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ANALYTICAL LETTERS · 2019 · IF 1.248

Electrochemical Determination of Aflatoxin B1 (AFB1) Using a Copper-Based Metal-Organic Framework (Cu-MOF) and Gold Nanoparticles (AuNPs) with Exonuclease III (Exo III) Assisted Recycling by Differential Pulse Voltammetry (DPV)

Chunyan Wang,Hui Zhang,Xiaoqing Jiang,Bo Zhou

A sensitive electrochemical biosensor was designed for determination of aflatoxin B1 (AFB1) using a copper-based metal-organic framework (Cu-MOF), which has strong electrochemical activity and exonuclease III (Exo III)-assisted recycling for dual signal amplification. Hairpin DNA (S1) was immobilized on the electrode. The AFB1 was recognized by aptamer DNA (S2) and complementary DNA (S3) was released. The S3 hybridized with the hairpin S1 to form the Exo III hydrolyzed double-stranded DNA, leaving a partial sequence of hairpin DNA (S1′) on the electrode and releasing S3 for the next cycle of the opening and digestion of hairpin S1. The amplified S1′ then was able to combine with more signal probes. Cu-MOF bond gold nanoparticles (AuNPs) by -NH2 were immobilized to capture DNA (S4) to obtain Cu-MOF/AuNPs/S4. This signal probe Cu-MOF/AuNPs/S4 was able to hybridize with the electrode and generate an amplified electrochemical signal. Under the optimized conditions, this electrochemical biosensor for AFB1 exhibited a low detection limit of 6.7 × 10−7 ng/mL at a signal-to-noise equal to 3 and a wide linear range from 10−6 to 1 ng/mL. The biosensor was also used to analyze AFB1-spiked beer sample with recovery values between 96% and 103%. This method has the potential to become a valuable technology for detecting various toxins by the selection of the appropriate aptamer DNA.

研究领域: 分析化学 · 生物技术 · 食品安全 · 环境科学
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JOURNAL OF APPLIED ELECTROCHEMISTRY · 2022 ·Vol. 52 ·期 11 ·1607-1616 · IF 2.925

Facile synthesis of Co3O4/C porous polyhedrons for voltammetric determination of quercetin in human serum and urine

Zhang Yi,Zhang Liwen,Gong Tingcui,Li Tianhao,Li Xuenuan,Feng Jun,Tang Tingfan,Cheng Hao

Due to the highly porous structure, metal organic framework (MOF)-derived materials are extensively applied in the field of electroanalysis. In this experiment, an effective electrochemical sensing based on Co 3 O 4 /C-derived ZIF-67 MOF had been constructed for ultrasensitive determination of quercetin at trace level. The resultant Co 3 O 4 /C porous polyhedron of morphology and nanostructure were carefully examined using transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Brunauer–Emmett–Teller (BET) techniques. Differential pulse anodic stripping voltammetry (DPV) method was adopted to analyze quercetin under the optimized conditions. The DPV response of Co 3 O 4 /C film-coated glass carbon electrode (Co 3 O 4 /C/GCE) for quercetin determination was achieved a long linearity ranging from 0.5 to 30 µM, achieving high sensitivity about 1.830 × 10 − 6  A cm − 2 µM − 1 , and the detection limit was calculated to be 0.022 µM (S/N = 3). Besides, the fabricated Co 3 O 4 /C/GCE displayed excellent selectivity, desirable repeatability, and good reproducibility. More importantly, the proposed sensor exhibited satisfactory recovery ranges and accuracy for the determination of trace quercetin in human urine and serum samples, which will make it as an alternative advantageous choice for practical on-site determination. Graphical abstract The porous Co 3 O 4 /C polyhedron derived by ZIF-67 MOF was successfully synthesized. The as-synthesized material was employed to prepare chemically modified electrode for ultrasensitive determination of quercetin. Then the Co 3 O 4 /C-modified glass carbon electrode is displayed good sensitivity and accuracy toward quercetin in urine and serum samples.

