Metal complexes hold significant promise in tumor diagnosis and treatment.However,their potential applications in photodynamic therapy(PDT)are hindered by issues such as poor photostability,low yield of reactive oxyge...Metal complexes hold significant promise in tumor diagnosis and treatment.However,their potential applications in photodynamic therapy(PDT)are hindered by issues such as poor photostability,low yield of reactive oxygen species(ROS),and aggregation-induced ROS quenching.To address these challenges,we present a molecular self-assembly strategy utilizing aggregation-induced emission(AIE)conjugates for metal complexes.As a proof of concept,we synthesized a mitochondrial-targeting cyclometalated Ir(Ⅲ)photosensitizer Ir-TPE.This approach significantly enhances the photodynamic effect while mitigating the dark toxicity associated with AIE groups.Ir-TPE readily self-assembles into nanoaggregates in aqueous solution,leading to a significant production of ROS upon light irradiation.Photoirradiated Ir-TPE triggers multiple modes of death by excessively accumulating ROS in the mitochondria,resulting in mitochondrial DNA damage.This damage can lead to ferroptosis and autophagy,two forms of cell death that are highly cytotoxic to cancer cells.The aggregation-enhanced photodynamic effect of Ir-TPE significantly enhances the production of ROS,leading to a more pronounced cytotoxic effect.In vitro and in vivo experiments demonstrate this aggregation-enhanced PDT approach achieves effective in situ tumor eradication.This study not only addresses the limitations of metal complexes in terms of low ROS production due to aggregation but also highlights the potential of this strategy for enhancing ROS production in PDT.展开更多
Recent advancements have led to the synthesis of various new metal-containing explosives,particularly energetic metal-organic frameworks(EMOFs),which feature high-energy ligands within well-ordered crystalline structu...Recent advancements have led to the synthesis of various new metal-containing explosives,particularly energetic metal-organic frameworks(EMOFs),which feature high-energy ligands within well-ordered crystalline structures.These explosives exhibit significant advantages over traditional compounds,including higher density,greater heats of detonation,improved mechanical hardness,and excellent thermal stability.To effectively evaluate their detonation performance,it is crucial to have a reliable method for predicting detonation heat,velocity,and pressure.This study leverages experimental data and outputs from the leading commercial computer code to identify suitable decomposition pathways for different metal oxides,facilitating straightforward calculations for the detonation performance of alkali metal salts,and metal coordination compounds,along with EMOFs.The new model enhances predictive reliability for detonation velocities,aligning more closely with experimental results,as evi-denced by a root mean square error(RMSE)of 0.68 km/s compared to 1.12 km/s for existing methods.Furthermore,it accommodates a broader range of compounds,including those containing Sr,Cd,and Ag,and provides predictions for EMOFs that are more consistent with computer code outputs than previous predictive models.展开更多
In some industrial wastewater,heavy metals combine with organic complexing agents to form heavy metal complexes(HMCs).These HMCs can be difficult to decompose and remove through conventional techniques due to their hi...In some industrial wastewater,heavy metals combine with organic complexing agents to form heavy metal complexes(HMCs).These HMCs can be difficult to decompose and remove through conventional techniques due to their higher stability than free heavy metal ions.In recent years,persulfate based advanced oxidation processes(PS-based AOPs)have been recognized as a viable technique for HMCs degradation.Nevertheless,a comprehensive and in-depth understanding of the relevant HMCs decomplexation mechanisms in PS-based AOPs is still lacking.This review delineates the current progress of HMCs decomplexation in PS-based AOPs.We discuss the distinctions between the two widely used oxidant types in PS-based AOPs techniques.Moreover,we summarize and highlight the decomplexation mechanisms based on electron and energy transfer,and degradation pathways of HMCs.We also emphasize the effects of environmental water constituents,namely p H,inorganic ions,and natural organic matter(NOM),on HMCs decomplexation.Ultimately,we identify the existing challenges and perspectives that will steer the direction of advancing PS-based AOPs to remove HMCs.展开更多
Adenosine triphosphate(ATP),known as a common metabolic product in organism,is not only importance to provide energy in various cellular activities but also is widely explored in the bio-inspired synthetic supramolecu...Adenosine triphosphate(ATP),known as a common metabolic product in organism,is not only importance to provide energy in various cellular activities but also is widely explored in the bio-inspired synthetic supramolecular area which becomes a fascinating topic with the rapid development of biology,chemistry and materials science.In this review,the recent advances about ATP interacted with functional small organic compounds and metal coordinated complexes are summarized.The design principles,its function as an active supramolecular matrix,the associated non-covalent binding modes and assembly induced properties including the optical properties,morphologies are presented in details.Besides,their applications for metal ion detecting,enzyme activity monitoring and drug delivery are described due to their excellently dynamic assembly properties,adjustability,and response to stimuli.Finally,an overview of the existing challenges and future prospects of ATP-induced supramolecular systems are also discussed.展开更多
