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Ru[bpy]32
ChemistrySelect · 2023 ·Vol. 8 ·期 5 ·e202204363 · IF 2.1

A Signal Amplification Strategy Using ATP as a Co-Reaction Accelerator for the Electrochemiluminescence of Ru(bpy)32+/HEPES System and Detection of Iodide Anions**

Tingting Xu,Panpan Xu,Guilin Xu,Mengyao Liu,Yinggui Zhu

Graphical In the study, Ru(bpy) 3 2+ was used as the luminophore, HEPES buffer was served as the co-reactant, and ATP was added to the system to amplify the luminous signal. It was speculated that ATP acts as an co-reaction accelerator to promote the oxidation of HEPES to HEPES + ⋅, more HEPES⋅ can be generated, which then reacts with oxidized Ru(bpy) 3 3+ to emit stronger ECL signals. Moreover, I - consumes ATP, Ru(bpy) 3 2+ , and HEPES, leading to a decrease in ECL signal. Adenosine triphosphate is an important biological molecule that provides energy and substrate for various cellular biochemical processes,it's ubiquitous in our lives. In this work, a novel electrochemiluminescence (ECL) sensor composed of Ru(bpy) 3 2+ , 2-[4-(2-hydroxyethyl)piperazin-1-yl] ethanesulfonic acid (HEPES) and adenosine 5’-triphosphate disodium salt (ATP) was developed for the first time. In this ECL system, Ru(bpy) 3 2+ was used as the luminophore, HEPES buffer was served as the co-reactant, and ATP was added to the system to amplify the luminous signal to investigate the ECL behavior. Through fluorescence spectroscopy, ECL spectroscopy, and cyclic voltammetry (CV), it can be hypothesized that the possible ECL mechanism is that ATP acts as an advanced co-reaction promoter to accelerate the oxidation of HEPES to HEPES + ⋅, more HEPES⋅ can be generated, which then reacts with oxidized Ru(bpy) 3 3+ to emit stronger ECL signals. Subsequently, the influence of the ATP concentrations and the CV scanning speed was investaged. Moreover, it was observed that I − could quench the ECL intensity, the linear relationship range of I − concentration is from 10 −3 to 10 −6 m , the limit of detection is 3.7×10 −8 m (signal/noise=3), therefore, a new, highly sensitive, and selective ECL approach for I − detection was created.

CAS / MDL: 7681-11-0 50525-27-4
研究领域: 分析化学 · 生物化学
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JOURNAL OF ELECTROANALYTICAL CHEMISTRY · 2023 · IF 4.5

Inhibiting effect of graphdiyne on Ru(bpy)32+ ECL and its application in drug detection based on the host–guest interaction of cucurbit[8]uril

Haifeng Yao,Yahui Zhang,Yongping Dong,Mingfu Ye

Graphdiyne (GDY) is considered as another promising carbon material in biosensing field. However, the application of GDY in ECL sensing is in its infancy stage, and different roles of GDY are urgent to be discovered. In this work, strong anodic Ru(bpy) 3 2+ electrochemiluminescence (ECL) was obtained at a cucurbit[8]uril (Q[8]) modified electrode. Although GDY exhibited electrocatalytic effect on the oxidation of Ru(bpy) 3 2+ , an apparent inhibiting effect of GDY on the ECL signal was observed due to the energy transfer. An “on-off-on” mode ECL sensor was fabricated to detect pancuronium (PMD) based on the competitive host–guest interaction between ferrocene (Fc), PMD and Q[8]. Fc modified single-stranded DNA was immobilized onto the surface of GDY, which could be attached onto the electrode through the interaction between Fc and Q[8]. The quenching effect of GDY could apparently decrease ECL signal. PMD exhibited stronger combining ability with Q[8] than Fc, and could replace Fc from the cavity of Q[8], leading to the recovery of ECL signal. The variation of ECL intensity changed linearly with the PMD concentration in the range of 10 nM to 50 μM with a detection limit of 5 nM (3σ). The proposed sensor has high sensitivity, outstanding specificity and accuracy, indicating that GDY has promising potential application in ECL sensing field based on its inhibiting effect.