CAS / MDL: 693-98-1
研究领域: 电化学 · 材料科学 · 分析化学 · 生物化学
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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES · 2024 · IF 7.7

An enzyme-responsive hydrogel of ferrocene-grafted carboxymethyl chitosan as a soft electrochemical sensor for MMP-9 detection

Jinze Wang,Haiqi Zhang,Hongtao Hu,Sentao Hu,Lie Ma

Matrix metalloproteinase 9 (MMP-9) plays an important role in wound healing. However, overexpression of MMP-9 leads to the degradation of the newly formed extracellular matrix, which delays wound healing, ultimately leading to chronic wounds. Therefore, timely monitoring of the MMP-9 activity using simple, cost-effective methods is important to prevent the formation of chronic wounds. In this work, ferrocene-modified MMP-9 cleavage peptide (Fc-MG) modified carboxymethyl chitosan hydrogels were prepared as electrochemical biosensors. In the presence of MMP-9, the peptide chain is sheared, and the electrochemically active ferrocene segment is released. Therefore, analyzing the electrochemical activity of hydrogels using differential pulse voltammetry (DPV) can be used to determine MMP-9 activity. The results showed that the DPV peaks were correlated with the MMP-9 concentration in phosphate-buffered saline (PBS, pH 7.4) and Dulbecco's modified Eagle's medium (DMEM). Specifically, the corresponding coefficient of determination (R 2 ) were 0.918 and 0.993. The limit of detections were 73.08 ng/mL and 131.71 ng/mL, respectively. Compared with the enzyme-linked immunosorbent assay, the hydrogel biosensor determined the concentration of MMP-9 in solution with simpler steps. This study demonstrates a novel strategy based on Fc-MG-modified hydrogels to monitor MMP-9 activity in cell secretion samples and shows the potential application in chronic wounds.

研究领域: 生物医学工程 · 分析化学 · 伤口愈合 · 生物传感器
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Materials Science & Engineering C-Materials for Biological Applications · 2019 · IF 4.959

Electrochemical endotoxin aptasensor based on a metal-organic framework labeled analytical platform

Yangyang Duan,Nan Wang,Zixu Huang,Hongxiu Dai,Ling Xu,Shengjun Sun,Houyi Ma,Meng Lin

An electrochemical aptasensor for the lipopolysaccharide (LPS) detection was constructed by using copper-based metal-organic framework (Cu-MOF) as a label and the LPS aptamer of specific single-stranded DNA as a probe. The carboxyl-functionalized polypyrrole nanowires (PPy NWs) were synthesized by electrochemical polymerization method, and the amino-terminated aptamer covalently coupling with the carboxyl group of the PPy NWs was immobilized onto the modified electrode. The aptamer can specifically combine with the target LPS molecules, and Cu-MOF was labeled by adsorption based on specific interactions of LPS carbohydrate portions with anionic groups. The fabrication processes of the aptasensor were characterized by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and electrochemical impedance spectroscopy (EIS). Differential pulse voltammetry (DPV) was used to measure electrochemical performance of the aptasensor, and the electrochemical signal can be directly measured by the electrochemical redox reaction of Cu(II)/Cu(I) existed in the Cu-MOF. The electrochemical aptasensor exhibited a high sensitivity toward LPS ranging from 1.0 pg/mL to 1.0 ng/mL with a detection limit of 0.29 pg/mL. Moreover, the developed sensor was found to have good selectivity, stability and regeneration properties, and the sensor also successfully detected LPS in real tap water samples.

研究领域: 分析化学 · 电化学 · 生物传感器 · 环境监测
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ANALYTICAL LETTERS · 2022 · IF 2.267

Novel Electrochemical Sensor for the Determination of Bisphenol A Using a Molybdenum(IV) Sulfide Quantum Dots Polysodium Styrene Sulfonate Functionalized Reduced Graphene Oxide Modified Glassy Carbon Electrode (GCE) by Differential Pulse Voltammetry (DPV)

Haiyang Wang,Yan Wang,Cuijie Zhang

A sensitive electrochemical platform for the determination of bisphenol A (BPA) was constructed. A hybrid of MoS2 quantum dots decorated poly sodium styrene sulfonate functionalized reduced graphene oxide (MoS2 QDS@PSS-rGO) was prepared by a simple method. The hybrid was cast on a bare glassy carbon electrode (GCE) to form the MoS2 QDs@PSS-rGO/GCE. The electrochemical response of BPA on the MoS2 QDs@PSS-rGO/GCE was significantly enhanced compared to the unmodified electrode, indicating that the nanocomposite possessed an electrocatalytic effect. A novel method was established to determine BPA with a detection limit of 0.008 μM. The applicability of the prepared sensor was demonstrated to determine BPA in real samples with high recoveries.

