CN109211859A - Hydrogel optical fiber based on luminous MOFs and preparation method thereof and sensing device - Google Patents
Hydrogel optical fiber based on luminous MOFs and preparation method thereof and sensing device Download PDFInfo
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- CN109211859A CN109211859A CN201811133196.6A CN201811133196A CN109211859A CN 109211859 A CN109211859 A CN 109211859A CN 201811133196 A CN201811133196 A CN 201811133196A CN 109211859 A CN109211859 A CN 109211859A
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- 239000000835 fiber Substances 0.000 claims abstract description 36
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- UATJOMSPNYCXIX-UHFFFAOYSA-N Trinitrobenzene Chemical compound [O-][N+](=O)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1 UATJOMSPNYCXIX-UHFFFAOYSA-N 0.000 description 2
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Classifications
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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
-
- 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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- Health & Medical Sciences (AREA)
- Immunology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Optics & Photonics (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention discloses hydrogel optical fiber based on luminous MOFs and preparation method thereof and sensing devices.MOFs micromeritics is uniformly mixed into hydrogel precursor by the preparation method, by hydrogel precursor, it is injected separately into coaxial double cartridge simultaneously, the core pack arrangement cylindrical body with suitable dimension is squeezed out from cartridge outlet by extrusion molding or biomaterial 3D printer, by in the coaxial core pack arrangement cylindrical sides sandwich layer for being inserted into extrusion in common silica fibre one end, the hydrogel optical fiber with ordinary optic fibre tail optical fiber is obtained after solidification.Sensing device includes exciting light sources, y-type optical fiber, delay optical fiber, optical fiber junction, hydrogel optical fiber, long pass filter piece, Fluorescence Spectrometer and signal processing unit.Overall technical architecture of the present invention can construct the highly selective fluorescence sense for realizing all-fiber, further realize the fluorescence detection and sensing of in situ, real-time, long-range even living body, promote the Application in Sensing for the MOFs material that shines.
Description
Technical field
The present invention relates to optical fiber fluorescence field of sensing technologies, more particularly to hydrogel optical fiber and its preparation side based on MOFs
Method and sensing device.
Background technique
Metal-organic frame (Metal-Organic Frameworks, abbreviation MOFs), is by organic ligand and metal
The novel porous materials that node is self-assembly of by coordinate bond have great specific surface area and lower cost, are sensing
The fields such as identification, catalytic luminescence, information storage have important application prospect.Luminous MOFs material based on lanthanide rare metal
It is a kind of important orderly crystalline compound, fluorescence can be generated under the effect of extraneous exciting light, fluorescence MOFs material has rich
Rich electronic structure and excellent photophysical property (such as characteristic emission peak sharp, high luminous efficiency and other features), in fluorescence sense
Aspect has many advantages, such as that fast detection speed, high sensitivity, selectivity are good, reliable and stable, becomes the desirable fluorescent probe of a new generation
Material.Various luminous MOFs materials are developed, be applied to as solion, volatile organic compounds, gas,
The highly selective sensing of explosive molecule, biomolecule etc..
