The preparation of three-color mechanofluorochromic molecules is of crucial importance in the development of mechanically responsive smart materials with multicolor switching feature. Unfortunately, the related mechano-responsive luminogenic compounds are rare. In this work, four fluorene derivatives, which contain various sites of biphenyl or naphthalene, were synthesized. Interestingly, compounds 1-4 exhibited diverse high-brightness solid-state fluorescence and observable fluorescent changes in response to mechanical force stimulus. For fluorophor 1 in the solid state, upon light grinding, an orange-yellow to yellow-green mechanofluorochromic transition with the notable blue shift of 85 nm was noticed, and the yellow-green to yellow bathochromic mechanofluorochromic response was observed after vigorous grinding. Therefore, fluorogen 1 showcased an unfrequent bidirectional tricolored mechanofluorochromism with a blue shift followed by a red shift. As for luminogens 2-4 exhibited diverse two-color reversible red-shifted mechanofluorochromic responses. Furthermore, their mechanochromic emissive mechanisms of 1-4 were investigated by X-ray powder diffraction tests.

Homogentisate solanesyltransferase (HST) is a crucial enzyme in the plastoquinone biosynthetic pathway and has recently emerged as a promising target for herbicides. In this study, we successfully expressed and purified a stable and highly pure form of seven times transmembrane protein Chlamydomonas reinhardtii HST ( Cr HST). The final yield of Cr HST protein obtained was 12.2 mg per liter of M9 medium. We evaluated the inhibitory effect on Cr HST using Des-Morpholinocarbony Cyclopyrimorate (DMC) and found its IC 50 value to be 3.63 ± 0.53 μM, indicating significant inhibitory potential. Additionally, we investigated the substrate affinity of Cr HST with two substrates, determining the K m values as 22.76 ± 1.70 μM for FPP and 48.54 ± 3.89 μM for HGA. Through sequence alignment analyses and three-dimensional structure predictions, we identified conserved amino acid residues forming the active cavity in the enzyme. The results from molecular docking and binding energy calculations indicate that DMC has a greater binding affinity with HST compared to HGA. These findings represent substantial progress in understanding Cr HST’s properties and potential for herbicide development. Key points • First high-yield transmembrane CrHST protein via E. coli system • Preliminarily identified active cavity composition via activity testing • Determined substrate and inhibitor modes via molecular docking

Lithium-sulfur batteries (LSBs) have attracted considerable attention due to their high capacity and energy density, however, the electrochemical performance of LSBs was limited by the difficult conversion of lithium polysulfides (LiPSs). Coordination supramolecular networks (CSNs) have flexible structures, abundant active sites, and intermolecular interactions, which can facilitate the transformation of LiPSs and ion/charge transport. Herein, we combined a zinc coordination supramolecular network (Zn-CSN) with MnO2 to synthesize Zn-CSN@MnO2via a one-pot method. Zn-CSN@MnO2 accelerates the evolution of LiPSs and promotes the migration of lithium ions. Zn-CSN@MnO2 as a sulfur host in LSBs displays outstanding rate performance (406.55 mAh g-1 at 4C). It has a high initial specific capacity of 1027.89 mAh g-1 at 0.5C, cycling 150 cycles with a capacity loss of 0.2% per cycle. Surprisingly, it runs 400 cycles at a high current density of 5C with a capacity retention of 80.5%. This synergistic strategy for CSNs and oxides has brightened the prospects of the practical applications of LSBs. Zinc coordination supramolecular network (Zn-CSN) combined with MnO2 to obtained the Zn-CSN@MnO2, Zn-CSN@MnO2 as a sulfur host achieves high-rate performance of lithium-sulfur batteries.

