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
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
Transition metal possesses a unique d-orbital electronic structure,which imparts a diverse range of physical and chemical properties.These properties render them significant in fields such as chemistry and materials s...Transition metal possesses a unique d-orbital electronic structure,which imparts a diverse range of physical and chemical properties.These properties render them significant in fields such as chemistry and materials science.The distinctive optical,electrical,and magnetic properties of these complexes can be attributed to the variations in the quantity of d-orbital electrons,thereby influencing their spin and orbital characteristics.The d-orbitals facilitate the formation of stable multidirectional bonds with ligands,resulting in a variety of geometric structures and rich coordination chemistry.These interactions result in variations in energy levels,thereby producing diverse electrical properties,including low attenuation coefficients,high rectification ratios,and unique multichannel transmission.Moreover,the unpaired electrons inthe d-orbitals can give rise to diverse magnetic behaviors,leading to magnetic effects such as spin-related interfaces,switches,and magnetoresistance.This paves the way for extensive possibilities in the design and application of single-molecule devices.This review elaborates on singlemolecule physical properties of transition metal complexes,including length attenuation,rectification,multi-channel transmission,thermoelectric effect,and spin regulation,which are vital for the functionalization and regulation of molecular electronics.In addition,this review also explores the correlation between these physical properties and the electronic structure of transition metals,discussing the broad prospects of transition metal complexes in the fields of nanoelectronics,optoelectronics,and quantum technology.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 this article the affiliation of Jin-Ke Shen,Nai-Teng Wu,Li-Yuan Wang,Gang Jiang,Jin Li,Gui-Long Liu,Xian-Ming Liu were incorrectly given as:State Key Laboratory of Chemistry and Utilization of Carbon Based Energy R...In this article the affiliation of Jin-Ke Shen,Nai-Teng Wu,Li-Yuan Wang,Gang Jiang,Jin Li,Gui-Long Liu,Xian-Ming Liu were incorrectly given as:State Key Laboratory of Chemistry and Utilization of Carbon Based Energy Resources,School of Chemical Engineering and Technology,Xinjiang University,Urumqi 830046,China.展开更多
Tin-based metal organic complexes with breakable coordination bonds,multiple active sites,and high theoretical capacity have attracted wide attentiorials for lithium-ion batteries(LIBs).However,the inferior electrical...Tin-based metal organic complexes with breakable coordination bonds,multiple active sites,and high theoretical capacity have attracted wide attentiorials for lithium-ion batteries(LIBs).However,the inferior electrical conductivity and significant volume changes have limited their electrochemical stability and practical application performance.This work proposes a universal doping strategy for the preparation of tin-phthalic acid complexes(Sn-MOF)doped with metal atoms(Al,Cr,Mn,Fe,Co,Ni,Cu,Zn).Metal atoms are uniformly dispersed within Sn-MOF for enhancing electrical conductivity and accommodating appropriate volume expansion,resulting in improved rate capability and cycling stability.Additionally,compared to a series of doped Sn-MOF,Zn-doped Sn-MOF exhibits the most exceptional electrochemical performance with a high reversible capacity of 1131 mAh·g^(-1)and stable cycling performance at a current density of 0.5 A·g^(-1),delivering a capacity of 1065 mAh·g^(-1)after 500 cycles.Zn-doping catalyzes the lithiation reaction between Sn-MOF and Li^(+),promoting their reaction kinetics during the first cycle.Furthermore,the Zn-doped Sn-MOF is inclined to form a thin and stable solid electrolyte interface film to maintain cyclic stability.展开更多
