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Hydrophobic antifouling polymers capable of self‐healing performance are highly desirable for industrial applications. However, the construction of self‐healing, hydrophobic antifouling polymers is challenging considering their complex fouling environments, which are humid in aqueous environment. In this work, a self‐healing hydrophobic polymer containing Fe3+‐catechol coordination applicable to antifouling is synthesized. The hydrophobic fluoroalkyl segments in the polymers formed unique domains dispersed in a polydimethylsiloxane matrix. The as‐synthesized polymers can completely restore their tensile strength, and their self‐healing efficiency is above 90% in both artificial seawater and pure water because of the dynamic Fe3+‐catechol coordination interactions. The as‐synthesized polymer exhibited self‐healing and antifouling properties against common marine bacteria. The colony adhesion and self‐healing processes of the damaged coating in artificial seawater containing marine bacteria are characterized by laser confocal microscopy. This strategy may be useful for the development of future polymeric antifouling materials. [ABSTRACT FROM AUTHOR]

Solid‐state lithium metal batteries (SSLMBs) with poly (ethylene oxide) (PEO)‐based electrolytes have increasingly become one of the most promising battery technologies due to high energy density and safety. However, adverse electrode/electrolyte interface compatibility issues hinder further application. Herein, a PEO‐based composite solid electrolyte with excellent anode and cathode interfacial compatibility is designed via the coordination modulation strategy induced by lithium difluorobis(oxalato)phosphate (DFBOP). By utilizing this electrolyte, the robust inorganic‐rich interphase involving LiF, LixPOyFz, and P─O components is in situ generated on lithium (Li) anode and LiNi0.8Co0.1Mn0.1O2 (NCM811) cathode surfaces via forceful coordination among PEO, lithium bis(trifluoromethanesulphonyl)imide, and DFBOP and subsequent adjustment of front orbital energy levels. It contributes to homogeneous lithium deposition and an effective impediment of PEO oxidation decomposition at high voltage, promoting superior interfacial stability. Consequently, Li‐symmetric cells with modified electrolyte can achieve a stable cycle over 7000 h at 0.2 mA cm−2. Specially, the cathode electrolyte interphase with a unique organic–inorganic interpenetration network structure enables the 4.5 V Li/NCM811 cells to cycle steadily over 100 cycles, with a high discharge capacity of 215.4 mAh g−1 and initial coulombic efficiency of 91.23%. This research has shed light on the interfacial design of PEO‐based electrolytes from the perspective of electrolyte coordination regulation to construct high‐performance SSLMBs. [ABSTRACT FROM AUTHOR]

Ionic thermoelectric (i‐TE) gels have attracted widespread attention in flexible electronics due to their flexibility, leakage‐free, low toxicity, and converting low‐grade waste heat into electricity. For practical application, it is strongly desirable to fabricate negative‐thermopower (n‐type) i‐TE gels with excellent mechanical performances, which is still a big challenge. Herein, a multi‐hierarchical network structure is proposed to simultaneously improve the TE and mechanical performance. Such structure including hierarchical hydrogen bonds, coordination bonds, and dense polymer chains is realized via the synergy of the coordination effect of polymer to cations and the Hofmeister effect of anions to polymer. As a result, the optimized gel exhibits not only negative thermopower up to −3.69 mV K−1 with a conductivity of 0.15 S m−1 at room temperature, but also outstanding tensile strength (>6.7 MPa), elongation at break (>1100%), and toughness (>43 MJ m−3), which is the toughest n‐type i‐TE gel reported to date. In addition, these n‐type i‐TE gels present good freeze tolerance (−58.53 °C) and dry resistance. Furthermore, the application potentials of the i‐TE device are proven in converting human thermal power into electricity. These findings provide a new way to obtain high‐performance n‐type i‐TE materials by synergistic anion and cation action on polymers. [ABSTRACT FROM AUTHOR]

Zinc‐based aqueous batteries (ZABs) are attracting extensive attention due to the low cost, high capacity, and environmental benignity of the zinc anode. However, their application is still hindered by the undesired zinc dendrites. Despite Zn‐surface modification being promising in relieving dendrites, a thick separator (i.e. glass fiber, 250–700 μm) is still required to resist the dendrite puncture, which limits volumetric energy density of battery. Here, we pivot from the traditional interphase plus extra separator categories, proposing an all‐in‐one ligand buffer layer (ca. 20 μm) to effectively modulate the Zn2+ transfer and deposition behaviors proved by in situ electrochemical digital holography. Experimental characterizations and density functional theory simulations further reveal that the catechol groups in the buffer layer can accelerate the Zn2+ reduction reaction (ZRR) through the electron‐donating p‐π conjugation effect, decreasing the negative charge in the coordination environment. Without extra separators, the elaborated system endows low polarization below 28.2 mV, long lifespan of 4950 h at 5 mA cm−2 in symmetric batteries, and an unprecedented volumetric energy density of 99.2 Wh L−1 based on the whole pouch cells. The concomitantly "separator‐free" and "dendrite‐free" conjugation effect with an accelerated ZRR process could foster the progression of metallic anodes and benefit energetic aqueous batteries. [ABSTRACT FROM AUTHOR]

Sulfur-doped biochar (S4BC) was prepared with cherry kernel powder as carbon source, Na2S2O3 as sulfur source and chemical activator. Na2S2O3 can activate biochar through the reaction with carbon, intercalation of alkali metals and the generated gas rushing out of pores, and at the same time, active sulfur atoms are doped into biochar during pyrolysis. The physical and chemical properties of S4BC adsorbent were evaluated by various characterization techniques. The results show that S4BC calcined at 800 °C has huge specific surface area of 959.6 m2/g, developed pore structure, and high content of S (18.84 wt%). Moreover, due to the existence of sulfur and oxygen functional groups, S4BC-800 provides sufficient active sites for the adsorption of Hg2+. According to Langmuir model, the maximum adsorption capacity of S4BC-800 for Hg2+ is 724 mg/g at 313 K, and the adsorption speed is fast with excellent stability and reusability. The microfiltration membrane device based on S4BC-800 can effectively remove the low concentration of Hg2+ in the solution. In this study, a simple method for preparing SBC materials is developed, which is not only of great significance as an adsorbent for Hg2+, but also provides a new choice for the preparation of heteroatom-doped materials.

Herein, a new type of super active nitrogen-doped biochar sheet (SNBC) was prepared by two-step pyrolysis and KOH chemical activation with melamine and cherry kernel powder as precursors of nitrogen and carbon source for removing Hg2+ from wastewater. The N2 adsorption/desorption and scanning electron microscope characterization revealed that the resulted SNBC under 600 °C calcination owned huge specific surface area of 2828 m2/g and plenty of well-developed micropores, and X-ray photoelectron spectroscopy and Fourier transform-infrared spectroscopy analysis testified the existence of functional groups containing N and O, which could provide adsorption sites for Hg2+. The SNBC-600 showed high adsorption capacity for Hg2+ even at low pH, and interfering cations had little effect on the adsorption. The adsorption process was rapid and dynamic data fit the pseudo-second-order dynamic model well. The maximum adsorption capacity of Hg2+ on SNBC-600 calculated by Langmuir model was 230 mg/g. After six times of reuse, the adsorption capacity still exceeded 200 mg/g, exhibiting good reusability. The designed microfiltration membrane device base on SNBC-600 could remove low concentration of Hg2+ effectively from solution. This study provided a simple and environment-friendly method for manufacturing nitrogen-doped biochar sheet, which was of great significance in the practical application of Hg2+ pollution treatment. [ABSTRACT FROM AUTHOR]

The new-generation polyimide films with simultaneously outstanding thermal stability and low coefficient of linear thermal expansion (CTE) are urgently needed. Herein, coordination bonds were employed to improve polyimide films' heat resistance and dimensional stability. Polyimide-Cu complex films were fabricated by incorporating α-diimide units (bidentate ligands) into the BPDA-ODA (the structure of commercially available Upilex-R® polyimide films) backbones. Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and Energy dispersive X-ray mapping results showed that the coordination interactions occur between α-diimide and copper ions. Wide-angle X-ray diffraction (WAXD) and two-dimensional small-angle X-ray scattering (SAXS) spectra demonstrated that Cu-α-diimide coordination structures introduced in intermolecular chains leading polyimide films transformed from a semi-crystalline state to amorphous state, and inhibited the long-period formation structures. The plateau modulus and longer characteristic relaxation time (τ∗ = 1996.5 s) revealed by dynamic thermomechanical analysis indicated that crosslink networks were successfully formed by constructing coordination bonds. As a result, polyimide films' thermal resistance and dimensional stability were simultaneously enhanced. The typical PI-Cu50 films exhibited elevated glass transition temperatures of 353 °C (pristine PI-Cu0 ∼ 302 °C) and a lower CTE of 47.4 ppm/K (pristine PI-Cu0 films ∼ 64.4 ppm/K) in ranges of 300–400 °C, showing a promising application in the field of high-temperature environments.