研究领域: 分析化学 · 生物传感 · 材料科学
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ANALYTICA CHIMICA ACTA · 2025 · IF 6

Development of a sandwich ECL aptamer sensor based on self-enhanced Ru(bpy)32+@ Zn-MOF luminophore and PoPD@Au NPs quencher for ultrasensitive EpCAM detection

Xiaoshuo Zhang,Rui Dai,Faqiong Zhao,Baizhao Zeng

Background Epithelial cell adhesion molecules (EpCAM) protein is one of the most frequently and intensely studied tumor-associated antigens because of its overexpression in most cancer cells. Thus, it is regarded as a tumor biomarker associated with a wide variety of carcinomas and reflects the existence and growth of tumors in the human body. It is highly required to detect low concentrations of EpCAM in early stage for ensuring human health. Results In this study, a novel sandwich electrochemiluminescence (ECL) aptasensor was developed for EpCAM detection. Wherein oxalate-based Zn-MOF supported tris(2,2′-bipyridyl)ruthenium (II) (Ru(bpy) 3 2+ @Zn-MOF) was used as luminophore and gold nanoparticle modified o-phenylenediamine (PoPD@Au NPs) as quencher. The 3D Ru(bpy) 3 2+ @Zn-MOF generated self-enhanced ECL without additional co-reactants. Furthermore, it remained stable and had short electron transfer distance, ensuring high and stable ECL signal. The ECL signal could be effectively quenched by PoPD@Au NPs through resonance energy transfer (RET) and electron transfer (ET), due to its absorption spectrum overlapping with the ECL emission spectrum of Ru(bpy) 3 2+ @Zn-MOF. In the presence of EpCAM, the aptamer acted as a linker between the luminophore and quencher, forming a sandwich structure that had reduced ECL intensity. Under optimal conditions, EpCAM could be sensitively detected over the range of 1 pg mL -1 -100 ng mL -1 , with a detection limit of 0.34 pg mL -1 . Significance This work developed a ECL aptasensor with self-enhanced Ru(bpy) 3 2+ @Zn-MOF luminophore for EpCAM detection. The ECL system was simple, but ultrasensitive for EpCAM monitoring, thanks to the ECL-RET and ET between Ru(bpy) 3 2+ @Zn-MOF and PoPD@Au NPs. It also could be applied to detect other biomolecules by replacing the aptamer, offering significant potential in disease diagnosis.

CAS / MDL: 1633-78-9 68-04-2
研究领域: 生物传感器 · 癌症诊断 · 分析化学 · 纳米材料 · 生物分析化学
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MICROCHEMICAL JOURNAL · 2021 · IF 4.821

A label-free ECL aptasensor for sensitive detection of carcinoembryonic antigen based on CdS QDs@MOF and TEOA@Au as bi-coreactants of Ru(bpy)32+

Xiu-hua Wei,Xing Qiao,Jie Fan,Yuan-qiang Hao,Yin-tang Zhang,Yan-li Zhou,Mao-tian Xu

Herein, a label-free electrochemiluminescence (ECL) biosensor for sensitive determination of carcinoembryonic antigen (CEA) was fabricated based on CdS quantum dots loaded onto metal organic framework (CdS QDs@MOF) and triethanolamine modified on gold nanoparticles (TEOA@AuNPs) as bi-coreactants of Ru(bpy) 3 2+ ECL system. The TEOA@AuNPs served as not only coreactant of Ru(bpy) 3 2+ but also nanocarrier for CEA aptamer which was bonded to the TEOA@AuNPs through Au–S bond. After incubated in CEA solution, the ECL signals decreased due to the poor conductivity of CEA and there was a linear correlation between the ECL intensity and log(C CEA ). Based on this result, a label-free ECL biosensor has been developed successfully and used to detect CEA with a detection limit of 8.5 × 10 −5 ng/mL. The proposed ECL aptasensor had good analytical performance in the detection of CEA in human serum samples.