One potential drawback of compost-based passive bioreactors,which is a promising biotechnology for acid mine drainage（AMD） treatment,is the transport of dissolved organic matter（DOM）-metal complexes in surface wat...One potential drawback of compost-based passive bioreactors,which is a promising biotechnology for acid mine drainage（AMD） treatment,is the transport of dissolved organic matter（DOM）-metal complexes in surface waters.To address this problem,the objective of this study was to assess the maximum capacity of organic substrates to release soluble DOM-metal complexes in treated water. The reactivities of DOM in maple wood chips and sawdust,composted poultry manure,and leaf compost were quantified toward Cd2＋,Ni2＋,Fe2＋,and Cu2＋ using fluorescence quenching.The DOM showed the highest reactivity toward Fe,but a limited number of available sites for sorption,whereas DOM-Cd complexes exhibited the lowest fluorescence quenching.Overall,the DOM from a mixture of wastes formed higher concentrations of DOM-metal complexes relative to sole substrates.Among DOM-metal complexes, the concentrations of DOM-Ni complexes were the highest.After reaching steady-state,low concentrations of DOM-metal complexes were released in treated water,which is in agreement with theoretical predictions based on geochemical modeling.Therefore,in addition to physicochemical characterization,fluorescence quenching technique is recommended for the substrate selection of bioreactors.展开更多
The complexation of Cr^3＋ with F^- undergoes a muhistep reversible process. An approach to research the involved equilibria and kinetics using suitable chemometrics methods to the online measured UV-Vis spectra is pr...The complexation of Cr^3＋ with F^- undergoes a muhistep reversible process. An approach to research the involved equilibria and kinetics using suitable chemometrics methods to the online measured UV-Vis spectra is proposed. By investigating the equilibrium spectra of the complexes at different molar ratios of M to L（ metal to ligand） and 50 ℃, the result of Principal Component Analysis（PCA） shows that three complexes, ML, ML2 and ML3, can be formed under the research conditions. The spectrum of each complex was then analyzed and the accumulated equilibrium constants were calculated by applying Target Testing Factor Analysis（TITA）. Meanwhile, a reactive intermediate was observed before the formation of MLx during the specific kinetic study at 15℃. The equilibrium constant and spectrum of the intermediate as well as the rate constants were all resolved by using TTFA.展开更多
Aim Cysteine proteases are closely associated with many human and non-human pathological processes and are potential targets for metal ions especially Hg^2＋ and the related species. In the present work, on the basis ...Aim Cysteine proteases are closely associated with many human and non-human pathological processes and are potential targets for metal ions especially Hg^2＋ and the related species. In the present work, on the basis of to the general study on the effects of some metal ions on the activity of papain, a well-known representative of cysteine protease family, the inhibitory effects of Hg^2＋ and polysulfide complexes were studied. Results All the metal ions tested （Hg^2＋, Cu^2＋, Ag^＋, Au^3＋, Zn^2＋, Cd^2＋, Fe^3＋, Mn^2＋, Pb^2＋, Yb^3＋） inhibit the activity of papain anda good correlation between the inhibitory potency and softness-and-hardness was observed. Among the metals, Hg^2＋ was shown to be a potent inhibitor of papain with a Kiof 2 × 10^-7 mol·L^-1 among. Excessive amounts of glutathione and cysteine could reactivate the enzyme activity of papain deactivated by Hg^2＋. These evidences supported that Hg^2＋ might bind to the catalytic site of papain. Interestingly, Hg （Ⅱ） polysulfide complexes were for the first time found to inhibit papain with a Ki of 7 × 10^-6 mol·L^-1, whose potency is close to a well known mercury compound, thimerosal （Ki=2.7 × 10^-6）. In addition, Hg （Ⅱ） polysulfide complexes exhibit good permeability （ 1.9 × 10-5 cm· s^-1） to caco-2 monolayer. Conclusion These results suggested that mercury polysulfide complexes might be potential bioactive species in the interaction with cysteine proteases and other- SH-content proteins, providing a new clue to understand the mechanism of the toxicological and pharmacological actions of cinnabar and other insoluble mercury compounds.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
