Antimonotungstate-Based Heterometallic Framework Formed by the Synergistic Strategy of In Situ-Generated Krebs-Type Building Units and the Substitution Reaction and Its High-Efficiency Biosensing KRAS Gene DOI
Peijun Gong,

Yanying Wang,

Jun‐Wei Zhao

et al.

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 64(1), P. 315 - 326

Published: Dec. 31, 2024

A novel antimonotungstate (AT)-based heterometallic framework {[Er(H2O)6]2[Fe4(H2pdc)4(B-β-SbW9O33)2]}·50H2O (1, H2pdc = pyridine-2,5-dicarboxylic acid) was obtained through a synergistic strategy of in situ-generated transition-metal-encapsulated polyoxometalate (POM) building units and the substitution reaction. Its structural unit is composed tetra-FeIII-substituted Krebs-type [Fe4(H2pdc)4(B-β-SbW9O33)2]6– subunit two [Er(H2O)6]3+ cations. This can be regarded as product carboxylic oxygen atoms ligands replacing active water [Fe4(H2O)10(B-β-SbW9O33)2]6– species. Apparently, action for ligands, together with coordination function Er3+ ions, plays connection role architecture three-dimensional (3-D) framework. Based on stability high redox activity 1, glassy carbon electrode modified by 1 used construction an electrochemical biosensor (ECBS). Thus, such 1-based ECBS sensitively detect KRAS gene (a key genetic marker identifying occurrence malignant tumors) displays low detection limit (0.106 pM), selectivity, reproducibility. work not only provides feasible approach to prepare multicomponent POM-based frameworks but also establishes new platform biosensing extends application scope functional materials.

Language: Английский

Anion-Guided Hierarchical Assembly of Heterometallic Clusters DOI
Weimin Huang, Qingsong Yang, Wanmin Chen

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 5, 2025

Anions are important as templates for the construction of many structurally sophisticated and functional supramolecular architectures. Deciphering specific role such remains a great challenge due to unique characteristics anions. Herein, three heterometallic Ce–Ni clusters, namely, [Ce24Ni36L36(μ4-OAc)6(OH)52(Cl)8]Cl6·110H2O (Ce24Ni36, OAc = acetate ion, L N-methyliminodiacetate), [Ce17Ni27L27(μ6-C2O4)6(OH)15(Cl)16(H2O)19](ClO4)2Cl6·45H2O (Ce17Ni27), [Ce21Ni30L30(μ6-C2O4)2(μ4-OAc)(OH)32(Cl)15(H2O)14](ClO4)4Cl7·55H2O (Ce21Ni30), were obtained characterized; formation these cage-like clusters was assisted, respectively, by acetate, oxalate, combination two templates. Structural analyses generate key information on anion-directed hierarchical assembly, starting from primary building block {CeNi3} anion-specific secondary blocks (SBUs)─the tetragonal {Ce4Ni8(OAc)} pentagonal {Ce5Ni9(C2O4)}. Further assembly steps guided curved SBUs, affording truncated octahedral Ce24Ni36 lantern-like Ce17Ni27, with oxalate being sole template, respectively. The combined use produced Ce21Ni30, cluster an unprecedented structure viewable hybrid octahedron dodecahedron.

Language: Английский

Citations

0
In Situ Reaction Forms Uniform Mixed Heterometallic LnIII2MnII4 (Ln = DyIII and GdIII) Clusters: Assembly Mechanism and Insights into Performance DOI
Dongze Wu, Ziying Li,

Qinhua Zhang

et al.

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 19, 2025

The unclear assembly mechanism seriously hinders the preparation and application of 3d-4f heterometallic clusters. Two new nanoclusters [Dy2Mn4(HL)4(OAc)6]·5EtOH·H2O (1) [Gd2Mn4(HL)4(OAc)6]·4EtOH·4H2O (2) were obtained from in situ condensation reaction 3-amino-1,2-propanediol with 2-hydroxy-1-naphthaldehyde. intermediate species cluster 1 synthesis process tracked by time-dependent high-resolution electrospray ionization mass spectrometry (HRESI-MS), further revealing possible formation (Dy → DyL2 →DyMn2L2 DyMn3L2 DyMn4L3 Dy2Mn4L4). Magnetic studies indicated that antiferromagnet LnIII-MnII (Ln = DyIII GdIII) interaction was operative both titled Furthermore, performance clusters regulated adjusting type rare earth ions (DyIII GdIII). research results showed 2 containing GdIII exhibited an excellent longitudinal relaxation rate (r1) 1.95 mM-1 s-1 under 0.5 T a relatively suitable r2/r1 value (3.88), which it can be used as efficient T1 MR contrast agent. Cluster displayed antipathogenic activities against clinical MRSA strain MIC 32 μg/mL. This work not only provided reference for but also confirmed its potential biomedical field.

