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ACS Applied Materials & Interfaces · 2026 · IF 7.8

GSH-Activated Cu-TCPP(Zn)/Ti3C2Tx Nanozymes for Fluorescence Imaging-Guided Synergistic Photodynamic/Chemodynamic Therapy of Oral Squamous Cell Carcinoma

Lidong Wang,Yongyan Sun,Yuting Sun,Changbin Zhang,Guixi Wang,Junnan He,Yan Zhao,Ming Li

Photodynamic therapy (PDT) holds promise for oral squamous cell carcinoma (OSCC) but is limited by the tumor microenvironment─specifically hypoxia, elevated glutathione (GSH), and the lack of tumor-selective photosensitizer activation. To overcome these barriers, we developed a GSH-activated nanoplatform Cu-TCPP(Zn)/Ti3C2Tx for fluorescence imaging-guided synergistic photodynamic/chemodynamic therapy (PDT/CDT). The system is constructed from two-dimensional Cu-TCPP(Zn) MOF nanosheets, where Cu2+ and Zn2+ completely quench the fluorescence and PDT activity of TCPP and surface-anchored Ti3C2Tx MXene. In the TME, overexpressed GSH reduces Cu2+ to Cu+ and abstracts Zn from the Zn–N4 complex, triggering nanocomposite disintegration to restore fluorescence, activate PDT, and simultaneously deplete GSH to reduce antioxidant defense. The resulting Cu+ catalyzes a Fenton-like reaction with endogenous H2O2 to generate •OH for CDT, while Ti3C2Tx acts as a catalase-like nanozyme, decomposing H2O2 into O2 to alleviate hypoxia, promote charge transfer, improve the utilization efficiency of photogenerated electrons, and enhance PDT efficacy. In vitro, the platform showed excellent biocompatibility and GSH-responsive activation, inducing 41.21% apoptosis in CAL-27 cells under 660 nm laser irradiation, significantly outperforming controls. In vivo, the nanocomposite accumulated efficiently in tumors via the EPR effect, suppressed tumor growth, and exhibited no observable systemic toxicity. This work provides a TME-responsive theranostic platform that integrates tumor-specific activation, GSH depletion, hypoxia alleviation, and enhanced ROS generation for precise and effective OSCC treatment.

✓ 已验证 产品关联 DOI PubMed 高影响因子
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TALANTA · 2026 · IF 6.7

Synergistic Ag/Cu-TCPP MOFs–based plasmonic SERS platform for non-invasive and time-resolved monitoring of salivary uric acid

Wenli Chen,Renjie Li,Wenxi Wang,Kaixi Yin,Xiandeng Hou,Li Wu

A facilely fabricated Ag/Cu-TCPP was developed as a SERS substrate. • Saliva uric acid (UA) was quantified with 0.04 μM detection limit. • Synergy in molecular enrichment and EM enhancement improved SERS sensitivity. • Time-resolved monitoring of UA fluctuations in real saliva samples was achieved. Surface-enhanced Raman scattering (SERS) methods offer high sensitivity for uric acid (UA) detection, but efficient molecular enrichment and reliable analysis in complex biological matrices remain challenging. Here, we developed an Ag/Cu-TCPP SERS platform for noninvasive determination of UA in saliva. The platform combined the electromagnetic enhancement provided by Ag nanoparticles (Ag NPs) with the molecular enrichment capability of Cu-TCPP. Density functional theory calculations further indicated that UA can be enriched on Cu-TCPP through weak Cu···O quasi-coordination between the UA carbonyl oxygen and exposed Cu centers, accompanied by interfacial charge redistribution. Consequently, the platform achieved a low detection limit of 0.04 μM and a wide linear range of 0.1–1000 μM. Beyond conventional single-point determination, the platform enabled time-resolved assessment of salivary UA concentration, revealing temporal fluctuations under physiological and feeding-related conditions. These results highlight the potential of MOF-integrated SERS platforms for noninvasive monitoring of small-molecule biomarkers. Download: Download high-res image (242KB) Download: Download full-size image

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Nanoscale · 2022 ·Vol. 14 ·期 47 ·17670-17680 · IF 8.307