研究领域: 分析化学 · 环境科学 · 材料科学
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MICROCHIMICA ACTA · 2024 ·Vol. 191 ·期 7 ·1-8 · IF 5.3

Atomically Co-dispersed nitrogen-doped carbon for sensitive electrochemical immunoassay of breast cancer biomarker CA15-3

Han Lei,Cai Shuanglong,Chen Xiaogeng

The development of an ultrasensitive and precise measurement of a breast cancer biomarker (cancer antigen 15-3; CA15-3) in complex human serum is essential for the early diagnosis of cancer in groups of healthy populations and the treatment of patients. However, currently available testing technologies suffer from insufficient sensitivity toward CA15-3, which severely limits early large-scale screening of breast cancer patients. We report a versatile electrochemical immunoassay method based on atomically cobalt-dispersed nitrogen-doped carbon (Co-NC)–modified disposable screen-printed carbon electrode (SPCE) with alkaline phosphatase (ALP) and its metabolite, ascorbic acid 2-phosphate (AAP), as the electrochemical labeling and redox signaling unit for sensitive detection of low-abundance CA15-3. During electrochemical detection by differential pulse voltammetry (DPV), it was found that the Co-NC-SPCE electrode did not have a current signal response to the AAP substrate; however, it had an extremely favorable response current to ascorbic acid (AA). Based on the above principle, the target CA15-3-triggered immunoassay enriched ALP-catalyzed AAP produces a large amount of AA, resulting in a significant change in the system current signal, thereby realizing the highly sensitive detection of CA15-3. Under the optimal AAP substrate concentration and ALP catalysis time, the Co-NC-SPCE-based electrochemical immunoassay demonstrated a good DPV current for CA15-3 in the assay interval of 1.0 mU/mL to 10,000 mU/mL, with a calculated limit of detection of 0.38 mU/mL. Since Co-NC-SPCE has an excellent DPV current response to AA and employs split-type scheme, the constructed electrochemical immunoassay has the merits of high preciseness and anti-interference, and its clinical diagnostic results are comparable to those of commercial kits. Graphical abstract

研究领域: 分析化学 · 生物化学 · 电化学 · 癌症诊断
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MICROCHEMICAL JOURNAL · 2021 · IF 4.821

A novel assay strategy based on isothermal amplification and cascade signal amplified electrochemical DNA sensor for sensitive detection of Helicobacter pylori

Xiaojie Song,Man-Man Lv,Qi-Yan Lv,Hui-Fang Cui,Jing Fu,Yu-Yang Huo

A novel and sensitive Helicobacter pylori assay strategy based on linear isothermal amplification reaction (LIAR) and DNAzymes catalyzed DNA sensor was developed. A 17 nt target DNA (tDNA) specific in the H. pylori genome was selected and used as primer in the LIAR. A template DNA was designed to produce an amplicon with Mg 2+ -dependent and RNA-cleaving DNAzyme (Md-Dz) activity. The amplicon (i.e. Md-Dz) was then detected with the DNA sensor. The DNA sensor was fabricated simply through immobilization of a hairpin DNA that contains both Md-Dz substrate and G-quadruplex DNAzyme (Gq-Dz), on gold electrodes. The Gq-Dz possesses peroxidase activity, catalyzing the electro-redox of the electrochemical signal probe hydroquinon. The LIAR, Md-Dz catalytic reaction, and DNA sensor fabrication and detection processes were characterized and optimized. The LIAR amplification efficiency is as high as ~5 × 10 5 fold, and the assay strategy is very sensitive, selective and repetitive. The differential pulse voltammetry (DPV) detection signals linearly correlate to the logarithmic tDNA concentration in the range of 0.1–10,000 fM, with a limit of detection (LOD) of 34 aM. The detection linear range for H. pylori genomic DNA is 2.1–67.2 pg, with an LOD of 1.3 pg . Muted DNA sequences and other pathogenic bacteria did not result in interferences. In addition, the DNA sensor is very stable in storage. More importantly, the DNA sensor and the assay strategy could be universally applicable to detect any biological sample and short DNA sequence of interests.

CAS / MDL: 123-31-9 9002-93-1
研究领域: 生物化学 · 分析化学 · 分子生物学 · 生物技术
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ANALYTICAL LETTERS · 2021 · IF 2.329

Ultrasensitive Electrochemical Immunoassay for Prostate Specific Antigen (PSA) Based Upon Silver-Functionalized Polyethyleneimine (PEI)–Silica Nanoparticles (NPs)

