Triazoliums are a family of five-membered heterocyclic cations that contain three nitrogen and two carbon atoms. In contrast to the widely studied imidazolium cations, triazoliums are less explored. In terms of the chemical structure, triazolium replaces a carbon atom in the imidazolium cation ring with an electron-withdrawing nitrogen atom, which makes the triazolium more polarized. Among the many physical properties, the thermal responsiveness of triazoliums is of particular interest to us but has been rarely investigated. In this contribution, we prepared a series of 1,2,4-triazolium-based poly(ionic liquid)s (PILs) with varying alkyl substituents and counteranions and studied their thermal-responsive behavior. We found that 1,2,4-triazolim-based PILs with a polymeric backbone structure similar to that of polyimidazoliums exhibited opposite thermal phase transition processes in solvents. For example, methyl-substituted 1,2,4-triazolium-based PILs exhibited an upper-critical-solution-temperature (UCST)-type phase transition in methanol when the counterion was I and a lower-critical-solution-temperature (LCST)-type phase transition in acetone when the counterion was PF . The thermal responsiveness was reversible and concentration-dependent. Interestingly, the thermal response of 1,2,4-triazolim-based PILs could be retained in the organogel form, which was applied in the pretreatment of anion-containing organic waste liquids and temperature-controlled "smart" switches.

Cross-linked polyolefins (XLPOs) constitute a significant portion of the plastics commercial market, with a market size of a similar order of magnitude to those of polystyrene and polyethylene terephthalate. However, few aspects of XLPO materials circularity have been examined relative to thermoplastic polyolefins. The cross-linking of polyolefins imparts superior performance properties, such as impact strength, chemical and electrical resistance, and thermal stability vs thermoplastic analogues, but it also makes the reprocessing of XLPOs to valuable products more challenging, as XLPOs cannot be molten. Thus, most XLPOs are incinerated or landfilled at the end of the first lifecycle, even though XLPO products are commonly collected as a relatively clean waste stream-providing a unique opportunity for valorization. In this review, we discuss approaches to improve XLPO circularity throughout the entire materials lifecycle by examining biobased feedstocks as alternative olefinic monomer sources and by assessing both traditional mechanical and advanced XLPO recycling methods based on industrial feasibility and potential product value. We also consider how advancing materials longevity can reduce environmental impacts and lifecycle costs and how recyclable-by-design strategies can enable better end-of-life opportunities for future generations of XLPO materials. Throughout this review, we highlight XLPO circularity routes that have the potential to balance the performance, circularity, and scalability necessary to impart economic and environmental viability at an industrial scale.

Despite the prevalence of non-Newtonian fluids in various practical applications, comprehensive dynamic wetting models are lacking. Existing models often oversimplify complex rheological behavior, limiting our ability to predict wetting dynamics. This work introduces and experimentally validates a generalized model for the dynamic wetting of non-Newtonian shear-thinning fluids (dilute polymer solutions) on solid substrates. We experimentally analyzed 12 different shear-thinning fluids using both a power-law model and Carreau-Yasuda model. The data clearly show that the dynamic contact angle can be generalized using an average viscosity to capture rheological changes during droplet spreading. The average viscosity was defined using the fluid's constitutive model over shear rates relevant to the spreading process. Using a small droplet approximation, we propose and validate a semianalytical spreading model to predict the basal radius of non-Newtonian droplets. The model agrees well with the experimental data. Additionally, the average viscosity was used to define a spreading time scale, which is capable of collapsing the spreading of different non-Newtonian fluids onto a master spreading curve. This work offers significant potential for predicting the dynamic shape and spreading of non-Newtonian fluids with complex rheologies in a range of applications and industrial processes.

