Supramolecular Photonic Hydrogel for High-Sensitivity Alkaline Phosphatase Detection via Synergistic Driving Force.

Structurally-colored photonic hydrogels which are fabricated by introducing hydrogels into thin films or photonic crystal structures are promising candidates for biosensing. Generally, the design of photonic hydrogel biosensors is based on the sensor-analyte interactions induced charge variation within the hydrogel matrix, or chemically grafting binding sites onto the polymer chains, to achieve significant volume change and color variation of the photonic hydrogel. However, relatively low anti-interference capability or complicated synthesis hinder the facile and low-cost fabrication of high-performance photonic hydrogel biosensors. Here, a facilely prepared supramolecular photonic hydrogel biosensor is developed for high-sensitivity detection of alkaline phosphatase (ALP), which is an extensively considered clinical biomarker for a variety of diseases. Responding to ALP results in the broken supramolecular crosslinking and thus increased lattice distancing of the photonic hydrogel driven by synergistic repulsive force between nanoparticles embedded in photonic crystal structure and osmotic swelling pressure. The biosensor shows sensitivity of 7.3 nm spectral shift per mU mL-1 ALP, with detection limit of 0.52 mU mL-1 . High-accuracy colorimetric detection can be realized via a smartphone, promoting point-of-care sensing and timely diagnosis of related pathological conditions.

C-N Coupling Reactions on Graphene with Aromatic Macromolecules and the Spatial Conformation of Grafted Macromolecules.

The fabrication of advanced graphene-based nanocomposites with high-performance polymers requires covalent modification of graphene with aromatic macromolecules. Herein, C-N coupling reactions between fluorinated graphene (FG) and aromatic polyamides containing the benzimidazole moiety are successfully achieved. The optimized conditions are presented based on the nucleophilic behavior of the C-N coupling reaction on graphene. Different from the C-N coupling reaction between two small aromatic molecules, the conformation of grafted aromatic polyamide after reaction changes from torsional to paralleled alignment on graphene with the molecular length increment. Non-covalent interactions between graphene and aromatic polyamides result in this conformational change owing to the extended π systems of graphene and aromatic polyamides, and the synergistic effect of covalent and non-covalent interactions is put forward. As a consequence, graphene dispersibility is greatly enhanced in the solution of aromatic polyamide.

Benzimidazole-containing aramid nanofiber for naked-eye detection of heavy metal ions.

The rapid detection of heavy metal ions in wastewater has received significant attention in modern society. Herein, we report the exploration of benzimidazole-containing aramid fibers (B-ANF) for the naked-eye detection of heavy metal ions in aqueous solution. Firstly, B-ANF was prepared by hydroxylation from benzimidazole-containing aramid fiber. The unique benzimidazole unit endows the nanofiber with the ability to coordinate with multiple kinds of heavy metal ions. When B-ANF comes in contact with trace heavy metal ions in solution, the coordination interaction induces rapid aggregation, which can be detected by the naked eye within 2 minutes. Therefore, it provides an easy and time-saving strategy for the detection of heavy metal ions. In addition, B-ANF could be used for the rapid detection of total concentration of heavy metals ions in the presence of multiple kinds of heavy metal ions, which makes up for the shortage of traditional methods and shows prospects for broad application. Lastly, it was noticed that B-ANF, after the detection of heavy metal ions, could be readily recycled by an HCl/NaOH treatment, with the detection efficiency being completely preserved after the recycling process. It is believed that B-ANF integrates the advantages of low cost, easy transportation and naked-eye detection of heavy metal ions, and could be used as promising recyclable detector for heavy metal ions.

Control of Head/Tail Isomeric Structure in Polyimide and Isomerism-Derived Difference in Molecular Packing and Properties.

Two sequence isomeric poly(amic acid)s (PAAs) are successfully synthesized from 3,3',4,4'-biphenyltetracarboxylic dianhydride and unsymmetrical 5(6)-amino-2-(4-aminobenzene) benzimidazole (PABZ). The syntheses are based on the site-selective reactivity of head/tail amino groups of PABZ and solubility differences of PABZ in good solvent (dimethyl sulfoxide, DMSO) and poor solvent (N-methyl-2-pyrrolidone, NMP). The proton nuclear magnetic resonance (1 H-NMR) results reveal that the content of head tail-head tail (HTHT) bonding units in PAA-DMSO (PAA synthesized in DMSO) is 37%, while this content increases to 54% in PAA-NMP (PAA synthesized in NMP). The wide-angle X-ray diffraction (WAXD) results indicate polyimide (PI)-NMP film with high HTHT content exhibits a semicrystalline structure, while PI-DMSO film is amorphous. Moreover, PI-NMP also shows higher in-plane orientation than PI-DMSO. The ordered molecular packing and higher in-plane orientation of PI-NMP lead to an increase in mechanical properties and a decrease in in-plane thermal expansion coefficient.

