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Atomic-Level Doping of Metal Clusters
摘要： Atomically precise noble metal (mainly silver and gold) nanoclusters are an emerging category of promising functional materials for future applications in energy, sensing, catalysis, and nanoelectronics. These nanoclusters are protected by ligands such as thiols, phosphines, and hydride and have sizes between those of atoms and plasmonic nanoparticles. In metallurgy, the properties of a pure metal are modified by the addition of other metals, which often offers augmented characteristics, making them more utilizable for real-life applications. In this Account, we discuss how the incorporation of various metal atoms into existing protected nanoclusters tunes their structure and properties. The process of incorporating metals into an existing cluster is known as doping; the product is known as a doped cluster, and the incorporated metal atom is called a dopant/foreign atom. We first present a brief historical overview of protected clusters and the need for doping and explain (with examples) the difference between an “alloy” and a “doped” cluster, which are two frequently confused terms. We then discuss several commonly observed challenges in the synthesis of doped clusters: (i) doping produces a mixture of compositions that prevents the growth of single crystals; (ii) doping with foreign atoms sometimes changes the overall composition and structure of the parent cluster; and (iii) doping beyond a certain number of foreign atoms decomposes the doped cluster. After delineating the challenges, we review a few potential synthetic methods for doped clusters: (i) the co-reduction method, (ii) the galvanic exchange method, (iii) ligand-induced conversion of bimetallic clusters to doped clusters, and (iv) intercluster reactions. As a foreign atom is able to occupy different positions within the structure of the parent cluster, we examine the structural relationship between the parent clusters and their different foreign-atom-doped clusters. We then show how doping enhances the stability, luminescence, and catalytic properties of clusters. The enhancement factor highly depends on the number and nature of the foreign atoms, which can also alter the charge state of the parent cluster. Atomic-level doping of foreign atoms in the parent cluster is confirmed by high-resolution electrospray ionization and matrix-assisted laser desorption ionization mass spectrometry techniques and single-crystal X-ray diffraction methods. The photophysical properties of the doped clusters are investigated using both time-dependent and steady-state luminescence and optical absorption spectroscopies. After presenting an overview of atomic-level doping in metal clusters and demonstrating its importance for enriching the chemistry and photophysics of clusters and extending their applications, we conclude this Account with a brief perspective on the field’s future.
关键词： applications,doping,properties,atomically precise,noble metal nanoclusters,alloy,synthesis,structure
更新于2025-09-09 09:28:46
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Aluminum(III) triggered aggregation-induced emission of glutathione-capped copper nanoclusters as a fluorescent probe for creatinine
摘要： Glutathione-capped copper nanoclusters (CuNCs) are presented that display aggregation-induced emission (AIE). This feature was exploited for selective and sensitive quantification of creatinine (CRN) which is an important diagnostic parameter. In the presence of Al3+ ions, such CuNCs rapidly aggregate, and this induces enhanced a red emission. The AIE nature of CuNCs was proven via TEM and fluorimetry. On addition of CRN, the coordination between CRN and Al3+ ions led to the quenching of fluorescence due to weakening the AIE. The best fluorescence intensity was measured at excitation/emission peaks of 360/585 nm. Quenched fluorescence intensity showed a linear dependence on the concentrations of CRN in the range of 2.5–34 μgL?1 with a detection limit of 0.63 μgL?1. The sensing mechanism of probe for CRN detection is discussed. The probe was applied to the determination of CRN in spiked human serum samples and gave satisfactory results.
关键词： Nanosensor,Renal biomarker,Serum analysis,Fluorescent nanomaterials,Metal nanoclusters,Nanoprobe,Paired t-test,Fluorometry,Real sample analysis
更新于2025-09-04 15:30:14