Search Results (8)

DNA as an intriguing organic ligand has been widely employed for synthesizing metal nanoclusters and engineering their properties. This review aims to present recent progress on DNA-encoded metal (Ag, Cu, Au, Ag/Pt, Cu/Ag, etc.) nanoclusters (DNA-MNCs), focusing on their applications in the fields of analysis, logic operation, and therapy based on properties including fluorescence, electrochemiluminescence (ECL), and antibacterial and catalytic activity, and summarizes the attractive features of the latest research. The key points are briefly described as follows. (1) Analytical systems have been constructed based on fluorescence regulation, and nuclease-assisted and enzyme-free amplification strategies have been extensively adopted with fluorescent DNA-MNCs for amplified analysis. (2) DNA-MNCs may play more than one role (emitter, quencher, or catalyst) in ECL-based analytical systems. (3) Apart from antibacterial activity, DNA-MNCs also possess apparent catalytic capability, such as enzyme-like activity (i.e., nanozymes), which has been applied in colorimetric systems. (4) Reversibly regulating the catalytic activity of DNA-MNCs has been attained with DNA systems. It is believed that through in-depth investigation of the relationship between atomic structure and property, more novel DNA-MNCs will be explored and applied in the future. Full article

Noble Metal nanoclusters (NCs) are promising electrochemiluminescence (ECL) emitters due to their amazing optical properties and excellent biocompatibility. They have been widely used in the detection of ions, pollutant molecules, biomolecules, etc. Herein, we found that glutathione-capped AuPt bimetallic NCs (GSH-AuPt NCs) emitted strong anodic ECL signals with triethylamine as co-reactants which had no fluorescence (FL) response. Due to the synergistic effect of bimetallic structures, the ECL signals of AuPt NCs were 6.8 and 94 times higher than those of monometallic Au and Pt NCs, respectively. The electric and optical properties of GSH-AuPt NCs differed from those of Au and Pt NCs completely. An electron-transfer mediated ECL mechanism was proposed. The excited electrons may be neutralized by Pt(II) in GSH-Pt and GSH-AuPt NCs, resulting in the vanished FL. Furthermore, abundant TEA radicals formed on the anode contributed electrons to the highest unoccupied molecular orbital of GSH-Au_2.5Pt NCs and Pt(II), booming intense ECL signals. Because of the ligand effect and ensemble effect, bimetallic AuPt NCs exhibited much stronger ECL than GSH-Au NCs. A sandwich-type immunoassay for alpha fetoprotein (AFP) cancer biomarkers was fabricated with GSH-AuPt NCs as signal tags, which displayed a wide linear range from 0.01 to 1000 ng·mL⁻¹ and a limit of detection (LOD) down to 1.0 pg·mL⁻¹ at 3S/N. Compared to previous ECL AFP immunoassays, this method not only had a wider linear range but also a lower LOD. The recoveries of AFP in human serum were around 108%, providing a wonderful strategy for fast, sensitive, and accurate cancer diagnosis. Full article

The synthetic method of Pt nanocluster-anchored hollow Ag-Au nanostructures and measurements of their electrocatalytic properties for methanol oxidation reaction (MOR) are reported here. In this synthesis, uniform Ag nanospheres were prepared by reduction of silver nitrate (AgNO₃) with sodium borohydride (NaBH₄) and then hollow Ag-Au nanostructures were synthesized via galvanic replacement of the as-prepared Ag nanospheres with Au³⁺. Finally, the reduction of potassium tetrachloroplatinate (II) (K₂PtCl₄) with ascorbic acid was performed to deposit Pt nanoclusters on the surface of hollow Ag-Au nanostructures. The hollow interior of Pt nanocluster-anchored Ag-Au nanostructures and change in the size of Pt nanoclusters by varying the injected molar ratio of Pt/Au were observed by transmission electron microscopy (TEM). Moreover, other morphological, compositional, and optical information of the obtained nanoscale materials were analyzed by X-ray diffraction analysis (XRD), inductively coupled plasma mass spectrometry (ICP-MS), and ultraviolet-visible spectroscopy (UV-vis). The electrocatalytic ability of the obtained Pt nanocluster-anchored hollow Ag-Au nanostructures toward MOR was confirmed by the results of cyclic voltametric (CV) measurements. The ease of three-step synthetic strategy and good electrocatalytic performance of the Pt nanocluster-anchored hollow Ag-Au nanostructures displayed their promising potential in the use of electrochemical oxidation of methanol. Full article

Metal nanoclusters (NCs), including Au, Ag, Cu, Pt, Ni and alloy NCs, have become more and more popular sensor probes with good solubility, biocompatibility, size-dependent luminescence and catalysis. The development of electrochemiluminescent (ECL) and chemiluminescent (CL) analytical methods based on various metal NCs have become research hotspots. To improve ECL and CL performances, many strategies are proposed, from metal core to ligand, from intermolecular electron transfer to intramolecular electron transfer. Combined with a variety of amplification technology, i.e., nanostructure-based enhancement and biological signal amplification, highly sensitive ECL and CL analytical methods are developed. We have summarized the research progresses since 2016. Also, we discuss the current challenges and perspectives on the development of this area. Full article

