阅读说明：本技术 基于双响应镧系mof的可视化水荧光微传感器、定水管装置、水可视化测定装置及其应用 (visual water fluorescence microsensor based on dual-response lanthanide MOF, water determination pipe device, water visualization determination device and application thereof ) 是由 肖玉秀 于龙 于 2019-08-22 设计创作，主要内容包括：本发明公开了一种基于双响应镧系MOF的可视化水荧光微传感器、定水管装置、水可视化测定装置及其应用。本发明所制备的水纸基微传感器具有响应快、灵敏度高、操作简便、耗时短等优点,解决了MOF分散液传感模式不稳定、准确度低的问题,结合新型定水管装置以及智能机辅助的可视化检测装置,首次实现了固体药物中微量水的快速准确定量,解决了现有方法只能实现液体溶剂中水含量测定的问题。本发明的水含量纸基荧光微传感器制备技术简单、成本低,适合大批量生产,不仅首次实现了固体样本中微量水的即时、可视化定量,而且本方法不消耗有机溶剂,更加环保绿色,在固体样本水含量的测定中具有广泛的应用前景。(the invention discloses a visual water fluorescence microsensor based on dual-response lanthanide MOF, a water-fixing pipe device, a water visual determination device and application thereof. The water-paper-based microsensor prepared by the invention has the advantages of quick response, high sensitivity, simplicity and convenience in operation, short consumed time and the like, solves the problems of unstable sensing mode and low accuracy of MOF dispersion liquid, and combines a novel water metering pipe device and an intelligent machine-assisted visual detection device to realize quick and accurate quantification of trace water in solid medicines for the first time and solve the problem that the existing method can only realize determination of water content in a liquid solvent. The paper-based fluorescence microsensor with the water content is simple in preparation technology, low in cost and suitable for mass production, not only realizes instant and visual quantification of trace water in a solid sample for the first time, but also does not consume organic solvent, is more environment-friendly and green, and has wide application prospect in determination of the water content of the solid sample.)

1. A visual water fluorescence microsensor based on dual response lanthanide MOF, its characterized in that: the visualized water fluorescence microsensor is prepared by soaking a fiber filter paper in a fluorescent MOF dispersion liquid and then drying, wherein the fluorescent MOF is lanthanide MOF sensitive to water and provided with lanthanide ions and ligand molecules as double luminescent centers; the particle size of the fluorescent MOF is 50-500nm, and the visualized water fluorescent microsensor is a paper-based wafer loaded with the fluorescent MOF, and the diameter of the paper-based wafer is 6 mm; the fluorescence MOF is prepared from lanthanide series metal salt, pyridine-2, 6-dicarboxylic acid and 2-amino terephthalic acid through a one-pot method, and the visualized water fluorescence micro-sensor is prepared by soaking fiber filter paper in MOF dispersion liquid.

2. The dual response lanthanide MOF based visualized water fluorescence microsensor according to claim 1, wherein: the lanthanide metal salt refers to any one of europium salt, terbium salt or dysprosium salt.

3. The dual response lanthanide MOF based visualized water fluorescence microsensor according to claim 1 or 2, wherein: ligand molecules of the fluorescent MOF comprise pyridine-2, 6-dicarboxylic acid and 2-aminoterephthalic acid.

4. a water holding pipe device constructed by the double response lanthanide MOF based visualized water fluorescence microsensor of claim 1, wherein: comprises a bottle body (2), a bottle cap (3), a rubber inner liner (4) and the visible water fluorescence microsensor (5) of claim 1; the visual water microsensor (5) is fixed on the surface of the rubber inner liner (4) and is arranged in the bottle cap (3), and the visual water microsensor (5) and the bottle body (2) form a closed water fixing pipe device (1).

5. A water content visual measuring device built based on the paper-based fluorescent microsensor according to claim 1, characterized in that: comprising the visualized water fluorescence microsensor (5) according to claim 1, a sample drawer (8), a 96-well plate (9) and a camera bellows (10); the 96-well plate (9) is arranged in a sample drawer (8), and the sample drawer (8) is positioned at the bottom of a dark box (10) and used for placing a visible water fluorescence microsensor (5); the top of the dark box (10) is provided with an ultraviolet lamp (11) and photographing equipment (12) used for photographing after sensitization.

6. Use of the dual response lanthanide MOF-based visualized aqueous fluorescent microsensor of claim 1 or 2 in the determination of aqueous content in a solid drug.

7. Use of the water tube device of claim 4 in water content determination of solid drugs.

8. Use of the device for the visual determination of water content according to claim 5 in the determination of water content in solid drugs.