To synthesize and characterize a novel metal complex of Mn(II) with emodin, and evaluate its anti-cancer activity. The elemental analyses, IR, UV-vis, atomic absorption spectroscopy, TG-DSC, 1H NMR, and 13 C NMR data ...To synthesize and characterize a novel metal complex of Mn(II) with emodin, and evaluate its anti-cancer activity. The elemental analyses, IR, UV-vis, atomic absorption spectroscopy, TG-DSC, 1H NMR, and 13 C NMR data were used to characterize the structure of the complex. The cytotoxicity of the complex against the human cancer cell lines HepG 2, HeL a, MCF-7, B16, and MDA-MB-231 was tested by the MTT assay and flow cytometry. Emodin was coordinated with Mn(II) through the 9-C=O and 1-OH, and the general formula of the complex was Mn(II)(emodin)2·2H2O. In studies of the cytotoxicity, the complex exhibited significant activity, and the IC50 values of the complex against five cancer cell lines improved approximately three-fold compared with those of emodin. The complex could induce cell morphological changes, decrease the percentage of viability, and induce G0/G1 phase arrest and apoptosis in cancer cells. The coordination of emodin with Mn(II) can improve its anticancer activity, and the complex Mn(II)(emodin)2·2H2O could be studied further as a promising anticancer drug.展开更多
Amine elimination of Ln[N(SiMe3)2]3(μ-Cl)Li(THF)3 with aminophenol H[ON]{H[ON]=2-(CH2 NC5 H10)-4,6-tBu2-C6 H3OH}in 1:2 molar ratio in THF gave the monometallic rare-earth metal amide complexes[ON]2 LnN(SiMe3)2(Ln=Yb(...Amine elimination of Ln[N(SiMe3)2]3(μ-Cl)Li(THF)3 with aminophenol H[ON]{H[ON]=2-(CH2 NC5 H10)-4,6-tBu2-C6 H3OH}in 1:2 molar ratio in THF gave the monometallic rare-earth metal amide complexes[ON]2 LnN(SiMe3)2(Ln=Yb(1),Y(2),Gd(3),Sm(4),Nd(5))in 57%-73%isolated yields.All these complexes were characterized by elemental analysis.The molecular structures of complexes 1-4 were determined by single crystal X-ray diffraction.These complexes are highly active for L-Iactide polymerization to give high molecular weight polymers with unimodal molecular weight distributions.In addition,these complexes can also initiate rac-lactide polymerization with high activity to afford heterotactic-rich polylactides.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
Five new transitional metal complexes with 4,4′-bis（1,2,4-triazol-1-ylmethyl）- biphenyl （L1）, 1,4-bis（1,2,4-triazol-1-ylmethyl）naphthalene （L2） and 1-（1H-1,2,4-triazol-l-yl）- 3-phenyl-2-one （L3） were synt...Five new transitional metal complexes with 4,4′-bis（1,2,4-triazol-1-ylmethyl）- biphenyl （L1）, 1,4-bis（1,2,4-triazol-1-ylmethyl）naphthalene （L2） and 1-（1H-1,2,4-triazol-l-yl）- 3-phenyl-2-one （L3） were synthesized and characterized by elemental analysis, IR and X-ray diffraction. Complexes 1-3 have one-dimensional （1-D） chain structures, and L1 adopts a gauche-gauche conformation with the shortest N...N distance between the two N donors in complexes 1-3; however, L2 adopts a trans-gauche conformation in complex 4. Complex 5 is a mononuclear structure, and L3 adopts a monodentate coordination mode. The fluorescence properties of ligands L1 and complexe 1 have been investigated.展开更多
Transition metal complexes of meso-tetra(4-myristyloxyphenyl)porphyrin TMPPM [M =Mn, Fe, Co, Ni, Cu, Zn; TMPP=mesotetra(4-myristyloxyphenyl)porphyrin] have been synthesized and characterized by means of elemental an...Transition metal complexes of meso-tetra(4-myristyloxyphenyl)porphyrin TMPPM [M =Mn, Fe, Co, Ni, Cu, Zn; TMPP=mesotetra(4-myristyloxyphenyl)porphyrin] have been synthesized and characterized by means of elemental analyses, UV-Vis spectra, infrared photoacoustic spectra, 1H NMR spectra, molar conductance and differential scanning calorimetry(DSC). The ligand and the Zn complex show liquid crystalline behavior. According to the DSC thermogram of the Zn complex, it exhibits a lower phase transition temperature -7.453 ℃ and a wide mesophase temperature span, 77 ℃.展开更多
