Search Results (73)

A new approach in amperometric enzyme electrodes production based on all-electrochemically assisted procedures will be described. Enzyme (glucose oxidase) immobilization was performed by in situ co-crosslinking of enzyme molecules through electrophoretic protein deposition, assuring enzyme immobilization exclusively onto the transducer surface (Pt electrode). Analogously, the poor selectivity of the transducer was dramatically improved by the electrosynthesis of non-conducting polymers with built-in permselectivity, permitting the formation of a thin permselective film onto the transducer surface, able to reject common interferents usually found in real samples. Since both approaches required a proper and distinct electrochemical perturbation (a pulsed current sequence for electrophoretic protein deposition and cyclic voltammetry for the electrosynthesis of non-conducting polymers), an appropriate coupling of the two all-electrochemical approaches was assured by a thorough study of the likely combinations of the electrosynthesis of permselective polymers with enzyme immobilization by electrophoretic protein deposition and by the use of several electrosynthesized polymers. For each investigated combination and for each polymer, the analytical performances and the rejection capabilities of the resulting biosensor were acquired so to gain information about their sensing abilities eventually in real sample analysis. This study shows that the proper coupling of the two all-electrochemical approaches and the appropriate choice of the electrosynthesized, permselective polymer permits the easy fabrication of novel glucose oxidase biosensors with good analytical performance and low bias in glucose measurement from typical interferent in serum. This novel approach, resembling classical electroplating procedures, is expected to allow all the advantages expected from such procedures like an easy preparation biosensor, a bi-dimensional control of enzyme immobilization and thickness, interferent- and fouling-free transduction of the electrodic sensor and, last but not the least, possibility of miniaturization of the biosensing device. Full article

Silicon oxycarbide coatings are the subject of research due to their exceptional optical, electronic, anti-corrosion, etc., properties, which make them attractive for a number of applications. In this article, we present a study on the synthesis and characterization of thin SiOC:H silicon oxycarbide films with the given composition and properties from a new organosilicon precursor octamethyl-1,4-dioxatetrasilacyclohexane (²D₂) and its macromolecular equivalent—poly(oxybisdimethylsily1ene) (POBDMS). Layers from ²D₂ precursor with different SiOC:H structure, from polymeric to ceramic-like, were produced in the remote microwave hydrogen plasma by CVD method (RHP-CVD) on a heated substrate in the temperature range of 30–400 °C. SiOC:H polymer layers from POEDMS were deposited from solution by spin coating and then crosslinked in RHP via the breaking of the Si-Si silyl bonds initiated by hydrogen radicals. The properties of SiOC:H layers obtained by both methods were compared. The density of the cross-linked materials was determined by the gravimetric method, elemental composition by means of XPS, chemical structure by FTIR spectroscopy, and NMR spectroscopy (¹³C, ²⁹Si). Photoluminescence analyses and ellipsometric measurements were also performed. Surface morphology was characterized by AFM. Based on the obtained results, a mechanism of initiation, growth, and cross-linking of the CVD layers under the influence of hydrogen radicals was proposed. Full article

Diblock copolymers (BCP) consisting of poly(methyl methacrylate) (PMMA) and poly(1H,1H,2H,2H-perfluorodecyl methacrylate) (PsfMA) blocks are employed as templates for controlled dispersion and localization of multi-walled carbon nanotubes (MWCNT). Short MWCNT are modified with perfluoroalkyl groups to increase the compatibility between MWCNT and the semifluorinated (PsfMA) phase and to promote a defined arrangement of MWCNT in the BCP morphology. Thin BCP and BCP/MWCNT composite films are prepared by dip-coating using tetrahydrofuran as solvent with dispersed MWCNT. Atomic force microscopy, scanning and transmission electron microscopy reveal a strong tendency of the BCP to form micelle-like domains consisting of a PMMA shell and a semifluorinated PsfMA core, embedded in a soft phase, containing also semifluorinated blocks. MWCNT preferentially localized in the embedding phase outside the micelles. Perfluoroalkyl-modification leads to significant improvement in the dispersion of MWCNT, both in the polymer solution and the resulting nanocomposite film due to increased interaction of MWCNT with the semifluorinated side chains in the soft phase outside the micelle domains. As a result, reliable electrical conductivity is observed in contrast to films with non-modified MWCNT. Thus, well-dispersed, modified MWCNT provide a defined electrical conduction path at the micrometer level, which is interesting for applications in electronics and vapor sensing. Full article

