This work presents a generic strategy to create a series of metal mercaptides complexes via coordination selfassembly between transition metals(Mn,Cu,Co,Fe,and Ni)and cysteine(Cys)by forming the sulfur-metal bridges.T...This work presents a generic strategy to create a series of metal mercaptides complexes via coordination selfassembly between transition metals(Mn,Cu,Co,Fe,and Ni)and cysteine(Cys)by forming the sulfur-metal bridges.This strategy involves dissolving metal chlorides and Cys into deep eutectic solvents(DES),followed by the precipitation of metal mercaptides complexes(such as Cys-Mn)by adding water as an antisolvent,where DES serves as the solvent,shape directing,and capping agent,thereby preventing the formation of other metal impurities.Interestingly,the prepared complexes possess both laccase and peroxidase-like properties,allowing the design of a technique for the detection of L-3,4-dihydroxyphenylalanine(L-DOPA)and uric acid,respectively.The prepared Cys-Mn can linearly oxidize L-DOPA with its concentrations from 0.1 to 130μM and the detection limit was calculated to be 75.5 n M.Additionally,the Cys-Mn can mimic the activity of peroxidase towards oxidization of o-phenylenediamine at neutral p H,allowing single-step and one-pot cascade reactions for visual and fluorometric measurements of uric acid(UA)that could work in the range of 0.2-500μM UA with a detection limit of 0.06μM and 0.054μМ,respectively.The assay was successful in detecting UA in serum and urine samples with relative standard deviation(RSD)ranging from 7.3%to 10.2%and 3.0%-8.5%respectively,suggesting that it may prove useful in medical diagnostic testing.展开更多
An emerging method for effectively improving the catalytic activity of metal oxide hybrids involves the creation of metal oxide interfaces for facilitating the activation of reagents. Here, we demonstrate that bilayer...An emerging method for effectively improving the catalytic activity of metal oxide hybrids involves the creation of metal oxide interfaces for facilitating the activation of reagents. Here, we demonstrate that bilayer vesicles formed from a hexavanadate cluster functionalized with two alkyl chains are highly efficient catalysts for the oxidation of 3,3＇,5,5＇-tetramethylbenzidine （TMB） with H2O2 at room temperature, a widely used model reaction mimicking the activity of peroxidase in biological catalytic oxidation processes. Driven by hydrophobic interactions, the double-tailed hexavanadate-headed amphiphiles can self-assemble into bilayer vesicles and create hydrophobic domains that segregate the TMB chromogenic substrate. The reaction of TMB with H2O2 takes place at the interface of the hydrophilic and hydrophobic domains, where the reagents also make contact with the catalytic hexavanadate clusters, and it is approximately two times more efficient compared with the reactions carried out with the corresponding unassembled systems. Moreover, the assembled vesicular system possesses affinity for TMB comparable to that of reported noble metal mimic nanomaterials, as well as a higher maximum reaction rate.展开更多
Rational design and exploitation of nanomaterials with superior treatment properties for suitable indications is a way out to relieve cost constraint of therapy and solve the unsatisfactory efficacy for cancer patient...Rational design and exploitation of nanomaterials with superior treatment properties for suitable indications is a way out to relieve cost constraint of therapy and solve the unsatisfactory efficacy for cancer patients.In this work,we propose a greatly facile approach to produce heterogeneous Pd-Au nanorods(Pd-Au NRs)that solve the current bottleneck problems of photothermal thermal therapy(PTT)as well as completely eliminate tumors in animal models without toxic side effects.Depositing Pd clusters on both tips of Au NRs offers Pd-Au NRs three novel functions,i.e.,the extension of the absorption into NIR-Ⅱ region,the activation of prodrug of 5-fluorouracil(5-Fu)via the bioorthogonal reaction,and the peroxidase-mimic activity to produce·OH.The heterogeneous nanorods showed a high and stable photothermal conversion efficiency(52.07%)in a safer NIR-Ⅱ irradiation region(1,064 nm),which not only eliminate most of tumor cells at only one dose of the irradiation for 5 min but also improve the in situ conversion of 5-fluoro-1-propargyluracil and H2O2 into active 5-Fu and·OH to eradicate residual tumors for inhibiting tumor metastasis.This dual catalytic activity-synergistic mechanism of PTT demonstrates the importance of material design in solving current bottleneck problem of tumor therapy.展开更多
基金supported by the National Natural Science Foundation of China(Nos.21822407 and 22074154)the Chinese Academy of Sciences-the World Academy of Sciences(CAS-TWAS)President’s Fellowship Program+2 种基金CAS“Light of West China”ProgramYouth Innovation Promotion Association CAS(2021420)the Foundation for Sci&Tech Research Project of Gansu Province(20JR5RA573,20JR10RA045)
文摘This work presents a generic strategy to create a series of metal mercaptides complexes via coordination selfassembly between transition metals(Mn,Cu,Co,Fe,and Ni)and cysteine(Cys)by forming the sulfur-metal bridges.This strategy involves dissolving metal chlorides and Cys into deep eutectic solvents(DES),followed by the precipitation of metal mercaptides complexes(such as Cys-Mn)by adding water as an antisolvent,where DES serves as the solvent,shape directing,and capping agent,thereby preventing the formation of other metal impurities.Interestingly,the prepared complexes possess both laccase and peroxidase-like properties,allowing the design of a technique for the detection of L-3,4-dihydroxyphenylalanine(L-DOPA)and uric acid,respectively.The prepared Cys-Mn can linearly oxidize L-DOPA with its concentrations from 0.1 to 130μM and the detection limit was calculated to be 75.5 n M.Additionally,the Cys-Mn can mimic the activity of peroxidase towards oxidization of o-phenylenediamine at neutral p H,allowing single-step and one-pot cascade reactions for visual and fluorometric measurements of uric acid(UA)that could work in the range of 0.2-500μM UA with a detection limit of 0.06μM and 0.054μМ,respectively.The assay was successful in detecting UA in serum and urine samples with relative standard deviation(RSD)ranging from 7.3%to 10.2%and 3.0%-8.5%respectively,suggesting that it may prove useful in medical diagnostic testing.