Various novel double metal cyanide （DMC） catalysts were successfully prepared by modifying the central metal （M） and one of cyanide ion （CN-） in Zna[M（CN）b]c complex. Such modifications have significant impact...Various novel double metal cyanide （DMC） catalysts were successfully prepared by modifying the central metal （M） and one of cyanide ion （CN-） in Zna[M（CN）b]c complex. Such modifications have significant impact on the catalytic efficiency as well as the polymer selectivity for the reaction of PO/CO2. Zn-Ni（Ⅱ） DMC is a potential catalyst for alternating copolymerization of PO/CO2,and DMC catalysts based on Zn3[Co（CN）5X]2 （X = Br^- and N3^-） exhibit moderate efficiency for the production of polycarbonates.This research presents the preliminary exploration of novel DMC complex via chemical modification of its central metal and ligand.展开更多
The simultaneous electro-oxidation of Ni(Ⅱ)-citrate and electrodeposition recovery of nickel metal were attempted in a combined electro-oxidation-electrodeposition reactor with a boron-doped diamond(BDD)anode and a p...The simultaneous electro-oxidation of Ni(Ⅱ)-citrate and electrodeposition recovery of nickel metal were attempted in a combined electro-oxidation-electrodeposition reactor with a boron-doped diamond(BDD)anode and a polished titanium cathode.Effects of initial nickel citrate concentration,current density,initial p H,electrode spacing,electrolyte type,and initial electrolyte dosage on electrochemical performance were examined.The efficiencies of Ni(Ⅱ)-citrate removal and nickel metal recovery were determined to be 100%and over 72%,respectively,under the optimized conditions(10 m A/cm^(2),pH 4.09,80 mmol/L Na_(2)SO_(4),initial Ni(Ⅱ)-citrate concentration of 75 mg/L,electrode spacing of 1 cm,and 180 min of electrolysis).Energy consumption increased with increased current density,and the energy consumption was 0.032 kWh/L at a current density of 10 m A/cm^(2)(pH 6.58).The deposits at the cathode were characterized by scanning electron microscopy(SEM),energy-dispersive spectrometry(EDS),X-ray diffraction(XRD),and X-ray photoelectron spectroscopy(XPS).These characterization results indicated that the purity of metallic nickel in cathodic deposition was over 95%.The electrochemical system exhibited a prospective approach to oxidize metal complexes and recover metallic nickel.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
Five new solid complexes were synthesized about transition metals with Schiff base（ L, C18H23NO2 ） derived from adamantaneamine and o-vanillin, and characterized by elemental analysis, molar conductance, infrared sp...Five new solid complexes were synthesized about transition metals with Schiff base（ L, C18H23NO2 ） derived from adamantaneamine and o-vanillin, and characterized by elemental analysis, molar conductance, infrared spectra, UV-vis spectra, thermal analysis. Their chemical formula are [ML2]（ClO4）2 （ M= Mn, Co, Ni, Cu, Zn）, and the coordination numbers are four, The antibacterial activity of Schiff base ligand and its complexes was studied.展开更多
Using nickel（II） acetate.-2,2＇-dipyridyl complex as template and N-vinyl-2-pyrrolidone （NVP） as coordinate functional monomer,.a new kind of metal-compiexing template molecularly impnnted polymer （MIP） was prep...Using nickel（II） acetate.-2,2＇-dipyridyl complex as template and N-vinyl-2-pyrrolidone （NVP） as coordinate functional monomer,.a new kind of metal-compiexing template molecularly impnnted polymer （MIP） was prepared..The results of equilibri.um binding experiments in. aqueous solution showed that the MIP had higher＇binding capacity for nickel（ II ）-2,2＇-dipyridyl than the non-imprinted polymer with the same chemical composition. Theinfluences of metal ions and pHof solution on the recognition performance of MIP were investigated. The bindingcharacteristics of MIP were evaluated by the Scatchard analysis with one-site and two-site binding equations, respectively. The results on substrate selectivity of imprinted polymer revealed that MIP had better binding affinityfor template among thetested compounds.展开更多