Recently, many tough synthetic hydrogels have been created as promising candidates in fields such as smart electronic devices. In this paper, we propose a simple strategy to construct tough and robust hydrogels. Two-dimensional Ti3C2Tx MXene nanosheets and metal ions were introduced into poly(acrylamide-co-acrylic acid) hydrogels, the MXene nanosheets acted as multifunctional cross-linkers and effective stress-transfer centers, and physical cross-links were formed between Fe3+ and carboxylic acid. Under deformation, the coordination interactions exhibit reversible dissociation and reorganization properties, suggesting a novel mechanism of energy dissipation and stress redistribution. The design enabled the hydrogel to exhibit outstanding and balanced mechanical properties (tensile strength of up to 5.67 MPa and elongation at break of up to 508%). This study will facilitate the diverse applications of metallosupramolecular hydrogels. [ABSTRACT FROM AUTHOR]

Antibacterial photodynamic therapy (APDT) can effectively kill bacteria by generating reactive oxygen species (ROS) under laser irradiation and does not produce drug resistance, which has given rise to interest in antimicrobial therapy. Boron dipyrromethene (BDP) scaffolds have been recognized as promising photosensitizers (PSs) for APDT with high efficiency. Here, we designed BDP nanobactericides (BCu NPs) for efficient photodynamic inactivation of bacteria through the coordination interaction between carboxyl groups and copper ions. BCu NPs can cause depression of the bacterial surface as well as leakage of the contents under green light irradiation, leading to an effective destruction of bacteria. In addition, the results of in vivo experiments proved that BCu NPs can effectively kill the bacteria on the skin surface, thus effectively accelerating skin wound healing. This work illustrates a facile tactics to enable the assembly of hydrophobic dyes into nanoparticles through conjugation. [ABSTRACT FROM AUTHOR]

Metallo‐supramolecular polymers represent a powerful platform to construct self‐assembled morphologies. Copper‐thiourea (Cu‐TU) coordination interactions, though have been extensively studied in small molecular system, the role of TU motifs in synthetic polymers using metal–ligand coordination to afford supramolecular aggregation and their morphology are often overlooked. Herein, an amphiphilic random copolymer, poly(oligo(ethylene glycol) ethyl acrylate‐r‐acylthiourea) (P(OEGEA‐r‐ATU)), bearing pendant TU motifs behaving as the ligand to coordinate Cu, a design characterized by core‐coordinated metallo‐supramolecular polymer is rationally synthesized. Indeed, rod‐like nano‐objects are successfully generated via the self‐assembly and coordination interaction between P(OEGEA‐r‐ATU) and Cu. The spatial distribution of TU moieties in polymer chain, along with their Cu chelating capability, featuring the interchain coordination interaction, is tightly related to metallo‐supramolecular polymer organization. The specific Cu‐TU coordination interactions enable the prompted robustness and stability of soft P(OEGEA‐r‐ATU), induce the polymer chain configuration, which eventually furnish efficient fabrication of rod‐like nano‐objects via straightforward nanoprecipitation procedure. These structural motifs of copper‐coordinated, rod‐like nano‐objects from such metallo‐supramolecular polymers endow the potential therapeutic properties, such as anti‐inflammatory and antitumor effects. [ABSTRACT FROM AUTHOR]

Circularly polarized luminescence (CPL) enabled by chiral self‐assembly is very promising in diversified applications. However, temperature‐triggered disassembly or self‐assembly transition often results in reduction or even silence of CPL. Here, a strategy of coordinating self‐assembly is reported that offers temperature enhanced and retainable CPL that is resistant to further temperature variation. Upon co‐assembling commercial dyes with the coordinating hydrogel of cholate‐calcium, the chirality transfer from cholate to the dyes allows generation of CPL. With increasing temperature, the CPL intensity can be enhanced 4 times and the emission dissymmetry factor gem can be promoted from 0.04 to 0.1, then they remain stable either upon further elevating or lowering temperature. Mechanism study reveals that increasing temperature has triggered the coordination transition between the carbonate groups and Ca2+ from the metastable bidentate chelating to the thermal stable bridging mode, which drives the transition from flexible nanohelices to stiff helical bunches. This promotes the alignment of the dyes and in the meantime decreases its mobility, thus leads to increased CPL intensity and gem. It is envisioned that the strategy of coordinating self‐assembly would be very promising in creating thermally stable CPL for diversified applications. [ABSTRACT FROM AUTHOR]

Non-rubber components are critical in the formation of the natural rubber (NR) vulcanization network, which leads to outstanding mechanical properties of NR. This study reports the effect of NR endogenous proteins (C-serum protein/lutoid protein [CSP/LP]) on the formation of vulcanization networks at the molecular level. Results indicate that CSP/LP has a positive effect on vulcanization. Fourier-transform infrared spectroscopy and X-ray photoelectron spectroscopy analyses demonstrate that the decrease in vulcanization time of CSP/LP is ascribed to coordination interaction between Zn2+ and amide bond. The interaction increases the availability of ZnO in the matrix, thereby promoting the formation of the vulcanized network. CSP/LP also participates in the construction of the vulcanization network as a new crosslinking point, thus increasing crosslinking density and improving the mechanical properties of the NR. This study provides new research ideas for studying the relationship among component–structure–property of NR materials and developing high-strength and high-toughness elastomer materials.

Sulfur-doped biochar (S 4 BC) was prepared with cherry kernel powder as carbon source, Na 2 S 2 O 3 as sulfur source and chemical activator. Na 2 S 2 O 3 can activate biochar through the reaction with carbon, intercalation of alkali metals and the generated gas rushing out of pores, and at the same time, active sulfur atoms are doped into biochar during pyrolysis. The physical and chemical properties of S 4 BC adsorbent were evaluated by various characterization techniques. The results show that S 4 BC calcined at 800 °C has huge specific surface area of 959.6 m2/g, developed pore structure, and high content of S (18.84 wt%). Moreover, due to the existence of sulfur and oxygen functional groups, S 4 BC-800 provides sufficient active sites for the adsorption of Hg2+. According to Langmuir model, the maximum adsorption capacity of S 4 BC-800 for Hg2+ is 724 mg/g at 313 K, and the adsorption speed is fast with excellent stability and reusability. The microfiltration membrane device based on S 4 BC-800 can effectively remove the low concentration of Hg2+ in the solution. In this study, a simple method for preparing SBC materials is developed, which is not only of great significance as an adsorbent for Hg2+, but also provides a new choice for the preparation of heteroatom-doped materials. [ABSTRACT FROM AUTHOR]

