Simultaneous realization of superior mechanical and antifouling properties is critical for a coating. The use of stereoscopic polysiloxanes in place of linear polysiloxanes to fabricate antifouling coatings can combine properties of organic and inorganic materials, i.e., they can exhibit both high hardness and wear resistance from inorganic components as well as the flexibility and tunability from organic components. This strategy is used to prepare hard yet flexible antifouling coatings or polymer-ceramic hybrid antifouling coatings. In this mini-review, we report the recent advances in this field. Particularly, the effects of stereoscopic polysiloxane structures on their mechanical and antifouling properties are discussed in detail.

In recent years, due to the rapid development of high-performance small molecule acceptor (SMA) materials, the researches on p-type electron donor materials for matching with current efficient SMAs have become important. By means of asymmetric strategies to optimize the energy levels and inter/intramolecular interactions of molecules, we designed and synthesized an asymmetric aromatic side chain quinoxaline-based polymer donor TPQ-0F. Meanwhile, we took advantage of F atom which could form noncovalent interaction and strong electron-withdrawing property, to obtain the optimized quinoxaline-based polymer donors TPQ-1F, TPQ-1Fi and TPQ-2F. Eventually, the binary device based on TPQ-2F achieved an efficient power conversion efficiency (PCE) of 16.27%, which attributed to balanced hole/electron mobilities, less charge carrier recombination, and more favorable aggregation morphology. Our work demonstrates the great potential of asymmetric aromatic side chain quinoxaline-based polymer donors on optimizing the morphology of blending films, improving inter/intramolecular interactions, and subtly tuning energy level, finally for more efficient organic solar cells.

Precisely optimizing the morphology of functional hybrid polymeric systems is crucial to improve its photophysical property and further extend their optoelectronic applications. The physic-chemical property of polymeric matrix in electrospinning (ES) processing is a key factor to dominate the condensed structure of these hybrid microstructures and further improve its functionality. Herein, we set a flexible poly(ethylene oxide) (PEO) as the matrix to obtain a series of polydiarylfluorenes (including PHDPF, PODPF and PNDPF) electrospun hybrid microfibers with a robust deep-blue emission. Significantly different from the rough morphology of their poly(N-vinylcarbazole) (PVK) ES hybrid fibers, polydiarylfluorenes/PEO ES fibers showed a smooth morphology and small size with a diameter of 1~2 μm. Besides, there is a relatively weak phase separation under rapid solvent evaporation during the ES processing, associated with the hydrogen-bonded-assisted network of PEO in ES fibers. These relative “homogeneous” ES fibers present efficient deep-blue emission (PLQY>50%), due to weak interchain aggregation. More interestingly, low fraction of planar (β) conformation appears in the uniform PODPF/PEO ES fibers, induced by the external traction force in ES processing. Meanwhile, PNDPF/PEO ES fibers present a highest sensitivity than those of other ES fibers, associated with the smallest diameter and large surface area. Finally, compared to PODPF/PVK fibers and PODPF/PEO amorphous ES fibers, PODPF/PEO ES fibers obtained from DCE solution exhibit an excellent quenching behavior toward a saturated DNT vapor, mainly due to the synergistic effect of small size, weak separation, β-conformation formation and high deep-blue emission efficiency.

One important subject in the field of all-polymer solar cells (all-PSCs) is the exploration of electron-deficient building blocks with optimized physicochemical properties to promote the performance of polymer acceptors. Here, two ladder-type heteroheptacene-containing small-molecule acceptors with branched 2-octyldodecyl or 2-hexyldecyl side-chains are synthesized and polymerized with the thiophene co-monomer to afford polymer acceptors (PW-OD and PW-HD) with strong near-infrared absorption. Experimental results reveal that the alkyl chain length has a large impact on the molecular packing behavior of the resulting polymers, which in turn affects their light-absorbing and charge transport properties, and thus the photovoltaic performance of the final devices. When blended with the polymer donor PM6, PW-HD-based all-PSCs deliver a higher power conversion efficiency (PCE) of 9.12% compared to the PCE of 6.47% for the PW-OD-based all-PSCs, mainly due to its more ordered inter-chain packing and more favorable blend morphology. This work provides a promising building block for the development of high-performance narrow-bandgap polymer acceptors and highlights the importance of side-chain substitution in optimizing the photovoltaic performance of polymer acceptors.

