In this work,the synthesis of uniform zeolitic imidazolate framework-coated Mo-glycerate spheres and their subsequent conversion into hierarchical architecture containing bimetallic selenides heterostructures and nitr...In this work,the synthesis of uniform zeolitic imidazolate framework-coated Mo-glycerate spheres and their subsequent conversion into hierarchical architecture containing bimetallic selenides heterostructures and nitrogen-doped carbon shell are reported.Selenization temperature plays a significant role in determining the phases,morphology,and lithium-ion storage performance of the composite.Notably,the optimal electrode demonstrates an ultrahigh reversible capacity of 1298.2 mAh/g after 100 cycles at 0.2 A/g and an outstanding rate capability with the capacity still maintained 505.7 mAh/g after 300 cycles at 1.0 A/g,surpassing the calculated theoretical capacity according to individual component and most of the reported MoSe@C-or ZnSe@C-based anodes.Furthermore,ex-situ X-ray diffraction patterns reveal the combined conversion and alloying reaction mechanisms of the composite.展开更多
Rationally design the morphology and structure of electroactive nanomaterials is an effective approach to enhance the performance of aqueous batteries.Herein,we co-engineered the hollow architecture and interlayer spa...Rationally design the morphology and structure of electroactive nanomaterials is an effective approach to enhance the performance of aqueous batteries.Herein,we co-engineered the hollow architecture and interlayer spacing of layered double hydroxides(LDH)to achieve high electrochemical activity.The hierarchical hollow LDH was prepared from bimetallic zeolitic imidazolate frameworks(ZIF)by a facile cation exchange strategy.Zn and Cu elements were selected as the second metals incorporated in Co-ZIF.The characteristics of the corresponding derivatives were studied.Besides,the transformation mechanism of CoZn-ZIF into nanosheet-assembled hollow Co Zn Ni LDH(denoted as CoZnNi-OH)was systematically investigated.Importantly,the interlayer spacing of CoZnNi-OH expands due to Zn^(2+)incorporation.The prepared CoZnNi-OH offers large surface area,exposed active sites,and rapid mass transfer/diffusion rate,which lead to a significant enhancement in the specific capacitance,rate performance,and cycle stability of CoZnNi-OH electrode.In addition,the aqueous alkaline CoZnNi-OH//Zn showed a maximum energy density/power density of 0.924 m Wh/cm^(2),8.479 m W/cm^(2).This work not only raises an insightful strategy for regulating the morphology and interlayer spacing of LDH,but also provides a reference of designing hollow nickel-based nanomaterials for aqueous batteries.展开更多
Biological nanotechnologies based on functional nanoplatforms have synergistically catalyzed the emergence of cancer therapies.As a subtype of metal-organic frameworks(MOFs),zeolitic imidazolate frameworks(ZIFs)have e...Biological nanotechnologies based on functional nanoplatforms have synergistically catalyzed the emergence of cancer therapies.As a subtype of metal-organic frameworks(MOFs),zeolitic imidazolate frameworks(ZIFs)have exploded in popularity in the field of biomaterials as excellent protective materials with the advantages of conformational flexibility,thermal and chemical stability,and functional controllability.With these superior properties,the applications of ZIF-based materials in combination with various therapies for cancer treatment have grown rapidly in recent years,showing remarkable achievements and great potential.This review elucidates the recent advancements in the use of ZIFs as drug delivery agents for cancer therapy.The structures,synthesis methods,properties,and various modifiers of ZIFs used in oncotherapy are presented.Recent advances in the application of ZIF-based nanoparticles as single or combination tumor treatments are reviewed.Furthermore,the future prospects,potential limitations,and challenges of the application of ZIF-based nanomaterials in cancer treatment are discussed.We except to fully explore the potential of ZIF-based materials to present a clear outline for their application as an effective cancer treatment to help them achieve early clinical application.展开更多
As a prevailing cathode material of lithium-ion batteries(LIBs),LiCoO_(2)(LCO)still encounters the tricky problems of structural collapse,whose morphological engineering and cation doping are crucial for surmounting t...As a prevailing cathode material of lithium-ion batteries(LIBs),LiCoO_(2)(LCO)still encounters the tricky problems of structural collapse,whose morphological engineering and cation doping are crucial for surmounting the mechanical strains and alleviating phase degradation upon cycling.Hereinafter,we propose a strategy using a zeolitic imidazolate framework(ZIF)as the self-sacrificing template to directionally prepare a series of LiNi_(0.1)Co_(0.9)O_(2)(LNCO)with tailorable electrochemical properties.The rational selection of sintering temperature imparts the superiority of the resultant products in lithium storage,during which the sample prepared at 700℃(LNCO-700)outperforms its counterparts in cyclability(156.8 mA h g^(-1)at 1 C for 200 cycles in half cells,1 C=275 mA g^(-1))and rate capability due to the expedited ion/electron transport and the strengthen mechanical robustness.The feasibility of proper Ni doping is also divulged by half/full cell tests and theoretical study,during which LNCO-700(167 mA h g^(-1)at 1 C for 100 cycles in full cells)surpasses LCO-700 in battery performance due to the mitigated phase deterioration,stabilized layered structu re,ameliorated electro nic co nductivity,a nd exalted lithium sto rage activity.This work systematically unveils tailorable electrochemical behaviors of LNCO to better direct their practical application.展开更多
