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SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY · 2024 · IF 4.3

Robust and sensitive colorimetric detection of glutathione with double-triggering MOF-Fe(DTNB)

Kaining Zhang,Hao Sun,Long Wei,Rui Hu,Hao Liu,Yongchao Lai,Xun Li

Glutathione (GSH) levels have been well validated to correlate with a variety of physiological and pathological conditions, such as malignancy, cardiovascular disease and aging, making the development of accurate, robust and sensitive GSH detection methods highly desirable. In this study, a novel metal–organic framework (MOF-Fe(DTNB))-based colorimetric method with a favorable dual-triggering function was proposed. MOF-Fe(DTNB) exhibits high peroxidase activity, which can catalyze the oxidation of colorless 3,3′,5,5′-tetramethylbenzidine (TMB) to blue ox-TMB by hydrogen peroxide (H 2 O 2 ). This oxidation process of TMB can be inhibited not only by the reducing action of GSH, but also by the thiol exchange reaction between DTNB and GSH, in which the disulfide bond of DTNB in MOF-Fe(DTNB) is cleaved. Thus, with this dual triggering mechanism, the GSH concentration can be robustly measured in the MOF-Fe(DTNB)-derived colorimetric strategy. Significantly, this method is accurate (RSD < 6 %), selective and sensitive in biological plasma samples, with satisfactory recovery rates (96.7–103.3 %). It requires less instrumentation and has less interference from other substances. The linear range of the method is 0–80 µM, and the detection limit is as low as 0.28 µM. This dual-triggering MOF-Fe(DTNB)-derived colorimetric strategy has greatly simplified the GSH detection processes with improved accuracy, in both acidic and basic environments, which has potent applications in biochemical analysis and point-of-care testing.

研究领域: 生物化学 · 分析化学 · 即时检测
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Science China-Chemistry · 2023 · IF 9.6

Raman imaging analysis of intracellular biothiols independent of the aggregation of sensing substrates

Zhang Min,Li Zijun,Zhang Mengyang,Heng Hang,Xu Shiying,Wang Zhaoyin,Dai Zhihui

The content of biothiols in cells is highly associated with the occurrence and development of several diseases. However, due to their active chemical properties, thiol-contained molecules are normally volatile during the detection process, rendering precise analysis of intracellular biothiols challenging. In this study, 5,5′-dithiobis-(2-nitrobenzoic acid) (DTNB) is covalently modified on the surface of gold nanorods (AuNRs), constructing sensing substrates for in situ Raman imaging analysis of biothiols in cells. AuNRs are able to serve as ideal surface-enhanced Raman scattering substrates, and thus Raman signals of DTNB are greatly amplified by AuNRs. Meanwhile, the disulfide bond of DTNB can be broken by thiols, thereby releasing part of DTNB from the surface of AuNRs. As a result, three kinds of main biothiols are sensitively quantified with DTNB-modified AuNRs according to the variation of Raman signals, and DTNB-modified AuNRs exhibit far better analytical performance than a commercial probe. In addition, the sensing substrates can be readily delivered to cytoplasm with the transmembrane of AuNRs, and are capable of responding to biothiols in cells. Notably, the Raman approach is established by the breaking of chemical bonds rather than the aggregation of substrates, which is more inclined to analyze intracellular biothiols with a desirable spatial resolution. Therefore, fluctuation of biothiols in glioma cells is evidently observed via Raman imaging. Overall, this work provides an alternative strategy for designing Raman sensors to visualize active molecules in cells.

研究领域: 分析化学 · 生物医学工程 · 细胞生物学
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NEW JOURNAL OF CHEMISTRY · 2022 ·Vol. 46 ·期 17 ·8022-8028 · IF 3.925

Fluorimetric and ratiometric colorimetric dual-mode detection of organophosphorus pesticides based on carbon dots/DTNB

