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CHEMICAL RESEARCH IN CHINESE UNIVERSITIES · 2022 ·Vol. 38 ·期 3 ·816-822 · IF 2.726

The Effect of Ionic Strength on the Electrochemiluminescence Generation by Tris(2,2′-bipyridyl)ruthenium(II)/Tri-n-propylamine

Hu Shifan,Wang Yafeng,Su Bin

Electrochemiluminescence(ECL) is a powerful transduction technique used in biosensing and in vitro diagnosis, while the mechanism of ECL generation is complicated and affected by various factors. Herein the effect of ionic strength on ECL generation by the classical tris(2,2′-bipyridyl)ruthenium(II)[Ru(bpy) 3 2+ ]/tri- n -propylamine(TPrA) system was investigated. It is clear that the ECL intensity decreases significantly with the increase of ionic strength, most likely arising from the reduced deprotonation rate of TPrA +· . We further combined microtube electrode(MTE) with ECL microscopy to unravel the evolution of ECL layer with the variation of ionic strength. At a low concentration of Ru(bpy) 3 2+ , the thickness of ECL layer(TEL) nearly kept unchanged with the ionic strength, indicating the surface-confined ECL generation is dominated by the oxidative-reduction route. While at a high concentration of Ru(bpy) 3 2+ , ECL generation is dominated by the catalytic route and TEL increases remarkably with the increase of ionic strength, because of the extended diffusion length of Ru(bpy) 3 3+ at a reduced concentration of TPrA · .

研究领域: 分析化学 · 生物传感 · 电化学
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MICROCHIMICA ACTA · 2024 ·Vol. 191 ·期 3 ·1-8 · IF 5.3

Electrochemiluminescent assay based on Co-MOF and TiO2 for determination of bisphenol A

Yang Shuning,Tian Li,Song Guanying,Li Huiling,Li Chao,Wu Qian,Shan Xiangyu,Zhao Lun

An electrochemiluminescence (ECL) sensor for determining bisphenol A (BPA) was prepared based on titanium dioxide (TiO 2 ) and Co-MOF. TiO 2 is a co-reaction promoter that amplifies the ECL signal in the Ru(bpy) 3 2+ -trinpropylamine (TPrA) system. When the electrode is modified with Co-MOF the ECL signal is significantly enhanced. This is because Co-MOF can not only be used as a co-reaction accelerator but also as a carrier to adsorb more luminescent substances. Possible mechanisms for amplifying the original signal through the synergistic action of the two substances are investigated. The ECL strength decreases with increasing concentrations of BPA, and the amount of BPA can be determined by the change in ECL signal strength (Δ I ). Under optimal experimental conditions, the linear range of BPA was 2.0 × 10 −10 to 2.0 × 10 −5  M, with a determination limit of 6.7 × 10 −11  M (3 σ / m ). The relative standard deviation (RSD) of the signal for ten consecutive measurements was 1.5%. The sensor can be used to detect BPA in bottled samples with recoveries of 96 to 105%. Graphical

研究领域: 分析化学 · 环境科学 · 材料科学 · 电化学 · 传感器技术
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CHIRALITY · 2025 ·Vol. 37 ·期 7 ·e70040 · IF 3

Electrochemiluminescent Chiral Sensor Based on Covalent Organic Frameworks for Discrimination of Phenylalanine Enantiomers

Qinhua Liu,Xuan Kuang

Chiral recognition of amino acids is crucial in pharmaceutical and clinical fields due to the enantiomer-dependent bioactivity of chiral compounds. Here, we report an electrochemiluminescent (ECL) sensor utilizing a chiral covalent organic framework (CC-MP CCTF) for the selective discrimination of phenylalanine (Phe) enantiomers. Critical experimental parameters, including buffer pH (optimized to 7.38), tripropylamine (TPrA) concentration (9.99 mM), and CC-MP CCTF dilution ratio (1.6×), were optimized to maximize sensitivity. The sensor achieved a linear detection range (0.2–1.0 mM) for both D- and L-Phe with a limit of detection (LOD) of 0.1 mM. Remarkably, it exhibited exceptional enantioselectivity, showing a 1.96-fold higher ECL response to D-Phe than L-Phe, which originates from the chiral confinement effect of the CC-MP CCTF. This study proposes a cost-effective and rapid strategy for chiral amino acid recognition, demonstrating potential applications in bioanalysis and quality control processes.

