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Micromachines · 2023 ·Vol. 14 ·期 4 ·739 · IF 3.4

4-Mercaptopyridine-Modified Sensor for the Sensitive Electrochemical Detection of Mercury Ions

Mingjie Han,Yong Xie,Ri Wang,Yang Li,Chao Bian,Shanhong Xia

As a highly toxic heavy metal ion, mercury ion (Hg2+) pollution has caused serious harm to the environment and human health. In this paper, 4-mercaptopyridine (4-MPY) was selected as the sensing material and decorated on the surface of a gold electrode. Trace Hg2+could be detected by both differential pulse voltammetry (DPV) and electrochemical impedance spectroscopy (EIS) methods. The proposed sensor displayed a wide detection range from 0.01 μg/L to 500 μg/L with a low limit of detection (LOD) of 0.002 μg/L by EIS measurements. Combined with molecular simulations and electrochemical analyses, the chelating mechanism between Hg2+and 4-MPY was explored. Through the analysis of binding energy (BE) values and stability constants, 4-MPY showed an excellent selectivity for Hg2+. In the presence of Hg2+, the coordination of Hg2+with the pyridine nitrogen of 4-MPY was generated at the sensing region, which caused a change in the electrochemical activity of the electrode surface. Due to the strong specific binding capability, the proposed sensor featured excellent selectivity and an anti-interference capability. Furthermore, the practicality of the sensor for Hg2+detection was validated with the samples of tap water and pond water, which demonstrated its potential application for on-site environmental detection.

CAS / MDL: 108-89-4
研究领域: 环境科学 · 分析化学
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SENSORS AND ACTUATORS B-CHEMICAL · 2024 · IF 8

Recyclable MXene film as SERS sensor with high sensitivity and flexibility adjusted with ZnO quantum dots

Yuhui Liu,Alei Dang,Xin Liu,Xiangkai Wang,Amir Zada,Jiahe Chen,Xiaoyi Fan,Tingkai Zhao,Jing Li,Tiehu Li

Developing flexible substrates with high sensitivity, good reproducibility and recyclability is a major challenge in surface enhanced Raman scattering (SERS) research. Herein, we prepare a recyclable Ti 3 C 2 MXene/ZnO quantum dots (Ti 3 C 2 /ZnO) heterostructure film as an efficient SERS sensor with remarkable flexibility using vacuum assisted filtration technique. Benefiting from the more charge transfer (CT) paths, higher CT efficiency provided by oxygen vacancies (OVs) in ZnO QDs and Schottky barrier between Ti 3 C 2 and ZnO QDs, the limit of detection (LOD) for 4-mercaptopyridine (4-MPY) molecules was as low as 1×10 −7 M. In addition, the prepared flexible SERS film provided uniform and stable signals for both temporal (storage at room temperature for 60 days) and spatial (RSD = 10.7 %) scales due to the optimal distribution of ZnO QDs in the macroscopic assembly of Ti 3 C 2 /ZnO hybrid with excellent reliability and durability. Moreover, the prepared novel flexible SERS sensor achieved self-cleaning by photocatalytically degrading methylene blue (MB) residues extracted from the surface of orange peels and showed exceptional reusability during the detection process. Thus, this high-efficiency and low-cost flexible recyclable SERS sensor may be useful for the in-situ molecular detection in food security and environmental protection.

研究领域: 材料科学 · 分析化学 · 环境科学
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CHEMICAL ENGINEERING JOURNAL · 2021 · IF 13.273

Bio-inspired strategy to enhance catalytic oxidative desulfurization by O-bridged diiron perfluorophthalocyanine axially coordinated with 4-mercaptopyridine

Ze Fang,Nan Li,Zhiguo Zhao,Zhexin Zhu,Wangyang Lu,Fengtao Chen,Junjie Wang,Wenxing Chen

