Under the condition of solvothermal synthesis,the viologen ligand 1,1′-bis(3-carboxyphenyl)-(4,4′-bipyri-dine)dichloride(H_(2)bcbpy·2Cl)and KI are coordinated with the metal cadmium ions.A case of thermochromic...Under the condition of solvothermal synthesis,the viologen ligand 1,1′-bis(3-carboxyphenyl)-(4,4′-bipyri-dine)dichloride(H_(2)bcbpy·2Cl)and KI are coordinated with the metal cadmium ions.A case of thermochromic coor-dination polymer[Cd(bcbpy)I_(2)]·2H_(2)O(1)was constructed.Complex 1 displays a 1D chain structure and exhibits thermochromic behavior.Under different temperature stimulation,the complex(ground)slowly changed from green to yellow-green,and with the increase of temperature,the color of complex 1 gradually deepened,and finally became orange-yellow.Therefore,complex 1 was prepared as a thermochromic film.In addition,we also performed electrochemical tests on complex 1,which showed that the complex is a semiconductor material.CCDC:2391802.展开更多
Mesoporous metals with large surface area,high pore volume,and uniform pore structure hold excellent advantages for various applications.However,the state-of-the-art synthesis methods are still limited to wet chemistr...Mesoporous metals with large surface area,high pore volume,and uniform pore structure hold excellent advantages for various applications.However,the state-of-the-art synthesis methods are still limited to wet chemistry,which requires excessive solvents and a time-consuming drying process.Here,we report a facile and general mechanochemical coordination self-assembly strategy to prepare mesoporous metals(e.g.,Rh,Ru,Ir,Pt,Pd,Ag,Co,and Ni)with remarkable porous properties by using metal chlorides and cationic polymer interplay.Compared with the wet chemistry process,this method proceeds without solvents and does not need complicated experimental conditions and long synthetic periods,which not only greatly reduces the consumption of cost and energy and environmental pollution,but also improves the synthesis efficiency and yield of target products.We believe the developed approach will provide a general pathway for the scalable preparation of advanced porous materials.展开更多
Polymerase chain reactions(PCR)are a very important tool for use in cloning,nucleic acid sequencing and diagnostic testing.The storage conditions of PCR reagents are limited to freezing and a lot of mixing steps are n...Polymerase chain reactions(PCR)are a very important tool for use in cloning,nucleic acid sequencing and diagnostic testing.The storage conditions of PCR reagents are limited to freezing and a lot of mixing steps are needed.In this paper,we report using metal ions to form coordination nanomaterials with the intrinsic components of the PCR reagents including dNTP,DNA primers and DNA polymerase as an integrated PCR reaction system.To complete PCR reactions,users need only to dissolve the coordination nanomaterials with a buffer and add template DNA.A few transition metal ions were screened and Cu^(2+)was found to be the most effective metal ion for this purpose.Then the encapsulation efficiency of PCR reagents was measured,which can reach close to 100%for the primers and DNA polymerase,but only 10%for dNTP because dNTP was excess.Further study also exhibited this integrated PCR reaction system can be used for DNA detection with a similar detection limit to the normal PCR,and showed good stability of encapsulated PCR nanomaterial after storage for a week.展开更多
Recently,hollow carbon nanospheres(HCSs)have garnered significant attention as potential Li metal hosts owing to their unique large voids and ease of fabrication.However,similar to other nanoscale hosts,their practica...Recently,hollow carbon nanospheres(HCSs)have garnered significant attention as potential Li metal hosts owing to their unique large voids and ease of fabrication.However,similar to other nanoscale hosts,their practical performance is limited by inhomogeneous agglomeration,increased binder requirements,and high tortuosity within the electrode.To overcome these problems and high tortuosity within the electrode,this study introduces a pomegranate-like carbon microcluster composed of primary HCSs(P-CMs)as a novel Li metal host.This unique nanostructure can be easily prepared using the spray-drying technique,enabling its mass production.Comprehensive analyses with various tools demonstrate that compared with HCS hosts,the P-CM host requires a smaller amount of binder to fabricate a sufficiently robust and even surface electrode.Furthermore,owing to reduced tortuosity,the well-designed P-CM electrode can provide continuous and shortened pathways for electron/ion transport,accelerating the Li-ion transfer kinetics and prohibiting preferential Li plating at the upper region of the electrode.Due to these characteristics,Li metal can be effectively encapsulated in the large inner voids of the primary HCSs constituting the P-CM,thereby enhancing the electrochemical performance of P-CM hosts in Li metal batteries.Specifically,the Coulombic efficiency of the P-CM host can be maintained at 97%over 100 cycles,with a high Li deposition areal capacity of 3 mAh·cm^(-2)and long cycle life(1000 h,1 mA·cm^(-2),and 1.0 mAh·cm^(-2)).Furthermore,a full cell incorporating a LiFePO4 cathode exhibits excellent cycle life.展开更多
With the boom in maritime activities,the need for highly reliable maritime communication is becoming urgent,which is an important component of 5G/6G communication networks.However,the bandwidth reuse characteristic of...With the boom in maritime activities,the need for highly reliable maritime communication is becoming urgent,which is an important component of 5G/6G communication networks.However,the bandwidth reuse characteristic of 5G/6G networks will inevitably lead to severe interference,resulting in degradation in the communication performance of maritime users.In this paper,we propose a safe deep reinforcement learning based interference coordination scheme to jointly optimize the power control and bandwidth allocation in maritime communication systems,and exploit the quality-of-service requirements of users as the risk value references to evaluate the communication policies.In particular,this scheme designs a deep neural network to select the communication policies through the evaluation network and update the parameters using the target network,which improves the communication performance and speeds up the convergence rate.Moreover,the Nash equilibrium of the interference coordination game and the computational complexity of the proposed scheme are analyzed.Simulation and experimental results verify the performance gain of the proposed scheme compared with benchmarks.展开更多
