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Nanomaterials
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Ultrasmall Metal Nanoclusters
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Ultrasmall Metal Nanoclusters

A special issue of Nanomaterials (ISSN 2079-4991). This special issue belongs to the section "Nanofabrication and Nanomanufacturing".

Deadline for manuscript submissions: closed (26 December 2022) | Viewed by 17673

Special Issue Editors

Prof. Dr. Qiaofeng Yao

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Guest Editor
Joint School of National University of Singapore and Tianjin University, International Campus of Tianjin University, Binhai New City, Fuzhou 350207, China
Interests: synthesis; self-assembly; application chemistry; metal nanoclusters
Prof. Dr. Xun Yuan

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Guest Editor
College of Materials Science and Engineering, Qingdao University of Science and Technology, Qingdao 266042, China
Interests: metal nanoclusters; photocatalysis; water treatment
Prof. Dr. Zhennan Wu

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Guest Editor
State Key Laboratory of Integrated Optoelectronics, College of Electronic Science and Engineering, Jilin University, 2699 Qianjin Street, Changchun 130012, China
Interests: colloidal synthesis dynamics; self-assembly chemistry; optical physics of functional nanocrystals; ultrasmall metal nanoclusters

Special Issue Information

Dear Colleagues,

Ultrasmall metal nanoclusters (MNCs) are tiny particles composed of a <3 nm metal core and an organic ligand shell, and have attracted a great deal of research attention in the past few decades. Owing to the enhanced quantum confinement effect in this ultra-small size regime, MNCs display intriguing molecule-like properties such as luminescence, magnetism, chirality, and HOMO–LUMO transition. Such molecule-like properties of MNCs, together with their intrinsic structural attributes (e.g., ultrasmall size, rich surface chemistry, and protein-like structural hierarchy), make them promising in various fields including environmental protection, catalysis, energy conversion, optoelectronics, sensor development, and biomedicine. At present, enormous research efforts have been devoted to the synthesis of MNCs towards atomically precise tunability of size, composition, atomic packing structure, and surface chemistry, which further fuels the advances of MNCs in diversified applications. In other words, the benign promotion between the synthesis and the application of MNCs will ensure their development with a more prosperous and promising future.

This Special Issue of Nanomaterials will attempt to cover the most recent advances in “Ultrasmall Metal Nanoclusters”, concerning the design, synthesis, characterization, fundamental understanding, and application of novel MNCs.

Prof. Dr. Qiaofeng Yao
Prof. Dr. Xun Yuan
Prof. Dr. Zhennan Wu
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Nanomaterials is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2900 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • Cluster Synthesis
  • Physicochemical Properties
  • Application
  • Catalysis
  • Sensor Development
  • Biomedicine
  • Energy Conversion

Published Papers (9 papers)