Rheological modifiers are an important component in the development of skin cream (SC) chassis for personal skin care products (PSCPs). The viscous behavior of a PSCP is critical to its effectiveness where its uniformity and material strength impact its processing, storage, and delivery of active ingredients. Due to the mildly acidic environment of the skin, PSCPs require a SC that will assist in maintaining their material strength at low pHs. We have investigated a coiled-coil protein hydrogel system for the ability to possess pH-responsiveness, where physical cross-linking and material strength is controlled by pH relative to the isoelectric point (pI) of the protein. We recently designed a coiled-coil protein hydrogel variant, Q5, which possesses a relatively low pI that we hypothesized to have improved supramolecular assembly into a hydrogel at acidic conditions. We demonstrate that Q5 can retain a partial solution-to-gel transition at pH 6.0 and acts as a soft hydrogel by rheology. We further tested Q5 to act as a rheological modifier in a standard SC at pH 6.0 and pH 8.0 to test conditions mediated by pH changes in the skin environment. Q5 reveals the ability to uniquely increase material strength at low pH in comparison to a standard rheological modifier like hydroxyethyl cellulose (HEC), suggesting modular protein-based coiled-coil rheological modifiers can be used in PSCPs.

Polyaniline (PANI) is an attractive electrochromic and storage material due to its reversible and sustainable electrochemical redox processes. However, the insufficient surface area and excessive charge intercalation after long-term cycling results in limited charge capacitance and unsatisfactory cycling stability. In this work, we demonstrate an innovative method to increase PANI's electrochromic and energy storage performance by incorporating MXene, to enhance electrochemical activity and reveal more active areas of ion/electron intercalation/deintercalation and charge transfer. The hydrogen bonds formed between N-H, C-H, and C-N of PANI and -OH and -O surface functional terminations of MXene further enhance the interface interaction. With substantial optical transmittance modulation and charge capacitance, excellent coloration efficiency, and outstanding durability, the PANI/MXene thin film demonstrates exceptional color-switching and energy storage characteristics. Furthermore, the sandwich device with a PANI/MXene thin film as the positive electrode and zinc foil as the negative electrode demonstrates exceptional electrochromic and Zn storage capability. This work raises possibilities for next-generation intelligent energy conversion and storage technologies and offers fresh perspectives on the design of ionic devices.

Petroleum-based plastic waste plagues the natural environment, but plastics solve many high-performance solutions across industries. For example, porous polymer membranes are used for air filtration, advanced textiles, energy, and biomedical applications. Sustainable and biodegradable Bioplastic membranes can compete with nonrenewable materials in strength, durability, and functionality but biodegrade under select conditions after disposal. Membranes electrospun using a blend of bioderived thermoplastic polyurethane (TPU) and polylactic acid (PLA) perform effectively under tensile and cyclic loading, act adequately as an air filter media, and biodegrade in a home-compost environment, with the aliphatic formulation of TPU showing greater biodegradability compared to the formulation containing aromatic moieties. Blending TPU with PLA dramatically increases the strain at break of the PLA membrane, while the addition of PLA in TPU stiffens the material considerably. Measurements of the pressure drop and filtration efficiency deem this electrospun membrane an effective air filter. This membrane provides a solution to the need for quality air filtration while decreasing the dependence on petroleum feedstocks and addressing the issue of plastic disposal through biodegradation.

Herein, we describe a solvent-free bioinspired approach for the polymerization of ethylene brassylate. Artificial plant cell walls (APCWs) with an integrated enzyme were fabricated by self-assembly, using microcrystalline cellulose as the main structural component. The resulting APCW catalysts were tested in bulk reactions and reactive extrusion, leading to high monomer conversion and a molar mass of around 4 kDa. In addition, we discovered that APCW catalyzes the formation of large ethylene brassylate macrocycles. The enzymatic stability and efficiency of the APCW were investigated by recycling the catalyst both in bulk and reactive extrusion. The obtained poly(ethylene brassylate) was applied as a biobased and biodegradable hydrophobic paper coating.