A tin-oxygen coordination driving self-assembly was developed in the block copolymers containing organotin, which were prepared by the radical addition-fraction transfer（RAFT） method and characterized by the gel-per...A tin-oxygen coordination driving self-assembly was developed in the block copolymers containing organotin, which were prepared by the radical addition-fraction transfer（RAFT） method and characterized by the gel-permeation chromatography（GPC） and 1H-NMR. And the self-assemblies of these block copolymers with various chain length ratios in the different concentrations in CHCl3 were stable according to the results of DLS and TEM. Additionally, it was also given an insight investigation on the regulation of self-assembly of the block copolymers by adding dibutyltin dichloride and a possible mechanism was proposed.展开更多
Four glycoluril-based amphiphilic molecular clips(AMCs)M1~M4 have been prepared for intracellular delivery of short DNA.M1~M4 have two methyl groups on its convex surface and four cations on its aromatic side arm,whic...Four glycoluril-based amphiphilic molecular clips(AMCs)M1~M4 have been prepared for intracellular delivery of short DNA.M1~M4 have two methyl groups on its convex surface and four cations on its aromatic side arm,which can be used to construct self-assembled nanoparticles in aqueous solution driven by hydrophobic interaction.Dynamic light scattering experiments show that M1 and M2 can be driven hydrophobically to aggregate into extremely stable nanoparticles in water at the micromolar concentrations.Fluorescence titration and zeta potential experiments support that the nanoparticles formed by M1 and M2 are able to efficiently encapsulate short DNA(sDNA).Fluorescence imaging and flow cytometry studies reveal that their nano sizes enable intracellular delivery of the encapsulated sDNA into both normal and cancer cells,with delivery percentage reaching up to 94%,while in vitro experiments indicate that the two compounds have excellent biocompatibility and low cytotoxicity.展开更多
Studying the coupling coordination development of new energy vehicles(NEVs)and the ecological environment in China is helpful in promoting the development of NEVs in the country and is of great significance in promoti...Studying the coupling coordination development of new energy vehicles(NEVs)and the ecological environment in China is helpful in promoting the development of NEVs in the country and is of great significance in promoting high-quality development of new energy in China.This paper constructs an evaluation index system for the development of NEVs and the ecological environment.It uses game theory combining weighting model,particle swarm optimized projection tracking evaluation model,coupling coordination degree model,and machine learning algorithms to calculate and analyze the level of coupling coordination development of NEVs and the ecological environment in China from 2010 to 2021,and identifies the driving factors.The research results show that:(i)From 2010 to 2021,the development index of NEVs in China has steadily increased from 0.085 to 0.634,while the ecological environment level index significantly rose from 0.170 to 0.884,reflecting the continuous development of China in both NEVs and the ecological environment.(ii)From 2010 to 2012,the two systems—new energy vehicle(NEV)development and the ecological environment—were in a period of imbalance and decline.From 2013 to 2016,they underwent a transition period,and from 2017 to 2021,they entered a period of coordinated development showing a trend of benign and continuous improvement.By 2021,they reached a good level of coordination.(iii)Indicators such as the number of patents granted for NEVs,water consumption per unit of GDP,and energy consumption per unit of GDP are the main driving factors affecting the coupling coordination development of NEVs and the ecological environment in China.展开更多
One Yb(Ⅲ)-based coordination polymer,{[Yb(H_(2)dhtp)1.5(H_(2)O)_(4)]·3H_(2)O}n(1)(H_(4)dhtp=2,5-dihydroxytere-phthalic acid),was fabricated and structurally characterized by single-crystal X-ray diffraction,IR,p...One Yb(Ⅲ)-based coordination polymer,{[Yb(H_(2)dhtp)1.5(H_(2)O)_(4)]·3H_(2)O}n(1)(H_(4)dhtp=2,5-dihydroxytere-phthalic acid),was fabricated and structurally characterized by single-crystal X-ray diffraction,IR,powder X-ray diffraction,X-ray diffraction,and elemental analysis.Complex 1 displays a 1D chain structure,and belongs to P1 group.The solid-state luminescent spectrum of 1 showed an emission band with the maximum at 508 nm(λex=408 nm).It exhibited the emission characteristic of the H_(4)dhtp ligand.The fluorescence of 1 in water displayed the stron-gest intensity.In detecting various metal ions,adding Zr^(4+)led to a blue shift in fluorescence,accompanied by an increase in intensity,whereas the presence of Fe^(3+)resulted in a decrease in luminescence.The changes observed in the IR spectrum indicate an interaction between Fe^(3+)/Zr^(4+)and complex 1,resulting in the variation of luminescence properties.展开更多