Technical Field

The invention belongs to the field of fluorescence sensors, and particularly relates to a visual water fluorescence microsensor based on dual-response lanthanide MOF, a water determination pipe device, a water visual determination device and application thereof.

Background

Whether for the production of medicines or the preparation of foods, the development of a simple, rapid and reliable chemical analysis method for the water content of a solid sample is urgently needed, wherein the water is common impurities, and the excessive existence of the water can generate adverse effects on the physicochemical properties of the medicines and the foods and easily induce the occurrence of mildew and putrefaction, thereby causing economic loss and potential threats to human health. Luminescent water sensors have attracted great research interest, since they have significant advantages over electrochemical sensors (no calibration required, in situ detection possible, simple preparation) while detection based on luminescent sensors is undoubtedly simpler than traditional karl-fischer water content assays (requiring specially made instruments and trained operators). Until now, a series of luminescence sensors for water content determination have been developed, wherein most of the luminescence sensors based on fluorescent small molecules have a high detection limit, accurate determination of water content of less than 1% cannot be achieved, and they are not easily recycled.

The MOFs are coordination polymers with potential gaps and open framework structures, wherein the luminescent MOFs are crystalline materials with rapid development and wide application prospects, and have been widely applied to various biological and chemical sensors due to the advantages of various luminescent forms, various and adjustable structures, simple preparation, capability of pre-concentrating analytes (improving sensitivity) and the like. In recent years, a series of water content sensors based on luminescent MOFs have been developed, some of which are based on single-emission fluorescence, which is not favorable for the detection accuracy, and fortunately, some of which are based on water content determination fluorescent MOFs emitted at two wavelengths, which improves the detection accuracy. However, it is worth noting that the stability of MOFs is limited due to their heterogeneity, and the accuracy of fluorometry based on the detection mode of the dispersion is to be further improved. On the other hand, the currently reported fluorescent MOFs for water detection can only realize the determination of the water content in an organic solvent, and the research reports that the luminous MOF can realize the rapid determination of the water content in a solid sample are not yet reported. It is undoubtedly more complex to determine the water content in solid samples and new detection methods need to be rationally designed to solve the above problems. Furthermore, the mechanism of measuring the water content based on the luminous MOFs also needs to be further researched by a theoretical calculation method, so that the molecular level theory of the luminous MOFs for measuring the water content is enriched, and a more sufficient theoretical guidance is provided for the research and development of the same type of luminous sensors based on the luminous MOFs.

Disclosure of Invention

in order to solve the technical problems, the invention provides a visual water fluorescence microsensor based on dual-response lanthanide MOF, a water fixing pipe device, a water visual determination device and application thereof.

In order to achieve the purpose, lanthanide series Eu ions are selected as metal nodes, pyridine-2, 6-dicarboxylic acid with strong lanthanide series ion sensitization is selected as an organic ligand 1, 2-aminoterephthalic acid is selected as an organic ligand 2, and the novel double-ligand lanthanide series MOF is synthesized through a one-pot method. The lanthanide MOFs have dual luminescent centers, red fluorescence is derived from the characteristic luminescence of Eu ions, and blue fluorescence is derived from the characteristic fluorescence of 2-aminoterephthalic acid. The synthesis ratio of the double ligands is optimized by taking the moisture response sensitivity as an index, the lanthanide MOF prepared by the optimal ligand ratio has the advantages that the blue fluorescence is gradually enhanced and the red fluorescence is gradually weakened along with the increase of the water content, and the turn-on and turn-off combined double response MOF further improves the detection sensitivity. Meanwhile, since blue fluorescence of the ligand 2 undergoes blue shift along with the increase of the water content, the long-range linearity of the method is poor, fortunately, the result deviation caused by the blue shift of the fluorescence can be effectively improved by colorimetric analysis based on multipoint correction, so that the long-range linearity is excellent, and the method further verifies that the analysis and detection mode based on ratio chromaticity has better effect, which is one of the advantages of subsequent visual detection. Then, the paper-based water content fluorescence microsensor is prepared by a simple soaking method, the paper-based microsensor has excellent water response reversibility, meanwhile, a small and exquisite and effective water pipe fixing device is constructed for a solid sample, and a visual detection device assisted by an intelligent machine is further combined, so that a simple, rapid, sensitive, efficient and feasible solid sample water content determination method is successfully constructed.