In this study, the photophysical properties of thin films of an Eu³⁺ dye, namely europium tetrakis(dibenzoylmethide) triethylammonium (EuD₄TEA), within deoxyribonucleic acid (DNA) biopolymer functionalized with hexadecyltrimethylammonium chloride (CTMA) were extensively investigated and compared with those of thin films of the same dye embedded in more conventional polymers, like poly(methyl methacrylate) and polycarbonate. The new materials obtained have good optical properties, as shown by their absorption and emission spectra. Remarkably, a large enhancement in photoluminescence was observed upon the interaction of EuD₄TEA with DNA-CTMA (2- and 17-fold increase in luminescence quantum yield with respect to PMMA and PC). Photophysical analyses suggest that the emission enhancement was mainly due to the increase in the sensitization efficiency (η_sens) from the ligands to the Eu³⁺ ion along with the suppression of the vibrational deactivation upon immobilization onto the DNA-CTMA matrix, as the concentration of the complex increased from 20 to 50%. These phenomena are primarily driven by the transformation of the Eu³⁺ micro-environments, which are created by the interactions between complex ligands and the DNA-CTMA matrix. Full article

Herein, we report a comprehensive investigation on the thermal transitions of thin films of poly [2,5-bis(2-octyldodecyl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione -3,6-diyl)-alt-(2,2′;5′,2″;5″,2′″-quaterthiophen-5,5′″-diyl)]PDPP4T, poly[2,6-(4,4-bis-(2-ethy-lhexyl)-4H-cyclopenta [2,1-b;3,4-b′]dithiophene)-alt-4,7(2,1,3-benzothiadiazole)] PCPDTBT, 1:1 blend of PDPP4T and PCPDTBT, and their composites with gold nanoparticles (AuNPs). The thermal transitions of these materials were studied using variable temperature spectroscopic ellipsometry (VTSE), with differential scanning calorimetry (DSC) serving as the reference method. Based on obtained VTSE results, for the first time, we have determined the phase diagrams of PDPP4T/PCPDTBT and their AuNPs composites. The VTSE measurements revealed distinct thermal transitions in the thin films, including characteristic temperatures corresponding to the pure phases of PDPP4T and PCPDTBT within their blends. These transitions were markedly different in the AuNPs composites compared to the neat materials, highlighting the unique interactions between the polymer matrix and AuNPs. Additionally, we explored the optical properties, surface morphology, and crystallinity of the materials. We hypothesize that the observed variations in thermal transitions, as well as the improvement in optical properties and crystallinity, are likely influenced by localized surface plasmon resonance (LSPR) and passivation phenomena induced by the AuNPs in the composite films. These findings could have important implications for the design and optimization of materials for optoelectronic applications. Full article