研究领域: 生物分析 · 药物分析 · 临床化学
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ANALYTICAL CHEMISTRY · 2024 · IF 6.7

Unary Au Nanocrystal with Prestored Electrons and Intrinsic Low Hole-Injected Potential for Low-Triggering Potential Electrochemiluminescence

Li Fu,Pengjie Dong,Zerui Liu,Qi Li,Yingshu Guo

Screening a novel electrochemiluminescence (ECL) system and lowering the ECL triggering potential are essential to ECL evolution. Herein, the near-infrared (NIR) ECL system with low-triggering potential ECL was constructed with weakly reductive tert-butylamine borane as coreactant and mercaptosuccinic acid/citrate (MSA/Cit)-capped Au (MSA/Cit@AuNCs) as luminophores. Toxic-element-free and dual-ligand MSA/Cit@AuNCs were prepared via ligand exchange and utilized as a model for developing unary metal NCs-based luminophores with more enhanced ECL performance than monoligand Au nanocrystals (AuNCs), which exhibited a two hole-injected process at around 0.48 and 0.80 V, respectively. Beneficial to the intrinsic low hole-injected potential of AuNCs, MSA/Cit@AuNCs exhibited similar low-triggering ECL potential at around 0.57 V with the participation of series coreactants or not, originating from the recombination of an internal prestored electron within the conduction band (CB) and electroinjected holes at around 0.25 V. Furthermore, the enhanced low-triggering potential around 0.57 V and NIR ECL around 835 nm of MSA/Cit@AuNCs was eventually obtained with the reductive tert-butylamine borane or N2H4·H2O containing a −C–N single-bond structure merely as coreactant. The low-triggering potential ECL of MSA/Cit@AuNCs/tert-butylamine borane system at 0.57 V can be harnessed to selectively determine a carcinoembryonic antigen (CEA) with one linear range spanning from 2 to 20000 fg/mL and a limit of detection of 0.33 fg/mL (S/N = 3). This study will contribute to a more comprehensive understanding of the ECL mechanism in terms of both regulating NCs and selecting coreactants.

研究领域: 分析化学 · 纳米技术 · 生物化学 · 生物医学工程
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TALANTA · 2024 · IF 5.6

An ultrasensitive solid-state electrochemiluminescence sensor based on Ni-MOF@Ru(bpy)32+ and Au NPs@TiO2 for determination of permethrin

Shuning Yang,Li Tian,Weiwei Fu,Huiling Li,Chao Li,Yujia Song,Ruidan Li,Yanjia Guo,Lun Zhao

The novel TiO 2 and Ni-MOF materials were synthesized and utilized for the detection of permethrin (PET). A highly sensitive solid-state electrochemiluminescence (ECL) sensor was developed based on Ni-MOF@Ru(bpy) 3 2+ and Au NPs@TiO 2 . In this sensing platform, Ru(bpy) 3 2+ -Tripropyl Amine (TPrA) was used as a luminescent signal, Ni-MOF acted as a carrier to carry more luminescent reagents Ru(bpy) 3 2+ . Au NPs acted as promoters facilitated electron transport and TiO 2 could further enhance the luminescence intensity of the system by synergistical interaction with Au NPs. The possible mechanisms of signal amplification were investigated. The ECL intensity decreased significantly with increasing PET concentration, enabling the determination of PET amount through the observation of the change in ECL signal intensity (ΔI). Under optimal experimental conditions, the linear range of PET concentration from 1.0 × 10 −11  mol L −1 to 1.0 × 10 −6  mol L −1 , with a detection limit of 3.3 × 10 −12  mol L −1 (3S/N). This method was successfully applied to determine PET in various vegetable samples.

研究领域: 分析化学 · 环境科学 · 食品科学
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ANALYTICAL CHEMISTRY · 2024 · IF 6.7

An Electrochemiluminescent Sensor Based on Glycosyl Imprinting and Aptamer for the Detection of Cancer-Related Extracellular Vesicles

Zejun Jiang,Kui Luo,Guangwei Yang,Yang Li,Ling Li,Guocong Wang,Tao Qin,Jianping Li

Cancer-related extracellular vesicles (EVs) are considered important biomarkers for cancer diagnosis because they can convey a large amount of information about tumor cells. In order to detect cancer-related EVs efficiently, an electrochemiluminescence (ECL) sensor for the specific identification and highly sensitive detection of EVs in the plasma of cancer patients was constructed based on dual recognitions by glycosyl-imprinted polymer (GIP) and aptamer. The characteristic glycosyl Neu5Ac-α-(2,6)-Gal-β-(1–4)-GlcNAc trisaccharide on the surface of EVs was used as a template molecule and 3-aminophenylboronic acid as a functional monomer to form a glycosyl-imprinted polymer by electropolymerization. After glycosyl elution, the imprinted film specifically recognized and adsorbed the EVs in the sample, and then the CD63 aptamer–bipyridine ruthenium (Aptamer–Ru(bpy)) was added to combine with the CD63 glycoprotein on the extracellular vesicle’s surface, thus providing secondary recognition of the EVs. Finally, the EVs were quantitatively detected according to the ECL signal produced by the labeled bipyridine ruthenium. When more EVs were captured by the imprinted film, more probes were obtained after incubation, and the ECL signal was stronger. Under the optimized conditions, the ECL signal showed a good linear relationship with the concentration of EVs in the range of 9.5 × 102 to 9.5 × 107 particles/mL, and the limit of detection was 641 particles/mL. The GIP sensor can discriminate between the EV contents of cancer patients and healthy controls with high accuracy. Because of its affordability, high sensitivity, and ease of use, it is anticipated to be employed for cancer early detection and diagnosis.

