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FOOD CHEMISTRY · 2022 · IF 9.231

High-performance homogeneous carboxymethylcellulose-stabilized Au@Ag NRs-CMC surface-enhanced Raman scattering chip for thiram detection in fruits

Bingxue Hu,Da-Wen Sun,Hongbin Pu,Zhibin Huang

Cellulose material holds considerable promise for effective surface-enhanced Raman scattering (SERS) substrate construction due to its extensive availability, chemically modifying capacity, ease of manufacture, high flexibility and low optical activity. A large-area, high-sensitivity, stable and uniform Au@Ag nanorods (NRs)-CMC substrate was successfully developed via electrostatic repulsion by using negatively-charged core–shell Au@Ag NRs as SERS active plasmonic nanomaterial, combined with negatively-charged carboxymethylcellulose (CMC) hydrogel for nanoparticles stabilization, homodisperse and protection. The obtained Au@Ag NRs-CMC substrate showed excellent sensitivity for the detection of thiram residues in fruits containing low and abundant pigment interferents, such as apples and blueberries, with detection limits of 58 and 78 ppb, respectively. Additionally, it retained more than 80% SERS performance after storage for 9 months under ambient conditions, demonstrating its great potential in facilitating the commercialization of cellulose-based SERS technology for cost-effective detection of food contaminants with advantages of facile preparation procedure, uniformity, reproducibility and long-term stability.

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ANALYTICAL CHEMISTRY · 2026 · IF 7.3

High-Throughput Fabrication of Bimetallic Au–Ag Annular Nanogap Arrays Featuring 5 nm Gaps for Surface-Enhanced Raman Spectroscopy

Yingfang Zhang,Sihai Luo,Sen Jiang,Hao Sun,Hongyi Shen,Lijuan Chen,Qi Yuan,Xiaoliang Chen,Nan Zhang,Fang Mi,Yi Lv,Fenggang Ren,Jinyou Shao

Abstract The confinement of light into nanometer-sized (typically <10 nm) metallic nanogaps can generate extremely high near-field enhancement, dramatically boosting absorption, emission, and Raman scattering of target molecules situated within the gaps. However, the scarcity of cost-effective, reliable, and high-throughput nanofabrication techniques capable of fabricating sub-10 nm gaps, particularly in binary nanostructures, has significantly hindered their practical applications. Here, a high-throughput nanofabrication strategy that combines anodic aluminum oxide (AAO) templates, molecular self-assembly, and glancing-angle ion-beam etching (IBE) is proposed to controllably produce large-scale bimetallic gold–silver (Au–Ag) arrays with approximately 5 nm gaps. These arrays serve as exceptional surface-enhanced Raman spectroscopy (SERS) substrates, allowing for the ultrasensitive detection of target molecules with limits of detection (LODs) as low as 10–11 M for rhodamine 6G (R6G) and 4-mercaptobenzoic acid (4-MBA) and 10–8 M for bilirubin. The bimetallic Au–Ag nanogap arrays leverage the synergistic effects of gold’s strong absorption and silver’s superior plasmonic properties, achieving significantly enhanced electromagnetic fields compared to monolithic Au–Au nanogap arrays. This cost-effective and efficient nanofabrication approach overcomes the limitations of conventional methods for fabricating binary nanostructures, providing a viable solution for developing high-sensitive and reliable SERS-based detection platforms toward chemical-/bio-sensing.

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Biosensors-Basel · 2023 ·Vol. 13 ·期 10 ·932 · IF 5.4

Development of a Novel H-Shaped Electrochemical Aptasensor for Detection of Hg2+ Based on Graphene Aerogels–Au Nanoparticles Composite