Covalent organic frameworks (COFs) are attractive materials for sample pretreatment due to their tunable structures and functions. However, the precise recognition of contaminant in complex environmental matrices by COFs remains challenging owing to their insufficient specific active sites. Herein, we report Co2+ coordination-assisted molecularly imprinted flexible COF (MI-COF@Co2+) for selective recognition of ochratoxin A (OTA). The MI-COF@Co2+ was prepared via one-step polymerization of 3,3-dihydroxybenzidine, 2,4,6-tris(4-formylphenoxy)− 1,3,5-triazine, Co2+ and template. The flexible units endowed COFs with the self-adaptable ability to regulate the molecular conformation and coordinate with Co2+ to locate the imprinted cavities. The coordination interaction greatly improved the adsorption capacity and selectivity of MI-COF@Co2+ for OTA. The prepared MI-COF@Co2+ was used as solid phase extraction adsorbent for high-performance liquid chromatography determination of OTA with the detection limit of 0.03 ng mL−1 and the relative standard deviation of < 2.5 %. In addition, this method permitted interference-free determination of OTA in real samples with recovery from 89.5 % to 102.8 %. This work provides a simple way to improve the selectivity of COFs for the determination of hazardous compounds in complex environments. [Display omitted] • Co2+ coordination molecularly imprinted flexible covalent organic framework was fabricated. • MI-COF@Co2+ showed excellent selectivity for OTA extraction. • MI-COF@Co2+ gave fast kinetics and high capacity for OTA extraction. • The developed method permitted selective extraction of OTA in real samples. [ABSTRACT FROM AUTHOR]

Functionalization of graphene enables precise control over interlayer spacing during film formation, thereby enhancing the separation efficiency of radioactive ions in graphene membranes. However, the systematic impact of interlayer spacing of graphene membranes on radioactive-ion separation remains unexplored. This study aims to elucidate how interlayer spacing in functionalized graphene membranes affects the separation of radioactive ions. Utilizing polyamidoxime (PAO) to modify graphene oxide, we controlled the interlayer spacing of graphene membranes. Experimental results indicate that tuning interlayer spacing enables control of the permeation flux of radioactive ions (UO 2 2+ 1.01 × 10−5–8.32 × 10−5 mol/m2·h, and K+ remains stable at 3.60 × 10−4 mol/m2·h), and the K+/UO 2 2+ separation factors up to 36.2 at an interlayer spacing of 8.8 Å. Using density functional theory and molecular dynamics simulations, we discovered that the effective separation is mainly determined via interlayer spacing and the quantity of introduced functional groups, explaining the anomalous high permeation flux of target ions at low interlayer spacing (4.3 Å). This study deepens our comprehension of interlayer spacing within nanoconfined spaces for ion separation and recovery via graphene membranes, offering valuable insights for the design and synthesis of high-performance nanomembrane materials. [Display omitted] • GO film with diverse interlayer distances was made via PAO modification. • PAO modified GO does not affect the diffusion rate of K+. • Separation ability of GO film influenced by interlayer distance and AO synergy. • GO film with high AO and small interlayer distance displays anomalous ion diffusion. • Theoretical calculations show multiple AOs interacting with a UO 2 2+ under low interlayer spacing. [ABSTRACT FROM AUTHOR]

Recently, many tough synthetic hydrogels have been created as promising candidates in fields such as smart electronic devices. In this paper, we propose a simple strategy to construct tough and robust hydrogels. Two-dimensional Ti3C2Tx MXene nanosheets and metal ions were introduced into poly(acrylamide-co-acrylic acid) hydrogels, the MXene nanosheets acted as multifunctional cross-linkers and effective stress-transfer centers, and physical cross-links were formed between Fe3+ and carboxylic acid. Under deformation, the coordination interactions exhibit reversible dissociation and reorganization properties, suggesting a novel mechanism of energy dissipation and stress redistribution. The design enabled the hydrogel to exhibit outstanding and balanced mechanical properties (tensile strength of up to 5.67 MPa and elongation at break of up to 508%). This study will facilitate the diverse applications of metallosupramolecular hydrogels.

Supramolecular metal‐organic materials are considered as the ideal candidates for membrane fabrication due to their excellent film forming characteristics, diverse metal centers and ligand sources, and designable structure and function. However, it remains challenging to rapidly construct highly permeable supramolecular metal‐organic membranes with high salt rejection. Herein, a novel ultrafast interfacial self‐assembly strategy to prepare supramolecular metal‐organic films through the strong coordination interaction between highly active 1,3,5‐triformylphloroglucinol (TFP) ligands and Fe3+, Sc3+, or Cu2+ at the organic–aqueous interface is reported. Benefiting from the self‐completing and self‐limiting characteristics of this interfacial self‐assembly, the new kind of supramolecular membrane with optimized composition can be assembled within 3.5 min and exhibits ultrathin, dense, defect‐free features, and thus shows an excellent water permeance (21.5 L m–2 h–1 bar–1) with a high Na2SO4 rejection above 95%, which outperforms almost all of the non‐polyamide membranes and commercially available nanofiltration membranes. This strong‐coordination interfacial self‐assembly method will open up a new way for the development of functional metal‐organic supramolecular films for high‐performance membrane separation and beyond. [ABSTRACT FROM AUTHOR]

The development of smart systems for pesticidal delivery presents a significant advancement in enhancing the utilization efficiency of pesticides and mitigating environmental risks. Here an acid-responsive pesticidal delivery system using microspheres formed by the self-assembly of halloysite clay nanotubes (HNTs) is proposed. Insecticide avermectin (AVM) and herbicide prometryn (PMT) are used as two models of hydrophobic pesticide and encapsulated within the porous microspheres, followed by a coating of tannic acid/iron (TA/Fe III ) complex films to generate two controlled-release pesticides, named as HCEAT and HCEPT, resulting in the loading capacity of AVM and PMT being 113.3 and 120.3 mg g -1 , respectively. Both HCEAT and HCEPT exhibit responsiveness to weak acid, achieving 24 h-release ratios of 85.8% and 80.5% at a pH of 5.5. The experiment and simulation results indicate that the coordination interaction between EDTA 2- and Ca 2+ facilitates the spherical aggregation of HNTs. Furthermore, these novel pesticide formulations demonstrate better resistance against ultraviolet (UV) irradiation, higher foliar affinity, and less leaching effect, with negligible impact of the carrier material on plants and terrestrial organisms. This work presents a promising approach toward the development of efficient and eco-friendly pesticide formulations, greatly contributing to the sustainable advancement of agriculture., (© 2024 Wiley‐VCH GmbH.)

Aqueous Zn-ion batteries (AZIBs) are promising candidates for grid-scale energy-storage applications, but uneven Zn 2+ flux distribution and undesirable water-related interfacial side reactions seriously hinder their practical application. Herein, a strategy of regulating the coordination interaction between Zn 2+ and artificial interphase layers (AILs) to modulate the interfacial Zn 2+ desolvation/transport behaviors and relieve side reactions for building stable Zn anodes is proposed. By selectively choosing appropriate polymers with different functional groups, it is shown that compared with the strong interaction offered by aryl groups in polystyrene-based AILs, cyano groups in polyacrylonitrile (PAN)-based AILs provide a moderate coordination interaction with Zn 2+ , which not only accelerates interfacial Zn 2+ desolvation kinetics but also enables efficient Zn 2+ transport within AILs. Moreover, the Zn 2+ transport kinetics of PAN-based AILs can be further enhanced with the incorporation of an ionic conductor, zinc phosphate (ZP). Because of these advantages, the Zn anodes decorated with the hybrid AILs composed of PAN and ZP can steadily operate for >2000 h at 0.2 mA cm -2 and >350 h at a high current density of 10 mA cm -2 . This work provides a valuable guideline for selective design of AILs at the molecular level for durable AZIBs., (© 2024 Wiley‐VCH GmbH.)