The transition metal complexes of triaminoguanidine(TAG-M,where M=Cobalt(Co)or Iron(Fe))have been prepared.The catalytic effect of these complexes on the thermolysis of energetic composite based on nitrocellulose and ...The transition metal complexes of triaminoguanidine(TAG-M,where M=Cobalt(Co)or Iron(Fe))have been prepared.The catalytic effect of these complexes on the thermolysis of energetic composite based on nitrocellulose and diethylene glycol dinitrate,has been investigated.Extensive characterization of the resulting energetic composites was carried out using scanning electron microscopy(SEM),X-ray diffraction(XRD),Fourier transform infrared spectroscopy(FTIR),and differential scanning calorimetry(DSC).Isoconversional kinetic analysis was performed to determine the Arrhenius parameters associated with the thermolysis of the elaborated energetic formulations.It is found that TAG-M complexes have strong catalytic effect on the thermo-kinetic decomposition of NC/DEGDN by decreasing the apparent activation energy and significantly increased the total heat release.The models that govern the decomposition processes are also studied,and it is revealed that different reaction processes are accomplished by introduction metal complexes of triaminoguanidine.Overall,this study serves as a valuable reference for future research focused on the investigation of catalytic combustion features of solid propellants.展开更多
This work deals with the synthesis and physicochemical characterizations of a new group of novel retinoidal ligands and their metal complexes. Their in vitro anti-proliferative activities have shown that ligand L1 is ...This work deals with the synthesis and physicochemical characterizations of a new group of novel retinoidal ligands and their metal complexes. Their in vitro anti-proliferative activities have shown that ligand L1 is effective against human breast cancer BT-20 and MCF-7 cell lines. At the same time, compound L2 exerts its effect on human prostate cancer PC-3 and human breast cancer MDA-MB-231 and MCF-7 cell lines respectively. The retinoid ligands exert their pleiotropic action toward retinoic acid receptors (RARs) than their metal complexes but all compounds exhibit concentration-dependent.展开更多
Heavy metal complexes with high mobility are widely distributed in wastewater from modern industries,which are mo re stable and refracto ry than free heavy metal ions.Their re movals from wastewater draw increasing at...Heavy metal complexes with high mobility are widely distributed in wastewater from modern industries,which are mo re stable and refracto ry than free heavy metal ions.Their re movals from wastewater draw increasing attentions and various technologies have been developed,among which advanced oxidation processes(AOPs)are more effectively and promising.Progresses on five representative types of AOPs,including Fenton(like)oxidation,electrochemical oxidation,photocatalytic oxidation,ozonation and discharge plasma oxidation for heavy metal complexe s degradation are summarized in this review.Their rationales,advantages,applications,challenges and prospects are introduced independently.Combinations among these AOPs,such as electrochemical Fenton oxidation and photoelectrocatalytic oxidation,are also comprehensively highlighted.Future efforts should be made to reduce acid requirement and scale up for practical applications of AOPs for heavy metal complex degradation efficiently and cost-effectively.展开更多
Objective： A series of 2-benzylideneaminonaphthothiazoles were designed and synthesized incorporating the lipophilic naphthalene ring to render them more capable of penetrating various biomembranes. Methods： Schiff ...Objective： A series of 2-benzylideneaminonaphthothiazoles were designed and synthesized incorporating the lipophilic naphthalene ring to render them more capable of penetrating various biomembranes. Methods： Schiff bases were synthesized by the reaction of naphtha[1,2-d]thiazol-2-amine with various substituted aromatic aldehydes. 2-（2＇-Hydroxy）ben- zylideneaminonaphthothiazole was converted to its Co（Ⅱ）, Ni（Ⅱ） and Cu（Ⅱ） metal complexes upon treatment with metal salts in ethanol. All the compounds were evaluated for their antibacterial activities by paper disc diffusion method with Gram positive Staphylococcus aureus and Staphylococcus epidermidis and Gram negative Escherichia coli and Pseudomonas aeruginosa bacteria. The minimum inhibitory concentrations of all the Schiff bases and metal complexes were determined by agar streak dilution method. Results： All the compounds moderately inhibited the growth of Cram positive and Gram negative bacteria. In the present study among all Schiff bases 2-（2＇-hydroxy）benzylideneaminonaphthothiazole showed maximum inhibitory activity and among metal complexes Cu（Ⅱ） metal complex was found to be most potent. Conclusion： The results obtained validate the hypothesis that Schiff bases having substitution with halogens, hydroxyl group and nitro group at phenyl ring are required for the antibacterial activity while methoxy group at different positions in the aromatic ring has minimal role in the inhibitory activity. The results also indicated that the metal complexes are better antibacterial agents as compared to the Schiff bases.展开更多