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financially supported by the National Key R&D Program of China(Nos.2021YFA1200102,2021YFA1200101,2023YFF1205803,2022YFE0128700)the National Natural Science Foundation of China(Nos.22173050,22150013,21727806,21933001)+1 种基金Beijing National Laboratory for Molecular Sciences(No.BNLMS-CXXM-202407)the Natural Science Foundation of Beijing(No.2222009)
文摘Transition metal possesses a unique d-orbital electronic structure,which imparts a diverse range of physical and chemical properties.These properties render them significant in fields such as chemistry and materials science.The distinctive optical,electrical,and magnetic properties of these complexes can be attributed to the variations in the quantity of d-orbital electrons,thereby influencing their spin and orbital characteristics.The d-orbitals facilitate the formation of stable multidirectional bonds with ligands,resulting in a variety of geometric structures and rich coordination chemistry.These interactions result in variations in energy levels,thereby producing diverse electrical properties,including low attenuation coefficients,high rectification ratios,and unique multichannel transmission.Moreover,the unpaired electrons inthe d-orbitals can give rise to diverse magnetic behaviors,leading to magnetic effects such as spin-related interfaces,switches,and magnetoresistance.This paves the way for extensive possibilities in the design and application of single-molecule devices.This review elaborates on singlemolecule physical properties of transition metal complexes,including length attenuation,rectification,multi-channel transmission,thermoelectric effect,and spin regulation,which are vital for the functionalization and regulation of molecular electronics.In addition,this review also explores the correlation between these physical properties and the electronic structure of transition metals,discussing the broad prospects of transition metal complexes in the fields of nanoelectronics,optoelectronics,and quantum technology.
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.
文摘In this article the affiliation of Jin-Ke Shen,Nai-Teng Wu,Li-Yuan Wang,Gang Jiang,Jin Li,Gui-Long Liu,Xian-Ming Liu were incorrectly given as:State Key Laboratory of Chemistry and Utilization of Carbon Based Energy Resources,School of Chemical Engineering and Technology,Xinjiang University,Urumqi 830046,China.
基金support from Natural Science Foundations of Henan Province(Nos.222300420502 and 232300420093)the Program for Science and Technology Innovation Talents in Universities of Henan Province(No.24HASTIT006)the Key Science and Technology Program of Henan Province(No.222102240044)。
文摘Tin-based metal organic complexes with breakable coordination bonds,multiple active sites,and high theoretical capacity have attracted wide attentiorials for lithium-ion batteries(LIBs).However,the inferior electrical conductivity and significant volume changes have limited their electrochemical stability and practical application performance.This work proposes a universal doping strategy for the preparation of tin-phthalic acid complexes(Sn-MOF)doped with metal atoms(Al,Cr,Mn,Fe,Co,Ni,Cu,Zn).Metal atoms are uniformly dispersed within Sn-MOF for enhancing electrical conductivity and accommodating appropriate volume expansion,resulting in improved rate capability and cycling stability.Additionally,compared to a series of doped Sn-MOF,Zn-doped Sn-MOF exhibits the most exceptional electrochemical performance with a high reversible capacity of 1131 mAh·g^(-1)and stable cycling performance at a current density of 0.5 A·g^(-1),delivering a capacity of 1065 mAh·g^(-1)after 500 cycles.Zn-doping catalyzes the lithiation reaction between Sn-MOF and Li^(+),promoting their reaction kinetics during the first cycle.Furthermore,the Zn-doped Sn-MOF is inclined to form a thin and stable solid electrolyte interface film to maintain cyclic stability.