Lithium-sulfur batteries suffer a lot from the huge volume change and the shuttle effect. However, conventional poly(vinylidene fluoride) binder has intrinsic drawbacks, such as low ion conductivity, weak polysulfide-trapping ability, poor mechanical properties, and requirement of organic solvents. Herein, we designed a functional emulsion binder with multi crosslinked structure. Such a structure was formed by the covalent crosslinking within and between the emulsion particles, which facilitates the adapting of the volume expansion of sulfur cathode, thereby ensuring the integrity of electrodes. Besides, the polar functional groups endow the binder with strong chemisorption of lithium polysulfide and fast lithium-ion migration ability. Thus, the assembled lithium-sulfur battery displayed a high initial discharge capacity of 1246 mAh·g⁻¹ at 0.1 C, and a capacity fading rate of 0.04% per cycle after 500 cycles at 0.5 C. Even at a high sulfur mass loading of 4.8 mg·cm^–2, a high capacity of 956 mAh·g⁻¹ was still obtained at 0.2 C.

Flexible strain wearable sensors have attracted considerable attention due to their advantages of low cost, lightweight, high sensitivity and good flexibility. However, the strain sensors are easy to be damaged in an extreme humidity environment or by the wearer's sweat in the process of use, resulting in detection disorder or even a short circuit. Furthermore, preparation of sensors with stable properties under extreme environments is one of the most important research directions. To fill this gap, a flexible sensor was prepared by using polyurethane and carbon nanotubes, then modified by polydopamine and 1H,1H,2H,2H-perfluorodecane-mercaptan. A typical tunnel model was used to explain the working mechanism of the sensor, the sensitivity of the sensor is also explained and evaluated by the tunneling theory. The results show that the sensor has good sensitivity (the sensor has a stable sensing signal output under a strain range from 2% to 300%) and stability over 8500 cycles. At the same time, the sensor has good superhydrophobicity, the water contact angle reaches 152°, and it is still stable in a humid environment. Moreover, this sensor shows excellent performance in monitoring human joint motion (such as finger, elbow, wrist and knee) and physiological signals (such as speaking and drinking). This work provides an effective design method for the sensor which can be applied in a high humidity environment.

Poly(butylene adipate-co-terephthalate) (PBAT) is currently the largest commercial biodegradable plastics with good toughness and film forming properties, whereas, the inferior barrier and mechanical properties hinder its applications. Biodegradable poly(propylene carbonate) (PPC) with excellent barrier properties and high strength is a natural choice to address above issue. However, it is challenging to improve the compatibility of these two polymers. Herein, we prepared a reactive compatibilizer with double bond side group through terpolymerization of CO₂/propylene oxide/glycidyl methacrylate to enhance the properties of PBAT/PPC blends. Upon addition of 1 wt% compatibilizer, the PBAT/PPC blends (75/25, W/W) showed an increased water vapor barrier property changed from 424 g·m⁻²·d⁻¹ to 204 g·m⁻²·d⁻¹ compared to the control sample. Moreover, the tensile strength and elongation at break increased from 24.7 MPa to 30.3 MPa and from 858% to 1142%, respectively. The PBAT/PPC composite also displayed excellent biodegradability under composting conditions, as confirmed by the significantly decreased molecular weight. The present work provides an efficient way to barrier biodegradable film from PBAT of practical utilization.

Interleukin 2 (IL-2) is widely used as an active immunotherapeutic agent in clinical metastatic cancers. However, its therapeutic concentrations do not last long due to its short half-life. Thus, only a transient proliferation of the anti-cancer CD8⁺ T cells can be achieved, resulting in poor efficacy. Therefore, the aim of this work was to create a system that promotes CD8⁺ T cell proliferation at the tumor site using IL-2 persistently present and activates an anti-cancer immune response. This goal was achieved by the design of the IL-2-loaded polypeptide nanoparticles (P-IL-2) where methoxy poly(ethylene glycol) block poly-[(N-2-hydroxyethyl)-aspartamide] phenylboronic acid was used to encapsulate IL-2 through boron-nitrogen coordination with poly(_L-lysine). P-IL-2 significantly prolonged the circulation time of IL-2 and achieved a selective drug release at the tumor site in the presence of high levels of reactive oxygen species, thus activating an anti-cancer immune response and exerting a better anti-cancer effect. The half-life of P-IL-2 was 3.15-fold higher than that of IL-2, and the quantity of CD8⁺ T cells after using P-IL-2 was 1.89-fold higher than that after using IL-2. In addition, the combination of P-IL-2 and anti-CTLA-4 monoclonal antibody resulted in an enhanced immune activation. Hence, this work provides a new approach to improve the efficacy of IL-2 in anti-cancer immunotherapy.

