Search Results (252)

Titanium is widely recognized as an interesting material for electrodes due to its excellent corrosion resistance, mechanical strength, and biocompatibility. However, further functionalization is often necessary to impart advanced interfacial properties, such as selective ion transport or stimuli responsiveness. In this context, the integration of smart polymers, such as poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA)—noted for its dual pH- and thermo-responsive behavior—has emerged as a promising approach to tailor surface properties for next-generation devices. This work compares two covalent immobilization strategies for PDMAEMA on titanium: the “graft-to” method, involving the attachment of pre-synthesized polymer chains, and the “graft-from” method, based on surface-initiated polymerization. The resulting materials were characterized with size exclusion chromatography (SEC) for molecular weight, Fourier-transform infrared spectroscopy (FTIR) for chemical structure, scanning electron microscopy (SEM) for surface morphology, and contact angle measurements for wettability. Electrochemical impedance spectroscopy and polarization studies were used to assess electrochemical performance. Both strategies yielded uniform and stable coatings, with the mode of grafting influencing both surface morphology and functional stability. These findings provide valuable insights into the development of adaptive, stimuli-responsive titanium-based interfaces in advanced electrochemical systems. Full article

Periodontitis, a chronic inflammatory disease, causes alveolar bone loss. Current treatments show limitations in achieving dual antimicrobial and anti-inflammatory effects. We evaluated an emodin-loaded thermoresponsive hydrogel as a local drug delivery system for periodontitis treatment. Emodin itself demonstrated antibacterial activity against Porphyromonas gingivalis, with minimal inhibitory and minimal bactericidal concentrations of 50 μM. It also suppressed mRNA expression of proinflammatory cytokines [tumor necrosis factor alpha, interleukin (IL)-1β, and IL-6] in lipopolysaccharide-stimulated RAW 264.7 cells. The hydrogel, formulated with poloxamers and carboxymethylcellulose, remained in a liquid state at room temperature and formed a gel at 34 °C, providing sustained drug release for 96 h and demonstrating biocompatibility with human periodontal ligament stem cells while exhibiting antibacterial activity against P. gingivalis. In a rat model of periodontitis, the hydrogel significantly reduced alveolar bone loss and inflammatory responses, as confirmed by micro-computed tomography and reverse transcription quantitative polymerase chain reaction of gingival tissue. The dual antimicrobial and anti-inflammatory properties of emodin, combined with its thermoresponsive delivery system, provide advantages over conventional treatments by maintaining therapeutic concentrations in the periodontal pocket while minimizing systemic exposure. This shows the potential of emodin-loaded thermoresponsive hydrogels as effective local delivery systems for periodontitis treatment. Full article

Zwitterionic hydrogels have emerged as eco-friendly anti-fouling materials owing to their superior hydration-mediated resistance to biofouling. Nevertheless, their practical utility remains constrained by intrinsically poor mechanical robustness. Herein, this study proposes a novel strategy to develop novel tough zwitterionic hydrogels by freezing the gels’ polymer network. As a proof of concept, a zwitterionic hydrogel was synthesized via copolymerization of hydrophobic monomer phenyl methacrylate (PMA) and hydrophilic cationic monomer N-(3-dimethylaminopropyl) methacrylamide (DMAPMA), followed by post-oxidation to yield a zwitterionic structure. At service temperature, the rigid and hydrophobic PMA segments remain frozen, while the hydrophilic zwitterionic units maintain substantial water content by osmotic pressure. Synergistically, the zwitterionic hydrogel achieves robust toughness and adhesiveness, with high rigidity (66 MPa), strength (4.78 MPa), and toughness (2.53 MJ/m³). Moreover, the hydrogel exhibits a distinct temperature-dependent behavior by manifesting softer and more stretchable behavior after heating, since the thawing of the gel network at high temperatures increases segmental mobility. Therefore, it achieved satisfactory adhesiveness to substrates (80 kPa). Additionally, the hydrogel demonstrated remarkable anti-fouling performance, effectively suppressing biofilm formation and larval attachment. In summary, this work opens up promising prospects for the development of zwitterionic hydrogels with high application potential. Full article