Glutamic acid-salicylaldehyde Schiff-base metal complexes are bound into bovine serum albumin （BSA）, which afforded BSA binding Schiff-base metal complexes （BSA-SalGluM, M=Cu, Co, Ni, Zn）. The BSA binding metal co...Glutamic acid-salicylaldehyde Schiff-base metal complexes are bound into bovine serum albumin （BSA）, which afforded BSA binding Schiff-base metal complexes （BSA-SalGluM, M=Cu, Co, Ni, Zn）. The BSA binding metal complexes were characterized by UV-vis spectra and Native PAGE. It showed that the protein structures of BSA kept after coordinating amino acid Schiff-bases metal complexes. The effect of the antioxidant activity was investigated. The results indicate that the antioxidant capacity of BSA increased more than 10 times after binding Schiff-base metal complexes.展开更多
The simultaneous removal of up to 92% of the surfactant template and chemical implantation of transition metal complexes into mesopores has been successfully achieved by treating as-synthesized pure siliceous MCM-41 w...The simultaneous removal of up to 92% of the surfactant template and chemical implantation of transition metal complexes into mesopores has been successfully achieved by treating as-synthesized pure siliceous MCM-41 with supercritical CO2 modified with CH2Cl2/MeOH mixture, resulting in the formation of functionalized material with uniform pore structure.展开更多
Seven kinds of Schiff base metal complexes(C1-C7)were synthesized by the reaction of substituted salicylaldehyde Schiff base with cobalt nitrate,nickel nitrate,and copper nitrate,respectively.The oxygen carrying perfo...Seven kinds of Schiff base metal complexes(C1-C7)were synthesized by the reaction of substituted salicylaldehyde Schiff base with cobalt nitrate,nickel nitrate,and copper nitrate,respectively.The oxygen carrying performance,and the catalytic property of complexes for the oxidation of model sulfides 1-hexanethiol,dibutyl sulfide,and 2-methylthiophene along with their influencing factors were explored,while the oxidized products of the model sulfides were also analyzed and characterized.The results show that the catalytic oxidation property of the complexes is determined by their oxygen carrying performance and solubility in n-octane.The oxygen carrying performance of the complexes is mainly affected by the central ion species,the electronic effects,and the spatial effects of the substituents as well as the degree of conjugation.More specifically,the oxygen carrying performance can be improved by enhancing the oxygenation capacity of the central metal ions,increasing the electron donating ability of the ligand substituent,and diminishing the steric hindrance as well as extending the conjugated chain.Complexes C7 were found to be with high oxygen carrying capacity and high solubility in n-octane,which shows the best catalytic oxidation property,and the oxidation conversion rates for 1-hexylthiol,dibutyl sulfide,and 2-methylthiophene are 74.2%,65.1%,and 22.7%,respectively.Upon using the oxidation catalyst of Schiff base metal complexes,three sulfides can be oxidized by oxygen to form sulfones and sulfoxides.1-Hexanethiol and dibutyl sulfide will continue to be oxidized to form sulfates and sulfites.展开更多
A series of half-sandwich group IV metal complexes with tridentate monoanionic phenoxy-imine arylsulfide [O-NS] ligand [2-Bu^t4-Me-6-（（2-（SC6H5）C6H4N = CHC6H2O）]- （La） and dianionic phenoxy-amine arylsulfide [O...A series of half-sandwich group IV metal complexes with tridentate monoanionic phenoxy-imine arylsulfide [O-NS] ligand [2-Bu^t4-Me-6-（（2-（SC6H5）C6H4N = CHC6H2O）]- （La） and dianionic phenoxy-amine arylsulfide [O-N-S] ligand [2-Bu^t4-Me-6-（（2-（SC6H5）C6H4N-CH2C6H2O）]2- （Lb） have been synthesized and characterized. Lb was obtained easily in high yield by reduction of ligand La with excess LiAlH4 in cool diethyl ether. Half-sandwich Group Ⅳ metal complexes CpTi[O-NS]Cl2 （1a）, CpZr[O-NS]Cl2 （1b）, CpTi[O-N-S]Cl （2a）, CpZr[O-N-S]Cl （2b） and CpZr[O-N-S]Cl （2c） were synthesized by the reactions of La and Lb with CpTiCl3, CpZrCl3 and Cp ZrCl3, and characterized by IR, ^1H-NMR, ^13C-NMR and elemental analysis. In addition, an X-ray structure analysis was performed on ligand Lb. The title Group IV half-sandwich bearing tridentate [O,N,S] ligands show good catalytic activities for ethylene polymerization in the presence of methylaluminoxane （MAO） as co-catalyst up to 1.58 × 10^7 g-PE.mol-Zr-1.h-1. The good catalytic activities can be maintained even at high temperatures such as 100 ℃ exhibiting the excellent thermal stability for these half-sandwich metal pre-catalysts.展开更多
Electron paramagnetic resonance(EPR)or electron spin resonance(ESR)has been widely employed to characterize transition metal complexes.However,because of the high degree of complexity of transition metal EPR spectra,h...Electron paramagnetic resonance(EPR)or electron spin resonance(ESR)has been widely employed to characterize transition metal complexes.However,because of the high degree of complexity of transition metal EPR spectra,how to extract the underlying electronicstructure information inevitably poses a major challenge to beginners,in particular for systems with S>1/2.In fact,the physical principles of transition metal EPR have long been well-established and since 1970s a series of dedicated voluminous monographs have been published already.Not surprisingly,they are not appropriate stating points for novices to grasp a panorama of the profound theory prior to scrutinizing in-depth references.The present review aims to fill this gap to provide a perspective of transition metal EPR and unveil some peculiar subtleties thereof on the basis of our recent work.展开更多