Three monomers,namely A2,B2,and GH,were designed and synthesized.By utilizing double host-vip interactions,the monomers A2+B2+GH underwent self-assembly to form a supramolecular linear polymer(SLP)at high concentrat...Three monomers,namely A2,B2,and GH,were designed and synthesized.By utilizing double host-vip interactions,the monomers A2+B2+GH underwent self-assembly to form a supramolecular linear polymer(SLP)at high concentrations.Long fibers could be pulled from the concentrated SLP solution.Upon the addition of PdCl_(2)(PhCN)_(2)into the SLP solution,a structural transformation occurred from SLP to a supramolecular crosslinked polymer(SCP)through metal coordination interaction.This transformation induced fluorescence quenching,test paper strips for ion detection experiment confirmed that the SLP had good detection ability for Pd^(2+).Furthermore,the SCP underwent a transformation into a gel when the concentration exceeded 145 mmol/L.The SCP gel demonstrated sensitivity to different stimuli,such as K^(+)ions and changes in temperature,accompanied by a reversible transition between sol and gel states.Additionally,rheological analyses indicated that the gel possessed favorable self-healing properties.展开更多
We report five coordination polymers(CPs)based on fluorescent ligands[1,6-di(1H-imidazol-1-yl)pyrene(dip),9,10-di(1H-imidazol-1-yl)anthracene(dia)]and anionic ligands[cyclohexane-1,4-dicarboxylic acid(H_(2)cda),campho...We report five coordination polymers(CPs)based on fluorescent ligands[1,6-di(1H-imidazol-1-yl)pyrene(dip),9,10-di(1H-imidazol-1-yl)anthracene(dia)]and anionic ligands[cyclohexane-1,4-dicarboxylic acid(H_(2)cda),camphoric acid(H_(2)cpa)].In[Cd(dip)(cda)]·4H_(2)O}_(n)(1),the Cd^(2+)ions,acting as tetrahedral nodes,are linked by dipand cda^(2-)ligands with four Cd^(2+)ions into five-fold interpenetrating network array of topology of dia.In{[Cd(dip)(cpa)]·4H_(2)O}_(n)(2),the Cd^(2+)ions,acting as a 4-connector,are linked by cpa^(2-)and dip ligands into a 3D framework ofcds topology.In{[Ni(dia)_(2)Cl_(2)]·DMF}_(n)(3),the Ni^(2+)ion is linked by four dia ligands into a layer structure,and 1Dchannels of a cross-section of 1.35 nm×0.96 nm are formed.In{[Cd(dia)_(2)(H_(2)O)_(2)](NO_(3))_(2)·2DMSO}n(4),the dia ligandsconnected Cd^(2+)ions into a 2D layer,and 1D channels are formed between adjacent layers with a cross-section of0.87 nm×0.43 nm.In[Zn(dip)Cl_(2)]_(n)(5),the Zn^(2+)ion is linked by dip ligands into an infinite 1D chain.The infrared,thermal gravimetric,and fluorescent emission data were collected and analyzed for these coordination polymers.CCDC:2356055,1;2440075,2;2356057,3;2356057,4;2356059,5.展开更多
Six coordination polymers based on 9,10-di(pyridine-4-yl)-anthracene(DPA)and 1,6-di(1H-imidazol-1-yl)pyrene(DIP)were obtained by solvothermal reactions.{[Zn(DPA)Cl_(2)]·DMF·2H_(2)O}n(1)and{[Zn_(1.5)(DPA)_(1....Six coordination polymers based on 9,10-di(pyridine-4-yl)-anthracene(DPA)and 1,6-di(1H-imidazol-1-yl)pyrene(DIP)were obtained by solvothermal reactions.{[Zn(DPA)Cl_(2)]·DMF·2H_(2)O}n(1)and{[Zn_(1.5)(DPA)_(1.5)Cl_(3)]·5H_(2)O}n(2)are framework isomers,which both contain zigzag chains formed by DPA,Zn^(2+),and Cl-.The zigzag chains in 1 are further assembled by C—H…Cl interactions into layers,and these layers exhibit two different orientations,displaying a rare 2D to 3D interpenetration mode.The zigzag chains in 2 are parallelly arranged.{[Zn_(3)(DPA)_(3)Br_(6)]·2DMF·_(1.5)H_(2)O}n(3)is isostructural to 2.3 was obtained using ZnBr_(2)instead of ZnCl_(2).[M(DPA)(formate)_(2)(H_(2)O)_(2)]n[M=Co(4),Cu(5)]are isostructural,contain chain structures formed by DPA,Cu^(2+)/Co^(2+),and for-mate ions,which were formed in situ in the solvothermal reaction.{[Zn(DIP)_(2)Cl]ClO_(4)}n(6)contains a layer structure formed by DIP and Zn^(2+).Free DPA and DIP ligands exhibited high fluorescence at room temperature,and coordina-tion polymers 3 and 6 displayed enhanced fluorescent emissions.展开更多
Two new Mn(Ⅱ)coordination polymers,namely{[Mn_(2)(HL)(phen)_(3)(H_(2)O)_(2)]·7.5H_(2)O}_n(1)and[Mn_(4)(HL)_(2)(1,4-bib)_(3)(H_(2)O)_(2)]_n(2),were synthesized under hydrothermal conditions by using Mn(Ⅱ)ions an...Two new Mn(Ⅱ)coordination polymers,namely{[Mn_(2)(HL)(phen)_(3)(H_(2)O)_(2)]·7.5H_(2)O}_n(1)and[Mn_(4)(HL)_(2)(1,4-bib)_(3)(H_(2)O)_(2)]_n(2),were synthesized under hydrothermal conditions by using Mn(Ⅱ)ions and 6-(3',4'-dicarboxylphenoxy)-1,2,4-benzenetricarboxylic acid(H_(5)L)in the presence of N-auxiliary ligands 1,10-phenanthroline(phen)and1,4-bis(1H-imidazol-1-yl)benzene(1,4-bib).The structures of coordination polymers 1 and 2 were characterized by infrared spectroscopy,single-crystal X-ray diffraction,thermogravimetric analysis,and powder X-ray diffraction.Single-crystal X-ray diffraction reveals that 1 has a 1D chain structure based on binuclear Mn(Ⅱ)units,while 2 features a(3,8)-connected 3D network structure based on tetranuclear Mn(Ⅱ)units.Magnetic studies show that 1 and 2exhibit antiferromagnetic interactions between manganese ions.2 shows stronger antiferromagnetic interactions due to the shorter Mn…Mn distances within the tetranuclear manganese units.CCDC:2357601,1;2357602,2.展开更多
A novel coordination polymer(CP){[Cd_(2)(L)(1,4-bimb)_(1.5)(DMF)_(2)]·DMF}n(1)(H_(4)L=5,5'-[1,1'-biphenyl-4,4'-diylbis(oxy)]diisophthalic acid,1,4-bimb=1,4-bis(imidazole-1-ylmethyl)-benzene)has been d...A novel coordination polymer(CP){[Cd_(2)(L)(1,4-bimb)_(1.5)(DMF)_(2)]·DMF}n(1)(H_(4)L=5,5'-[1,1'-biphenyl-4,4'-diylbis(oxy)]diisophthalic acid,1,4-bimb=1,4-bis(imidazole-1-ylmethyl)-benzene)has been designed and synthesized through solvothermal reaction.Structural analysis shows that Cd(Ⅱ)is connected by H4L and 1,4-bimb to form a 2D network,and 1,4-bimb further expands the 2D network into a 3D framework.CP 1 can be used as an excellent fluorescence sensor for Fe^(3+)and 4-nitrophenol(4-NP),with low detection limits and good anti-interference.The detection limits of Fe^(3+)and 4-NP were 0.034 and 0.031μmol·L^(-1),respectively.In addition,the fluorescence quenching mechanism was studied.1 was successfully applied to determine Fe^(3+)and 4-NP content in the Yanhe River water sample.CCDC:2351092.展开更多
