Utilizing two polycarboxylic acids as primary ligands and 1,10-phenanthrolion as an auxiliary ligand in the existence of lanthanide nitrates,two lanthanide-based complexes formulated as[Nd4(2,6-pydc OH)6(Phen)4(H2O)2]...Utilizing two polycarboxylic acids as primary ligands and 1,10-phenanthrolion as an auxiliary ligand in the existence of lanthanide nitrates,two lanthanide-based complexes formulated as[Nd4(2,6-pydc OH)6(Phen)4(H2O)2](H2O)2(1)and[Yb2(mBDC)3(Phen)2]n(2)(2,6-H2 pydc OH=4-hydroxypyridine-2,6-dicarboxylic acid,m-H_2BDC=isophthalic acid,Phen=1,10-phenanthroline)have been solvothermally synthesized.They have been fully characterized by satisfactory elemental analysis,FT-IR spectra,TGA and single-crystal X-ray diffraction.Single-crystal X-ray diffraction study reveals that 1 has a zero-dimensional structure and 2 exhibits a rare cds topological net structure.Compounds 1 and 2 exhibit strong characteristic emissions of Nd(Ⅲ)and Yb(Ⅲ)ions in the near-infrared(NIR)region.展开更多
Accurate detection of multiple small end-metabolic biomarkers is more sensitive than large biomoleculesto provide real-time feedbacks of physiological/pathologicalstate, but is more challenging due to lack of specific...Accurate detection of multiple small end-metabolic biomarkers is more sensitive than large biomoleculesto provide real-time feedbacks of physiological/pathologicalstate, but is more challenging due to lack of specific identifyinggroups. Current optical platforms suffer from unsatisfactoryresolutions to differentiate each target because they producesimilar output to different targets using a single excitation,and inevitably involve non-functional components that increase chances of interacting with non-target molecules.Herein, by taking full advantage of each building unit’sfunctionality to integrate multivariate recognition elements inone interface, a dual-excitation-driven full-component-responsive metal-organic framework (MOF)-based luminescentprobe, namely CeTMA-TMA-Eu, is successfully custom-tailored for detecting both pseudouridine (Ψ) and N-acetylaspartate (NAA), the diagnostic hallmarks of cancer andneurodegenerative disorder. Remarkably, Ψ interacts withMOF’s organic building unit (trimesic acid, TMA) and filtersout its absorptions of 262 nm-light to reduce its energytransferred to Eu^(3+), while NAA induces the valence transitionof Ce^(4+)/Ce^(3+) nodes to improve the cooperative energy transferefficacy from TMA and Ce^(3+) to Eu^(3+). As a result, this platformexhibits completely reverse photoresponses towards Ψ(“switch-off” at 262 nm excitation) and NAA (“switch-on”upon 296 nm excitation), and demonstrates excellent selectivity and sensitivity in complex biofluids, with low detection limits of 0.16 and 0.15 μM, and wide linear ranges of0–180 and 0–100 μM, respectively. Such full-componentresponsive probe with dual-excitation-mediated reverse responses for multi-small targets intrinsically minimizes its interaction with non-target molecules and amplifies resolutionto discriminate each target, providing a new strategy for improving assay accuracy of multi-small biomarkers in diagnostics.展开更多
The large size of lasers limits their applications in confined spaces,such as in biosensing and in vivo brain tissue imaging.In this regard,micron-sized lasers have been developed.They exhibit great potential for biol...The large size of lasers limits their applications in confined spaces,such as in biosensing and in vivo brain tissue imaging.In this regard,micron-sized lasers have been developed.They exhibit great potential for biological detecting,remote sensing,and depth tracking due to their small sizes,sensitive properties of their spectral fingerprints,and flexible positional modulation in the microenvironment.Lanthanide-based luminescent materials that possess long excited-state lifetime,narrow emission bandwidth,and upconversion behaviors are promising as gain mediums for novel microlasers.In addition,lanthanide-based microlasers could be generated under natural ambient conditions with pumped or continuous light sources,which significantly promotes the practical applications of microlasers.Recent progress in the design,synthesis,and biomedical applications of lanthanide-based microlasers has been outlined in this review.Lanthanide ions doped and upconverted lanthanide-based microlasers are highlighted,which exhibit advantageous structures,miniaturized dimensions,and high lasing performance.The applications of lanthanide-based microlasers are further discussed,the upconverted microlasers show great advantages for biological applications owing to their tunable excitation and emission characteristics and excellent environmental stability.Moreover,perspectives and challenges in the field of lanthanide-based microlasers are presented.展开更多