A novel ligand N-4-hydroxyacetophenone isonicotinoyl hydrazone and its manganese(II) and nickel(II) metal complexes have been synthesized. The synthesized Schiff base and its metal complexes have been characterized by...A novel ligand N-4-hydroxyacetophenone isonicotinoyl hydrazone and its manganese(II) and nickel(II) metal complexes have been synthesized. The synthesized Schiff base and its metal complexes have been characterized by physical state determination, melting point and solubility measurements in different solvents, infrared, proton nuclear magnetic resonance, mass spectrometric and powder X-ray spectroscopic techniques. The thermal properties of the prepared compounds were obtained from TG/DTG measurements. On the basis of the analytical techniques, the ligand was found to be bidentate in nature coordinating to the metal ions through the azomethine nitrogen and carbonyl oxygen atoms leading to distorted octahedral geometries of the metal complexes which were modeled using MM2 force field. The ligand and its metal(II) complexes were evaluated for antifungal activity against <i>Aspergillus fumigatus, Aspergillus niger, Candida albicans and Rhizopus stolonifera.</i> The antifungal evaluation results revealed an enhanced activity upon coordination of the ligand with the metal(II) ions. The activity of the metal complex to the tested fungal strains was in the order Ni(II) > Mn(II).展开更多
The complexes of metals(Mg,Ca,Sr,Ba,La,Y and Lu)with ethylenediamine-N,N′-diacetate-N, N′-di-β-propionate have been studied by proton nuclear magnetic resonance(PMR).The interesting quartet spectral pattern of acet...The complexes of metals(Mg,Ca,Sr,Ba,La,Y and Lu)with ethylenediamine-N,N′-diacetate-N, N′-di-β-propionate have been studied by proton nuclear magnetic resonance(PMR).The interesting quartet spectral pattern of acetate protons and multiplet spectral pattern of protons of propionate groups for the complexes of metal ions of high charge density have been observed.The results show that the chemical bond for these complexes is predominantly ionic and the lability of metal-nitrogen bond as well as metal- oxygen bond decreases with increasing charge density of cations.展开更多
The metal complexes of norfloxacin were prepared, and their structures were characterized using spectroscopic techniques like IR, 1H NMR, UV, atomic absorption, and CHN analysis. The solubility, melting point, and con...The metal complexes of norfloxacin were prepared, and their structures were characterized using spectroscopic techniques like IR, 1H NMR, UV, atomic absorption, and CHN analysis. The solubility, melting point, and conductance measurements were also performed. These studies suggested that norfloxacin formed complexes with the metals utilizing carbonyl oxygen atom of the ring and carboxylic group oxygen atom. The antibacterial activities of these metal complexes against 14 different Gram-positive and Gram-negative microorganisms were studied by the disk susceptibility method. It was observed that the complexes of norfloxacin with magnesium, calcium, cobalt, nickel, and copper showed improved activity compared with the stated drug.展开更多
Four novel transitional metal complexes with 3-（4-pyridly）-4-phenyl-5-sulfhydryl- 1,2,4- triazole （HL1） and 3-（3-pyridly）-4-phenyl-5-sulfhydryl-l,2,4-triazole （HLz） were synthesized and characterized by elemen...Four novel transitional metal complexes with 3-（4-pyridly）-4-phenyl-5-sulfhydryl- 1,2,4- triazole （HL1） and 3-（3-pyridly）-4-phenyl-5-sulfhydryl-l,2,4-triazole （HLz） were synthesized and characterized by elemental analysis, IR and X-ray diffraction. Complexes 1, 3 and 4 have two-dimensional （2-D） neutral rhombohedral grid with a （4, 4） topology. In 1, 3 and 4, all the metal ions are six-coordinated to four nitrogen atoms of four distinct ligands and two O atoms from water molecules. Complex 2 has tetranuclear CuaCI4 units which are interconnected by four desulfuri- zation ligands （L1-S） via Cu-N bonds to form a 2-D layer with （4,4） topology.展开更多
In the course of investigating the catalytic behavior of metal complexes for ring opening metathesis polymerization of cycloolefins, metathesis, hydroformylation and selective hydrogenation of olefins experimental res...In the course of investigating the catalytic behavior of metal complexes for ring opening metathesis polymerization of cycloolefins, metathesis, hydroformylation and selective hydrogenation of olefins experimental results time and again indicate the presence of effects of macromolecular supports - the utilization of macromolecular supports increases obviously the activity, selectivity, and stability of the catalysts and so as to increase the conversion of substrates, yields of reactions, properties of formed polymers and so on. Discussed these effects on the basis of the authors' experiments. (Author abstract) 18 Refs.展开更多