Although there is highly selective luminous MOFs fluorescence detection material to have obtained extensively quickly development, based on hair
In the fluorescence detection practical application of light MOFs material, there is seriously hinder it to develop towards functionization aspect.Firstly,
Fluorescence detection of the overwhelming majority based on luminous MOFs material is that the MOFs particle powder that will be prepared is immersed in analysans
It samples in solution, or is exposed in gas and steam to be analyzed, and to be injected into active somatic cell medium, then these are made
Sample, which is placed under fluorescence spectrum equipment, carries out offline spectral measurement analysis.Due to uneven distribution of the MOFs particle in sampling solution
And erratic motion and MOFs pressed powder the problems such as easily being dispelled by air-flow in gaseous environment, it is strong to will cause fluorescence spectrum
It spends fluctuation and makes measurement inaccuracy, while also resulting in fluorescence detection material rapid wear to cause the service life too short and be difficult to recycle secondary benefit
The problems such as with caused waste, researcher propose preparation MOFs film or composite membrane, realize that MOFs particle in-situ is grown in load
Body substrate surface or the composite membrane for constructing MOFs particle and other materials, overcome the powder dispersed of MOFs material to bring inconvenience survey
Amount and service life short equal application problems (such as existing patent of invention 201710667152.0,201511027933.0,
201610751719.8 waiting).But strong mechanical bonding force, uniform MOFs in large size needed for building industrialization and commercialization
Film still has huge challenge.Secondly, the sensor based on MOFs material can not be imposed on by direct cloth it is harsh severe true
In real application environment, because fluorescence measurement needs accurate reliable optical path to realize the importing of exciting light and the collection of fluorescence, absolutely
The large commercial fluorescence measurement equipment that the sensing demonstration of most of MOFs material all relies on lab platform does offline sampling
Measurement, this measurement method limit significantly shine MOFs material further realize original position, living body, in real time and at a distance etc. advanced biography
The function of sense.Scheme more with potential applications is to realize that fluorescence sense, ordinary optic fibre are used for based on MOFs material integrated optical fiber
Effectively transmission laser light and fluorescence is collected, without the accurate optical path of large-scale instrument, shining MOFs Material growth or is wrapped in
(Sens. Actuators B:Chem. 2016,232,43-51) or long-period fiber grating are gone on cladded-fiber outer diameter
(Opt. Lett. on (Sens. Actuators B:Chem. 2015,221,891-899) or fiber end face on outer diameter
2016,41,1696-1699) guide-lighting low efficiency, but in these schemes is still remained, shine MOFs material and mechanical fiber optic knot
Weak and MOFs mold materials directly contact adverse circumstances and service life short grade application problems with joint efforts.
In view of the globality of optical measurement, completely new luminous MOFs material integrated-type permeability optical fiber is invented, it can be significantly
Enhance the injection of the ambient adaptability, exciting light of the MOFs material that shines and the collection of week fluorescent, while analysans passes through infiltration
With the luminous MOFs material in permeability optical fiber useful effect can occur for effect thoroughly, can optimize and be promoted the reality of luminous MOFs material
Border application.
Summary of the invention
The purpose of the present invention is to overcome the shortcomings of the existing technology and deficiency, provides the hydrogel based on luminous MOFs material
Optical fiber and preparation method thereof and sensing device.Selection has the hydrogel of good light permeability, ion permeability and biocompatibility
Material is matrix material of optic fibre, allows the hydrogel optical fiber based on its preparation more low-loss guide-lighting and realization is efficient just
Prompt exciting light imports and phosphor collection.The MOFs micromeritics that will be provided with highly selective fluorescence sense function is uniformly mixed into water-setting
In glue presoma, the hydrogel precursor of various concentration is deployed to meet the refractive index design requirement of fibre core and covering, is adjusted simultaneously
The viscoplasticity of whole hydrogel precursor passes through extrusion molding or biomaterial to being injected separately into coaxial double cartridge after higher
3D printer squeezes out the core pack arrangement cylindrical body with suitable dimension from cartridge outlet, by the common coaxial insertion in silica fibre one end
Into the core pack arrangement cylindrical sides sandwich layer of extrusion, the water-setting with ordinary optic fibre tail optical fiber is obtained after solidifying under ultraviolet radiation
Glue optical fiber.The integrated water gelatinous sensor optical fiber based on fluorescence MOFs material is prepared accordingly, by being connected to hydrogel optical fiber
The ordinary optic fibre of tail end can efficiently realize the importing of exciting light and the collection of fluorescence, and analysans can be entered by osmosis
Fibre core or covering and have an effect with the fluorescence MOFs particle being fixed therein, therefore, the hydrogel optical fiber prepared based on this
It can effectively realize the fluorescence monitoring and sensing function of in situ, real-time, long-range even living body, significant increase fluorescence MOFs material
Application in Sensing.