Lanthanide-based microlasers have attracted considerable attention owing to their large anti-Stokes shifts,multiple emission bands,and narrow linewidths.Various applications of microlasers,such as optical communicatio...Lanthanide-based microlasers have attracted considerable attention owing to their large anti-Stokes shifts,multiple emission bands,and narrow linewidths.Various applications of microlasers,such as optical communication,optical storage,and polarization imaging,require selecting the appropriate laser polarization mode and remote control of the laser properties.Here,we propose a unique plasmon-assisted method for the mode selection and remote control of microlasing using a lanthanide-based microcavity coupled with surface plasmon polaritons(SPPs)that propagate on a silver microplate.With this method,the transverse electrical(TE)mode of microlasers can be easily separated from the transverse magnetic(TM)mode.Because the SPPs excited on the silver microplate only support TM mode propagation,the reserved TE mode is resonance-enhanced in the microcavity and amplified by the local electromagnetic field.Meanwhile,lasingmode splitting can be observed under the near-field excitation of SPPs due to the coherent coupling between the microcavity and mirror microcavity modes.Benefiting from the long-distance propagation characteristics of tens of micrometers of SPPs on a silver microplate,remote excitation and control of upconversion microlasing can also be realized.These plasmon-assisted polarization mode-optional and remote-controllable upconversion microlasers have promising prospects in on-chip optoelectronic devices,encrypted optical information transmission,and high-precision sensors.展开更多
Three lanthanide-based coordination polymers(Ln-CPs) with layered structure,{[La_(2)(L)_(3)(DMF)(H_(2)O)_(3)]·H_(2)O}_n(1),{[Eu_(2)(L)_(3)(DMF)_(2)(H_(2)O)]·(H_(2)O)}_n(2){Tb_(2)(L)_(3)(DMF)_(2)(H_(2)O)]...Three lanthanide-based coordination polymers(Ln-CPs) with layered structure,{[La_(2)(L)_(3)(DMF)(H_(2)O)_(3)]·H_(2)O}_n(1),{[Eu_(2)(L)_(3)(DMF)_(2)(H_(2)O)]·(H_(2)O)}_n(2){Tb_(2)(L)_(3)(DMF)_(2)(H_(2)O)]·H_(2)O}n(3) were successfully synthesized from H_(2)L(N,N'-bis(4-carbozylbenzyl)aniline).Remarkably,compound 3 has extremely high sensitivity to 4-nitrophenol.When the concentration of 4-nitrophenol reaches 5.98 × 10^(-3) mmol/L,the fluorescence intensity of compound 3 is quenched by 59%.The calculated K_(SV) is 7.56 × 10~4 and limit of detection(LOD) is 4.73 μg/L.3 exhibits a highly sensitive detection towards Fe^(3+) and compound 2 shows outstanding antibacterial effects on Staphylococcus aureus,re spectively.The white light emission was also investigated by changing the mixing ratio of LaNO_(3),EuNO_(3) and TbNO_(3) during the preparation of coordination polymers.展开更多
Two new europium-based metal-organic-frameworks （MOFs）, namely [NMen][Eu（m- BDC）2] （1） and [Eu3（p-BDC）4（ClO4）（H2O）4] （2）, have been synthesized and structurally characte- rized. Single-crystal X-ray diff...Two new europium-based metal-organic-frameworks （MOFs）, namely [NMen][Eu（m- BDC）2] （1） and [Eu3（p-BDC）4（ClO4）（H2O）4] （2）, have been synthesized and structurally characte- rized. Single-crystal X-ray diffraction studies reveal that 1 crystallizes in the monoclinic system, space group P21/n with a 2D layer structure, while 2 crystallizes in the orthorhombic system, space group Pccn with a 3D net structure. Both 1 and 2 have strong characteristic Eu（Ⅲ） emissions at visible red region and the quantum yields can reach up to 78.1 and 46.0%, respectively. The high luminescent efficiency may be attributed to the efficient energy transition from the ligands to the Eu（Ⅲ） center.展开更多
A new fluorescent coordination polymer(NKU-115) was constructed under solvothermal condition based on Tb^(3+)ion and H_2L(5-(4 H-1,2,4-triazol-4-yl) benzene-1,3-dicarboxylic acid) ligand, featuring high solvent and wa...A new fluorescent coordination polymer(NKU-115) was constructed under solvothermal condition based on Tb^(3+)ion and H_2L(5-(4 H-1,2,4-triazol-4-yl) benzene-1,3-dicarboxylic acid) ligand, featuring high solvent and water stability. Luminescent investigations revealed that NKU-115 shows fluorescence quenching response toward Fe^(3+)in aqueous solution and the mechanism of quenching was analyzed.展开更多
基金supported by the National Basic Research Program of China(973 Program,2012CB821702)the National Natural Science Foundation of China(21233009 and 21571175)the State Key Laboratory of Structural Chemistry
文摘Utilizing two polycarboxylic acids as primary ligands and 1,10-phenanthrolion as an auxiliary ligand in the existence of lanthanide nitrates,two lanthanide-based complexes formulated as[Nd4(2,6-pydc OH)6(Phen)4(H2O)2](H2O)2(1)and[Yb2(mBDC)3(Phen)2]n(2)(2,6-H2 pydc OH=4-hydroxypyridine-2,6-dicarboxylic acid,m-H_2BDC=isophthalic acid,Phen=1,10-phenanthroline)have been solvothermally synthesized.They have been fully characterized by satisfactory elemental analysis,FT-IR spectra,TGA and single-crystal X-ray diffraction.Single-crystal X-ray diffraction study reveals that 1 has a zero-dimensional structure and 2 exhibits a rare cds topological net structure.Compounds 1 and 2 exhibit strong characteristic emissions of Nd(Ⅲ)and Yb(Ⅲ)ions in the near-infrared(NIR)region.