In this study,the electronic transition properties and structural analysis of the metal complexes(Ni(Ⅱ),Co(Ⅱ),Cu(Ⅱ)and Mn(Ⅱ))of three different polymer ligands were performed by using XRF and X-ray diffraction(XRD...In this study,the electronic transition properties and structural analysis of the metal complexes(Ni(Ⅱ),Co(Ⅱ),Cu(Ⅱ)and Mn(Ⅱ))of three different polymer ligands were performed by using XRF and X-ray diffraction(XRD)techniques,respectively.The structural analysis of the polymers and their complexes were performed by XRD technique and some of the polymers were found to be in the face-centred cubic(fcc)structure.In addition,the values of the present K X-ray intensity ratios are significantly greater than the values reported in literature.展开更多
基金support from the National Natural Science Foundation of China(Nos.22277056,21977052)the Distinguished Young Scholars of Jiangsu Province(No.BK20230006)+2 种基金the Natural Science Foundation of Jiangsu Province(Nos.BK20230977,BK20231090)the Natural Science Foundation of the Higher Education Institutions of Jiangsu Province(No.23KJB150020)the Jiangsu Excellent Postdoctoral Program(No.2022ZB758)。
文摘Metal complexes hold significant promise in tumor diagnosis and treatment.However,their potential applications in photodynamic therapy(PDT)are hindered by issues such as poor photostability,low yield of reactive oxygen species(ROS),and aggregation-induced ROS quenching.To address these challenges,we present a molecular self-assembly strategy utilizing aggregation-induced emission(AIE)conjugates for metal complexes.As a proof of concept,we synthesized a mitochondrial-targeting cyclometalated Ir(Ⅲ)photosensitizer Ir-TPE.This approach significantly enhances the photodynamic effect while mitigating the dark toxicity associated with AIE groups.Ir-TPE readily self-assembles into nanoaggregates in aqueous solution,leading to a significant production of ROS upon light irradiation.Photoirradiated Ir-TPE triggers multiple modes of death by excessively accumulating ROS in the mitochondria,resulting in mitochondrial DNA damage.This damage can lead to ferroptosis and autophagy,two forms of cell death that are highly cytotoxic to cancer cells.The aggregation-enhanced photodynamic effect of Ir-TPE significantly enhances the production of ROS,leading to a more pronounced cytotoxic effect.In vitro and in vivo experiments demonstrate this aggregation-enhanced PDT approach achieves effective in situ tumor eradication.This study not only addresses the limitations of metal complexes in terms of low ROS production due to aggregation but also highlights the potential of this strategy for enhancing ROS production in PDT.
基金the research committee at Malek Ashtar University of Technology (MUT) for their invaluable support of this project
文摘Recent advancements have led to the synthesis of various new metal-containing explosives,particularly energetic metal-organic frameworks(EMOFs),which feature high-energy ligands within well-ordered crystalline structures.These explosives exhibit significant advantages over traditional compounds,including higher density,greater heats of detonation,improved mechanical hardness,and excellent thermal stability.To effectively evaluate their detonation performance,it is crucial to have a reliable method for predicting detonation heat,velocity,and pressure.This study leverages experimental data and outputs from the leading commercial computer code to identify suitable decomposition pathways for different metal oxides,facilitating straightforward calculations for the detonation performance of alkali metal salts,and metal coordination compounds,along with EMOFs.The new model enhances predictive reliability for detonation velocities,aligning more closely with experimental results,as evi-denced by a root mean square error(RMSE)of 0.68 km/s compared to 1.12 km/s for existing methods.Furthermore,it accommodates a broader range of compounds,including those containing Sr,Cd,and Ag,and provides predictions for EMOFs that are more consistent with computer code outputs than previous predictive models.
基金financially supported by National Natural Science Foundation of China(Nos.U22A20403,22006047)Natural Science Foundation of Hebei Province(Nos.E2021203140,B2021203016)Hebei Industrial Innovation and Entrepreneurship team(No.215A7608D)。
文摘In some industrial wastewater,heavy metals combine with organic complexing agents to form heavy metal complexes(HMCs).These HMCs can be difficult to decompose and remove through conventional techniques due to their higher stability than free heavy metal ions.In recent years,persulfate based advanced oxidation processes(PS-based AOPs)have been recognized as a viable technique for HMCs degradation.Nevertheless,a comprehensive and in-depth understanding of the relevant HMCs decomplexation mechanisms in PS-based AOPs is still lacking.This review delineates the current progress of HMCs decomplexation in PS-based AOPs.We discuss the distinctions between the two widely used oxidant types in PS-based AOPs techniques.Moreover,we summarize and highlight the decomplexation mechanisms based on electron and energy transfer,and degradation pathways of HMCs.We also emphasize the effects of environmental water constituents,namely p H,inorganic ions,and natural organic matter(NOM),on HMCs decomplexation.Ultimately,we identify the existing challenges and perspectives that will steer the direction of advancing PS-based AOPs to remove HMCs.