Gang Peng,Mengxue Guo,Yuting Liu,Han Yang,Zuorui Wen,Xiaojun Chen

Hg2+, a highly toxic heavy metal, poses significant environmental and health risks, necessitating rapid detection methods. In this study, we employed an electrochemical aptasensor for rapid and sensitive detection of Hg2+based on DNA strands (H2 and H3) immobilized graphene aerogels-Au nanoparticles (GAs-AuNPs) hybrid recognition interface and exonuclease III (Exo III)-mediated cyclic amplification. Firstly, Gas-AuNPs were modified on the surface of the ITO electrode to form a sensing interface to increase DNA loading and accelerate electron transfer. Then, DNA helper was generated with the addition of Hg2+via Exo III-mediated cycling. Finally, the hairpin structures of H2 and H3 were opened with the DNA helper, and then the methylene blue (MB) functionalized DNA (A1 and A2) combined with the H2 and H3 to form an H-shaped structure. The current response of MB as an electrochemical probe was proportional to the concentration of Hg2+. Under optimal conditions, the aptasensor showed excellent performance for Hg2+, achieving a linear range from 1 fM to 10 nM and a detection limit of 0.16 fM. Furthermore, the aptasensor was used to detect Hg2+in spiked milk samples, achieving a high recovery rate and demonstrating promising application prospects.Keywords:graphene aerogels–Au nanoparticles;Hg2+;H-shaped;aptasensor;milk sample

CAS / MDL: 1633-78-9
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ANALYST · 2023 ·Vol. 148 ·期 21 ·5435-5444 · IF 4.2

Ultrasensitive detection of thiram based on surface-enhanced Raman scattering via Au@Ag@Ag core/shell/shell bimetallic nanorods

Yuqiu Wang,Shuchang Liu,Yongjun Hu,Cuicui Fu,Weiqiang Chen

We developed a highly sensitive and stable SERS-active substrate of Au@Ag@Ag core/shell/shell nanorods, formed by encapsulating Au nanorods (Au NRs) into a bilayer silver shell with Raman reporter molecules (4-mercaptobenzoic acid (4-MBA) and thiram) in the shell–shell gap. The core/shell/shell nanostructures demonstrated a high SERS enhancement and easy assembly. The important role of the bilayer silver shell in boosting the SERS intensity and detection sensitivity was revealed by comparing the performances of the Au@Ag@4-MBA@Ag NRs, Au@Ag@4-MBA NRs, and Au@4-MBA NRs. The obtained Au@Ag@4-MBA@Ag NRs exhibited a significantly promoted SERS intensity, which could reach around 2.6 times and 240 times that of the Au@Ag@4-MBA NRs and Au@4-MBA NRs, where the enhancement factor was found to be strongly correlated with the shell thickness. The controllable plasma properties and SERS effect of the Au@Ag@4-MBA@Ag NRs could be optimized by adjusting the dose of silver nitrate. The SERS substrate comprising core/shell/shell nanorods was highly reproducible and stable (retaining 83% SERS intensity after one month). Moreover, the highly sensitive detection of the pesticide thiram with a detection limit as low as 1.74 × 10−9 M was achieved by taking advantage of the great SERS response of the core/shell/shell nanostructures, which was 1–2 orders of magnitude lower than for other SERS substrates. The developed SERS substrate could be readily extended to embed other target analytes into the core/shell/shell nanostructure for novel and sensitive detection. This study could enable fresh approaches toward next-generation ultrasensitive analyte detection.

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FOOD CHEMISTRY · 2023 · IF 8.8

Au-Ag OHCs-based SERS sensor coupled with deep learning CNN algorithm to quantify thiram and pymetrozine in tea

Huanhuan Li,Xiaofeng Luo,Suleiman A. Haruna,Muhammad Zareef,Quansheng Chen,Zhen Ding,Yiyong Yan

Pesticide residue detection in food has become increasingly important. Herein, surface-enhanced Raman scattering (SERS) coupled with an intelligent algorithm was developed for the rapid and sensitive detection of pesticide residues in tea. By employing octahedral Cu 2 O templates, Au-Ag octahedral hollow cages (Au-Ag OHCs) were developed, which improved the surface plasma effect via rough edges and hollow inner structure, amplifying the Raman signals of pesticide molecules. Afterward, convolutional neural network (CNN), partial least squares (PLS), and extreme learning machine (ELM) algorithms were applied for the quantitative prediction of thiram and pymetrozine. CNN algorithms performed optimally for thiram and pymetrozine, with correlation values of 0.995 and 0.977 and detection limits (LOD) of 0.286 and 29 ppb, respectively. Accordingly, no significant difference ( P  greater than 0.05) was observed between the developed approach and HPLC in detecting tea samples. Hence, the proposed Au-Ag OHCs-based SERS technique could be utilized for quantifying thiram and pymetrozine in tea.