Developing efficient and environmentally friendly catalytic system is significant for the removal of sulfide in fuel. O-bridged diiron perfluorophthalocyanine/4-mercaptopyridine (FePcF 16 -O-FePcF 16 /4-Mpy) as a novel composite catalyst was designed and prepared by axial coordination. The catalyst characterization was conducted through ultraviolet–visible spectroscopy, fourier transform infrared spectroscopy, X-ray diffractometry, electrospray ionization–mass spectrometry and density-functional theory technology. A high-efficient extraction oxidative desulfurization system is composed of hydrogen peroxide (H 2 O 2 ), the mixture of ethanol and water and FePcF 16 -O-FePcF 16 /4-Mpy. Notably, the coordination of 4-Mpy greatly enhanced the catalytic activity of FePcF 16 -O-FePcF 16 , 99.4% of the desulfurization rate was achieved in 20 min at 30 °C. The catalyst system was cycled 8 times without significantly reducing the removal of dibenzothiophene. Electron paramagnetic resonance and gas chromatography–mass spectroscopy proved the high-valent iron-oxo intermediates were the main active substances in the FePcF 16 -O-FePcF 16 /4-Mpy/H 2 O 2 system, and the pathway of catalytic oxidation DBT was proposed. This work provided useful insights to select suitable ligands to improve the activity of metal phthalocyanine, and offered a novel idea for the construction of efficient oxidative desulfurization system.

研究领域: 化学工程 · 环境科学 · 材料科学
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Materials Research Express · 2016 ·Vol. 3 ·期 6 ·065018 · IF 0.968

Synthesis and characterization of Ag@Cu nano/microstructure ordered arrays as SERS-active substrates

Pinhua Zhang,Guangliang Cui,Chuanhai Xiao,Mingzhe Zhang,Li Chen,Changmin Shi

We fabricated an Ag decorated Cu (Ag@Cu) nano/microstructure ordered array by facile template-free 2D electrodeposition combined with a galvanic reduction method for SERS applications. The Cu nano/microstructure ordered arrays were first synthesized by a 2D electrodeposition method, then Ag nanocubes were decorated on the arrays by galvanic reduction without any capping agent. The pollution-free surface and edge-to-face heterostructure of Ag nanocubes and Cu nano/microstructure arrays provide the powerful field-enhancements for SERS performance. The results verified that the Ag@Cu nano/microstructure ordered arrays have excellent activity for 4-Mercaptopyridine, and the sensitivity limit is as low as 10−8 M. Therefore, this facile route provides a useful platform for the fabrication of a SERS substrate based on nano/microstructure ordered arrays.

研究领域: 材料科学 · 纳米技术 · 光谱学
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Nanomaterials · 2021 ·Vol. 11 ·期 8 ·2063 · IF 5.076

Charge-Transfer Process in Surface-Enhanced Raman Scattering Based on Energy Level Locations of Rare-Earth Nd3+-Doped TiO2 Nanoparticles

Zihao Zhao,Xiang Zhao,Mu Zhang,Xudong Sun

Surface-enhanced Raman scattering (SERS) for semiconductor nanomaterial systems is limited due to weak Raman signal intensity and unclear charge-transfer (CT) processes for chemical enhancement. Here, rare-earth element neodymium-doped titanium dioxide (Nd-TiO2) nanoparticles (NPs) were synthesized by the sol–gel method. The characterizations show that the doping of Nd ions causes TiO2NPs to show an increase in the concentration of defects and change in the energy level structure. The CT process between Nd-TiO2NPs substrate and probe molecule 4-Mercaptopyridine (4-Mpy) was innovatively analyzed using the relative energy level location relationship of the Dorenbos model. The SERS signal intensity exhibits an exponential enhancement with increasing Nd doping concentration and reaches its optimum at 2%, which is attributed to two factors: (1) The increase in the defect concentration is beneficial to the CT process between the TiO2and the probe molecule; (2) the introduction of 4felectron orbital energy levels of rare-earth ions created unique CT process between Nd3+and 4-Mpy. Moreover, the Nd-TiO2NPs substrate shows excellent SERS performance in Raman signal reproducibility (RSD = 5.31%), the limit of detection (LOD = 10−6M), and enhancement factor (EF = 3.79 × 104). Our work not only improves the SERS performance of semiconductor substrates but also provides a novel approach to the development of selective detection of probe molecules.