Ultrathin metal–organic framework nanosheets as building blocks of lamellar nanofilms for ultrafast molecular sieving

Guitu Wang,Jingyu Lu,Chuanjie Fang,Wenzhang Fang,Xinsheng Peng,Hongbo Zeng,Liping Zhu

Metal–organic framework (MOF) nanosheets have significant potential applications including separation, catalysis, and sensors. However, the on-demand design with tunable thickness and morphology remains a great challenge, leading to difficulties in modulating their hierarchical assembly for the preparation of macroscopic films. Herein, we report the successful synthesis of smooth and ultrathin MOF (Cu-TCPP (TCPP = 4,4,4,4-(porphine-5,10,15,20-tetrayl)tetrakis(benzoic acid))) nanosheets used in lamellar nanofilms for the rejection of organic molecules from water. Dopamine hydrochloride (DA-HCl) is used as an adjuvant in the synthesis. Facilitated by a HCl acid environment and DA competitive coordination, the normal and lateral growths of Cu-TCPP nanosheets are modulated to achieve the desired thickness and morphology. DA-HCl can be also easily removed from the nanosheets without affecting their physicochemical properties. The as-synthesized nanosheets are utilized as nanofilm building blocks in which they are stacked into ordered bricks. The obtained membrane displays an ultrahigh water permeance of 2540 L m−2 h−1 bar−1, which is two orders of magnitude higher than the currently reported polymer membranes, while it does not sacrifice the solute rejection as completely determined by the intrinsic pore size of the nanosheets (i.e., 98.8% for molecules larger than 1.3 nm). This work provides a novel and facile strategy to tailor the morphology of the MOF nanosheets for maximizing their functionalities and structure superiority in many engineering applications.

研究领域: 材料科学 · 化学工程 · 纳米技术
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SENSORS AND ACTUATORS B-CHEMICAL · 2025 · IF 7.7

Photoelectrochemical surface-enhanced Raman scattering dual-mode aptasensor based on WS₂/Cu-TCPP MOFs Z-scheme heterojunction for microcystin-LR detection

Siyuan Wang,Shuda Liu,Shuyun Meng,Yuqing Li,Na Dong,Zuo Chen,Wenjia Li,Dong Liu,Tianyan You

Microcystin-LR (MC-LR), a toxic cyanotoxin, poses severe risks to environmental and human health with its efficient detection urgently required for water safety monitoring. Here, we reported a photoelectrochemical (PEC)-surface-enhanced Raman scattering (SERS) dual-mode aptasensor based on WS 2 /copper(II) meso-tetra(4-carboxyphenyl) porphyrin (WS₂/Cu-TCPP) MOFs Z-scheme heterojunction with a single laser source to produce photocurrent and SERS signals. To access interference between PEC and SERS signals, their correlation was systematically examined by applying a certain bias voltage. This bias voltage drives photogenerated electrons into external circuit, thereby enhancing carrier separation efficiency and suppressing the return of Raman photons to the ground state. In this way, a complementary “PEC-enhancement/SERS-attenuation” signal pattern can be achieved to allow better reliability for biosensing. The presence of ascorbic acid (AA) replicated an identical response to confirm competitive coupling between PEC and SERS derived from WS₂/Cu-TCPP heterojunction. Based on this signal transduction mechanism and localized generated AA by magnetic separation, a dual-mode aptasensor was developed for MC-LR detection with superior sensitivity and interference resistance. It allowed a linear range of 0.01–50 ng mL −1 and a detection limit of 0.14 pg mL −1 for MC-LR as well as high selectivity and stability for real water samples analysis. This work should offer an efficient paradigm for precise analysis of hazardous pollutants in complex matrices.