The scheme provided by the invention is as follows:

The invention provides a visual water fluorescence microsensor based on dual-response lanthanide MOF, which is characterized in that: the visualized water fluorescence microsensor is prepared by soaking a fiber filter paper in a fluorescent MOF dispersion liquid and then drying, wherein the fluorescent MOF is lanthanide MOF sensitive to water and provided with lanthanide ions and ligand molecules as double luminescent centers; the particle size of the fluorescent MOF is 50-500nm, and the visualized water fluorescent microsensor is a paper-based wafer loaded with the fluorescent MOF, and the diameter of the paper-based wafer is 6 mm; the fluorescence MOF is prepared from lanthanide series metal salt, pyridine-2, 6-dicarboxylic acid and 2-amino terephthalic acid through a one-pot method, and the visualized water fluorescence micro-sensor is prepared by soaking fiber filter paper in MOF dispersion liquid.

Preferably, the lanthanide metal salt is any one of europium salt, terbium salt and dysprosium salt.

Further, the ligand molecules of the fluorescent MOF include pyridine-2, 6-dicarboxylic acid, 2-aminoterephthalic acid.

the invention also provides a water fixing pipe device constructed by utilizing the visual water fluorescence microsensor based on the dual-response lanthanide MOF, which is characterized in that: comprises a bottle body, a bottle cap, a rubber inner liner and the visual water fluorescence microsensor; the visual water microsensor is fixed on the surface of the rubber lining pad and is arranged in the bottle cap, and the visual water microsensor and the bottle body form a closed water fixing pipe device together.

the invention provides a water content visual measuring device based on the paper-based fluorescence microsensor as claimed in claim 1, which is characterized in that: comprises the visual water fluorescence microsensor, a sample drawer, a 96-hole plate and a dark box; the 96-hole plate is arranged in the sample drawer, and the sample drawer is positioned at the bottom of the dark box and used for placing the visible water fluorescence microsensor; the camera bellows top is provided with the ultraviolet lamp, still is equipped with the equipment of shooing that is used for the sensitization back to shoot.

the invention provides application of the visualized water fluorescence microsensor based on the dual-response lanthanide MOF in water content determination of solid medicines.

The invention also provides the application of the water metering pipe device in water content measurement of solid medicines.

the invention provides an application of the water content visual determination device in the determination of the water content in the solid medicine.

The novel fluorescent MOF, the paper-based water content microsensor, the water determination pipe device and the water visualization determination device provided by the invention can be effectively applied to water content detection in organic solvents and solid samples.

the invention has the following advantages and beneficial effects:

(1) The novel fluorescent MOF provided by the invention has the characteristic of high sensitive water response;

(2) The fluorescent MOF provided by the invention can be used for preparing a paper-based microsensor for water detection, and the visual analysis and detection of the water content in a solid sample can be realized by combining a self-designed water fixing pipe device and a visual water content determination device;

(3) the detection technology based on the sensor provided by the invention has the unique advantages of observing space and time distribution, and has the advantages of simple operation, quick response and high sensitivity;

(4) The water detection paper-based microsensor has good reversibility and can be repeatedly used;

(5) the fluorescence sensor designed by the invention realizes the water content determination in the solid medicine for the first time, and can be widely applied to the water content determination in other types of solid samples.

drawings

FIG. 1 is a transmission electron micrograph of a lanthanide metal-organic framework material;

FIG. 2 is a water holding tube and a water detection fluorescent test paper;

Wherein: 1. a water pipe fixing device; 2. a bottle body; 3. a bottle cap; 4. a rubber inner liner; 5. a visual water fluorescence micro-sensor; 6. pictures of water microsensors in daylight; 7. pictures of the water microsensor under 254nm ultraviolet light irradiation;

FIG. 3 is a proposed apparatus for the visual determination of water content in a solid sample;

Wherein: 8. a sample drawer; 9. a 96-well plate; 10. a dark box; 11. an ultraviolet lamp; 12. a photographing device;

FIG. 4 is a flow chart of a solid sample water visualization assay;

wherein: 13. granules; 14. capsules; 15. a constant temperature shaking table; 16. visualizing the detection result;

FIG. 5 is a fluorescence spectrum of the response of a fluorescence sensor to water content in an organic solvent;

FIG. 6 is a standard curve of the response of the fluorescence sensor dual wavelength ratio (I _443nm/I _620nm) to the water content in organic solvent;

FIG. 7 is a result of color coordinate conversion of the fluorescence spectrum of FIG. 5;

FIG. 8 is a standard curve of color coordinates as a function of water content;

FIG. 9 shows the results of the fluorescence sensor for the visual determination of water content in different organic solvents (in the figure: A, B, C represents methanol, ethanol and acetonitrile, respectively, with different water contents);

FIG. 10 is a standard curve for visual determination of water content in solid granules;

FIG. 11 is a standard curve for visual determination of water content in solid capsules;

FIG. 12 is a reversibility evaluation of a water detection microsensor;

fig. 13 is a response speed of the water detecting micro sensor.

Detailed Description

The invention is described in further detail below with reference to the figures and specific examples.