Digital light processing (DLP) 3D printing has shown great advantages such as high resolution in the fabrication of 3D objects toward a range of applications. Despite the rapid development of photocurable materials for DLP printing, tailoring properties to meet the specific demands for various applications remains challenging. Herein, we introduce copolymers of caprolactone and allyl caprolactone offering built-in functionality for thiol-ene photochemistry, thereby omitting the need for postfunctionalization. A crystalline block copolymer and an amorphous statistical copolymer were synthesized with the same comonomer composition and molecular weight. Thio-ene photocuring with a tetrafunctional thiol cross-linker was studied at different thiol to double-bond ratios for the copolymers and their blends. All formulations undergo rapid photocuring within several seconds of irradiation with slightly higher gel fractions observed for the statistical copolymer over the block copolymer under the same conditions, suggesting a somewhat higher cross-link density. Thermal properties of the networks were dependent on the presence of the semicrystalline block copolymer, where higher melting enthalpies were reached at higher block copolymer content. Similarly, crystallinity was found to be the main contributor to the mechanical properties. For a comparable composition, the modulus of a block copolymer network was found to be 31 times higher than that of the statistical copolymer network (27.7 vs 0.89 MPa). Intermediate moduli could be obtained by blending the two copolymers. DLP-printed scaffolds from these copolymers retained their thermal properties, therefore offering an efficient approach to tailoring mechanical properties, through crystallinity. Moreover, the printed scaffold displayed shape memory properties as the first example of poly(carprolactone) (PCL) copolymers in DLP printing. These materials are readily synthesized, offer fast and high-resolution 3D printing, and are degradable and cell compatible. They offer a straightforward approach to tailoring properties of PCL-based biomaterials and devices.

In this work, a flexible polyurethane (PU) foam/polymer/clay (PUF/PAASep) composite is prepared via a simple dip-coating method. The composite exhibits excellent damping properties under quasi-static compression, vibration transmissibility, and impact resistance. For the composite preparation, sepiolite (Sep) dispersion in a polyacrylic acid (PAA) solution is first homogenized and evaluated using microscopy, and the obtained PAASep suspension is used to coat the PU foam uniformly for optimization of the quasi-static mechanical performance of the foam composites. The PU foam struts coated with 1 wt % PAA and 3 wt % sepiolite are strengthened, resulting in an 8-fold improvement of the stiffness and three-times increase of the impact force resistance compared to the uncoated PU foams. More importantly, the PU foam composites show a remarkable vibration damping capability, with the loss modulus 57 times that of the uncoated PU foams, enabled by micro friction and stick-slip effects mediated by the PAASep coatings. The facile prepared PAASep-coated PU foams have significant potential for cushioning, packaging, and broad engineering applications involving energy absorption.

[This corrects the article DOI: 10.1021/acsapm.4c00485.].

In this study, evaporation-induced size segregation and interparticle interactions are harnessed to tune the microstructure of photocatalytic colloidal coatings containing TiO nanoparticles and polymer particles. This enabled the fabrication of a library of five distinct microstructures: TiO-on-top stratification, a thin top layer of polymer or TiO, homogeneous films of raspberry particles, and a sandwich structure. The photocatalytic and antibacterial activities of the coatings were evaluated by testing the viability of Methicillin-resistant (MRSA) bacteria using the ISO-27447 protocol, showing a strong correlation with the microstructure. UVA irradiation for 4 h induces a reduction in MRSA viability in all coating systems, ranging from 0.6 to 1.1 log. Films with TiO-enriched top surfaces exhibit better resistance to prolonged exposure to disinfection and bacterial testing. The remaining systems, nonetheless, present higher antibacterial activity because of a larger number of pores and coating defects that enhance light and water accessibility for the generation and transport of reactive oxygen species. This work establishes design rules for photocatalytic coatings based on the interplay between performance and film architecture, offering valuable insights for several applications, including antibacterial surfaces, self-cleaning/antifogging applications, and water purification.