CAS / MDL: 50-81-7
研究领域: 环境监测 · 分析化学 · 生物传感器 · 纳米材料 · 水质检测
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BIOSENSORS & BIOELECTRONICS · 2026 · IF 11.8

Bioinspired molecular recognition via pore confinement and interfacial electric-field regulation in g-C3N5@Zn-TCPP for selective breath ammonia sensing

Kai Liu,Yuanyuan Ren,Jun Wang,Xue Zhang,Jiaxing Sun,Huitong Xu,Kewei Zhang,Song Yang

Ammonia (NH 3 ) in exhaled breath is a promising biomarker for non-invasive monitoring of metabolic disorders, but achieving selective and sensitive detection under complex breath environments remains challenging. Here, we report a bioinspired g-C 3 N 5 @Zn-TCPP heterojunction formed through π-π stacking that enables molecular-recognition-driven breath NH 3 sensing. Inspired by the synergistic functions of ammonium transporter (AmtB) and ammonia monooxygenase (AMO), this heterostructure integrates pore-confined molecular enrichment with interfacial electric-field regulation. The intrinsic aperture of Zn-TCPP (∼2.8 Å), closely matching the kinetic diameter of NH 3 (2.6 Å), enables size-selective molecular sieving, while the g-C 3 N 5 -induced interfacial electric field modulates the electronic environment of Zn 2+ active sites and strengthens Lewis acid-base interactions with NH 3 molecules. Benefiting from this synergistic molecular recognition mechanism, the optimized 0.08@g-;C 3 N 5 @Zn-TCPP sensor achieves a remarkable response (R 0 /R g  = 223 toward 5 ppm NH 3 ), a low detection limit of 232 ppb, and excellent durability over 1000 bending cycles at room temperature. Machine-learning-assisted analysis further enables accurate discrimination of NH 3 from interfering gases (R 2  = 0.91). The sensor also distinguishes breath NH 3 variations between healthy individuals and disease-related samples, highlighting its potential for intelligent non-invasive breath analysis. This work establishes a bioinspired molecular recognition strategy by coupling pore confinement with interfacial electric-field regulation, providing a new paradigm for selective gas sensing and wearable health-monitoring platforms.

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ACS Omega · 2026 · IF 5.2

Construction of a Portable Colorimetric Biosensing Platform Based on the Co-TCPP (Fe)-MOF Nanosheet and Its Application in Glucose Detection

Kermue Vasco Jarnda,Heng Dai,Huiting Hu,Yuan Tian,Richmond Anaman,Pian Wu,Ping Ding

Recent advancements in microfluidic paper-based analytical devices (μPADs) have demonstrated their significant potential for point-of-care testing (POCT), particularly in low-resource settings. These devices are especially promising for monitoring glucose levels in patients with diabetes, offering a cost-effective and portable solution. However, one of the primary challenges hindering the widespread adoption of smartphone-coupled μPADs has been their sensitivity to varying ambient lighting conditions, which can interfere with accurate colorimetric detection. To address this issue, researchers have introduced a novel approach involving a metal–organic framework (MOF), specifically Co-TCPP (Fe) [cobalt Fe(III) meso-tetra(4-carboxyphenyl) porphyrin chloride], synthesized using a straightforward method. Co-TCPP (Fe) exhibits remarkable peroxidase-like activity when exposed to hydrogen peroxide (H2O2), enabling it to interact effectively with classic chromogenic substrates and thus improving the colorimetric reaction crucial for accurate glucose detection. In this study, the team developed paper-based μPADs that incorporate the Co-TCPP (Fe) MOF, allowing it to accurately detect glucose levels across a wide concentration range. The limit of detection (LOD) achieved was 5.3 μM, with a linear detection range from 5 to 750 μM. This innovation addresses previous concerns regarding the impact of environmental lighting fluctuations and varying shooting angles, ensuring the reliability of glucose measurements under uncontrolled conditions. By integrating this algorithm into a smartphone-coupled μPAD system, the researchers have created a portable, high-resolution platform that delivers dependable results, even in challenging and fluctuating environments. This breakthrough marks a significant step toward enhancing the practicality and accessibility of glucose monitoring in resource-constrained settings, providing a valuable tool for both clinical and everyday use.

