Metal–organic gel(MOG)derived composites are promising multi-functional materials due to their alterable composition,identifiable chemical homogeneity,tunable shape,and porous structure.Herein,stable metal–organic h...Metal–organic gel(MOG)derived composites are promising multi-functional materials due to their alterable composition,identifiable chemical homogeneity,tunable shape,and porous structure.Herein,stable metal–organic hydrogels are prepared by regulating the complexation effect,solution polarity and curing speed.Meanwhile,collagen peptide is used to facilitate the fabrication of a porous aerogel with excellent physical properties as well as the homogeneous dispersion of magnetic particles during calcination.Subsequently,two kinds of heterometallic magnetic coupling systems are obtained through the application of Kirkendall effect.FeCo/nitrogen-doped carbon(NC)aerogel demonstrates an ultra-strong microwave absorption of−85 dB at an ultra-low loading of 5%.After reducing the time taken by atom shifting,a FeCo/Fe3O4/NC aerogel containing virus-shaped particles is obtained,which achieves an ultra-broad absorption of 7.44 GHz at an ultra-thin thickness of 1.59 mm due to the coupling effect offered by dual-soft-magnetic particles.Furthermore,both aerogels show excellent thermal insulation property,and their outstanding radar stealth performances in J-20 aircraft are confirmed by computer simulation technology.The formation mechanism of MOG is also discussed along with the thermal insulation and electromagnetic wave absorption mechanism of the aerogels,which will enable the development and application of novel and lightweight stealth coatings.展开更多
BACKGROUND Norcantharidin(NCTD)is suitable for the treatment of primary liver cancer,especially early and middle primary liver cancer.This compound can reduce tumors and improve immune function.However,the side effect...BACKGROUND Norcantharidin(NCTD)is suitable for the treatment of primary liver cancer,especially early and middle primary liver cancer.This compound can reduce tumors and improve immune function.However,the side effects of NCTD have limited its application.There is a marked need to reduce the side effects and increase the efficacy of NCTD.AIM To develop a nanomaterial carrier,NCTD-loaded metal-organic framework IRMOF-3 coated with a temperature-sensitive gel(NCTD-IRMOF-3-Gel),aiming to improve the anticancer activity of NCTD and reduce the drug dose.METHODS NCTD-IRMOF-3-Gel was obtained by a coordination reaction.The apparent characteristics and in vitro release of NCTD-IRMOF-3-Gel were investigated.Cell cytotoxicity assays,flow cytometry,and apoptosis experiments in mouse hepatoma(Hepa1-6)cells were used to determine the anti-liver cancer activity of NCTD-IRMOF-3-Gel in in vitro models.RESULTS The particle size of NCTD-IRMOF-3-Gel was 50-100 nm,and the particle size distribution was uniform.The release curve showed that NCTD-IRMOF-3-Gel had an obvious sustained-release effect.The cytotoxicity assays showed that the free drug NCTD and NCTD-IRMOF-3-Gel treatments markedly inhibited Hepa1-6 cell proliferation,and the inhibition rate increased with increasing drug concentration.By flow cytometry,NCTD-IRMOF-3-Gel was observed to block the Hepa1-6 cell cycle in the S and G2/M phases,and the thermosensitive gel nanoparticles may inhibit cell proliferation by inducing cell cycle arrest.Apoptosis experiments showed that NCTD-IRMOF-3-Gel induced the apoptosis of Hepa1-6 cells.CONCLUSION Our results indicated that the NCTD-IRMOF-3-Gel may be beneficial for liver cancer disease treatment.展开更多
A novel heterogeneous catalyst for ultrasound-assisted oxidative desulfurization(UAODS)was designed and synthesized by confining polyoxometalates(POMs)clusters within porous metal-organic gel.The catalyst microstructu...A novel heterogeneous catalyst for ultrasound-assisted oxidative desulfurization(UAODS)was designed and synthesized by confining polyoxometalates(POMs)clusters within porous metal-organic gel.The catalyst microstructures were characterized by XRD,SEM-EDX,FT-IR,N_(2)adsorption-desorption,and XPS.Effects of POM loading,catalyst dosage,and ultrasonic power were also investigated.Results indicate that 60%-PMA@MOX(Al)exhibits optimal catalytic activity,with a sulfur removal rate of 98.61%and excellent reusability.Moreover,a kinetic study of different desulfurization approaches demonstrates that the unique thermal and cavitation effects of ultrasound can effectively improve the efficiency of oxidative desulfurization.展开更多