Biomimetic-Mineralization-Assisted Self-Activation Creates a Delicate Porous Structure in Carbon Material for High-Rate Sodium Storage.

Porous carbons have shown their potential in sodium-ion batteries (SIBs), but the undesirable initial Coulombic efficiency (ICE) and rate capability hinder their practical application. Herein, learning from nature, we report an efficient method for fabricating a carbon framework (CK) with delicate porous structural regulation by biomimetic mineralization-assisted self-activation. The abundant pores and defects of the CK anode can improve the ICE and rate performance of SIBs in ether-based electrolytes, whereas they are confined in carbonate ester-based electrolytes. Notably, ether-based electrolytes enable CK anode to possess excellent ICE (82.9%) and high-rate capability (111.2 mAh g-1 at 50 A g-1). Even after 5500 cycles at a large current density of 10 A g-1, the capacity retention can still be maintained at 73.1%. More importantly, the full cell consisting of the CK anode and Na3V2(PO4)3 cathode delivers a high energy density of 204.4 Wh kg-1, with a power density of 2828.2 W kg-1. Such outstanding performance of the CK anode is attributed to (1) hierarchical pores, oxygen doping, and defects that pave the way for the transportation and storage of Na+, further enhancing ICE; (2) a high-proportion NaF-based solid-electrolyte-interphase (SEI) layer that facilitates Na+ storage kinetics in ether-based electrolytes; and (3) ether-based electrolytes that determine Na+ storage kinetics further to dominate the performance of SIBs. These results provide compelling evidence for the promising potential of our synthetic strategy in the development of carbon-based materials and ether-based electrolytes for electrochemical energy storage.

High-toughness, extensile and self-healing PDMS elastomers constructed by decuple hydrogen bonding.

Elastomers are widely used in traditional industries and new intelligent fields. However, they are inevitably damaged by electricity, heat, force, etc. during the working process. With the continuous improvement of reliability and environmental protection requirements in human production and living, it is vital to develop elastomer materials with good mechanical properties that are not easily damaged and can self-heal after being damaged. Nevertheless, there are often contradictions between mechanical properties and self-healing as well as toughness, strength, and ductility. Herein, a strong and dynamic decuple hydrogen bonding based on carbon hydrazide (CHZ) is reported, accompanied with soft polydimethylsiloxane (PDMS) chains to prepare self-healing (efficiency 98.7%), recyclable, and robust elastomers (CHZ-PDMS). The strategy of decuple hydrogen bonding will significantly impact the study of the mechanical properties of elastomers. High stretchability (1731%) and a high toughness of 23.31 MJ m-3 are achieved due to the phase-separated structure and energy dissipation. The recyclability of CHZ-PDMS further supports the concept of environmental protection. The application of CHZ-PDMS as a flexible strain sensor exhibited high sensitivity.

Polymer Fiber Rigid Network with High Glass Transition Temperature Reinforces Stability of Organic Photovoltaics.

Organic photovoltaics (OPVs) need to overcome limitations such as insufficient thermal stability to be commercialized. The reported approaches to improve stability either rely on the development of new materials or on tailoring the donor/acceptor morphology, however, exhibiting limited applicability. Therefore, it is timely to develop an easy method to enhance thermal stability without having to develop new donor/acceptor materials or donor-acceptor compatibilizers, or by introducing another third component. Herein, a unique approach is presented, based on constructing a polymer fiber rigid network with a high glass transition temperature (Tg) to impede the movement of acceptor and donor molecules, to immobilize the active layer morphology, and thereby to improve thermal stability. A high-Tg one-dimensional aramid nanofiber (ANF) is utilized for network construction. Inverted OPVs with ANF network yield superior thermal stability compared to the ANF-free counterpart. The ANF network-incorporated active layer demonstrates significantly more stable morphology than the ANF-free counterpart, thereby leaving fundamental processes such as charge separation, transport, and collection, determining the device efficiency, largely unaltered. This strategy is also successfully applied to other photovoltaic systems. The strategy of incorporating a polymer fiber rigid network with high Tg offers a distinct perspective addressing the challenge of thermal instability with simplicity and universality.

The adsorption of aromatic macromolecules on graphene with entropy-tailored behavior and its utilization in exfoliating graphite.

Aromatic macromolecules tend to form a compact conformation after physically adsorbed on graphene and it brings about great entropy loss for physisorption, due to the strong interaction between aromatic macromolecules and graphene. However, previous researches have validated the availability of aromatic macromolecules to stabilize graphene based on physisorption. In order to clarify the underlying mechanism of this physisorption process on graphene, a series of aromatic polyamide copolymers are used as models in this research. Apart from their adsorbed conformations on graphene, the conformations of these copolymers as the free states in diluted solutions are taken into consideration. Although these copolymers present the fully extended conformation on graphene, their conformations in diluted solutions vary largely with the copolymer composition. It is verified that the copolymer with smaller conformational change could have the better stabilization effectiveness for graphene, rather than the one having stronger interaction with graphene. Therefore, the entropy-tailored behavior for the adsorption of aromatic macromolecules on graphene is put forward. Based on this mechanism, the chemical structure of aromatic polyamide is optimized and furthermore it is utilized to directly exfoliate natural graphite flakes. Eventually, high-quality graphene nanosheets with a large dimension and low defects are obtained. Moreover, its exfoliating effectiveness is superior to those of the commonly used exfoliating agents nowadays.

