Access to fresh water,its availability,and its quality are a global challenge to humanity,largely due to human activities in the environment.Thus,global water security has been jeopardized,requiring urgent remediation...Access to fresh water,its availability,and its quality are a global challenge to humanity,largely due to human activities in the environment.Thus,global water security has been jeopardized,requiring urgent remediation to safeguard our very existence.Hence,a novel and facilely engineered zirconium and polyethylenimine adsorbent based on tiger nut residue (TNR) was prepared,and its adsorptive capabilities towards a model dyestuff and nutrient were invested through a batch adsorption method.The developed adsorbent,zirconium-polyethylenimine-engineered tiger nut residue (TNR@PEI–Zr) was characterised by scanning electron microscopy,Fourier-transform infrared spectroscopy,X-ray diffraction analysis,and X-ray photoelectron spectroscopy to understand its morphology and surface chemistry and predict its adsorption mechanism.TNR@PEI–Zr had a p H point of zero charge (pH_(zpc)) of 6.7.The introduction of salts inhibited the removal efficiency of Alizarin red (AR) and phosphate (PO_(4)^(3–)) in the order of HCO_(3)^(-)>SO_(4)^(2–)>Cl^(-).Increasing temperatures (293–313 K) favoured the adsorption process at pH 3.The Langmuir model suited the adsorption processes of both AR and PO_(4)^(3–),implying homogenous and monolayer removal of pollutants with a maximal capacity of 537.8 mg·g^(-1)and 100.5 mg·g^(-1)at a dose of 0.01 g,respectively.The rate-determining steps of AR and PO_(4)^(3–)followed a pseudo-secondorder kinetic model and were thermodynamically spontaneous with an increase in randomness at the solid-solution interface.The adsorbent’s recyclability was notable and outperformed most adsorbents in terms of removal efficiency.TNR@PEI–Zr was found to be stable,and its use in practical wastewater decontamination was effective,ecologically acceptable and free of secondary pollution problems.展开更多
The adverse effects of eutrophication have prompted the use of various remediation techniques for phosphate(PO_(4)^(3-))removal owing to it being the major causative agent.Herein,the influence of different solvents an...The adverse effects of eutrophication have prompted the use of various remediation techniques for phosphate(PO_(4)^(3-))removal owing to it being the major causative agent.Herein,the influence of different solvents and ratios of 2-aminoterepthalicacid on the efficiency of magnetic biomass metal-organic framework composites based on the in situ growth of NH_(2)-MIL-101(Fe)onto magnetized peanut husks towards PO_(4)^(3-)removal was assessed via the adsorption technique.The magnetic biocomposite labelled as MPN@NH2-MIL-101(Fe)exhibited the best efficiency owing to its mesoporous structures and presence of abundant oxygen and nitrogen possessing functional groups.Adsorption results confirmed MPN@NH2-MIL-101(Fe)to have a high adsorption capacity of(14.0±0.3)mg·L^(-1)at a PO43-concentration of 20 mg·L^(-1)with an associated high stability within pH 2-10.The adsorption kinetics for the process was well described by both Elovich and pseudo-second-order kinetic models and was mediated by both internal diffusion and liquid film diffusion.The Temkin and Freundlich models fitted the equilibrium data well signifying occurrence of both physical and chemical adsorption on a heterogeneous surface.It is concluded that MPN@NH2-MIL-101(Fe)is a promising adsorbent for the effective removal of phosphate from a water body.展开更多
Atomically precise gold nanoclusters(NCs),possessing characteristics of molecules and nanoparticles,offer a promising solution to the challenges faced by existing pyroptosis inducers.Their abilities to catalyze the ge...Atomically precise gold nanoclusters(NCs),possessing characteristics of molecules and nanoparticles,offer a promising solution to the challenges faced by existing pyroptosis inducers.Their abilities to catalyze the generation of reactive oxygen species and enhance radiosensitization position them as effective agents for activating pyroptosis.However,their catalytic efficiency is often compromised by limited geometrically accessible spaces around the active sites and the lack of suitable ligands.Leveraging the exposed metal centers in mononuclear organometallic