Flexible polymer-based piezoelectric nanogenerators (PENGs) have gained significant interest due to their ability to deliver clean and sustainable energy for self-powered electronics and wearable devices. Recently, the incorporation of fillers into the ferroelectric polymer matrix has been used to improve the relatively low piezoelectric properties of polymer-based PENGs. In this study, we investigated the effect of various nanofillers such as titania (TiO₂), zinc oxide (ZnO), reduced graphene oxide (rGO), and lead zirconate titanate (PZT) on the PENG performance of the nanocomposite thin films containing the nanofillers in poly(vinylidene fluoride-co-trifluoro ethylene) (P(VDF-TrFE)) matrix. The nanocomposite films were prepared by depositing molecularly thin films of P(VDF-TrFE) and nanofiller nanoparticles (NPs) spread at the air/water interface onto the indium tin oxide-coated polyethylene terephthalate (ITO-PET) substrate, and they were characterized by measuring their microstructures, crystallinity, β-phase contents, and piezoelectric coefficients (d₃₃) using SEM, FT-IR, XRD, and quasi-static meter, respectively. Multiple PENGs incorporating various nanofillers within the polymer matrix were developed by assembling thin film-coated substrates into a sandwich-like structure. Their piezoelectric properties, such as open-circuit output voltage (V_OC) and short-circuit current (I_SC), were analyzed. As a result, the PENG containing 4 wt% PZT, which was named P-PZT-4, showed the best performance of V_OC of 68.5 V with the d₃₃ value of 78.2 pC/N and β-phase content of 97%. The order of the maximum V_OC values for the PENGs of nanocomposite thin films containing various nanofillers was PZT (68.5 V) > rGO (64.0 V) > ZnO (50.9 V) > TiO₂ (48.1 V). When the best optimum PENG was integrated into a simple circuit comprising rectifiers and a capacitor, it demonstrated an excellent two-dimensional power density of 20.6 μW/cm² and an energy storage capacity of 531.4 μJ within 3 min. This piezoelectric performance of PENG with the optimized nanofiller type and content was found to be superior when it was compared with those in the literature. This PENG comprising nanocomposite thin film with optimized nanofiller type and content shows a potential application for a power source for low-powered electronics such as wearable devices. Full article

Access to clean and reliable water has become a critical concern due to the global water crisis. High sulfate levels in drinking water raise health concerns for humans and animals and can cause serious corrosion in industrial systems. Sulfated waters represent a major challenge on the Canadian prairies, leading to many cattle deaths. While reverse osmosis (RO) membranes effectively remove sulfates, they are costly due to high-pressure requirements. Nanofiltration (NF) membranes present a more affordable alternative, outperforming traditional methods like adsorption, desalination, and ion exchange. Developing low-pressure ultrafiltration (UF) and microfiltration (MF) membranes could also reduce costs. This review explores advancements in polymeric materials and membrane technology to enhance sulfate removal, focusing on methods used to reduce fouling and improve permeate flux. Techniques discussed include phase inversion (PI), thin-film composite (TFC), and thin-film nanocomposite (TFN) membranes. The review also highlights recent fabrication methods for pristine and nanomaterial-enhanced membranes, acknowledging both benefits and limitations. Continued innovations in polymer-based membranes are expected to drive further performance and cost-efficiency improvements. This review found that studies in the literature dealt mainly with sulfate concentrations below 2000 mg/L, indicating a need to address higher concentrations in future studies. Full article

Bone defects restoration has always been an arduous challenge in the orthopedic field due to the limitations of conventional grafts. Bone tissue engineering offers an alternative approach by using biomimetic materials, stem cells, and growth factors that are able to improve the regeneration of bone tissue. Different biomaterials have attracted great interest in BTE applications, including the poly(3-hexylthiofene) (P3HT) conductive polymer, whose primary advantage is its capability to provide a native extracellular matrix-like environment. Based on this evidence, in this study, we evaluated the biological response of human adipose-derived mesenchymal stem cells cultured on P3HT thin polymer film for 14 days. Our results suggest that P3HT represents a good substrate to induce osteogenic differentiation of osteoprogenitor cells, even in the absence of specific inductive growth factors, thus representing a promising strategy for bone regenerative medicine. Therefore, the system provided may offer an innovative platform for next-generation biocompatible materials for regenerative medicine. Full article