基金the Zhejiang Provincial Natural Science Foundation of China(Nos.LR22B010001,LQ23B010001)the National Natural Science Foundation of China(Nos.22201057,21871297)+1 种基金the Natural Science Foundation of Guangdong Province for Distinguished Young Scholars(No.2019B151502051)the Hangzhou Normal University(Nos.2021QDL001,2021QDL065)。
文摘Adenosine triphosphate(ATP),known as a common metabolic product in organism,is not only importance to provide energy in various cellular activities but also is widely explored in the bio-inspired synthetic supramolecular area which becomes a fascinating topic with the rapid development of biology,chemistry and materials science.In this review,the recent advances about ATP interacted with functional small organic compounds and metal coordinated complexes are summarized.The design principles,its function as an active supramolecular matrix,the associated non-covalent binding modes and assembly induced properties including the optical properties,morphologies are presented in details.Besides,their applications for metal ion detecting,enzyme activity monitoring and drug delivery are described due to their excellently dynamic assembly properties,adjustability,and response to stimuli.Finally,an overview of the existing challenges and future prospects of ATP-induced supramolecular systems are also discussed.
文摘The transition metal complexes of triaminoguanidine(TAG-M,where M=Cobalt(Co)or Iron(Fe))have been prepared.The catalytic effect of these complexes on the thermolysis of energetic composite based on nitrocellulose and diethylene glycol dinitrate,has been investigated.Extensive characterization of the resulting energetic composites was carried out using scanning electron microscopy(SEM),X-ray diffraction(XRD),Fourier transform infrared spectroscopy(FTIR),and differential scanning calorimetry(DSC).Isoconversional kinetic analysis was performed to determine the Arrhenius parameters associated with the thermolysis of the elaborated energetic formulations.It is found that TAG-M complexes have strong catalytic effect on the thermo-kinetic decomposition of NC/DEGDN by decreasing the apparent activation energy and significantly increased the total heat release.The models that govern the decomposition processes are also studied,and it is revealed that different reaction processes are accomplished by introduction metal complexes of triaminoguanidine.Overall,this study serves as a valuable reference for future research focused on the investigation of catalytic combustion features of solid propellants.
文摘This work deals with the synthesis and physicochemical characterizations of a new group of novel retinoidal ligands and their metal complexes. Their in vitro anti-proliferative activities have shown that ligand L1 is effective against human breast cancer BT-20 and MCF-7 cell lines. At the same time, compound L2 exerts its effect on human prostate cancer PC-3 and human breast cancer MDA-MB-231 and MCF-7 cell lines respectively. The retinoid ligands exert their pleiotropic action toward retinoic acid receptors (RARs) than their metal complexes but all compounds exhibit concentration-dependent.
基金the National Natural Science Foundation of China(NSFC)(No.41672237)the Beijing Natural Science Foundation(No.8192040)。
文摘Heavy metal complexes with high mobility are widely distributed in wastewater from modern industries,which are mo re stable and refracto ry than free heavy metal ions.Their re movals from wastewater draw increasing attentions and various technologies have been developed,among which advanced oxidation processes(AOPs)are more effectively and promising.Progresses on five representative types of AOPs,including Fenton(like)oxidation,electrochemical oxidation,photocatalytic oxidation,ozonation and discharge plasma oxidation for heavy metal complexe s degradation are summarized in this review.Their rationales,advantages,applications,challenges and prospects are introduced independently.Combinations among these AOPs,such as electrochemical Fenton oxidation and photoelectrocatalytic oxidation,are also comprehensively highlighted.Future efforts should be made to reduce acid requirement and scale up for practical applications of AOPs for heavy metal complex degradation efficiently and cost-effectively.
文摘Objective： A series of 2-benzylideneaminonaphthothiazoles were designed and synthesized incorporating the lipophilic naphthalene ring to render them more capable of penetrating various biomembranes. Methods： Schiff bases were synthesized by the reaction of naphtha[1,2-d]thiazol-2-amine with various substituted aromatic aldehydes. 2-（2＇-Hydroxy）ben- zylideneaminonaphthothiazole was converted to its Co（Ⅱ）, Ni（Ⅱ） and Cu（Ⅱ） metal complexes upon treatment with metal salts in ethanol. All the compounds were evaluated for their antibacterial activities by paper disc diffusion method with Gram positive Staphylococcus aureus and Staphylococcus epidermidis and Gram negative Escherichia coli and Pseudomonas aeruginosa bacteria. The minimum inhibitory concentrations of all the Schiff bases and metal complexes were determined by agar streak dilution method. Results： All the compounds moderately inhibited the growth of Cram positive and Gram negative bacteria. In the present study among all Schiff bases 2-（2＇-hydroxy）benzylideneaminonaphthothiazole showed maximum inhibitory activity and among metal complexes Cu（Ⅱ） metal complex was found to be most potent. Conclusion： The results obtained validate the hypothesis that Schiff bases having substitution with halogens, hydroxyl group and nitro group at phenyl ring are required for the antibacterial activity while methoxy group at different positions in the aromatic ring has minimal role in the inhibitory activity. The results also indicated that the metal complexes are better antibacterial agents as compared to the Schiff bases.