Abstract Supramolecular metal‐organic materials are considered as the ideal candidates for membrane fabrication due to their excellent film forming characteristics, diverse metal centers and ligand sources, and designable structure and function. However, it remains challenging to rapidly construct highly permeable supramolecular metal‐organic membranes with high salt rejection. Herein, a novel ultrafast interfacial self‐assembly strategy to prepare supramolecular metal‐organic films through the strong coordination interaction between highly active 1,3,5‐triformylphloroglucinol (TFP) ligands and Fe3+, Sc3+, or Cu2+ at the organic–aqueous interface is reported. Benefiting from the self‐completing and self‐limiting characteristics of this interfacial self‐assembly, the new kind of supramolecular membrane with optimized composition can be assembled within 3.5 min and exhibits ultrathin, dense, defect‐free features, and thus shows an excellent water permeance (21.5 L m–2 h–1 bar–1) with a high Na2SO4 rejection above 95%, which outperforms almost all of the non‐polyamide membranes and commercially available nanofiltration membranes. This strong‐coordination interfacial self‐assembly method will open up a new way for the development of functional metal‐organic supramolecular films for high‐performance membrane separation and beyond.

A kind of terpyridine derivative (NH2-Tpy) in which the amino was incorporated by a short alkyl chain was synthesized. Through grafting of terpyridine units into the hydrophilic copolymers of maleic anhydride and acrylic acid PAAMa via the reaction of the amino groups in NH2-Tpy and the maleic anhydride units, a series of gelator polymers—P1, P2, and P3—containing different contents of terpyridine units was synthesized. Under coordination of Ni2+ and terpyridine ligands in linear polymers, the supramolecular hydrogels H1, H2, and H3 with different cross-linking degrees were prepared. The linear polymers P1–P3 had a strong absorption peak at about 290 nm in the UV-vis spectra which was attributed to π–π* transition, and there was a new peak at about 335 nm led by the metal-to-ligands charge transfer (MLCT) when coordinated with Ni2+ ions. According to the rheological behaviors, the storage modulus (G′) was larger than the loss modulus (G′′). These hydrogels showed typical gel-like characteristics when the terpyridine content of the hydrogels exceeded 10%, and the hydrogels showed liquid-like characteristics when the terpyridine content of the hydrogels was less than 7%. The results of the micromorphological investigation of the xerogels from SEM illustrated the metal–terpyridine coordination cross-linking could have an important influence on the microstructures of the resulting hydrogels. Furthermore, these hydrogels based on supramolecular cross-links exhibited reversible solution–gel transition at different environmental temperatures. At the same time, the equilibrium swelling of the supramolecular hydrogels was 8.0–12.3 g/g, which increased with the decrease in the content of the terpyridine units in the resulting hydrogels. [ABSTRACT FROM AUTHOR]

Experiencing positive emotions together facilitates interpersonal understanding and promotes subsequent social interaction among individuals. However, the neural underpinnings of such emotional-social effect remain to be discovered. The current study employed the functional near-infrared spectroscopy–based hyperscanning to investigate the abovementioned relationship. After participants in dyad watched movie clips with happily or neutral emotion, they were asked to perform the interpersonal cooperative task, with their neural activation of prefrontal cortex being recorded simultaneously via functional near-infrared spectroscopy. Results suggested that compared with the neutral movie watching together, a higher interpersonal neural synchronization (INS) in left inferior frontal gyrus during participant dyads watching happiness movie together was observed. Subsequently, dyads in happiness showed more effective coordination interaction during the interpersonal cooperation task compared to those in the neutral condition, and such facilitated effect was associated with increased cooperation-related INS at left middle frontal cortex. A mediation analysis showed that the coordination interaction fully mediated the relationship between the emotion-induced INS during the happiness movie-viewing and the cooperation-related INS in interpersonal cooperation. Taken together, our findings suggest that the faciliatory effect experiencing happiness together has on interpersonal cooperation can be reliably reflected by the INS magnitude at the brain level. [ABSTRACT FROM AUTHOR]

Developing fully rigid-chain polyimides with reversible sol-gel/gel-sol transitions is of great interest for designing high-performance materials. To date, few approaches have been employed to construct polyimide gels other than hydrogen bonding. Here, we report a polyimide-Zn(II) complex with thermo-responsive sol-gel/gel-sol transition behavior by introducing supramolecular coordination interactions. The tunable dynamic sol-gel behaviors of polyimide-Zn(II) complexes were confirmed using rheological methods. Microstructure analysis shows that coordination interactions occur between the benzimidazole molecules and Zn(II) ions. As a result, the apparent viscosity of the polyimide-Zn(II) complex even rises approximately four orders of magnitude higher than that of the PI-neat oligomer solution. Based on the 2D-correlation spectra and X-ray diffraction results, we deduced that the formation of dense chain stacking caused by coordination effects plays an essential part in the reversible sol-gel transition. As a preliminary experiment, this work gives a novel strategy to construct polyimide gels, showing application prospects in the fabrication of porous polyimide membranes, high-performance polyimide fibers, and aerogels, etc.

Metalloproteins, naturally occurring in living organisms, play crucial structural and functional roles through their unique interactions with metallic elements. Inspired by these delicate metalloproteins, a diverse array of nanostructures has been constructed based on the strategy of peptide-coordination self-assembly by virtue of metal-ligand interactions between peptide building blocks and metal ions, combined with other noncovalent interactions. The resulting peptide nanomaterials possess a variety of functions, making them a favorable option for biomedical applications due to their excellent biocompatibility and biodegradability. In this review, we provide a comprehensive overview of peptide-coordination self-assembly systems, with a specific focus on molecular design, metal-ligand coordination, and their biomedical applications. This review aims to shed light on the challenges associated with peptide-coordination self-assembly and provides critical insights for future design and applications. [Display omitted] • Nanomaterials based on peptide-coordination self-assembly are summarized. • The key interactions in peptide-coordination self-assembly are analyzed. • Biomedical applications of peptide-metal nanomaterials are discussed. [ABSTRACT FROM AUTHOR]

Thin-film composite (TFC) membranes prepared by the interfacial polymerization (IP) of amines and trimesoyl chloride (TMC) have been widely utilized for Li+/Mg2+ separation from salt-lake brine. The relatively high lithium rejection hinders the achievement of high lithium extraction efficiency. In this study, a polyphenol-metal-assisted method was designed to regulate the structure of polyethylenimine (PEI)-based polyamide nanofiltration (NF) membranes. Tannic acid (TA) was first deposited onto the substrate, followed by the impregnation of the Cu2+ ions-incorporated aqueous PEI monomer solution to establish ternary interactions among PEI, TA, and Cu2+ ions. Based on the synergistic effect of ternary interactions, the resultant PA-TA-Cu membrane possesses ultrathin thickness (≈11 nm), high positive charge, and relatively loose structure. It exhibited a high MgCl 2 rejection (95.9 %) and a low LiCl rejection (17.1 %), with a pure water permanence of 4.87 L m−2 h−1 bar−1. Furthermore, the NF membrane exhibits a high Li+/Mg2+ separation factor (26.5) and excellent long-term stability. This study provides an efficient strategy for fabricating an excellent NF membrane for lithium extraction from salt-lake brines. [ABSTRACT FROM AUTHOR]

[Display omitted] • A novel NIR fluorescent probe was designed for GSH detection. • The probe is thioctic acid-modified Ag/Au NCs (ThA@ Ag/Au NCs). • In presence of Fe3+, ThA@ Ag/Au NCs was aggregated, decreasing fluorescence emission. • Addition of GSH, it chelated Fe3+ from the surface of NCs, recovering the fluorescence emission. • The fluorescent probe was used to detect GSH in different biological samples. Accurate determination of glutathione (GSH) levels in biological fluids and food supplements is paramount. To address this need, we developed a near-infrared (NIR) fluorescent probe with high sensitivity and selectivity for GSH detection. This probe comprises thioctic acid-functionalized silver and gold nanoclusters (ThA@Ag/Au NCs), emitting red light at 720 nm upon excitation at 310 nm. In the presence of Fe3+ ions, which form complexes with ThA, the fluorescence of ThA@Ag/Au NCs is quenched due to aggregation. However, upon addition of GSH, a potent chelator for Fe3+, the fluorescence of the probe is restored, leading to enhanced emission. Under optimized conditions, the fluorescence response (F/F°) exhibits a linear relationship with increasing GSH concentration within the range of 0.03–95 µM, achieving a limit of detection (LOD) of 9.0 nM. This designed scheme demonstrates excellent selectivity, sensitivity, and accuracy for GSH detection. Furthermore, the NIR fluorescent probe effectively estimated GSH levels in various matrices, including capsules, serum, urine, and saliva samples, yielding recoveries % ranging from 97.2 % to 103.2 %, with RSD % below 4.34 %. Due to its NIR properties, this fluorescent probe holds promise for diagnosing various diseases and potential in vivo applications. [ABSTRACT FROM AUTHOR]