CAS / MDL: 50-81-7
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JOURNAL OF ALLOYS AND COMPOUNDS · 2023 · IF 6.2

Facile synthesis of thiolated silica-encapsulated magnetic adsorbents: Effective adsorption and rapid separation of Au(Ⅰ) from thiosulfate solution

Juan Li,Shuliang Chen,Yunlong Chen,Li Zhao,Xinrong Li,Haiwen Wang,Xianzhi Hu,Futing Zi

It is important to develop a facile and highly efficient synthetic strategy to fabricate an adsorbent exhibiting excellent adsorption performance and separation ability to recover Au from thiosulfate solutions. Herein, we report a magnetic silica composite (Fe 3 O 4 @SiO 2 -SH) that was successfully fabricated using an economical, one-pot synthesis method for efficient Au(I) adsorption. The results revealed that the performance of the adsorbent was pH dependent, and the single saturated adsorption capacity was 15.11 mg/g. The adsorption process could be well-explained by the Elovich kinetic model and Langmuir isotherm model, indicating that chemical adsorption dominated the monolayer adsorption process. Furthermore, the adsorption process was exothermic. The chemical structures and properties of the adsorbents were analyzed using various characterization and analysis methods. The chelating interaction between -SH and Au(I) promoted the adsorption of Au on Fe 3 O 4 @SiO 2 -SH. The gold-loaded, highly reusable adsorbent could be readily eluted using Na 2 S 2 O 3 (3 mol/L), and > 90% of the gold could be recovered from the adsorbent in a thiosulfate gold leaching solution with Cu 2+ -NH 3 -S 2 O 3 2- as the leaching system. Most of the adsorbent in the pulp could be collected using a magnet, and this reduced the separation cost. The adsorbent can recover more than 90% of gold in both simulated and actual thiosulfate-based gold leaching solutions, indicating that the results reported herein provide a cost-effective strategy for the fabrication of magnetic silica composites characterized by a satisfactory adsorption capacity.

CAS / MDL: 4420-74-0 78-10-4
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JOURNAL OF WUHAN UNIVERSITY OF TECHNOLOGY-MATERIALS SCIENCE EDITION · 2023 ·Vol. 38 ·期 2 ·274-279 · IF 1.6

The Fabrication and SERS Performance of Multi-layer Hollow Au-Ag Alloy Nano Urchins Structure-based SERS Fiber Probe

Hao Zhenbang,Tian Qihang,Cao Shiyi,Han Xiaoyu,Zhang Jihong,Xie Jun,Zhao Xiujian

Novel hollow Au Ag alloy nano urchins were synthesized via Ag seeds growth method, and self-assembly coated on the wall and end-tip of silica fiber for fiber probe fabrication. The nano urchins homogeneously distributed on fiber surface because of fiber silanization. The sizes and tip sharpness of the nano-urchins could be controlled by Ag seeds. The elements distribution analysis indicated there was high Ag content in tip-top for better surface enhance Raman scattering performance. The detectable concentration could be as low as 10 −8 M using crystal violet molecules as analyte. Moreover, the fiber probes were stable in air, due to Au in the alloy. This fiber probe could be used for low content single molecular analysis.