Zheng Chang,Yimeng Xu,Yuting Shen

A novel sandwich-type electrochemical immunosensor was fabricated for the ultrasensitive electrochemical determination of prostate specific antigen (PSA) using silver-functionalized polyethyleneimine (PEI)-silica nanoparticles (NPs) (Ag+/PEI/SiO2 NPs) as electrochemical labels. First, the immunosensor platform was prepared by covalently immobilizing capture antibodies on a poly diallyldimethyl ammonium chloride/carboxylated-gold nanoparticles (PDDA/AuNPs) modified glassy carbon electrode (GCE). After sandwich-type immunoreactions, the detection antibody was labeled by the amino-containing Ag+/PEI/SiO2 NPs by strongly binding to carboxyl groups of protein. Next, many Ag+ with good complexing performance from each PEI/SiO2 nanoparticles released after hydrofluoric acid (HF) in situ etching. Here, the AuNPs acted as a catalyst to reduce Ag+ into metallic Ag using PEI as the reducing agent. Accordingly, an extremely sharp voltammetric peak of electro-oxidized metallic Ag can be determined directly through differential pulse voltammetry (DPV) without metal pre-concentration, and had a close relationship with the concentrations of PSA antigen. Under the optimized conditions, the immunoassay exhibited good sensitivity and selectivity for the determination of PSA with a linear range from 0.01 to 10 pg·mL−1 and a detection limit of 3.5 fg·mL−1. The new strategy provides a reliable, highly sensitive determination of the prostate cancer biomarker in biological samples with great potential for the fabrication of devices for clinical diagnostics.

研究领域: 分析化学 · 生物化学 · 纳米技术 · 生物医学工程 · 临床诊断
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MICROCHIMICA ACTA · 2019 ·Vol. 186 ·期 7 ·1-9 · IF 5.479

A sandwich-type electrochemical aptasensor for the carcinoembryonic antigen via biocatalytic precipitation amplification and by using gold nanoparticle composites

Xu Lingling,Liu Zi,Lei Sheng,Huang Di,Zou Lina,Ye Baoxian

A sandwich-type electrochemical aptasensor is described for detecting the carcinoembryonic antigen (CEA) with high sensitivity and accuracy. Two kinds of nanomaterials are used. The first was obtained by modifying gold nanoparticles with reduced graphene oxide and hemin (Hemin-rGO-AuNPs). The second consists of horseradish peroxidase-modified organic-inorganic hybrid nanoflowers linked to gold nanoparticles to obtain an architecture of type HRP-Cu 3 (PO 4 ) 2 -HNF-AuNPs). These serve as carriers for two aptamers (apt1 and apt2) against CEA. Simultaneously, they were used to catalyze the precipitation reaction between 4-chloro-1-naphthol(4-CN) and H 2 O 2 . A sandwich-type assay linked to enzyme inhibition amplification was established for electrochemical determination of CEA. Under optimal experimental conditions and by using differential pulse voltammetry, the response peak currents (best measured at −0.34 V vs. Ag/AgCl) increases linearly with the logarithm of the CEA concentration in the range between 100 fg mL −1 and 100 ng mL −1 . The detection limit is as low as 29 fg mL −1 . Schematic representation of the sandwich-type electrochemical aptasensor based on signal inhibition amplification from biocatalytic precipitation reaction. (HRP-Cu 3 (PO 4 ) 2 hybrid nanoflowers: Horseradish Peroxidase-Cu 3 (PO 4 ) 2 hybrid nanoflowers; AuNPs: Gold Nanoparticles; Hemin-rGO-AuNPs: Hemin-Reduced Graphene Oxide-Gold Nanoparticles; BSA: Bovine Serum Albumin; CEA: Carcinoembryonic Antigen; CEA apt1 : 5′-SH-(CH 2 ) 6 -ATA CCA GCT TAT TCA ATT-3′; CEA apt2 : 5′-NH 2 -(CH 2 ) 6 -AGG GGG TGA AGG GAT ACC C-3′; GCE: Glassy carbon electrode; 4-CN: 4-Chloro-1-naphthol; DPV: Differential pulse voltammetry).

CAS / MDL: 51805-45-9
研究领域: 生物化学 · 分析化学 · 纳米技术 · 癌症诊断
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ELECTROANALYSIS · 2020 ·Vol. 32 ·期 8 ·1772-1779 · IF 2.544

Fabrication of Superoxide Dismutase (SOD) Imprinted Poly(ionic liquid)s via eATRP and its Application in Electrochemical Sensor

Yifei Yang,Yue Sun,Mingzhu Jin,Ru Bai,Yutong Liu,Yingqi Wu,Wei Wang,Xuewei Feng,Siyu Li

Superoxide dismutase (SOD) plays an important role in nearly all living cells. In this study, SOD imprinted poly(ionic liquid)s (SIPILs) were prepared on the surface of the bare Au electrode modified with nano-palladium and nano-gold (Au/nPd/nAu/SIPILs). SIPILs was synthesized with 1-vinyl-3-propyl imidazole sulfonate ionic liquids as functional monomers via electrochemically mediated atom transfer radical polymerization (eATRP) catalyzed by SOD. The Au/nPd/nAu/SIPILs was examined by cyclic voltammetry (CV), scanning electron microscope (SEM), energy-dispersive spectrometer (EDS) and X-ray photoelectron spectroscopy (XPS). The Au/nPd/nAu/SIPILs was also used as an electrochemical sensor to determine SOD by differential pulse voltammetry (DPV). Under the optimal conditions, the detection range of SOD was from 1.0×10 −8 to 1.0×10 2 mg L −1 with a limit of detection of 8.90×10 −9 mg L −1 (S/N=3). Compared with other methods, the sensor based on SIPILs had the broader linear range and lower detection limit.