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Research

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10 pages, 3294 KiB  
Article
Gold Nanocluster-Based Fluorometric Banoxantrone Assay Enabled by Photoinduced Electron Transfer
by Kai-Yuan Huang, Wen-Hui Weng, Xin Huang, Hong-Xiang Huang, Hamada A. A. Noreldeen, Hao-Hua Deng and Wei Chen
Nanomaterials 2022, 12(11), 1861; https://doi.org/10.3390/nano12111861 - 30 May 2022
Viewed by 1714
Abstract
Monitoring the blood concentration of banoxantrone (AQ4N) is important to evaluate the therapeutic efficacy and side effects of this new anticancer prodrug during its clinical applications. Herein, we report a fluorescence method for AQ4N detection through the modulation of the molecule-like photoinduced electron [...] Read more.
Monitoring the blood concentration of banoxantrone (AQ4N) is important to evaluate the therapeutic efficacy and side effects of this new anticancer prodrug during its clinical applications. Herein, we report a fluorescence method for AQ4N detection through the modulation of the molecule-like photoinduced electron transfer (PET) behavior of gold nanoclusters (AuNCs). AQ4N can electrostatically bind to the surface of carboxylated chitosan (CC) and dithiothreitol (DTT) co-stabilized AuNCs and quench their fluorescence via a Coulomb interaction-accelerated PET process. Under optimized experimental conditions, the linear range of AQ4N is from 25 to 200 nM and the limit of detection is as low as 5 nM. In addition, this assay is confirmed to be reliable based on its successful use in AQ4N determination in mouse plasma samples. This work offers an effective strategy for AQ4N sensing based on fluorescent AuNCs and widens the application of AuNCs in clinical diagnosis and pharmaceutical analysis. Full article
(This article belongs to the Special Issue Ultrasmall Metal Nanoclusters)
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10 pages, 3111 KiB  
Article
Manipulating the Assembly of Au Nanoclusters for Luminescence Enhancement and Circularly Polarized Luminescence
by Chen Wang, Luyao Feng, Junxiao Liu, Jing Fu, Jinglin Shen and Wei Qi
Nanomaterials 2022, 12(9), 1453; https://doi.org/10.3390/nano12091453 - 25 Apr 2022
Cited by 2 | Viewed by 1649
Abstract
Au nanocluster (AuNCs)-based luminescent functional materials have attracted the interest of researchers owing to their small size, tractable surface modification, phosphorescence lifetime and biocompatibility. However, the poor luminescence quantum yield (QY) of AuNCs limits their practical applications. Herein, we synthesized a type of [...] Read more.
Au nanocluster (AuNCs)-based luminescent functional materials have attracted the interest of researchers owing to their small size, tractable surface modification, phosphorescence lifetime and biocompatibility. However, the poor luminescence quantum yield (QY) of AuNCs limits their practical applications. Herein, we synthesized a type of AuNCs modified by 4,6-diamino-2-mercaptopyrimidine hydrate (DPT-AuNCs). Furthermore, organic acids, i.e., citric acid (CA) and tartaric acid (TA), were chosen for co-assembly with DPT-AuNCs to produce AuNCs-based luminescent materials with enhanced emission. Firstly, it was found that CA could significantly enhance the emission of DPT−AuNCs with the formation of red emission nanofibers (QY = 17.31%), which showed a potential for usage in I− detection. The n···π/π···π interaction between the CA and the DPT ligand was proposed as crucial for the emission. Moreover, chiral TA could not only improve the emission of DPT-AuNCs, but could also transfer its chirality to DPT-AuNCs and induce the formation of circularly polarized luminescence (CPL)-active nanofibers. It was demonstrated that the CPL signal could increase 4.6-fold in a ternary CA/TA/DPT-AuNCs co-assembly system. This work provides a convenient way to build AuNCs-based luminescent materials as probes, and opens a new avenue for building CPL-active materials by achiral NCs through a co-assembly strategy. Full article
(This article belongs to the Special Issue Ultrasmall Metal Nanoclusters)
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11 pages, 1791 KiB  
Article
Highly Selective Detection of Paraoxon in Food Based on the Platform of Cu Nanocluster/MnO2 Nanosheets
by Shuo Liu, Peng Zhang, Yuming Miao, Chenmin Li, Yu-e Shi, Jinhua Liu, Yun-kai Lv and Zhenguang Wang
Nanomaterials 2022, 12(9), 1429; https://doi.org/10.3390/nano12091429 - 22 Apr 2022
Cited by 1 | Viewed by 1601
Abstract
