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Nano Research · 2021 ·Vol. 15 ·期 4 ·3065-3072 · IF 8.897

Wet-milling synthesis of immobilized Pt/Ir nanoclusters as promising heterogeneous catalysts

Du Peng,Huang Kai,Fan Xiaoyuan,Ma Jingteng,Hussain Naveed,Wang Ruyue,Deng Bohan,Ge Binghui,Tang Haolin,Zhang Ru,Lei Ming,Wu Hui

Being a typical state of the art heterogeneous catalyst, supported noble metal catalyst often demonstrates enhanced catalytic properties. However, a facile synthetic method for realizing large-scale and low-cost supported noble metal catalyst is strictly indispensable. To this end, by making use of the strong metal-support interaction (SMSI) and mechanochemical reaction, we introduce an efficient synthetic route to obtain ultrafine Pt and Ir nanoclusters immobilized on diverse substrates by wet chemical milling. We further demonstrate the scaling-up effect of our approach by large-scale ball-milling production of Pt nanoclusters immobilized on TiO 2 substrate. The synthesized Pt/Ir@Co 3 O 4 catalysts exhibit superior oxygen evolution reaction (OER) performance with only 230 and 290 mV overpotential to achieve current density of 10 and 100 mA·cm −2 , beating the catalytic performance of Co 3 O 4 supported Pt or Ir clusters and commercial Ir/C. It is envisioned that the present work strategically directs facile ways for fabricating supported noble metal heterogeneous catalysts.

研究领域: 材料科学 · 催化化学
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DALTON TRANSACTIONS · 2020 ·Vol. 50 ·期 2 ·562-567 · IF 4.174

Fast and high-yield synthesis of thiolate Ag44 and Au12Ag32 nanoclusters via the CTAB reverse micelle method

Lubing Qin,Feng Zhang,Xiaoshuang Ma,Yun Tang,Guanyu Ma,Zhenghua Tang

To advance the development of atomically precise Ag and Ag-alloyed nanoclusters, it is critical to develop effective synthetic methods. Herein, we successfully extend the CTAB (cetyl trimethyl ammonium bromide) reverse micelle method to synthesize a high-purity Ag44(p-MBA)30 (p-MBA = para-mercaptobenzoic acid) nanocluster and its corresponding alloy cluster Au12Ag32(p-MBA)30 in a short time (15 min and 5 min), with a high yield of ∼83% and ∼85%, respectively. Furthermore, the mechanism regarding the reverse micelle method has been clearly elucidated. Through characterizing the reaction system by Raman spectroscopy and NMR spectroscopy techniques, it can be revealed that employing CTAB to form reverse micelles to construct a sealed chemical environment is critical for realizing the fast and high-yield synthesis.

研究领域: 材料科学 · 化学
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SENSORS AND ACTUATORS B-CHEMICAL · 2022 · IF 9.221

Metal nanoclusters combined with CRISPR-Cas12a for hepatitis B virus DNA detection

Yu Tao,Ke Yi,Haixia Wang,Kai Li,Mingqiang Li

Since hepatitis B virus (HBV) infection can cause chronic viral hepatitis, increase the risk of liver fibrosis and cirrhosis, and ultimately result in hepatoma, it is of great significance to explore convenient, rapid, and sensitive diagnostic strategies for HBV DNA detection. In this study, we developed a novel and sensitive fluorescent biosensor for HBV detection based on the sensing system consisting of CRISPR-Cas12a enzymes and metal nanoclusters as the luminescent nanoprobes, involving gold nanoclusters (AuNCs), silver nanoclusters (AgNCs), and copper nanoclusters (CuNCs). The DNA probes could effectively be applied as the template for the preparation of fluorescent metal nanoclusters. In the presence of the HBV target, the trans-cleavage capability of Cas12a was able to be initiated to degrade DNA probes, which brought about the inhibition of metal nanoclusters formation, thereby giving minimal fluorescence signals. In comparison with AuNCs and AgNCs, the CuNCs-based nanosensor exhibited much higher sensitivity. In addition, the fluorescence response of CuNCs to HBV detection was significantly faster, which could be completed within 25 min without the requirements of sophisticated equipment or harsh reaction conditions. Moreover, the practical application of this analysis method was also demonstrated to detect HBV DNA target in human serum samples with satisfactory recovery, which was promising for simple, rapid, sensitive, and label-free HBV DNA bioanalysis .

