-responsive membranes, ion-responsive membranes, molecule-responsive membranes, UV-light-responsive membranes, glucose-responsive membranes, magnetic-responsive membranes, and redox-responsive membranes are the current kinds of smart membranes. Because of their smart structures, they have the potential to improve performance by providing high selectivity without reducing permeability, high mechanical stability, and high resistance against fouling, and can meet requirements such as molecular weight cut-off (MWCO), removal efficiencies, and wastewater quality. Smart membranes can show tunable features based on the condition of the stimulus or stimuli present internally or externally, resulting in improved and desirable controllability over the process of pollutant removal from water. Because of their physicochemical stability, repeatability, and long life, stimuli-responsive smart materials (mainly adsorbents and filtration membranes) have the potential to be key materials for membrane production, particularly in the field of water treatment. Smart membranes have a bright future, and it is important to investigate and encourage their use and advancement. This review provides a comprehensive overview of smart membranes. Full article

Humins waste valorization is considered to be an essential pathway to improve the economic viability of many biorefinery processes and further promote their circularity by avoiding waste formation. In this research, the incorporation of humins in a Diels–Alder (DA) polymer network based on furan-maleimide thermoreversible crosslinks was studied. A considerable enhancement of the healing efficiency was observed by just healing for 1 h at 60 °C at the expense of a reduction of the material mechanical properties, while the unfilled material showed no healing under the same conditions. Nevertheless, the thermal healing step favored the irreversible humins polycondensation, thus strengthening the material while keeping the enhanced healing performance. Our hypothesis states a synergistic healing mechanism based on humins flowing throughout the damage, followed by thermal humins crosslinking during the healing trigger, together with DA thermoreversible bonds recombination. A multi-material soft robotic gripper was manufactured out of the proposed material, showing not only improved recovery of the functional performance upon healing but also stiffness-tunable features by means of humins thermal crosslinking. For the first time, both damage healing and zone reinforcement for further damage prevention are achieved in a single intrinsic self-healing system. Full article

Polymers crosslinked via furan/maleimide thermo-reversible chemistry have been extensively explored as reprocessable and self-healing thermosets and elastomers. For such applications, it is important that the thermo-reversible features are reproducible after many reprocessing and healing cycles. Therefore, side reactions are undesirable. However, we have noticed irreversible changes in the mechanical properties of such materials when exposing them to temperatures around 150 °C. In this work, we study whether these changes are due to the self-reaction of maleimide moieties that may take place at this rather low temperature. In order to do so, we prepared a furan-grafted polyketone crosslinked with the commonly used aromatic bismaleimide (1,1′-(methylenedi-4,1-phenylene)bismaleimide), and exposed it to isothermal treatments at 150 °C. The changes in the chemistry and thermo-mechanical properties were mainly studied by infrared spectroscopy, ¹H-NMR, and rheology. Our results indicate that maleimide self-reaction does take place in the studied polymer system. This finding comes along with limitations over the reprocessing and self-healing procedures for furan/maleimide-based reversibly crosslinked polymers that present their softening (decrosslinking) point at relatively high temperatures. On the other hand, the side reaction can also be used to tune the properties of such polymer products via in situ thermal treatments. Full article

The shape memory effect (SME) refers to the ability of a material to recover its original shape, but only in the presence of a right stimulus. Most polymers, either thermo-plastic or thermoset, can have the SME, although the actual shape memory performance varies according to the exact material and how the material is processed. Vitrimer, which is between thermoset and thermo-plastic, is featured by the reversible cross-linking. Vitrimer-like shape memory polymers (SMPs) combine the vitrimer-like behavior (associated with dissociative covalent adaptable networks) and SME, and can be utilized to achieve many novel functions that are difficult to be realized by conventional polymers. In the first part of this paper, a commercial polymer is used to demonstrate how to characterize the vitrimer-like behavior based on the heating-responsive SME. In the second part, a series of cases are presented to reveal the potential applications of vitrimer-like SMPs and their composites. It is concluded that the vitrimer-like feature not only enables many new ways in reshaping polymers, but also can bring forward new approaches in manufacturing, such as, rapid 3D printing in solid state on space/air/sea missions. Full article

