Synthesizing atomically precise Ag nanoclusters(NCs),which is essential for the general development of NCs,is quite challenging.In this study,we report the synthesis of high-purity atomically precise Ag NCs via a kine...Synthesizing atomically precise Ag nanoclusters(NCs),which is essential for the general development of NCs,is quite challenging.In this study,we report the synthesis of high-purity atomically precise Ag NCs via a kinetically controlled strategy.The Ag NCs were prepared using a mild reducing agent via a one-pot method.The as-prepared Ag NCs were confirmed to be Ag_(49)(D-pen)_(24)(D-pen:D-penicillamine)on the basis of their matrix-assisted laser desorption ionization time-of-flight mass spectrometric and thermogravimetric characteristics.The interfacial structures of the Ag NCs were illustrated by proton nuclear magnetic resonance and Fourier-transform infrared spectroscopy.The Ag NCs were supported on activated carbon(AC)to form Ag NCs/AC,which displayed excellent activity for the catalytic reduction of 4-nitrophenol with a kinetic reaction rate constant k of 0.21 min^(-1).Such a high k value indicates that the composite could outperform several previously reported catalysts.Moreover,the catalytic activity of Ag NCs/AC remained nearly constant after six times of recycle,which suggests its excellent stability.展开更多
Silver nanoclusters（NCs） embedded in soda-lime glass was synthesized by the electric fieldassisted diffusion（EFAD） and successive annealing. The samples were characterized by UV-Vis absorption spectroscopy, photol...Silver nanoclusters（NCs） embedded in soda-lime glass was synthesized by the electric fieldassisted diffusion（EFAD） and successive annealing. The samples were characterized by UV-Vis absorption spectroscopy, photoluminescence spectroscopy, X-ray photoelectron spectroscopy（XPS）, and lifetime measurements. The experimental results show that the growth of silver clusters is favored by the annealing temperature and dwell time. The as-diffused and annealed glass samples show photoluminescence around 550 nm under UV excitation, which can be associated with the presence of L-center and Ag3~＋ cluster. And the increasing of the annealing temperature and dwell time results in an appearance of the SPR peak and the decreasing of the luminescence intensities because the Ag3~＋ clusters grow up into the Ag nanoparticles.展开更多
In this paper, the DNA-templated Ag/Pt bimetallic nanoclusters were successfully synthesized using an optimized synthetic scheme. The obtained DNA-Ag/Pt NCs have an ultrasmall particle size and excellent distribution....In this paper, the DNA-templated Ag/Pt bimetallic nanoclusters were successfully synthesized using an optimized synthetic scheme. The obtained DNA-Ag/Pt NCs have an ultrasmall particle size and excellent distribution. The DNA-Ag/Pt NCs show intrinsic peroxidase-mimicking activity and can effectively catalyze the H2O2-mediated oxidation of a substrate, 3,30,5,50-tetramethylbenzidine（TMB）, to produce a blue colored product. Based on this specific property, we employed the aptamer of VEGF to design a label-free electrochemical biosensor for VEGF detection. Under the optimized experimental conditions, a linear range from 6.0 pmol/L to 20 pmol/L was obtained with a detection limit of 4.6 pmol/L. The proposed biosensor demonstrated its high specificity for VEGF and could directly detect the VEGF concentration in human serum samples of breast cancer patients with satisfactory results. This novel electrochemical aptasensor was simple and convenient to use and was cost-effective and label-free in design, and would hold potential applications in medical diagnosis and treatment.展开更多