文摘Glutamic acid-salicylaldehyde Schiff-base metal complexes are bound into bovine serum albumin （BSA）, which afforded BSA binding Schiff-base metal complexes （BSA-SalGluM, M=Cu, Co, Ni, Zn）. The BSA binding metal complexes were characterized by UV-vis spectra and Native PAGE. It showed that the protein structures of BSA kept after coordinating amino acid Schiff-bases metal complexes. The effect of the antioxidant activity was investigated. The results indicate that the antioxidant capacity of BSA increased more than 10 times after binding Schiff-base metal complexes.
文摘The simultaneous removal of up to 92% of the surfactant template and chemical implantation of transition metal complexes into mesopores has been successfully achieved by treating as-synthesized pure siliceous MCM-41 with supercritical CO2 modified with CH2Cl2/MeOH mixture, resulting in the formation of functionalized material with uniform pore structure.
基金This work was supported by the National Natural Science Foundation of China(No.21576292).
文摘Seven kinds of Schiff base metal complexes(C1-C7)were synthesized by the reaction of substituted salicylaldehyde Schiff base with cobalt nitrate,nickel nitrate,and copper nitrate,respectively.The oxygen carrying performance,and the catalytic property of complexes for the oxidation of model sulfides 1-hexanethiol,dibutyl sulfide,and 2-methylthiophene along with their influencing factors were explored,while the oxidized products of the model sulfides were also analyzed and characterized.The results show that the catalytic oxidation property of the complexes is determined by their oxygen carrying performance and solubility in n-octane.The oxygen carrying performance of the complexes is mainly affected by the central ion species,the electronic effects,and the spatial effects of the substituents as well as the degree of conjugation.More specifically,the oxygen carrying performance can be improved by enhancing the oxygenation capacity of the central metal ions,increasing the electron donating ability of the ligand substituent,and diminishing the steric hindrance as well as extending the conjugated chain.Complexes C7 were found to be with high oxygen carrying capacity and high solubility in n-octane,which shows the best catalytic oxidation property,and the oxidation conversion rates for 1-hexylthiol,dibutyl sulfide,and 2-methylthiophene are 74.2%,65.1%,and 22.7%,respectively.Upon using the oxidation catalyst of Schiff base metal complexes,three sulfides can be oxidized by oxygen to form sulfones and sulfoxides.1-Hexanethiol and dibutyl sulfide will continue to be oxidized to form sulfates and sulfites.
基金financially supported by the Shanghai Science and Technology Committee(08DZ2270500,08DJ1400103)Shanghai Leading Academic Discipline Project(B108)the National Basic Research Program of China(2009CB825300,2010DFA41160)
文摘A series of half-sandwich group IV metal complexes with tridentate monoanionic phenoxy-imine arylsulfide [O-NS] ligand [2-Bu^t4-Me-6-（（2-（SC6H5）C6H4N = CHC6H2O）]- （La） and dianionic phenoxy-amine arylsulfide [O-N-S] ligand [2-Bu^t4-Me-6-（（2-（SC6H5）C6H4N-CH2C6H2O）]2- （Lb） have been synthesized and characterized. Lb was obtained easily in high yield by reduction of ligand La with excess LiAlH4 in cool diethyl ether. Half-sandwich Group Ⅳ metal complexes CpTi[O-NS]Cl2 （1a）, CpZr[O-NS]Cl2 （1b）, CpTi[O-N-S]Cl （2a）, CpZr[O-N-S]Cl （2b） and CpZr[O-N-S]Cl （2c） were synthesized by the reactions of La and Lb with CpTiCl3, CpZrCl3 and Cp ZrCl3, and characterized by IR, ^1H-NMR, ^13C-NMR and elemental analysis. In addition, an X-ray structure analysis was performed on ligand Lb. The title Group IV half-sandwich bearing tridentate [O,N,S] ligands show good catalytic activities for ethylene polymerization in the presence of methylaluminoxane （MAO） as co-catalyst up to 1.58 × 10^7 g-PE.mol-Zr-1.h-1. The good catalytic activities can be maintained even at high temperatures such as 100 ℃ exhibiting the excellent thermal stability for these half-sandwich metal pre-catalysts.