Water-borne coatings often contain nanofillers to enhance their mechanical or optical properties. The aggregation of these fillers may, however, lead to undesired effects such as brittle and opaque coatings, reducing their performance and lifetime. By controlling the distribution and structural arrangement of the nanofillers in the coatings and inserting reversible chemical bonds, both the elasticity and strength of the coatings may be effectively improved, while healing properties, via the reversible chemistry, extend the coating's lifetime. Aqueous dispersions of polymer-core/silica-corona supracolloidal particles were used to prepare water-borne coatings. Polymer and silica nanoparticles were prefunctionalized with thiol/disulfide groups during the supracolloid assembly. Disulfide bridges were further established between a cross-linker and the supracolloids during drying and coating formation. The supracolloidal nanocomposite coatings were submitted to intentional (physical) damages, i.e., blunt and sharp surface scratches or cut through into two pieces, and subsequently UV irradiated to induce the recovery of the damage(s). The viscoelasticity and healing properties of the coatings were examined by dynamic, static, and surface mechanical analyses. The nanocomposite coatings showed a great extent of interfacial restoration of cut damage and surface scratches. The healing properties are strongly related to the coating's viscoelasticity and interfacial (re)activation of the disulfide bridges. Nanocomposite coatings with silica concentrations below their critical volume fraction show higher in situ healing efficiency, as compared to coatings with higher silica concentration. This work provides insights into the control of nanofillers distribution in water-borne coatings and strategies to increase the coating lifetime via mechanical damage recovery.

As textiles contribute considerably to overall anthropogenic pollution and resource consumption, increasing their circularity is essential. We report the melt-spinning of long-chain polyesters, materials recently shown to be fully chemically recyclable under mild conditions, as well as biodegradable. High-quality uniform fibers are enabled by the polymers' favorable combination of thermal stability, crystallization ability, melt strength, and homogeneity. The polyethylene-like crystalline structure endows these fibers with mechanical strength, which is further enhanced by its orientation upon drawing (tensile strength of up to 270 MPa). In vitro depolymerization by high concentrations of cutinase underlines the accessibility of the fibers for enzymatic degradation, which can proceed from the surface and through the entire fiber within days, depending on the choice of the fiber material. Fibers and knitted fabrics withstand stress, as encountered in machine washing.

The efficient transport of small molecules through dense hydrogel networks is crucial for various applications, including drug delivery, biosensing, catalysis, nanofiltration, water purification, and desalination. In dense polymer matrices, such as collapsed microgels, molecular transport follows the solution-diffusion principle: Molecules dissolve in the polymeric matrix and subsequently diffuse due to a concentration gradient. Employing dynamical density functional theory (DDFT), we investigate the nonequilibrium release kinetics of nonionic subnanometer-sized molecules from a microgel particle, using parameters derived from prior molecular simulations of a thermoresponsive hydrogel. The kinetics is primarily governed by the microgel radius and two intensive parameters: the diffusion coefficient and solvation free energy of the molecule. Our results reveal two limiting regimes: a diffusion-limited regime for large, slowly diffusing, and poorly soluble molecules within the hydrogel; and a reaction-limited regime for small, rapidly diffusing, and highly soluble molecules. These principles allow us to derive an analytical equation for release time, demonstrating excellent quantitative agreement with the DDFT results-a valuable and straightforward tool for predicting release kinetics from microgels.

Nonfluorinated polymers have been widely proposed to replace Nafion as raw materials for redox flow battery ion-exchange membranes. Hereby, block copolymers based on polysulfone (PSU) and polyphenylsulfone (PPSU) are synthesized and employed as precursors of membranes for vanadium redox flow batteries. A series of copolymers with varying molar proportions of PSU (75/25, 60/40, 50/50 mol %) were prepared. The 60/40 and 75/25 copolymers exhibit concentrated sulfonic groups predominantly in the PSU unit, favoring the formation of hydrophobic and hydrophilic domains. The 50/50 copolymer presents a balanced degree of sulfonation between the two units, leading to a homogeneous distribution of sulfonic groups. An study of these materials comprising vanadium ion permeability and chemical and mechanical stability was performed. The best performance is achieved with 50/50 membranes, which exhibited performance comparable to commercial Nafion membranes. These results signify a promising breakthrough in the pursuit of high-performance, sustainable membranes for next-generation VRFBs.