Prussian blue analogs (PBAs) have been considered as a kind of promising cathode materials, but its poor cycle performance severely hinders their industrialization. Herein, by combining a zinc ferrocyanide (ZnHCF) cathode with aqueous ZnSO4/LiTFSI electrolyte and zinc metal anode, we achieved a stable anion insertion-type aqueous dual-ion battery (DIB) which displays a discharge specific capacity of 75.9 mAh g–1, an energy density of 124 Wh kg–1, and a discharge plateau of 1.8 V at 5 A g–1. Its specific capacity can still reach 57.4 mAh g–1 after 1200 cycles with a Coulombic efficiency of 97 %. A reversible anion insertion mechanism of ZnHCF cathode based on the changes of the valency of iron and the insertion of TFSI– ion on crystal surface caused by electrostatic interaction is proposed and confirmed with a series of characterizations and density functional theory calculations (DFT). This work proposes the study of anion energy storage mechanism of PBAs and brings more opportunities for their large-scale applications in the future.

Iodine has great potential in the energy storage, but high solubility of I 3 − has seriously delayed its promotion. Benefited from abundant active sites and the open channel, two-dimensional coordination supramolecular networks (2D CSNs) is considered to be a candidate for the energy storage. Herein, a 2D porphyrin-CSN cathode named Zn-TCPP for aqueous iodine dual-ion battery (DIB) shows an excellent specific capacity of 278 mAh g −1 , and a high energy density of 340 Wh kg −1 at 5 A g −1 , as well as a durable cycle performance of 5000 cycles and a high Coulombic efficiency of 98 %. Molecular orbital theory, UV/VIS, Raman spectroscopy and density functional theory (DFT) calculations reveal charge-transfer interaction between the donor of porphyrin nitrogen and the acceptor of I 3 − , and computational fluid dynamics (CFD) simulations demonstrate the contribution of 2D layered network structure of Zn-TCPP to the penetration of I 3 − .

Aqueous zinc metal batteries (ZMBs) are a promising sustainable technology for large-scale energy storage applications. However, the water is often associated with problematic parasitic reactions on both anode and cathode, leading to the low durability and reliability of ZMBs. Here, a multifunctional separator for the Zn-V2 O5 batteries by growing the coordination supramolecular network (CSN:Zn-MBA, MBA = 2-mercaptobenzoic acid) on the conventional non-woven fabrics (NWF) is developed. CSN tends to form a stronger coordination bond as a softer cation, enabling a thermodynamically preferred Zn2+ to VO2+ substitution in the network, leading to the formation of VO2 -MBA interface, that strongly obstructs the VO2 (OH)2- penetration but simultaneously allows Zn2+ transfer. Moreover, Zn-MBA molecules can adsorb the OTF- and distribute the interfacial Zn2+ homogeneous, which facilitate a dendrite-free Zn deposition. The Zn-V2 O5 cells with Zn-MBA@NWF separator realize high capacity of 567 mAh g-1 at 0.2 A g-1 , and excellent cyclability over 2000 cycles with capacity retention of 82.2% at 5 A g-1 . This work combines the original advantages of the template and new function of metals via cation metathesis within a CSN, provides a new strategy for inhibiting vanadium oxide dissolution.

The search for high-energy and fast Li-ion transportation of lithium-ion battery (LIB) anode materials instead of graphite has aroused the wide attention of scientists. Coordination supramolecular networks (CSNs) are a class of active materials that can be used in energy storage devices because of their adjustable structural characteristics and various intermolecular forces. In this work, 1D-CoCSN {[Co3(stp)2(bpy)5(H2O)6]n} and 3D-CoCSN {[Co3(stp)2(bpy)(H2O)4]n} were synthesized by regulating the coordination reaction of 2-sulfoterephthalic acid monosodium salt (NaH2stp), 4,4 '- bipyridine (bpy), and cobalt ions. The X-ray photoelectron spectroscopy (XPS), ex situ Fourier transform infrared spectroscopy (FTIR), and density functional theory (DFT) analyses show that the carboxylic, sulfonic, and pyridine active groups of 1D-CoCSN are synergically involved in the storage process of lithium ions, and electrons could be transferred in the Z-shaped chain structure through the pi-d-pi conjugation effect. Hence, 1D-CoCSN exhibits a high capacity of 567 mAh g-1 after 200 cycles at 0.5 A g-1 and even runs 1000 cycles at 2 A g-1 with a capacity of 233 mAh g-1. Structural regulation of CSNs provides a new approach to designing LIB anodes with high capacity and stable cycling performance.