研究领域: 生物传感 · 医学检测 · 纳米技术
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FOOD CHEMISTRY · 2023 · IF 8.8

An ultrasensitive ratiometric aptasensor based on the dual-potential electrochemiluminescence of Ru(bpy)32+ in a novel ternary system for detection of Patulin in fruit products

Liangrui Lv,QingQing Chen,Chunyang Jing,Xiaoying Wang

To sensitively monitor trace-level of toxic patulin (PAT), an ultrasensitive PAT ratiometric aptasensor based on the dual-potential electrochemiluminescence (ECL) of Ru(bpy) 3 2+ was first proposed. Noteworthily, Ru(bpy) 3 2+ -doped trimetallic nanocube ( [email protected] ) innovatively integrated the luminophore and cathode coreaction accelerator (CCA), which could generate strong cathodic ECL in the existence of low concentration of K 2 S 2 O 8 . Simultaneously, anthocyanin-derived carbon quantum dots (anth-CQDs) prepared from purple potato skins was first served as a green anodic coreactant. And SiO 2 -coated anth-CQDs ( [email protected] 2 ) exhibited excellent performance for enhancing anodic ECL of [email protected] Based on this, a novel ternary ECL system was established. In the presence of PAT, the ECL intensity ratio of anode to cathode ( I ECL-A / I ECL-C ) was significantly increased, and a low detection limit of 0.05 pg mL −1 was obtained. Moreover, when proposed method and high performance liquid chromatography (HPLC) were simultaneously applied to series of fruit products, the obtained results were completely consistent, reflecting its practicability.

研究领域: 食品科学 · 分析化学
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MICROCHIMICA ACTA · 2024 ·Vol. 191 ·期 4 ·1-10 · IF 5.3

Ultrasensitive solid-state electrochemiluminescence sensor based on lotus root shaped carbon fiber, CdSe QDs and Fe3O4 synergically amplify Ru(bpy)32+ luminophore signal for detection of cyfluthrin

Shan Xiangyu,Lu Juan,Li Chao,Wu Qian,Li Huiling,Yang Shuning,Guo Yanjia,Song Yujia,Li Ruidan,Tian Li

An efficient and innovative electrochemiluminescence (ECL) sensor was developed for trace detection of cyfluthrin. The sensor utilized materials such as lotus root shaped carbon fiber (Co CNFs), cadmium selenide quantum dots (CdSe QDs), and Fe 3 O 4 to amplify Ru(bpy) 3 2+ signals. Co CNFs, with its large specific surface area and porosity, served the purpose of not only enhancing the stability of the sensor by fixing CdSe QDs and Ru(bpy) 3 2+ on the Co CNFs/GCE, but also facilitating electron transfer. CdSe QDs was involved in the luminescence reaction and collaborated with Ru(bpy) 3 2+ to enhance the sensor's sensitivity, while Fe 3 O 4 promoted electron transfer in the system due to its large surface area. The solid-state ECL sensor achieved satisfactory signal under the synergistic action of these components. The ECL signal of the sensor was quenched by cyfluthrin, and a favorable linear relationship was observed between the sensor and cyfluthrin in the concentration range 1 × 10 –12 to 1 × 10 –6 M. The detection limit of the sensor was 3.3 × 10 –13 M (S/N = 3). The utilization of lotus root shaped carbon fiber, CdSe QDs, and Fe 3 O 4 in the Ru(bpy) 3 2+ system demonstrated a synergistic effect for cyfluthrin detection, presenting a new approach for the rapid determination analysis of pesticide residues in foods. Graphical

研究领域: 分析化学 · 环境监测 · 食品安全 · 纳米材料 · 电分析化学
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BIOSENSORS & BIOELECTRONICS · 2017 · IF 7.78

Electrochemiluminescent competitive immunosensor based on polyethyleneimine capped SiO2 nanomaterials as labels to release Ru(bpy)32+ fixed in 3D Cu/Ni oxalate for the detection of aflatoxin B1