Adsorption for recovery of low-concentration platinum (Pt) from the complex composition of acidic digestates was challenging because of slow kinetic and poor affinity. It was expected to be overcome by the improvement of pore size distribution and adsorption site activity. Herein, a series of Prussian blue etchings (PBE) with porosity-rich and activity-high cyano (CN) was synthesized to recover low-concentration Pt. The N 2 isotherm results showed that the pore structure evolved from mesoporous to microporous. The Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculations results revealed that the modulation of electronic structure converted FeII to FeIII in [FeII(CN) 6 ]4−. The coexistence of micro- and meso-pore structures provided channels to accelerate adsorption and ensured PtII enrichment. The regulation of Fe valence state activated CN, which reinforced the strength of coordination interaction between Pt and Fe-CN- at N-atom. The adsorption rate and maximum capacity of PBE1 were 4.4 and 2.5 times higher than those of PB, respectively, due to the dual efficacy of accelerated kinetic and reinforced coordination. This study systematically analyzes the pivotal role of pore and electronic structure modulation in adsorption kinetic and affinity, which provides a novel strategy for PtII targeted recovery. [Display omitted] • A porosity-rich and CN-activated Prussian blue is prepared by simple acid etching. • PBE1 exhibits 2.5- and 4.4-fold rise in adsorption capacity and rate compared to PB. • Modulating pore structure accelerates adsorption kinetic and ensures PtII enrichment. • Regulating Fe valence state to activate CN and reinforce coordination with PtII. [ABSTRACT FROM AUTHOR]

Zinc-based aqueous batteries (ZABs) are attracting extensive attention due to the low cost, high capacity, and environmental benignity of the zinc anode. However, their application is still hindered by the undesired zinc dendrites. Despite Zn-surface modification being promising in relieving dendrites, a thick separator (i.e. glass fiber, 250-700 μm) is still required to resist the dendrite puncture, which limits volumetric energy density of battery. Here, we pivot from the traditional interphase plus extra separator categories, proposing an all-in-one ligand buffer layer (ca. 20 μm) to effectively modulate the Zn 2+ transfer and deposition behaviors proved by in situ electrochemical digital holography. Experimental characterizations and density functional theory simulations further reveal that the catechol groups in the buffer layer can accelerate the Zn 2+ reduction reaction (ZRR) through the electron-donating p-π conjugation effect, decreasing the negative charge in the coordination environment. Without extra separators, the elaborated system endows low polarization below 28.2 mV, long lifespan of 4950 h at 5 mA cm -2 in symmetric batteries, and an unprecedented volumetric energy density of 99.2 Wh L -1 based on the whole pouch cells. The concomitantly "separator-free" and "dendrite-free" conjugation effect with an accelerated ZRR process could foster the progression of metallic anodes and benefit energetic aqueous batteries., (© 2024 Wiley-VCH GmbH.)

[Display omitted] • A novel hybrid for sensitive, selective, and reliable determination of P 2 O 7 4− was constructed. • The hybrid is constructed between Al-N@CQDs and GSH@CuNCs. • Al-N@CQDs induces the fluorescence enhancement of GSH@CuNCs via AIE. • Addition of P 2 O 7 4− hindered the AIE and FRET between Al-N@CQDs and GSH@CuNCs. • The sensor was applied to detect P 2 O 7 4− in serum, urine, and water samples. In this study, a novel composite material was developed for the ratiometric detection of pyrophosphate anion (P 2 O 7 4−). This composite consisted of Al and nitrogen co-doped carbon dots (Al-N@CQDs) and glutathione-capped copper nanoclusters (GSH@CuNCs). The Al-N@CQDs component, with its high reserved coordination capacity of Al3+, induced the non-luminescent behavior of GSH@CuNCs, resulting in an aggregation-induced emission (AIE) effect. The hybrid material (Al-N@CQDs/GSH@CuNCs) exhibited dual-emission signals at 620 nm and 450 nm after integrating the two independent materials utilizing the AIE effect and the fluorescence resonance energy transfer (FRET) approach. This approach represents the first utilization of this composite for ratiometric detection. Nevertheless, upon the addition of P 2 O 7 4−, the AIE and FRET processes were hindered due to the higher coordination interaction of Al3+ towards P 2 O 7 4− compared to the amino/carboxyl groups on Al-N@CQDs. This successful interference of the AIE and FRET processes allowed for the effective estimation of P 2 O 7 4−. The response ratio (F 450 /F 620) increased with increasing the concentration of P 2 O 7 4− in the range of 0.035–160 µM, with an impressive detection limit of 0.012 µM. This innovative approach of utilizing hybrid CQDs/thiolate-capped nanoclusters as a ratiometric fluorescent sensor for analytical applications introduces new possibilities in the field. The as-fabricated system was successfully applied to detect P 2 O 7 4− in different real samples such as water, serum, and urine samples with acceptable results. [ABSTRACT FROM AUTHOR]

• Proposed a facile and eco-friendly modification method to graft CNTs onto titanium surface. • The interface between titanium and PEEK was interlinked by "coordination bridges" and CNTs network. • The interfacial shear strength between modified titanium and PEEK had an increment of 205.4 %. • The flexural strength (210.0 %), and ILSS (95.2 %) of modified CF/PEEK-Ti composites were significantly enhanced. The primary challenge of fiber metal laminates (FMLs) is the insufficient interfacial adhesion between metal and resin, which impedes the realization of the full potential. To address this issue, a two-step strategy has been proposed: firstly, via the cerium coordination-based approach, followed by grafting carbon nanotubes onto the titanium surface. This modification enhances the interfacial behavior between titanium sheets and polyetheretherketone (PEEK), resulting in increased roughness and wettability on the titanium surface, facilitating tight contact between PEEK and titanium sheets while reducing defects at the interface. Compared to CF/PEEK-sandblasted Ti, the modified CF/PEEK-Ti composites exhibit significantly enhanced interfacial shear strength, equivalent flexural strength, and interlaminate shear strength with an increase of 205.4 % (39.4 MPa), 133.3 % (1434.3 MPa) and 95.2 % (93.7 MPa), respectively. Additionally, the failure mode has shifted from interfacial failure to cohesive failure. The interface enhancement mechanism can be attributed to the synergistic effects of coordination bonding, mechanical interlocking, and multiple interactions. This facile two-step modification method demonstrates the potential to enhance the interfacial properties of CF/PEEK-Ti composites. [Display omitted] [ABSTRACT FROM AUTHOR]

A kind of terpyridine derivative (NH2-Tpy) in which the amino was incorporated by a short alkyl chain was synthesized. Through grafting of terpyridine units into the hydrophilic copolymers of maleic anhydride and acrylic acid PAAMa via the reaction of the amino groups in NH2-Tpy and the maleic anhydride units, a series of gelator polymers—P1, P2, and P3—containing different contents of terpyridine units was synthesized. Under coordination of Ni2+ and terpyridine ligands in linear polymers, the supramolecular hydrogels H1, H2, and H3 with different cross-linking degrees were prepared. The linear polymers P1–P3 had a strong absorption peak at about 290 nm in the UV-vis spectra which was attributed to π–π* transition, and there was a new peak at about 335 nm led by the metal-to-ligands charge transfer (MLCT) when coordinated with Ni2+ ions. According to the rheological behaviors, the storage modulus (G′) was larger than the loss modulus (G′′). These hydrogels showed typical gel-like characteristics when the terpyridine content of the hydrogels exceeded 10%, and the hydrogels showed liquid-like characteristics when the terpyridine content of the hydrogels was less than 7%. The results of the micromorphological investigation of the xerogels from SEM illustrated the metal–terpyridine coordination cross-linking could have an important influence on the microstructures of the resulting hydrogels. Furthermore, these hydrogels based on supramolecular cross-links exhibited reversible solution–gel transition at different environmental temperatures. At the same time, the equilibrium swelling of the supramolecular hydrogels was 8.0–12.3 g/g, which increased with the decrease in the content of the terpyridine units in the resulting hydrogels.

