Luminescent solar concentrators (LSCs) are attractive for building-integrated photovoltaics but require host matrices combining high transparency, stability, and sustainability. Here, half bio-based, isocyanate-free polyhydroxyurethanes (PHUs) are introduced as covalently functional host materials for transparent LSCs. Two aromatic fluorescent aldehydes based on fluorene and 8-hydroxycoumarin were synthesized and grafted onto a tailor-made PHU backbone via a facile post-synthetic modification strategy, yielding PHU1-Flu and PHU1-Coum with high degrees of functionalization (up to 80%). The resulting polymers were directly processed into thin-film LSCs by spin coating, acting simultaneously as host matrix and photoactive component. The devices exhibited excellent optical transparency and colour neutrality, with an average visible transmittance of similar to 90%, comparable to clear glass. Among the two systems, PHU1-Flu showed superior performance, achieving external and internal photon efficiencies of 2.19% and 37.27%, respectively, a device efficiency of 0.34%, and a light utilization efficiency of 0.30%. By covalently immobilizing the luminophores, PHU-based LSCs inherently suppress dye migration and phase separation, addressing key stability limitations of conventional systems. These results demonstrate that bio-based PHUs represent not only sustainable but also functionally superior host matrices for durable and transparent LSCs.

Despite the progress achieved in ionic-based sensors, the growing demand for soft and flexible devices has highlighted several key requirements for the next generation of materials: (1) complete elimination of liquid phases that may evaporate or leak; (2) sufficient mechanical robustness for stable operation over repeated loading cycles; (3) facile device assembly; (4) high voltage output and sensitivity; and (5) a broad operational pressure range. To address these challenges, two complementary ionic liquid-like monomers (ILMs) were designed and synthesized: a cationic (M-BIM) and an anionic (M-TFSI) monomer, each incorporating a butylimidazolium (BIM+) or bis(trifluoromethylsulfonyl)imide (TFSI-) fragment covalently bonded to a methacrylate group together with their complementary counterions (respectively, TFSI- or BMIM+). Their copolymerization with poly(ethylene glycol) monomethacrylate (PEGM) and dimethacrylate (PEGDM) and optimization of the composition afforded flexible, self-standing, highly ion-conductive films combining good mechanical properties (E' = 0.4-1.0 MPa) with high ionic conductivities (up to 2.3 × 10-6 S cm-1 at 25 °C). Systematic optimization of film thickness, interfacial electrode layer (IEL) geometry, and IEL metal type revealed that sputtered gold IELs effectively suppressed signal drift and shortened response times, while platinum IELs markedly enhanced voltage generation. Comparison among sensors with mobile anions, mobile cations, and mixed carriers demonstrated that the charge-carrier type critically governs both sensitivity and voltage amplitude. The optimized sensor, based on the anionic M-TFSI formulation, featuring a 0.35 mm-thick film and rectangular Pt IEL exhibited a linear potential-pressure dependence across the entire range (0-80 kPa), an ultrafast recovery time of 0.2 s, and an exceptional output voltage of 190 mV, maintaining stable operation over 1000 loading cycles.

Piezoionic materials rely on mechanical-to-ionic transduction for transient voltage generation with respect to fluid-driven ion transport upon mechanical stimulation.

