CN109211859B - Hydrogel optical fiber based on luminous MOFs (metal-organic frameworks), preparation method thereof and sensing device - Google Patents
Hydrogel optical fiber based on luminous MOFs (metal-organic frameworks), preparation method thereof and sensing device Download PDFInfo
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6432—Quenching
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- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention discloses a hydrogel optical fiber based on luminous MOFs, a preparation method thereof and a sensing device. According to the preparation method, MOFs micro-particles are uniformly mixed into a hydrogel precursor, meanwhile, the hydrogel precursor is respectively injected into coaxial double cylinders, a cylinder with a core-package structure and a proper size is extruded from an outlet of the cylinder through an extrusion molding method or a biomaterial 3D printer, one end of a common quartz optical fiber is coaxially inserted into a side core layer of the extruded cylinder with the core-package structure, and the hydrogel optical fiber with a common optical fiber tail fiber is obtained after solidification. The sensing device comprises an excitation light source, a Y-shaped optical fiber, a delay optical fiber, an optical fiber connection part, a hydrogel optical fiber, a long-pass filter, a fluorescence spectrometer and a signal processing unit. The whole technical scheme of the invention can construct and realize all-fiber high-selectivity fluorescence sensing, further realize in-situ, real-time, remote and even living body fluorescence detection and sensing, and promote the sensing applicability of the luminous MOFs material.
Description
Technical Field
The invention relates to the technical field of optical fiber fluorescence sensing, in particular to a MOFs-based hydrogel optical fiber, a preparation method thereof and a sensing device.
Background
The Metal-organic frameworks (MOFs) are novel porous materials formed by self-assembling organic ligands and Metal nodes through coordination bonds, have extremely large specific surface area and lower cost, and have important application prospects in the fields of sensing identification, catalytic luminescence, information storage and the like. The luminescent MOFs material based on lanthanide rare earth metal is an important ordered crystalline compound, and can generate fluorescence under the action of external excitation light, and the fluorescent MOFs material has the advantages of rich electronic structure, excellent photophysical properties (such as sharp characteristic emission peak, high luminous efficiency and the like), high detection speed, high sensitivity, good selectivity, stability, reliability and the like in the aspect of fluorescence sensing, and becomes an ideal fluorescent probe material of a new generation. Various luminescent MOFs materials have been developed for use in highly selective sensing of such things as solution ions, volatile organic compounds, gases, explosive molecules, biomolecules, and the like.
Although luminescent MOFs fluorescent detection materials having high selectivity have been widely and rapidly developed, there is a problem that the development of the materials toward practical use is seriously hindered in practical applications of fluorescent detection based on luminescent MOFs materials. First, most of fluorescence detection based on luminescent MOFs materials is to soak the prepared MOFs particle powder in a sample solution of an analyte, or to expose the powder to be analyzed in gas and steam, to inject the powder into living cells, and then to place the sample under a fluorescence spectroscopy device for offline spectrometry analysis. Because of the uneven distribution and irregular movement of MOFs particles in a sampling solution, and the problems that MOFs powder tablets are easily blown away by air flow in a gas environment, the measurement is inaccurate due to fluctuation of fluorescence spectrum intensity, and meanwhile, the problems that a fluorescence detection material is easy to damage, the service life is too short, waste caused by difficult recycling and secondary utilization are caused, researchers propose to prepare MOFs films or composite films, realize in-situ growth of MOFs particles on the surface of a carrier substrate or construct the composite films of MOFs particles and other materials, and overcome the application problems that the powder dispersion state of MOFs materials is inconvenient to measure, the service life is short and the like (such as the prior patent of the invention 201710667152.0, 201511027933.0, 201610751719.8). The construction of uniform and large-sized MOFs membranes with the strong mechanical bonding forces required for industrialization and commercialization remains a significant challenge. Secondly, the sensor based on MOFs material cannot be directly applied to harsh real application environments, because the fluorescence measurement needs a precise and reliable light path to achieve the introduction of excitation light and the collection of fluorescence, most of the sensing demonstration of MOFs material depends on large commercial fluorescence measurement equipment on a laboratory platform to conduct offline sampling measurement, and the measurement method greatly limits the luminous MOFs material to further achieve advanced sensing functions such as in-situ, living body, real-time and long-distance. The scheme with application potential is to realize fluorescence sensing based on MOFs material integrated optical fiber, the common optical fiber is used for effectively transmitting laser light and collecting fluorescence, so that a precise optical path of a large instrument is not needed, the luminous MOFs material grows or wraps on the outer diameter of a decovered optical fiber (sens. Acters B: chem, 2016, 232, 43-51), or on the outer diameter of a long-period optical fiber grating (sens. Acters B: chem, 2015, 221, 891-899), or on the end face of the optical fiber (Opt. Lett. 2016, 41, 1696-1699), but the scheme still has the application problems of low light guiding efficiency, weak mechanical binding force between the luminous MOFs material and the optical fiber, short service life due to direct contact between the luminous MOFs material and the MOFs material and severe environment.