A dimeric Y(III)-containing antimonotungstate[Y_(4)(H_(2)O)_(8)(mal)_(2)(OAc)O(Sb_(2)W_(2)^(V)W_(19)^(VI)O_(72))_(2)]^(21-)(Y_(4)mal_(2),H_(3)mal=DL-malic acid),resembling a“handshake”configuration,was synthesized a...A dimeric Y(III)-containing antimonotungstate[Y_(4)(H_(2)O)_(8)(mal)_(2)(OAc)O(Sb_(2)W_(2)^(V)W_(19)^(VI)O_(72))_(2)]^(21-)(Y_(4)mal_(2),H_(3)mal=DL-malic acid),resembling a“handshake”configuration,was synthesized and characterized.The polyanion of Y_(4)mal_(2)consists of two Dawson-derived{Y_(2)Sb_(2)W_(21)}moieties that are further linked by two mal ligands and oneμ_(2)-bridging acetate to form an asymmetric polyanion.Notably,the chiral configuration induced by the D-or L-configuration of the mal ligand results in both{Y_(2)Sb_(2)W_(21)}moieties within one polyanion exhibiting identical chirality,leading to the racemate crystallization of Y_(4)mal_(2).Moreover,Y_(4)mal_(2)exhibits excellent Lewis acid catalytic activity for environmentally friendly synthesis of imidazoles.展开更多
Hybrid metal-organic framework(MOF)derivatives play a significant role in the novel catalyst development in energy conversion reactions.Here,we demonstrated the low-temperature fully fluorinated zeolitic imidazole fra...Hybrid metal-organic framework(MOF)derivatives play a significant role in the novel catalyst development in energy conversion reactions.Here,we demonstrated the low-temperature fully fluorinated zeolitic imidazole framework(ZIF)coupled with a three-dimensional open framework Prussian blue analog(PBA)with combined advantages for electrocatalytic oxygen evolution reaction(OER)in water splitting reaction.The spectroscopic analysis and the electrochemical studies revealed the combined advantages of efficient electronic effect and active site synergism.Because of good conductivity improvement by Ndoped carbon derived from ZIF and the high electrochemical surface area and active site exposure from PBA derivatives,good catalytic performance was obtained on the optimal catalyst of Co Ni ZIF/Co Fe-PBAF-300,which required a low overpotential of 250 m V to reach 10 m A/cm^(2)loaded on the glassy carbon electrode,with Tafel slope of 47.4 m V/dec,and very high dynamic and steady stability.In addition,the multi-component with the mixed structure from highly polar metal fluorides promoted the easy formation of the active phase as revealed by the post-sample analysis.The current results showed a novel composite catalyst materials development from the hybrid MOF derivatives,which would be promising in the electrolysis of water oxidation reactions and energy-relevant catalysis reactions.展开更多
Zeolite imidazole frameworks(ZIFs),a class of the metal organic framework,have been extensively studied in environmental applications.However,their environmental fate and potential ecological impact on plants remain u...Zeolite imidazole frameworks(ZIFs),a class of the metal organic framework,have been extensively studied in environmental applications.However,their environmental fate and potential ecological impact on plants remain unknown.Here,we investigated the phytotoxicity,transformation,and bioaccumulation processes of two typical ZIFs(ZIF-8 and ZIF-67)in rice(Oryza sativa L.)under hydroponic conditions.ZIF-8 and ZIF-67 in the concentration of 50 mg/L decreased root and shoot dry weight maximally by 55.2%and 27.5%,53.5%and 37.5%,respectively.The scanning electron microscopy(SEM)imaging combined with X-ray diffraction(XRD)patterns revealed that ZIFs on the root surface gradually collapsed and transformed into nanosheets with increasing cultivation time.The fluorescein isothiocyanate(FITC)labeled ZIFs were applied to trace the uptake and translocation of ZIFs in rice.The results demonstrated that the transformed ZIFs were mainly distributed in the intercellular spaces of rice root,while they cannot be transported to culms and leaves.Even so,the Co and Zn contents of rice roots and shoots in the ZIFs treated groups were increased by 1145%and 1259%,145%and 259%,respectively,compared with the control groups.These findings suggested that the phytotoxicity of ZIFs are primarily attributed to the transformed ZIFs and to a less extent,the metal ions and their ligands,and they were internalized by rice root and increased the Co and Zn contents of shoots.This study reported the transformation of ZIFs and their biological effectiveness in rice,highlighting the potential environmental hazards and risks of ZIFs to crop plants.展开更多
An efficient protocol for the one-pot multicomponent synthesis of various 2,4,5 -triaryl- 1H-imidazoles and 1,2,4,5 -tetraaryl- 1H- imidazoles using PEG-400 as reaction medium is described. This method has the advanta...An efficient protocol for the one-pot multicomponent synthesis of various 2,4,5 -triaryl- 1H-imidazoles and 1,2,4,5 -tetraaryl- 1H- imidazoles using PEG-400 as reaction medium is described. This method has the advantages of good yields, less pollution and simple reaction conditions.展开更多
Metal-organic frameworks(MOFs)have been intensely studied for the past few decades as an enormous family of highly tunable porous materials with promisingly applicable functionalities in adsorption,separation,catalysi...Metal-organic frameworks(MOFs)have been intensely studied for the past few decades as an enormous family of highly tunable porous materials with promisingly applicable functionalities in adsorption,separation,catalysis,sensing,electrochemistry,and a great number of emerging purposes.As a classic MOF,zeolitic imidazolate framework-8(ZIF-8)is conventionally one of the very few MOF members that has been commercialized with considerable production.展开更多
We report here the synthesis and in vivo anticonvulsant/neurotoxicity activities of a series of compounds belonging to 2-aryl-4-arylidene-1-phenyl-1H-imidazol-5(4H)-one. The scaffold is based on the commonality of 5-m...We report here the synthesis and in vivo anticonvulsant/neurotoxicity activities of a series of compounds belonging to 2-aryl-4-arylidene-1-phenyl-1H-imidazol-5(4H)-one. The scaffold is based on the commonality of 5-membered lactam ring structures as successful anticonvulsant agents. The present compounds exhibited a range of anticonvulsant activity in pentylenetetrazole (PTZ)-induced seizure test. In particular, the protection was excellent by compounds bearing furylmethylidene on C4, possibly due to good pharmacokinetic properties. It was found that high lipophilicity and/or electron deficient aryl ring substitution at C4 compromised the anticonvulsant activities. For example, chloro analogues were found much less active than unsubstituted phenyl or furyl derivatives. Regarding side effects, active compounds exerted no observable neurotoxic effect at their therapeutic doses in Chimney test.展开更多