✓ 已验证 产品关联 DOI PubMed 高影响因子
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ACS Catalysis · 2021 · IF 13.084

Fabrication of Pd/In2O3 Nanocatalysts Derived from MIL-68(In) Loaded with Molecular Metalloporphyrin (TCPP(Pd)) Toward CO2 Hydrogenation to Methanol

Zhongjie Cai,Meng Huang,Jiajun Dai,Guowu Zhan,Fu-li Sun,Gui-Lin Zhuang,Yiying Wang,Pan Tian,Bin Chen,Shafqat Ullah,Jiale Huang,Qingbiao Li

Methanol synthesis from CO2 hydrogenation with H2 produced from renewable energy has emerged as a promising method for carbon neutrality. The supported Pd/In2O3 catalyst has attracted great attention due to its superior activity and methanol selectivity, but the formation of the In–Pd bimetallic phase upon over-reduction would lead to quick catalyst deactivation. In this work, we elucidate the reduction behavior of Pd/In2O3 catalysts by using TCPP(Pd)@MIL-68(In) as precursors. During catalyst fabrication, metalloporphyrins (viz., TCPP(Pd)) served as both a capping agent for the growth of MIL-68(In) and a shuttle for transporting the Pd2+, which enhanced the dispersion of Pd0 species on In2O3–x during the calcination and reduction treatments and prevented the formation of In–Pd bimetallic phase by over-reduction. With a low Pd loading of 0.53 wt %, the resultant Pd/In2O3 catalyst exhibited a maximum methanol space–time yield of 81.1 gMeOH h–1 gPd–1 with a CO2 conversion of 8.0% and a methanol selectivity of 81% over 50 h on stream (295 °C, 3.0 MPa, 19,200 mL gcat–1 h–1). In contrast, the comparative Pd/In2O3 catalyst prepared by the impregnation of PdCl2 in MIL-68(In) showed poor activity and stability due to the formation of InPd/In2O3–x surface structures. In addition, we found a strong connection between the reduced degree of In2O3 and the catalytic performance of the supported Pd/In2O3 catalysts by integrating catalyst characterization results with density functional theory (DFT) calculations. Interestingly, the surface In/O ratio detected by XPS can reflect information about both metal–support interaction and the amount of oxygen vacancy, which is highly related to the catalytic activity. The DFT calculation also shows that the Pd/In2O3 catalyst has excellent thermodynamic selectivity for the CH3OH product. This work provides an alternative synthetic strategy for Pd/In2O3 nanocatalysts and sheds light on the deactivation mechanism of the supported catalysts.

CAS / MDL: 7647-10-1 100-21-0
研究领域: 催化化学 · 材料科学 · 环境科学
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ENVIRONMENTAL SCIENCE AND POLLUTION RESEARCH · 2020 ·Vol. 27 ·期 31 ·39186-39197 · IF 3.056

Microwave-assisted hydrothermal assembly of 2D copper-porphyrin metal-organic frameworks for the removal of dyes and antibiotics from water

Zhao Shiyin,Li Shun,Zhao Zhicheng,Su Yiping,Long Yangke,Zheng Zuquan,Cui Daling,Liu Yong,Wang Chunfei,Zhang Xuanjun,Zhang Zuotai

Adsorption and photocatalysis are promising strategies to remove pollutants of dyes and antibiotics from wastewater. In this study, we demonstrate a rapid microwave-assisted hydrothermal route for the assembly of 2D copper-porphyrin Metal-Organic Frameworks (Cu-TCPP MOFs) within 1 h. The resulting 2D Cu-TCPP nanosheets with excellent crystallinity and a large surface area (342.72 m 2 /g) exhibited outstanding adsorption performance for typical dyes with adsorption capacities of about 185 mg/g for rhodamine B, 625 mg/g for methylene blue, and 290 mg/g for Congo red, respectively, as well as for representative antibiotics with adsorption capacities of about 130 mg/g for oxytocin, 150 mg/g for tetracycline, and 50 mg/g for norfloxacin, respectively. Meanwhile, the as-prepared 2D Cu-TCPP showed good photocatalytic degradation activity of pollutants after adsorption under irradiation by visible light, reaching removal efficiencies of 81.2 and 86.3% toward rhodamine B and norfloxacin, respectively. These results demonstrate the promising potential of 2D Cu-TCPP for use in the removal of contaminants from wastewater.