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CATALYSIS LETTERS · 2023 · IF 2.8

Highly Stable Au@CeO2/MnOx Core–Shell Structured Catalyst for One-Step Oxidation Esterification of Methacrolein to Methyl Methacrylate

Chen Yao,Li Shuyue,Li Yuchao,Zheng Yanxia,Zuo Cuncun,Ge Tingting,Xu Rui,Huang Haofei,An Jiutao

Nano-Au particles are commonly used as an active component in oxidation esterification reactions. To inhibit the agglomeration of nano-Au particles, a series of highly stable Au@CeO 2 /MnO x core–shell structured catalysts were synthesized using inverse microemulsion technology for the oxidative esterification to prepare methyl methacrylate (MMA). The core–shell structured catalysts were prepared by using two different surfactants (CTAB and CO-520) and adjusting the molar ratio of water to oil (ω). XRD, Raman, N 2 adsorption, ICP−MS, TEM, UV–vis, FT-IR, XPS, and H 2 -TPR were applied to characterize the samples. The nano-Au particles were encapsulated by CeO 2 , forming a core–shell structure confirmed with TEM. The Au@CeO 2 /MnO x -C-ω = 10 catalyst prepared with CTAB as the surfactant has the best activity. The Au@CeO 2 /MnO x -C-ω = 10 catalyst has the highest hydrogen consumption and Ce 3+ content, indicating that the catalyst has the strongest interaction among Ce, Au, and Mn and more active oxygen. Active oxygen is beneficial to methanol activation and hemiacetal dehydrogenation, accelerating the formation of esters. The active oxygen content, Ce 3+ content, and H 2 consumption were correlated with the catalytic performance positively. After the catalyst was reused 10 times, the activity remained unchanged and the Au nanoparticles did not agglomerate due to the core–shell structure. Graphical Abstract

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INTERNATIONAL JOURNAL OF PHARMACEUTICS · 2023 · IF 5.8

Red blood cell membrane-coated functionalized Au nanocage as a biomimetic platform for improved MicroRNA delivery in hepatocellular carcinoma

Shengnan Huang,Chengzhi Song,Jinxin Miao,Xiali Zhu,Yongyan Jia,Yafei Liu,Dongjun Fu,Benyi Li,Mingsan Miao,Shaofeng Duan,Zhenzhong Zhang,Yurong Hu

Dysregulation of microRNAs (miRNAs) expression is closely related to cancers and managing miRNA expression holds great promise for cancer therapy. However, their wide clinical application has been hampered by their poor stability, short half-life and non-specific biodistribution in vivo . Herein, a novel biomimetic platform designated as RHAuNCs-miRNA for improved miRNA delivery was prepared through wrapping miRNA-loaded functionalized Au nanocages (AuNCs) with red blood cell (RBC) membrane. RHAuNCs-miRNA not only successfully loaded miRNAs but also effectively protected them from enzymatic degradation. With good stability, RHAuNCs-miRNA had the characteristics of photothermal conversion and sustained release. Cellular uptake of RHAuNCs-miRNA by SMMC-7721 cells was in a time-dependent manner via clathrin- and caveolin-mediated endocytosis. The uptake of RHAuNCs-miRNAs was affected by cell types and improved by mild near infrared (NIR) laser irradiation. More importantly, RHAuNCs-miRNA exhibited a prolonged circulation time without the occurrence of accelerated blood clearance (ABC) in vivo, resulting in efficient delivery to tumor tissues. This study may demonstrate the great potential of RHAuNCs-miRNA for improved miRNAs delivery.

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SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY · 2023 · IF 4.4

Nb2C MXene self-assembled Au nanoparticles simultaneously based on electromagnetic enhancement and charge transfer for surface enhanced Raman scattering

Ziheng Yang,Li Jiang,Weidan Zhao,Boya Shi,Xiangwen Qu,Yekai Zheng,Pengwei Zhou

Recent years, two-dimensional transition metal carbonitrides (MXene) have attracted much attention in the field of surface-enhanced Raman scattering (SERS). However, the relatively low enhancement of MXene is a major challenge. Herein, Nb 2 C-Au NPs nanocomposites were prepared by electrostatic self-assembly method, which have a synergistically conjugated SERS effect. The EM hot spots of Nb 2 C-Au NPs are significantly enlarged and expanded, while the surface Fermi level is decreased. This synergistic effect could improve the SERS performance of the system. Consequently, for the dye molecules CV and MeB, the detection limits reach 10 −10 M and 10 −9 M, respectively, while for biomolecule adenine, the detection limit is as low as 5 × 10 −8 M. The results also show the good concentration-dependent linearity, uniformity, reproducibility and stability of SERS substrate. Nb 2 C-Au NPs could be a fast, sensitive and stable SERS platform for label-free and non-destructive detection. This work may expand the application of MXene based materials in the field of SERS.