研究领域: 材料科学 · 光谱学
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Nanoscale · 2013 ·Vol. 5 ·期 13 ·5905-5911 · IF 6.233

Ultrasensitive surface-enhanced Raman scattering detection of trypsin based on anti-aggregation of 4-mercaptopyridine-functionalized silver nanoparticles: an optical sensing platform toward proteases

Lingxin Chen,Xiuli Fu,Jinhua Li

In this work, a simple and sensitive surface-enhanced Raman scattering (SERS) strategy was developed for recognition and detection of trypsin, by using anti-aggregation of 4-mercaptopyridine (4-MPY)-functionalized silver nanoparticles (AgNPs) based on the interaction between protamine and trypsin. The polycationic protamine not only served as a substrate for enzyme hydrolysis but also worked as a medium for SERS enhancement, which could bind negatively charged 4-MPY-functionalized AgNPs and induce their aggregation. The hydrolysis catalyzed with trypsin in sample solution decreased the concentration of free protamine, resulting in the dispersion of AgNPs and thus decreasing the Raman intensity of 4-MPY, by which the trypsin could be sensed optically. A detection level down to 0.1 ng mL−1 for trypsin was obtained. The induced accumulation of AgNPs modified with Raman reporter 4-MPY largely enhanced the SERS responses. A good linearity was found within the wide range over five orders of magnitude and reasonable relative standard deviations (between 2.4 and 11.6%) were attained. By using trypsin as a model, the new concept can provide an excellent platform for ultrasensitive SERS measurements of various proteases/enzymes which can lead to nanoparticles stability change through catalyzed hydrolysis toward substrate.

CAS / MDL: 989-38-8
研究领域: 生物化学 · 分析化学 · 纳米技术
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MICROCHEMICAL JOURNAL · 2024 · IF 4.9

Electrostatic self-assembly of ZIF-8/Ag nanocomposites as versatile SERS substrates for sensitive detection of environmental pollutants

Yang Feng,Mengyi Yuan,Lan Zhang,Tingting Zhang,Shiying Wu,Lujie Li,Lingling Wang,Weihua Li,Rui Lu

This study reports the development of an electrostatic self-assembly surface-enhanced Raman scattering (SERS) substrate based on zeolitic imidazolate framework-8 (ZIF-8) decorated with silver nanoparticles (AgNPs). A seed-mediated growth method was employed to synthesize AgNPs with an average diameter of 30 nm, and a mild synthesis process was used to prepare ZIF-8 nanoparticles with an average diameter of 350 nm. The ZIF-8/Ag nanocomposites have been optimized and characterized using a variety of techniques. As a probe molecule, 4-aminothiophenol was used to evaluate the SERS performance of the ZIF-8/Ag nanocomposites, demonstrating low limit of detection to 8.32 × 10 −8  M, respectively. ZIF-8/Ag nanocomposites also demonstrated good signal reproducibility with a relative standard deviation of 12.5 % for 10 −6  M 4-aminothiophenol. Furthermore, the ZIF-8/Ag nanocomposites have successfully been used to detect 4-mercaptopyridine and the pesticide thiram in laboratory tap water with recoveries ranging from 87 % to 113 %. The ZIF-8/Ag nanocomposites were further investigated for their potential use as SERS substrates for the detection of thiram residues on the surface of apples. A finite difference time-domain simulation was also conducted to investigate the SERS enhancement mechanism of the ZIF-8/Ag nanocomposites.

CAS / MDL: 693-98-1
研究领域: 材料科学 · 环境科学 · 分析化学
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JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY · 2024 · IF 5.7

Ultra-Sensitive Abscisic Acid Detection Using Gold and 4-Mercaptopyridine Perovskite-Engineered Robust Nanofibers (GLAMPER-NFs) under Surface-Enhanced Raman Spectroscopy

Syed Muhammad Zaigham Abbas Naqvi,Jingkai Zhao,Muhammad Naveed Tahir,Muhammad Awais,Yanyan Zhang,Junfeng Wu,Shakeel Ahmed,Linze Li,Vijaya Raghavan,Jiandong Hu