In high-slope substrates, special requirements are imposed on sprayed ecological soil, which needs to exhibit high rheological properties before spraying and rapid curing after spraying. Traditional stabilizers are often unable to meet these demands. This study developed a thermo-responsive hydrogel stabilizer (HSZ) and applied it to ecological soil. The effects of HSZ on the rheological, mechanical, and vegetation performance of ecological soil were investigated, and the mechanism of the responsive carrier in the stabilizer was explored. The experimental results show that the ecological soil containing HSZ has high flowability before response, but its flowability rapidly decreases and consistency sharply increases after response. After the addition of HSZ, the 7 d unconfined compressive strength of the ecological soil reaches 1.55 MPa. The pH value of the ecological soil generally ranges from 6.5 to 8.0, and plant growth in a simulated vegetation box is favorable. Conductivity and viscosity tests demonstrate that the core–shell microcarriers, upon thermal response, release crosslinking components from the carrier, which rapidly react with the precursor solution components to form a curing system. This study provides a novel method for regulating ecological soil using a responsive stabilizer, further expanding its capacity to adapt to various complex scenarios. Full article

The design of emulsions at the nanoscale is a significant application of nanotechnology. For spherical droplets and a given volume of dispersed phase, the nanometre size of droplets inversely increases the total area, $A={\displaystyle \frac{3V}{r}}$, allowing greater contact with organic and inorganic materials during application. In topical applications, not only is cell contact increased, but also permeability in the cell membrane. Nanoemulsions typically achieve kinetic stability rather than thermodynamic stability, so their commercial application requires reasonable resistance to flocculation and coalescence, which can be affected by temperature changes. Therefore, their thermoresponsive characterisation becomes relevant. In this work, we analyse this response in an O/W nanoemulsion of Palmarosa for antibacterial purposes that has already shown stability for one year at controlled room temperature. We now study hysteresis processes and the behaviour of the statistical distribution in droplet size by Dynamic Light Scattering, obtaining remarkable stability under temperature changes up to 50 °C. This includes a maintained chemical composition observed using Fourier Transform Infrared Spectroscopy and the preservation of antibacterial properties analysed through optical density tests on cultures and the Spread-Plate technique for bacteria colony counting. We obtain practically closed hysteresis curves for some tracers of droplet size distributions through controlled thermal cycles between 10 °C and 50 °C, exhibiting a non-linear behaviour in their distribution. In general, the results show notable physical, chemical, and antibacterial stability, suitable for commercial applications. Full article

It is widely recognized that fine surface structures found in nature contribute to surface functionality, and studies on the design of functional materials based on biomimetics have been actively conducted. In this study, polymer thin films with hierarchically ordered surface structure were prepared by combining both nanoimprinting using anodically oxidized porous alumina (AAO) as a template and surface-initiated atom transfer radical polymerization (SI-ATRP). To prepare such polymer films, we designed a new copolymer (poly{[2-(4-methyl-2-oxo-2H-chromen-7-yloxy)ethyl methacrylate]-co-[2-(2-bromo-2-methylpropionyloxy)ethyl methacrylate]}; poly(MCMA-co-HEMABr)) with coumarin moieties and α-haloester moieties in the pendants. The MCMA repeating units function to fix the pillar structure by photodimerization, and the HEMABr ones act as the polymerization initiation sites for SI-ATRP on the pillar surfaces. Surface structures consisting of vertically oriented multiple pillars were fabricated on the spin-coated poly(MCMA-co-HEMABr) thin films by nanoimprinting using an AAO template. Then, the coumarin moieties inside each pillar were crosslinked by UV light irradiation to fix the pillar structure. SEM observation confirmed that the internally crosslinked pillar structures were maintained even when immersed in organic solvents such as 1,2-dichloroethane and anisole, which are employed as solvents under SI-ATRP conditions. Finally, poly(2,2,2-trifluoroethyl methacrylate) and poly(N-isopropylacrylamide) chains were grafted onto the thin film by SI-ATRP, respectively, to prepare the hierarchically ordered surface structure. Furthermore, in this study, the surface properties as well as the thermoresponsive hydrophilic/hydrophobic switching of the obtained polymer films were investigated. The surface morphology and chemistry of the films with and without pillar structures were compared, especially the interfacial properties expressed as wettability. Grafting poly(TFEMA) increased the static contact angle for both flat and pillar films, and the con-tact angle of the pillar film surface increased from 104° for the flat film sample to 112°, suggesting the contribution of the pillar structure. Meanwhile, the pillar film surface grafted with poly(NIPAM) brought about a significant change in wettability when changing the temperature between 22 °C and 38 °C. Full article