A novel thiazolothiazole-bridged imidazole derivative(1) was found to exhibit blue fluorescence in gaseous state or in methanol and yellow fluorescence in solid state. The N-alkylation of imidazole subunit(s) in 1 usi...A novel thiazolothiazole-bridged imidazole derivative(1) was found to exhibit blue fluorescence in gaseous state or in methanol and yellow fluorescence in solid state. The N-alkylation of imidazole subunit(s) in 1 using n-propyl iodide generated unsymmetrically or symmetrically alkylated thiazolothiazolebridged imidazolium salts with good water solubility and remarkably strong emission in solution. Furthermore, the replacement of iodide counter-anion by triflate or bis(trifluoromethane sulfonyl)imide achieved remarkably strong emission in solid state and in solution as well as good water solubility. The strong fluorescence of dicationic salts with triflate and NTf_(2)^(-)counter-anions in solid state can be ascribed to their twisted and rigid structures induced by interionic C-H···F hydrogen bonding.展开更多
Hydrothermal reactions of two imidazole derivatives （1,3,5-tib = 1,3,5-tris（1H- imidazol- 1 -yl）benzene, 1,4-bimb = 1,4-bis（1 H-imidazol- 1 -ylmethyl）benzene） and the ZnⅡ cations in the presence of oxalic acid ...Hydrothermal reactions of two imidazole derivatives （1,3,5-tib = 1,3,5-tris（1H- imidazol- 1 -yl）benzene, 1,4-bimb = 1,4-bis（1 H-imidazol- 1 -ylmethyl）benzene） and the ZnⅡ cations in the presence of oxalic acid （H2ox） afford two coordination polymers, namely, {[Zn（ox）（1,3,5- tib）]·2（H20）}n （1） and [Znl.5（OX）1.5（1,4-bimb）l.5]n （2）. Their structures have been determined by single-crystal X-ray diffraction analyses, elemental analyses, IR spectra, and powder X-ray diffraction （PXRD） analyses. Both complexes 1 and 2 are based on the 1D zigzag [Zn（ox）]n chains, and their final structures are controlled by the two different imidazole linkers, which expanded the structure along different directions, finally giving a 3D dia net for 1 and a 2D sql layer for 2. Moreover, the luminescent properties of 1 and 2 have been investigated.展开更多
A new synthesis of 1 - (ω- haloalkyl ) -imidazole has been developed. The synthesisinvolves a Hoffmann-type elimination of the 2-cyanoethyl group from inddazolium salts obtainedby the reaction of α,ω-dihalide with ...A new synthesis of 1 - (ω- haloalkyl ) -imidazole has been developed. The synthesisinvolves a Hoffmann-type elimination of the 2-cyanoethyl group from inddazolium salts obtainedby the reaction of α,ω-dihalide with 1-(2-cyanoethyl)-imidazole.展开更多
A novel imidazole derivative with functional group and π-conjugated system, 1- [trans-4-（4-diethylaminostyryl）phenyl]imidazole （abbreviated as L）, and its Con complex （COCl2L4）2 （Co2C168H184N24Cl4, Mr = 2799....A novel imidazole derivative with functional group and π-conjugated system, 1- [trans-4-（4-diethylaminostyryl）phenyl]imidazole （abbreviated as L）, and its Con complex （COCl2L4）2 （Co2C168H184N24Cl4, Mr = 2799.05 ） have been synthesized and the crystal structure of the latter was determined by X-ray diffraction. The crystal is of triclinic, space group PI with a = 8.823（3）, b = 18.799（7）, c =23.065（9） A, α = 77.349（6）, β = 83.128（7）, ）, γ= 80.942（3）°, V = 3671.5（12） A^3, Z = 1, Dc = 1.266 g/cm^3,/z = 0.361 mm^-1 F（000） = 1482, the final R = 0.0587 and wR = 0.1284 for 6562 observed reflections with I 〉 2σ（I）. In the molecular structure of （COCl2L4）2, there are two crystallographically unique units. The Co^Ⅱ atoms are six-coordinated by four N atoms from four imidazole ligands （L） and two Cl atoms to form a distorted octahedral geometry. The optical properties of complex （COCl2L4）2 have been experimentally studied.展开更多
Zeolitic imidazolate frameworks(ZIFs)as smart drug delivery systems with microenvironment-triggered release have attracted much attention for tumor therapy.However,the exploration of ZIFs in biomedicine still encounte...Zeolitic imidazolate frameworks(ZIFs)as smart drug delivery systems with microenvironment-triggered release have attracted much attention for tumor therapy.However,the exploration of ZIFs in biomedicine still encounters many issues,such as inconvenient surface modification,fast drug release during blood circulation,undesired damage to major organs,and severe in vivo toxicity.To address the above issues,we developed an Mn-ZIF-90 nanosystem functionalized with an originally designed active-targeting and pH-responsive magnetic resonance imaging(MRI)Y1 receptor ligand[Asn28,Pro30,Trp32]-NPY(25-36)for imaging-guided tumor therapy.After Y1 receptor ligand modification,the Mn-ZIF-90 nanosystem exhibited high drug loading,better blood circulation stability,and dual breast cancer cell membrane and mitochondria targetability,further favoring specific microenvironment-triggered tumor therapy.Meanwhile,this nanosystem showed promising T1-weighted magnetic resonance imaging contrast in vivo in the tumor sites.Especially,this nanosystem with fast clean-up had almost no obvious toxicity and no damage occurred to the major organs in mice.Therefore,this nanosystem shows potential for use in imaging-guided tumor therapy.展开更多
The interactions of nine rare earth perchlorate complexes with alanine and imidazole were studied in methanol. The general formulae of these compounds are RE(Ala) 2Im(ClO 4) 3· n H 2O(RE=Ce, Pr, Nd, Sm, Eu,...The interactions of nine rare earth perchlorate complexes with alanine and imidazole were studied in methanol. The general formulae of these compounds are RE(Ala) 2Im(ClO 4) 3· n H 2O(RE=Ce, Pr, Nd, Sm, Eu, Gd, Tb, Yb) and La(Ala) 3Im(ClO 4) 3·H 2O, respectively. The composition and structure of the prepared compounds were determined by the chemical analysis, elemental analysis, IR spectroscopy, UV, FS spectroscopy, X ray powder diffraction, 1H NMR and solubility. The thermal decomposition processes of these complexes were studied on the basis of TG DTG. The preliminary bioassay shows that the compounds have a remarkable bacteriostasis effect on nine varieties of microbe.展开更多