Even though great advances have been achieved in the synthesis of luminescent metal nanoclusters, it is still challenging to develop metal nanoclusters with high quantum efficiency as well as multiple sensing function...Even though great advances have been achieved in the synthesis of luminescent metal nanoclusters, it is still challenging to develop metal nanoclusters with high quantum efficiency as well as multiple sensing functionalities. Here, we demonstrate the rapid preparation of glutathione-capped Au/Ag nanoclusters （GS-Au/Ag NCs） using microwave irradiation and their unique sensing capacities. Compared to bare GS-Au NCs, the doped Au/Ag NCs possess an enhanced quantum yield （7.8% compared to 2.2% for GS-Au NCs）. Several characterization techniques were used to elucidate the atomic composition, particulate character, and electronic structure of the fabricated NCs. According to the X-ray photoelectron spectroscopy （XPS） and X-ray absorption near-edge structure （XANES） spectra, a significant amount of Au exists in the oxidized state as Au（I）, and the Ag atoms are positively charged. In contrast to those nanoclusters that detect only one analyte, the GS-Au/Ag NCs can be used as a versatile sensor for metal ions, anions, and small molecules. In this manner, the NCs can be regarded as a unique sensor-on-a-nanoparticle.展开更多
Ultrasmall silver nanoclusters(Ag NCs)with rich surface chemistry and good biocompatibility are promising in antibacterial application,however,further development of Ag NCs for practical settings has been constrained ...Ultrasmall silver nanoclusters(Ag NCs)with rich surface chemistry and good biocompatibility are promising in antibacterial application,however,further development of Ag NCs for practical settings has been constrained by their relatively weak antibacterial activity.Using the nutritionally-rich medium for bacteria(e.g.,Luria-Bertani(LB)medium)to coat active Ag NCs could further improve their antibacterial activity.Here,we provide a delicate design of a highly efficient Ag NCs@ELB antibacterial agent(ELB denotes the extract of LB medium)by anchoring Ag NCs inside the ELB species via light irradiation.The as-designed Ag NCs with bacterium-favored nutrients on the surface can be easily swallowed by the bacteria,boosting the production of the intracellular reactive oxygen species(ROS,about 2-fold of that in the pristine Ag NCs).Subsequently,a higher concentration of ROS generated in Ag NCs@ELB leads to enhanced antibacterial activity,and enables to reduce the colony forming units(CFU)of both gram-positive and gram-negative bacteria with 3–4 orders of magnitude less than that treated with the pristine Ag NCs.In addition,the Ag NCs@ELB also shows good biocompatibility.This study suggests that surface engineering of active species(e.g.,Ag NCs)with nutritionally-rich medium of the bacteria is an efficient way to improve their antibacterial activity.展开更多
Alloying is an important strategy in tailoring the functionality of materials.In metal nanoclusters(NCs),the introduction of a heterometal leads to alloy nanoclusters that often outperform the homometal ones in terms ...Alloying is an important strategy in tailoring the functionality of materials.In metal nanoclusters(NCs),the introduction of a heterometal leads to alloy nanoclusters that often outperform the homometal ones in terms of the physical and chemical properties.In this work,a series of four M_(144)(PET)60 alloy NCs(where,M=Au/Ag,PET=–SCH_(2)CH_(2)Ph)are synthesized and characterized.The silver doping into the homogold template(Au_(144))leads to more prominent optical absorption features in the steady-state spectrum in the visible range.Femtosecond transient absorption spectroscopy reveals the effect of Ag doping on the electronic relaxation dynamics compared to Au_(144)and the pump fluence independent dynamics.Electrochemical results reflect a narrowing of HOMO–LUMO gap(E_(g))induced by Ag doping.A temperature dependence of the single-electron charging is also observed for the series of alloy NCs,in which the E_(g)values of the alloy NCs enlarge as the temperature decreases,which is characteristic of semiconducting behavior.展开更多
基金financially supported by the Huaibei Normal University Doctoral Research Start-up Funding(No.15601012)the Natural Science Foundation of Anhui Provincial Department of Education(No.KJ2019A0598)+1 种基金the Excellent Young Talents Fund Program of Higher Education Institutions of Anhui Province,China(No.gxyq2019168)the Team of Superior Discipline of Chemistry(No.GFXK202108).