In consideration of the integrity of optical measurement, the novel light-emitting MOFs material integrated permeable optical fiber is invented, so that the environmental applicability of the light-emitting MOFs material, the injection of excitation light and the collection of weak fluorescence can be greatly enhanced, meanwhile, an analyte can effectively act with the light-emitting MOFs material in the permeable optical fiber through permeation, and the practical applicability of the light-emitting MOFs material can be optimized and improved.
Disclosure of Invention
The invention aims to overcome the defects and shortcomings of the prior art and provides a hydrogel optical fiber based on a luminous MOFs material, a preparation method thereof and a sensing device. Hydrogel materials with good light transmittance, ion permeability and biocompatibility are selected as fiber matrix materials, so that the hydrogel fiber prepared based on the hydrogel materials can guide light with lower loss and realize efficient and convenient excitation light guide and fluorescence collection. MOFs micro-crystal grains with high-selectivity fluorescence sensing function are uniformly mixed into a hydrogel precursor, hydrogel precursors with different concentrations are prepared to meet refractive index design requirements of fiber cores and cladding, meanwhile, the viscoelasticity of the hydrogel precursor is adjusted to be high, the hydrogel precursor is respectively injected into coaxial double cylinders, a cylinder with a core-cladding structure with proper size is extruded from an outlet of the cylinder through an extrusion molding method or a biomaterial 3D printer, one end of a common quartz fiber is coaxially inserted into a side core layer of the extruded cylinder with the core-cladding structure, and the hydrogel fiber with a common fiber tail fiber is obtained after curing under ultraviolet radiation. According to the preparation method, the integrated hydrogel sensing optical fiber based on the fluorescent MOFs material can be prepared, the introduction of excitation light and the collection of fluorescence can be efficiently realized through the common optical fiber connected to the tail end of the hydrogel optical fiber, and analytes can enter the fiber core or the cladding layer through permeation to act with fluorescent MOFs particles fixed in the fiber core or the cladding layer, so that the fluorescence monitoring and sensing functions of in-situ, real-time, remote and even living bodies can be effectively realized based on the prepared hydrogel optical fiber, and the sensing applicability of the fluorescent MOFs material is greatly improved.
In order to achieve the above purpose, the present invention adopts the following technical scheme.
The preparation method of the hydrogel optical fiber based on MOFs comprises the following steps:
(1) Preparation of luminescent MOFs particle composite hydrogel materials.
(1.1) preparing a luminous MOFs material, and respectively preparing a high-concentration hydrogel precursor A and a low-concentration hydrogel precursor B, wherein the hydrogel precursor is formed by mixing a hydrogel monomer, a photoinitiator and deionized water.
(1.2) finely grinding the luminous MOFs material to submicron level, and uniformly mixing the ground luminous MOFs material into the hydrogel precursor A;
(1.3) after the hydrogel precursors A and B are subjected to microporous filtration, the hydrogel precursors A and B are uniformly mixed and blended under the condition of magnetic stirring.