The use of transdermal delivery for nucleic acid administration is an interesting approach to overcoming limitations of systemic administration routes, such as first-pass effects, the painful needle injection, or their poor biodistribution. Thus, the use of a microneedle-based patch could represent a turning point for nucleic acid delivery, thanks to the possibility of self-administration of the actives in a painless and easy procedure. However, the design of transdermal systems with a higher degree of precision release is a clear need that has not been fully resolved. Committed to tackling this challenge, we present here a microneedle patch that involves a smart delivery system supported by the well-established ability of boronic acid to interact with carbohydrates in a pH-dependent manner. This system builds up a multilayer structure over a solid microneedle platform whose surface has been modified to immobilize glucosamine units that are able to interact with an oligopeptide-end terminated poly(β-aminoester) that presents a 4-carboxy-3-fluorophenylboronic acid (Bor-pBAE). Thus, sequential layers of the Bor-pBAE and plasmid DNA have been assembled, thanks to the ability of the polymer to interact with the nucleic acid at a basic pH and then gradually release the plasmid under two different conditions of pH (the physiological pH = 7.4 and the acidic pH = 5.1). We set up the design and implementation of this first proof of concept while demonstrating microneedles' safety and functionality. Additionally, we have shown the efficacy of the construct to express the encoded genes in model cell lines. In conclusion, we have established the basis to confirm that this generation of borylated poly(β-aminoesters) holds great promise as a transdermal local nucleic acid delivery system.

Mixed matrix membranes (MMMs) were formed by using seven polymeric matrices with a wide range of permeabilities. All of the polymeric matrices have been polyimides, namely: P84, Pi-DAPOH, Pi-DAROH, Matrimid, Pi-HABAc, PI-DAM, and PIM-1 in the order of increasing O permeability. A fixed (10%) concentration of a microporous organic polymer (TFAP-Trp), formed by the combination of trifluoroacetophenone and triptycene, was added as a porous filler. The material properties as well as their separation performances for multiple pure gases, specifically the permeabilities of He, N, O, CH, and CO, were measured. The correlation between the relative increase in permeability in MMMs and that of the matrix polymeric membrane has been quantitatively analyzed. This study proves that the increased permeability of MMMs is largely linked to the contribution of the high permeability of the filler. The addition of the TFAP-Trp porous filler proves to be especially beneficial for matrices with low to moderate permeabilities, significantly enhancing the matrix permeability overall. The fitted relationship is approximately linear in accordance with the existing models to predict permeability in dual-phase systems for low proportions of the dispersed phase. An extrapolation allows the evaluation of the permeability of the pure microporous organic polymer, which agrees with the previous values described by the group for different filler contents and in other polymeric matrices. In all cases, the selectivity remains approximately constant while the permeability increases. The addition of TFAP-Trp to all the polymeric matrices led to a moderate improvement of the MMM separation performances, mainly centered on their permeabilities.

Dye-sensitized solar cells (DSSCs) have recently entered the market for indoor photovoltaics. Fast electron injection from dye to titania, the lifetime of the excited dye, and the suppression of back electron recombination at the photoanode/electrolyte interface are crucial for a high photocurrent conversion efficiency (PCE). This study presents block copolymers of poly(4-vinylpyridine) and poly(styrene)-P4VP--PSt as efficient accelerators of electron injection from dye to titania with extended lifetime excited states and long-lasting back electron recombination suppression. P4VP--PSt and P4VP--PSt rendered devices with PCEs of 10.0 and 9.8%, respectively, under AM 1.5G light; PCEs of 19.4 and 16.4% under 1000 lx LED light were attained. Copolymers provided a stable PCE with the two most popular I /3I electrolytes based on ACN and 3-methoxypropionitrile solvents; PCE history was tracked in the dark and under 1000 h of continuous light soaking with passive load according to ISOS-D1 and ISOS-L2 aging protocols, respectively. The impact of the polymer molecular structure on electron recombination, charge injection, dye anchoring, light absorption, photocurrent generation, and PCE and the long-term history of photovoltaic metrics are discussed.