High-entropy alloy(HEA)nanoparticles(NPs)have attracted great attention in electrocatalysis due to their tailorable complex compositions and unique properties.Herein,we introduce Fe,Co,Ni,Cr and Mn into the metal-poly...High-entropy alloy(HEA)nanoparticles(NPs)have attracted great attention in electrocatalysis due to their tailorable complex compositions and unique properties.Herein,we introduce Fe,Co,Ni,Cr and Mn into the metal-polyphenol coordination system to prepare HEA NPs enclosed in N-doped carbon(FeCoNiCrMn)with great potential for catalyzing oxygen reduction reaction(ORR)and oxygen evolution reaction(OER).The unique high-entropy structural characteristics in FeCoNiCrMn facilitate effective interplay between metal species,leading to improved ORR(E_(1/2)=0.89 V)and OER(η=330 mV,j=10 mA·cm^(−2))activity.Additionally,FeCoNiCrMn exhibits excellent open-circuit voltage(1.523 V),power density(110 mW·cm^(−2))and long-term durability,outperforming Pt/C+IrO_(2) electrodes as a cathode catalyst in Zn-air batteries(ZABs).Such polyphenol-assisted alloying method broadens and simplifies the development of HEA electrocatalysts for high-performance ZABs.展开更多
A low-cost 1D cobalt-based coordination polymer(CP)[Co(BGPD)(DMSO)_(2)(H_(2)O)_(2)](Co-BD;H2BGPD=N,N'-bis(glycinyl)pyromellitic diimide;DMSO=dimethyl sulfoxide)was synthesized by a simple method,and its crystal st...A low-cost 1D cobalt-based coordination polymer(CP)[Co(BGPD)(DMSO)_(2)(H_(2)O)_(2)](Co-BD;H2BGPD=N,N'-bis(glycinyl)pyromellitic diimide;DMSO=dimethyl sulfoxide)was synthesized by a simple method,and its crystal structure was characterized.In a three-electrode system,Co-BD,as the electrode material for supercapacitors,achieved a specific capacitance of 830 F·g^(-1)at 1 A·g^(-1),equivalent to a specific capacity of 116.4 mAh·g^(-1),and exhibited high-rate capability,reaching 212 F·g^(-1)at 20 A·g^(-1).Impressively,Co-BD||rGO(reduced graphene oxide),representing an asymmetrical supercapacitor,owns a higher energy density of 14.2 Wh·kg^(-1)at 0.80 kW·kg^(-1),and an excellent cycle performance(After 4000 cycles at 1 A·g^(-1),the capacitance retention was up to 94%).CCDC:2418872.展开更多
Reaction of the non-substituted/substituted unsymmetric pinene-derived complex[Pt(N^C^N')Cl]with the aryl isocyanide 2,6-dimethylphenyl isocyanide(CNXyl)afforded a mixture of two isomeric species:the ionic complex...Reaction of the non-substituted/substituted unsymmetric pinene-derived complex[Pt(N^C^N')Cl]with the aryl isocyanide 2,6-dimethylphenyl isocyanide(CNXyl)afforded a mixture of two isomeric species:the ionic complex[Pt(κ^(3)-N^C^N')(CNXyl)]Cl([A]Cl)and the molecular complex[Pt(κ^(2)-N^C^N')(CNXyl)Cl](B).Isomer B was almost the dominating product.The structures of the isomer B derivatives bearing-CF_(3)and-Cl substituents on the pyridine ring of the pinene moiety(5B and 7B,respectively)have been confirmed by single-crystal X-ray diffraction,revealing a slightly distorted square planar geometry with trans-N_(N^C^N'),CNR configuration(The terminal N atom of theκ^(2)-N^C^N'ligand is trans to the isocyanide ligand CNXyl.).Isomer B is thermodynamically more stable,as confirmed by theoretical calculations.CCDC:2416415,5B;2416414,7B.展开更多
Two new transition-metal coordination polymers,{[Cd(oba)(L)_(2)]·H_(2)O}_n(1)and[Cd(4-nph)(L)_(2)]_n(2)(H_(2)oba=4,4'-oxydibenzoic acid,4-H_(2)nph=4-nitrophthalic acid,L=2,2'-biimidazole),were successfull...Two new transition-metal coordination polymers,{[Cd(oba)(L)_(2)]·H_(2)O}_n(1)and[Cd(4-nph)(L)_(2)]_n(2)(H_(2)oba=4,4'-oxydibenzoic acid,4-H_(2)nph=4-nitrophthalic acid,L=2,2'-biimidazole),were successfully synthesized under hydrothermal conditions and characterized structurally by IR spectroscopy,elemental analyses,single-crystal X-ray diffraction,powder X-ray diffraction,and thermogravimetric analysis.The results of single-crystal X-ray diffraction show that complex 1 presents a 1D zigzag chain structure and further extends to a 2D network through N—H…O hydrogen bonds andπ-πstacking interactions.Meanwhile,complex 2 has a zero-dimensional structure and also extends to form a 2D network through N—H…O hydrogen bonds andπ-πstacking interactions.In addition,both 1and 2 exhibited luminescent properties in the solid state.Furthermore,quantum chemical calculations were carried out on the"molecular fragments"extracted from the crystal structures of 1 and 2 using the PBE0/LANL2DZ method constructed by the Gaussian 16 program.The calculated values signify a significant covalent interaction between the coordination atoms and the Cd(Ⅱ)ions.CCDC:2332173,1;2332176,2.展开更多
A coordination polymer{[Cd(H_(2)dpa)(bpy)]·3H_(2)O}_(n)(Cd-CP)was designed and hydrothermal synthesized based on 4-(2,4-dicarboxyphenoxy)phthalic acid(H_(4)dpa),2,2'-bipyridine(bpy)and Cd(NO_(3))_(2)·4H_...A coordination polymer{[Cd(H_(2)dpa)(bpy)]·3H_(2)O}_(n)(Cd-CP)was designed and hydrothermal synthesized based on 4-(2,4-dicarboxyphenoxy)phthalic acid(H_(4)dpa),2,2'-bipyridine(bpy)and Cd(NO_(3))_(2)·4H_(2)O.The structure was characterized by single-crystal X-ray diffraction,powder X-ray diffraction,elemental analysis,and infrared spectroscopy.Cd-CP belongs to the monoclinic crystal system with the P2_1/c space group and performs in a 1D double-chain structure.The adjacent double chains further form a 3D supramolecular network structure through hydrogen bonding.Thermogravimetric analysis shows that Cd-CP has good thermal stability.Fluorescence analysis showed that Cd-CP had good choosing selectively and was sensitive to metal ions(Fe^(3+)and Zn^(2+)),2,4,6-trinitrophenylhydrazine(TRI),and pyrimethanil(Pth).Interestingly,when Cd-CP was used for fluorescence detection of metal ions,it was found to have a fluorescence quenching effect on Fe^(3+)but had an obvious enhancement effect on Zn^(2+).Therefore,we designed an“on-off-on”logic gate.In addition,the mechanism of fluorescence sensing has been deeply explored.CCDC:2258625.展开更多