Selective and sensitive identification of paraoxon residue in agricultural products is greatly significant for food safety but remains a challenging task. Herein, a detection platform was developed by integrating Cu nanoclusters (Cu NCs) with MnO2 nanosheets, where the fluorescence of Cu NCs [...] Read more.
Selective and sensitive identification of paraoxon residue in agricultural products is greatly significant for food safety but remains a challenging task. Herein, a detection platform was developed by integrating Cu nanoclusters (Cu NCs) with MnO2 nanosheets, where the fluorescence of Cu NCs was effectively quenched. Upon introducing butyrylcholinesterase and butyrylcholine into the system, their hydrolysate, thiocholine, leads to the decomposition of the platform through a reaction between the MnO2 nanosheets and thiol groups on thiocholine. The electron-rich groups on thiocholine can further promote the fluorescence intensity of Cu NCs through host–guest interactions. Adding paraoxon results in the failure of fluorescence recovery and further promotion, which could be utilized for the quantitative detection of paraoxon, and a limit of detection as low as 0.22 ng/mL can be achieved. The detection platform shows strong tolerance to common interference species, which endows its applications for the detection of paraoxon in vegetables and fruit. These presented results not only open a new door for the functionalization of metal nanoclusters but also offer an inspiring strategy for analytic techniques in nanomedicine and environmental science. Full article
(This article belongs to the Special Issue Ultrasmall Metal Nanoclusters)
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11 pages, 1747 KiB  
Article
The Precise Detection of HER-2 Expression in Breast Cancer Cell via Au25 Probes
by Xu Han, Zhesheng He, Wenchao Niu, Chunyu Zhang, Zhongying Du, Xueyun Gao and Gengmei Xing
Nanomaterials 2022, 12(6), 923; https://doi.org/10.3390/nano12060923 - 11 Mar 2022
Cited by 1 | Viewed by 1971
Abstract
Triple-negative breast cancer (TNBC) accounts for nearly one-quarter of all breast cancer cases, but effective targeted therapies for this disease remain elusive because TNBC cells lack the expression of the most common three receptors seen in other subtypes of breast cancers. The medium-term [...] Read more.
Triple-negative breast cancer (TNBC) accounts for nearly one-quarter of all breast cancer cases, but effective targeted therapies for this disease remain elusive because TNBC cells lack the expression of the most common three receptors seen in other subtypes of breast cancers. The medium-term diagnosis of breast cancers is essential for development and prognosis. According to reports, patients with TNBC may be converted to a positive epidermal growth factor receptor 2(HER-2) after chemotherapy, and trastuzumab treatment will have a better prognosis. Therefore, it is important to accurately quantify the expression of HER-2 in breast cancer cells. Herein, we design a red fluorescent Au25 probe synthesized with BSA-biotin as the ligand, which is accurately quantified by HER-2 primary antibody-biotin using the avidin system. The quantitative detection of the expression of HER-2 in breast cancers is helpful for the companion diagnostic of breast cancer treatment and provides follow-up treatment. Full article
(This article belongs to the Special Issue Ultrasmall Metal Nanoclusters)
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13 pages, 1725 KiB  
Article
Engineering Au Nanoclusters for Relay Luminescence Enhancement with Aggregation-Induced Emission
by Pei Zhou, Nirmal Goswami, Tiankai Chen, Xiaoman Liu and Xin Huang
Nanomaterials 2022, 12(5), 777; https://doi.org/10.3390/nano12050777 - 25 Feb 2022
Cited by 2 | Viewed by 1823
Abstract
The research of aggregation-induced emission (AIE) has been growing rapidly for the design of highly luminescent materials, as exemplified by the library of AIE-active materials (or AIEgens) fabricated and explored for diverse applications in different fields. Herein, we reported a relay luminescence enhancement [...] Read more.
The research of aggregation-induced emission (AIE) has been growing rapidly for the design of highly luminescent materials, as exemplified by the library of AIE-active materials (or AIEgens) fabricated and explored for diverse applications in different fields. Herein, we reported a relay luminescence enhancement of luminescent Au nanoclusters (Au NCs) through AIE. In addition, we demonstrated the emergence of reduced aggregation-caused luminescence by adjusting the temperature of the Au NC solution. The key to induce this effect is to attach a thermosensitive polymer poly(N-isopropylacrylamide) (PNIPAAm) on the surface of Au NCs, which will shrink at high temperature. More interestingly, the as-synthesized Au NCs-PNIPAAm can self-assemble into vesicles, resulting in an obvious decrease in the luminescence intensity in aqueous solution. The combination of relay luminescence enhancement (by AIE) and luminescence decrease (induced by thermosensitive polymers) will be beneficial to the understanding and manipulation of the optical properties of Au NCs, paving the way for their practical applications. Full article