Recently, the development of high-performance bifunctional oxygen catalysts integrated with flexible conductive scaffolds f or rechargeable metal-air batteries has attracted considerable interest, driving by fastgrowi...Recently, the development of high-performance bifunctional oxygen catalysts integrated with flexible conductive scaffolds f or rechargeable metal-air batteries has attracted considerable interest, driving by fastgrowing wearable electronics. Herein, we report a flexible bifunctional oxygen catalyst thin film consisting of Co–N–C bifunctional catalysts embedding in carbon nanotube(CNT) networks. The catalyst is readily prepared by pyrolysis of cobalt-based zeolitic imidazolate frameworks(ZIF-67) that are in-situ synthesized in CNT networks. Such catalyst film demonstrates very high catalytic activities for oxygen reduction(onset potential: 0.91 V, and half-wave potential: 0.87 V vs. RHE) and oxygen evolution(10 m Acm^-2 at 1.58 V) reactions, high methanol tolerance property, and long-term stability(97% current retention). Moreover, our integrated catalyst film shows very good structure flexibility and robustness. Based on the obtained film air electrodes, flexible Zn–air batteries demonstrate low charging and discharging overpotentials(0.82 V at 1 m A cm^-1) and excellent structure stability in the bending tests. These results indicate that presently reported catalyst films are potential air electrodes for flexible metal–air batteries.展开更多
The geometries of imidazole and its derivatives were respectively optimized by using ab initio method, and the molecular orbital energy levels and the charge densities were obtained for their optimum geometries. The f...The geometries of imidazole and its derivatives were respectively optimized by using ab initio method, and the molecular orbital energy levels and the charge densities were obtained for their optimum geometries. The frontier orbital energy levels, and the net charges of N (1) atom and the imidazole ring of those molecules were obtained with ab initio and SCC-DV-Xα methods. It was found that the inhibition properties of those compounds change with the highest occupied molecular orbital energy levels, and the net charges of N (1) atom. We took four iron atoms on the crystal plane (100) of α-iron as the surface which was used to study the adsorption towards the inhibitors. The adsorption models of the inhibitor to be adsorbed on the Fe-cluster surface were optimized with SCC-DV-Xα method. It turns out that the most favorable model is that the inhibitor molecule is adsorbed on the Fe-cluster surface in an inclined state. The calculation shows that the stabilization energies of the systems are well correlated with the inhibition efficiencies.展开更多
Objective:To synthesis 2-substituted-4,5-diphenyl-N- alkyl imidazole derivatives,and evaluate their antibacterial activity.Methods:A mixture of benzil（10 mmol） and ammonium acetate（0.1 mol）（immediately fused） in...Objective:To synthesis 2-substituted-4,5-diphenyl-N- alkyl imidazole derivatives,and evaluate their antibacterial activity.Methods:A mixture of benzil（10 mmol） and ammonium acetate（0.1 mol）（immediately fused） in glacial acetic acid（25 mL） was stirred at 80-100℃for 1 h under nitrogen atmosphere（to prevent incorporation of any atmospheric impurities and moisture）. Substituted aldehydes（10 mmol） in glacial acetic acid（5 mL） was added drop-wise over a period of 15-20 min at the same temperature and stirred for another 4 h,the progress of the reaction was monitored by TLC test using ethyl acetate as eluent.The newly synthesized compounds were characterized by IR,<sup>1</sup>HNMR,<sup>13</sup>CNMR and by mass spectroscopy.Results:All the synthesized compounds were confirmed by spectroscopical techniques and evaluated for antimicrobial activity against Staphylococcus aureus（S.aurius）,Bacilus subtilus（B.subtilus）,and Escheria coli （E.coli）.These compounds showed antibacterial activity（zone of inhibition） against S.aurius ranged from 3 mm to 9 mmin diameter,B.subtilus,4 -8 mm,and E.coli 5 -12 mm.Out of 2a-2e, only 2a and 2b showed some sort of activity but none of them had considerable activity compared with that of the standard.Conclusions:All the synthesized compounds show moderate activity against the tested bacteria S.aurius,B.subtilus,and E.coli.So,further structural modification is necessary to improve the antibacterial action of 2-substituted-4,5-diphenyl-N-alkyl imidazole derivatives.展开更多
The X-ray single-crystal structure analyses have been determined for two metal imidazole chlorides: [Fe(Im)6]Cl24H2O 1 and [CuCl(Im)4]Cl 2 (Im = imidazole). The red crystal of compound 1 is of triclinic, space group P...The X-ray single-crystal structure analyses have been determined for two metal imidazole chlorides: [Fe(Im)6]Cl24H2O 1 and [CuCl(Im)4]Cl 2 (Im = imidazole). The red crystal of compound 1 is of triclinic, space group Pi with Mr = 607.31 (C18H32Cl2FeN12O4), a = 8.797(2), b = 9.068(2), c = 10.581(2) ? a = 75.35(3), ?= 83.20(3), ? = 61.85(3)o, V = 720.0(2) 3, Z = 1, Dc = 1.401 g/cm3, F(000) = 316, = 0.755 mm-1, R = 0.0353 and wR = 0.1227. The blue crystal of compound 2 belongs to monoclinic, space group P21/c with Mr = 406.77 (C12H16Cl2CuN8), a = 13.909(3), b = 8.8933(18), c = 15.086(7) ? ?= 118.32(2), V = 1642.7(9) 3, Z = 4, Dc = 1.645 g/cm3, F(000) = 828, = 1.666 mm-1, R = 0.0609 and wR = 0.1726. In solid state, both 1 and 2 form three-dimensional hydrogen bond networks to stabilize the structures which were also characterized by TG and elemental analyses. The thermal gravity (TG) data indicate that the residues are Fe and Cu for 1 and 2, respectively.展开更多
基金supported by the National Natural Science Foundation of China(No.22265017)the Open Fund of Key Laboratory of Eco-functional Polymer Materials of the Ministry of Education(No.KF-21-04).