Redox-active organic compounds have received much attention as high-capacity electrodes for rechargeable batteries.However,the high solubility in organic electrolytes during charge and discharge processes hinders the ...Redox-active organic compounds have received much attention as high-capacity electrodes for rechargeable batteries.However,the high solubility in organic electrolytes during charge and discharge processes hinders the practical exploitation of organic compounds.This study presents a cobalt-based metal–organic coordination compound with bifunctional coordinated water(Co-MOC-H_(2)O)for sodium-ion storage.The coordinated water enhances interactions between sodium ions and nitrogen atoms in organic ligands through chelation,activating the inert sodium-ion storage sites(C=N).Moreover,the stable hydrogen bonded framework formed by the coordinated water molecules prevents the active organic compounds from dissolving into the electrolyte,thereby enhancing cycling stability.With the bifunctional coordinated water molecules,the Co-MOC-H_(2)O electrode delivers a high capacity of 403 mAh g^(-1)at 0.2 A g^(-1)over 600 cycles and exhibits a capacity retention of 77.9%at 2 A g^(-1)after 1100 cycles.This work highlights the crucial role of the coordinated water molecules in constructing high capacity and long-life sodium-ion storage materials.展开更多
文摘Under the condition of solvothermal synthesis,the viologen ligand 1,1′-bis(3-carboxyphenyl)-(4,4′-bipyri-dine)dichloride(H_(2)bcbpy·2Cl)and KI are coordinated with the metal cadmium ions.A case of thermochromic coor-dination polymer[Cd(bcbpy)I_(2)]·2H_(2)O(1)was constructed.Complex 1 displays a 1D chain structure and exhibits thermochromic behavior.Under different temperature stimulation,the complex(ground)slowly changed from green to yellow-green,and with the increase of temperature,the color of complex 1 gradually deepened,and finally became orange-yellow.Therefore,complex 1 was prepared as a thermochromic film.In addition,we also performed electrochemical tests on complex 1,which showed that the complex is a semiconductor material.CCDC:2391802.
基金supported by the National Natural Science Foundation of China(22105033,22105192)the National Key Research and Development Program of China(2023YFA1506300)+1 种基金the Programme of Introducing Talents of Discipline to Universities(B17020)the Jilin Province Science and Technology Development Plan(YDZJ202101ZYTS137,20210101123JC).
文摘Mesoporous metals with large surface area,high pore volume,and uniform pore structure hold excellent advantages for various applications.However,the state-of-the-art synthesis methods are still limited to wet chemistry,which requires excessive solvents and a time-consuming drying process.Here,we report a facile and general mechanochemical coordination self-assembly strategy to prepare mesoporous metals(e.g.,Rh,Ru,Ir,Pt,Pd,Ag,Co,and Ni)with remarkable porous properties by using metal chlorides and cationic polymer interplay.Compared with the wet chemistry process,this method proceeds without solvents and does not need complicated experimental conditions and long synthetic periods,which not only greatly reduces the consumption of cost and energy and environmental pollution,but also improves the synthesis efficiency and yield of target products.We believe the developed approach will provide a general pathway for the scalable preparation of advanced porous materials.
基金the Natural Sciences and Engineering Research Council of Canada(NSERC)the National Natural Science Foundation of China(Nos.31901776 and 32072181)+1 种基金Agricultural Science and Technology Innovation Program(No.CAAS-ASTIP-2021-IFST-SN2021-05)received a China Scholarship Council(CSC)Scholarship to visit the University of Waterloo。
文摘Polymerase chain reactions(PCR)are a very important tool for use in cloning,nucleic acid sequencing and diagnostic testing.The storage conditions of PCR reagents are limited to freezing and a lot of mixing steps are needed.In this paper,we report using metal ions to form coordination nanomaterials with the intrinsic components of the PCR reagents including dNTP,DNA primers and DNA polymerase as an integrated PCR reaction system.To complete PCR reactions,users need only to dissolve the coordination nanomaterials with a buffer and add template DNA.A few transition metal ions were screened and Cu^(2+)was found to be the most effective metal ion for this purpose.Then the encapsulation efficiency of PCR reagents was measured,which can reach close to 100%for the primers and DNA polymerase,but only 10%for dNTP because dNTP was excess.Further study also exhibited this integrated PCR reaction system can be used for DNA detection with a similar detection limit to the normal PCR,and showed good stability of encapsulated PCR nanomaterial after storage for a week.
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korean government(MSIT)(No.2020R1C1C1003375)。
文摘Recently,hollow carbon nanospheres(HCSs)have garnered significant attention as potential Li metal hosts owing to their unique large voids and ease of fabrication.However,similar to other nanoscale hosts,their practical performance is limited by inhomogeneous agglomeration,increased binder requirements,and high tortuosity within the electrode.To overcome these problems and high tortuosity within the electrode,this study introduces a pomegranate-like carbon microcluster composed of primary HCSs(P-CMs)as a novel Li metal host.This unique nanostructure can be easily prepared using the spray-drying technique,enabling its mass production.Comprehensive analyses with various tools demonstrate that compared with HCS hosts,the P-CM host requires a smaller amount of binder to fabricate a sufficiently robust and even surface electrode.Furthermore,owing to reduced tortuosity,the well-designed P-CM electrode can provide continuous and shortened pathways for electron/ion transport,accelerating the Li-ion transfer kinetics and prohibiting preferential Li plating at the upper region of the electrode.Due to these characteristics,Li metal can be effectively encapsulated in the large inner voids of the primary HCSs constituting the P-CM,thereby enhancing the electrochemical performance of P-CM hosts in Li metal batteries.Specifically,the Coulombic efficiency of the P-CM host can be maintained at 97%over 100 cycles,with a high Li deposition areal capacity of 3 mAh·cm^(-2)and long cycle life(1000 h,1 mA·cm^(-2),and 1.0 mAh·cm^(-2)).Furthermore,a full cell incorporating a LiFePO4 cathode exhibits excellent cycle life.