This study delves into the distinctive selective property exhibited by a non-conjugated cholesterol-based polymer, poly(CEM₁₁-b-EHA₇), in sorting semiconducting single-walled carbon nanotubes (s-SWCNTs) within isooctane. Comprised of 11 repeating units of cholesteryloxycarbonyl-2-hydroxy methacrylate (CEM) and 7 repeating units of 2-ethylhexyl acrylate (EHA), this non-conjugated polymer demonstrates robust supramolecular interactions across the sp² surface structure of carbon nanotubes and graphene. When coupled with the Double Liquid-Phase Extraction (DLPE) technology, the polymer effectively segregates s-SWCNTs into the isooctane phase (nonpolar) while excluding metallic SWCNTs (m-SWCNTs) in the water phase (polar). DLPE proves particularly efficient in partitioning larger-diameter s-SWCNTs (0.85–1.0 nm) compared to those dispersed directly in isooctane by poly(CEM₁₁-b-EHA₇) using direct liquid-phase exfoliation (LPE) techniques for diameters ranging from 0.75 to 0.95 nm. The DLPE method, bolstered by poly(CEM₁₁-b-EHA₇), successfully eliminates impurities from s-SWCNT extraction, including residual metallic catalysts and carbonaceous substances, which constitute up to 20% of raw HiPCO SWCNTs. DLPE emerges as a scalable and straightforward approach for selectively extracting s-SWCNTs in nonpolar, low-boiling-point solvents like alkanes. These dispersions hold promise for fabricating fast-drying s-SWCNT inks, which are ideal for printed and flexible thin-film transistors. Full article

Polyvinylidene fluoride (PVDF)-based materials are the most researched polymers in the field of energy harvesting. Their production in thin-film form through printing technologies can potentially offer several manufacturing and performance advantages, such as low-cost, low-temperature processing, use of flexible substrates, custom design, low thermal inertia and surface-scaling performance. However, solution-based processes, like printing, miss fine control of the microstructure during film-forming, making it difficult to achieve a high level of polarization, necessary for PVDF to exhibit electroactive characteristics. Here, corona treatment is investigated for the poling of gravure-printed polyvinylidene fluoride–trifluoroethylene (PVDF-TrFE) films, as a particularly suitable poling method for printing since it is rapid, contactless and scalable, and no metal electrodes are required. Effects of corona conditioning on the functional properties of the printed films were examined and discussed. Electroactive properties of corona-poled printed films improved manyfold when they were treated at 9 kV, near room temperature (30 °C) and using very short treatment time (30 s). In particular, piezoelectric and pyroelectric coefficients improved tenfold and by two orders of magnitude, respectively. Considering the upscaling potential of roll-to-roll gravure printing and corona poling, combined with the area-scaling performance of thin-film-based generators, our results can enable the corona-printing process for mass production of future electroactive flexible PVDF-based devices. Full article

Metal–elastomer assemblies, such as aluminum–NBR and stainless steel–FKM, widely used for sealing or damping functions in various fields, are currently prepared with highly toxic bonding agents. To substitute the use of these liquids, plasma technologies were applied. The chemical nature of the plasma polymerized adhesives is found to have no influence on the viscoelastic properties of the elastomer. Furthermore, cohesive assemblies were prepared with acetylene, acrylic acid or maleic anhydride as plasma polymerized layers. Their adhesive performances were evaluated thanks to a tack-like test. Their adhesion mechanisms, even if complex, are namely identified as the interdiffusion of elastomer chains within the plasma-based polymer film and the thermodynamic adhesion. Specifically, we propose that the adhesiveness of metal–rubber assemblies, correlated to the maximum stress at failure in the tack-like test, is proportional to an energy per unit volume. This new variable is determined as the ratio of the surface tension to the thinness of the plasma adhesive. Full article

Thin films of poly(arylene ethynylene)-conjugated polymers, including low-energy-gap donor–acceptor polymers, can be prepared via stepwise polymerization utilizing surface-confined Sonogashira cross-coupling. This robust and efficient polymerization protocol yields conjugated polymers with a precise molecular structure and with nanometer-level control of the organization and the uniform alignment of the macromolecular chains in the densely packed film. In addition to high stability and predictable and well-defined molecular organization and morphology, the surface-confined conjugated polymer chains experience significant interchain electronic interactions, resulting in dominating intermolecular π-electron delocalization which is primarily responsible for the electronic and spectroscopic properties of polymer films. The fluorescent films demonstrate remarkable performance in chemosensing applications, showing a turn-off fluorescent response on the sub-ppt (part per trillion) level of nitroaromatic explosives in water. This unique sensitivity is likely related to the enhanced exciton mobility in the uniformly aligned and structurally monodisperse polymer films. Full article