Access to clean water remains a critical global challenge, exacerbated by population growth, industrial activity, and climate change. In response, this study presents the development and characterization of thermo-responsive and salt-adaptive ultrafiltration membranes functionalized with a poly(N-isopropylacrylamide)–co-poly(dimethylacrylamide) (PNIPAM-co-PDMAC) copolymer. By combining the thermo-responsive properties of PNIPAM with the hydrophilic characteristics of PDMAC, these membranes exhibit dual-stimuli responsiveness to temperature and ionic strength, allowing for precise control of permeability and fouling resistance. The experimental results demonstrated that the copolymer’s hydration state and dynamic pore size modulation are sensitive to changes in salinity and temperature, with sodium chloride (NaCl) significantly influencing the transition behavior. Preliminary fouling tests confirmed the antifouling capabilities of these membranes, with salt-triggered hydration transitions effectively reducing irreversible fouling and extending membrane durability. The membranes’ reversible properties and adaptability to dynamic operating conditions highlight their potential to enhance the efficiency and sustainability of water treatment processes. Future investigations will focus on scaling up the fabrication process and assessing the long-term stability of these membranes under real-world conditions. This study underscores the promise of smart membrane systems for advancing global water sustainability. Full article

Reversible addition–fragmentation chain-transfer (RAFT) polymerization was used to synthesize novel thermoresponsive cationic molecular brushes with high yields—namely of copolymers of methoxyoligo(ethylene glycol) methacrylate, alkoxyoligo(ethylene glycol) methacrylate, and N-methacryloylaminopropyl-N,N-dimethyl-N-propylammonium bromide. Controlled polymerization yielded polymers with a molecular weight dispersity of ≤1.3 and conversions exceeding 80%. The influence of the cationic molecular brushes’ composition on their solubility in water and organic solvents, interfacial tension at the water–oil interface, and aggregation behavior in aqueous solutions was investigated. For the first time, we report the design of thermoresponsive cationic molecular brushes combining an antibacterial potential and tunable hydrophilic–hydrophobic properties, enabling highly precise control over their LCST behavior (17–68 °C) through composition tuning. The solubilization capacity of the hydrophobic compounds of brush micelles in water increased with the hydrophobic comonomer content. These polymers exhibited interfacial activity, significantly reducing the water–oil interfacial tension, with critical micelle concentrations (CMCs) of 3–10 mg/L. It was shown that the amphiphilic properties of the copolymers in aqueous solutions can be easily tuned in a desired direction by varying the content of the comonomer units. The obtained data indicate the potential of the polymers as micellar nanocarriers for controlled drug delivery. Full article

The present work deals with the mixing of two green polymers at several definite ratios that led to the receiving of biodegradable polylactic acid (PLA)/polycaprolactone (PCL) blends possessing well-expressed macromechanical and shape memory properties. Four non-compatibilized polymer compositions were prepared by using a twin-screw melt extrusion technique, allowing for a homogeneous dispersion of the PCL droplets in the PLA matrix and higher interfacial adhesion between the two phases. The mechanical behavior of the specimens was estimated by tensile experiments conducted at three particular crosshead velocities. It was established that the addition of PCL as a soft segment redounded to an increment of the toughness and elongation at ultimate strength of the polymer composite at the expense of the maximum tensile stress and Young’s modulus. These latter two parameters were found to be more sensitive, in terms of reaching high values, to the content of PLA as a hard segment in the polymer blend. Performing thermoresponsive shape memory tests disclosed an overwhelming reversibility between the temporary and permanent states of the composite materials, including significant shape fixation ($R_f$) and shape recovery ($R_r$) rates. SEM analysis of the PLA/PCL compositions revealed a distinct phase-separated microstructure, confirming the immiscibility of the two polymers in the blend. Full article

