High ionic conductivity poly(ionic liquid)s (PILs) are of growing interest for their thermal and electrochemical stability, processability, and potential in safe, flexible all-solid-state electrochemical devices. While various approaches to enhance the ionic conductivity are reported, the influence of cation substituents is rarely addressed. Moreover, some of the asymmetric anions recently developed for high-conductivity ionic liquids were never tested in PILs. We report the design and synthesis of twelve novel cationic PILs prepared via quaternization of N-substituted imidazoles by commercially available poly(epichlorohydrin-co-ethylene oxide) (poly(EPCH-r-EO)) with subsequent ion metathesis. They differ by imidazolium side chain length (C1–C6 alkyl) and presence of heteroatoms (silyl, siloxane, and fluoroalkyl) and by anion type (bis(trifluoromethylsulfonyl)imide (TFSI), 2,2,2-trifluoromethylsulfonyl-N-cyanoamide (TFSAM), tetrafluoroborate (BF4), trifluoro(trifluoromethyl)borate (BF3CF3), and tricyanofluoroborate (BF(CN)3)). TFSI-based PILs with alkyl side chains gave lower glass transition temperatures (Tg) and higher ionic conductivities than those bearing heteroatomic substituents, with n-butyl side chains providing a conductivity of 4.7 × 10–6 S cm–1 at 25 °C under anhydrous conditions. This increased to 1.0 × 10–5 and 4.5 × 10–4 S cm–1 at 25 and 70 °C, respectively, when the TFSI anion was replaced with BF(CN)3. All PILs showed good electrochemical (>3.2 V vs Ag+/Ag) and thermal (>185 °C) stability, making them excellent candidates for solid-state electrolytes in electrochemical devices.
Antibacterial coatings on model silicon wafers and implants, based on chitosan (CHI), poly(acrylic acid) (PAA), and the antibacterial agent chlorhexidine digluconate (CHX), were obtained using a layer-by-layer assembly method. The surface roughness and 2D and 3D images of the surfaces of CHI/PAA/CHX coatings obtained from different pH assemblies were investigated by atomic force microscopy, revealing that pH 6 enabled optimal inclusion of CHX in the multilayer film. The structure and elemental composition before and after implementation of CHX into the coating were investigated via scanning electron microscopy and energy-dispersive X-ray spectroscopy. The obtained films exhibited antimicrobial efficacy against Staphylococcus aureus and Staphylococcus epidermidis. The effects of CHX concentration and duration of contact with the coating on bacterial activity were investigated, and the quantitative release of CHX from coated implants in phosphate buffer was determined as a function of the incubation time. The biocompatibility of the PAA/CHI/CHX coatings was investigated using human mononuclear cells (HMNCs) and quantified using an MTT assay. HMNCs demonstrated high viability in eluted solutions obtained from implants coated with PAA/CHI/CHX (0.025%) and PAA/CHI/CHX (0.0125%), while the extract of implants coated with PAA/CHI/CHX (0.05%) induced slight cytotoxicity.
Antibacterial coatings on model silicon wafers and implants, based on chitosan (CHI), poly(acrylic acid) (PAA), and the antibacterial agent chlorhexidine digluconate (CHX), were obtained using a layer-by-layer assembly method. The surface roughness and 2D and 3D images of the surfaces of CHI/PAA/CHX coatings obtained from different pH assemblies were investigated by atomic force microscopy, revealing that pH 6 enabled optimal inclusion of CHX in the multilayer film. The structure and elemental composition before and after implementation of CHX into the coating were investigated via scanning electron microscopy and energy-dispersive X-ray spectroscopy. The obtained films exhibited antimicrobial efficacy against Staphylococcus aureus and Staphylococcus epidermidis. The effects of CHX concentration and duration of contact with the coating on bacterial activity were investigated, and the quantitative release of CHX from coated implants in phosphate buffer was determined as a function of the incubation time. The biocompatibility of the PAA/CHI/CHX coatings was investigated using human mononuclear cells (HMNCs) and quantified using an MTT assay. HMNCs demonstrated high viability in eluted solutions obtained from implants coated with PAA/CHI/CHX (0.025%) and PAA/CHI/CHX (0.0125%), while the extract of implants coated with PAA/CHI/CHX (0.05%) induced slight cytotoxicity.