CAS / MDL: 7447-39-4 68-04-2
研究领域: 分子生物学 · 医学诊断 · 纳米技术
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Nano Research · 2023 · IF 9.9

Interfacial charge effects of supported-metal-cluster heterostructures on azo hydrogenation catalyzation

Gu Zhenhua,Zhang Jingli,Zhang Zijun,Mu Qingxue,Yu Liangchong,Sun Taolei,Shen Lei,Gao Guanbin

The impact of interfacial charge on catalytic performance of supported-metal-cluster (SMC) heterostructures remains unclear, hindering efforts to develop high-performance SMC catalysts. Herein we systematically investigated interfacial charge effects of SMCs using a model system of graphene-supported gold-nanoclusters (AuNCs/rGO) for azo hydrogenation. Three types of SMCs with different interfacial charges were synthesized by anchoring electropositive 2-aminoethanethiol (CSH), amphoteric cysteine (Cys), and electronegative 3-mercaptopropionic-acid (MPA) onto AuNCs/rGO, respectively. All three SMCs exhibited high and selective catalytic activity to azo-hydrogenation in four representative azo dyes. The catalytic activity of Cys@AuNCs/rGO was lower than that of CSH@AuNCs/rGO but higher than that of MPA@AuNCs/rGO. However, the cyclic stability of Cys@AuNCs/rGO was inferior to that of both CSH@AuNCs/rGO and MPA@AuNCs/rGO. Further mechanistic studies revealed that amino ligands modified CSH@AuNCs and Cys@AuNCs agglomerated into large-size gold nanoparticles on rGO surface during catalytic reaction under NaBH 4 action, leading to reduced efficiency and cyclic stability. Conversely, non-amino ligand modified MPA@AuNCs only partially detached from rGO surface without agglomeration, resulting in better cyclic stability. Protection of amino groups in ligands such as modifying -NH 3 + group in Cys into imine to form N-isobutyryl-L-cysteine (NIBC) substantially improved the cyclic stability while maintaining the high activity in the NIBC@AuNCs/rGO catalyst system. Our work provides an approach for developing a highly-active and stable SMC heterostructure catalyst via manipulating interfacial charges in SMC.

研究领域: 材料科学 · 催化化学 · 表面科学
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SENSORS AND ACTUATORS B-CHEMICAL · 2018 · IF 5.667

Bimetallic gold/silver nanoclusters-gold nanoparticles based fluorescent sensing platform via the inner filter effect for hyaluronidase activity detection

Qing Liu,Xu Yan,Qi Lai,Xingguang Su

Bimetallic nanoclusters , compared to monometallic nanoclusters, possess better chemical performance. Herein, with the assistance of chondroitin sulfate , a novel fluorescent gold/silver nanoclusters (Au/Ag NCs) have been developed and applied to establish a sensing platform for sensitive detection of hyaluronidase (HAase). The Au/Ag NCs fluorescence intensity can be distinctly quenched by gold nanoparticles (Au NPs) due to the inner-filter effect (IFE). With the introduction of protamine (PRO), the positively charged PRO can bind to negatively charged Au NPs via electrostatic attraction resulting in the aggregation of gold nanoparticles. When PRO was preferential interaction with the negatively charged hyaluronic acid (HA), it would lead to the disaggregation of Au NPs and quench the fluorescence again. However, HAase can hydrolyze HA into small fragments which prevented HA interacting with protamine, and leading to the aggregation of Au NPs and weaken the IFE of Au NPs on Au/Ag NCs. Thus, the fluorescence of bimetallic nanoclusters was “turn-on”. This “turn-on” sensing system can be utilized to detect HAase level in the range of 0.5–37.5 U mL −1 . The developed strategy not only expands the application scope of bimetallic nanoclusters, but also provides a new approach for the determination of HAase.

研究领域: 生物化学 · 分析化学
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Journal of Materials Chemistry A · 2021 ·Vol. 10 ·期 4 ·1899-1908 · IF 12.732

Electronic structure regulation of cobalt oxide clusters for promoting photocatalytic hydrogen evolution

Bo Yan,Yan He,Guowei Yang

Photocatalysis for water decomposition under solar light is a promising route to produce clean hydrogen energy. Although both single atom catalysts (SACs) and atomic cluster catalysts effectively improve photocatalytic hydrogen evolution, their performances are different in different applications. In this study, we used the electrochemical method to deposit single atoms, clusters, and nanoparticles of cobalt on carbon nitride (CN) by adjusting the deposition time. It was found that among the three catalysts, atomic cluster catalysts showed the best photocatalytic hydrogen production performance, up to 129 μmol g−1 h−1 than that of 87.2 μmol g−1 h−1 for Co1/CN SACs, and 110.3 μmol g−1 h−1 for CoOx-nanoparticle/CN. DFT calculations suggested that the electronic structure of the load species can be regulated by CN through the interaction between cobalt species and CN substrate. When the cluster is loaded on CN, the charge of the cluster can flow to the CN. As the cluster size increases, this charge flow can be suppressed. When the cluster with an appropriate size is loaded on CN, the electronic structure would be regulated to an optimal state for photocatalytic hydrogen evolution. These results provide a new understanding of the influence of the interaction between CN substrate and loading species on photocatalytic activities and may inspire further developments in the conversion of solar energy to hydrogen energy.