基金the financial support from Chinese Academy of Sciences,National Science Foundation of China(92161204)Max-Planck Society。
文摘Electron paramagnetic resonance(EPR)or electron spin resonance(ESR)has been widely employed to characterize transition metal complexes.However,because of the high degree of complexity of transition metal EPR spectra,how to extract the underlying electronicstructure information inevitably poses a major challenge to beginners,in particular for systems with S>1/2.In fact,the physical principles of transition metal EPR have long been well-established and since 1970s a series of dedicated voluminous monographs have been published already.Not surprisingly,they are not appropriate stating points for novices to grasp a panorama of the profound theory prior to scrutinizing in-depth references.The present review aims to fill this gap to provide a perspective of transition metal EPR and unveil some peculiar subtleties thereof on the basis of our recent work.
文摘A novel ligand N-4-hydroxyacetophenone isonicotinoyl hydrazone and its manganese(II) and nickel(II) metal complexes have been synthesized. The synthesized Schiff base and its metal complexes have been characterized by physical state determination, melting point and solubility measurements in different solvents, infrared, proton nuclear magnetic resonance, mass spectrometric and powder X-ray spectroscopic techniques. The thermal properties of the prepared compounds were obtained from TG/DTG measurements. On the basis of the analytical techniques, the ligand was found to be bidentate in nature coordinating to the metal ions through the azomethine nitrogen and carbonyl oxygen atoms leading to distorted octahedral geometries of the metal complexes which were modeled using MM2 force field. The ligand and its metal(II) complexes were evaluated for antifungal activity against <i>Aspergillus fumigatus, Aspergillus niger, Candida albicans and Rhizopus stolonifera.</i> The antifungal evaluation results revealed an enhanced activity upon coordination of the ligand with the metal(II) ions. The activity of the metal complex to the tested fungal strains was in the order Ni(II) > Mn(II).
文摘The complexes of metals(Mg,Ca,Sr,Ba,La,Y and Lu)with ethylenediamine-N,N′-diacetate-N, N′-di-β-propionate have been studied by proton nuclear magnetic resonance(PMR).The interesting quartet spectral pattern of acetate protons and multiplet spectral pattern of protons of propionate groups for the complexes of metal ions of high charge density have been observed.The results show that the chemical bond for these complexes is predominantly ionic and the lability of metal-nitrogen bond as well as metal- oxygen bond decreases with increasing charge density of cations.
文摘The metal complexes of norfloxacin were prepared, and their structures were characterized using spectroscopic techniques like IR, 1H NMR, UV, atomic absorption, and CHN analysis. The solubility, melting point, and conductance measurements were also performed. These studies suggested that norfloxacin formed complexes with the metals utilizing carbonyl oxygen atom of the ring and carboxylic group oxygen atom. The antibacterial activities of these metal complexes against 14 different Gram-positive and Gram-negative microorganisms were studied by the disk susceptibility method. It was observed that the complexes of norfloxacin with magnesium, calcium, cobalt, nickel, and copper showed improved activity compared with the stated drug.
基金Financially supported by the Natural Science Foundation of Xinjiang Province(No.2011211A009)
文摘Four novel transitional metal complexes with 3-（4-pyridly）-4-phenyl-5-sulfhydryl- 1,2,4- triazole （HL1） and 3-（3-pyridly）-4-phenyl-5-sulfhydryl-l,2,4-triazole （HLz） were synthesized and characterized by elemental analysis, IR and X-ray diffraction. Complexes 1, 3 and 4 have two-dimensional （2-D） neutral rhombohedral grid with a （4, 4） topology. In 1, 3 and 4, all the metal ions are six-coordinated to four nitrogen atoms of four distinct ligands and two O atoms from water molecules. Complex 2 has tetranuclear CuaCI4 units which are interconnected by four desulfuri- zation ligands （L1-S） via Cu-N bonds to form a 2-D layer with （4,4） topology.
基金The project was supported by the National Natural Science Foundation of China, "Macromolecular ligand effects of catalytic system for ring opening metathesis polymerization of dicydopentadiene" (Approval No. 29474160) & "Polymeric metal complex catalysts
文摘In the course of investigating the catalytic behavior of metal complexes for ring opening metathesis polymerization of cycloolefins, metathesis, hydroformylation and selective hydrogenation of olefins experimental results time and again indicate the presence of effects of macromolecular supports - the utilization of macromolecular supports increases obviously the activity, selectivity, and stability of the catalysts and so as to increase the conversion of substrates, yields of reactions, properties of formed polymers and so on. Discussed these effects on the basis of the authors' experiments. (Author abstract) 18 Refs.
基金Scientific Research Fund of Kahramanmaras Sutcu Imam University,Turkey(2012/3-7YLS)
文摘In this study,the electronic transition properties and structural analysis of the metal complexes(Ni(Ⅱ),Co(Ⅱ),Cu(Ⅱ)and Mn(Ⅱ))of three different polymer ligands were performed by using XRF and X-ray diffraction(XRD)techniques,respectively.The structural analysis of the polymers and their complexes were performed by XRD technique and some of the polymers were found to be in the face-centred cubic(fcc)structure.In addition,the values of the present K X-ray intensity ratios are significantly greater than the values reported in literature.