In recent years, numerous applications of hydrogels using polysaccharides have evolved, benefiting from their widespread availability, excellent biodegradability, biocompatibility, and nonpoisonous nature. These natural polymers are typically sourced from renewable materials or from manufacturing processes, contributing collaboratively to waste management and demonstrating the potential for enhanced and enduring sustainability. In the field of novel bioactive molecule carriers for biotherapeutics, natural polymers are attracting attention due to their inherent properties and adaptable chemical structures. These polymers offer versatile matrices with a range of architectures and mechanical properties, while retaining the bioactivity of incorporated biomolecules. However, conventional polysaccharide-based hydrogels suffer from inadequate mechanical toughness with large swelling properties, which prohibit their efficacy in real-world applications. This review offers insights into the latest advancements in the development of diverse polysaccharide-based hydrogels for biotherapeutic administrations, either standalone or in conjunction with other polymers or drug delivery systems, in the pharmaceutical and biomedical fields.
In recent years, numerous applications of hydrogels using polysaccharides have evolved, benefiting from their widespread availability, excellent biodegradability, biocompatibility, and nonpoisonous nature. These natural polymers are typically sourced from renewable materials or from manufacturing processes, contributing collaboratively to waste management and demonstrating the potential for enhanced and enduring sustainability. In the field of novel bioactive molecule carriers for biotherapeutics, natural polymers are attracting attention due to their inherent properties and adaptable chemical structures. These polymers offer versatile matrices with a range of architectures and mechanical properties, while retaining the bioactivity of incorporated biomolecules. However, conventional polysaccharide-based hydrogels suffer from inadequate mechanical toughness with large swelling properties, which prohibit their efficacy in real-world applications. This review offers insights into the latest advancements in the development of diverse polysaccharide-based hydrogels for biotherapeutic administrations, either standalone or in conjunction with other polymers or drug delivery systems, in the pharmaceutical and biomedical fields.
The nanoconfinement effects of glassy polymer thin films on their thermal and mechanical properties have been investigated thoroughly, especially with an emphasis on its altered glass transition behavior compared to bulk polymer, which has been known for almost three decades. While research in this direction is still evolving, reaching new heights to unravel the underlying physics of phenomena observed in confined thin polymer films, we have a much clearer picture now. This, in turn, has promoted their application in miniaturized and functional applications. To extract the full potential of such confined films, starting from their fabrication, function, and various applications, we must realize the necessity to have an understanding and availability of robust characterization protocols that specifically target thin film thermo-mechanical stability. Being nanometer-sized in thickness, often atop a solid substrate, direct mechanical testing on such films becomes extremely challenging and often encounters serious complexity from the dominating effect of the substrate. In this review, we have compiled together a few important novel and promising techniques for mechano-rheological characterization of glassy polymer thin films. The conceptual background involved in each technique, constitutive equations, methodology, and current status of research are touched upon following a pedagogical tutorial approach. Further, we discussed each technique’s success and limitations, carefully covering the puzzling or contradicting observations reported within the broad nexus of glass transition temperature–viscosity–modulus–molecular mobility (including diffusion and relaxation).
This study focuses on the design concepts that contribute to the C–H activation in bithiophene-flanked monomers incorporating naphthalene diimide (NDI), perylene diimide (PDI), and fluorene (FLU) and their polymerization by direct heteroarylation. Density functional theory (DFT) calculations reveal distinct energy requirements for C–H bond abstraction, which is dictated by the electron-withdrawing strength of the central aromatic core flanked by bithiophene. These provide insights into the reactivity of each monomer for C–H bond activation. Proton NMR spectroscopic experimental results confirm the favorable energetic profiles predicted by DFT, with NDI- and PDI-flanked monomers exhibiting lower energy requirements than fluorene-flanked monomers. Successful polymer synthesis is demonstrated for NDI and PDI, while the fluorene-flanked monomer shows challenges due to its higher energy demands.