CAS / MDL: 108-78-1
研究领域: 材料科学 · 能源化学 · 催化科学
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Frontiers in Bioengineering and Biotechnology · 2021 · IF 5.89

Aggregation-Induced Emission of Au/Ag Alloy Nanoclusters for Fluorescence Detection of Inorganic Pyrophosphate and Pyrophosphatase Activity

Lei Zhongli,Zhou Jie,Liang Miao,Xiao Yan,Liu Zhihong

The development of sensitive and accurate detection of inorganic pyrophosphate (PPi) and pyrophosphatase activity (PPase) is important as they play vital roles in biological systems. However, it is still not satisfactory for most of the analytical methods for PPi and PPase because of their Cu2+-dependence and poor accuracy. Although the metal ion triggered aggregation-induced emission (AIE) of metal nanoclusters (NCs) offers a new approach to design a Cu2+-free strategy for the accurate determination of PPi and PPase recently, current methods are all focused on utilizing pure metal NCs. Alloy NCs incorporating the advantages of diverse metal usually can achieve improved behaviors in the application, such as enhanced sensitivity and stability. In this work, glutathione stabilized alloy Au/Ag NCs were synthesized via a simple method and used for the fluorescence detection of PPi and PPase based on a Zn2+-regulated AIE strategy. The controlled release of Zn2+ by PPi and PPase could regulate the AIE of Au/Ag NCs and be employed to response PPi concentration and PPase activity. This method processes simple procedure, high sensitivity and stability, and low toxicity. In addition, we also studied the AIE behaviors of this Au/Ag NCs and offer some fundamental understanding of the AIE properties of water-soluble alloy NCs. This study not only provides a straightforward and new approach for PPi and PPase determination but a basis for further study on the AIE properties of alloy NCs and their application.

研究领域: 分析化学 · 生物化学
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Journal of Analysis and Testing · 2025 · IF 7

Multichannel Sensor Arrays Based on Surface-Engineered Fluorescent Metal Clusterzymes for Differential Sensing of Cancer Cells

Liang Yunyan,Zhou Xiaomeng,Liu Wenfeng,Shang Li

Rapid and effective differentiation of cancerous cells is essential for early diagnosis and treatment of tumors. Here, a multichannel sensor array is developed based on four surface-engineered gold-silver nanoclusters (AuAgNCs) to discriminate multiple cancerous and normal cells. Different binding affinities between various cells and AuAgNCs lead to changes in the intrinsic fluorescence of AuAgNCs as well as their peroxide-like activity. Based on the distinct response of dual fluorescence signals of four AuAgNCs, a multichannel sensor array is established, which is capable of accurately identifying both normal and cancerous cells, even cells of different subtypes and homologous cells from various individuals with high sensitivity. Moreover, this fluorescent clusterzyme-based sensor array enables quantitative detection of cancerous cells (e.g., HeLa cells) with good performance, which holds great potential as a promising platform for further cancer diagnosis.

研究领域: 生物化学 · 医学诊断 · 纳米技术
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JOURNAL OF HAZARDOUS MATERIALS · 2023 · IF 13.6

An enzymatic activity regulation-based clusterzyme sensor array for high-throughput identification of heavy metal ions

Yueyuan Li,Zhaode Mu,Yonghua Yuan,Jing Zhou,Lijuan Bai,Min Qing

The accurate identification and sensitive quantification of heavy metal ions are of great significance, considering that pose a serious threat to environment and human health. Most array-based sensing platforms, to date, utilize nanozymes as sensing elements, but few studies have explored the application of the peroxidase-like activity of clusterzymes in identification of multiple analytes. Herein, for the first time, we developed a clusterzyme sensor array utilizing gold nanoclusters (AuNCs) as sensing elements for five heavy metal ions identification including Hg 2+ , Pb 2+ , Cu 2+ , Cd 2+ and Co 2+ . The heavy metal ions can differentially regulate the peroxidase-like activity of AuNCs, and that can be converted into colorimetric signals with 3,3′,5,5′-tetramethylbenzidine (TMB) as the chromogenic substrate. Subsequently, the generated composite responses can be interpreted by combining pattern recognition algorithms. The developed clusterzyme sensor array can identify five heavy metal ions at concentrations as low as 0.5 μM and their multi-component mixtures. Especially, we demonstrated the successful identification of multiple heavy metal ions in tap water and traditional Chinese medicine, with an accuracy of 100% in blind test. This study provided a simple and effective method for identification and quantification of heavy metal ions, rendering a promising technique for environmental monitoring and drug safety assurance.