Yaoyao Feng,Yujiao Qu,Xiaobo Sun,Wei Pan,Jinping Wang

In this work, a fluorimetric and ratiometric colorimetric dual-mode detection method was developed for the detection of organophosphorus pesticides (OPs) based on carbon dots (CDs)/5,5-dithiobis-(2-nitrobenzoic acid) (DTNB). Its main mechanism is that OPs inhibit the catalysis of acetylcholinesterase (AChE) in the hydrolysis of acetylthiocholine (ATCh) to form thiocholine (TCh). It specifically reacts with DTNB which has a characteristic absorption band at 325 nm to produce 5-thio-2-nitrobenzoic acid (TNB) with an absorption peak at 410 nm overlapped with the excitation spectrum of the CDs. Thus, TNB can exert an inner filter effect (IFE) on the CDs. Upon the addition of chlorpyrifos (CPF, a representative of OPs), the activity of AChE is gradually inhibited, resulting in an increase in absorbance at 325 nm and a decrease in absorbance at 410 nm, as well as a weakening of the IFE on the CDs. Therefore, a good linear relationship between the fluorescence intensity of the CDs and the logarithm of the concentration of CPF was established in a broad range from 0.3 to 200 ng mL−1 with a limit of detection (LOD) of 0.081 ng mL−1. Furthermore, an excellent linear relationship was fitted between the ratio of absorbance at 410 nm to that at 325 nm (R410/325) and the logarithm of the concentration of CPF in the range of 0.3–200 ng mL−1 with a LOD of 0.054 ng mL−1. The proposed dual-mode method could recover CPF from the tap water and pork samples in the range from 93.3% to 108.8%. Therefore, it can be potentially developed as a reliable detection method for OPs with high selectivity, sensitivity and accuracy.

研究领域: 分析化学 · 环境科学 · 食品科学 · 农药检测
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FOOD CHEMISTRY · 2025 · IF 9.8

Multifunctional au-DTNB-ag nanoparticles immunoprobes based on color-Raman properties for lateral flow immunoassay detection of Glycinin

Peng Bo Huang,Jing Long Qu,Shuo Yang,Tian Jiao Shui,Huan Huan Yang,Li Ping Cheng,Yang Qin,Jun Xi

Glycinin is a common food allergen, which may cause allergic shock in severe cases, thus posing a threat to public health. Therefore, rapid and accurate detection of glycinin is crucial. In this study, we synthesized Au Ag core–shell nanoparticles loaded with the Raman reporter molecule 5,5′-dithiobis(2-nitrobenzoic acid) (DTNB), which provides both colorimetric and Raman signal capabilities. These nanoparticles were applied to colorimetric lateral flow immunoassay (CM-LFIA) and surface-enhanced Raman scattering-based lateral flow immunoassay (SERS-LFIA), respectively. The CM-LFIA achieved a visual limit of detection (LOD) of 1 ng/mL, while the SERS-LFIA exhibited a LOD of 40 pg/mL, with good linearity over the range of 1 ng/mL to 10 4  ng/mL (R 2  = 0.997). Moreover, the quantitative SERS-LFIA demonstrated satisfactory performance in spiked food matrix samples, achieving acceptable recoveries of 82–88 % and RSD ranging from 4.88 % to 6.97 %.

研究领域: 食品科学 · 免疫学 · 纳米技术
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SENSORS · 2025 ·Vol. 25 ·期 8 ·2457 · IF 3.5

SERS-Based Immunochromatographic Assay for Sensitive Detection of Escherichia coli O157:H7 Using a Novel WS2-AuDTNB Nanotag

Deying Wang,Yan Chen,Qi Zhang,Junfei Chen,Changhao Li,Yunjing Luo,Yong Jin,Xiaohua Qi

HighlightsWhat are the main findings?Developed a novel WS2-Au nanocomposite coupled with 5,5′-dithiobis-(2-nitrobenzoic acid) (DTNB) and antibodies as sensitive surface-enhanced Raman scattering (SERS) nanotags forE. coliO157:H7 detection.Demonstrated a broad linear detection range (8 × 102–8 × 107CFU/mL), a low detection limit (175 CFU/mL), high specificity and good accuracy in real food samples (milk, pork).What are the implications of the main findings?A rapid assay for qualitative and quantitative detection ofE. coliO157:H7, overcoming limitations of traditional ICA methods.A cost-effective, user-friendly surface-enhanced Raman scattering (SERS)-based immunochromatographic assay (SERS-ICA) platform with great potential for point-of-care testing and detection of other foodborne pathogens.E. coliO157:H7 contamination in food and the environment poses a serious threat to human health. Rapid and sensitive identification of foodborne pathogens remains challenging. Here, we prepared tungsten disulfide (WS2)–Au nanocomposites coupled with the Raman signal molecule 5,5′-dithio-bis-(2-nitrobenzoic acid) (DTNB) and antibodies to replace the conventional colloidal gold nanoparticles and applied SERS-active nanotags in the SERS-ICA method for highly sensitive detection ofE. coliO157:H7. The large surface area and numerous effective SERS hotspots of WS2-Au nanotags provide superior SERS signals. Under optimized conditions, this ICA achieves the quantitative detection ofE. coliO157:H7 in a broad linear range of 8 × 102–8 × 107CFU/mL and at a low detection limit of 175 CFU/mL. In addition, the test strip indicates high specificity forE. coliO157:H7 identification, favorable reproducibility, and shows good accuracy in the detection of actual food samples, such as milk and pork. The proposed assay can be used for rapid qualitative and quantitative detection ofE. coliO157:H7 and has great potential for field application.