(2) Preparation of an integrated hydrogel fiber based on luminescent MOFs materials. Mixing the ground luminous MOFs material into a hydrogel precursor A and injecting the hydrogel precursor A into an inner charging barrel of a coaxial double charging barrel, and injecting a hydrogel precursor B into an outer charging barrel of the coaxial double charging barrel; applying pressure to the coaxial double-charging barrel by using an extrusion molding method or using a biological material 3D printer, and extruding a precursor colloid of the round rod-shaped core-in-package structure at the outlet hole of the coaxial double-charging barrel; the core pack structure includes: an inner core layer formed by the hydrogel precursor A and an outer cladding layer formed by the hydrogel precursor B; one end of the quartz optical fiber is coaxially inserted into the inner core package structure along the axial direction, and is irradiated and solidified into the hydrogel optical fiber under ultraviolet light.
The preparation method of the hydrogel optical fiber comprises the following specific steps:
(2.1) adopting coaxial double-charging barrels, wherein the inner charging barrel and the outer charging barrel are coaxially fixed in the same sleeve, the outlet hole of the inner charging barrel is a round hole, the outlet hole of the outer charging barrel is a round hole concentric with the center, and the size of the outlet hole directly determines the diameters of a fiber core and a cladding for preparing the hydrogel optical fiber;
(2.2) injecting the prepared hydrogel precursor A containing the uniform luminous MOFs material into an inner cylinder of the coaxial double cylinder, and injecting the hydrogel precursor B into an outer cylinder of the coaxial double cylinder;
(2.3) applying pressure to the coaxial double-cylinder by using an extrusion molding method or using a biomaterial 3D printer, extruding a hydrogel precursor with high viscoelasticity of a round rod-shaped core-in-core structure at an outlet hole of the coaxial double-cylinder, wherein an inner core layer of the rod-shaped core-in-core structure is a hydrogel precursor A, and an outer cladding layer of the rod-shaped core-in-core structure is a hydrogel precursor B;
(2.4) taking a certain length of common quartz-based optical fiber, removing a coating layer and an end surface bevel angle, and axially and coaxially inserting a certain length into the inner cladding of the hydrogel precursor with high viscoelasticity of the prepared round rod-shaped core-in-package structure; the tail fiber of the other section is butted with the output end of the delay optical fiber.
(2.5) placing the round bar-shaped hydrogel precursor with the quartz-based optical fiber under ultraviolet light for radiation curing to obtain the hydrogel optical fiber.
Further, the preparation method of the MOFs-based hydrogel optical fiber comprises the following steps:
(1) Preparing a hydrogel precursor A and a hydrogel precursor B respectively, wherein the two hydrogel precursors are formed by mixing hydrogel monomers, a photoinitiator and deionized water, the concentration range of the hydrogel monomers in the hydrogel precursor A is 0.4-0.7 g/ml, the concentration range of the hydrogel monomers in the hydrogel precursor B is 0.3-0.6 g/ml, and the concentration of the hydrogel monomers in the hydrogel precursor A is 0.05-0.15 g/ml higher than that of the hydrogel B.
(2) Mixing the ground metal organic framework particles into a hydrogel precursor A and injecting the hydrogel precursor A into an inner charging barrel of a coaxial double charging barrel, and injecting a hydrogel precursor B into an outer charging barrel of the coaxial double charging barrel; applying pressure to the coaxial double-cylinder by using an extrusion molding method or using a biomaterial 3D printer, and extruding a mixed precursor of the round rod-shaped core-in-package structure at an outlet hole of the coaxial double-cylinder; the core pack structure includes: an inner core layer formed by the hydrogel precursor A and an outer cladding layer formed by the hydrogel precursor B; one end of the quartz optical fiber is coaxially inserted into the inner core layer structure along the axial direction, and is irradiated and solidified into the hydrogel optical fiber under ultraviolet light.