CAS / MDL: 75-59-2
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CHEMICAL ENGINEERING JOURNAL · 2023 · IF 15.1

Plasmon driven super-high HER activity of electronic structure and lattice strain engineered single atomic layer Pd@Au nanorods

Yi-Bai Sun,Miao Ni,Chen Chi,Dong-Rui Yang,Xue-Lu Chen,Qi Qi,Jian Li,Xing-Hua Xia

The development of efficient catalysts with low energy consumption has always been a key issue for sustainable hydrogen energy. Here, we report a catalyst comprising a single atomic Pd layer deposited on Au nanorods (ML-Pd@Au NRs) that shows a super-high HER activity and ultra-low overpotential under localized surface plasmon resonance condition. The Au NR plays triple determining roles in HER performance via adjusting the electronic structure and lattice strain of Pd that effectively reduces the adsorption energy of H-adatoms, eliminating the penetration of H adatoms in multilayer Pd crystal that decreases the H adatoms diffusion kinetics, and providing high energetic hot charge carriers under near-IR light irradiation that decreases the activation energy and onset potential of HER. The single atomic Pd layer on Au NRs ensures the hot electron transfer as the main dissipation pathway of the plasmonic hot charge carriers for HER. Thus, under near-IR light irradiation, HER on ML-Pd@Au NRs occurs with a high mass activity of 17.47 mA mg −1 at 100 mV and a very low overpotential of 13 mV at 10 mA cm −2 , which are superior to the commercial Pd/C and commercial Pt/C catalysts under the same conditions.

CAS / MDL: 16940-66-2
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ACS Applied Materials & Interfaces · 2023 · IF 9.5

Positively Charged-Amylose-Entangled Au-Nanoparticles Acting as Protein Carriers and Potential Adjuvants to SARS-CoV-2 Subunit Vaccines

Baochao Fan,Jun Gu,Bin Deng,Weilu Guo,Shuaifeng Zhang,Li Li,Bin Li

The COVID-19 pandemic continues to spread worldwide. To protect and control the spread of SARS-CoV-2, varieties of subunit vaccines based on spike (S) proteins have been approved for human applications. Here, we report a new subunit vaccine design strategy that functions as both an antigen carrier and an adjuvant in immunization to elicit high-level immune responses. The complex of 2-hydroxypropyl-trimethylammonium chloride chitosan and amylose entangles Au nanoparticles (HTCC/amylose/AuNPs) forming 40 nm nanocarriers with a positive charge. The obtained positively charged nanoparticles reveal many merits, including the larger S protein loading capacity in PBS buffer, higher cellular uptake ability, and lower cell cytotoxicity, supporting their potential as safe vaccine nanocarriers. Two functionalized nanoparticle subunit vaccines are prepared via loading full-length S proteins derived from SARS-CoV-2 variants. In mice, both prepared vaccines elicit high specific IgG antibodies, neutralize antibodies, and immunoglobulin IgG1 and IgG2a. The prepared vaccines also elicit robust T- and B-cell immune responses and increase CD19+ B cells, CD11C+ dendritic cells, and CD11B+ macrophages at the alveoli and bronchi of the immunized mice. Furthermore, the results of skin safety tests and histological observation of organs indicated in vivo safety of HTCC/amylose/AuNP-based vaccines. Summarily, our prepared HTCC/amylose/AuNP have significant potential as general vaccine carriers for the delivery of different antigens with potent immune stimulation.

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