The rapid and increasing use of the nanomaterials (NMs), nanostructured materials (NSMs), metal nanoclusters (MNCs) or nanocomposites (NCs) in the development of electrochemiluminescence (ECL) nanobiosensors is a significant area of study for its massive potential in the practical application of nanobiosensor fabrication. Recently, NMs or NSMs (such as AuNPs, AgNPs, Fe₃O₄, CdS QDs, OMCs, graphene, CNTs and fullerenes) or MNCs (such as Au, Ag, and Pt) or NCs of both metallic and non-metallic origin are being employed for various purposes in the construction of biosensors. In this review, we have selected recently published articles (from 2014–2017) on the current development and prospects of label-free or direct ECL nanobiosensors that incorporate NCs, NMs, NSMs or MNCs. Full article

Studies of metal nanocluster (M-NCs)-based sensors for specific analyte detection have achieved significant progress in recent decades. Ultra-small-size (<2 nm) M-NCs consist of several to a few hundred metal atoms and exhibit extraordinary physical and chemical properties. Similar to organic molecules, M-NCs display absorption and emission properties via electronic transitions between energy levels upon interaction with light. As such, researchers tend to apply M-NCs in diverse fields, such as in chemosensors, biological imaging, catalysis, and environmental and electronic devices. Chemo- and bio-sensory uses have been extensively explored with luminescent NCs of Au, Ag, Cu, and Pt as potential sensory materials. Luminescent bi-metallic NCs, such as Au-Ag, Au-Cu, Au-Pd, and Au-Pt have also been used as probes in chemosensory investigations. Both metallic and bi-metallic NCs have been utilized to detect various analytes, such as metal ions, anions, biomolecules, proteins, acidity or alkalinity of a solution (pH), and nucleic acids, at diverse detection ranges and limits. In this review, we have summarized the chemosensory applications of luminescent M-NCs and bi-metallic NCs. Full article

Understanding the molecular interaction behavior of transition metal nanoclusters lies at the heart of their efficient use in, e.g., heterogeneous catalysis, medical therapy and solar energy harvesting. For this purpose, we have evaluated the applicability of the surface electrostatic potential [V_S(r)] and the local surface electron attachment energy [E_S(r)] properties for characterizing the local Lewis acidity of a series of low-energy TM₁₃ transition metal nanoclusters (TM = Au, Cu, Ru, Rh, Pd, Ir, Pt, Co), including also Pt₇Cu₆. The clusters have been studied using hybrid Kohn–Sham density functional theory (DFT) calculations. The V_S(r) and E_S(r), evaluated at 0.001 a.u. isodensity contours, are used to analyze the interactions with H₂O. We find that the maxima of V_S(r), σ-holes, are either localized or diffuse. This is rationalized in terms of the nanocluster geometry and occupation of the clusters’s, p and d valence orbitals. Our findings motivate a new scheme for characterizing σ-holes as σ_s (diffuse), σ_p (localized) or σ_d (localized) depending on their electronic origin. The positions of the maxima in V_S(r) (and minima in E_S(r)) are found to coincide with O-down adsorption sites of H₂O, whereas minima in V_S(r) leads to H-down adsorption. Linear relationships between V_S,max (and E_S,min) and H₂O interaction energies are further discussed. Full article

The past few decades have witnessed significant advances in the development of functionalized metal/metal oxide nanoparticles including those of inorganic noble metals and magnetic materials stabilized by various polymeric ligands. Recent applications of such functionalized nanoparticles, including those in bio-imaging, sensing, catalysis, drug delivery, and other biomedical applications have triggered the need for their facile and reproducible preparation with a better control over their size, shape, and surface chemistry. In this perspective, the multidentate polymer ligands containing functional groups like thiol, thioether, and ester are important surface ligands for designing and synthesizing stable nanoparticles (NPs) of metals or their oxides with reproducibility and high yield. These ligands have offered an unprecedented control over the particle size of both nanoparticles and nanoclusters with enhanced colloidal stability, having tunable solubility in aqueous and organic media, and tunable optical, magnetic, and fluorescent properties. This review summarizes the synthetic methodologies and stability of nanoparticles and fluorescent nanoclusters of metals (Au, Ag, Cu, Pt, and other transition metal oxides) prepared by using thioether based ligands and highlights their applications in bio-imaging, sensing, drug delivery, magnetic resonance imaging (MRI), and catalysis. The future applications of fluorescent metal NPs like thermal gradient optical imaging, single molecule optoelectronics, sensors, and optical components of the detector are also envisaged. Full article