All solid-state electrolytes have the advantages of good mechanical and thermal properties for safer energy storage,but their energy density has been limited by low ionic conductivity and large interfacial resistance ...All solid-state electrolytes have the advantages of good mechanical and thermal properties for safer energy storage,but their energy density has been limited by low ionic conductivity and large interfacial resistance caused by the poor Li~+transport kinetics due to the solid-solid contacts between the electrodes and the solid-state electrolytes.Herein,a novel gel polymer electrolyte(UPP-5)composed of ionic liquid incorporated metal-organic frameworks nanoparticles(IL@MOFs)is designed,it exhibits satisfying electrochemical performances,consisting of an excellent electrochemical stability window(5.5 V)and an improved Li^(+)transference number of 0.52.Moreover,the Li/UPP-5/LiFePO_(4) full cells present an ultra-stable cycling performance at 0.2C for over 100 cycles almost without any decay in capacities.This study might provide new insight to create an effective Li^(+)conductive network for the development of all-solid-state lithium-ion batteries.展开更多
Three multi-responsiveness supramolecular metal-organic gels(MOGs)have been prepared upon Ba(OAc)_(2),CdSO_(4)•8H_(2)O and Pb(NO_(3))_(2) with a simple ligand(G17)based on a carboxyl-functionalized benzimidazole deriv...Three multi-responsiveness supramolecular metal-organic gels(MOGs)have been prepared upon Ba(OAc)_(2),CdSO_(4)•8H_(2)O and Pb(NO_(3))_(2) with a simple ligand(G17)based on a carboxyl-functionalized benzimidazole derivative in alcoholic-water solutions.The MOGs display the formation of well-developed nanofibrillar networks composed of intertwined fibers which provide stability to gels structures through coordination,hydrogen bonding and π-π interactions characterized by using field emission scanning electron microscopy(FESEM),the fourier transform infrared(FT-IR)spectroscopy and powder X-ray diffraction(XRD)techniques.MOG-1 shows good stimuli responsiveness toward the changes in K_(2)CrO_(4),both MOG-2 and MOG-3 do good job toward the changes in Na_(2)S.Moreover,because these MOGs were formed easily by gelator with some heavy metal ion,such as Cd(Ⅱ)and Pb(Ⅱ),it might provide the basis for heavy metal ion capture and removal.展开更多
Nanoscale metal-organic frameworks (NMOFs) have attracted increased attention in recent years for miniaturized and/or biological applications.However,the synthesis of ultrasmall NMOFs with good stability is a great ...Nanoscale metal-organic frameworks (NMOFs) have attracted increased attention in recent years for miniaturized and/or biological applications.However,the synthesis of ultrasmall NMOFs with good stability is a great challenge.In this study,sub-5-nm nano-HKUST-1 was prepared for the first time via a mild metalorganic gel route without surfactants or capping agents.Controlling the gelation process via anion-ligand self-assembly is the key to the formation of NMOFs.The Tyndall effect,zeta potential,and liquid adsorption indicated strong stability of the obtained nano-HKUST-1,even in water.Adsorption experiments were performed using different dyes (crystal violet and methylene blue) to demonstrate the size-dependent adsorption thermodynamics and kinetics of this famous MOF.The results of this study provide new insights regarding the synthesis of NMOFs and their efficient applications.展开更多
A novel smart metal-organic gel(MOG) formed from biscarboxyl-functionalized benzimidazole derivative(D11) in the presence of lead nitrate has been investigated.The critical gel concentration for the formation of M...A novel smart metal-organic gel(MOG) formed from biscarboxyl-functionalized benzimidazole derivative(D11) in the presence of lead nitrate has been investigated.The critical gel concentration for the formation of MOG was just 0.36 wt%,which exhibits a super gelation capability of D11.The coordination of the metal to the ligand D11 was found to play a vital role in the construction of the supramolecular MOG.Microstructures determined by SEM observation demonstrated that the MOG was formed by intertwined fibrils.Interestingly,the MOG exhibits pH-induced,thermo-induced,and chemical-induced reversible gel-sol transition.Meanwhile,this supramolecular MOG shows desirable absorption ability of methyl orange dye molecules in aqueous solution.展开更多