Metal-organic framework (MOF) based stimuli-responsive polymers (coordination polymers) exhibit reversible phase-transition behavior and demonstrate attractive properties that are capable of altering physical and/or chemical properties upon exposure to external stimuli, including pH, temperature, ions, etc., in a dynamic fashion. Thus, their conformational change can be imitated by the adsorption/desorption of target analytes (guest molecules), temperature or pressure changes, and electromagnetic field manipulation. MOF-based stimuli responsive polymers have received great attention due to their advanced optical properties and variety of applications. Herein, we summarized some recent progress on MOF-based stimuli-responsive polymers (SRPs) classified by physical and chemical responsiveness, including temperature, pressure, electricity, pH, metal ions, gases, alcohol and multi-targets. [ABSTRACT FROM AUTHOR]

Antibiotic residues in wastewater have attracted great attention for their potential toxicity to environment. In this work, a zirconium-based metal–organic framework (PCN-777) was synthesized as adsorbent to remove cephalexin from water. Attributed to synergistic effect of the electrostatic interaction and coordination interaction between MOF framework and cephalexin, PCN-777 exhibits a high adsorption capacity of 442.48 mg·g−1, which is higher than those of reported adsorbents. The adsorption behavior follows Langmuir model and pseudo-second-order model. Besides, this MOF can be reused via a simple method. Therefore, PCN-777 may have a promising potential application for purification of waste water containing trace antibiotics. [ABSTRACT FROM AUTHOR]

The new reform of power system promotes the market‐oriented operation of microgrids. The ubiquitous power internet of things provide support in information, data, and computation to microgrids in market operation, energy management, and coordination interaction. This study takes the park microgrid with multi‐stakeholder as the object, establishes a two‐level optimisation model of microgrid bidding transaction based on multi‐agent system. In the lower level optimisation, considering the deviation penalty of power generation and the previous round bidding results, the optimal bidding strategy model is established by the bidding unit agent to maximise its benefit. In the upper‐level model, bidding strategies of distributed energy resources (DERs) as constraints, a multiple objective mixed‐integer linear programming model was built to optimise the overall objectives of clearing price and imbalanced deviation, searching for the optimal clearing price and the generation plan of DERs. The results were fed back to the DERs to help them form the next round of strategies until the result reaches equilibrium. The proposed optimised operation mode is compared with the traditional operation mode in the case study, verifying that the proposed method can realise the optimal operation of the microgrid and the coordinated interaction with the main grid, increasing the benefit of stakeholders. [ABSTRACT FROM AUTHOR]

A rapid, sensitive, and selective fluorometric assay is described for the determination of chromium(VI) in real waters and living cells. The method is making use of nitrogen, phosphorus, and sulfur tri-doped carbon dots (NPS-CDs) which have absorption/emission maxima at 360/505 nm/nm. Cr(VI) has an absorption maximum at 350 nm and causes an inner filter effect (IFE) on the blue fluorescence of the NPS-CDs. The NPS-CDs were hydrothermally synthesized using p-aminobenzenesulfonic acid and tetrakis(hydroxymethyl)phosphonium chloride as precursors. The NPS-CDs were characterized by transmission electron microscopy, X-ray diffraction, and several spectroscopic methods. They are biocompatible and negligibly cytotoxic when tested with HeLa cells and MCF-7 cells even after 48 h of incubation. The NPS-CDs were used as fluorescent probes for Cr(VI). The detection limit is 0.23 μM (three times standard deviation versus slope), and the linear response covers the 1 to 500 μM chromate concentration range. The NPS-CDs were applied to the determination of Cr(VI) in real waters and living cells (HeLa and MCF-7) and gave satisfying results. [ABSTRACT FROM AUTHOR]

The formation and conservation of renewable radiation into chemical fuels via photocatalytic water splitting (WS) maintains a perspective for maximizing the economic condition and limiting the worldwide climate consequence. Photocatalytic water splitting (PWS) employing powdered semiconductors has enormous opportunity for sustainable fuel, since this crossroad connecting biological, material science, and physical sciences depicts a field with exciting multidisciplinary issues. Development in PWS has been accomplished in past decades, encompassing from basic science investigation to innovative extensible technologies. Semiconductor-based photocatalysis is regarded as a potential sustainable solution. In this regard, graphitic carbon nitride (g-C 3 N 4) is classed as a metal-free photocatalyst to overcome this energy demand and ecological challenges, because of its superior electronic structure with band energy of around 2.7 eV, strong photochemical stabilization, and higher light efficiency. The photocatalytic activity of g-C 3 N 4 is inadequate, because of its small surface area (SA) and high rate of charge recombination. Various chemical alteration techniques have been developed to address such problems, broaden the functionality ranges, and improve the characteristics of g-C 3 N 4. The present review provides an in-depth evaluation of the chemical modification techniques for g-C 3 N 4 , comprising covalently and non-covalently techniques. Covalent techniques demonstrate the formation of chemical bonding among the g-C 3 N 4 configuration and the chemical activator via oxidation/carboxylation, amidation, composite inoculation, etc., even though non-covalent techniques entail the formation of physiological bonds and interfacial properties via van der Waals connections, hydrophobic forces, etc. After these fabrication approaches, the photocatalytic performance increased due to the generation of photoinduced electrons and holes, improved light absorption ability, and boosted SA, which provides more space for photocatalytic reaction. In this review, various metals, non-metals, metals oxide, sulfides, and ferrites have been integrated with g-C 3 N 4 to form mono, bimetallic, heterojunction, Z-scheme, and S-scheme-based materials for boosting the photocatalytic performance. Also, different varieties of g–C 3 N 4 –based materials have been utilized for different aspects of photocatalytic applications such as water reduction (HER), water oxidation (OER), and overall water splitting (OWS). Therefore, we have assembled a summary of the latest modern g-C 3 N 4 nanocomposites, as well as their uses in solar energy adaptation and environmental management. This research explains the details of the mechanism for all these photocatalytic processes for the next steps, as well as many new insights to overcome the current challenges. Proposed illustration of the overview of the current aspect of g-C 3 N 4. [Display omitted] • The g-C 3 N 4 is a metal-free photocatalyst (∼2.7 eV), with strong photochemical stabilization. • The chemical modification techniques have been discussed in detail. • Advanced fabrication approaches have been discussed briefly. • Specific properties and physicochemical aspects have been depicted briefly. • Potential photocatalytic applications have been discussed in detail. [ABSTRACT FROM AUTHOR]