catalysts and the tunable ligand of NCs,herein,ethynylferrocene(EFc)was utilized to amplify the peroxidase(POD)-like activity of gold NCs by establishing the unshielded catalytic center and electron donor-acceptor interaction between EFc and Au core.The resulting Au_(8)Fe_(2) NCs with excellent POD-mimicking activity could efficiently trigger pyroptosis by inducing intracellular oxidative stress.Moreover,the Au_(8)Fe_(2) NCs,with their potential to deplete glutathione and enable magnetic resonance imaging,could also induce ferroptosis and serve as a diagnostic tool for tumors.All of these processes can be further potentiated by X-ray radiation,taking advantage of the high atomic number of gold.This work opens new avenues for engineering the catalytic properties of NCs and broadens their potential applications in biomedicine.展开更多
Luminescence is one of the most important properties for metal nanoclusters;however,clearly revealing its origin remains challenging.The different luminescence properties of the two prototypical 8e nanoclusters Au_(11...Luminescence is one of the most important properties for metal nanoclusters;however,clearly revealing its origin remains challenging.The different luminescence properties of the two prototypical 8e nanoclusters Au_(11)and Au_(13)remain elusive—Au_(11)is always nonluminescent,whereas Au_(13)is luminescent.In this work,by using a designed unique aromatic ligand(quinoline-2-thiol),we obtained new atomically precise phosphine-thiolate-protected neutral Au_(11)-SH and cationic Au_(13)-SH.In comparison with the classic phosphine-halide-protected Au_(11)-Cl and Au_(13)-Cl,the Cl-to-thiol alteration triggered room-temperature luminescence of the Au_(11)core and dramatically modulated that of the Au_(13)core.Ultrafast ultraviolet/infrared(UV/IR)spectroscopy,which is sensitive to organic aromatic groups,together with ultrafast transient absorption(TA)spectroscopy unprecedently revealed a relaxation process from the ligand to core state affecting the dynamics in excited states and some critical intermediate states favouring efficient room-temperature emission of these nanoclusters.This work provides some new insights into the origin of photoluminescence of metal nanoclusters and opens an avenue to modulate the dynamics of their excited states using aromatic ligands,which would have direct applications in lighting,light harvesting,and photocatalysis.展开更多
文摘Access to fresh water,its availability,and its quality are a global challenge to humanity,largely due to human activities in the environment.Thus,global water security has been jeopardized,requiring urgent remediation to safeguard our very existence.Hence,a novel and facilely engineered zirconium and polyethylenimine adsorbent based on tiger nut residue (TNR) was prepared,and its adsorptive capabilities towards a model dyestuff and nutrient were invested through a batch adsorption method.The developed adsorbent,zirconium-polyethylenimine-engineered tiger nut residue (TNR@PEI–Zr) was characterised by scanning electron microscopy,Fourier-transform infrared spectroscopy,X-ray diffraction analysis,and X-ray photoelectron spectroscopy to understand its morphology and surface chemistry and predict its adsorption mechanism.TNR@PEI–Zr had a p H point of zero charge (pH_(zpc)) of 6.7.The introduction of salts inhibited the removal efficiency of Alizarin red (AR) and phosphate (PO_(4)^(3–)) in the order of HCO_(3)^(-)>SO_(4)^(2–)>Cl^(-).Increasing temperatures (293–313 K) favoured the adsorption process at pH 3.The Langmuir model suited the adsorption processes of both AR and PO_(4)^(3–),implying homogenous and monolayer removal of pollutants with a maximal capacity of 537.8 mg·g^(-1)and 100.5 mg·g^(-1)at a dose of 0.01 g,respectively.The rate-determining steps of AR and PO_(4)^(3–)followed a pseudo-secondorder kinetic model and were thermodynamically spontaneous with an increase in randomness at the solid-solution interface.The adsorbent’s recyclability was notable and outperformed most adsorbents in terms of removal efficiency.TNR@PEI–Zr was found to be stable,and its use in practical wastewater decontamination was effective,ecologically acceptable and free of secondary pollution problems.
基金supported by the National Key Research and Development Program of China (2018YFD0401402–04)Zhongyuan Scholars Foundation (202101510005).