Rapid advances in mild aqueous zinc metal batteries (AZMBs) have provided broader prospects for energy storage. However, practical application of AZMBs is hampered by issues such as formation of dendrites, by-products and hydrogen evolution. Herein, we report a new type of zinc anodes coated with Coordination Supramolecular Networks (CSNs) of zinc dithiosalicylate (Zn-DTA) prepared by in-situ chemical growth. The Zn-DTA layer acts as a natural barrier to inhibit the two-dimensional diffusion of zinc ions on the surface, leading to the uniform deposition. Abundant active sites provided by the coordination network also effectively facilitates the rapid transport of zinc ions inside and improves the electrochemical kinetics. As a result, symmetrical cells assembled with Zn-DTA@Zn electrode exhibit prominent performance of working stably for 2000 h at 1 mA cm −2 . The zinc-copper cells operated for 2000 h while Coulombic efficiency closing to 100%. In addition, the Zn//V 2 O 5 full batteries reveal excellent rate performance and cycled for 1500 h at 2 A g −1 . We believe that introduction of the multifunctional CSNs can irritate new ideas for the design of anodes. The facile and efficient in-situ growth Zn-DTA coating also makes the scale application of AZMBs step forward.

Aqueous zinc-metal batteries (ZMBs) have stood out from other rechargeable metal batteries due to their high safety, low cost, and stability in neutral electrolytes. However, the capacity decay and sluggish kinetics of the cathode hinder further commercial application of ZMBs. Herein, we construct a novel vanadium coordination supramolecular network (V-CSN) via a facile one-step hydrothermal synthesis, as a cathode for aqueous ZMBs. The multiple active sites and dual energy storage mechanism originate from the redox of the vanadium oxygen center (V5+/V4+) and the donors on the ligand (carboxyl group and S atoms), which are synergistically involved in the storage of zinc ions, effectively enhancing the reversible cycle performance. Meanwhile, the large interplanar spacing, small band gap, and flexible CSN structure of V-CSN endowed it with fast kinetics and effectively hinder the dissolution of active materials. Consequently, the V-CSN cathode exhibits an outstanding rate capacity of 177.1 mA h g-1 at 0.2 A g-1 and ultra-long cycle lifespan of over 20 000 cycles at 5 A g-1 with a coulombic efficiency of & SIM;100 %. Moreover, density functional theory calculations reveal that the cathode has remarkable electrical conductivity and strong adsorption effect with zinc ions (& UDelta;Eads = -2.9 eV). This work offers a new insight into the construction of a CSN host with abundant active sites, providing a new strategy for the design of high-performance rechargeable aqueous ZMBs. A novel vanadium coordination supramolecular network was synthesized, and employed as the cathode for zinc metal batteries, and exhibit excellent rate performance and ultra-long cycle life.

L-kynurenine (L-kyn) is a marker of prostate cancer.At present,the expensive instruments are usually applied to detect L-kyn clinically,which limits its wide application for cancer diagnosis.Herein,three lanthanide metal-organic frameworks ([Ln(CHO2)3]n,Ln Eu,Gd,and Tb) were designed and obtained,and detailly characterized by single crystal X-ray diffraction (SCXRD),powder X-ray diffraction(PXRD),Fourier transform infrared spectroscopy (FT-IR),thermogravimetric analysis (TGA),and lumi-nescence spectroscopy.Further study reveals that[Tb(CHO2)3]n is a highly selective,ultra-sensitive,of strong anti-interference,highly stable,and non-expensive sensor for prostate cancer marker L-kyn.The limit of detection (LOD) for L-kyn sensing is a highly sensitive value of 1.0 × 10-9 mol/L.Furthermore,the sensing mechanism is discussed in detail.