Incorporation of phosphine-Pd catalytic centers in gel network is an important strategy to develop highly active catalysts.In this contribution we show that catalytically active phosphine-Pd(II)gels can be readily obt...Incorporation of phosphine-Pd catalytic centers in gel network is an important strategy to develop highly active catalysts.In this contribution we show that catalytically active phosphine-Pd(II)gels can be readily obtained via re-action of rigid bridging terpyridyl phosphines and Pd(II).The terpyridyl phosphines,Py2P2 and Py2P,contain one 4,2':6',4"-terpyridyl group and two/one diphenylphosphino groups.Reactions of Py2P2/Py2P and Pd(II)in CHCl_(3)-MeOH afforded the corresponding phosphine-Pd(II)gels at room temperature or at elevated temperature(40℃).The gelation is driven by formation of metal-organic coordination.Mild heating is important in triggering the formation of Py2P-Pd(II)gel.The gels have a coherent,rigid spongy porous network of continuous nanome-ter-sized particles.The phosphine-Pd(II)gels showed high activity in the Suzuki-Miyaura reactions of aryl bro-mides under ambient conditions and could be recycled and reused.展开更多
Efficient removal of non-biodegradable and hazardous dyes from wastewater remains a hot research topic.Herein,a rationally designed a Cu(Ⅱ)-based metal–organic gel(Cu-MOG)with a nanoporous 3 D network structure prep...Efficient removal of non-biodegradable and hazardous dyes from wastewater remains a hot research topic.Herein,a rationally designed a Cu(Ⅱ)-based metal–organic gel(Cu-MOG)with a nanoporous 3 D network structure prepared via a simple one-step mixing method was successfully employed for the removal of cationic dyes.The Cu-MOG exhibited high efficiency,with an adsorption capacity of up to 650.32 mg/g,and rapid adsorption efficiency,with the ability to adsorb 80%of Neutral Red within 1 min.The high adsorption efficiency was attributed to its large specific surface area,which enabled it to massively bind cationic dyes through electrostatic interaction,and a nanoporous structure that promoted intra-pore diffusion.Remarkably,the Cu-MOG displayed size-selective adsorption,based on adsorption studies concerning dyes of different sizes as calculated by density functional theory.Additionally,the adsorption performance of the Cu-MOG still maintained removal efficiency of 100%after three regeneration cycles.These results suggested that the Cu-MOG could be expected to be a promising and competitive candidate to conveniently process wastewater.展开更多
基金the National Natural Science Foundation of China(22265021)the Aeronautical Science Foundation of China(2020Z056056003).
文摘Metal–organic gel(MOG)derived composites are promising multi-functional materials due to their alterable composition,identifiable chemical homogeneity,tunable shape,and porous structure.Herein,stable metal–organic hydrogels are prepared by regulating the complexation effect,solution polarity and curing speed.Meanwhile,collagen peptide is used to facilitate the fabrication of a porous aerogel with excellent physical properties as well as the homogeneous dispersion of magnetic particles during calcination.Subsequently,two kinds of heterometallic magnetic coupling systems are obtained through the application of Kirkendall effect.FeCo/nitrogen-doped carbon(NC)aerogel demonstrates an ultra-strong microwave absorption of−85 dB at an ultra-low loading of 5%.After reducing the time taken by atom shifting,a FeCo/Fe3O4/NC aerogel containing virus-shaped particles is obtained,which achieves an ultra-broad absorption of 7.44 GHz at an ultra-thin thickness of 1.59 mm due to the coupling effect offered by dual-soft-magnetic particles.Furthermore,both aerogels show excellent thermal insulation property,and their outstanding radar stealth performances in J-20 aircraft are confirmed by computer simulation technology.The formation mechanism of MOG is also discussed along with the thermal insulation and electromagnetic wave absorption mechanism of the aerogels,which will enable the development and application of novel and lightweight stealth coatings.
基金Supported by National Natural Science Foundation of China,No.82074025 and No.82074271the Heilongjiang Traditional Chinese Medicine Research Project,No.ZHY18-047and Scientific Research Project of Heilongjiang Health Committee,No.2020-293.