CAS / MDL: 552-16-9 9005-64-5
研究领域: 食品科学 · 分析化学 · 微生物学
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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2023 · IF 9.9

Magnetic polyphosphazene@Au particles as substrates for multiple-detection of immunoproteins by surface-enhanced Raman spectroscopy

Lijun You,Baohua Zhong,Ci Huang,Jumei Li,Zhijuan Zheng,Yang Wang

Au coated magnetic polyphosphazene (MPCTP) composite particles ( [email protected] ) were fabricated with sensitive SERS activity. The MPCTP particles were generated by coating polyphosphazene on Fe 3 O 4 nanoparticles through precipitation polycondensation of hexachlorocyclotriphosphazene and phloroglucinol . [email protected] composite particles were obtained by deposition of Au nanoparticles on MPCTP by the reduction of HAuCl 4 . The size and the thickness of the Au shell can be controlled by varying the amount of HAuCl 4 . The magnetic core endowed the composite particles with good magnetic responsiveness, which allowed the analyte to be enriched and separated from the complex matrix, and significantly simplifying the sample pretreatment procedure. The SERS activity of [email protected] composite particles were evaluated by DTNB as model Raman reporter, and the limits of detection (LOD) of DTNB was 10 -8 mol/L. A high efficient SERS immunoassay system based on the [email protected] substrates for the detection of immunoproteins was developed. Human IgG and rabbit IgG were quantitatively determinated simultaneously by this immunoassay system. The quantitative determination of the immunoglobulin G (IgG) was achieved and the LOD of human IgG, rabbit IgG and the mixture of human IgG and rabbit IgG were as low as 10 fg/mL, 100 pg/mL and 1 ng/mL, respectively. The results showed that the [email protected] composite particles have broad application prospects as high performance SERS active substrates for immunoprotein analysis.

研究领域: 材料科学 · 分析化学 · 生物技术
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Food Analytical Methods · 2024 · IF 2.6

A SERS and Fluorescence Dual-Signal Aptasensor for AFB1 Detection Based on DTNB Labeled AuNPs and CdTe Quantum Dots

Ma Xiaoyuan,Wei Jinxiang,Jiang Caiyun,Wang Zhouping

Herein, an aptasensor with stable surface-enhanced Raman scattering (SERS) and fluorescence dual-signal output had been developed for the detection of aflatoxin B 1 (AFB 1 ). The quantum dots were encapsulated within silica to ensure the stability of fluorescence signal. The gold nanoparticles (AuNPs) were modified with SERS signal molecule DTNB and the complementary sequence (cDNA) of AFB 1 aptamer and then connected on the surface of silica to obtain the signal probes. In the meantime, Fe 3 O 4 was coated with silica which was modified with aptamer to gain capture probes. The two probes could bind specifically based on the base complementary pairing principle. Then, the mixture was separated and gathered by an external magnet. At this time, the maximum SERS signal could be detected in the precipitate, and there was no fluorescence signal in the supernatant. Upon introduction of AFB 1 into the system, the signal probes would be released, resulting in fluorescence recovery in the supernatant while SERS signal weakened in the precipitate. The developed method showed a linear relationship of AFB 1 for the SERS signal in the range of 10 −4 –10 3  ng/mL, with a detection limit of 0.087 pg/mL. The linear range for the fluorescence signal was from 10 −4 to 10 2  ng/mL, with a detection limit of 0.100 pg/mL. The proposed technique was highly sensitive and accurate, which showed promising application prospects in food safety detection.