Iodine is considered to have broad application prospects in the field of electrochemical energy storage. However, the high solubility of I3- severely hampers its practical application, and the lack of research on the anchoring mechanism of I3- has seriously hindered the development of advanced cathode materials for iodine batteries. Herein, based on the molecular orbital theory, we studied the charge-transfer interaction between the acceptor of I3- with a σ* empty antibonding orbital and the donor of pyrimidine nitrogen with lone-pair electrons, which is proved by the results of UV-vis absorption spectroscopy, Raman spectroscopy, and density functional theory (DFT) calculations. The prepared dual-ion battery (DIB) exhibits a high voltage platform of 1.2 V, a remarkable discharge-specific capacity of up to 207 mAh g-1, and an energy density of 233 Wh kg-1 at a current density of 5 A g-1, as well as outstanding cycle stability (operating stably for 5000 cycles) with a high Coulombic efficiency of 97%, demonstrating excellent electrochemical performance and a promising prospect in stationary energy storage.

The level of L-kynurenine (L-kyn) can reflect the health state of human body, and the determination of L-kyn can be used for the medical diagnosis of several cancers and neurological diseases. In this work, a series of air-, water-, and thermo-stable dinuclear lanthanide nanoclusters [Ln2(2,5-DFBA)6(phen)2] (Tb 1, Eu 2, Gd 3, 2,5-DFBA = 2,5-difluorobenzoic acid, phen = 1,10-phenanthroline) are obtained by a facial method. 1 and 2 show very high luminescence quantum yields (QYs) of 71.7% and 81.8%, respectively. Interestingly, investigation reveals that 1 is a quick, highly sensitive and selective sensor for L-kyn in real samples of urine and serum. Furthermore, transmission electron microscope (TEM) results reveal that nanocluster 1 is stable in solution and can be uniform distributed on the base, suggesting it can be deposited on various supports to fabricate sensing devices. Thus, 1 is fabricated into a sensitive test paper for the eye-readable detection of L-kyn in real samples of human urine and serum. The limit of detection (LOD) as low as 0.3 μM, which is enough to rapidly determine L-kyn in human body liquor (usually 5 μM in healthy human body).

Commercialization of aqueous zinc-metal batteries remains unrealistic due to the substantial dendrite growth and side reaction issues on the zinc anodes. It is highly demanded to develop easy-to-handle approaches for constructing stable, dense, as well as homogeneous solid anode/electrolyte interfaces. Herein, the authors construct the zinc anode interface with a close-packed Zn-TSA (TSA = thiosalicylate) coordination supramolecular network through the facile and up-scalable wet-chemical method. The hydrophobic Zn-TSA network can block solvated water and establish a solid-state diffusion barrier to well-distribute the interfacial Zn2+ , thus inhibiting hydrogen evolution and zinc dendrite growth on the anode. Meanwhile, the Zn-TSA network induces the formation of a uniform and stable solid electrolyte interphase composed of multiple inorganic-organic compounds. This denser structure can accommodate and self-heal the crack/degradation of the anode interphase associated with the repeated volume changes, and suppress the generation of detrimental by-product, Znx (OTF- )y (OH)2x-y ·nH2 O. Such a rationally fabricated anode/electrolyte interface further endows the assembled symmetric cells with superior plating/stripping stability for over 2000 h without dendrite formation (at 1 mA cm-2 and 1 mAh cm-2 ). Furthermore, this zinc anode has practical application in the Zn-MoS2 and Zn-V2 O5 full cells. This study provides a new train of thought for constructing the dense interface of zinc-metal anode.