Yaoguang Wang,Guanhui Zhao,Xiaojian Li,Li Liu,Wei Cao,Qin Wei

In this work, a highly-efficient competitive method-based electrochemiluminescence (ECL) immunosensor was proposed based on {[Ru(bpy) 3 ][Cu 2x Ni 2(1−x) (ox) 3 ]} n (Cu/Ni/Ru) as luminophor to efficiently detect aflatoxins B1 (AFB1). Cu/Ni/Ru exhibited excellent ECL behavior. While polyethyleneimine capped silicon dioxide (PEI@SiO 2 ) could decrease the ECL performance of Cu/Ni/Ru due that PEI could destroy the structure of Cu/Ni/Ru via producing the complex between PEI and metal ions (Cu(II)/Ni(II)), inducing the release of Ru(bpy) 3 2+ . Since Au nanoparticles can directly combine with antibody and antigen, the Cu/Ni/Ru and PEI@SiO 2 was functionalized by Au nanoparticles . The quantitative detection of AFB1 was based on the competitive binding between AFB1-bovine serum albumin labeled Au-PEI@SiO 2 (Au-PEI@SiO 2 -AFB1-BSA) and free AFB1 with antibody-AFB1 which immobilized on Au-Cu/Ni/Ru. The ECL signal increased with augmenting the concentrations of the free AFB1 due to less Au-PEI@SiO 2 -AFB1-BSA combining with antibodies. Under optimal conditions, the proposed immunosensor exhibited a wide linear range from 0.01   ng   mL −1 to 100   ng   mL −1 with a detection limit of 0.0039   ng   mL −1 (S/N = 3). The proposed immunosensor also provides a promising approach for ultrasensitive detection of other mycotoxins .

研究领域: 分析化学 · 食品安全检测 · 生物传感技术
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Chemical Science · 2019 ·Vol. 10 ·期 15 ·4141-4147 · IF 9.556

Spatiotemporal imaging of electrocatalytic activity on single 2D gold nanoplates via electrogenerated chemiluminescence microscopy

Ming-Ming Chen,Wei Zhao,Meng-Jiao Zhu,Xiang-Ling Li,Cong-Hui Xu,Hong-Yuan Chen,Jing-Juan Xu

Uncovering the relationship between the structure, surface properties and electrochemical activity of nanoparticles is of great importance for constructing novel nanocatalysts and highly efficient electrocatalytic devices. Here we report a study of the heterogeneously distributed electrocatalytic activity on individual 2D gold nanoplates. On the basis of electrogenerated chemiluminescence (ECL) microscopy, the size, shape, and site-specific catalytic activity of 2D nanocrystals could be directly imaged at the single particle level with submicron resolution. Since the microelectrode effect with higher fluxes at the perimeter was offset by diffusion of excited species of Ru(bpy)32+, calculated by finite element simulation, the ECL distribution was supposed to be uniform on the micro-sized plates. Therefore, it is highly possible that the observed nonuniform ECL distribution at single nanoplates reflected distinct surface electrocatalytic activities at different sites. Furthermore, ECL microscopy allows continuous in situ imaging, which elucidates the time-varying changes in the spatial distribution of electrocatalytic activity on individual nanoplates, indicating that the corners and edges with more defect sites exhibit higher reactivity, but lower stability than the flat facet. We believe that real-time and high-throughput ECL microscopy may lead to more comprehensive understanding of reactivity patterns of single nanocatalysts.