Oleogels must replicate the rheological behavior of saturated fats at processing and consumption temperatures to maintain their physical stability and sensory acceptance. Thus, multicomponent oleogels present a promising approach since oleogelators can exhibit structuring and melting at different temperatures. The aim of the study was to produce a mixture of ultra-chain-long esters capable of structuring and modulating rheological behavior in response to temperature exposure. Therefore, enzymatic transesterification between sorbitol and fully hydrogenated crambe oil (FHCO) was performed to produce a mixture of ultra-long-chain sorbitan esters (SB) for efficient structuring of sunflower oil. SB generated in a reaction medium consisting exclusively of ethanol (60 °C, 200 rpm, 1:1 molar ratio) was selected for its high sorbitol consumption (~95%). While SB oleogels exhibited higher gel strength at 5 °C, at 25 °C, FHCO oleogels were stiffer, showing the gradual melting of SB oleogels evaluated by temperature-dependent rheological analyses and thermal properties. Oleogelation inhibited hydroperoxide formation compared to sunflower oil over 30 days. Results highlight the potential of multicomponent oleogels based on ultralong-chain esters for healthier and more stable high-lipid products. Modulating rheological thermoresponsiveness ensures physical stability under refrigeration while providing a texture similar to saturated fats during spreading and swallowing. Full article

Hydrogels are innovative materials characterized by a water-swollen, crosslinked polymeric network capable of retaining substantial amounts of water while maintaining structural integrity. Their unique ability to swell or contract in response to environmental stimuli makes them integral to biomedical applications, including drug delivery, tissue engineering, and wound healing. Among these, “smart” hydrogels, sensitive to stimuli such as pH, temperature, and light, showcase reversible transitions between liquid and semi-solid states. Thermoresponsive hydrogels, exemplified by poly(N-isopropylacrylamide) (PNIPAM), are particularly notable for their sensitivity to temperature changes, transitioning near their lower critical solution temperature (LCST) of approximately 32 °C in water. Structurally, PNIPAM-based hydrogels (PNIPAM-HYDs) are chemically versatile, allowing for modifications that enhance biocompatibility and functional adaptability. These properties enable their application in diverse therapeutic areas such as cancer therapy, phototherapy, wound healing, and tissue engineering. In this review, the unique properties and behavior of smart PNIPAM are explored, with an emphasis on diverse synthesis methods and a brief note on biocompatibility. Furthermore, the structural and functional modifications of PNIPAM-HYDs are detailed, along with their biomedical applications in cancer therapy, phototherapy, wound healing, tissue engineering, skin conditions, ocular diseases, etc. Various delivery routes and patents highlighting therapeutic advancements are also examined. Finally, the future prospects of PNIPAM-HYDs remain promising, with ongoing research focused on enhancing their stability, responsiveness, and clinical applicability. Their continued development is expected to revolutionize biomedical technologies, paving the way for more efficient and targeted therapeutic solutions. Full article

The rational design of ordered chromogenic supramolecular polymeric systems is critical for the advancement of next-generation stimuli-responsive, optical, and semiconducting materials. Previously, we reported the design of a stimuli-responsive, lamellar self-assembled platform composed of an imidazole-appended perylene diimide of varying methylene spacer length (n = 3, 4, and 6) and a commercially available diacid-functionalized diacetylene monomer, 10, 12 docosadiynedioic acid, in a 1:1 molar ratio. Herein, we expound on the importance of the composition of the imidazole-appended perylene diimide of varying methylene spacer length (n = 3, 4, and 6) and 10, 12 docosadiynedioic acid in the ratio of 2:1 to the supramolecular self-assembly, final morphology, and properties. Topochemical polymerization of the drop-cast films by UV radiation yielded blue-phase polydiacetylene formation, and subsequent thermal treatment of the films produced a thermoresponsive blue-to-red phase transformation. Differential scanning calorimetry (DSC) studies revealed a dual dependence of the methylene spacer length and stimuli treatment (UV and/or heat) on the thermal transitions of the films. Furthermore, small-angle X-ray scattering (SAXS) and wide-angle X-ray scattering (WAXS) showed well-defined hierarchical semiconducting nanostructures with interconnected “chessboard”-patterned lamellar stacking. Upon doping with an ionic liquid, the 2:1 platform showed higher ionic conductivity than the previous 1:1 one. The results presented here illustrate the importance of the composition and architecture to the ionic domain connectivity and ionic conductivity, which will have far-reaching implications for the rational design of semiconducting polymers for energy applications including fuel cells, batteries, ion-exchange membranes, and mixed ionic conductors. Full article