Poly(propylene carbonate) (PPC) is gaining significant momentum as a biodegradable polymer using CO₂ as an abundant, low-cost and renewable feedstock. Yet, PPC suffers from unsatisfactory thermal and mechanical properties, and its blends with other synthetic polymers as the second component typically exhibit poor compatibility. Herein, novel furan-based non-isocyanate polyurethanes (NIPUs) with high molecular weights and narrow distributions have been synthesized starting from 5-hydroxymethylfurfural (HMF) via a four-step procedure including reduction, glycidylation, carbonation of CO₂ and step-growth polymerization with diamines. Owing to the structural similarity and intermolecular hydrogen bonding interactions, furan-based NIPUs display good compatibility with PPC. A sea-island morphology can be observed in SEM images of PPC/NIPU blends, where the NIPU phases are randomly dispersed in the PPC matrix. Moreover, the blends exhibit only one T_g (higher than both that of PPC and the corresponding NIPU) on the DSC curves, which first increase and then decrease when increasing the content of NIPUs from 0 wt% to 15 wt%. Notably, the physical crosslinking formed by hydrogen bonding interactions, coupled with the rigidity of furan rings, confer simultaneous improvements of elongation at the break and tensile strength, affording high-performance CO₂-based biodegradable polymeric materials with low carbon footprint, good sustainability, and ideal biocompatibility.

Polyglycolide (PGA) fibers applied as surgical sutures strongly depend on their microstructure. The structural evolution of PGA nascent fibers during single low-temperature stretching and segmented high-temperature stretching was analyzed based on a combination of in situ WAXD/SAXS and DSC measurements. The results indicated that the hot stretching was conducive to the crystal perfection and the local fragmentation and recrystallization of the lamellar crystals may occur under stress induction. The single low-temperature stretching of PGA nascent fibers could be divided into three stages: the stretching of amorphous regions, stretch-induced crystallization and the stretching of crystalline regions. The elongation at break of the fibers can be substantially increased by adopting a segmented stretching method, and the high-temperature stretching can also significantly increase the crystallinity and orientation. The amorphous orientation peak appearing in the low-temperature stretching was gradually converted to crystallization peak during the heating process, which greatly improved the crystallinity and orientation of the fibers. High-temperature stretching compared with low-temperature stretching was more favorable for crystal perfection and structural evolution, where lamellar crystals underwent stress-induced fragmentation recrystallization to transform to fibrous crystals as the strain increased.

The inherent brittleness of biodegradable poly(glycolic acid) (PGA) restricts its utilization in the packaging field. Traditional toughening methods usually require additional components accompanied by a sacrifice of strength. In the present work, PGA films with simultaneously enhanced strength and ductility are achieved via “casting-stretching-annealing” technology. The reinforced chain entanglement network of PGA induced by the intense extensional stress and the highly oriented crystals grown and refined during the stretching and annealing process endowed the improved ductility and strength of the PGA films, respectively. The relationships among the stretching process, microstructure and mechanical properties of the PGA films have been systematically investigated. As a result, the PGA film (SA-2) with low stretch ratios exhibits excellent ductility with an increase in elongation at break from 22% to 220% and tensile strength from 56 MPa to 130 MPa. Meanwhile, the PGA film (SA-4) with large stretch ratios features much higher tensile strength (335 MPa) while maintaining good ductility (elongation at break of 66%). In addition, highly oriented crystals result in obvious enhancement of heat resistance and dimensional stability of the PGA films. Therefore, this work provides an effective route to fabricate PGA films with both high strength and ductility which may promote the application of PGA materials.

Physical cross-linking by hydrogen-bonds (H-bonds), providing a good combination of application properties of thermosets and processability of thermoplastics, is a potential strategy to resolve the recycling problem of traditional chemically cross-linked polyethylene. However, ureidopyrimidone (UPy), the most widely used H-bonding motif, is unfavorable for large-scale industrial application due to its poor thermal stability. In this work, H-bonds cross-linked polyethylene was successfully prepared by reactive melt blending maleic anhydride grafted polyethylene (PE-g-MAH) with 3-amino-1,2,4-triazole (ATA) to form amide triazole ring-carboxylic acid units. Triazole ring can easily generate multiple H-bonds with carboxylic acid and amide. More importantly, these units are more thermal stable than UPy due to the absence of unstable urea group of UPy. The introduction of H-bonds cross-linking leads to an obvious improvement in mechanical properties and creep resistance and a good maintain in thermal properties and recyclability. Furthermore, the reinforcement effect monotonically improves with increasing the density of H-bonds. The obtained good properties are mainly attributed to largely enhanced interchain interactions induced by H-bonds cross-linking and intrinsic reversibility of H-bonds. This work develops a novel way for the simple fabrication of H-bonds cross-linked PE with high performance through reactive melt blending.