CAS / MDL: 57-09-0 6132-04-3
研究领域: 纳米技术 · 电化学 · 催化 · 显微技术 · 材料科学
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Nanoscale · 2020 ·Vol. 12 ·期 13 ·7321-7329 · IF 6.895

Size-selected and surface-passivated CsPbBr3 perovskite nanocrystals for self-enhanced electrochemiluminescence in aqueous media

Yue Cao,Wenlei Zhu,Lingling Li,Ziyi Zhang,Zixuan Chen,Yuehe Lin,Jun-Jie Zhu

In this work, CsPbBr3 perovskite nanocrystals (NCs) synthesized via a ligand-assisted reprecipitation method (LCPB) were discovered to emit self-enhanced electrochemiluminescence (ECL) with the surface oleylamine as both a coreactant and a stabilizer. Solvent regulation and tri-n-octylphosphine post-treatment were manipulated for size-selected and surface-passivated LCPBs, which showed remarkable aqueous ECL performance with respect to efficiency and stability. Furthermore, thanks to the self-enhancement mode with a shorter charge transfer pathway and less energy loss, the ECL efficiency obtained for these as-synthesized LCPBs in aqueous solution without any additional coreactant was up to 57.08% using the Ru(bpy)32+-tripropylamine system as the standard. As a proof-of-concept, the products were successfully employed for the bioanalyses of hydrogen peroxide, ascorbic acid, and cancer cells based on inhibition, coreaction, and impedance detection principles, respectively. More importantly, the basic properties of LCPBs in aqueous media including surface chemistry, charge transfer process, and ECL mechanism were studied systematically. Such efforts are aimed at perfecting the fundamental research of all-inorganic perovskite NCs and opening an avenue for the design of highly crystalline and luminescent perovskites as advanced ECL emitters for applications in the ECL domain.

研究领域: 材料科学 · 电化学 · 纳米技术 · 分析化学 · 生物医学工程
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ACS Applied Nano Materials · 2024 · IF 5.3

Electrochemical Immunosensor for Simultaneous Detection of Oral Cancer Dual Markers Based on a Functionalized Magnetic Electrode and a Photoelectric-Material-Doped Nanoalloy

Liangrui Lv,Wei Yuan,Juanjuan Hu,Xuyuan Chen,Tingting Zhang,Jie Cheng,Xiaoying Wang

Protein tumor marker (PTM) analysis is of great significance for the early diagnosis and process monitoring of tumors. However, the clinical reference value of a single PTM is restricted, and existing tests for multiple PTMs majorly suffer from complex processes and poor sensitivity. Herein, a cancerous inhibitor of protein phosphatase 2A (CIP2A) and protein c-Myc (AGc-Myc) with a positive feedback path in oral squamous cell carcinoma (OSCC) was chosen as a dual PTM, and a magnetic electrochemical immunosensor (MEI) for their simultaneous detection was successfully established. Fe3O4 coated with a gold nanoparticle (MAu)-functionalized magnetic electrode (f-MGE) was of benefit to immobilize two capture antibodies (CAb) through internal forces and external magnetic fields. By a mechanical alloying (MA) method, two photoelectric materials osmosed bimetallic-matrix nanospheres (Bi-MPE), including luminol and Ru(bpy)32+ osmosed AuNPs–AgNPs nanoalloy (Lu@AuAg and Ru@AuAg), were prepared as innovative signal probes. Lu@AuAg and Ru@AuAg not only exhibit superior electrochemical properties than photoelectric material osmosed monometallic-matrix nanospheres but can directly label detection antibodies (DAb) without complex reaction conditions and additional functionalization. After immunological reactions, the distinguishable differential voltammetry pulse signals were obtained at +0.48 and +1.13 V, corresponding to AGc-Myc and CIP2A, respectively. The proposed assay showed a good linear response range from 5 pg L–1 to 5 ng L–1 for AGc-Myc and 50 pg L–1 to 50 ng L–1 for CIP2A, and a low limit of detection of 2.5 pg L–1 and 25 pg mL–1, respectively. The MEI also exhibited satisfactory selectivity, stability, and reproducibility. Moreover, when the proposed method and the ELISA kit were simultaneously applied to saliva samples of OSCC patients, the obtained results were completely consistent, reflecting the clinical practicability of this work.

研究领域: 生物化学 · 生物技术 · 分析化学 · 医学诊断 · 纳米技术 · 电化学 · 癌症研究
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