研究领域: 食品安全检测 · 生物传感技术 · 纳米技术
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FOOD CONTROL · 2023 · IF 6

Satellite nanostructures composed of CdTe quantum dots and DTNB-labeled AuNPs used for SERS-fluorescence dual-signal detection of AFB1

Jinxiang Wei,Yifei He,Zhiyi Song,Imran Mahmood Khan,Zhouping Wang,Caiyun Jiang,Xiaoyuan Ma

Herein, a surface-enhanced Raman scattering (SERS) and fluorescence dual-signal aptasensor has been developed for aflatoxin B 1 (AFB 1 ) detection. Fluorescence signal source CdTe quantum dots were decorated on the outer of silica nanoparticles and further functionalized with AFB 1 aptamer. Raman reporter molecules DTNB were decorated on the surface of gold nanoparticles (AuNPs) together with the aptamer complementary chains. The two parts of nanomaterials were combined by the base complementary pairing principle, to form satellite nanostructures with high SERS and low fluorescence signals following LSPR and FRET effect. The addition of AFB 1 led to the shedding of AuNPs due to the higher sensitivity of the aptamer towards the target and resulting in recovered fluorescence and decreased SERS signals. The developed method showed a linear relationship in the range of 10 −4 -10 3  ng/mL, with detection limit of 0.094 pg/mL. This technology had strong application prospects due to simplicity of operation and high accuracy.

研究领域: 分析化学 · 食品安全 · 纳米技术
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Nanomaterials · 2024 ·Vol. 14 ·期 12 ·1046 · IF 4.4

Preparation of Hybrid Magnetic Nanoparticles for Sensitive and Rapid Detection of Phorate Residue in Celery Using SERS Immunochromatography Assay

Xiangyang Li,Hean Qian,Jin Tao,Mingshuo Cao,Meng Wang,Wenlei Zhai

Extensive use of pesticides in agricultural production has been causing serious health threats to humans and animals. Among them, phorate is a highly toxic organophosphorus insecticide that has been widely used in planting. Due to its harmful effects on human and animal health, it has been restricted for use in many countries. Analytical methods for the rapid and sensitive detection of phorate residues in agricultural products are urgently needed. In this study, a new method was developed by combining surface-enhanced Raman spectroscopy (SERS) and immunochromatography assay (ICA). Hybrid magnetic Fe3O4@Au@DTNB-Ab nanoprobes were prepared by modifying and growing Au nanoseeds on an Fe3O4core. SERS activity of the nanoprobe was optimized by adjusting the concentration of the Au precursor. A rapid and sensitive assay was established by replacing the traditional colloidal gold-based ICA with hybrid SERS nanoprobes for SERS-ICA. After optimizing parameters including coating antibody concentrations and the composition and pH of the buffer solution, the limit of detection (LOD) for phorate could reach 1 ng/mL, with a linear range of 5~100 ng/mL. This LOD is remarkably lower than the maximum residue limit in vegetables and fruits set by the Chinese government. The feasibility of this method was further examined by conducting a spiking test with celery as the real sample. The result demonstrated that this method could serve as a promising platform for rapid and sensitive detection of phorate in agricultural products.

研究领域: 分析化学 · 环境科学 · 纳米技术 · 农业科学 · 食品安全
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Materials Chemistry Frontiers · 2023 ·Vol. 7 ·期 6 ·1100-1109 · IF 7

Highly homogeneous bimetallic core–shell Au@Ag nanoparticles with embedded internal standard fabrication using a microreactor for reliable quantitative SERS detection

Suyang Li,Junjie Chen,Wanbing Xu,Biao Sun,Jiechen Wu,Qiang Chen,Pei Liang

Bimetallic gold core–silver shell (Au@Ag) surface-enhanced Raman scattering tags draw broad interest in the fields of biological and environmental analyses. Herein, an efficient hybrid microfluidic chip was designed to prepare uniform Au@Ag core–shell nanoparticles, and DTNB was used as the internal standard tag molecule to prepare Au@DTNB@Ag for SERS detection. Homogeneous core–shell nanoparticles with a particle size of 90 nm were prepared by mixing a silver precursor and a gold core in a microfluidic chip. The relative standard deviation (RSD) of the particle size distribution was close to 10%, and the detection limit of 4-MBA was as low as 10-10 M. In order to solve the influence of SERS signal fluctuation, a uniform Au@DTNB@Ag core–molecule–shell structure was synthesized in a microfluidic chip, and the characteristic peak of the analyte was corrected by the relative intensity of the DTNB characteristic peak (1335 cm−1). The experimental results showed that the SERS detection was achieved with high reproducibility, and the SERS peak intensity had a good linear correlation with the concentration. The homogeneous SERS substrate prepared using a microfluidic chip has potential for sensitive and reliable detection of environmental chemical contaminants.