研究领域: 环境科学 · 材料科学 · 化学工程 · 纳米技术
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CHEMICAL ENGINEERING JOURNAL · 2026 · IF 12.5

Single-atom Cu in TCPP-hydrogen-bonded organic framework/PFC-1 hydrogen-bonded organic framework Z-scheme heterojunctions for photocatalytic hydrogen production

Na Song,Yuting Zhu,Fan He,Mengnan Zhang,Mingfu Ye,Shengjun Liu,Kui Zhang

HOF/HOF-based Z-scheme heterojunctions were successfully synthesized. • Z-scheme heterojunctions and Cu single atoms boost charge separation. • TCPP(M)-HOF/PFC-1 exhibits the highest H 2 evolution rate of 42.7 mmol g −1  h −1 . Hydrogen-bonded organic frameworks (HOFs) have exhibited extraordinarily broad application prospects in the field of photocatalysis owing to their unique structural merits. Nevertheless, pristine HOF materials generally suffer from the bottleneck of low separation efficiency for photogenerated charge carriers, which severely restricts their practical industrial applications in photocatalysis. To address this issue, herein we have successfully constructed a series of Z -scheme heterojunction photocatalysts based on the two-dimensional HOF/HOF system (denoted as TCPP (H or M)-HOF/PFC-1, where M = Cu, Zn, Ni), with the targeted composite heterostructure fabricated from TCPP(Cu)-HOF and PFC-1 HOF as the core product. Among them, the porphyrin-based TCPP(Cu)-HOF effectively broadens the spectral response range of light absorption for the composite; the precise construction of the Z -scheme heterojunction greatly enhances the separation and transport efficiency of photogenerated charges; meanwhile, the single-atom Cu sites (Cu-SA) can significantly shorten the charge migration pathway and accelerate the directional and rapid transfer of photogenerated electrons, ultimately enabling the efficient conversion of solar energy into chemical energy. Furthermore, the excellent energy level matching between TCPP(Cu)-HOF and PFC-1 HOF in the composite, coupled with the synergistic regulation of single-atom active sites, further facilitates the efficient directional migration of photogenerated charge carriers. Experimental test data confirm that the optimized TCPP(Cu)-HOF/PFC-1 heterojunction photocatalyst delivers a photocatalytic hydrogen evolution rate of up to 42.7 mmol·g −1 ·h −1 . This work fully demonstrates the outstanding advantages of HOF/HOF Z -scheme heterostructures in precisely tailoring photogenerated charge carrier dynamics, providing a novel and feasible research strategy for efficiently boosting photocatalytic hydrogen evolution performance and designing high-performance heterojunction catalysts for solar energy conversion. Here, we present a Z -scheme heterojunction photocatalyst based on two-dimensional HOF/HOF composites, specifically TCPP(M)-HOF/PFC-1 (M = Cu, Zn, Ni), with TCPP(Cu)-HOF and PFC-1 HOF as the representative system. Owing to the favorable energy level alignment between the two HOF components and the introduction of single-atom Cu sites, the directional migration of photogenerated charge carriers is significantly enhanced. Download: Download high-res image (117KB) Download: Download full-size image

CAS / MDL: 1571-08-0 50-81-7
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CHEMICAL ENGINEERING JOURNAL · 2025 · IF 13.2

Ultra-sensitive, multi-component, and real-time detection of heavy metal ions via AgNPs@Cu-TCPP(Pt) sensitized strong coupling plasmonic sensor

Jie Yan,Runcheng Liu,Jian Shi,Wen Yang,Shouzhen Jiang,Zihao Zhang,Mingshun Jiang

The high toxicity and bioaccumulation of heavy metal ion pollutants pose severe threats to the environment and public health. Tilted fiber Bragg grating-based surface plasmon resonance (TFBG-SPR) sensors have emerged as effective tools for heavy metal ion sensing owing to their portability and rapid response. These sensors typically feature a single plasmonic structure. And they are constrained by hardware restrictions and complex spectral analyses. Thus, these conventional designs render multicomponent detection and precise analysis challenging. To address these limitations, this study introduces a lightweight multichannel sensing platform based on a composite plasmonic TFBG structure. A two-dimensional metal–organic framework (2D MOF Cu-TCPP(Pt)) and silver nanoparticles (AgNPs) are integrated onto a gold (Au)-coated TFBG surface. This configuration enables strong coupling between the SPR and localized SPR (LSPR). Hence, the signal sensitivity is enhanced. The molecular sieve effect of the Cu-TCPP(Pt) improves the target analyte enrichment and suppresses the background interference, thereby ensuring a stable signal output. Additionally, a DNA aptamer conformational switching strategy ensures selective target analyte recognition. This platform integrates an AgNPs@Cu-TCPP(Pt)/Au/TFBG sensor, optical channel array, and real-time signal processing module and enables simultaneous detection of Pb 2+ , Cd 2+ , and Hg 2+ within 6 min, with detection limits of 0.007, 0.012, and 0.005 nM, respectively. The proposed sensor effectively mitigates background interference in complex matrices, demonstrating excellent linearity and recovery. Compared with conventional TFBG-based methods, this platform offers high sensitivity, short detection times, and enhanced robustness, and presents a novel solution for real-time multicomponent detection in complex matrices.