文摘The adverse effects of eutrophication have prompted the use of various remediation techniques for phosphate(PO_(4)^(3-))removal owing to it being the major causative agent.Herein,the influence of different solvents and ratios of 2-aminoterepthalicacid on the efficiency of magnetic biomass metal-organic framework composites based on the in situ growth of NH_(2)-MIL-101(Fe)onto magnetized peanut husks towards PO_(4)^(3-)removal was assessed via the adsorption technique.The magnetic biocomposite labelled as MPN@NH2-MIL-101(Fe)exhibited the best efficiency owing to its mesoporous structures and presence of abundant oxygen and nitrogen possessing functional groups.Adsorption results confirmed MPN@NH2-MIL-101(Fe)to have a high adsorption capacity of(14.0±0.3)mg·L^(-1)at a PO43-concentration of 20 mg·L^(-1)with an associated high stability within pH 2-10.The adsorption kinetics for the process was well described by both Elovich and pseudo-second-order kinetic models and was mediated by both internal diffusion and liquid film diffusion.The Temkin and Freundlich models fitted the equilibrium data well signifying occurrence of both physical and chemical adsorption on a heterogeneous surface.It is concluded that MPN@NH2-MIL-101(Fe)is a promising adsorbent for the effective removal of phosphate from a water body.
基金supported by the National Natural Science Foundation of China(92356304,92061201 and 22301284)the National Key R&D Program of China(2021YFA1200301),China Postdoctoral Science Foundation(2023TQ0297 and 2023M743167)+5 种基金Zhongyuan Thousand Talents(Zhongyuan Scholars)Program of Henan Province(234000510007)Henan Province Science and Technology Research and Development Joint Fund(242301420004)Tianjian Laboratory of Advanced Biomedical Sciences,National University of Singapore(NUHSRO/2020/133/Startup/08,NUHSRO/2023/008/NUSMed/TCE/LOA,NUHSRO/2021/034/TRP/09/Nanomedicine,23-0173-A0001)National Medical Research Council(MOH-001388-00,CG21APR1005,MOH-001500-00,MOH-001609-00,MOH-001740-01)Singapore Ministry of Education(MOE-000387-00,MOE-MOET32023-004)National Research Foundation(NRF-000352-00).
文摘Atomically precise gold nanoclusters(NCs),possessing characteristics of molecules and nanoparticles,offer a promising solution to the challenges faced by existing pyroptosis inducers.Their abilities to catalyze the generation of reactive oxygen species and enhance radiosensitization position them as effective agents for activating pyroptosis.However,their catalytic efficiency is often compromised by limited geometrically accessible spaces around the active sites and the lack of suitable ligands.Leveraging the exposed metal centers in mononuclear organometallic catalysts and the tunable ligand of NCs,herein,ethynylferrocene(EFc)was utilized to amplify the peroxidase(POD)-like activity of gold NCs by establishing the unshielded catalytic center and electron donor-acceptor interaction between EFc and Au core.The resulting Au_(8)Fe_(2) NCs with excellent POD-mimicking activity could efficiently trigger pyroptosis by inducing intracellular oxidative stress.Moreover,the Au_(8)Fe_(2) NCs,with their potential to deplete glutathione and enable magnetic resonance imaging,could also induce ferroptosis and serve as a diagnostic tool for tumors.All of these processes can be further potentiated by X-ray radiation,taking advantage of the high atomic number of gold.This work opens new avenues for engineering the catalytic properties of NCs and broadens their potential applications in biomedicine.
基金supported by the National Natural Science Foundation of China(Nos.U21A20277,92061201,21825106,21975065,12174012,22203006,and 22103072)Zhengzhou University.
文摘Luminescence is one of the most important properties for metal nanoclusters;however,clearly revealing its origin remains challenging.The different luminescence properties of the two prototypical 8e nanoclusters Au_(11)and Au_(13)remain elusive—Au_(11)is always nonluminescent,whereas Au_(13)is luminescent.In this work,by using a designed unique aromatic ligand(quinoline-2-thiol),we obtained new atomically precise phosphine-thiolate-protected neutral Au_(11)-SH and cationic Au_(13)-SH.In comparison with the classic phosphine-halide-protected Au_(11)-Cl and Au_(13)-Cl,the Cl-to-thiol alteration triggered room-temperature luminescence of the Au_(11)core and dramatically modulated that of the Au_(13)core.Ultrafast ultraviolet/infrared(UV/IR)spectroscopy,which is sensitive to organic aromatic groups,together with ultrafast transient absorption(TA)spectroscopy unprecedently revealed a relaxation process from the ligand to core state affecting the dynamics in excited states and some critical intermediate states favouring efficient room-temperature emission of these nanoclusters.This work provides some new insights into the origin of photoluminescence of metal nanoclusters and opens an avenue to modulate the dynamics of their excited states using aromatic ligands,which would have direct applications in lighting,light harvesting,and photocatalysis.