Further, the hydrogel monomer is polyethylene glycol diacrylate, polyvinyl alcohol, polylactic acid-glycolic acid copolymer, polymethyl methacrylate and alginic acid.
Furthermore, the hydrogel precursor is selected to have proper concentration so as to obtain good light transmittance, refractive index, swelling rate and mechanical property.
Further, the Metal Organic Frameworks (MOFs) are carboxylic acid ligand MOFs, zirconium-based porphyrin MOFs, nitrogen-containing ligand MOFs, zeolite-like imidazole MOFs, fluorinated MOFs, and europium-doped naphthalene dicarboxylic acid MOFs.
Further, the luminescent MOFs material is ground to submicron order and then mixed and doped into the hydrogel precursor A.
The sensing device of the hydrogel optical fiber based on MOFs comprises an excitation light source, a Y-shaped optical fiber, a delay optical fiber, an optical fiber joint, a hydrogel optical fiber, a long-pass filter, a fluorescence spectrometer and a signal processing unit; the optical fiber output interface of the excitation light source is connected with a first port on the double end side of the Y-shaped optical fiber, the port on the single end side of the Y-shaped optical fiber is connected with a delay optical fiber, the output end of the delay optical fiber is in butt joint with a quartz optical fiber tail fiber of a hydrogel optical fiber at the optical fiber connection position, the hydrogel optical fiber is used as a sensing unit to be placed in an environment to be detected, a reflected light signal generated in the hydrogel optical fiber returns to the double end side of the Y-shaped optical fiber through an original path, a second port on the double end side of the Y-shaped optical fiber is connected to a long-pass filter, a fluorescent signal obtained after the scattered light of excitation light is filtered is connected to a fluorescent spectrometer or a high-sensitivity photoelectric detector, the fluorescent spectrum is measured in real time through the fluorescent spectrometer, measured data is input into a signal processing unit, the concentration condition of an object to be detected is demodulated according to the real-time fluorescent spectrum, and the calibration and sensing application of the concentration of the external object to be detected are realized based on the change of the fluorescent spectrum intensity or the fluorescence service life.
Further, the excitation light source is an LED light source, a semiconductor laser or a fiber laser, and the emission wavelength of the excitation light source is the same as the excitation wavelength corresponding to the MOFs material.
Further, the cut-off wavelength of the long-pass filter is larger than the wavelength of the excitation light source and smaller than the fluorescence wavelength emitted by the MOFs material.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the hydrogel material adopted by the invention has good light conductivity, ion permeability and biocompatibility, the high-selectivity luminous MOFs particle material is integrated into the hydrogel fiber core, the analyte can enter the fiber core through the permeation effect to act with the luminous MOFs particles fixed in the fiber core, and the mechanical combination property of the luminous MOFs material and the optical fiber can be greatly enhanced by the composite fixation mode of the MOFs material, so that the stable long-term application in a severe environment is realized.
2. According to the invention, the integrated hydrogel sensing optical fiber based on the luminous MOFs material is prepared, the introduction of excitation light and the collection of fluorescence can be efficiently realized by connecting the common quartz optical fiber fixed at the tail end of the hydrogel optical fiber, the fluorescence monitoring and sensing functions of in-situ, real-time, remote and even living bodies are further effectively realized, and the sensing applicability of the luminous MOFs material is greatly improved.
3. The invention adopts an all-fiber structure, has simple structure and low cost, is easy to integrate with the existing fiber system, constructs a large-scale fiber sensing monitoring network, and realizes the real-time monitoring application of distributed and multi-parameter.