This study explores the development and application of gold and 4-mercaptopyridine (MPY) perovskite-engineered robust nanofibers (GLAMPER-NFs) for the ultrasensitive detection of Abscisic acid (ABA) under Raman spectroscopy, a crucial plant hormone. The GLAMPER-NFs composite material, consisting of MAPbCl3 nanofibers integrated with MPY-coated gold nanostructures, demonstrates exceptional performance in surface-enhanced Raman scattering (SERS)-based sensing. The study elucidates the material structure and properties through comprehensive characterization using scanning electron microscopy (SEM), UV–vis spectroscopy, fluorescence spectroscopy, Fourier transform infrared, and Raman spectroscopy. The SEM analysis reveals uniform nanofibers with diameter of 107.8 ± 3.06 nm, while spectroscopic studies confirm the successful synthesis and integration of the composite components. The SERS-based detection of ABA showcases remarkable sensitivity, with a linear detection range (R2 = 0.9957) spanning 7 orders of magnitude (10–14–10–7 M) and presented a limit of detection of 10–11 and enhancement factor of 1.08 × 107. This surpasses the performance of existing sensing platforms, demonstrating clear spectral responses even at femtomolar concentrations. The synergistic effects of the perovskite structure, plasmonic gold nanoparticles, and MPY linking molecules contributed exceptional sensing capabilities to the GLAMPER-NFs material. Fluorescence studies further corroborate the sensitivity and provide insights into the photophysical interactions between ABA and the composite material. This research advances the understanding of perovskite-based hybrid materials and presents a promising GLAMPER-NFs as SERS substrate for ultrasensitive plant hormone detection, with potential applications in agricultural monitoring and plant science research.

CAS / MDL: 7758-95-4
研究领域: 植物科学 · 材料科学 · 分析化学
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ANALYST · 2023 ·Vol. 148 ·期 17 ·4044-4052 · IF 4.2

Highly sensitive and selective SERS substrates with 3D hot spot buildings for rapid mercury ion detection

Jia Li,Wei Peng,An Wang,Mingjie Wan,Yadong Zhou,Xia-Guang Zhang,Shangzhong Jin,Fan-Li Zhang

Heavy metal ions, which are over-emitted from industrial production, pose a major threat to the ecological environment and human beings. Among the present detection technologies, achieving rapid and on-site detection of contaminants remains a challenge. Herein, capillaries with three-dimensional (3D) hot spot constructures are fabricated to achieve repaid and ultrasensitive mercury ion (Hg2+) detection in water based on surface-enhanced Raman scattering (SERS). The 4-mercapto pyridine (4-Mpy) serves as the Raman reporter with high selectivity, enabling the detection of Hg2+ by changes in adsorption configuration at the trace level. Under optimized conditions, the SERS response of 4-Mpy for Hg2+ exhibits good linearity, ranging from 1 pM to 0.1 μM in a few minutes, and the detection limit of 0.2 pM is much lower than the maximum Hg2+ concentration of 10 nM allowed in drinking water, as defined by the US Environmental Protection Agency (EPA). Simultaneously, combined with the theoretical simulation and experimental results, the above results indicate that the SERS substrates possess outstanding performances in specificity, recovery rate and stability, which may hold great potential for achieving rapid and on-site environmental pollutant detection using a portable Raman spectrometer.

研究领域: 环境科学 · 分析化学
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ACS Applied Nano Materials · 2023 · IF 5.9

Boron-Doped Diamond Modified with 4-Mercaptopyridine-Functionalized Gold Nanoparticles for Trace Mercury Detection

Mingjie Han,Yuhao Xu,Ri Wang,Yong Xie,Yuekun Wang,Chao Bian,Shanhong Xia

Mercury ions (Hg2+) are highly toxic, which can contaminate the environment and cause serious harm to human health. In this work, we report a portable, high-performance, and reusable boron-doped diamond (BDD) electrochemical sensor, which takes the advantages of 4-mercaptopyridine-functionalized gold nanoparticles (4-MPY/Au NPs) as the sensing element. Due to the specific coordination between Hg2+ and nitrogen of pyridine, Hg2+ can be captured by the 4-MPY to form a Hg(pyridine)2 complex, which leads to the reduction of electrochemical activity at the electrode surface. The current variations are monitored by differential pulse voltammetry (DPV) in solution containing the [Fe(CN)6]3–/4– redox probe. Under optimal conditions, the proposed sensor exhibits an excellent logarithmic relationship in the range of 0.001–10 μg/L with a low limit of detection (LOD) of 0.358 ng/L. In addition, the sensor is validated with satisfactory recovery of tap water samples, demonstrating its potential for on-site monitoring of the water environment.