Because of safety concerns associated with the use of liquid electrolytes and electrolyte solutions, options for non-liquid materials like gels and polymers to be used as ion-conducting electrolytes have been explored intensely, and they attract steadily growing interest from researchers. The low ionic conductivity of most hard and soft solid materials was initially too low for practical applications in supercapacitors, which require low internal resistance of a device and, consequently, highly conducting materials. Even if an additional separator may not be needed when the solid electrolyte already ensures reliable separation of the electrodes, the electrolytes prepared as films or membranes as thin as practically acceptable, resistance may still be too high even today. Recent developments with gel electrolytes sometimes approach or even surpass liquid electrolyte solutions, in terms of effective conductance. This includes materials based on biopolymers, renewable raw materials, materials with biodegradability, and better environmental compatibility. In addition, numerous approaches to improving the electrolyte/electrode interaction have yielded improvements in effective internal device resistance. Reported studies are reviewed, material combinations are sorted out, and trends are identified. Full article

The optical characterization of non-absorbing, homogeneous, isotropic polymer-like thin films with correlated, differently rough boundaries is essential in optimizing their performance in various applications. A central aim of this study is to derive the general formulae necessary for the characterization of such films. The applicability of this theory is illustrated through the characterization of a polymer-like thin film deposited by plasma-enhanced chemical vapor deposition onto a silicon substrate with a randomly rough surface, focusing on the analysis of its rough boundaries over a wide range of spatial frequencies. The method is based on processing experimental data obtained using variable-angle spectroscopic ellipsometry and spectroscopic reflectometry. The transition layer is considered at the lower boundary of the polymer-like thin film. The spectral dependencies of the optical constants of the polymer-like thin film and the transition layer are determined using the Campi–Coriasso dispersion model. The reflectance data are processed using a combination of Rayleigh–Rice theory and scalar diffraction theory in the near-infrared and visible spectral ranges, while scalar diffraction theory is used for the processing of reflectance data within the ultraviolet range. Rayleigh–Rice theory alone is sufficient for the processing of the ellipsometric data across the entire spectral range. We accurately determine the thicknesses of the polymer-like thin film and the transition layer, as well as the roughness parameters of both boundaries, with the root mean square (rms) values cross-validated using atomic force microscopy. Notably, the rms values derived from optical measurements and atomic force microscopy show excellent agreement. These findings confirm the reliability of the optical method for the detailed characterization of thin films with differently rough boundaries, supporting the applicability of the proposed method in high-precision film analysis. Full article

Loratadine (LOR) is a second-generation antihistamine that exhibits a low and variable oral bioavailability (10–40%) and delayed onset owing to poor solubility and an extensive first-pass effect. Therefore, in light of the clinical need, the main goal of the present study was to develop sublingual fast-dissolving thin films of LOR–citric acid co-amorphous systems (LOR-CAs) with the aim of eliciting a faster onset and improving the bioavailability. We formulated sublingual fast-dissolving thin films of LOR by a film-casting technique using hydrophilic polymers like hydroxypropyl methylcellulose (HPMC E15), polyvinyl pyrrolidone K30 (PVP K30), and hydroxypropyl cellulose EL (HPC-EF) and citric acid as a pH modulator, while glycerin served as a plasticizer. The sublingual fast-dissolving thin films were characterized by FTIR, SEM, DSC, and XRD and evaluated for in vitro dissolution and ex vivo mucoadhesion. The best formulation (F1) developed using HPMC E15 as a polymer, glycerin as a plasticizer, and citric acid as a pH modulator was found to be the optimized formulation as it was smooth, clear, flexible, and displayed good mucoadhesion (11.27 ± 0.418 gm/cm²) and uniform thickness (0.25 ± 0.02 mm). The formulation F1 was found to display a significantly shorter DT (30.30 ± 0.6 s) and rapid release of LOR (92.10 ± 2.3% in 60 min) compared to other formulations (ANOVA, p < 0.001). The results indicated that the prepared sublingual films are likely to elicit a faster therapeutic effect, avoid first-pass metabolism, and improve the bioavailability. Full article