文摘BACKGROUND Norcantharidin(NCTD)is suitable for the treatment of primary liver cancer,especially early and middle primary liver cancer.This compound can reduce tumors and improve immune function.However,the side effects of NCTD have limited its application.There is a marked need to reduce the side effects and increase the efficacy of NCTD.AIM To develop a nanomaterial carrier,NCTD-loaded metal-organic framework IRMOF-3 coated with a temperature-sensitive gel(NCTD-IRMOF-3-Gel),aiming to improve the anticancer activity of NCTD and reduce the drug dose.METHODS NCTD-IRMOF-3-Gel was obtained by a coordination reaction.The apparent characteristics and in vitro release of NCTD-IRMOF-3-Gel were investigated.Cell cytotoxicity assays,flow cytometry,and apoptosis experiments in mouse hepatoma(Hepa1-6)cells were used to determine the anti-liver cancer activity of NCTD-IRMOF-3-Gel in in vitro models.RESULTS The particle size of NCTD-IRMOF-3-Gel was 50-100 nm,and the particle size distribution was uniform.The release curve showed that NCTD-IRMOF-3-Gel had an obvious sustained-release effect.The cytotoxicity assays showed that the free drug NCTD and NCTD-IRMOF-3-Gel treatments markedly inhibited Hepa1-6 cell proliferation,and the inhibition rate increased with increasing drug concentration.By flow cytometry,NCTD-IRMOF-3-Gel was observed to block the Hepa1-6 cell cycle in the S and G2/M phases,and the thermosensitive gel nanoparticles may inhibit cell proliferation by inducing cell cycle arrest.Apoptosis experiments showed that NCTD-IRMOF-3-Gel induced the apoptosis of Hepa1-6 cells.CONCLUSION Our results indicated that the NCTD-IRMOF-3-Gel may be beneficial for liver cancer disease treatment.
基金the Project of Jilin Provincial Department of Education (JJKH20190827KJ)the Outstanding Young Talents Fund Project of Jilin Provincial Department of Science and Technology (20190103117JH) for financially support
文摘A novel heterogeneous catalyst for ultrasound-assisted oxidative desulfurization(UAODS)was designed and synthesized by confining polyoxometalates(POMs)clusters within porous metal-organic gel.The catalyst microstructures were characterized by XRD,SEM-EDX,FT-IR,N_(2)adsorption-desorption,and XPS.Effects of POM loading,catalyst dosage,and ultrasonic power were also investigated.Results indicate that 60%-PMA@MOX(Al)exhibits optimal catalytic activity,with a sulfur removal rate of 98.61%and excellent reusability.Moreover,a kinetic study of different desulfurization approaches demonstrates that the unique thermal and cavitation effects of ultrasound can effectively improve the efficiency of oxidative desulfurization.
基金financially supported by National Natural Science Foundation of China (No.21701083)。
文摘All solid-state electrolytes have the advantages of good mechanical and thermal properties for safer energy storage,but their energy density has been limited by low ionic conductivity and large interfacial resistance caused by the poor Li~+transport kinetics due to the solid-solid contacts between the electrodes and the solid-state electrolytes.Herein,a novel gel polymer electrolyte(UPP-5)composed of ionic liquid incorporated metal-organic frameworks nanoparticles(IL@MOFs)is designed,it exhibits satisfying electrochemical performances,consisting of an excellent electrochemical stability window(5.5 V)and an improved Li^(+)transference number of 0.52.Moreover,the Li/UPP-5/LiFePO_(4) full cells present an ultra-stable cycling performance at 0.2C for over 100 cycles almost without any decay in capacities.This study might provide new insight to create an effective Li^(+)conductive network for the development of all-solid-state lithium-ion batteries.
基金the National Natural Science Foundation of China(Nos.21064006,21262032 and 21161018)the Program for Changjiang Scholars and Innovative Research Team in University of Ministry of Education of China(No.IRT1177)+1 种基金the Natural Science Foundation of Gansu Province(No.1010RJZA018)the Youth Foundation of Gansu Province(No.1208RJYA048 and NWNU-LKQN-11-32).
文摘Three multi-responsiveness supramolecular metal-organic gels(MOGs)have been prepared upon Ba(OAc)_(2),CdSO_(4)•8H_(2)O and Pb(NO_(3))_(2) with a simple ligand(G17)based on a carboxyl-functionalized benzimidazole derivative in alcoholic-water solutions.The MOGs display the formation of well-developed nanofibrillar networks composed of intertwined fibers which provide stability to gels structures through coordination,hydrogen bonding and π-π interactions characterized by using field emission scanning electron microscopy(FESEM),the fourier transform infrared(FT-IR)spectroscopy and powder X-ray diffraction(XRD)techniques.MOG-1 shows good stimuli responsiveness toward the changes in K_(2)CrO_(4),both MOG-2 and MOG-3 do good job toward the changes in Na_(2)S.Moreover,because these MOGs were formed easily by gelator with some heavy metal ion,such as Cd(Ⅱ)and Pb(Ⅱ),it might provide the basis for heavy metal ion capture and removal.