基金supported by the Natural Sciences and Engineering Research Council of Canada (NSERC) through the Industrial NSERC Polytechnique/UQAT Chair in Environment and Mine Waste Management and the Chair’s partners
文摘One potential drawback of compost-based passive bioreactors,which is a promising biotechnology for acid mine drainage（AMD） treatment,is the transport of dissolved organic matter（DOM）-metal complexes in surface waters.To address this problem,the objective of this study was to assess the maximum capacity of organic substrates to release soluble DOM-metal complexes in treated water. The reactivities of DOM in maple wood chips and sawdust,composted poultry manure,and leaf compost were quantified toward Cd2＋,Ni2＋,Fe2＋,and Cu2＋ using fluorescence quenching.The DOM showed the highest reactivity toward Fe,but a limited number of available sites for sorption,whereas DOM-Cd complexes exhibited the lowest fluorescence quenching.Overall,the DOM from a mixture of wastes formed higher concentrations of DOM-metal complexes relative to sole substrates.Among DOM-metal complexes, the concentrations of DOM-Ni complexes were the highest.After reaching steady-state,low concentrations of DOM-metal complexes were released in treated water,which is in agreement with theoretical predictions based on geochemical modeling.Therefore,in addition to physicochemical characterization,fluorescence quenching technique is recommended for the substrate selection of bioreactors.
基金Supported by the National Natural Science Foundation of China(No. 50478106)
文摘The complexation of Cr^3＋ with F^- undergoes a muhistep reversible process. An approach to research the involved equilibria and kinetics using suitable chemometrics methods to the online measured UV-Vis spectra is proposed. By investigating the equilibrium spectra of the complexes at different molar ratios of M to L（ metal to ligand） and 50 ℃, the result of Principal Component Analysis（PCA） shows that three complexes, ML, ML2 and ML3, can be formed under the research conditions. The spectrum of each complex was then analyzed and the accumulated equilibrium constants were calculated by applying Target Testing Factor Analysis（TITA）. Meanwhile, a reactive intermediate was observed before the formation of MLx during the specific kinetic study at 15℃. The equilibrium constant and spectrum of the intermediate as well as the rate constants were all resolved by using TTFA.
文摘Aim Cysteine proteases are closely associated with many human and non-human pathological processes and are potential targets for metal ions especially Hg^2＋ and the related species. In the present work, on the basis of to the general study on the effects of some metal ions on the activity of papain, a well-known representative of cysteine protease family, the inhibitory effects of Hg^2＋ and polysulfide complexes were studied. Results All the metal ions tested （Hg^2＋, Cu^2＋, Ag^＋, Au^3＋, Zn^2＋, Cd^2＋, Fe^3＋, Mn^2＋, Pb^2＋, Yb^3＋） inhibit the activity of papain anda good correlation between the inhibitory potency and softness-and-hardness was observed. Among the metals, Hg^2＋ was shown to be a potent inhibitor of papain with a Kiof 2 × 10^-7 mol·L^-1 among. Excessive amounts of glutathione and cysteine could reactivate the enzyme activity of papain deactivated by Hg^2＋. These evidences supported that Hg^2＋ might bind to the catalytic site of papain. Interestingly, Hg （Ⅱ） polysulfide complexes were for the first time found to inhibit papain with a Ki of 7 × 10^-6 mol·L^-1, whose potency is close to a well known mercury compound, thimerosal （Ki=2.7 × 10^-6）. In addition, Hg （Ⅱ） polysulfide complexes exhibit good permeability （ 1.9 × 10-5 cm· s^-1） to caco-2 monolayer. Conclusion These results suggested that mercury polysulfide complexes might be potential bioactive species in the interaction with cysteine proteases and other- SH-content proteins, providing a new clue to understand the mechanism of the toxicological and pharmacological actions of cinnabar and other insoluble mercury compounds.
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.