文摘In this work,the synthesis of uniform zeolitic imidazolate framework-coated Mo-glycerate spheres and their subsequent conversion into hierarchical architecture containing bimetallic selenides heterostructures and nitrogen-doped carbon shell are reported.Selenization temperature plays a significant role in determining the phases,morphology,and lithium-ion storage performance of the composite.Notably,the optimal electrode demonstrates an ultrahigh reversible capacity of 1298.2 mAh/g after 100 cycles at 0.2 A/g and an outstanding rate capability with the capacity still maintained 505.7 mAh/g after 300 cycles at 1.0 A/g,surpassing the calculated theoretical capacity according to individual component and most of the reported MoSe@C-or ZnSe@C-based anodes.Furthermore,ex-situ X-ray diffraction patterns reveal the combined conversion and alloying reaction mechanisms of the composite.
基金supported by the National Natural Science Foundation of China(Nos.52371240,U1904215)Natural Science Foundation of Jiangsu Province(No.BK20200044)Changjiang scholars’program of the Ministry of Education(No.Q2018270)。
文摘Rationally design the morphology and structure of electroactive nanomaterials is an effective approach to enhance the performance of aqueous batteries.Herein,we co-engineered the hollow architecture and interlayer spacing of layered double hydroxides(LDH)to achieve high electrochemical activity.The hierarchical hollow LDH was prepared from bimetallic zeolitic imidazolate frameworks(ZIF)by a facile cation exchange strategy.Zn and Cu elements were selected as the second metals incorporated in Co-ZIF.The characteristics of the corresponding derivatives were studied.Besides,the transformation mechanism of CoZn-ZIF into nanosheet-assembled hollow Co Zn Ni LDH(denoted as CoZnNi-OH)was systematically investigated.Importantly,the interlayer spacing of CoZnNi-OH expands due to Zn^(2+)incorporation.The prepared CoZnNi-OH offers large surface area,exposed active sites,and rapid mass transfer/diffusion rate,which lead to a significant enhancement in the specific capacitance,rate performance,and cycle stability of CoZnNi-OH electrode.In addition,the aqueous alkaline CoZnNi-OH//Zn showed a maximum energy density/power density of 0.924 m Wh/cm^(2),8.479 m W/cm^(2).This work not only raises an insightful strategy for regulating the morphology and interlayer spacing of LDH,but also provides a reference of designing hollow nickel-based nanomaterials for aqueous batteries.
基金National Natural Science Foundation of China(52073278)the“Medical Science+X”Cross-innovation Team of the Norman Bethune Health Science of Jilin University(2022JBGS10)+2 种基金the Jilin Province Science and Technology Development Program(20190201044JC20230101045JC)the Education Department of Jilin Province(JJKH20231205KJ).
文摘Biological nanotechnologies based on functional nanoplatforms have synergistically catalyzed the emergence of cancer therapies.As a subtype of metal-organic frameworks(MOFs),zeolitic imidazolate frameworks(ZIFs)have exploded in popularity in the field of biomaterials as excellent protective materials with the advantages of conformational flexibility,thermal and chemical stability,and functional controllability.With these superior properties,the applications of ZIF-based materials in combination with various therapies for cancer treatment have grown rapidly in recent years,showing remarkable achievements and great potential.This review elucidates the recent advancements in the use of ZIFs as drug delivery agents for cancer therapy.The structures,synthesis methods,properties,and various modifiers of ZIFs used in oncotherapy are presented.Recent advances in the application of ZIF-based nanoparticles as single or combination tumor treatments are reviewed.Furthermore,the future prospects,potential limitations,and challenges of the application of ZIF-based nanomaterials in cancer treatment are discussed.We except to fully explore the potential of ZIF-based materials to present a clear outline for their application as an effective cancer treatment to help them achieve early clinical application.
基金the financial support from the Special Funds for the Cultivation of Guangdong College Students’Scientific and Technological Innovation(“Climbing Program”Special Funds,pdjh2023b0145)Guangdong Provincial International Joint Research Center for Energy Storage Materials(2023A0505090009)。
文摘As a prevailing cathode material of lithium-ion batteries(LIBs),LiCoO_(2)(LCO)still encounters the tricky problems of structural collapse,whose morphological engineering and cation doping are crucial for surmounting the mechanical strains and alleviating phase degradation upon cycling.Hereinafter,we propose a strategy using a zeolitic imidazolate framework(ZIF)as the self-sacrificing template to directionally prepare a series of LiNi_(0.1)Co_(0.9)O_(2)(LNCO)with tailorable electrochemical properties.The rational selection of sintering temperature imparts the superiority of the resultant products in lithium storage,during which the sample prepared at 700℃(LNCO-700)outperforms its counterparts in cyclability(156.8 mA h g^(-1)at 1 C for 200 cycles in half cells,1 C=275 mA g^(-1))and rate capability due to the expedited ion/electron transport and the strengthen mechanical robustness.The feasibility of proper Ni doping is also divulged by half/full cell tests and theoretical study,during which LNCO-700(167 mA h g^(-1)at 1 C for 100 cycles in full cells)surpasses LCO-700 in battery performance due to the mitigated phase deterioration,stabilized layered structu re,ameliorated electro nic co nductivity,a nd exalted lithium sto rage activity.This work systematically unveils tailorable electrochemical behaviors of LNCO to better direct their practical application.