Conventional methods for synthesizing thermoplastic polyurethanes (TPUs) typically rely on isocyanates and tin-based catalysts, both of which pose significant environmental and safety risks. To mitigate these issues, alternative routes for synthesizing nonisocyanate polyurethanes (NIPUs) have been explored since the 1980s. However, most reported approaches yield polymers with molecular weights below 35 kg/mol and only a few exceptions reaching 50-70 kg/mol, often requiring oligomeric monomers or postmodification. This limitation has been a major barrier to the broader application and production of NIPUs. In this study, we demonstrate a direct polyaddition strategy for synthesizing high-molecular-weight poly-(hydroxyurethane)-s (PHUs, a subclass of NIPUs) from low-mass difunctional monomers without relying on macromonomers, oligomers, catalysts, or postcondensation/modification steps. The key to this achievement was the rational design of the monomers. The reactivity of cyclic carbonates was enhanced by incorporating aromatic rings into the structure of 7,7,7',7'-tetramethyl-6,6',7,7'-tetrahydro-5,5'-spirobi-[indeno-[5,6-d]-[1,3]-dioxole]-2,2'-dione. Model reactions of this bis-(cyclic carbonate) with secondary amines revealed that steric and electronic effects are decisive with alicyclic secondary amines markedly outperforming their linear analogues. Further pairing of activated aromatic bis-(cyclic carbonate) with alicyclic secondary diamines enabled nearly quantitative monomer conversion under mild, catalyst-free conditions (at 50 °C), yielding linear PHUs with a record-high degree of polymerization (DPn) of up to 220 and a number-average molecular weight (M n) of 105 kg/mol. This strategy was further extended to another aromatic cyclic carbonate, 5,5'-(9H-fluorene-9,9-diyl)-bis-(benzo-[d]-[1,3]-dioxol-2-one), producing PHUs with M n values of up to 100 kg/mol.

Dynamic ion gels (DIGs) obtained via complex coacervation of oppositely charged poly-(ionic liquid)-s (PILs) address the inherent trade-off between ionic conductivity (σDC) and mechanical strength (G') of PILs by providing both enhanced ion transport and robust viscoelastic properties. In order to tune the strength of ionic cross-links through charge delocalization of ion pairs, we study a series of four DIGs obtained from the combination of a cationic PIL (PIL + ) containing pendant imidazolium groups and free bis-(trifluoromethylsulfonyl)-imide (TFSI) counteranions with four anionic PILs (PIL - ) bearing pendant sulfonate anions and various free counter cations (i.e., 1-methyl-3-butylimidazolium, trimethylpropylammonium, tetrabutylammonium, and tetrabutylphosphonium). These new DIGs are produced via the formation of ionic cross-links with ion pairs having more localized charges (i.e., cations paired with sulfonate instead of TFSI). This results in stronger electrostatic interactions with counterions, reducing their mobility and significantly increasing the enthalpic driving force for ion exchange-induced coacervation. As a consequence, the four resulting DIGs release different free ionic liquids (ILs) consisting of TFSI anions associated with imidazolium, ammonium or phosphonium cations. The physical, ion-conducting, and viscoelastic properties of the resulting DIGs are systematically investigated by differential scanning calorimetry, broadband dielectric spectroscopy and rheology. The DIG having sulfonate-imidazolium ionic cross-links and releasing EMIM-TFSI ILs exhibits the best compromise between G' = 62 kPa (at 25 °C, 1 rad s-1) and σDC = 6.5 × 10-6 S cm-1 (at 25 °C), significantly outperforming the parent PILs. These results highlight DIGs as a highly promising class of materials with enhanced processability and mechanical integrity, making them ideal candidates for electrochemical applications such as supercapacitors, soft robotics, electrochromic devices, sensors, and solar cells.

Sulfide-based solid electrolytes (SEs) are promising enablers of next-generation solid-state batteries (SSBs), yet their practical implementation is limited by interfacial instability with anode and cathode active materials. Current interfacial mitigation strategies rely primarily on inorganic coatings, which are often unable to accommodate chemo-mechanical strain. Here, we introduce a new dynamic ion gel nanocoating that stabilizes both cathode and anode interfaces in sulfide-based SSBs. It is a type of ion-conductive polyelectrolyte complex (PEC), which is formed via complex coacervation between oppositely charged polyelectrolytes. Controlled mixing of a polycation bearing ammonium groups with TFSI- counteranions and a polyanion featuring pendant TFSI- groups with Li+ countercations yields a homogeneous, solution-processable dynamic ion gel accompanied by LiTFSI release. This enables uniform, thin (≈1-3 nm), and scalable PEC nanocoatings on active material particles via spray drying. Dynamic ionic cross-linking endows the PEC with enhanced viscoelasticity and improved ionic conductivity relative to the parent polycation, allowing it to adapt to solid-solid interfaces while maintaining efficient ion transport. SSBs employing PEC-coated silicon anodes and PEC-coated LiNiO2 cathodes exhibit improved cycling stability through suppression of interfacial side reactions. Thus, the PEC nanocoating acts as a scalable stabilizer of solid-solid interfaces in SSBs.