Drawings
FIG. 1 is a schematic diagram of a coaxial dual cartridge based on the preparation of hydrogel optical fibers;
FIG. 2 is a diagram of the polyethylene glycol diacrylate hydrogel fiber prepared in example 1;
FIG. 3 is a diagram showing the connection of a composite hydrogel fiber optic sensing device based on europium-doped naphthalene dicarboxylic acid MOFs material in example 1;
FIG. 4a is a graph showing the fluorescence spectrum of the explosive 2, 4, 6-trinitrophenol concentration monitoring based on europium-doped naphthalene dicarboxylic acid MOFs material composite hydrogel optical fiber in example 1;
FIG. 4b is a graph showing the correlation between the concentration of explosive 2, 4, 6-trinitrophenol and the fluorescence intensity decay in example 1 based on europium-doped naphthalene dicarboxylic acid MOFs material composite hydrogel optical fiber.
In the figure: 1-an excitation light source; 2-Y-type optical fiber; 3-delay optical fiber; 4-optical fiber connection; 5-hydrogel optical fiber; 6-an environment to be tested; 7-a long-pass filter; 8-fluorescence spectrometer; 9-a signal processing unit; 101-an inner barrel; 102-an outer cartridge; 103-an inner cartridge outlet aperture; 104-outer cartridge outlet aperture.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but embodiments of the present invention are not limited thereto, and it should be noted that the following processes or symbols, if any, are not specifically described in detail, will be understood or implemented by those skilled in the art with reference to the prior art.
Example 1
A method of preparing a hydrogel fiber based on a luminescent metal organic framework material.
Step one: preparing the europium-doped naphthalene dicarboxylic acid MOFs material with high hydrothermal stability: europium-doped naphthalene dicarboxylic acid MOFs of the formula
(CH 3 ) 2 NH 2 ] 2 [Eu 6 (m 3 -OH) 8 (1,4-NDC) 6 (H 2 O) 6 Wherein the mass fraction of Eu is 36%. The europium-doped naphthalene dicarboxylic acid MOFs is synthesized by solvothermal method, specifically by reacting 1, 4-naphthalene dicarboxylic acid (9.41 mg, 0.0435 mmol), eu (NO) 3 ) 3 ·6H 2 O (19.4 mg, 0.0435 mmol), 2-fluorobenzoic acid (48.7 mg, 0.348 mmol) were dissolved in dimethylformamide (2.2 mL), H 2 O (0.5 mL), and HNO 3 (0.3. 0.3 mL, concentration is 3.5 mol/L, solvent is dimethylformamide) and then the glass bottle with the mixed liquid is placed at 115 ℃ for reaction for 60 hours.
The hydrogel precursor is formed by mixing polyethylene glycol diacrylate, 2-hydroxy-2-methyl propiophenone and deionized water, wherein 53ml of deionized water and 45ml of polyethylene glycol diacrylate (solution density is 1.12 g/ml) and 2ml of 2-hydroxy-2-methyl propiophenone (solution density is 1 g/ml) are used for mixing to prepare 100ml of hydrogel precursor A, and the concentration of the polyethylene glycol diacrylate is 0.5g/ml; 100ml of hydrogel precursor B was prepared by mixing 62ml of deionized water, 36ml of polyethylene glycol diacrylate (solution density 1.12 g/ml), 2ml of 2-hydroxy-2-methylpropionophenone (solution density 1 g/ml), and the concentration of polyethylene glycol diacrylate was 0.4g/ml. Finely grinding europium-doped naphthalene dicarboxylic acid MOFs material to submicron order, taking 10mg of ground europium-doped naphthalene dicarboxylic acid MOFs material and uniformly mixing into the hydrogel precursor A.