基金This work was supported by the National Natural Science Foundation of China (No. 21571193), Open Funds of the state key Laboratory of Rare Earth Resource Utilization (No. RERU2013012), Science Foundation of Guangdong Province (No. 2015A030312007) and National Postdoctoral Program for Innovative Talents (No. BX201600195).
文摘Nanoscale metal-organic frameworks (NMOFs) have attracted increased attention in recent years for miniaturized and/or biological applications.However,the synthesis of ultrasmall NMOFs with good stability is a great challenge.In this study,sub-5-nm nano-HKUST-1 was prepared for the first time via a mild metalorganic gel route without surfactants or capping agents.Controlling the gelation process via anion-ligand self-assembly is the key to the formation of NMOFs.The Tyndall effect,zeta potential,and liquid adsorption indicated strong stability of the obtained nano-HKUST-1,even in water.Adsorption experiments were performed using different dyes (crystal violet and methylene blue) to demonstrate the size-dependent adsorption thermodynamics and kinetics of this famous MOF.The results of this study provide new insights regarding the synthesis of NMOFs and their efficient applications.
基金supported by the National Natural Science Foundation of China(Nos.21064006,21161018 and 21262032)the Program for Changjiang Scholars and Innovative Research Team in University of Ministry of Education of China(No.IRT1177)+2 种基金the Natural Science Foundation of Gansu Province(No. 1010RJZA018)the Youth Foundation of Gansu Province(No.1208RJYA048)NWNU-LKQN-11-32
文摘A novel smart metal-organic gel(MOG) formed from biscarboxyl-functionalized benzimidazole derivative(D11) in the presence of lead nitrate has been investigated.The critical gel concentration for the formation of MOG was just 0.36 wt%,which exhibits a super gelation capability of D11.The coordination of the metal to the ligand D11 was found to play a vital role in the construction of the supramolecular MOG.Microstructures determined by SEM observation demonstrated that the MOG was formed by intertwined fibrils.Interestingly,the MOG exhibits pH-induced,thermo-induced,and chemical-induced reversible gel-sol transition.Meanwhile,this supramolecular MOG shows desirable absorption ability of methyl orange dye molecules in aqueous solution.
基金National Natural Science Founda-tion of China (21273007 and 21350110212)Program for New Century Excellent Talents in University (NCET-13-0615)the Fundamental Research Funds for the Central Universities (14lgpy05)for support.
文摘Incorporation of phosphine-Pd catalytic centers in gel network is an important strategy to develop highly active catalysts.In this contribution we show that catalytically active phosphine-Pd(II)gels can be readily obtained via re-action of rigid bridging terpyridyl phosphines and Pd(II).The terpyridyl phosphines,Py2P2 and Py2P,contain one 4,2':6',4"-terpyridyl group and two/one diphenylphosphino groups.Reactions of Py2P2/Py2P and Pd(II)in CHCl_(3)-MeOH afforded the corresponding phosphine-Pd(II)gels at room temperature or at elevated temperature(40℃).The gelation is driven by formation of metal-organic coordination.Mild heating is important in triggering the formation of Py2P-Pd(II)gel.The gels have a coherent,rigid spongy porous network of continuous nanome-ter-sized particles.The phosphine-Pd(II)gels showed high activity in the Suzuki-Miyaura reactions of aryl bro-mides under ambient conditions and could be recycled and reused.
基金supported by the National Natural Science Foundation of China (No. 21575117)
文摘Efficient removal of non-biodegradable and hazardous dyes from wastewater remains a hot research topic.Herein,a rationally designed a Cu(Ⅱ)-based metal–organic gel(Cu-MOG)with a nanoporous 3 D network structure prepared via a simple one-step mixing method was successfully employed for the removal of cationic dyes.The Cu-MOG exhibited high efficiency,with an adsorption capacity of up to 650.32 mg/g,and rapid adsorption efficiency,with the ability to adsorb 80%of Neutral Red within 1 min.The high adsorption efficiency was attributed to its large specific surface area,which enabled it to massively bind cationic dyes through electrostatic interaction,and a nanoporous structure that promoted intra-pore diffusion.Remarkably,the Cu-MOG displayed size-selective adsorption,based on adsorption studies concerning dyes of different sizes as calculated by density functional theory.Additionally,the adsorption performance of the Cu-MOG still maintained removal efficiency of 100%after three regeneration cycles.These results suggested that the Cu-MOG could be expected to be a promising and competitive candidate to conveniently process wastewater.