研究领域: 纳米技术 · 分析化学 · 环境科学 · 材料科学
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MICROCHIMICA ACTA · 2021 ·Vol. 188 ·期 12 ·1-9 · IF 5.833

SERS-based immunoassay based on gold nanostars modified with 5,5′-dithiobis-2-nitrobenzoic acid for determination of glial fibrillary acidic protein

Zhao Peng,Sun Jingyi,Zhao Shijun,Song Yanan,Gao Feng,Wang Hongbin,Ni Qingbin,Wang Ying,Sun Baoliang

A surface-enhanced Raman scattering (SERS)–based immunoassay with gold nanostars (GNSs) is utilized for determination of the subarachnoid hemorrhage (SAH) biomarker glial fibrillary acidic protein (GFAP) at very low concentration levels, which allows for early diagnosis and guides clinical decision-making to treat SAH-induced complications. The Raman reporter 5,5′-dithiobis-2-nitrobenzoic acid (DTNB) modified on GNSs was selected as the SERS tags. The SERS immunoassay was assembled by SERS tag and GFAP probe-immobilized ITO substrate. Therefore, the level of GFAP can be detected by monitoring the characteristic Raman peak intensity of GFAP-conjugated GNSs at 1332 cm −1 with a very low detection limit. Under optimized conditions, the assay can work in the GFAP concentration range from 1 pg⋅mL −1 to 1 μg⋅mL −1 , with a detection limit as low as 0.54 fg⋅mL −1 . The performance of the SERS immunoassay proven by the detection of GFAP is equivalent to that of the conventional enzyme-linked immunosorbent assay (ELISA). Graphical abstract Scheme 1. Schematic illustration of GNSs SERS immunoassay for ultrasensitive dynamic change detection of GFAP. (SAH: Subarachnoid hemorrhage, SCF: Cerebrospinal fluid; GNSs: gold nanostars; SERS: surface-enhanced Raman scattering; GFAP: glial fibrillary acidic protein)

研究领域: 纳米技术 · 分析化学 · 生物标志物检测 · 医学诊断
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ANALYTICA CHIMICA ACTA · 2022 · IF 6.911

Self-calibration SERS sensor with “core-satellite” structure for detection of hyaluronidase activity

Xi Chen,Qian Huang,Shuyan Ruan,Feili Luo,Ruiyun You,Shangyuan Feng,Lanjin Zhu,Yang Wu,Yudong Lu

Hyaluronidase expression is known to be upregulated in various pathological conditions. A method based on a combination of ratiometric surface-enhanced Raman scattering (SERS) and magnetic separation is described for the determination of hyaluronidase (HAase) activity. Gold nanospheres (AuNPs) functionalized by 4-mercaptophenylboronic acid (4-MPBA) form stable cyclic esters with diol on hyaluronic acid (HA) by the boronic acid group, while Fe 3 O 4 @ [email protected] modified with mercaptoethylamine (MEA) was used as a capture substrate to bind to the carboxyl group on the surface of HA, forming the “ [email protected] @HA/Fe 3 O 4 @ [email protected] @MEA” “core-satellite” structure. When HAase is present, HA is enzymatically disrupted, resulting in the destruction of the “core-satellite” structure, the SERS signal of 4-MPBA is subsequently weakened. The gold shell in the substrate protects the 5,5′-Dithio bis-(2-nitrobenzoic acid) (DTNB) from the external environment, which makes it become an ideal internal standard (IS) molecule for subsequent calibration. Under optimal conditions, the I 1075 /I 1324 varied in the range of 10 −3 - 10 U‧mL −1 HAase activity, with a limit of detection (LOD) of 0.32 mU‧mL −1 ,below the level of HAase in normal human body fluids. This method has been successfully applied to the determination of HAase activity in urine and is expected to provide a new method in disease detection, especially in the non-invasive detection of bladder cancer.

研究领域: 分析化学 · 纳米技术 · 生物标志物检测 · 癌症诊断 · 生物医学工程
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