文摘With the boom in maritime activities,the need for highly reliable maritime communication is becoming urgent,which is an important component of 5G/6G communication networks.However,the bandwidth reuse characteristic of 5G/6G networks will inevitably lead to severe interference,resulting in degradation in the communication performance of maritime users.In this paper,we propose a safe deep reinforcement learning based interference coordination scheme to jointly optimize the power control and bandwidth allocation in maritime communication systems,and exploit the quality-of-service requirements of users as the risk value references to evaluate the communication policies.In particular,this scheme designs a deep neural network to select the communication policies through the evaluation network and update the parameters using the target network,which improves the communication performance and speeds up the convergence rate.Moreover,the Nash equilibrium of the interference coordination game and the computational complexity of the proposed scheme are analyzed.Simulation and experimental results verify the performance gain of the proposed scheme compared with benchmarks.
基金financially supported by the National Natural Science Foundation of China(Nos.21072099,21202084 and 21372120)
文摘A tin-oxygen coordination driving self-assembly was developed in the block copolymers containing organotin, which were prepared by the radical addition-fraction transfer（RAFT） method and characterized by the gel-permeation chromatography（GPC） and 1H-NMR. And the self-assemblies of these block copolymers with various chain length ratios in the different concentrations in CHCl3 were stable according to the results of DLS and TEM. Additionally, it was also given an insight investigation on the regulation of self-assembly of the block copolymers by adding dibutyltin dichloride and a possible mechanism was proposed.
文摘Four glycoluril-based amphiphilic molecular clips(AMCs)M1~M4 have been prepared for intracellular delivery of short DNA.M1~M4 have two methyl groups on its convex surface and four cations on its aromatic side arm,which can be used to construct self-assembled nanoparticles in aqueous solution driven by hydrophobic interaction.Dynamic light scattering experiments show that M1 and M2 can be driven hydrophobically to aggregate into extremely stable nanoparticles in water at the micromolar concentrations.Fluorescence titration and zeta potential experiments support that the nanoparticles formed by M1 and M2 are able to efficiently encapsulate short DNA(sDNA).Fluorescence imaging and flow cytometry studies reveal that their nano sizes enable intracellular delivery of the encapsulated sDNA into both normal and cancer cells,with delivery percentage reaching up to 94%,while in vitro experiments indicate that the two compounds have excellent biocompatibility and low cytotoxicity.
基金Supported by the Postgraduate Research&Practice Innovation Program of Jiangsu Province(KYCX24_0102)the China Scholarship Council Program(202406190114)。
文摘Studying the coupling coordination development of new energy vehicles(NEVs)and the ecological environment in China is helpful in promoting the development of NEVs in the country and is of great significance in promoting high-quality development of new energy in China.This paper constructs an evaluation index system for the development of NEVs and the ecological environment.It uses game theory combining weighting model,particle swarm optimized projection tracking evaluation model,coupling coordination degree model,and machine learning algorithms to calculate and analyze the level of coupling coordination development of NEVs and the ecological environment in China from 2010 to 2021,and identifies the driving factors.The research results show that:(i)From 2010 to 2021,the development index of NEVs in China has steadily increased from 0.085 to 0.634,while the ecological environment level index significantly rose from 0.170 to 0.884,reflecting the continuous development of China in both NEVs and the ecological environment.(ii)From 2010 to 2012,the two systems—new energy vehicle(NEV)development and the ecological environment—were in a period of imbalance and decline.From 2013 to 2016,they underwent a transition period,and from 2017 to 2021,they entered a period of coordinated development showing a trend of benign and continuous improvement.By 2021,they reached a good level of coordination.(iii)Indicators such as the number of patents granted for NEVs,water consumption per unit of GDP,and energy consumption per unit of GDP are the main driving factors affecting the coupling coordination development of NEVs and the ecological environment in China.
文摘One Yb(Ⅲ)-based coordination polymer,{[Yb(H_(2)dhtp)1.5(H_(2)O)_(4)]·3H_(2)O}n(1)(H_(4)dhtp=2,5-dihydroxytere-phthalic acid),was fabricated and structurally characterized by single-crystal X-ray diffraction,IR,powder X-ray diffraction,X-ray diffraction,and elemental analysis.Complex 1 displays a 1D chain structure,and belongs to P1 group.The solid-state luminescent spectrum of 1 showed an emission band with the maximum at 508 nm(λex=408 nm).It exhibited the emission characteristic of the H_(4)dhtp ligand.The fluorescence of 1 in water displayed the stron-gest intensity.In detecting various metal ions,adding Zr^(4+)led to a blue shift in fluorescence,accompanied by an increase in intensity,whereas the presence of Fe^(3+)resulted in a decrease in luminescence.The changes observed in the IR spectrum indicate an interaction between Fe^(3+)/Zr^(4+)and complex 1,resulting in the variation of luminescence properties.
基金supported by the National Natural Science Foundation of China(Nos.22161020,22022107,21801100)the Natural Science Foundation of Jiangxi Province(No.20212BAB203014)the Program of Qingjiang Excellent Young Talents,Jiangxi University of Science and Technology。
文摘Three monomers,namely A2,B2,and GH,were designed and synthesized.By utilizing double host-vip interactions,the monomers A2+B2+GH underwent self-assembly to form a supramolecular linear polymer(SLP)at high concentrations.Long fibers could be pulled from the concentrated SLP solution.Upon the addition of PdCl_(2)(PhCN)_(2)into the SLP solution,a structural transformation occurred from SLP to a supramolecular crosslinked polymer(SCP)through metal coordination interaction.This transformation induced fluorescence quenching,test paper strips for ion detection experiment confirmed that the SLP had good detection ability for Pd^(2+).Furthermore,the SCP underwent a transformation into a gel when the concentration exceeded 145 mmol/L.The SCP gel demonstrated sensitivity to different stimuli,such as K^(+)ions and changes in temperature,accompanied by a reversible transition between sol and gel states.Additionally,rheological analyses indicated that the gel possessed favorable self-healing properties.