基金supported by the National Natural Science Foundation of China(Nos.22301034,22301033)the Jiangxi Provincial Natural Science Foundation(No.20232ACB213005)。
文摘A dimeric Y(III)-containing antimonotungstate[Y_(4)(H_(2)O)_(8)(mal)_(2)(OAc)O(Sb_(2)W_(2)^(V)W_(19)^(VI)O_(72))_(2)]^(21-)(Y_(4)mal_(2),H_(3)mal=DL-malic acid),resembling a“handshake”configuration,was synthesized and characterized.The polyanion of Y_(4)mal_(2)consists of two Dawson-derived{Y_(2)Sb_(2)W_(21)}moieties that are further linked by two mal ligands and oneμ_(2)-bridging acetate to form an asymmetric polyanion.Notably,the chiral configuration induced by the D-or L-configuration of the mal ligand results in both{Y_(2)Sb_(2)W_(21)}moieties within one polyanion exhibiting identical chirality,leading to the racemate crystallization of Y_(4)mal_(2).Moreover,Y_(4)mal_(2)exhibits excellent Lewis acid catalytic activity for environmentally friendly synthesis of imidazoles.
基金the finical support of the National Natural Science Foundation of China(Nos.21972124,22272148)a project funded by the Priority Academic Program Development of Jiangsu Higher Education Institution。
文摘Hybrid metal-organic framework(MOF)derivatives play a significant role in the novel catalyst development in energy conversion reactions.Here,we demonstrated the low-temperature fully fluorinated zeolitic imidazole framework(ZIF)coupled with a three-dimensional open framework Prussian blue analog(PBA)with combined advantages for electrocatalytic oxygen evolution reaction(OER)in water splitting reaction.The spectroscopic analysis and the electrochemical studies revealed the combined advantages of efficient electronic effect and active site synergism.Because of good conductivity improvement by Ndoped carbon derived from ZIF and the high electrochemical surface area and active site exposure from PBA derivatives,good catalytic performance was obtained on the optimal catalyst of Co Ni ZIF/Co Fe-PBAF-300,which required a low overpotential of 250 m V to reach 10 m A/cm^(2)loaded on the glassy carbon electrode,with Tafel slope of 47.4 m V/dec,and very high dynamic and steady stability.In addition,the multi-component with the mixed structure from highly polar metal fluorides promoted the easy formation of the active phase as revealed by the post-sample analysis.The current results showed a novel composite catalyst materials development from the hybrid MOF derivatives,which would be promising in the electrolysis of water oxidation reactions and energy-relevant catalysis reactions.
基金This work was supported by the National Natural Science Foundation of China(Nos.30800705 and 31101599)the Provincial Natural Science Foundation of Zhejiang(Nos.LY15C150004 and LY18C150007)the Key Research and Devel opment Projects of Social Development of Jinhua Science and Technology Program(No.2021C22750).
文摘Zeolite imidazole frameworks(ZIFs),a class of the metal organic framework,have been extensively studied in environmental applications.However,their environmental fate and potential ecological impact on plants remain unknown.Here,we investigated the phytotoxicity,transformation,and bioaccumulation processes of two typical ZIFs(ZIF-8 and ZIF-67)in rice(Oryza sativa L.)under hydroponic conditions.ZIF-8 and ZIF-67 in the concentration of 50 mg/L decreased root and shoot dry weight maximally by 55.2%and 27.5%,53.5%and 37.5%,respectively.The scanning electron microscopy(SEM)imaging combined with X-ray diffraction(XRD)patterns revealed that ZIFs on the root surface gradually collapsed and transformed into nanosheets with increasing cultivation time.The fluorescein isothiocyanate(FITC)labeled ZIFs were applied to trace the uptake and translocation of ZIFs in rice.The results demonstrated that the transformed ZIFs were mainly distributed in the intercellular spaces of rice root,while they cannot be transported to culms and leaves.Even so,the Co and Zn contents of rice roots and shoots in the ZIFs treated groups were increased by 1145%and 1259%,145%and 259%,respectively,compared with the control groups.These findings suggested that the phytotoxicity of ZIFs are primarily attributed to the transformed ZIFs and to a less extent,the metal ions and their ligands,and they were internalized by rice root and increased the Co and Zn contents of shoots.This study reported the transformation of ZIFs and their biological effectiveness in rice,highlighting the potential environmental hazards and risks of ZIFs to crop plants.
基金support from the Natural Science Foundation of Gansu Province(No.3ZS061-A25-019)the Scientific Research Fund of Gansu Provincial Education Department(No.0601-25).
文摘An efficient protocol for the one-pot multicomponent synthesis of various 2,4,5 -triaryl- 1H-imidazoles and 1,2,4,5 -tetraaryl- 1H- imidazoles using PEG-400 as reaction medium is described. This method has the advantages of good yields, less pollution and simple reaction conditions.
基金This work was supported by the National Natural Science Foundation of China(Grant Nos.51603052 and 51573216)the Fundamental Research Funds for the Central Universities(Grant Nos.18lgpy02 and 16lgjc66).
文摘Metal-organic frameworks(MOFs)have been intensely studied for the past few decades as an enormous family of highly tunable porous materials with promisingly applicable functionalities in adsorption,separation,catalysis,sensing,electrochemistry,and a great number of emerging purposes.As a classic MOF,zeolitic imidazolate framework-8(ZIF-8)is conventionally one of the very few MOF members that has been commercialized with considerable production.