研究领域: 环境科学 · 分析化学 · 生物医学工程
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Nanoscience and Nanotechnology Letters · 2019 ·Vol. 11 ·期 8 ·1139-1144 · IF 0

Development of Ochratoxin Aptasensor Based on DNA Metal Nanoclusters

Gu Mengqiao,Liu Jiali,Li Delei,Wang Min,Chi Kuanneng,Zhang Xi,Deng Yan,Ma Yuchan,Hu Rong,Yang Yunhui

In this paper, a signal-off aptasensor was constructed based on the specificity of OTA and OTA aptamer (DNA2), it can detect the small molecule ochratoxin A (OTA). DNA1 chain with mercapto modified at 3′-end was firstly immobilized on gold electrode, which cross-fertilize with DNA 2 to form double strands. 30 thymine T modified at the end of DNA2 were used as templates to synthesize Cu NCs which is peroxidase mimics and can catalyze hydrogen peroxide. Presence of OTA, it specifically binds to DNA2, which made DNA2 dissociated, and so did Cu NCs. The more OTA in solution, the more the aptamers and Cu NCs dissociated from the gold electrode, the less copper nanoclusters remained on the electrode, and the smaller the current response value of the electrode measured by chronoamperometry. Thus, the quantitative determination of OTA can be achieved. This aptasensor provides a simple and fast technique for OTA detection in red wine samples.

研究领域: 分析化学 · 食品安全 · 纳米技术 · 生物传感器
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Nanomaterials · 2022 ·Vol. 12 ·期 5 ·736 · IF 5.719

A Visual Discrimination of Existing States of Virus Capsid Protein by a Giant Molybdate Cluster

Yarong Xue,Mingfen Wei,Dingyi Fu,Yuqing Wu,Bo Sun,Xianghui Yu,Lixin Wu

We report a unique phenomenon, the opposite color response of a giant polyoxometalate, (NH4)42[Mo132O372(CHCOO)30] (H2O)72([Mo132]), to the existing states of human papillomavirus (HPV) major capsid protein, L1-pentamer (L1-p), and virus-like particles (VLPs). The color responses originate from the different assembly forms between [Mo132] and the capsid protein. The latter were inspected and separated by using CsCl gradient centrifugation, and validated in detail by sodium dodecyl sulfate-polyacrylamide gel-electrophoresis (SDS-PAGE), dynamic light scattering (DLS), and transmission electron microscopy (TEM) imaging. Furthermore, the intrinsic mechanisms were investigated in-depth by using XPS-based semi-quantitative analysis and well-designed peptides, revealing the critical points of L1 that determine the charge–transfer ratio between Mo(V) to Mo(VI), and consequently, the levels of [Mo132] hypochromic in different assemblies. Such a unique phenomenon is significant as it supplies a colorimetry approach to distinguish the existing states of the HPV capsid protein and would be significant in the quality assay of the HPV vaccine and existing states of other viruses in the future.Keywords:colorimetric discrimination;giant polyoxometalate;HPV capsid protein;hypochromic of molybdate clusters;opposite color response

CAS / MDL: 7647-14-5 1132-61-2
研究领域: 化学 · 病毒学 · 材料科学
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SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY · 2019 · IF 2.931

Sensitive detection of molybdenum through its catalysis and quenching of gold nanocluster fluorescence

Xinyi Wang,Zhu Su,Liang Li,Yifeng Tu,Jilin Yan

Molybdenum (Mo) is an essential nutrient for the proper functioning of some enzymes in living organisms as human beings. Conventional methods for its detection require complicated instrumentations as atomic absorption or mass spectrometers. In this work, a sensitive kinetic fluorescence was developed as an alternative. Gold nanoclusters (AuNCs) with red fluorescence emission were synthesized, and this fluorescence was effectively quenched by iodine through an etching process. It was found that the presence of Mo significantly speeded up a reaction for the generation of iodine, and thus enhanced the quenching. This effect was then adopted for the development of a sensitive fluorescent measurement toward Mo. The method was capable of detecting Mo down to 0.2 nM and was successfully applied for the analyses of mung bean and tea leaf samples.

CAS / MDL: 12054-85-2
研究领域: 分析化学 · 生物化学
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