CAS / MDL: 30418-59-8 102-69-2
研究领域: 生物医学工程 · 分析化学 · 肿瘤学
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Journal of the American Chemical Society · 2024 · IF 14.4

Controllable and Low-Loss Electrochemiluminescence Waveguide Supported by a Micropipette Electrode

Yingying Xu,Xiaojin Huang,Yulan Wang,Weiyu Qu,Weiliang Guo,Bin Su,Zhihui Dai

One-dimensional molecular crystal waveguide (MCW) can transmit self-generated electrochemiluminescence (ECL), but heavy optical loss occurs because of the small difference in the refractive index between the crystal and its surroundings. Herein, we report a micropipette electrode-supported MCW (MPE/MCW) for precisely controlling the far-field transmission of ECL in air with a low optical loss. ECL is generated from one terminal of the MCW positioned inside the MPE, which is transmitted along the MCW to the other terminal in air. In comparison with conventional waveguides on solid substrates or in solutions, the MPE/MCW is propitious to the total internal reflection of light at the MCW/air interface, thus confining the ECL efficiently in MCW and improving the waveguide performance with an extremely low-loss coefficient of 4.49 × 10–3 dB μm–1. Moreover, by regulation of the gas atmosphere, active and passive waveguides can be resolved simultaneously inside MPE and in air. This MPE/MCW offers a unique advantage of spatially controlling and separating ECL signal readout from its generation, thus holding great promise in biosensing without or with less electrical/chemical disturbance.

研究领域: 分析化学 · 生物传感 · 材料科学
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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH · 2024 · IF 3.8

Continuous-Flow Photobromination/Debromination Cascade for Synthesis of the Trifloxystrobin Intermediate

Fujun Li,Peihao Cheng,Xinghai Li,Yun Zou,Shengyang Tao

Bromination reactions involving bromine monomers tend to be polybrominated, resulting in poor product selectivity and subsequent separation difficulties. This proposal outlines a multistep cascade for continuous flow synthesis involving photobromination and debromination. The process comprises five units: bromine generation, photobromination, quenching, water/oil separation, and photodebromination. A full-process continuous and efficient synthesis of the trifluorostrolibin intermediate (E)-Methyl-2-(2-broMoMethylphenyl)-2-MethoxyiMinoacetate (MBPA) was achieved. This process converts the byproduct (E)-Methyl-2-(2-dibroMoMethylphenyl)-2-MethoxyiMinoacetate into the target product MBPA. At a total residence time of 12.9 min, the conversion of (E)-Methy-2-(methoxyimino)-2-(o-toly) acetate reached 99.0%, and the total yield of MBPA reached 94.2%. Machine learning and quantum chemical calculations enhance the comprehension of photodebromination mechanisms. Simultaneously, through comprehensive simulations involving sensitivity and scenario analyses, the optimization of photon utilization emerged as a pivotal factor for improving the overall applicability of the production process. This method of synthesizing halogenated products is anticipated to play a crucial role in pharmaceuticals or pesticides.

研究领域: 有机化学 · 农药合成 · 制药工程
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ANALYTICAL CHEMISTRY · 2024 · IF 6.7

Conductivity-Regulated Bipolar Electrochemiluminescence Sensing Platform for Indicator-Free Homogeneous Bioassay

Jiancong Ni,Bifang Yang,Liyang Liu,Xiaohui Dai,Weiqiang Yang,Qingxiang Wang,Xiaoping Chen,Zhiping Song,Zhenyu Lin

Electrochemiluminescence (ECL) sensors have been widely developed because of their high sensitivity and low background. However, most of them suffered from tedious probe modification on the electrode and cross-interferences within the sensing and reporting reactions. The bipolar electrode based ECL (BPE-ECL) can effectively eliminate interference by physically separating the sensing and reporting cells, but there is still a need for exogenous electroactive indicators to transduce the variations between two poles of a BPE. Herein, based on the discovery that conductivity can be regulated in aqueous medium by homogeneous bioreaction, we showed a novel BPE-ECL sensing platform that combined the conductivity-based biosensing technology with ECL reporting system for the first time. Compared to many short nucleic acids, the target induced a hybridization chain reaction to produce the long nucleic acid aggregates, resulting in a conductivity decrease of the sensing cell and finally reducing the ECL response in the reporting cell. The BPE-ECL platform has already been applied to detect microRNA-21 for a demonstration. This innovative system not only separates the target sensing and reporting reactions but also avoids the use of electrochemical indicators for measurement. The BPE-ECL biosensing platform can be developed to detect different targets by changing the probe used.