CAS / MDL: 52-90-4 16903-35-8
研究领域: 分析化学 · 材料科学 · 电化学 · 生物传感器
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SENSORS AND ACTUATORS B-CHEMICAL · 2019 · IF 6.393

A multiple signal amplification based on PEI and rGO nanocomposite for simultaneous multiple electrochemical immunoassay

Xiaoqing Zhao,Jing Wang,Hou Chen,Hui Xu,Liangjiu Bai,Wenxiang Wang,Huawei Yang,Donglei Wei,Baiqing Yuan

A novel electrochemical immunoassay platform for multi-signal amplification has been constructed and applied to the simultaneous detection of three tumor markers (TMs). The platform was successfully developed by polyethyleneimine (PEI)-polydopamine (PDA)/reduced graphene oxide (rGO) nanocomposites. PDA/rGO as the substrates can simultaneously load with detection antibodies (Ab 2 ) and large amounts of PEI, which PEI were further used to immobilize different signal labels. Three TMs of carcinoembryonic antigen (CEA), prostate specific antigen (PSA) and alpha fetoprotein (AFP) were employed as potential factors. Ferrocenecarboxylic acid (Fc), anthraquinone-2-carboxylic acid (Aq) and acetylsalicylic acid (ASA) were employed as distinguishable signal labels. Electrochemical responses of designed sandwich-type immunosensor were successfully investigated by cyclic voltammetry (CV) and differential pulse voltammetry (DPV). The multiplexed immunoassay displayed excellent linear response in the range of 0.102 pg/mL–112 ng/mL for CEA and PSA, 0.117 pg/mL–117 ng/mL for AFP. The detection limit of three TMs were 91 fg/mL, 101 fg/mL and 83 fg/mL for CEA, PSA and AFP, respectively. Moreover, this electrochemical immunoassay platform exhibited excellent reproducibility, sensitivity and selectivity for the simultaneous detection of multiple biomarkers.

CAS / MDL: 9002-98-6
研究领域: 生物医学工程 · 分析化学 · 纳米技术 · 电化学 · 生物传感器
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SENSORS AND ACTUATORS B-CHEMICAL · 2024 · IF 8

Development of a dual-mode Ru-UiO-TPEA MOF probe for highly sensitive and accurate detection of Cu2+ in biological systems

Qian Long,Hanfeng Cui,Jing Zhang,Qiqi Fan,Ting Huang,Hai Shuai,Xiaocui Yin,Guobing Wei,Huanwen Chen,Hao Fan

Cu 2+ serves as a significant biomarker in various physiological processes. This study presents the development of a novel Ru-UiO-TPEA functionalized metal-organic framework (MOFs) probe for Cu 2+ detection, employing both electrochemiluminescence (ECL) and electrochemical (EC) methods. Employing a dual ligand-assisted energy transfer approach, we synthesized Ru-UiO with optimal ECL and EC properties by adjusting the synthesis ratio of biphenyldicarboxylic acid to Ru(dcbpy) 3 2+ . This was followed by its conjugation with N-(2-aminoethyl)-N, N′, N′-tris(pyridin-2-ylmethyl) ethane-1,2-diamine (AE-TPEA) to form the highly conjugated Ru-UiO-TPEA probe for Cu 2+ detection. As the Cu 2+ concentration increased, the probe exhibited a diminished ECL signal and an enhanced differential pulse voltammetry (DPV) signal. The dual-mode detection method enabled cross-validation of the ECL and EC signals, enhancing accuracy and effectively minimizing errors. The ECL and EC methods had detection limits of 0.26 nM (range: 1 nM to 10 μM) and 0.65 nM (range: 2 nM to 80 μM), respectively. Meanwhile, these two methods can effectively detect Cu 2+ in rat brain microdialysis fluid. Notably, the measured concentrations correlated well with those determined by Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES), highlighting its potential in biological and clinical bioelectronic sensing applications.

研究领域: 分析化学 · 生物化学 · 生物医学工程 · 材料科学
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