Flexible pressure sensors with high pressure sensitivity and low detection limit using a unique honeycomb-designed polyimide/reduced graphene oxide composite aerogel.

It is still a challenge to fabricate flexible pressure sensors that possess high sensitivity, ultralow detection limit, wide sensing range, and fast response for intelligent electronic devices. We here demonstrate superelastic and highly pressure-sensitive polyimide (PI)/reduced graphene oxide (rGO) aerogel sensors with unique honeycomb structure, which were designed and fabricated using a bidirectional freezing technique. This unique honeycomb structure with large aspect ratio is composed of aligned thin lamellar layers and interconnected bridges. The combination of the aligned lamellar layers and the bridges endows the aerogel sensors with high pressure sensitivity (1.33 kPa-1), ultralow detection limit (3 Pa), broad detection range (80% strain, 59 kPa), fast response time (60 ms), and excellent stability during cycling (over 1000 cycles). Remarkably, the aerogel sensors maintain stable piezoresistive performance at -50 °C, 100 °C, and 200 °C in air, indicating promising potential applications in harsh environments. Owing to the high sensitivity and wide sensing range, the aerogel sensors have been used to detect a full-range of human motion including small-scale motion monitoring (wrist pulse, blowing, puffing) and large-scale movement monitoring (finger bending, elbow bending, walking, running). These advantages make the composite aerogels attractive for high-performance flexible pressure sensors and wearable electronic devices.

Biocompatible In Situ Polymerization of Multipurpose Polyacrylamide-Based Hydrogels on Skin via Silver Ion Catalyzation.

Free radical polymerization is a mature method and can be used for preparing multifunctional hydrogels by simply changing the commercial monomers, but the harsh and time-consuming initiation conditions restrict its injectable ability, which further limits its application in the biomedical field. Though some catalysts can be used to accelerate the polymerization, their application is restrained by the biotoxicity. Hence, finding a biocompatible catalyzer for in situ free radical polymerization of hydrogels has a great prospect in biomedical application but is still challenging. In this study, we discovered that silver ions could catalyze free radical polymerization under ambient by transforming hydrone into hydroxyl radicals in the presence of ammonium persulfate, and the in situ-formed hydrogels prepared by this way showed great histocompatibility, hemocompatibility, cytocompatibility, and immunocompatibility. Benefitting from its convenience and biocompatibility, the in situ polymerization of polyacrylamide-based hydrogels for tissue adhesion, wound dressing, and conductive materials on the skin could be realized by simply blending diverse ingredients. Furthermore, this discovery may be a step toward the in situ-polymerized hydrogels for biomedical applications.

The Friedel-Crafts reaction of fluorinated graphene for high-yield arylation of graphene.

Herein, we report the Friedel-Crafts reaction of fluorinated graphene with aryl molecules including methylbenzene, chlorobenzene and polystyrene. The reaction achieved the high-yield arylation functionalization of graphene under mild reaction conditions and extends the range of the Friedel-Crafts reaction to the field of two-dimensional materials.

Facile preparation of highly hydrophilic, recyclable high-performance polyimide adsorbents for the removal of heavy metal ions.

To obtain high-performance adsorbents that combine excellent adsorption ability, thermal stability, service life and recycling ability, polyimide (PI)/silica powders were prepared via a facile one-pot coprecipitation process. A benzimidazole unit was introduced into the PI backbone as the adsorption site. The benzimidazole unit induced more hydroxyls onto the silica, which provided hydrophilic sites for access by heavy metal ions. By comprehensively analyzing the effect of hydrophilcity, agglomeration, silica polycondensation, specific surface area and PI crystallinity, 10% was demonstrated to be the most proper feed silica content. The equilibrium adsorption amount (Qe) for Cu(2+) of PI/silica adsorbents was 77 times higher than that of pure PI. Hydrogen chloride (HCl) was used as a desorbent for heavy metal ions and could be decomplexed with benzimidazole unit at around 300°C, which was lower than the glass transition temperature of PI. The complexation and decomplexation process of HCl made PI/silica adsorbents recyclable, and the adsorption ability remained steady for more than 50 recycling processes. As PI/silica adsorbents possess excellent thermal stability, chemical resistance and radiation resistance and hydrophilicity, they have potential as superior recyclable adsorbents for collecting heavy metal ions from waste water in extreme environments.