Adsorption stands out as a leading wastewater treatment method for ion removal or recovery. Polymeric fibers, notably electrospun ones, are gaining prominence due to their high capacity and easy recovery. Electrospinning offers a cost-effective means to produce fibers with a large surface area and high adsorption capacity. These fibers can be further functionalized with chemical substances acting as specific ligands for metal ions, bolstering their adsorption capabilities. In this study, dithioester-functionalized electrospun fibers were synthesized as an alternative to conventional sorbents for palladium recovery from acidic chloride solutions, similar to those used in hydrometallurgical processes for platinum group metal recovery (Pd, Pt, Rh···) from spent catalysts. Fibers with identical chemical composition but varying morphology were examined to assess their impact on palladium adsorption efficiency (i.e., beads-free and beads-on-string morphologies). Experimental investigations involved model solutions with varying palladium concentration, temperature, acidity (adjusted with HCl content), and salinity (adjusted with NaCl), utilizing both pure and dithioester-functionalized fibers. Experimental results demonstrate enhanced adsorption efficiency at lower temperatures and in 0.1 M HCl, with a negligible influence from solution salinity. Moreover, both pure polymeric and dithioester-functionalized electrospun fibers exhibit highly efficient palladium recovery. Furthermore, under optimal conditions, starting from an 80 mg/L palladium solution, a 95% recovery of palladium can be achieved with a sorbent dosage below 4 g/L of functionalized electrospun fibers. The adsorption data are well described by the Langmuir isotherm model for the pure polymeric fibers. At the same time, the contribution of dithioesters has been separately accounted for to describe the behavior of functionalized electrospun fibers. Thermal recovery of palladium from the spent sorbents has also been investigated.

Efficient near-infrared (NIR) laser marking on transparent polymers like polypropylene, epoxy, and polyethylene has posed a big challenge due to their lack of absorption in the NIR. Currently, inorganic additives are used to improve NIR laser marking efficiency, but they come with issues such as toxicity, high loading requirement, adverse effects on color/opaqueness, and the need for low laser head speeds. Herein, we report a new strategy of incorporating a food-grade, MgAl-CO LDH as a boosting coadditive alongside the commercial NIR laser marking additive (Iriotech 8815) in an epoxy system. Our findings demonstrate that the incorporation of MgAl-CO LDH can significantly increase both the darkness and contrast of marking even at high laser head speed (5000 mm/s), while minimizing surface damage. Notably, by replacing 95% of Iriotech 8815 with MgAl-CO LDH, an epoxy plate can exhibit high transparency, while producing dark, sharply defined markings with excellent readable QR code markings at high laser speeds. This result offers a promising solution for enhancing high-speed NIR laser marking on transparent polymers with additional advantages of lower toxicity and cost and with minimal optical interference from high additive loadings.

Glutamate (Glu) and histamine (His) are two major neurotransmitters that play many critical roles in brain physiological functions and neurological disorders. Therefore, specific and sensitive monitoring of Glu and His is essential in the diagnosis and treatment of various mental health and neurodegenerative disorders. Both being non-electroactive species, direct electrochemical detection of Glu and His has been challenging. Herein, we report a stimuli-responsive polymer-based biosensor for the electrochemical detection of Glu and His. The polymer-based target receptors consist of a linear chain stimuli-responsive templated polymer hybrid that is labeled with an osmium-based redox-active reporter molecules to elicit conformation-dependent electrochemical responses. The polymers are then attached to a gold electrode to implement an electrochemical sensor. The cyclic voltammetry (CV) and square-wave voltammetry (SWV) results confirmed the polymers' conformational changes due to the specific target (i.e., Glu and His) recognition and the corresponding electrochemical detection capabilities. The voltammetry results indicate that this biosensor can be used as a 'signal-on' and 'signal-off' sensors for the detection of Glu and His concentrations, respectively. The developed biosensor also showed excellent regeneration capability by fully recovering the initial current signal after rinsing with deionized water. To further validate the polymer's utility as a target bioreceptor, the surface plasmon resonance (SPR) technique was used to characterize the binding affinity between the designed polymers and the target chemical. The SPR results exhibited the equilibrium dissociation constants (K) of 2.40 μM and 1.54 μM for the polymer-Glu and polymer-His interactions, respectively. The results obtained this work strongly suggest that the proposed sensing technology could potentially be used as a platform for monitoring non-electroactive neurochemicals from animal models.