(This article belongs to the Special Issue Ultrasmall Metal Nanoclusters)
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11 pages, 1932 KiB  
Article
Metal Nanoclusters/Polyvinyl Alcohol Composite Films as the Alternatives for Fabricating Remote-Type White Light-Emitting Diodes
by Zhaoyu Liu, Dong Yao, Huiwen Liu and Hao Zhang
Nanomaterials 2022, 12(2), 204; https://doi.org/10.3390/nano12020204 - 08 Jan 2022
Cited by 5 | Viewed by 1645
Abstract
Packing luminescent metal nanoclusters (MNCs) into polymers and fabricating novel MNCs/polymer composite materials is effective in obtaining high-performance light-emitting diodes (LEDs). Herein, water soluble Cu and Au nanoclusters are encapsulated in polyvinyl alcohol (PVA) by a casting method. The obtained MNCs/PVA composite films [...] Read more.
Packing luminescent metal nanoclusters (MNCs) into polymers and fabricating novel MNCs/polymer composite materials is effective in obtaining high-performance light-emitting diodes (LEDs). Herein, water soluble Cu and Au nanoclusters are encapsulated in polyvinyl alcohol (PVA) by a casting method. The obtained MNCs/PVA composite films are highly emissive with triple primary colors, and inherit the merits of PVA, such as transparency, flexibility, machinability, stability and self-healing ability. By employing the MNCs/PVA composite films as down-conversions, remote type monochromic and white LEDs are fabricated. The white LEDs (WLEDs) exhibit a maximum color rendering index (CRI) of 86 with a Commission Internationale de l’Eclairage (CIE) color coordinate of (0.33,0.35). By varying the three MNCs/PVA film arrangement, the correlated color temperature (CCT) of the WLEDs is tuned from 5582 to 9490 K, which signifies the possibility of MNCs/PVA as alternative light-emitting materials for advanced illumination and display in the future. Full article
(This article belongs to the Special Issue Ultrasmall Metal Nanoclusters)
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15 pages, 4389 KiB  
Article
Qualitative and Quantitative Analysis of Tumor Cell Invasion Using Au Clusters
by Xiangchun Zhang, Qinqin Zheng, Ziqi Wang, Chao Xu, Haolei Han, Aiping Li, Guicen Ma, Jiaojiao Li, Chengyin Lu, Hongping Chen and Zhichao Zhang
Nanomaterials 2022, 12(1), 145; https://doi.org/10.3390/nano12010145 - 31 Dec 2021
Cited by 7 | Viewed by 1849
Abstract
Tumor invasion/metastasis is still the major cause of death in cancer patients. Membrane type-1 matrix metalloproteinase (MT1-MMP) is directly related to tumor invasion/metastasis. To accurately and quickly distinguish the risk of invasion/metastasis of primary tumor cells, it is urgent to develop a simple [...] Read more.
Tumor invasion/metastasis is still the major cause of death in cancer patients. Membrane type-1 matrix metalloproteinase (MT1-MMP) is directly related to tumor invasion/metastasis. To accurately and quickly distinguish the risk of invasion/metastasis of primary tumor cells, it is urgent to develop a simple and precise quantitative method to distinguish the expression level of MT1-MMP. In this work, we have constructed red fluorescent Au clusters with peroxidase-like properties that could specifically bind to MT1-MMP on human cervical cancer cells. After MT1-MMP was labelled with Au clusters, we could visually see red fluorescence of MT1-MMP on cervical cancer cells via fluorescence microscopy and catalytic color imaging using an ordinary optical microscope. The constructed Au clusters contained 26 Au atoms; thus, the amount of MT1-MMP on cervical cancer cells could be accurately quantified using inductively coupled plasma mass spectrometry (ICP-MS). More importantly, the invasion/metastasis capabilities of the cervical cancer Siha, Caski and Hela cells with different MT1-MMP amounts could be accurately distinguished by fluorescence/catalysis qualitative imaging and ICP-MS quantitative analysis. This method of qualitative/quantitative analysis of tumor-associated proteins on cancer cells has great potential for accurately diagnosing aggressive tumor cells and assessment of their invasion/metastasis risk. Full article
(This article belongs to the Special Issue Ultrasmall Metal Nanoclusters)
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Review