基金We gratefully acknowledge the financially support by the National Natural Science Foundation of China （Nos. 21631007, 21401050, 21471087 and 21271068）, Beijing Natural Science Foundation （No. 2164063）, China Postdoctoral Science Foundation （No. 2014M560948）, the State Key Laboratory of Natural and Biomimetic Drugs （No. K20160202）, the National Natural Science Foundation of Hubei Province （No. 2015CFA131） and Wuhan Applied Basic Research Program （No. 2014010101010020）. T. B. L. acknowledges support from the National Science Foundation （No. CHE1607138） and the University of Akron.
文摘An emerging method for effectively improving the catalytic activity of metal oxide hybrids involves the creation of metal oxide interfaces for facilitating the activation of reagents. Here, we demonstrate that bilayer vesicles formed from a hexavanadate cluster functionalized with two alkyl chains are highly efficient catalysts for the oxidation of 3,3＇,5,5＇-tetramethylbenzidine （TMB） with H2O2 at room temperature, a widely used model reaction mimicking the activity of peroxidase in biological catalytic oxidation processes. Driven by hydrophobic interactions, the double-tailed hexavanadate-headed amphiphiles can self-assemble into bilayer vesicles and create hydrophobic domains that segregate the TMB chromogenic substrate. The reaction of TMB with H2O2 takes place at the interface of the hydrophilic and hydrophobic domains, where the reagents also make contact with the catalytic hexavanadate clusters, and it is approximately two times more efficient compared with the reactions carried out with the corresponding unassembled systems. Moreover, the assembled vesicular system possesses affinity for TMB comparable to that of reported noble metal mimic nanomaterials, as well as a higher maximum reaction rate.
基金This work was supported by grants from the National Natural Science Foundation of China(Nos.31870946,81421004,52027801,31470916,and 51631001)the Natural Science Foundation of Beijing Municipality(No.2191001)+2 种基金the Funding of Double First-rate discipline construction(No.CPU2018GF07)the Priority Academic Program Development of Jiangsu Higher Education Institutionsthe Open Project Program of MOE Key Laboratory of Drug Quality Control and Pharmacovigilance(No.DQCP20/21MS01).
文摘Rational design and exploitation of nanomaterials with superior treatment properties for suitable indications is a way out to relieve cost constraint of therapy and solve the unsatisfactory efficacy for cancer patients.In this work,we propose a greatly facile approach to produce heterogeneous Pd-Au nanorods(Pd-Au NRs)that solve the current bottleneck problems of photothermal thermal therapy(PTT)as well as completely eliminate tumors in animal models without toxic side effects.Depositing Pd clusters on both tips of Au NRs offers Pd-Au NRs three novel functions,i.e.,the extension of the absorption into NIR-Ⅱ region,the activation of prodrug of 5-fluorouracil(5-Fu)via the bioorthogonal reaction,and the peroxidase-mimic activity to produce·OH.The heterogeneous nanorods showed a high and stable photothermal conversion efficiency(52.07%)in a safer NIR-Ⅱ irradiation region(1,064 nm),which not only eliminate most of tumor cells at only one dose of the irradiation for 5 min but also improve the in situ conversion of 5-fluoro-1-propargyluracil and H2O2 into active 5-Fu and·OH to eradicate residual tumors for inhibiting tumor metastasis.This dual catalytic activity-synergistic mechanism of PTT demonstrates the importance of material design in solving current bottleneck problem of tumor therapy.
