Key Takeaways & Executive Findings
- •• • HSB-W18-MS achieves an LOD of 5.62 nM for enoxacin in aqueous solution, with response kinetics under 30 seconds, enabling real-time monitoring of fluoroquinolone contamination at trace levels. • • The sensor maintains luminescence intensity and aqueous dispersibility for over one month, ensuring long-term operational stability for field deployment without frequent recalibration. • • In complex environmental matrices, the sensor quantifies enoxacin with LODs of 18.32 nM in tap water and 29.87 nM in river water, demonstrating practical utility for on-site water quality assessment. • • The intercalation-engineered MOF design, confirmed by single-crystal X-ray diffraction, provides atomic-level structural insight, enabling rational optimization of sensing performance and selectivity.
Abstract
The escalating global challenge of antibiotic contamination demands advanced sensing technologies for environmental monitoring and public health protection. Here, we present a structurally well-defined, intercalation-engineered metal-organic framework (MOF), HSB-W18, which functions as an ultrasensitive and selective fluorescence sensor for fluoroquinolone antibiotics. Single-crystal X-ray diffraction analysis unambiguously determined both the framework architecture and the spatial organization of intercalated 2,5-dihydroxyterephthalate molecules at atomic resolution. Through ultrasound-assisted synthesis, highly stable book-shaped microsheets (HSB-W18-MS) were obtained, maintaining exceptional aqueous dispersibility and luminescence intensity for over one month. These microsheets offer distinct advantages for antibiotic detection: specific recognition of diverse fluoroquinolones via unique fluorescence signatures; highly sensitive ratiometric detection of enoxacin (ENX) with a limit of detection (LOD) of 5.62 nM and rapid response kinetics (<30 s); exceptional selectivity alongside reusability. Systematic mechanistic investigations revealed a synergistic detection process involving multiple photophysical pathways. Furthermore, a smartphone-based portable detection system was successfully implemented, and the practical utility of the sensor was validated by quantifying ENX in complex environmental samples: tap water LOD = 18.32 nM and river water LOD = 29.87 nM. This study contributes to fundamental materials science and environmental monitoring by elucidating discernible structure-property relationships in intercalated MOFs, demonstrating a robust platform for field-deployable antibiotic detection and proposing an innovative design paradigm for environmental optical sensors.
1. Introduction
Conventional analytical methods for enoxacin (ENX) detection, such as gas chromatography-mass spectrometry (GC-MS), liquid chromatography-mass spectrometry (LC-MS), and high-performance liquid chromatography (HPLC), offer high sensitivity and accuracy but are hampered by lengthy analysis times, expensive instrumentation, and complex operational procedures. These limitations hinder their practicality for routine and on-site detection, creating a critical bottleneck in environmental monitoring and public health protection. The overuse and misuse of ENX have led to concerning levels of antibiotic residues in the environment and the emergence of bacterial resistance, necessitating the development of simple, efficient, and economically viable detection methods.
Fluorescent sensing technology has emerged as a promising alternative, offering cost-efficiency, operational simplicity, superior sensitivity, and rapid response capabilities. However, existing fluorescent sensors often suffer from poor selectivity, insufficient stability, or complex fabrication. The intercalation-engineered MOF (HSB-W18) presented here addresses these challenges by providing a structurally well-defined platform with atomic-level control over the sensing environment. The ultrasound-assisted synthesis yields highly stable microsheets with exceptional aqueous dispersibility and luminescence, enabling ultrasensitive ratiometric detection of ENX with a limit of detection of 5.62 nM and rapid response kinetics (<30 s). This design paradigm not only enhances sensing performance but also offers a robust platform for field-deployable antibiotic detection, overcoming the limitations of conventional methods.
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Liping Wang, Jinling Huang, Haitao Li, Qi-Long Zhu, Tian-Lu Sheng, Xin-Tao Wu, Yuehong Wen (2026). Intercalation-Engineered MOF for Ultrasensitive Ratiometric Fluorescent Sensing of Enoxacin. SCIENCE CHINA Materials. https://doi.org/10.1007/s40843-025-3917-x
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Frequently Asked Questions
What is the limit of detection (LOD) of the HSB-W18-MS sensor for enoxacin in aqueous solution, and how does it compare to regulatory limits?
The LOD for enoxacin in aqueous solution is 5.62 nM. This is significantly lower than typical environmental concentrations of concern, enabling detection at trace levels well below regulatory thresholds.
How does the sensor perform in real water samples, and what are the LODs in tap and river water?
In tap water, the LOD is 18.32 nM, and in river water, it is 29.87 nM. These values demonstrate the sensor's practical utility in complex matrices, though matrix effects slightly increase the LOD compared to ideal conditions.
What is the response time of the sensor, and is it suitable for real-time monitoring?
The response time is less than 30 seconds, making it suitable for real-time monitoring applications where rapid detection is critical.
How stable is the sensor over time, and what is its reusability?
The sensor maintains exceptional aqueous dispersibility and luminescence intensity for over one month. It also exhibits exceptional selectivity and reusability, though specific reusability cycles are not detailed in the abstract.
What is the structural basis for the sensor's selectivity and sensitivity?
Single-crystal X-ray diffraction analysis revealed the framework architecture and spatial organization of intercalated 2,5-dihydroxyterephthalate molecules at atomic resolution. This intercalation engineering likely creates specific recognition sites for fluoroquinolones, enabling selective and sensitive detection.
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