研究领域: 环境科学 · 分析化学
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Chemosensors · 2023 ·Vol. 11 ·期 6 ·347 · IF 4.2

Recyclable Multifunctional Magnetic Fe3O4@SiO2@Au Core/Shell Nanoparticles for SERS Detection of Hg (II)

Chao Liu,Hui Wang,Shengmin Xu,Hongbao Li,Yilin Lu,Chuhong Zhu

Mercury ions can be enriched along the food chain and even low concentrations of mercury ions can seriously affect human health and the environment. Therefore, rapid, sensitive, and highly selective detection of mercury ions is of great significance. In this work, we synthesized Fe3O4@SiO2@Au three-layer core/shell nanoparticles, and then modified 4-MPy (4-mercaptopyridine) to form a SERS sensor. Mercury ions in water can be easily captured by 4-MPy which were used as the reporter molecules, and the concentration of mercury ions can be evaluated based on the spectral changes (intensification and reduction of peaks) from 4-MPy. After the mercury ion was combined with the pyridine ring, the peak intensity at 1093 cm−1increased with the concentration of mercury ion in the range of 10 ppm–1 ppb, while the Raman intensity ratio I (416 cm−1)/I (436 cm−1) decreased with the increase of mercury ion concentration. This magnetically separatable and recyclable SERS sensor demonstrates good stability, accuracy, and anti-interference ability and shows the potential to detect actual samples. Furthermore, we demonstrate that the probe is applicable for Hg2+imaging in macrophage cells.Keywords:core/shell nanoparticles;4-pyridinethiol;surface-enhanced Raman spectroscopy (SERS);Mercury (II) ion;Raman cell imaging

研究领域: 纳米技术 · 分析化学 · 环境科学 · 材料科学 · 生物医学工程
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ANALYST · 2025 · IF 3.3

Gold nanoparticles-enhanced hollow fiber surface plasmon resonance sensor for highly sensitive detection of mercury(II) ions

Yangyang Xu,Xiao-song Zhu,Yi-wei Shi

Mercury(II) ions (Hg2+) are one of the most common and highly toxic heavy metal ions, which can contaminate the environment and damage the human health. Therefore, the precise detection of trace Hg2+ concentration is particularly important. Herein, gold nanoparticles-enhanced silver-coated hollow fiber (HF) surface plasmon resonance (SPR) sensor was developed for the highly sensitive detection of Hg2+ ions. Due to the inherent difficulty in directly detecting Hg2+ ions on the sensing surface, the advantages of gold nanoparticles (AuNPs) as signal amplification labels were exploited to improve the sensitivity of the sensor. In the presence of Hg2+ ions, we chemically modified the sensing silver film of the sensor with 4-mercaptopyridine (4-MPY) and 4-mercaptopyridine-functionalized gold nanoparticles (AuNPs/4-MPY). Owing to the specific coordination between Hg2+ and the nitrogen of pyridine, Hg2+ could be captured by 4-MPY to form a Hg(pyridine)2 complex. After adsorption of the Hg2+ ions, the strong electromagnetic coupling between the AuNPs and the silver film led to a wavelength shift of the SPR resonance peak. Experiments for the detection of Hg2+ ions were performed in the concentration range of 5 nM to 1 μM to investigate the performance of the present sensor. The sensor achieved a limit of detection (LOD) as low as 5 nM. Moreover, the developed fiber sensor exhibited excellent performance in terms of sensitivity and repeatability. Our results show this strategy has widespread applications in the field of on-site heavy metal detection and biomedical monitoring.

CAS / MDL: 4556-23-4 7646-78-8
研究领域: 分析化学 · 纳米技术 · 环境监测 · 生物传感器 · 光学传感器
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