文摘Synthesizing atomically precise Ag nanoclusters(NCs),which is essential for the general development of NCs,is quite challenging.In this study,we report the synthesis of high-purity atomically precise Ag NCs via a kinetically controlled strategy.The Ag NCs were prepared using a mild reducing agent via a one-pot method.The as-prepared Ag NCs were confirmed to be Ag_(49)(D-pen)_(24)(D-pen:D-penicillamine)on the basis of their matrix-assisted laser desorption ionization time-of-flight mass spectrometric and thermogravimetric characteristics.The interfacial structures of the Ag NCs were illustrated by proton nuclear magnetic resonance and Fourier-transform infrared spectroscopy.The Ag NCs were supported on activated carbon(AC)to form Ag NCs/AC,which displayed excellent activity for the catalytic reduction of 4-nitrophenol with a kinetic reaction rate constant k of 0.21 min^(-1).Such a high k value indicates that the composite could outperform several previously reported catalysts.Moreover,the catalytic activity of Ag NCs/AC remained nearly constant after six times of recycle,which suggests its excellent stability.
基金Funded by the Shanghai Science and Technology Committee(12nm0504700)
文摘Silver nanoclusters（NCs） embedded in soda-lime glass was synthesized by the electric fieldassisted diffusion（EFAD） and successive annealing. The samples were characterized by UV-Vis absorption spectroscopy, photoluminescence spectroscopy, X-ray photoelectron spectroscopy（XPS）, and lifetime measurements. The experimental results show that the growth of silver clusters is favored by the annealing temperature and dwell time. The as-diffused and annealed glass samples show photoluminescence around 550 nm under UV excitation, which can be associated with the presence of L-center and Ag3~＋ cluster. And the increasing of the annealing temperature and dwell time results in an appearance of the SPR peak and the decreasing of the luminescence intensities because the Ag3~＋ clusters grow up into the Ag nanoparticles.
基金support of the National Natural Science Foundation of China (Nos. 21375017, 21105012 and 21205015)the National Science Foundation for Distinguished Young Scholars of Fujian Province (No. 2013J06003)+3 种基金the Key Project of Fujian Science and Technology (No. 2013Y0045)the Program for New Century Excellent Talents of Colleges and Universities in Fujian Province (Nos. JA13130 and JA13088)the Program for Fujian University Outstanding Youth Scientific Research (Nos. JA11105 and JA10295)the Foundation of Fuzhou Science and Technology Bureau (No. 2013-S-122-4)
文摘In this paper, the DNA-templated Ag/Pt bimetallic nanoclusters were successfully synthesized using an optimized synthetic scheme. The obtained DNA-Ag/Pt NCs have an ultrasmall particle size and excellent distribution. The DNA-Ag/Pt NCs show intrinsic peroxidase-mimicking activity and can effectively catalyze the H2O2-mediated oxidation of a substrate, 3,30,5,50-tetramethylbenzidine（TMB）, to produce a blue colored product. Based on this specific property, we employed the aptamer of VEGF to design a label-free electrochemical biosensor for VEGF detection. Under the optimized experimental conditions, a linear range from 6.0 pmol/L to 20 pmol/L was obtained with a detection limit of 4.6 pmol/L. The proposed biosensor demonstrated its high specificity for VEGF and could directly detect the VEGF concentration in human serum samples of breast cancer patients with satisfactory results. This novel electrochemical aptasensor was simple and convenient to use and was cost-effective and label-free in design, and would hold potential applications in medical diagnosis and treatment.
基金This work is financially supported by the National Basic Research Program of China （Nos. 2014CB931800 and 2013CB931800）, the National Natural Science Foundation of China （Nos. 21407140, 21431006 and 91227103）, and Scientific Research Grant of Hefei Science Center of CAS （No. 2015SRG-HSC038）. J. Zhang appreciates the Grants from the China Postdoctoral Science Foundation （No. 2013M531515） and the Fun- damental Research Funds for the Central Universities （No. WK2060190036）. The authors also thank beamline BL14W1 （Shanghai Synchrotron Radiation Faculty） for providing the beam time.