CAS / MDL: 16903-35-8 102-69-2
研究领域: 分析化学 · 生物化学 · 生物技术 · 分子生物学
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LANGMUIR · 2025 · IF 3.9

Tailored Noble Metal Nanoarrays via Nanoxerography

Ying Wei,Zhouzhou Zhu,Jiahao Pan,Yuchen Zhang,Weihua Zhang,Zhenda Lu

Noble metal nanoarrays have become essential in fields such as bioanalysis, catalysis, and optoelectronics. Their unique properties, often tuned through precise control of the size, morphology, and metal composition, have driven significant advancements. This research introduces atomic force microscopy (AFM)-assisted nanoxerography as a versatile technique for fabricating customizable noble metal nanoarrays. By integrating nanoxerography with in situ growth and annealing, we demonstrated precise control over spot dimensions, structural features, and metal diversity. The nanoscale precision of AFM scanning enables the creation of arbitrary patterns and the hybridization of various materials. The high tunability and efficiency of nanoxerography provide promising avenues for advancing applications of noble metal nanoarrays across diverse scientific application.

研究领域: 材料科学 · 纳米技术 · 生物分析 · 催化 · 光电子学
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JOURNAL OF ELECTROANALYTICAL CHEMISTRY · 2024 · IF 4.1

Electrochemiluminescent properties of CdTe quantum dots in different potential ranges and their application to the ultra-sensitive detection of phenylephrine hydrochloride and paliperidone

Shuangshuang Tian,Liqiang Chen,Hong Zhang,Liangquan Sheng,Xinxin Wang,Deqian Huang

CdTe quantum dots (CdTe QDs) were synthesized using mercaptopropionic acid (MPA) as a stabilizer. The electrochemiluminescence (ECL) mechanism of CdTe QDs was examined at cathodic (−2.1 to 0 V) and anodic (0–1.5 V) potentials. Utilizing dissolved oxygen as a co-reactant for cathodic CdTe QDs, the addition of phenylephrine hydrochloride (PEH) triggers a burst effect on the intermediate OH at the electrode surface, resulting in a reduction of electron hole formation. Consequently, a novel method for detecting PEH in the concentration range of 0.2–10 μM has been developed. A strong linear correlation was observed between Lg C PEH and the ECL intensity ratio ( I/I 0 ) of cathodic CdTe QDs, with a detection limit of 37 nM. Tri- n -propylamine (TPrA) was utilized as a co-reactant for the anode of CdTe QDs. The addition of paliperidone (PP) occupies the oxidized vacancies of TPrA, leading to a diminished ECL signal. A new method was subsequently established to detect PP in the concentration range of 0.2 nM–1.0 μM with a detection limit of 18 pM. This method has been successfully applied to detect PEH in urine and in compound tropicamide eye drops, as well as to quantify PP content in paliperidone sustained-release tablets and serum, demonstrating excellent recovery and selectivity.

研究领域: 分析化学 · 生物医学工程
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DALTON TRANSACTIONS · 2024 ·Vol. 53 ·期 11 ·5284-5290 · IF 3.5

Electrochemiluminescence of iridium(III)/ruthenium(II) complexes with naphthyl tags in solutions and host–guest thin films

Weiyu Qu,Xinrui Yang,Xiaojin Huang,Weiliang Guo,Zhihui Dai

Herein we report electrochemiluminescence (ECL) generation from three new iridium(III)/ruthenium(II) (Ir(III)/Ru(II)) complexes with naphthyl (nap) tags in solutions and host–guest thin films. In comparison with its parent structure, the addition of a nap tag to [4-(2-naphthalenyl)-1,10-phenanthroline]bis(2,2′-bipyridine)ruthenium(II) results in a 6.1-fold enhancement in the ECL efficiency. Moreover, the nap tag enables the non-covalent immobilization of Ir(III)/Ru(II) complexes via host–guest interactions. Therefore, a molecular thin film was constructed by hydrophobic effects between the cavity of β-cyclodextrin and the nap tags, which emits stable and strong ECL emission in the presence of tri-n-propylamine (TPrA). These results give a mechanistic insight into ECL generation from (Ir(III)/Ru(II)) complexes with host–guest recognition tags and may help in the development of host–guest thin film-based ECL sensors.

研究领域: 分析化学 · 材料科学
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