基金supported by the National Key Research and Development Program of China (2022YFC2403203, 2024YFF0508601)the National Natural Science Foundation of China (52172279)+3 种基金the Basic Research Program of Shanghai (21JC1406003)the Shanghai Rising-Star Program (21QA1402200)the Leading Talents in Shanghai in 2018, the Key Field Research Program (2023AB054)the Higher Education Discipline Innovation Project (B14018)。
文摘Accurate detection of multiple small end-metabolic biomarkers is more sensitive than large biomoleculesto provide real-time feedbacks of physiological/pathologicalstate, but is more challenging due to lack of specific identifyinggroups. Current optical platforms suffer from unsatisfactoryresolutions to differentiate each target because they producesimilar output to different targets using a single excitation,and inevitably involve non-functional components that increase chances of interacting with non-target molecules.Herein, by taking full advantage of each building unit’sfunctionality to integrate multivariate recognition elements inone interface, a dual-excitation-driven full-component-responsive metal-organic framework (MOF)-based luminescentprobe, namely CeTMA-TMA-Eu, is successfully custom-tailored for detecting both pseudouridine (Ψ) and N-acetylaspartate (NAA), the diagnostic hallmarks of cancer andneurodegenerative disorder. Remarkably, Ψ interacts withMOF’s organic building unit (trimesic acid, TMA) and filtersout its absorptions of 262 nm-light to reduce its energytransferred to Eu^(3+), while NAA induces the valence transitionof Ce^(4+)/Ce^(3+) nodes to improve the cooperative energy transferefficacy from TMA and Ce^(3+) to Eu^(3+). As a result, this platformexhibits completely reverse photoresponses towards Ψ(“switch-off” at 262 nm excitation) and NAA (“switch-on”upon 296 nm excitation), and demonstrates excellent selectivity and sensitivity in complex biofluids, with low detection limits of 0.16 and 0.15 μM, and wide linear ranges of0–180 and 0–100 μM, respectively. Such full-componentresponsive probe with dual-excitation-mediated reverse responses for multi-small targets intrinsically minimizes its interaction with non-target molecules and amplifies resolutionto discriminate each target, providing a new strategy for improving assay accuracy of multi-small biomarkers in diagnostics.
基金supported by the National Natural Science Foundation of China(Nos.22020102003,22207104,and 22125701)the National Key R&D Program of China(Nos.2022YFF071000 and 2021YFF0701800)+2 种基金Natural Science Foundation of Jilin Province(No.20230101102JC)China Postdoctoral Science Foundation(Nos.2020M681055 and 2022T150634)Young Elite Scientists Sponsorship Program by CAST(Nos.2021-2023QNRC and YESS20210067).
文摘The large size of lasers limits their applications in confined spaces,such as in biosensing and in vivo brain tissue imaging.In this regard,micron-sized lasers have been developed.They exhibit great potential for biological detecting,remote sensing,and depth tracking due to their small sizes,sensitive properties of their spectral fingerprints,and flexible positional modulation in the microenvironment.Lanthanide-based luminescent materials that possess long excited-state lifetime,narrow emission bandwidth,and upconversion behaviors are promising as gain mediums for novel microlasers.In addition,lanthanide-based microlasers could be generated under natural ambient conditions with pumped or continuous light sources,which significantly promotes the practical applications of microlasers.Recent progress in the design,synthesis,and biomedical applications of lanthanide-based microlasers has been outlined in this review.Lanthanide ions doped and upconverted lanthanide-based microlasers are highlighted,which exhibit advantageous structures,miniaturized dimensions,and high lasing performance.The applications of lanthanide-based microlasers are further discussed,the upconverted microlasers show great advantages for biological applications owing to their tunable excitation and emission characteristics and excellent environmental stability.Moreover,perspectives and challenges in the field of lanthanide-based microlasers are presented.