High crystallinity in PEO-based solid polymer electrolytes limits ion transport and stability in Li-metal batteries. Two asymmetric, low-melting thioether-TFSI Li salts were synthesized via a thiol-ene route and incorporated into PEO. They suppress crystallinity while maintaining conductivity and electrochemical performance, and reduce Al corrosion via stable passivation layer formation. The resulting SPEs have improved Li compatibility and enable stable Li||LiFePO4 cells cycling with high capacity retention and coulombic efficiency.

A straightforward and efficient thiol-ene Michael addition “click” chemistry route was developed to introduce asymmetry into the TFSI anion, enabling the synthesis of four ionic liquids (ILs) by coupling 1-ethyl-3-methylimidazolium (EMIM) cation with thioether-functionalized anions. This method offers high yields, excellent purities, mild reaction conditions, and versatile functionalization. The resulting ILs exhibit suppressed crystallization and vitrification behavior, with low glass transition temperatures (−75 to −62°C), ensuring liquid-state stability over a wide temperature range. Compared to common ILs, such as EMIM TFSI, EMIM 2,2,2-(trifluoromethyl)sulfonyl-N-cyanoamide (TFSAM) and EMIM 2,2,2-trifluoro-N-(trifluoromethylsulfonyl)acetamide (TSAC), the synthesized ILs display higher viscosities, which reduce CO₂ diffusion and lower overall permeabilities (133–221 Barrer). Nevertheless, they demonstrate enhanced CO2/N2 selectivity (up to 41), with EMIM C₂H₅-S-TFSI combining the highest permeability (221 Barrer) with excellent selectivity. These findings highlight the potential of thioether-modified TFSI ILs for gas separation applications where selectivity is of primary importance.

Infusible thermoplastics based on acrylic resins have gained increasing interest in fibre-reinforced composite manufacturing, primarily due to their low viscosity (100 mPa), enabling efficient fibre impregnation and facilitates processing at low temperatures (<100 degrees C). Their compatibility with UV and thermal curing system offers further manufacturing flexibility. To integrate self-healing ability, a UV-curable acrylic resin incorporating Zn(II)-acetate complexes as reversible cross-links was developed. Self-healing performance at the fibre-matrix interface was quantitatively evaluated using a novel single-fibre pull-out test methodology employing, real-time optical crack monitoring and paused healing cycles combined with -CT tomography for 3D interfacial validation. This approach demonstrated up to 95% recovery of the apparent interfacial shear strength (IFSS). Functionalizing glass fibres with Zn(OAc)(2) significantly improved baseline interfacial adhesion (35% IFSS increase) while maintaining self-healing capability, outperforming conventional epoxy/acrylic sizings. Structural glass fibre-reinforced composites were manufactured using the Vacuum-Assisted Resin Infusion Molding (VARIM) process, and the healing effect of Zn(OAc)(2) complexes was demonstrated by achieving an 85% recovery of the interlaminar shear strength (ILSS) after delamination and subsequent thermal healing treatment. This work presents a scalable approach to integrating self-healing functionality into acrylic-based composites for enhanced structural durability.