文摘We report five coordination polymers(CPs)based on fluorescent ligands[1,6-di(1H-imidazol-1-yl)pyrene(dip),9,10-di(1H-imidazol-1-yl)anthracene(dia)]and anionic ligands[cyclohexane-1,4-dicarboxylic acid(H_(2)cda),camphoric acid(H_(2)cpa)].In[Cd(dip)(cda)]·4H_(2)O}_(n)(1),the Cd^(2+)ions,acting as tetrahedral nodes,are linked by dipand cda^(2-)ligands with four Cd^(2+)ions into five-fold interpenetrating network array of topology of dia.In{[Cd(dip)(cpa)]·4H_(2)O}_(n)(2),the Cd^(2+)ions,acting as a 4-connector,are linked by cpa^(2-)and dip ligands into a 3D framework ofcds topology.In{[Ni(dia)_(2)Cl_(2)]·DMF}_(n)(3),the Ni^(2+)ion is linked by four dia ligands into a layer structure,and 1Dchannels of a cross-section of 1.35 nm×0.96 nm are formed.In{[Cd(dia)_(2)(H_(2)O)_(2)](NO_(3))_(2)·2DMSO}n(4),the dia ligandsconnected Cd^(2+)ions into a 2D layer,and 1D channels are formed between adjacent layers with a cross-section of0.87 nm×0.43 nm.In[Zn(dip)Cl_(2)]_(n)(5),the Zn^(2+)ion is linked by dip ligands into an infinite 1D chain.The infrared,thermal gravimetric,and fluorescent emission data were collected and analyzed for these coordination polymers.CCDC:2356055,1;2440075,2;2356057,3;2356057,4;2356059,5.
文摘Six coordination polymers based on 9,10-di(pyridine-4-yl)-anthracene(DPA)and 1,6-di(1H-imidazol-1-yl)pyrene(DIP)were obtained by solvothermal reactions.{[Zn(DPA)Cl_(2)]·DMF·2H_(2)O}n(1)and{[Zn_(1.5)(DPA)_(1.5)Cl_(3)]·5H_(2)O}n(2)are framework isomers,which both contain zigzag chains formed by DPA,Zn^(2+),and Cl-.The zigzag chains in 1 are further assembled by C—H…Cl interactions into layers,and these layers exhibit two different orientations,displaying a rare 2D to 3D interpenetration mode.The zigzag chains in 2 are parallelly arranged.{[Zn_(3)(DPA)_(3)Br_(6)]·2DMF·_(1.5)H_(2)O}n(3)is isostructural to 2.3 was obtained using ZnBr_(2)instead of ZnCl_(2).[M(DPA)(formate)_(2)(H_(2)O)_(2)]n[M=Co(4),Cu(5)]are isostructural,contain chain structures formed by DPA,Cu^(2+)/Co^(2+),and for-mate ions,which were formed in situ in the solvothermal reaction.{[Zn(DIP)_(2)Cl]ClO_(4)}n(6)contains a layer structure formed by DIP and Zn^(2+).Free DPA and DIP ligands exhibited high fluorescence at room temperature,and coordina-tion polymers 3 and 6 displayed enhanced fluorescent emissions.
文摘Two new Mn(Ⅱ)coordination polymers,namely{[Mn_(2)(HL)(phen)_(3)(H_(2)O)_(2)]·7.5H_(2)O}_n(1)and[Mn_(4)(HL)_(2)(1,4-bib)_(3)(H_(2)O)_(2)]_n(2),were synthesized under hydrothermal conditions by using Mn(Ⅱ)ions and 6-(3',4'-dicarboxylphenoxy)-1,2,4-benzenetricarboxylic acid(H_(5)L)in the presence of N-auxiliary ligands 1,10-phenanthroline(phen)and1,4-bis(1H-imidazol-1-yl)benzene(1,4-bib).The structures of coordination polymers 1 and 2 were characterized by infrared spectroscopy,single-crystal X-ray diffraction,thermogravimetric analysis,and powder X-ray diffraction.Single-crystal X-ray diffraction reveals that 1 has a 1D chain structure based on binuclear Mn(Ⅱ)units,while 2 features a(3,8)-connected 3D network structure based on tetranuclear Mn(Ⅱ)units.Magnetic studies show that 1 and 2exhibit antiferromagnetic interactions between manganese ions.2 shows stronger antiferromagnetic interactions due to the shorter Mn…Mn distances within the tetranuclear manganese units.CCDC:2357601,1;2357602,2.
文摘A novel coordination polymer(CP){[Cd_(2)(L)(1,4-bimb)_(1.5)(DMF)_(2)]·DMF}n(1)(H_(4)L=5,5'-[1,1'-biphenyl-4,4'-diylbis(oxy)]diisophthalic acid,1,4-bimb=1,4-bis(imidazole-1-ylmethyl)-benzene)has been designed and synthesized through solvothermal reaction.Structural analysis shows that Cd(Ⅱ)is connected by H4L and 1,4-bimb to form a 2D network,and 1,4-bimb further expands the 2D network into a 3D framework.CP 1 can be used as an excellent fluorescence sensor for Fe^(3+)and 4-nitrophenol(4-NP),with low detection limits and good anti-interference.The detection limits of Fe^(3+)and 4-NP were 0.034 and 0.031μmol·L^(-1),respectively.In addition,the fluorescence quenching mechanism was studied.1 was successfully applied to determine Fe^(3+)and 4-NP content in the Yanhe River water sample.CCDC:2351092.
基金supported by the Fundamental Research Funds for the Central Universities(No.22120230104).
文摘High-entropy alloy(HEA)nanoparticles(NPs)have attracted great attention in electrocatalysis due to their tailorable complex compositions and unique properties.Herein,we introduce Fe,Co,Ni,Cr and Mn into the metal-polyphenol coordination system to prepare HEA NPs enclosed in N-doped carbon(FeCoNiCrMn)with great potential for catalyzing oxygen reduction reaction(ORR)and oxygen evolution reaction(OER).The unique high-entropy structural characteristics in FeCoNiCrMn facilitate effective interplay between metal species,leading to improved ORR(E_(1/2)=0.89 V)and OER(η=330 mV,j=10 mA·cm^(−2))activity.Additionally,FeCoNiCrMn exhibits excellent open-circuit voltage(1.523 V),power density(110 mW·cm^(−2))and long-term durability,outperforming Pt/C+IrO_(2) electrodes as a cathode catalyst in Zn-air batteries(ZABs).Such polyphenol-assisted alloying method broadens and simplifies the development of HEA electrocatalysts for high-performance ZABs.