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23 pages, 4346 KiB  
Review
Engineering Coinage Metal Nanoclusters for Electroluminescent Light-Emitting Diodes
by Tingting Li, Zhenyu Wang, Ying Zhang and Zhennan Wu
Nanomaterials 2022, 12(21), 3837; https://doi.org/10.3390/nano12213837 - 30 Oct 2022
Cited by 4 | Viewed by 1801
Abstract
Coinage metal nanoclusters (MNCs) are a new type of ultra-small nanoparticles on the sub-nanometer (typically < three nm) scale intermediate between atoms and plasmonic nanoparticles. At the same time, the ultra-small size and discrete energy levels of MNCs enable them to exhibit molecular-like [...] Read more.
Coinage metal nanoclusters (MNCs) are a new type of ultra-small nanoparticles on the sub-nanometer (typically < three nm) scale intermediate between atoms and plasmonic nanoparticles. At the same time, the ultra-small size and discrete energy levels of MNCs enable them to exhibit molecular-like energy gaps, and the total structure involving the metal core and surface ligand together leads to their unique properties. As a novel environmentally friendly chromophore, MNCs are promising candidates for the construction of electroluminescent light-emitting diodes (LEDs). However, a systematic summary is urgently needed to correlate the properties of MNCs with their influences on electroluminescent LED applications, describe the synthetic strategies of highly luminescent MNCs for LEDs’ construction, and discuss the general influencing factors of MNC-based electroluminescent LEDs. In this review, we first discuss relevant photoemissions of MNCs that may have major influences on the performance of MNC-based electroluminescent LEDs, and then demonstrate the main synthetic strategies of highly luminescent MNCs. To this end, we illustrate the recent development of electroluminescent LEDs based on MNCs and present our perspectives on the opportunities and challenges, which may shed light on the design of MNC-based electroluminescent LEDs in the near future. Full article
(This article belongs to the Special Issue Ultrasmall Metal Nanoclusters)
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17 pages, 4693 KiB  
Review
Engineering Gold Nanostructures for Cancer Treatment: Spherical Nanoparticles, Nanorods, and Atomically Precise Nanoclusters
by Wei He, Guanyu Ma, Quanli Shen and Zhenghua Tang
Nanomaterials 2022, 12(10), 1738; https://doi.org/10.3390/nano12101738 - 19 May 2022
Cited by 9 | Viewed by 2510
Abstract
Cancer is a major global health issue and is a leading cause of mortality. It has been documented that various conventional treatments can be enhanced by incorporation with nanomaterials. Thanks to their rich optical properties, excellent biocompatibility, and tunable chemical reactivities, gold nanostructures [...] Read more.
Cancer is a major global health issue and is a leading cause of mortality. It has been documented that various conventional treatments can be enhanced by incorporation with nanomaterials. Thanks to their rich optical properties, excellent biocompatibility, and tunable chemical reactivities, gold nanostructures have been gaining more and more research attention for cancer treatment in recent decades. In this review, we first summarize the recent progress in employing three typical gold nanostructures, namely spherical Au nanoparticles, Au nanorods, and atomically precise Au nanoclusters, for cancer diagnostics and therapeutics. Following that, the challenges and the future perspectives of this field are discussed. Finally, a brief conclusion is summarized at the end. Full article
(This article belongs to the Special Issue Ultrasmall Metal Nanoclusters)
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