基金supported by the Natural Science Foundation Project of CQ CSTC(No.2011BB5109)Program for Innovation Team Building at Institutions of Higher Education in Chongqing(KJTD201325)+1 种基金Visiting Scholar Foundation of Key Laboratory of Biorheological Science and Technology(Chongqing University),Ministry of Education(CQKLBST-2012007)the Scientific Research Foundation for the Returned Overseas Chinese Scholars,State Education Ministry
文摘To synthesize and characterize a novel metal complex of Mn(II) with emodin, and evaluate its anti-cancer activity. The elemental analyses, IR, UV-vis, atomic absorption spectroscopy, TG-DSC, 1H NMR, and 13 C NMR data were used to characterize the structure of the complex. The cytotoxicity of the complex against the human cancer cell lines HepG 2, HeL a, MCF-7, B16, and MDA-MB-231 was tested by the MTT assay and flow cytometry. Emodin was coordinated with Mn(II) through the 9-C=O and 1-OH, and the general formula of the complex was Mn(II)(emodin)2·2H2O. In studies of the cytotoxicity, the complex exhibited significant activity, and the IC50 values of the complex against five cancer cell lines improved approximately three-fold compared with those of emodin. The complex could induce cell morphological changes, decrease the percentage of viability, and induce G0/G1 phase arrest and apoptosis in cancer cells. The coordination of emodin with Mn(II) can improve its anticancer activity, and the complex Mn(II)(emodin)2·2H2O could be studied further as a promising anticancer drug.
基金Project supported by the National Natural Science Foundation of China(21572205,21971130,21871198,21674070)the Natural Science Foundation of Zhejiang Province(LY19B040002)+2 种基金the State Key Laboratory of Polymer Physics and Chemistry,Changchun Institute of Applied Chemistry,Chinese Academy of Sciencesthe Natural Science Foundation of Ningbo Municipal(2019A610030,2019A610129)K.C.Wong Magna Fund in Ningbo University。
文摘Amine elimination of Ln[N(SiMe3)2]3(μ-Cl)Li(THF)3 with aminophenol H[ON]{H[ON]=2-(CH2 NC5 H10)-4,6-tBu2-C6 H3OH}in 1:2 molar ratio in THF gave the monometallic rare-earth metal amide complexes[ON]2 LnN(SiMe3)2(Ln=Yb(1),Y(2),Gd(3),Sm(4),Nd(5))in 57%-73%isolated yields.All these complexes were characterized by elemental analysis.The molecular structures of complexes 1-4 were determined by single crystal X-ray diffraction.These complexes are highly active for L-Iactide polymerization to give high molecular weight polymers with unimodal molecular weight distributions.In addition,these complexes can also initiate rac-lactide polymerization with high activity to afford heterotactic-rich polylactides.
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.
基金Financially supported by the Natural Science Foundation of Xinjiang Province (No. 2011211A009)
文摘Five new transitional metal complexes with 4,4′-bis（1,2,4-triazol-1-ylmethyl）- biphenyl （L1）, 1,4-bis（1,2,4-triazol-1-ylmethyl）naphthalene （L2） and 1-（1H-1,2,4-triazol-l-yl）- 3-phenyl-2-one （L3） were synthesized and characterized by elemental analysis, IR and X-ray diffraction. Complexes 1-3 have one-dimensional （1-D） chain structures, and L1 adopts a gauche-gauche conformation with the shortest N...N distance between the two N donors in complexes 1-3; however, L2 adopts a trans-gauche conformation in complex 4. Complex 5 is a mononuclear structure, and L3 adopts a monodentate coordination mode. The fluorescence properties of ligands L1 and complexe 1 have been investigated.
文摘Transition metal complexes of meso-tetra(4-myristyloxyphenyl)porphyrin TMPPM [M =Mn, Fe, Co, Ni, Cu, Zn; TMPP=mesotetra(4-myristyloxyphenyl)porphyrin] have been synthesized and characterized by means of elemental analyses, UV-Vis spectra, infrared photoacoustic spectra, 1H NMR spectra, molar conductance and differential scanning calorimetry(DSC). The ligand and the Zn complex show liquid crystalline behavior. According to the DSC thermogram of the Zn complex, it exhibits a lower phase transition temperature -7.453 ℃ and a wide mesophase temperature span, 77 ℃.