文摘We report here the synthesis and in vivo anticonvulsant/neurotoxicity activities of a series of compounds belonging to 2-aryl-4-arylidene-1-phenyl-1H-imidazol-5(4H)-one. The scaffold is based on the commonality of 5-membered lactam ring structures as successful anticonvulsant agents. The present compounds exhibited a range of anticonvulsant activity in pentylenetetrazole (PTZ)-induced seizure test. In particular, the protection was excellent by compounds bearing furylmethylidene on C4, possibly due to good pharmacokinetic properties. It was found that high lipophilicity and/or electron deficient aryl ring substitution at C4 compromised the anticonvulsant activities. For example, chloro analogues were found much less active than unsubstituted phenyl or furyl derivatives. Regarding side effects, active compounds exerted no observable neurotoxic effect at their therapeutic doses in Chimney test.
基金National Natural Science Foundation of China(Nos.U20041101,21772034,U1704251)the Top-notch Personnel Fund of Henan Agricultural University(No.30500418)for financial support。
文摘A novel thiazolothiazole-bridged imidazole derivative(1) was found to exhibit blue fluorescence in gaseous state or in methanol and yellow fluorescence in solid state. The N-alkylation of imidazole subunit(s) in 1 using n-propyl iodide generated unsymmetrically or symmetrically alkylated thiazolothiazolebridged imidazolium salts with good water solubility and remarkably strong emission in solution. Furthermore, the replacement of iodide counter-anion by triflate or bis(trifluoromethane sulfonyl)imide achieved remarkably strong emission in solid state and in solution as well as good water solubility. The strong fluorescence of dicationic salts with triflate and NTf_(2)^(-)counter-anions in solid state can be ascribed to their twisted and rigid structures induced by interionic C-H···F hydrogen bonding.
基金supported by the National Natural Science Foundation of China(20873150)the Natural Science Foundation of Shandong Province(ZR2010BL012,ZR2010BQ023)
文摘Hydrothermal reactions of two imidazole derivatives （1,3,5-tib = 1,3,5-tris（1H- imidazol- 1 -yl）benzene, 1,4-bimb = 1,4-bis（1 H-imidazol- 1 -ylmethyl）benzene） and the ZnⅡ cations in the presence of oxalic acid （H2ox） afford two coordination polymers, namely, {[Zn（ox）（1,3,5- tib）]·2（H20）}n （1） and [Znl.5（OX）1.5（1,4-bimb）l.5]n （2）. Their structures have been determined by single-crystal X-ray diffraction analyses, elemental analyses, IR spectra, and powder X-ray diffraction （PXRD） analyses. Both complexes 1 and 2 are based on the 1D zigzag [Zn（ox）]n chains, and their final structures are controlled by the two different imidazole linkers, which expanded the structure along different directions, finally giving a 3D dia net for 1 and a 2D sql layer for 2. Moreover, the luminescent properties of 1 and 2 have been investigated.
文摘A new synthesis of 1 - (ω- haloalkyl ) -imidazole has been developed. The synthesisinvolves a Hoffmann-type elimination of the 2-cyanoethyl group from inddazolium salts obtainedby the reaction of α,ω-dihalide with 1-(2-cyanoethyl)-imidazole.
基金This work was supported by the National Natural Science Foundation of China (50532030, 50335050, and 50325311) and Education Committee of Anhui Province (2006KJ158B)
文摘A novel imidazole derivative with functional group and π-conjugated system, 1- [trans-4-（4-diethylaminostyryl）phenyl]imidazole （abbreviated as L）, and its Con complex （COCl2L4）2 （Co2C168H184N24Cl4, Mr = 2799.05 ） have been synthesized and the crystal structure of the latter was determined by X-ray diffraction. The crystal is of triclinic, space group PI with a = 8.823（3）, b = 18.799（7）, c =23.065（9） A, α = 77.349（6）, β = 83.128（7）, ）, γ= 80.942（3）°, V = 3671.5（12） A^3, Z = 1, Dc = 1.266 g/cm^3,/z = 0.361 mm^-1 F（000） = 1482, the final R = 0.0587 and wR = 0.1284 for 6562 observed reflections with I 〉 2σ（I）. In the molecular structure of （COCl2L4）2, there are two crystallographically unique units. The Co^Ⅱ atoms are six-coordinated by four N atoms from four imidazole ligands （L） and two Cl atoms to form a distorted octahedral geometry. The optical properties of complex （COCl2L4）2 have been experimentally studied.
基金financially supported by Natural Science Foundation of China(No.81871411)National Key R&D Program of China(2018YFC0910601)+1 种基金Youth Innovation Promotion Association Foundation of CAS(2017340)The Science&Technology Bureau of Ningbo City(2015B11002).
文摘Zeolitic imidazolate frameworks(ZIFs)as smart drug delivery systems with microenvironment-triggered release have attracted much attention for tumor therapy.However,the exploration of ZIFs in biomedicine still encounters many issues,such as inconvenient surface modification,fast drug release during blood circulation,undesired damage to major organs,and severe in vivo toxicity.To address the above issues,we developed an Mn-ZIF-90 nanosystem functionalized with an originally designed active-targeting and pH-responsive magnetic resonance imaging(MRI)Y1 receptor ligand[Asn28,Pro30,Trp32]-NPY(25-36)for imaging-guided tumor therapy.After Y1 receptor ligand modification,the Mn-ZIF-90 nanosystem exhibited high drug loading,better blood circulation stability,and dual breast cancer cell membrane and mitochondria targetability,further favoring specific microenvironment-triggered tumor therapy.Meanwhile,this nanosystem showed promising T1-weighted magnetic resonance imaging contrast in vivo in the tumor sites.Especially,this nanosystem with fast clean-up had almost no obvious toxicity and no damage occurred to the major organs in mice.Therefore,this nanosystem shows potential for use in imaging-guided tumor therapy.