文摘Even though great advances have been achieved in the synthesis of luminescent metal nanoclusters, it is still challenging to develop metal nanoclusters with high quantum efficiency as well as multiple sensing functionalities. Here, we demonstrate the rapid preparation of glutathione-capped Au/Ag nanoclusters （GS-Au/Ag NCs） using microwave irradiation and their unique sensing capacities. Compared to bare GS-Au NCs, the doped Au/Ag NCs possess an enhanced quantum yield （7.8% compared to 2.2% for GS-Au NCs）. Several characterization techniques were used to elucidate the atomic composition, particulate character, and electronic structure of the fabricated NCs. According to the X-ray photoelectron spectroscopy （XPS） and X-ray absorption near-edge structure （XANES） spectra, a significant amount of Au exists in the oxidized state as Au（I）, and the Ag atoms are positively charged. In contrast to those nanoclusters that detect only one analyte, the GS-Au/Ag NCs can be used as a versatile sensor for metal ions, anions, and small molecules. In this manner, the NCs can be regarded as a unique sensor-on-a-nanoparticle.
基金supported by the Taishan Scholar Foundation(No.tsqn201812074)the Young Talents Joint Fund of Shandong Province(No.ZR2019YQ07)+2 种基金the Original Innovation Project of Qingdao City(No.18-2-2-58-jch)the Open Fund of Shandong Key Laboratory of Biochemical Analysis(No.QUSTHX201901)the Ministry of Education,Singapore,Academic Research Grant R-279-000-538-114.
文摘Ultrasmall silver nanoclusters(Ag NCs)with rich surface chemistry and good biocompatibility are promising in antibacterial application,however,further development of Ag NCs for practical settings has been constrained by their relatively weak antibacterial activity.Using the nutritionally-rich medium for bacteria(e.g.,Luria-Bertani(LB)medium)to coat active Ag NCs could further improve their antibacterial activity.Here,we provide a delicate design of a highly efficient Ag NCs@ELB antibacterial agent(ELB denotes the extract of LB medium)by anchoring Ag NCs inside the ELB species via light irradiation.The as-designed Ag NCs with bacterium-favored nutrients on the surface can be easily swallowed by the bacteria,boosting the production of the intracellular reactive oxygen species(ROS,about 2-fold of that in the pristine Ag NCs).Subsequently,a higher concentration of ROS generated in Ag NCs@ELB leads to enhanced antibacterial activity,and enables to reduce the colony forming units(CFU)of both gram-positive and gram-negative bacteria with 3–4 orders of magnitude less than that treated with the pristine Ag NCs.In addition,the Ag NCs@ELB also shows good biocompatibility.This study suggests that surface engineering of active species(e.g.,Ag NCs)with nutritionally-rich medium of the bacteria is an efficient way to improve their antibacterial activity.
基金R.J.thanks the financial support from the National Science Foundation(No.DMR-1808675)G.W.acknowledges the funding support from National Science Foundation PAPID CHE(No.2034498)H.W.thanks the financial support from,the Air Force Office of Scientific Research(AFOSR)Nos.(FA9550-17-1-0099 and sFA9550-21-1-0192).
文摘Alloying is an important strategy in tailoring the functionality of materials.In metal nanoclusters(NCs),the introduction of a heterometal leads to alloy nanoclusters that often outperform the homometal ones in terms of the physical and chemical properties.In this work,a series of four M_(144)(PET)60 alloy NCs(where,M=Au/Ag,PET=–SCH_(2)CH_(2)Ph)are synthesized and characterized.The silver doping into the homogold template(Au_(144))leads to more prominent optical absorption features in the steady-state spectrum in the visible range.Femtosecond transient absorption spectroscopy reveals the effect of Ag doping on the electronic relaxation dynamics compared to Au_(144)and the pump fluence independent dynamics.Electrochemical results reflect a narrowing of HOMO–LUMO gap(E_(g))induced by Ag doping.A temperature dependence of the single-electron charging is also observed for the series of alloy NCs,in which the E_(g)values of the alloy NCs enlarge as the temperature decreases,which is characteristic of semiconducting behavior.