基金the National Natural Science Foundation of China(No.50273031)China Postdoctoral Science Foundation(No.20060400339).
文摘Various novel double metal cyanide （DMC） catalysts were successfully prepared by modifying the central metal （M） and one of cyanide ion （CN-） in Zna[M（CN）b]c complex. Such modifications have significant impact on the catalytic efficiency as well as the polymer selectivity for the reaction of PO/CO2. Zn-Ni（Ⅱ） DMC is a potential catalyst for alternating copolymerization of PO/CO2,and DMC catalysts based on Zn3[Co（CN）5X]2 （X = Br^- and N3^-） exhibit moderate efficiency for the production of polycarbonates.This research presents the preliminary exploration of novel DMC complex via chemical modification of its central metal and ligand.
基金supported by Major Science and Technology Program for Water Pollution Control and Treatment in China(No.2017ZX07202-001-007)the National Science Fund for Distinguished Young Scholars(No.51625801)+4 种基金the Guangdong Innovation Team Project for Colleges and Universities(No.2016KCXTD023)Guangdong Provincial Science and Technology Project(No.2017A020216014)the National Science Fund,China(No.21777106)Pearl River S&T Noval Program of Guangzhou,China(No.201710010065)the key projects of Dongguan social science and technology development plan(No.2019507140204)。
文摘The simultaneous electro-oxidation of Ni(Ⅱ)-citrate and electrodeposition recovery of nickel metal were attempted in a combined electro-oxidation-electrodeposition reactor with a boron-doped diamond(BDD)anode and a polished titanium cathode.Effects of initial nickel citrate concentration,current density,initial p H,electrode spacing,electrolyte type,and initial electrolyte dosage on electrochemical performance were examined.The efficiencies of Ni(Ⅱ)-citrate removal and nickel metal recovery were determined to be 100%and over 72%,respectively,under the optimized conditions(10 m A/cm^(2),pH 4.09,80 mmol/L Na_(2)SO_(4),initial Ni(Ⅱ)-citrate concentration of 75 mg/L,electrode spacing of 1 cm,and 180 min of electrolysis).Energy consumption increased with increased current density,and the energy consumption was 0.032 kWh/L at a current density of 10 m A/cm^(2)(pH 6.58).The deposits at the cathode were characterized by scanning electron microscopy(SEM),energy-dispersive spectrometry(EDS),X-ray diffraction(XRD),and X-ray photoelectron spectroscopy(XPS).These characterization results indicated that the purity of metallic nickel in cathodic deposition was over 95%.The electrochemical system exhibited a prospective approach to oxidize metal complexes and recover metallic nickel.
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Five new solid complexes were synthesized about transition metals with Schiff base（ L, C18H23NO2 ） derived from adamantaneamine and o-vanillin, and characterized by elemental analysis, molar conductance, infrared spectra, UV-vis spectra, thermal analysis. Their chemical formula are [ML2]（ClO4）2 （ M= Mn, Co, Ni, Cu, Zn）, and the coordination numbers are four, The antibacterial activity of Schiff base ligand and its complexes was studied.
基金Supported by the Special Funds for Major State Basic Research Program of China(973 Project,No.2003CB615705).
文摘Using nickel（II） acetate.-2,2＇-dipyridyl complex as template and N-vinyl-2-pyrrolidone （NVP） as coordinate functional monomer,.a new kind of metal-compiexing template molecularly impnnted polymer （MIP） was prepared..The results of equilibri.um binding experiments in. aqueous solution showed that the MIP had higher＇binding capacity for nickel（ II ）-2,2＇-dipyridyl than the non-imprinted polymer with the same chemical composition. Theinfluences of metal ions and pHof solution on the recognition performance of MIP were investigated. The bindingcharacteristics of MIP were evaluated by the Scatchard analysis with one-site and two-site binding equations, respectively. The results on substrate selectivity of imprinted polymer revealed that MIP had better binding affinityfor template among thetested compounds.