Step two: as shown in fig. 1, in a coaxial dual-cylinder design, an inner cylinder 101 and an outer cylinder 102 are coaxially fixed in the same sleeve, an outlet hole of the inner cylinder 101 is a round hole, an outlet hole of the outer cylinder 102 is a concentric circular hole, the prepared hydrogel precursor A containing europium-doped naphthalene dicarboxylic acid MOFs material is injected into the inner cylinder 101, and a hydrogel precursor B is injected into the outer cylinder 102; applying pressure to the coaxial double cylinders by using an extrusion molding method or using a biomaterial 3D printer, extruding a hydrogel precursor with a round rod-shaped core-in-package structure at the outlet holes of the coaxial double cylinders, extruding an inner core layer of the hydrogel precursor A by using an inner cylinder outlet hole 103, and extruding an outer core layer of the hydrogel precursor B by using an outer cylinder outlet hole 104; taking a section of common quartz optical fiber, removing a coating layer at one end and beveling the end face of the common quartz optical fiber by an angle of 8 degrees, coaxially inserting the common quartz optical fiber into an inner core layer of the prepared hydrogel precursor with the round rod-shaped core-in-package structure along the axial direction, and radiating the common quartz optical fiber under 365nm ultraviolet light, wherein the energy density of the ultraviolet light radiation is 5mW/cm 2 Ultraviolet curing for 1-5 minutes for molding, and the common quartz fiber pigtail at the other end is used for welding.
Fig. 2 shows a schematic diagram of a composite hydrogel fiber based on europium-doped naphthalene dicarboxylic acid MOFs material prepared in example one.
The sensing device based on the luminous MOFs material hydrogel optical fiber comprises an excitation light source 1, a Y-shaped optical fiber 2, a delay optical fiber 3, an optical fiber joint 4, a hydrogel optical fiber 5, an environment to be detected 6, a long-pass filter 7, a fluorescence spectrometer 8 and a signal processing unit 9, as shown in fig. 3. The connection steps of the sensing device are as follows:
(a) Connecting an optical fiber output interface of the excitation light source 1 with tail fiber output with a first port 201 at the two end sides of the Y-shaped optical fiber 2;
(b) After a single-end side output port 201 of a Y-shaped optical fiber 2 is connected with a delay optical fiber 3 with a certain length, the single-end side output port is butted with a quartz fiber tail fiber of an integrated hydrogel optical fiber 5 sensing head prepared in the steps at an optical fiber connection part 4 and the output end of the delay optical fiber 3, and the hydrogel optical fiber is partially immersed or fully immersed in an actual water sensing environment 6 to be measured;
(c) At the second port 203 of the dual-port side of the Y-shaped optical fiber 2, a long-pass filter 7 is connected to filter out the scattered excitation light influence in the reflected light, and the reflected light signal generated in the hydrogel optical fiber 5 returns to the dual-end side of the Y-shaped optical fiber 2 via the original path.
(d) And the long-pass filter 7 is connected with the fluorescence spectrometer 8, a fluorescence signal obtained after scattered light of excitation light is filtered is injected into the fluorescence spectrometer 8, a fluorescence spectrum is measured in real time through the fluorescence spectrometer, measurement data is input into the signal processing unit 9, the concentration condition of an object to be measured is demodulated according to the real-time fluorescence spectrum, and the calibration and sensing application of the concentration of the external object to be measured are realized based on the change of the fluorescence spectrum intensity or the fluorescence service life.
The excitation light source 1 is an 365nm LED light source, has output power of 10mW and is provided with an optical fiber output interface.
The Y-shaped optical fiber 2 is made of an ultraviolet-resistant quartz Y-shaped optical fiber, a port 201 at the two end sides of the Y-shaped optical fiber is connected with an output port of an excitation light source optical fiber, a port 202 at the single end side of the Y-shaped optical fiber realizes the introduction of excitation light, and a port 203 at the two end sides of the Y-shaped optical fiber realizes the collection of reflection fluorescence.
The delay optical fiber 3 adopts quartz multimode optical fibers, the diameter sizes of a fiber core and a cladding are 400 mu m and 440 mu m respectively, and the length is 1 m, so that long-range low-loss light transmission and collection are realized.
And the optical fiber connecting part 4 adopts an optical fiber fusion splicer to fuse the output end of the delay optical fiber 3 with the quartz optical fiber tail fiber of the hydrogel optical fiber so as to realize the communication of optical paths.
The hydrogel optical fiber 5 is a reflection type fiber fluorescence sensor and is provided with a quartz tail fiber which is completely consistent with the model of the delay optical fiber 3.