To achieve the above object, the present invention adopts the following technical scheme that.
A kind of preparation method of the hydrogel optical fiber based on MOFs, comprising the following steps:
(1) preparation of luminous MOFs Particles dispersed hydrogel material.
(1.1) it first prepares luminous MOFs material, then the hydrogel precursor A and low concentration of high concentration is prepared respectively
Hydrogel precursor B, hydrogel precursor are made of the mixing of hydrogel monomer, photoinitiator and deionized water.
(1.2) fine gtinding shines MOFs material to sub-micrometer scale, by the luminous uniform blending of MOFs material after grinding
Into hydrogel precursor A；
(1.3) above-mentioned hydrogel precursor A and B is all placed in uniform blending under the conditions of magnetic agitation using after micro porous filtration.
(2) preparation of the integrated water gel optical fiber based on luminous MOFs material.Luminous MOFs material after grinding is mixed
The interior barrel of coaxial double cartridge is mixed in hydrogel precursor A and is injected into, hydrogel precursor B is injected into coaxial double cartridge
Outer barrel；Using extrusion molding or biomaterial 3D printer is used, applies pressure, the outlet of coaxial double cartridge to coaxial double cartridge
The presoma colloid of circle stock core pack arrangement is squeezed out at hole；The core pack arrangement includes: the inner sandwich layer that hydrogel precursor A is constituted
The surrounding layer constituted with hydrogel precursor B；Silica fibre one end is co-axially inserted one section to inner core pack arrangement, juxtaposition along axial direction
Radiation curing is at hydrogel optical fiber under ultraviolet light.
Specific step is as follows for the preparation of the hydrogel optical fiber:
(2.1) coaxial double cartridge is used, interior barrel is coaxial with outer barrel to be fixed in same sleeve, and interior cartridge outlet hole is circle
Hole, outer cartridge outlet hole are the annulus hole with concentric, and the directly decision of outlet orifice sizes size prepares the fibre core of hydrogel optical fiber
With cladding diameter；
(2.2) prepare includes that the hydrogel precursor A of uniformly light-emitting MOFs material is injected into coaxial double cartridge by above-mentioned
Interior barrel in, hydrogel precursor B is injected into the outer barrel of coaxial double cartridge；
(2.3) using extrusion molding or using biomaterial 3D printer, apply pressure to coaxial double cartridge, squeezed out at outlet opening
Circle stock core pack arrangement has high viscoelastic hydrogel precursor, and the inner sandwich layer of stock core pack arrangement is hydrogel precursor
A, surrounding layer are hydrogel precursor B；
(2.4) the common silica-based optical fiber of certain length is taken, one section is removed coat and end face sharping, is co-axially inserted along axial direction
Certain length is into the inner cladding with high viscoelastic hydrogel precursor of the above-mentioned circle stock core pack arrangement being prepared；
Another section of tail optical fiber is docked with the output end of delay optical fiber.
(2.5) the pole shape hydrogel precursor by above-mentioned with silica-based optical fiber is placed in radiation curing Cheng Shui under ultraviolet light
Gel optical fiber.
Further, the preparation method of the hydrogel optical fiber based on MOFs, comprising the following steps:
(1) hydrogel precursor A and hydrogel precursor B is prepared respectively, and two kinds of hydrogel precursors are by hydrogel monomer, light
Initiator and deionized water mixing composition, wherein concentration range shared by hydrogel monomer is 0.4 ~ 0.7 in hydrogel precursor A
Concentration range shared by hydrogel monomer is 0.3 ~ 0.6 g/ml, water in hydrogel precursor A in g/ml, hydrogel precursor B
0.05 ~ 0.15 g/ml higher than hydrogel B of concentration shared by gel monomers.