We demonstrate the first application of dynamic ion gels (DIGs) from the coacervation of two oppositely charged poly(ionic-liquid)s in the fabrication of quasi-solid-state supercapacitor devices, able to operate at high temperature without liquid leakage. The formation of the DIG enables the spontaneous in situ release of free ionic liquid (IL) avoiding the need to boost the ionic conductivity by the addition of exogeneous IL. Remarkably, the DIG maintains its solid-like behavior at elevated temperatures, enabling safe operation across a wide temperature range (25-80 degrees C) without leakage. Used as quasi-solid-state electrolyte, binder, separator and ionic-conducting filler for the rGO-based electrodes, various parameters are optimized, including the use of single cationic/ anionic poly(ionic-liquid), their association modes and DIG content. Combined with rGO-MWCNTs, DIG made from poly(1-butyl-3-[oxiran-2-ylmethyl]-1-imidazole-3-ium-s-ethylene oxide) bis (trifluoromethyl sulfonyl) imide and poly[(1-butyl-3-methylimidazolium 1-[3-(methacryl oyloxy)propylsulfonyl]-1-(trifluoromethane sulfonyl)imide)-r-(poly(ethyleneglycol) methyl ether methacrylate) yields optimal electrochemical performance of 27.2 F g- 1 at 1 mV s- 1 (at 25 degrees C) with device's excellent stability, maintaining 80% of capacitance after 4700 cycles and 60.1 F g- 1 (at 80 degrees C) in open air conditions. Accordingly, the maximum energy/power densities of 17 Wh kg-1/137 W kg- 1 at 25 degrees C and 31.4 Wh kg- 1/366 W kg- 1 at 80 degrees C are obtained.

In the present work, a galactomannan isolated from the endosperm of red clover (Trifolium pratense L.) seeds was studied for its feasibility as a thickening and gelling agent in food applications. Red clover seed galactomannan (RCG) had a mannose-to-galactose ratio of 1.12, a molecular weight of 1500 kDa (SEC-MALS) and an intrinsic viscosity of 13.6 dL g-1. The solvation affinity of RCG in water was equivalent to 0-solvent, according to the estimated Kraemer and Huggins coefficients. The critical coil overlap concentration of the RCG solutions in water was estimated to be c* = 0.35 wt %, whereas the concentration dependence of specific viscosity in the dilute and semi-dilute regimes was a c2.3 and c4.2, respectively. The water vapour sorption dynamics of RCG were controlled by a solution-like sorption mechanism. RCG exhibited a semi-crystalline structure with the glass transition occurring at Tg,onset approximate to 44 degrees C. The viscoelastic behaviour of the RCG solutions (1-7 wt %) obeyed the concentration superposition principle with a breakpoint in the relaxation dynamics to occur at c approximate to 2 wt %. A time-temperature-concentration super master curve was successfully constructed for c >= 2 wt % and temperatures between 5 and 65 degrees C with an Arrhenius kinetics calculated activation energy of 23.5 kJ/mol.

While polyhydroxyurethanes (PHUs) have been offered as "greener" alternatives to conventional polyurethanes (PUs) for ∼15 years, their low molecular weights, high hydrophilicity, and water uptake limit practical utility. In this study, we directly address these limitations by coupling pendant hydroxyl groups in tailored thermoplastic PHUs with 1,4-phenylenediboronic acid to form tough, robust PHU vitrimers, whose enhanced viscoelastic properties and reduced moisture sensitivity significantly differentiate them from existing linear and vitrimeric PHUs. Three families of PHU vitrimers incorporate either dioxaborolane or dioxazaborocane moieties based on aromatic or aliphatic amines. A fundamental comparison of structure-property relationships confirmed that dioxazaborocanes stabilized by aliphatic nitrogen atoms improve thermal and hydrolytic stability, as demonstrated through direct observations via solid-state NMR. In contrast to aromatic nitrogens, aliphatic nitrogens form N→B dative bonds, reducing chain mobility and increasing T g. This significantly enhances mechanical performance (+65-170% tensile strength, +125-300% break strain, ∼4-11× increase in tensile toughness) vs the parent PHUs and allows the resulting vitrimers to maintain their viscoelastic properties even at elevated humidity levels. Moreover, these N-stabilized dioxazaborocane PHU vitrimers are readily recyclable, both mechanically (up to at least 3×) and chemically (using ethanol/NaOHaq), without loss of performance.