Language: Английский

Citations

0
Lanthanide-Incorporated PIII–SbIII-Heteroatom-Templated Tetrahedral Heteropolyoxometalate Cluster for Detecting Early Tumor Marker MicroRNA-155 DOI
Yu Liu, Zhigang Tang, Yanfeng Pu

et al.

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 26, 2025

Heteropolyoxometalates have garnered widespread attention owing to their diverse structures and intriguing physicochemical properties. Herein, we successfully synthesized a unique lanthanide-incorporated PIII–SbIII-heteroatom-templated tetrahedral polyoxometalate cluster [H2N(CH3)2]20Na7H7{[Er6(H2O)6][W4O16][HPSbW15O54]4}·132H2O (1). The polyoxoanion of 1 can be perceived as four trilacunary Dawson [HPSbW15O54]11– {PSbW15} building blocks encapsulating deca-nuclear heterometallic [Er6(H2O)6W4O16]10+ cluster. This comprises an inner [W4O16]8– ({W4}) core surrounded by octahedral [Er6(H2O)6]18+ ({Er6}) shell. Consequently, the exhibits distinctive ({W4} ⊂ {Er6} [{PSbW15}]4) three-shell structure. Considering electron transfer characteristics 1, it was coelectropolymerized with N-methylpyrrole (NMPy) fabricate 1–PNMPy film (PNMPy = polyNMPy). Notably, incorporation improves distribution within PNMPy backbone, thereby narrowing band gap enhancing conductive performance film. Therefore, is utilized modified electrode material construct electrochemical biosensor for sensitive detection tumor marker microRNA-155. research not only provides viable approach fabrication multishell heteropolyoxometalates but also promotes exploration application multicomposition polyoxometalates in biosensing microRNA.

Language: Английский

Citations

0
Water-Stable Al3Ni4 Polynuclear Heterometallic Compound for Near-Infrared Photothermal Conversion DOI
Yanyan Gao, Lixing Zhao,

Qingyu Du

et al.

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 18, 2025

In this paper, a polynuclear heterometallic compound (H3O)[Al3Ni4(OH)6(MBA-NO2)6(H2O)6] (Al3Ni4, H2MBA-NO2 = 2-hydroxy-3-methoxy-5-nitrobenzoic acid) with seven-star disk metal core has been synthesized by the solvothermal method. Al3Ni4 good stability in water and several organic solvents, its solid powder shows photothermal effect under 980 nm laser irradiation, temperature can reach 138.8 °C within 100 s 1.0 W cm-2 power irradiation. Considering effect, evaporation of was measured. It be further used as material seawater evaporation.

Language: Английский

Citations

0
Electrospray Ionization Mass Spectrometry Insights into the Assembly of Lanthanide-Containing Clusters DOI

Ming-Qiang Qi,

Ming‐Hao Du, Xiang‐Jian Kong

et al.

Accounts of Chemical Research, Journal Year: 2025, Volume and Issue: unknown

Published: April 29, 2025

ConspectusAtomically precise metal clusters with well-defined crystal structures have emerged as a rapidly growing field within coordination and materials chemistry. Among them, lanthanide-containing (LCCs) are particularly notable for their aesthetically pleasing architectures intriguing properties. Achieving synthesis accurate structural characterization of these is crucial unlocking potential applications. Mass spectrometry (MS), electrospray ionization mass (ESI-MS), has proven to be powerful tool, providing exceptional sensitivity clarity in revealing the formation mechanisms details clusters. In this Account, we explore synthesis, characterization, assembly LCCs utilizing ESI-MS. We begin by tracing historical development LCCs, emphasizing critical role single-crystal X-ray diffraction confirmation challenges associated it. then discuss application ESI-MS characterizing highlighting how technique can monitor processes determine molecular weights charge states. introduce difference fingerprint isomorphism (MDFI) method, which facilitate rapid analysis LCCs' data. Furthermore, state solution characterization. By ESI-MS, enhance understanding propose new strategies designing synthesizing tailored functions. Looking forward, method will play increasingly significant roles LCC research. The continued technologies deepen structure-property relationships. With ongoing convergence computational chemistry information science, anticipate more design leading broader applications magnetism, optics, catalysis.