The environment to be measured 6 is a simulation environment of a hydrogel optical fiber sensing test, in this embodiment a culture dish solution, to which the concentration of explosives 2, 4, 6-trinitrophenol is added gradually.
The long-pass filter 7 is an optical fiber integrated optical wave plate, fluorescence with the wavelength higher than 500 nm can pass through, the scattering of the excitation light with the wavelength lower than 500 nm is cut off, and the measurement interference of the scattered light with the wavelength of the excitation light 365nm on the fluorescence is reduced.
The fluorescence spectrometer 8 is provided with an optical fiber input interface to realize the measurement of fluorescence spectrum.
The signal processing unit 9 is a fluorescence monitoring processing unit of an optical fiber sensor, and demodulates the concentration condition of the explosive 2, 4, 6-trinitrophenol to be detected according to a real-time fluorescence spectrum.
In the first embodiment, the optical fiber output interface of the excitation light source 1 is connected to the first port 201 on the two end sides of the Y-shaped optical fiber 2, the port 202 on the single end side of the Y-shaped optical fiber 2 is connected to the delay optical fiber 3, the output end of the delay optical fiber 3 is in fusion connection with the quartz fiber tail 501 of the hydrogel optical fiber 5 at the optical fiber connection site 4, the hydrogel optical fiber 5 is placed as a sensing unit in the environment 6 to be measured, the reflected light signal generated in the hydrogel optical fiber 5 returns to the Y-shaped optical fiber 2 through the original path, the second port 203 on the two end sides of the Y-shaped optical fiber 2 derives the reflected light signal and is connected to the long-pass filter 7, the fluorescent signal obtained after filtering the scattered light of the excitation light therein is connected to the optical fiber input interface of the fluorescent spectrometer 8, the fluorescent spectrum is measured in real time by the fluorescent spectrometer 8, the relevant measured data is input to the signal processing unit 9, and the concentration condition of the explosives 2, 4, 6-trinitrophenol to be measured as shown in fig. 4a and 4b is demodulated according to the real-time fluorescent spectrum. As the concentration of 2, 4, 6-trinitrophenol is gradually increased from 0 μl to 140 μl, fluorescence is gradually quenched along with the increase of the concentration, as in a fluorescence spectrum shown in fig. 4a, taking the peak intensity of the fluorescence spectrum as the concentration correlation value of the to-be-detected object, the fluorescence intensity is inversely proportional to the concentration of the to-be-detected explosive 2, 4, 6-trinitrobenzene, and fitting to obtain a concentration-intensity variation curve shown in fig. 4b, wherein it is found that the fluorescence intensity is linearly reduced along with the increase of the concentration of the to-be-detected explosive 2, 4, 6-trinitrobenzene.
Because the polyethylene glycol diacrylate hydrogel material has good light conductivity, ion permeability and biocompatibility, the high-selectivity fluorescent europium-doped naphthalene dicarboxylic acid MOFs particle material for explosives 2, 4, 6-trinitrophenol is integrated into the fiber core of the hydrogel fiber 5, and the concentration-related quenching of fluorescence is caused by the fact that the explosives 2, 4, 6-trinitrophenol molecules enter the fiber core through the permeation effect and react with the luminescent europium-doped naphthalene dicarboxylic acid MOFs particles fixed in the fiber core, the mechanical combination property of the luminescent MOFs material and the fiber is greatly enhanced by the MOFs-integrated hydrogel fiber, the introduction of excitation light and the collection of fluorescence can be effectively realized by connecting the common quartz fiber fixed at the tail end of the hydrogel fiber 5, and the in-situ, real-time and remote fluorescence monitoring and sensing application for the explosives 2, 4, 6-trinitrophenol can be effectively realized. The embodiment adopts an all-fiber structure, has simple structure and low cost, is easy for the integration of the existing fiber system, and further constructs a large-scale fiber sensing monitoring network.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (8)