Single-ion conducting polyelectrolytes transport only lithium ions, thereby increasing the lithium transference number and reducing concentration polarization in batteries. While this improves the electrochemical performance and safety, it remains challenging to balance ionic conductivity and mechanical strength (viscoelastic properties). A promising solution can be ionic block copolymers (BCPs), in which one charged block enables ion conduction while the neutral block with a high glass transition temperature provides mechanical reinforcement. Ionic conductivity in these BCPs is strongly dependent on their microphase-separated morphology. Although bicontinuous structures were believed to offer optimal ion conduction, synthesizing such morphologies is difficult, because they form in a narrow phase-space window requiring precise control of block volume fractions, molecular weights, and interaction parameters. To address this, we combined theoretical and experimental approaches to study a series of poly[(LiM n -r-PEGM m )-b-PhEtM k ] block copolymers, where the ion-conducting block comprises lithium 1-[3-(methacryloyloxy)propylsulfonyl]-1-(trifluoromethanesulfonyl)imide (LiM) and poly(ethylene glycol)methyl ether methacrylate (PEGM), and the neutral block is poly(2-phenylethyl methacrylate) (PhEtM k ). The length of the LiM n -r-PEGM m block was fixed at n = 20 and m = 80, while k was varied from 70 to 140. Dissipative particle dynamics simulations, coupled with a 3D scattering-diagram analysis, revealed stability regions for hexagonally packed cylinders, lamellae, and bicontinuous phases, predicting that bicontinuous phases emerge at k = 110 divided by 120. To validate this, a series of poly[(LiM n -r-PEGM m )-b-PhEtM k ] block copolymers with k ranging from 79 to 174 was synthesized. In keeping with predictions, morphologies consistent with the existence of a (disordered) bicontinuous structure were observed via AFM at k = 96 and 110. At the same time, while the storage modulus (G ') increased with rising k, the ionic conductivity decreased monotonically. The polymers with (disordered) bicontinuous structures demonstrated an optimal balance of viscoelastic properties and ionic conductivity, highlighting their potential, despite the absence of a significant conductivity enhancement in this series of BCPs.

Ionogels, an emerging class of solid polymer electrolytes (SPEs), break ground in the field of soft electronics combining ionic conductivity with the mechanical resilience of elastomeric polymer networks. To support the integration of ionogels into the next generation of flexible electronics devices, recent research efforts showcased the potential of covalent adaptable networks (CANs) to prolong their operational lifetime. In this study, we present the design of a flexible and recyclable ionogel based on a stretchable polybenzoxazine vitrimer containing dynamic ester bonds. Ionic conductivity is imparted by swelling the vitrimer matrix with an ionic liquid (IL), 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([EMIm]TFSI) at various swelling ratios (from 50 to 150 wt.%). The influence of [EMIm]TFSI uptake on the ionogel properties has been investigated with ionic conductivities in the range of 0.1 to 2 mScm-1 and alpha-mechanical relaxation temperatures ranging from -31 to -58 degrees C. The advantages of vitrimer chemistry through internally catalyzed transesterification reactions were highlighted by their stress relaxation as short as 10 s at 170 degrees C, enabling fast mechanical reprocessing. At low IL content, recycled vitrimer ionogels retain identical ionic, thermal, mechanical, and dynamic properties over multiple reprocessing cycles, showcasing excellent compatibility between the cross-linked network and the ionic species. Finally, the vitrimer ionogel was successfully incorporated into the design of an electrostimulated actuator, illustrating its potential to serve as a sustainable and high-performance material for advanced soft electronic applications.

The additive manufacturing of a bio-based, UV active, recyclable and reshapable polybenzoxazine is demonstrated.

Block copolymers with an AB-block, consisting of a random copolymer of an anionic monomer bearing Li+ and poly(ethylene glycol) methyl ether methacrylate, and a C-block based on poly(2-indanyl methacrylate), were synthesized by the RAFT-polymerization technique. The variation in molecular weights (62–71 kDa) and mass ratio between the ionic (AB) and neutral (C) blocks (MAB/MC = 1.92–2.18) allowed to obtain the copolymers that combine ionic conductivity of up to 6×10–7 S/cm (25 °C) and enhanced mechanical (viscoelastic) properties. This combination was gained owing to microphase separation caused by the incompatibility of AB and C blocks. The AFM study indicated the formation of lamellar structures.