Infrastructure systems play a crucial role in ensuring the safety of cities and the well-being of residents after earthquakes. Meanwhile, infrastructure systems are vulnerable to earthquakes and may fail to provide necessary services, highlighting the significant need to improve seismic emergency performance. Nevertheless, the seismic emergency performance of infrastructure systems still lacks effective enhancement strategies and optimization models, which makes it challenging to devise and benchmark appropriate emergency enhancement actions. This study proposes an emergency performance optimization model for infrastructure systems against earthquakes. The model aims at maximizing the effects of resistance actions and short-term recovery actions on infrastructure systems with consideration of residents' expectations of infrastructure performance after earthquakes. The efficacy of the proposed model is tested by a case study in China. Experiments and results illustrate advantages of the seismic emergency performance optimization and prioritize resistance and short-term recovery activities within constraints set by available resources.

Two series of three dimensional (3D) lanthanide metal-organic frameworks (LnMOFs) of [Ln(tftpa)1.5(phen)(H2O)]n (Ln = Sm 1a, Eu 1b, Tb 1c, Dy 1d, H2tftpa = tetrafluoroterephthalic acid, phen = 1,10-phenanthrolin) and [Ln(tftpa)1.5(bpy)((HO)-O-2)]n (Ln = Sm 2a, Eu 2b, Tb 2c, Dy 2d, bpy = 2,2?-bipyridine) are obtained by structural regulation. Results reveal that the 3D LnMOFs show high water-and thermal-stability. Interestingly, through selecting the perfluorinated ligand, and using bpy as an auxiliary ligand to hold back the solvents near to the lanthanide ions, 2b, and 2c show high luminescence quantum yield (QY) of 74.50% and 60.03%, respectively. In order to further improve the luminescence QY, the auxiliary ligand of phen with larger conjugation and more rigid structure is synthesized to replace bpy, and fortunately, higher luminescence QY of 80.73% (1b) and 75.17% (1c) are realized.

In this work, based on two ligands of 2,4-difluorobenzoic acid (2,4-DFBA) and 1,10-phenanthroline (phen), a series of new lanthanide complexes [Ln(2)(2,4-DFBA)(6)phen(2), Ln = Tb 1a, Eu 1b, Gd 1c) and Tb,Eu co-doped complex [2, Tb1.976Eu0.0244(2,4-DFBA)(6)phen(2)] were successfully synthesized. It was found that 2 is an interesting multichannel readout pattern and self-calibrated temperature sensor, with a wide temperature sensing range in 77-300 K. It shows a high sensitivity up to 2.3%/K.

A new lanthanide coordination polymer (LnCPs) of {[Tb-2(4-BMBA)(6)(H2O)(4)]center dot(4,4' -bpy)} n (TbCPs, 4-BMBA = 4-bromo-3-methylbenzoic acid, 4,4'-bpy = 4,4'-bpy) was obtained successfully by the introduction of 4-BMBA. The optical properties of TbCPs are studied, and in the subsequent sensing experiments, it is found the TbCPs is a highly selective sensor for Ca2+, and it shows excellent electrochemical property. (C) 2021 Elsevier B.V. All rights reserved.

Real-time and visual monitoring of pollutants in the air is of great importance since they are usually cannot be seen, smelled, or touched. Lanthanide nano-cluster is a kind of luminescent sensor for various species. However, controlling synthesis of lanthanide nano-cluster remains experimentally challenging. In this work, four series of lanthanide-barium (Ln-Ba) nano-clusters of Dy2Ba (1), Tb2Ba2 (2), Ln4Ba3 (Ln = Tb, 3a; Eu, 3b), Tb4Ba4 (4) were assembled through precisely controlling the pH of the reactant solutions. The work features the first example that the number of cluster's nuclei changes regularly with the pH. Moreover, investigation reveals that nano-cluster 3a is a highly selective and sensitive sensor towards acetylacetone (acac) and aniline. Interestingly, easy-to-use sensing devices of test paper, agarose gel, and five kinds of film on CaCO3, polyfoam, coin, mask, and wall that based on 3a were fabricated by facile methods. The seven sensing devices showed remarkable ability to sense aniline and acac vapors with visibility to the naked eyes. This is the first work on multiple real-time and visual sensing devices based on the lanthanide nano-cluster.