[Display omitted] • Co-based ionic liquid catalyst to selectively oxidise cyclohexane into adipic acid. • Coordination between anion and Co(II) in IL impacts cyclohexane oxidation. • O 2 .− and R . radicals are the active species for the cyclohexane oxidation. • Hydrogen-bond interaction improves the selectivity of adipic acid. • This protocol has great potential for the industrial production of adipic acid. Adipic acid is a significant building block of polymers and is manufactured on a massive scale, primarily to produce nylon. However, the current route depends heavily on using corrosive HNO 3 while releasing N 2 O as a potent greenhouse gas. Herein, we developed an efficient strategy for the highly selective aerobic oxidation of cyclohexane into adipic acid using metal-based ionic liquid as a catalyst. Particularly, the optimised catalyst 1-carboxymethyl-3-methylimidazolium chloride cobalt exhibited a high selectivity towards adipic acid (73.9%). It was discovered that the electron-donating ability of anions and the electrostatic between cations and anions could influence the charge density of Co(II) by anion coordination and then influence the oxidation performance. Meanwhile, the hydrogen bond interaction between the hydrogen-bond donor groups of the IL and cyclohexanone, as well as between the hydrogen-bond donor groups of the IL and the carboxylic radicals could promote the formation of adipic acid. This simple, efficient and green protocol has great potential for industrial applications in adipic acid production. [ABSTRACT FROM AUTHOR]

Abstract It is important to establish sensitive and simple analysis methods for adenosine 5′‑triphosphate (ATP). A label-free fluorescent probe for the determination of ATP was constructed based on glutathione modified silver nanoclusters (AgNCs/GSH). AgNCs/GSH showed aggregation-induced emission enhancement (AIEE) property in the organic solvent. The effects of metal ions on the fluorescence of AgNCs/GSH were also studied. Only zinc ion enhanced the fluorescence of AgNCs/GSH obviously. This was because Zn2+ coordinated with AgNCs/GSH to cause the aggregation of AgNCs/GSH, which was sufficiently proved by TEM. With the addition of ATP, Zn2+ bound with ATP through Zn O P bond and the binding between Zn2+ and AgNCs/GSH was inhibited. Hence the fluorescence of AgNCs/GSH was decreased with increasing the ATP concentration. The fluorescence response was linear in the ATP concentration range of 1–110 μM, and the detection limit was 0.8 μM. Then this method was successfully applied for determining ATP in the samples of human urine and rat serum, the recoveries were in the range of 97.6%–103%. Graphical abstract Unlabelled Image Highlights • A label-free fluorescent probe for ATP is constructed based on AgNCs/GSH with AIEE property. • Only Zn2+ causes aggregation and fluorescence enhancement of AgNCs/GSH, which is proved by TEM and fluorescence spectra. • The detection method for ATP is simple, fast, and has the practical application in detecting biological samples. [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • A ferric-chitosan complex was formed and introduced into the hydrogels. • The hydrogels exhibited tough and superior adhesive behavior. • The existence of ferric and chlorine ions endows the hydrogel conductivity. Abstract In general, chitosan should be dissolved in strong acidic media (such as acetic acid) before it could be applied as hydrogels. However, it was found that chitosan could also be dissolved in the ferric solution to form ferric-chitosan complex via coordination interaction. Subsequently, the ferric-chitosan complex was successfully introduced into the hydrogel system to obtain tough, adhesive and conductive chitosan-polyacrylamide double network (CS-PAAm DN) hydrogels. Surprisingly, CS-PAAm DN hydrogel could repeatedly adhere to various solid materials and biological tissues through physical interactions. The maximum peeling force was 256 N/m on the aluminum surface. Moreover, the hydrogel exhibited adequate mechanical performance (135 kPa, 2332%). And the introduction of ferric chloride could also endow the hydrogel with conductive performance. As a result, the strategy based on tough, adhesive and conductive polysaccharide hydrogels mediated by ferric solution would broaden the path to fabricate a new generation of soft materials for wide applications. [ABSTRACT FROM AUTHOR]

Flower-shaped organic-inorganic hybrid nanostructures, termed nanoflowers, have received considerable recent attention as they possess greatly enhanced activity, stability, durability, and even selectivity of entrapped organic biomolecules, which are much better than those from the conventional methods. They can be synthesized simply via co-incubation of organic and inorganic components in aqueous buffer at room temperature and yield hierarchical nanostructures with large surface-to-volume ratios, allowing for low-cost production by easy scale-up, as well as the high loading capacity of biomolecules without severe mass transfer limitations. Since a pioneering study reported on hybrid nanoflowers prepared with protein and copper sulfate, many other organic and inorganic components, which endow nanoflowers with diverse functionalities, have been employed. Thanks to these features, they have been applied in a diverse range of areas, including biosensors and biocatalysis. To highlight the progress of research on organic-inorganic hybrid nanoflowers, this review discusses their synthetic methods and mechanisms, structural and biological characteristics, as well as recent representative applications. Current challenges and future directions toward the design and development of multi-functional nanoflowers for their widespread utilization in biotechnology are also discussed. [ABSTRACT FROM AUTHOR]

Herein, we report the successful construction of a new family of dual stimuli‐responsive AIE cross‐linked supramolecular polymer through the strategy of hierarchical self‐assembly. A novel dipyridyl donor building block G1 containing tetraphenylethylene (TPE) moiety was designed and synthesized. Notably, two nitrile units were attached onto G1, which were employed as the guest for the further host‐guest interaction with pillar[n]arene derivatives. The rhomboidal metallacycle G2 with four nitrile units was firstly constructed through coordination‐driven self‐assembly. Subsequently, the cross‐linked supramolecular polymers H2⊃G2 were then generated through host‐guest interactions. It should be noted that the obtained supramolecular polymer displayed interesting AIE properties due to the restriction of TPE intramolecular motions within the polymeric network. More importantly, by taking advantages of dynamic nature of both coordination bonds and host‐guest interactions, the resultant supramolecular polymer displayed dual stimuli‐responsive fluorescent transitions under different stimuli such as the competitive guest and halide anion. [ABSTRACT FROM AUTHOR]

Magnetic-assisted DNA testing technology has attracted much attention in genetics, clinical diagnostics, environmental microbiology, and molecular biology. However, achieving satisfying DNA adsorption and desorption efficiency in real samples is still a big challenge. In this paper, a new kind of high-quality magnetic composite microsphere of MM@PGMA-PA-Ti 4+ was designed and prepared for DNA extraction and detection based on the strong interaction of Ti 4+ and phosphate groups. By taking the advantages of high magnetic susceptibility and high Ti 4+ content, the MM@PGMA-PA-Ti 4+ microspheres possessed remarkable extraction capacity for mimic biological samples (salmon sperm specimens) with saturated loadings up to 533.0 mg/g. When the DNA feeding amount was 100 μg and the MM@PGMA-PA-Ti 4+ dosage was 1 mg, the adsorption and desorption efficiencies were 80 and 90%, respectively. The kinetic and equilibrium extraction data were found to fit well with the pseudo-second-order model and Freundlich isotherm model. Furthermore, the MM@PGMA-PA-Ti 4+ microspheres were successfully employed for DNA extraction from mouse epithelial-like fibroblasts. The extraction ability (84 ± 4 μg/mg) and DNA purity were superior to the comparative commercial spin kits, as evaluated by electrophoresis assays and qPCR analysis. The experimental results suggest that the MM@PGMA-PA-Ti 4+ microspheres possess great potential as an adsorbent for DNA purification from complex biological samples.

Pursuing high energy and power density in all-solid-state lithium batteries (ASSLBs) has been the focus of attention. However, due to their inferior ion transport, their rate performance is limited compared to traditional lithium-ion batteries. Herein, a dual-coordination mechanism is first proposed to construct a high-performance poly(vinylidene fluoride)/Li 6.4 Ga 0.2 La 3 Zr 2 O 12 /succinonitrile (PVDF/LLZO/SN) composite solid electrolyte. The dual-coordination interactions of SN with both LLZO and Li + in lithium salts allow SN to act like a branched chain of PVDF, realizing an increase in the free volume of the composite electrolyte. Meanwhile, SN molecules are immobilized within the electrolyte membrane by coordinating with LLZO, ensuring good interfacial stability. Profiting from the dual-coordination mechanism, the PVDF/LLZO/SN composite solid electrolyte combines enhanced electrochemical performance and interfacial compatibility. When applied to ASSLBs, the composite solid electrolyte enables the battery to operate at rates up to 6 C. The LiFePO 4 /Li batteries operated at 4 C can still deliver a high capacity retention rate of 96.4% after 50 cycles. Notably, these batteries also exhibit good long-cycle stability. After 500 cycles at 0.5 C, the discharge capacity was maintained at 145.9 mAh g -1 .