Nonisocyanate polyurethanes (NIPUs) are broadly investigated as a potential replacement for conventional polyurethanes (PUs) to eliminate the use of toxic isocyanates and reduce occupational hazards. One of the most popular approaches to NIPU synthesis is the polyaddition of cyclic bis(carbonate)s and diamines to form poly(hydroxyurethane)s (PHUs). However, such PHUs are highly hydrophilic due to the presence of two hydroxyl groups per repeat unit, and the resulting moisture absorption significantly degrades their thermomechanical performance and physical stability upon exposure to humidity, thus limiting their utility. Here, we introduce a simple and scalable approach for the modification of PHUs to increase hydrophobicity and adjust their properties. The proposed reaction between aldehydes and appropriately spaced hydroxyl groups in the polymer backbone resulted in high degrees of modification (up to 84%) and up to 3-fold reductions in water uptake at 85% RH. Furthermore, the use of aromatic aldehydes in particular enabled the retention of mechanical properties over a wide range of humidity levels, resulting in performance comparable to conventional PUs. Finally, we note that this approach is not limited to reducing moisture sensitivity alone and provides ample opportunities for imparting a broad range of novel properties to PHUs through an appropriate selection of functional aldehydes.

A cationic poly(ionic liquid) (PIL) with pendent butyl imidazolium cations and free bis(trifluoromethylsulfonyl)imide (TFSI) anions and an anionic PIL with pendent TFSI anions and free 1-butyl-3-methylimidazolium cations are synthesized by postpolymerization chemical modification and reversible addition-fragmentation chain-transfer radical copolymerization, respectively. Upon mixing solutions of these two PILs in acetone with stoichiometric amounts of ion pairs, ionic exchanges induce coacervation and, after solvent evaporation, lead to the formation of a dynamic ion gel (DIG) and the concomitant release of free [1-methyl-3-butyl imidazolium]TFSI ionic liquid (IL). A comparison of thermal (T g), ion conducting (sigma DC), and viscoelastic (elastic moduli (G ')) properties for DIGs and their parent polyelectrolytes, as well as extracted and IL-doped DIGs, demonstrates the formation of ionic cross-links and the ability to easily produce polymer electrolytes with enhanced ionic conductivity (sigma DC up to 4.5 x 10(-5) S cm(-1) at 30 degrees C) and higher elastic moduli (G ' up to 4 kPa at 25 degrees C and 1 rad s(-1)), making them highly desirable in many electrochemical applications, including supercapacitors, soft robotics, electrochromic devices, sensors, and solar cells.

Polyurethanes (PUs) are common commodity plastics that cover a wide range of applications. However, PUs are based on isocyanates, the toxic compounds that pose respiratory and dermal hazards. As a more sustainable alternative, polyhydroxyurethanes (PHUs) have gained attention as PU substitutes. Nevertheless, their utility is often limited by low molecular weights and inferior properties. To overcome these shortcomings, the present study focuses on the application of reactive extrusion (REx) to the synthesis of thermoplastic PHUs, allowing rapid production without compromising molecular weight. First, a series of cyclic carbonate monomers were synthesized; in particular, a BPA-based bis(cyclic carbonate) was prepared from the commercial bis(epoxide), while two additional bis(cyclic carbonates) were prepared from the relevant bisphenols via sequential epoxidation and carbonation with CO2. Spectroscopic analyses confirm the successful synthesis of high-purity monomers. Second, PHUs were prepared via REx of the synthesized bis(cyclic carbonates) with various diamines following optimization of the process using a model system with the aim of maximizing the molecular weight and yield. The resulting series of linear PHUs possessed molecular weights of up to 21800 g/mol (as assessed via GPC), high strengths (up to 60 MPa as determined by quasi-static tensile testing), and attractive thermal properties (T g up to 110 degree celsius via DSC; T onset > 195 degree celsius via TGA). The viscoelastic and rheological behavior of selected PHUs is also reported. Finally, PHUs with comparable properties to traditional PUs were foamed, and the resulting foams were shown to possess densities and compressive and thermal properties comparable to conventional rigid PU foams.