基金supported by the National Natural Science Foundation of China(Grant Nos.U22A6005,92150110,12074237,and 12304426)the National Key R&D Program of China(Grant Nos.2020YFA0211300 and 2021YFA1201500)+3 种基金the Natural Science Foundation of Shaanxi Province(Grant No.2024JC-JCQN-07)the Fundamental Science Foundation of Shaanxi(Grant No.22JSZ010)the Fundamental Research Funds for Central Universities(Grant Nos.GK202201012,GK202308001,and LHRCTS23065)the Xi’an Young Elite Scientists Sponsorship Program(Grant No.1203050367)
文摘Lanthanide-based microlasers have attracted considerable attention owing to their large anti-Stokes shifts,multiple emission bands,and narrow linewidths.Various applications of microlasers,such as optical communication,optical storage,and polarization imaging,require selecting the appropriate laser polarization mode and remote control of the laser properties.Here,we propose a unique plasmon-assisted method for the mode selection and remote control of microlasing using a lanthanide-based microcavity coupled with surface plasmon polaritons(SPPs)that propagate on a silver microplate.With this method,the transverse electrical(TE)mode of microlasers can be easily separated from the transverse magnetic(TM)mode.Because the SPPs excited on the silver microplate only support TM mode propagation,the reserved TE mode is resonance-enhanced in the microcavity and amplified by the local electromagnetic field.Meanwhile,lasingmode splitting can be observed under the near-field excitation of SPPs due to the coherent coupling between the microcavity and mirror microcavity modes.Benefiting from the long-distance propagation characteristics of tens of micrometers of SPPs on a silver microplate,remote excitation and control of upconversion microlasing can also be realized.These plasmon-assisted polarization mode-optional and remote-controllable upconversion microlasers have promising prospects in on-chip optoelectronic devices,encrypted optical information transmission,and high-precision sensors.
基金supported by the Science and Technology Development Planning of Jilin Province,China (20210101129JC)。
文摘Three lanthanide-based coordination polymers(Ln-CPs) with layered structure,{[La_(2)(L)_(3)(DMF)(H_(2)O)_(3)]·H_(2)O}_n(1),{[Eu_(2)(L)_(3)(DMF)_(2)(H_(2)O)]·(H_(2)O)}_n(2){Tb_(2)(L)_(3)(DMF)_(2)(H_(2)O)]·H_(2)O}n(3) were successfully synthesized from H_(2)L(N,N'-bis(4-carbozylbenzyl)aniline).Remarkably,compound 3 has extremely high sensitivity to 4-nitrophenol.When the concentration of 4-nitrophenol reaches 5.98 × 10^(-3) mmol/L,the fluorescence intensity of compound 3 is quenched by 59%.The calculated K_(SV) is 7.56 × 10~4 and limit of detection(LOD) is 4.73 μg/L.3 exhibits a highly sensitive detection towards Fe^(3+) and compound 2 shows outstanding antibacterial effects on Staphylococcus aureus,re spectively.The white light emission was also investigated by changing the mixing ratio of LaNO_(3),EuNO_(3) and TbNO_(3) during the preparation of coordination polymers.
基金supported by the National Basic Research Program of China(973 Program,2012CB821702)the National Natural Science Foundation of China(21233009 and 21173221)the State Key Laboratory of Structural Chemistry
文摘Two new europium-based metal-organic-frameworks （MOFs）, namely [NMen][Eu（m- BDC）2] （1） and [Eu3（p-BDC）4（ClO4）（H2O）4] （2）, have been synthesized and structurally characte- rized. Single-crystal X-ray diffraction studies reveal that 1 crystallizes in the monoclinic system, space group P21/n with a 2D layer structure, while 2 crystallizes in the orthorhombic system, space group Pccn with a 3D net structure. Both 1 and 2 have strong characteristic Eu（Ⅲ） emissions at visible red region and the quantum yields can reach up to 78.1 and 46.0%, respectively. The high luminescent efficiency may be attributed to the efficient energy transition from the ligands to the Eu（Ⅲ） center.
基金supported by the National Natural Science Foundation of China (Nos. 21531005 and 21673120)the Natural Science Foundation of Tianjin (Nos. 15JCZDJC38800 and 16JCZDJC36900)
文摘A new fluorescent coordination polymer(NKU-115) was constructed under solvothermal condition based on Tb^(3+)ion and H_2L(5-(4 H-1,2,4-triazol-4-yl) benzene-1,3-dicarboxylic acid) ligand, featuring high solvent and water stability. Luminescent investigations revealed that NKU-115 shows fluorescence quenching response toward Fe^(3+)in aqueous solution and the mechanism of quenching was analyzed.