1. The preparation method of the hydrogel optical fiber based on MOFs is characterized by comprising the following steps of:
(1) Preparing a hydrogel precursor A and a hydrogel precursor B respectively, wherein the two hydrogel precursors are formed by mixing hydrogel monomers, a photoinitiator and deionized water, the concentration range of the hydrogel monomers in the hydrogel precursor A is 0.4-0.7 g/ml, the concentration range of the hydrogel monomers in the hydrogel precursor B is 0.3-0.6 g/ml, and the concentration of the hydrogel monomers in the hydrogel precursor A is 0.05-0.15 g/ml higher than that of the hydrogel B;
(2) Mixing the ground Metal Organic Frameworks (MOFs) particles into a hydrogel precursor A and injecting the hydrogel precursor A into an inner cylinder of a coaxial double cylinder, and injecting a hydrogel precursor B into an outer cylinder of the coaxial double cylinder; applying pressure to the coaxial double-cylinder by using an extrusion molding method or using a biomaterial 3D printer, and extruding a mixed precursor of the round rod-shaped core-in-package structure at an outlet hole of the coaxial double-cylinder; the core pack structure includes: an inner core layer formed by the hydrogel precursor A and an outer cladding layer formed by the hydrogel precursor B; one end of the quartz optical fiber is coaxially inserted into the inner core layer structure along the axial direction, and is irradiated and solidified into the hydrogel optical fiber under ultraviolet light.
2. The method for preparing the hydrogel optical fiber based on the luminous MOFs, according to claim 1, wherein the hydrogel monomer is polyethylene glycol diacrylate, polyvinyl alcohol, polylactic acid-glycolic acid copolymer, polymethyl methacrylate or alginic acid.
3. The method of claim 1, wherein the Metal Organic Frameworks (MOFs) are carboxylic acid ligand MOFs, zirconium porphyrin MOFs, nitrogen ligand MOFs, zeolite-like imidazole MOFs, fluorinated MOFs, and europium-doped naphthalene dicarboxylic acid MOFs.
4. The method of claim 1, wherein the Metal Organic Frameworks (MOFs) are ground to submicron order and then blended into the hydrogel precursor a.
5. A MOFs-based hydrogel optical fiber made by the method of any one of claims 1-4.
6. A sensing device using the MOFs-based hydrogel fiber according to claim 5, comprising an excitation light source, a Y-type fiber, a delay fiber, a fiber junction, a hydrogel fiber, a long-pass filter, a fluorescence spectrometer, and a signal processing unit; the optical fiber output interface of the excitation light source is connected with a first port of the double end side of the Y-shaped optical fiber, the port of the single end side of the Y-shaped optical fiber is connected with a delay optical fiber, the output end of the delay optical fiber is in butt joint with a quartz optical fiber tail fiber of a hydrogel optical fiber at the optical fiber connection position, the hydrogel optical fiber is used as a sensing unit to be placed in an environment to be detected, a reflected light signal generated in the hydrogel optical fiber returns to the double end side of the Y-shaped optical fiber through an original path, a second port of the double end side of the Y-shaped optical fiber is connected to a long-pass filter, a fluorescent signal obtained after the scattered light of excitation light is filtered is connected to a fluorescent spectrometer, the fluorescent spectrum is measured in real time through the fluorescent spectrometer, measurement data is input to a signal processing unit, and the concentration condition of an object to be detected is demodulated according to the real-time fluorescent spectrum.
7. The sensing device of claim 6, wherein the excitation light source is an LED light source, a semiconductor laser, or a fiber laser, and the emission wavelength of the excitation light source is the same as the excitation wavelength corresponding to metal-organic frameworks (MOFs).
8. The sensing device of claim 6, wherein the cut-off wavelength of the long pass filter is greater than the wavelength of the excitation light source and less than the wavelength of fluorescence emitted by Metal Organic Frameworks (MOFs).
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| CN110724293A (en) * | 2019-09-10 | 2020-01-24 | 上海电力大学 | Preparation method of hydrogel optical fiber cladding |
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