研究领域: 环境科学 · 传感技术 · 材料科学
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APPLIED SURFACE SCIENCE · 2024 · IF 6.3

A reliable gold nanoparticle/Cu-TCPP 2D MOF/gold/D-shaped fiber sensor based on SPR and LSPR coupling for dopamine detection

Jinjuan Gao,Wen Yang,Runcheng Liu,Jingwen Feng,Yaru Li,Mingshun Jiang,Shouzhen Jiang

The optical fiber sensor, which exploits surface plasmon resonance (SPR), finds extensive application in biological detection owing to its miniaturized and real-time measurement capabilities. Nevertheless, SPR sensors alone exhibit limited sensitivity when detecting small biological molecules. This paper presents a novel gold nanoparticle (AuNPs)/two-dimensional metal–organic framework (2D MOF Cu-TCPP)/Au/D-shaped fiber SPR sensor for dopamine detection. The composite structure of AuNPs/2D MOF/Au was designed to facilitate the coupling of SPR and local surface plasmon resonance (LSPR), resulting in a substantial enhancement of the intensity of the surface electric field. A 104.61 % increase in sensitivity and a 73.87 % increase in figure of merit (FOM) were achieved by optimizing the optimal deposition concentration of AuNPs/2D MOF . The finite element method was utilized in COMSOL software to demonstrate that the coupling of SPR and LSPR can significantly enhance the sensitivity value (10,000 nm/RIU). Additionally, the sensitization mechanism of the sensor is elucidated by the energy band theory. Moreover, probe DNA was utilized as a linker to capture dopamine molecules, achieving a low limit of detection (LOD) of 1.07 ± 0.07*10 −14 M. These results demonstrated that the proposed sensor enables accurate and highly sensitive detection of dopamine molecules.

CAS / MDL: 50-81-7 69-93-2 51-61-6
研究领域: 生物医学工程 · 纳米技术 · 光学传感
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FOOD CHEMISTRY · 2024 · IF 8.5

Dramatic fluorescence enhancement of PCN-224 and its application in “turn off” immunoassay for sensitive detection of E. coli O157:H7 in milk

Bolong Fang,Xin Liu,Juan Peng,Yuzhi Li,Zhiyong Gong,Weihua Lai

In this study, a type of luminescent porous coordination network-224 (PCN-224) in alkaline conditions was synthesized with the dramatic fluorescence enhancement by 20.4 times, which was explained by the fact that the decrease of Zr 4+ content in alkaline conditions resulted in the partial recovery of the electron cloud density of 4,4′,4′′,4′′′-(Porphine-5,10,15,20-tetrayl) tetrakis(benzoic acid) (TCPP). Given the large overlap between the excitation spectrum of PCN-224 and the absorption band of Ag nanoparticles (Ag NPs), the coating of the Ag layer on PCN-224 triggered the fluorescence quenching effect, which was applied to “turn off” fluorescence immunoassay for sensitive detection of Escherichia coli O157:H7 ( E. coli O157:H7) in milk. The proposed immunoassay reached a low limit of detection (LOD) of 3.3 × 10 2 CFU mL −1 , 29.7 times more sensitive than the conventional ELISA. It will provide a novel alternative strategy for sensitively detecting pathogenic bacteria in the field of food safety.

研究领域: 材料科学 · 分析化学 · 食品安全 · 生物传感器
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