Dental infections can disrupt root development in immature permanent teeth, making traditional endodontic treatment challenging. Apexogenesis, a regenerative approach that promotes natural root development, offers a potential solution. However, issues related to disinfection and material biocompatibility still remain. The objective of this study was to evaluate the synergistic antimicrobial and antibiofilm properties of double and triple antibiotic combinations against common oral pathogens, and to incorporate the most effective combination into a thermosensitive hydrogel, to develop an alternative intracanal medication. Antibiotics were tested alone and in combination in planktonic and biofilm conditions of oral bacteria and Candida albicans. The antibiotic combinations with potential antimicrobial synergy were tested on Enterococcus faecalis biofilms in radicular dentin by confocal microscopy. Metronidazole (ME), ciprofloxacin (CI), and fosfomycin (FO) were incorporated into poly(N-vinylcaprolactam) (PNVCL) hydrogels, and their antibiofilm activity was compared to PNVCL hydrogels containing chlorhexidine (CHX) or calcium hydroxide (CH). The cytotoxicity of the hydrogels was assessed on MDPC-23 odontoblast-like cells using metiltetrazolium assays. A statistical analysis was performed using ANOVA followed by Tukey’s test (p < 0.05). The combination of ME + CI + FO showed superior antibiofilm effects in mono- and dual-species biofilms and on biofilms inside dentinal tubules, comparable to CHX. PNVCL hydrogels with ME + CI + FO significantly reduced E. faecalis biofilms in dentinal tubules, exhibiting a higher efficacy than PNVCL + CH. Cytotoxicity tests revealed minimal effects on cell viability for both PNVCL hydrogels with and without antibiotics. In conclusion, ME + CI + FO showed potent antimicrobial synergy and, when loaded in thermosensitive PNVCL hydrogel, demonstrated significant antibiofilm activity and low cytotoxicity. These findings emphasize the potential of this formulation as an effective and biocompatible endodontic medication, especially for the treatment of immature permanent teeth. Full article

Chitosan is widely used in drug delivery applications, due to its biocompatibility, bio-degradability, and low toxicity. Nevertheless, its properties can be enhanced through the physical or chemical modification of its amino and hydroxyl groups. This work explores the electrostatic complexation of two chitosan samples of differing lengths with two poly(N-isopropylacrylamide) (PNIPAM) homopolymers of different molecular weight carrying a chargeable carboxyl end group. This interaction enables the electrostatic binding of PNIPAM side chains onto the chitosan backbone through the amino groups, and could be considered as an alternative grafting method. Dynamic and electrophoretic light scattering techniques were employed in order to study the solution/dispersion properties of the formed complexes as a function of the PNIPAM concentration, or, equivalently, the molar/charge ratio of the two components. The obtained results revealed that their mass, size, and charge mostly depend on the length of the two individual constituents, as well as their mixing ratio. Furthermore, their response to changes in their environment, namely temperature and ionic strength, was also examined, demonstrating the effect of either the thermoresponsiveness of PNIPAM or the electrostatic charge screening, respectively. Fluorescence spectroscopy, utilizing pyrene as a probe, provided information regarding the hydrophobicity of the formed complexes, while images from scanning transmission electron and atomic force microscopies further elucidated their morphology, which was found to be closely related to that of the corresponding chitosan molecule. Finally, their potential as drug delivery vehicles was also investigated, utilizing curcumin as a model drug at various loading concentrations. Full article

The effect of the presence of guar gum (0–0.75 wt%) in a thermo-responsive triple-network (TN) PVA/TA/PVA-MA-g-PNIPAAm hydrogel (PVA: polyvinyl alcohol; MA: methacrylate, PNIPAAm: poly-N-isopropyl acryl amide; TA: tannic acid) with respect to the structural, mechanical, and viscoelastic properties was mapped. A comprehensive analysis, using large-amplitude oscillatory shear (LAOS), SEM imaging, XRD, and mechanical analysis revealed that guar enhances hydrogel crystallinity (up to 30% at 0.75 wt%), which goes along with a strain hardening. The hydrogel achieved superior mechanical performance at a gum concentration of 0.5 wt% with a 40% increase in shear-thickening, an enhanced strain tolerance in nonlinear regimes, and a good mechanical robustness (maximum elongation to break of 500% and stress of 620 kPa). The hydrogel with 0.5 wt% guar exhibited also a good thermal response (equilibrium swelling ratio changed from 8.4 at 5 °C to 2.5 at 50 °C) and an excellent thermal cycling dimensional stability. Higher guar concentrations reduce structural resilience, leading to brittle hydrogels with lower extensibility and viscoelastic stability. Full article