Language: Английский

Citations

0
Saddle-Shaped Heterometallic 3d–4f Cluster: Structure and Magnetocaloric Effect DOI
Qingxin Liu, Min Feng, Wanmin Chen

et al.

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 7, 2025

Heterometallic 3d-4f cluster complexes have enjoyed much recent interest because of their structural esthetics, unique properties, and useful applications. A the formula [Gd68Co60(OH)116(CH3COO)8(IDA)56(CO3)4(C2O4)8(H2O)92Cl16]Cl48·10H2O·60CH3OH (Gd68Co60, IDA: iminodiacetate), obtained by cohydrolysis Gd3+ Co2+ in presence IDA, is herein reported. Crystallographic studies revealed its saddle-shaped cyclic structure featuring a nanometer-sized central cavity. maximum magnetic entropy change 38.58 J·K-1·kg-1 was achieved at 3.0 K 7.0 T, placing Gd68Co60 favorably alongside better-performing clusters for cooling

Language: Английский

Citations

0
Electrochemical Biosensor Based on Dual-Ligand Functionalized Lanthanide-Encapsulated Polyoxometalate Conductive Polymer Film for Detecting Broad-Spectrum Tumor Marker MicroRNA-155 DOI

Lina Meng,

Xiaodan Jia,

Zhigang Tang

et al.

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(46), P. 22149 - 22161

Published: Nov. 1, 2024

In this work, a dual-ligand functionalized lanthanide-encapsulated selenotungstate [H2N(CH3)2]16Na2H10[Ho6(H2O)10(HPACA)4W10O28(Ac)2][SeW9O33]6 · 60H2O (1, HPACA = 2-pyrazinecarboxylic acid, HAc acetic acid) was successfully acquired by simultaneously incorporating rigid and flexible Ac– ligands to one reaction system. Interestingly, the polyanion [Ho6(H2O)10(HPACA)4W10O28(Ac)2][SeW9O33]628– of 1 is composed six trivacant Keggin-type [B-α-SeW9O33]8– units interconnected through an organic–inorganic hybrid bimetallic [Ho6(H2O)10(HPACA)4W10O28(Ac)2]20+ cluster. Moreover, 1@PNMPy film (PNMPy poly(N-methylpyrrole)) prepared electrochemical polymerization strategy. The doping significantly narrows bandgap in film, which enables exhibit remarkable conductivity rapid electron transfer capability. Then, film-modified glassy carbon electrode used construct 1@PNMPy-based biosensor (ECBS), achieves sensitive detection (a low limit 0.108 fM wide concentration range 10–8–10–15 M) for broad-spectrum tumor marker microRNA-155. Also, ECBS has good specific recognition performance microRNA-155 variety interfering media. research not only contributes deeper understanding synthetic chemistry multicomponent polyoxometalate (POM)-based materials but also can further expand innovative applications POM-based devices.

Language: Английский

Citations

2
Antimonotungstate-Based Heterometallic Framework Formed by the Synergistic Strategy of In Situ-Generated Krebs-Type Building Units and the Substitution Reaction and Its High-Efficiency Biosensing KRAS Gene DOI
Peijun Gong,

Yanying Wang,

Jun‐Wei Zhao

et al.

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 64(1), P. 315 - 326

Published: Dec. 31, 2024

A novel antimonotungstate (AT)-based heterometallic framework {[Er(H2O)6]2[Fe4(H2pdc)4(B-β-SbW9O33)2]}·50H2O (1, H2pdc = pyridine-2,5-dicarboxylic acid) was obtained through a synergistic strategy of in situ-generated transition-metal-encapsulated polyoxometalate (POM) building units and the substitution reaction. Its structural unit is composed tetra-FeIII-substituted Krebs-type [Fe4(H2pdc)4(B-β-SbW9O33)2]6– subunit two [Er(H2O)6]3+ cations. This can be regarded as product carboxylic oxygen atoms ligands replacing active water [Fe4(H2O)10(B-β-SbW9O33)2]6– species. Apparently, action for ligands, together with coordination function Er3+ ions, plays connection role architecture three-dimensional (3-D) framework. Based on stability high redox activity 1, glassy carbon electrode modified by 1 used construction an electrochemical biosensor (ECBS). Thus, such 1-based ECBS sensitively detect KRAS gene (a key genetic marker identifying occurrence malignant tumors) displays low detection limit (0.106 pM), selectivity, reproducibility. work not only provides feasible approach to prepare multicomponent POM-based frameworks but also establishes new platform biosensing extends application scope functional materials.

Language: Английский

Citations

0