文摘A low-cost 1D cobalt-based coordination polymer(CP)[Co(BGPD)(DMSO)_(2)(H_(2)O)_(2)](Co-BD;H2BGPD=N,N'-bis(glycinyl)pyromellitic diimide;DMSO=dimethyl sulfoxide)was synthesized by a simple method,and its crystal structure was characterized.In a three-electrode system,Co-BD,as the electrode material for supercapacitors,achieved a specific capacitance of 830 F·g^(-1)at 1 A·g^(-1),equivalent to a specific capacity of 116.4 mAh·g^(-1),and exhibited high-rate capability,reaching 212 F·g^(-1)at 20 A·g^(-1).Impressively,Co-BD||rGO(reduced graphene oxide),representing an asymmetrical supercapacitor,owns a higher energy density of 14.2 Wh·kg^(-1)at 0.80 kW·kg^(-1),and an excellent cycle performance(After 4000 cycles at 1 A·g^(-1),the capacitance retention was up to 94%).CCDC:2418872.
文摘Reaction of the non-substituted/substituted unsymmetric pinene-derived complex[Pt(N^C^N')Cl]with the aryl isocyanide 2,6-dimethylphenyl isocyanide(CNXyl)afforded a mixture of two isomeric species:the ionic complex[Pt(κ^(3)-N^C^N')(CNXyl)]Cl([A]Cl)and the molecular complex[Pt(κ^(2)-N^C^N')(CNXyl)Cl](B).Isomer B was almost the dominating product.The structures of the isomer B derivatives bearing-CF_(3)and-Cl substituents on the pyridine ring of the pinene moiety(5B and 7B,respectively)have been confirmed by single-crystal X-ray diffraction,revealing a slightly distorted square planar geometry with trans-N_(N^C^N'),CNR configuration(The terminal N atom of theκ^(2)-N^C^N'ligand is trans to the isocyanide ligand CNXyl.).Isomer B is thermodynamically more stable,as confirmed by theoretical calculations.CCDC:2416415,5B;2416414,7B.
文摘Two new transition-metal coordination polymers,{[Cd(oba)(L)_(2)]·H_(2)O}_n(1)and[Cd(4-nph)(L)_(2)]_n(2)(H_(2)oba=4,4'-oxydibenzoic acid,4-H_(2)nph=4-nitrophthalic acid,L=2,2'-biimidazole),were successfully synthesized under hydrothermal conditions and characterized structurally by IR spectroscopy,elemental analyses,single-crystal X-ray diffraction,powder X-ray diffraction,and thermogravimetric analysis.The results of single-crystal X-ray diffraction show that complex 1 presents a 1D zigzag chain structure and further extends to a 2D network through N—H…O hydrogen bonds andπ-πstacking interactions.Meanwhile,complex 2 has a zero-dimensional structure and also extends to form a 2D network through N—H…O hydrogen bonds andπ-πstacking interactions.In addition,both 1and 2 exhibited luminescent properties in the solid state.Furthermore,quantum chemical calculations were carried out on the"molecular fragments"extracted from the crystal structures of 1 and 2 using the PBE0/LANL2DZ method constructed by the Gaussian 16 program.The calculated values signify a significant covalent interaction between the coordination atoms and the Cd(Ⅱ)ions.CCDC:2332173,1;2332176,2.
文摘A coordination polymer{[Cd(H_(2)dpa)(bpy)]·3H_(2)O}_(n)(Cd-CP)was designed and hydrothermal synthesized based on 4-(2,4-dicarboxyphenoxy)phthalic acid(H_(4)dpa),2,2'-bipyridine(bpy)and Cd(NO_(3))_(2)·4H_(2)O.The structure was characterized by single-crystal X-ray diffraction,powder X-ray diffraction,elemental analysis,and infrared spectroscopy.Cd-CP belongs to the monoclinic crystal system with the P2_1/c space group and performs in a 1D double-chain structure.The adjacent double chains further form a 3D supramolecular network structure through hydrogen bonding.Thermogravimetric analysis shows that Cd-CP has good thermal stability.Fluorescence analysis showed that Cd-CP had good choosing selectively and was sensitive to metal ions(Fe^(3+)and Zn^(2+)),2,4,6-trinitrophenylhydrazine(TRI),and pyrimethanil(Pth).Interestingly,when Cd-CP was used for fluorescence detection of metal ions,it was found to have a fluorescence quenching effect on Fe^(3+)but had an obvious enhancement effect on Zn^(2+).Therefore,we designed an“on-off-on”logic gate.In addition,the mechanism of fluorescence sensing has been deeply explored.CCDC:2258625.
基金supported by the National Natural Science Foundation of China(22121005,92372203,92372001,52072186,and 52301278)the National Key Research and Development Program of China(2022YFB2402200)+3 种基金the Science and Technology Plans of Tianjin(23JCYBJC00170)the Fundamental Research Funds for the Central Universities,Nankai University(63241206 and 9242000710)Shanghai Jiao Tong University Shaoxing Research Institute of Renewable Energy and Molecular Engineering(JDSX2023003)the Natural Science Foundation of Jiangsu Province(BK20230937).
文摘Redox-active organic compounds have received much attention as high-capacity electrodes for rechargeable batteries.However,the high solubility in organic electrolytes during charge and discharge processes hinders the practical exploitation of organic compounds.This study presents a cobalt-based metal–organic coordination compound with bifunctional coordinated water(Co-MOC-H_(2)O)for sodium-ion storage.The coordinated water enhances interactions between sodium ions and nitrogen atoms in organic ligands through chelation,activating the inert sodium-ion storage sites(C=N).Moreover,the stable hydrogen bonded framework formed by the coordinated water molecules prevents the active organic compounds from dissolving into the electrolyte,thereby enhancing cycling stability.With the bifunctional coordinated water molecules,the Co-MOC-H_(2)O electrode delivers a high capacity of 403 mAh g^(-1)at 0.2 A g^(-1)over 600 cycles and exhibits a capacity retention of 77.9%at 2 A g^(-1)after 1100 cycles.This work highlights the crucial role of the coordinated water molecules in constructing high capacity and long-life sodium-ion storage materials.