Construction of nanochannels with a delicate structure in nanocomposite membranes has emerged as a promising way to realize selective permeation, but is always stumbled by the organic-inorganic incompatibility and poor nanofiller dispersion. As such, much effort focuses on introducing weak noncovalent or strong covalent interactions by tailoring the composition of nanofiller surface. However, too weak or too strong interfacial interactions may lead to unfavorable interfacial structures with inefficiency for ion/organic molecule separation. Herein, inspired by the metal-fortified adhesion phenomenon of marine mussels, we developed a facile interfacial polymerization approach mediated by moderate catechol-Ti IV coordination interactions to fabricate TiO 2 -polyarylate (PAR) thin-film nanocomposite (TFN) membranes with selective interfacial nanochannels. Tannic acid (TA), a polyphenol rich in pyrogallol groups, was selected as the aqueous monomer with tetrabutyl titanate (TBT) in organic solution as the TiO 2 precursor. TA could partially chelate with Ti IV , control the sol-gel reaction and generate homogeneously dispersed TiO 2 nanoparticles (NPs) during membrane formation. The residual catechol/pyrogallol groups in the PAR matrix can further form moderate catechol-Ti IV coordinates during water compaction, constructing interfacial nanochannels with tunable structures ( e.g. size and connectivity) spontaneously. The permeation of water and ions was facilitated, leading to an enhanced water flux as well as superior ion/organic molecule selectivity. Meanwhile, the TFN membrane showed a good long-term operational stability for dye/salt separation. Since the catechol groups can coordinate with various metal-based materials, this approach is applicable to tailor the organic-inorganic interfaces for a broad range of TFN membranes. [ABSTRACT FROM AUTHOR]

The authors have immobilized nanowires made from zirconium glycerolate (ZrGly) on magnetite (Fe3O4) nanoparticles by applying a solvothermal growth process using metal-glycerolate as a precursor. The structure and the dissolutionrecrystallization mechanism of the resulting Fe3O4@ZrGly composite were investigated by attenuated total reflection-FTIR, energy-dispersive X-ray analysis, thermogravimetric analysis and solid-state cross polarization/magic angle spinning 13C NMR spectroscopy. The interaction between the zirconium glycerolate in Fe3O4@ZrGly and cis-diols leads to efficient adsorption of riboncleosides which then can be quantified by HPLC with UV detection. The sorbent was successfully applied to the selective enrichment of adenosine, cytidine, uridine and guanosine from spiked human urine samples. The detection limit of the method is in the range from 1.7 to 19 ng⋅mL-1 of nucleosides in spiked human urine, with relative standard deviations of lower than 12.4% and recoveries ranging from 90.6 to 113%. [ABSTRACT FROM AUTHOR]

Layered double hydroxides (LDHs) have gained much attention in absorption and extraction fields due to their special structure and properties like high porosity, large surface area and excellent anion exchange capacity. However, LDHs are rarely used in capillary electrochromatography (CEC) by date due to the lack of appropriate immobilization method. In this work, by utilizing the unique coordination bonding between metal ions on LDHs and catechol groups on polydopamine layer, a polydopamine modification method was developed for in situ immobilization of LDHs on the inner surface of fused silica capillary. The formation of CoAl-LDHs on polydopamine-immobilized capillary has been characterized by scanning electron microscopy, Fourier transform infrared spectroscopy and X-ray diffraction. The CoAl-LDHs-modified open-tubular capillary exhibited good separation performance towards neutral compounds by cation-π interaction and hydrophobic interaction. More interestingly, by virtue of the coordination interaction between metal ions on LDHs layer and phenolic hydroxyl groups, the LDHs-modified capillary has shown good separation efficiency towards various phenolic compounds. Repeatability of the column was studied, with the relative standard deviations for intra-day, inter-day and column-to-column lower than 4.3%. [ABSTRACT FROM AUTHOR]

Lead is a toxic heavy metal that is highly harmful to humans. Developing fast, efficient, and separable materials to treat lead-contaminated wastewater is challenging. In this paper, Cu-based MOF composite (SCC-CuMOF) was prepared by in-situ growth method and used for the removal of Pb2+ from aqueous solutions. The obtained materials were characterized by field emission scanning electron microscope (FESEM), energy dispersive spectroscopy (EDS) mapping, Brunauer-Emmett-Teller (BET) specific surface area, X-ray diffraction (XRD) and infrared spectroscopy (IR). The effects of pH, coexisting ions, contact time, initial ion concentration, and temperature on the removal of Pb2+ were investigated. SCC-CuMOF exhibited excellent adsorption performance on Pb2+. Adsorption of Pb2+ on SCC-CuMOF were in accordance with the pseudo-second-order model and Langmuir model. The adsorption thermodynamic study suggested that the adsorption process was spontaneous and endothermic. The results revealed that Pb2+ might be adsorbed onto SCC-CuMOF via ion exchange and coordination interaction. In general, SCC-CuMOF has the potential to remove Pb2+ from wastewater rapidly and efficiently. The study prepared SCC-CuMOF composites by in situ growth of Cu-based MOF on the hydrogel SCC-Cu surface for the removal of Pb2+ from aqueous solutions. [Display omitted] • Cu-based MOF composite (SCC-CuMOF) was prepared by in-situ growth method. • SCC-CuMOF exhibited excellent adsorption performance on Pb2+. • The maximum adsorption capacity for Pb2+ was 531.38 ​mg/g at 308 ​K. • The mechanism of Pb2+ adsorption on composites is thoroughly discussed. [ABSTRACT FROM AUTHOR]

Polyether surfactant was employed for the regeneration of a poisoned by calcium V 2 O 5 -WO 3 /TiO 2 catalyst. The OP-10 (alkylphenol polyoxyethylene (10) ether) surfactant exhibited better CaO removal performance than EL-60 (cremophor EL 60) and AEO9 (polyethyleneglycol (9) mono-dodecyl ether). The Ca 2 + -aromatic interactions developed in OP-10 increased the solubility of CaO in water and Ca 2 + could be removed by washing. The high Ca 2 + removal rate by OP-10 surfactant led to the reversible improvement of surface acid sites and active oxygen species. Compared with the traditional method of dilute sulfuric acid solution, the OP-10 presented higher Ca 2 + removal rate with lower V 2 O 5 loss, which is expected to be a facile and environmental benign method for the regeneration of Ca 2 + -poisoned NH 3 -SCR industrial catalysts. [ABSTRACT FROM AUTHOR]

The nanofiltration (NF) membranes with the specific separation accuracy for molecules with the size of 0.5–2 nm have been applied in various industries. However, the traditional polymeric NF membranes still face problems like the trade-off effect, organic solvent consumption, and weak durability in harsh conditions. The participation of coordination action or metal-organic coordination compounds (MOCs) brings the membrane with uniform pores, better antifouling properties, and high hydrophilicity. Some of the aqueous-phase reactions also help to introduce a green fabrication process to NF membranes. This review critically summarizes the recent research progress in coordination chemistry relevant NF membranes. The participation of coordination chemistry was classified by the various functions in NF membranes like additives, interlayers, selective layers, coating layers, and cross-linkers. Then, the effect and mechanism of the coordination chemistry on the performance of NF membranes are discussed in depth. Perspectives are given for the further promotion that coordination chemistry can make in NF processes. This review also provides comprehensive insight and constructive guidance on high-performance NF membranes with coordination chemistry. [Display omitted] • The roles coordination chemistry plays in NF membrane are summarized. • The advantages of coordination chemistry in NF membrane are discussed. • The mechanism of coordination action in NF membrane are explained. • Fundamental and practical challenges in the coordination chemistry for NF membrane are presented. [ABSTRACT FROM AUTHOR]