Blending of poly(levorotatory-lactic acid) (PLLA) and poly(dextrorotatory-lactic acid) (PDLA) produces the stereocomplex crystallites (PLA SC), which present higher melting temperature and mechanical properties than that of neat PLLA or PDLA. However, in the PLLA/PDLA blends with higher molecular weights, the phase separation occurs and the SC exhibits weak memory after melting, which lead to a small amount of SC together with a large amount of homochiral crystallites (HC) develop during crystallization from the melt. In this study, a small content of graphite oxide was blended with PLLA and PDLA to form ternary blends, and it was exciting to find that the formation of SC was enhanced gradually with the content of graphite oxide. The SC exclusively developed when 2 wt% graphite oxide was incorporated into the PLLA/PDLA, and the crystallinity with ~50% was received even during fast cooling from the melt (−50 °C/min). The acceleration formation of SC was speculated due to the interaction between PLA molecular chains and the hydroxyl groups on the surface of graphite oxide and the obstruction of proliferation of graphite oxide.

Binary biodegradable polymers films, poly(butylene adipate-co-terephthalate) (PBAT) and poly(glycolic acid) (PGA), were prepared through batch melt mixing to obtain Film I and Film II under two different processing conditions. PGA crystals played a major role in enhancing the mechanical and barrier properties of the films. For Film I, there were initial PGA crystals before the film blowing process, the PGA molecular chain further crystallized, forming the oriented crystallization of PGA. Moreover, the X_c and crystalline size in Film I were higher than those in Film II. Compared with the different processing methods, Film I has excellent mechanical and oxygen barrier properties due to the crystallization and orientation. The tensile strength reached 45.0 MPa, and tear strength exceeded 138.2 kN/m, while the elongation at break was as high as 750% for PBAT/PGA 85/15 in Film I. The WVTR, WVP coefficients, and OP coefficients of PBAT/PGA films were decreased obviously with increasing the PGA content both in Film I and Film II. Moreover, the barrier properties of oxygen in Film I were better than that in Film II. This work reveals a feasible processing technique by introducing of initial crystallization of PGA to blow PBAT/PGA films with excellent mechanical and barrier properties.

Methyl vinyl silicone rubber (MVQ)/polypropylene (PP) thermoplastic vulcanizate (TPV) combines the good melt processability, recyclability and sealing performance as well as biosafety, stain and fluid resistance, and thus it is especially suitable in bio-safety areas and wearable electronic devices, etc. Nevertheless, the compatibility between MVQ and PP phases is poor. A big challenge on the compatibilization of MVQ/PP blends is that neither MVQ nor PP contains any reactive groups. In this study, a dual reactive compatibilizer composed of ethylene-methyl acrylate-glycidyl methacrylate terpolymer (EMA-co-GMA) and maleic anhydride grafted polypropylene (PP-g-MAH) was designed for the compatibilization of MVQ/PP blends. During melt blending, a copolymer compatibilizer at the MVQ/PP interface can be formed because of the in situ reaction between EMA-co-GMA and PP-g-MAH. The thermodynamic predict of its compatibilization effect through calculating the spreading coefficient of the in situ formed copolymer indicates that it can well compatibilize MVQ/PP blends. The experimental results show that under the GMA/MAH molar ratio of 0.5/1, the interface thickness largely increase from 102 nm for non-compatibilized blend to 406 nm, and the average size of MVQ dispersed phase largely decreases from 2.3 μm to 0.36 μm, the T_g of the two phases shifts toward each other, the mixing torque and mechanical properties of the blend are increased, all indicating its good compatibilization effect. This study provides a good compatibilizing method for immiscible MVQ/PP blends with no reactive groups in both components for the preparation of high performance MVQ/PP TPVs.

Design of rapidly detachable adhesives with high initial bonding strength is of great significance but it is full of great challenge. Here, we report the fast electrically detaching behavior (100% detaching efficiency in just 1 min under dozens of DC voltage) and high initial bonding strength (>12 MPa) of epoxy-based ionic conductive adhesives (ICAs). The epoxy-based ICAs are fabricated by introducing polyethylene glycol dimethyl ether (PEGDE) and 1-ethyl-3-methylimidazolium trifluoromethanesulfonate ([EMIM]OTF) into epoxy. The combination of PEGDE and [EMIM]OTF enables the free ions to migrate directively in electric field, and the anchoring of PEG chains onto epoxy chains ensures the long-term reliability of ICAs. The investigation on the electrically detaching mechanism suggests that the enrichment and following rapid interfacial electrochemical reactions of [EMIM]OTF lead to formation of metal hydroxide (Me(OH)_n) nanoparticles at the bonding interfaces, thus the strong interactions containing interlocked forces, van de Waals’ forces and hydrogen bonding interactions between ICAs and bonding substrates are destroyed. This work provides a promising direction for detachable adhesives with both high initial bonding strength and high detaching efficiency in short time.