(2) the Metal-organic frame particle blending after grinding into hydrogel precursor A and is injected into coaxial extra quality
The interior barrel of cylinder, hydrogel precursor B are injected into the outer barrel of coaxial double cartridge；It is beaten using extrusion molding or using biomaterial 3D
Print machine applies pressure to coaxial double cartridge, the mixing presoma of circle stock core pack arrangement is squeezed out at the outlet opening of coaxial double cartridge；
The core pack arrangement includes: the surrounding layer that the inner sandwich layer that hydrogel precursor A is constituted and hydrogel precursor B are constituted；It will be quartzy
Optical fiber one end is co-axially inserted one section to inner sandwich layer structure along axial direction, is placed under ultraviolet light radiation curing into hydrogel optical fiber.
Further, the hydrogel monomer is polyethyleneglycol diacrylate, polyvinyl alcohol, poly lactic-co-glycolic acid
Copolymer, polymethyl methacrylate, alginic acid.
Further, the hydrogel precursor selects suitable concentration, with the translucency, refractive index, molten obtained
Swollen rate and mechanical property.
Further, the Metal-organic frame (MOFs) is carboxylate ligand figure MOFs, zirconium base porphyrin MOFs, nitrogenous matches
Figure MOFs, class zeolite imidazole type MOFs, it is fluorinated MOFs and mixes europium naphthalenedicarboxylic acid MOFs.
Further, the luminous MOFs material is ground to after sub-micrometer scale blending again into hydrogel precursor A.
The sensing device of hydrogel optical fiber based on MOFs, including exciting light sources, y-type optical fiber, delay optical fiber, optical fiber connect
Connect place, hydrogel optical fiber, long pass filter piece, Fluorescence Spectrometer, signal processing unit；The optical fiber output of the exciting light sources connects
The port of the first port of mouth connection y-type optical fiber both-end side, the single-ended side of y-type optical fiber is connect with delay optical fiber, postpones the defeated of optical fiber
Outlet is docked with the silica fibre tail optical fiber of hydrogel optical fiber in optical fiber junction, and hydrogel optical fiber is placed in be measured as sensing unit
In environment, the reflected light signal generated in hydrogel optical fiber is via backtracking to y-type optical fiber both-end side, y-type optical fiber both-end side
Second port be connected to long pass filter piece, filter out the fluorescence signal obtained after the scattering light of exciting light and be connected to Fluorescence Spectrometer
Or in highly sensitive photodetector, fluorescence spectrum is measured in real time through Fluorescence Spectrometer, measurement data is input at signal
It manages unit and the concentration levels of determinand is demodulated according to real-time fluorescence spectrum, based on photoluminescence spectrum intensity or fluorescence lifetime
The calibration and Application in Sensing of extraneous testing concentration are realized in variation.
Further, the exciting light sources are LED light source, semiconductor laser or optical fiber laser, exciting light sources
Outgoing wavelength excitation wavelength corresponding with MOFs material it is identical.
Further, the cutoff wavelength of the long pass filter is greater than the wavelength of exciting light sources, and is less than MOFs material
The wavelength of fluorescence emitted.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1, the hydrogel material that the present invention uses has good light conductivity, ion permeability and biocompatibility, by high selection
Property shine MOFs granular materials be integrated into hydrogel fiber core, analysans can enter fibre core and fixation by osmosis
Have an effect in luminous MOFs particle therein, the compound fixed form of this MOFs material can greatly enhance luminous MOFs material with
The mechanical bond of optical fiber realizes the stabilization prolonged application in harsh environment.
2, the present invention prepares the integrated water gelatinous sensor optical fiber based on luminous MOFs material, by being fastened on water
The common silica fibre of gel optical fiber tail-end can efficiently realize the importing of exciting light and the collection of fluorescence, further effectively realize
The fluorescence monitoring and sensing function of in situ, real-time, long-range even living body, the Application in Sensing of the luminous MOFs material of significant increase.
3, the present invention uses all optical fibre structure, and structure is simple, at low cost, is easy to existing fibre system and integrates, building is big
The optical fiber sensing monitoring network of type realizes distributed and multi-parameter real-time monitoring application.