文摘The interactions of nine rare earth perchlorate complexes with alanine and imidazole were studied in methanol. The general formulae of these compounds are RE(Ala) 2Im(ClO 4) 3· n H 2O(RE=Ce, Pr, Nd, Sm, Eu, Gd, Tb, Yb) and La(Ala) 3Im(ClO 4) 3·H 2O, respectively. The composition and structure of the prepared compounds were determined by the chemical analysis, elemental analysis, IR spectroscopy, UV, FS spectroscopy, X ray powder diffraction, 1H NMR and solubility. The thermal decomposition processes of these complexes were studied on the basis of TG DTG. The preliminary bioassay shows that the compounds have a remarkable bacteriostasis effect on nine varieties of microbe.
基金financial supports from the National Natural Science Foundation of China(21773293 , 21603264)CAS Pioneer Hundred Talents Program (J. Di)+1 种基金The National Key Research and Development Program of China(2016YFA0203301)Key Research Program of Frontier Science of Chinese Academy of Sciences(QYZDB-SSW-SLH031)
文摘Recently, the development of high-performance bifunctional oxygen catalysts integrated with flexible conductive scaffolds f or rechargeable metal-air batteries has attracted considerable interest, driving by fastgrowing wearable electronics. Herein, we report a flexible bifunctional oxygen catalyst thin film consisting of Co–N–C bifunctional catalysts embedding in carbon nanotube(CNT) networks. The catalyst is readily prepared by pyrolysis of cobalt-based zeolitic imidazolate frameworks(ZIF-67) that are in-situ synthesized in CNT networks. Such catalyst film demonstrates very high catalytic activities for oxygen reduction(onset potential: 0.91 V, and half-wave potential: 0.87 V vs. RHE) and oxygen evolution(10 m Acm^-2 at 1.58 V) reactions, high methanol tolerance property, and long-term stability(97% current retention). Moreover, our integrated catalyst film shows very good structure flexibility and robustness. Based on the obtained film air electrodes, flexible Zn–air batteries demonstrate low charging and discharging overpotentials(0.82 V at 1 m A cm^-1) and excellent structure stability in the bending tests. These results indicate that presently reported catalyst films are potential air electrodes for flexible metal–air batteries.
基金Supported by the National Natural Science Foundation of China(No. 29703003).
文摘The geometries of imidazole and its derivatives were respectively optimized by using ab initio method, and the molecular orbital energy levels and the charge densities were obtained for their optimum geometries. The frontier orbital energy levels, and the net charges of N (1) atom and the imidazole ring of those molecules were obtained with ab initio and SCC-DV-Xα methods. It was found that the inhibition properties of those compounds change with the highest occupied molecular orbital energy levels, and the net charges of N (1) atom. We took four iron atoms on the crystal plane (100) of α-iron as the surface which was used to study the adsorption towards the inhibitors. The adsorption models of the inhibitor to be adsorbed on the Fe-cluster surface were optimized with SCC-DV-Xα method. It turns out that the most favorable model is that the inhibitor molecule is adsorbed on the Fe-cluster surface in an inclined state. The calculation shows that the stabilization energies of the systems are well correlated with the inhibition efficiencies.
文摘Objective:To synthesis 2-substituted-4,5-diphenyl-N- alkyl imidazole derivatives,and evaluate their antibacterial activity.Methods:A mixture of benzil（10 mmol） and ammonium acetate（0.1 mol）（immediately fused） in glacial acetic acid（25 mL） was stirred at 80-100℃for 1 h under nitrogen atmosphere（to prevent incorporation of any atmospheric impurities and moisture）. Substituted aldehydes（10 mmol） in glacial acetic acid（5 mL） was added drop-wise over a period of 15-20 min at the same temperature and stirred for another 4 h,the progress of the reaction was monitored by TLC test using ethyl acetate as eluent.The newly synthesized compounds were characterized by IR,<sup>1</sup>HNMR,<sup>13</sup>CNMR and by mass spectroscopy.Results:All the synthesized compounds were confirmed by spectroscopical techniques and evaluated for antimicrobial activity against Staphylococcus aureus（S.aurius）,Bacilus subtilus（B.subtilus）,and Escheria coli （E.coli）.These compounds showed antibacterial activity（zone of inhibition） against S.aurius ranged from 3 mm to 9 mmin diameter,B.subtilus,4 -8 mm,and E.coli 5 -12 mm.Out of 2a-2e, only 2a and 2b showed some sort of activity but none of them had considerable activity compared with that of the standard.Conclusions:All the synthesized compounds show moderate activity against the tested bacteria S.aurius,B.subtilus,and E.coli.So,further structural modification is necessary to improve the antibacterial action of 2-substituted-4,5-diphenyl-N-alkyl imidazole derivatives.
基金This work was supported by the Natural Science Foundation of Shandong Province (No.Y2002B06)
文摘The X-ray single-crystal structure analyses have been determined for two metal imidazole chlorides: [Fe(Im)6]Cl24H2O 1 and [CuCl(Im)4]Cl 2 (Im = imidazole). The red crystal of compound 1 is of triclinic, space group Pi with Mr = 607.31 (C18H32Cl2FeN12O4), a = 8.797(2), b = 9.068(2), c = 10.581(2) ? a = 75.35(3), ?= 83.20(3), ? = 61.85(3)o, V = 720.0(2) 3, Z = 1, Dc = 1.401 g/cm3, F(000) = 316, = 0.755 mm-1, R = 0.0353 and wR = 0.1227. The blue crystal of compound 2 belongs to monoclinic, space group P21/c with Mr = 406.77 (C12H16Cl2CuN8), a = 13.909(3), b = 8.8933(18), c = 15.086(7) ? ?= 118.32(2), V = 1642.7(9) 3, Z = 4, Dc = 1.645 g/cm3, F(000) = 828, = 1.666 mm-1, R = 0.0609 and wR = 0.1726. In solid state, both 1 and 2 form three-dimensional hydrogen bond networks to stabilize the structures which were also characterized by TG and elemental analyses. The thermal gravity (TG) data indicate that the residues are Fe and Cu for 1 and 2, respectively.