Poloxamer 407 copolymer is a versatile and widely used thermo-reversible material. Its use has many advantages, such as bio-adhesion, enhanced solubilization of poorly water-soluble drugs and many applications fields like oral, rectal, topical, nasal drug administration. Hydrogels made up of Poloxamer 407 are characterized by specific rheological features, which are affected by temperature, concentration and presence of other compounds. A strategic approach in topical therapeutic treatments may be the inclusion of drug delivery systems, such as ethosomes, transfersomes and niosomes, into hydrogel poloxamer formulation. The evaluation of the interaction between colloidal carriers and the Poloxamer 407 hydrogel network is essential for a suitable design of an innovative topical dosage form. For this reason, the Rheolaser Master™, based on diffusing wave spectroscopy, and a Kinexus Rotational Rheometer were used to evaluate the influence of nanocarriers on the microrheological features of hydrogels. The advantages of the Rheolaser Master™ analyzer are: (i) its ability to determine viscoelastic parameter, without altering or destroying the sample and at rest (zero shear); (ii) possibility of aging analysis on the same sample. This study provide evidence that vesicular systems do not influence the rheological features of the gel, supporting the possibility to encapsulate an innovative system into a three-dimensional network. Full article

Temperature influences the life of many organisms in various ways. A great number of organisms live under conditions where their ability to adapt to changes in temperature can be vital and largely determines their fitness. Understanding the mechanisms and principles underlying this ability to adapt can be of great advantage, for example, to improve growth conditions for crops and increase their yield. In times of imminent, increasing climate change, this becomes even more important in order to find strategies and help crops cope with these fundamental changes. There is intense research in the field of acclimation that comprises fluctuations of various environmental conditions, but most acclimation research focuses on regulatory effects and the observation of gene expression changes within the examined organism. As thermodynamic effects are a direct consequence of temperature changes, these should necessarily be considered in this field of research but are often neglected. Additionally, compensated effects might be missed even though they are equally important for the organism, since they do not cause observable changes, but rather counteract them. In this work, using a systems biology approach, we demonstrate that even simple network motifs can exhibit temperature-dependent functional features resulting from the interplay of network structure and the distribution of activation energies over the involved reactions. The demonstrated functional features are (i) the reversal of fluxes within a linear pathway, (ii) a thermo-selective branched pathway with different flux modes and (iii) the increased flux towards carbohydrates in a minimal Calvin cycle that was designed to demonstrate temperature compensation within reaction networks. Comparing a system’s response to either temperature changes or changes in enzyme activity we also dissect the influence of thermodynamic changes versus genetic regulation. By this, we expand the scope of thermodynamic modelling of biochemical processes by addressing further possibilities and effects, following established mathematical descriptions of biophysical properties. Full article

Poloxamer 407, also known by the trademark Pluronic^® F127, is a water-soluble, non-ionic triblock copolymer that is made up of a hydrophobic residue of polyoxypropylene (POP) between the two hydrophilic units of polyoxyethylene (POE). Poloxamer 407-based hydrogels exhibit an interesting reversible thermal characteristic. That is, they are liquid at room temperature, but they assume a gel form when administered at body temperature, which makes them attractive candidates as pharmaceutical drug carriers. These systems have been widely investigated in the development of mucoadhesive formulations because they do not irritate the mucosal membranes. Based on these mucoadhesive properties, a simple administration into a specific compartment should maintain the required drug concentration in situ for a prolonged period of time, decreasing the necessary dosages and side effects. Their main limitations are their modest mechanical strength and, notwithstanding their bioadhesive properties, their tendency to succumb to rapid elimination in physiological media. Various technological approaches have been investigated in the attempt to modulate these properties. This review focuses on the application of poloxamer 407-based hydrogels for mucosal drug delivery with particular attention being paid to the latest published works. Full article

Conductive rubber nanocomposites were prepared by dispersing conductive nanotubes (CNT) in thermoreversibly cross-linked ethylene propylene rubbers grafted with furan groups (EPM-g-furan) rubbers. Their features were studied with a strong focus on conductive and mechanical properties relevant for strain-sensor applications. The Diels-Alder chemistry used for thermoreversible cross-linking allows for the preparation of fully recyclable, homogeneous, and conductive nanocomposites. CNT modified with compatible furan groups provided nanocomposites with a relatively large tensile strength and small elongation at break. High and low sensitivity deformation experiments of nanocomposites with 5 wt % CNT (at the percolation threshold) displayed an initially linear sensitivity to deformation. Notably, only fresh samples displayed a linear response of their electrical resistivity to deformations as the resistance variation collapsed already after one cycle of elongation. Notwithstanding this mediocre performance as a strain sensor, the advantages of using thermoreversible chemistry in a conductive rubber nanocomposite were highlighted by demonstrating crack-healing by welding due to the joule effect on the surface and the bulk of the material. This will open up new technological opportunities for the design of novel strain-sensors based on recyclable rubbers. Full article