Detailed description of the invention
Fig. 1 is based on the coaxial double cartridge schematic diagram for preparing hydrogel optical fiber；
Fig. 2 is the two double methacrylate hydrogel optical fiber pictorial diagram of polyethylene glycol being prepared in embodiment 1；
Fig. 3 is to be based on mixing europium naphthalenedicarboxylic acid MOFs Material cladding hydrogel fibre-optical sensing device connection figure in embodiment 1；
Fig. 4 a is to carry out explosive 2,4,6- based on europium naphthalenedicarboxylic acid MOFs Material cladding hydrogel optical fiber is mixed in embodiment 1
The fluorescence spectrum result figure of trinitrophenol concentration monitor；
Fig. 4 b is to demodulate explosive 2,4,6- based on europium naphthalenedicarboxylic acid MOFs Material cladding hydrogel optical fiber is mixed in embodiment 1
Trinitrophenol concentration result figure relevant to fluorescence-intensity decay.
In figure: 1- exciting light sources；2-Y type optical fiber；3- postpones optical fiber；4- optical fiber junction；5- hydrogel optical fiber；6- is waited for
Survey environment；7- long pass filter piece；8- Fluorescence Spectrometer；9- signal processing unit；Barrel in 101-；The outer barrel of 102-；In 103-
Cartridge outlet hole；The outer cartridge outlet hole 104-.
Specific embodiment
Present invention will now be described in further detail with reference to the embodiments and the accompanying drawings, but embodiments of the present invention are unlimited
In this, if it is noted that the following process or symbol for having not special detailed description, is that those skilled in the art can refer to now
Have technology understand or realize.
Embodiment one
A kind of method for preparing hydrogel optical fiber based on luminescent metal organic framework materials.
Step 1: prepare hydrothermal stability it is high mix europium naphthalenedicarboxylic acid MOFs material: mix the chemistry of europium naphthalenedicarboxylic acid MOFs
Formula is
(CH3)2NH2]2[Eu6(m3-OH)8(1,4-NDC)6(H2O)6, wherein the mass fraction of Eu is 36%.This mixes europium naphthalenedicarboxylic acid
MOFs's is synthesized by solvent thermal process, specifically by Isosorbide-5-Nitrae-naphthalenedicarboxylic acid (9.41 mg, 0.0435 mmol), Eu
(NO3)3·6H2O (19.4 mg, 0.0435 mmol), 2- fluobenzoic acid (48.7 mg, 0.348 mmol) are dissolved in diformazan
Base formamide (2.2 mL), H2O (0.5 mL), and HNO3(0.3 mL, concentration are 3.5 mol/Ls, and solvent is dimethyl
Formamide) mixed solution in, then equipped with mixing liquid vial be placed in 115 degrees Celsius react 60 hours.
Hydrogel precursor is mixed by two double methacrylate of polyethylene glycol, 2- hydroxy-2-methyl propiophenone and deionized water
Composition, wherein with the deionized water of 53ml, two double methacrylate (solution density 1.12g/ml) of polyethylene glycol of 45ml, 2ml
2- hydroxy-2-methyl propiophenone (solution density 1g/ml), 100ml hydrogel precursor A is mixed and made into, wherein poly- second two
The concentration of two double methacrylate of alcohol is 0.5g/ml；Two double methacrylate of polyethylene glycol with the deionized water of 62ml, 36ml is (molten
Liquid density is 1.12g/ml), the 2- hydroxy-2-methyl propiophenone (solution density 1g/ml) of 2ml is mixed with the water of 100ml
Gel Precursor B, wherein two double methacrylate concentration of polyethylene glycol is 0.4g/ml.Fine gtinding mixes europium naphthalenedicarboxylic acid MOFs material
For material to sub-micrometer scale, the 10mg after taking grinding mixes the uniform blending of europium naphthalenedicarboxylic acid MOFs material into hydrogel precursor A.
Step 2: as shown in Figure 1, a kind of coaxial double cartridge design, interior barrel 101 is coaxial with outer barrel 102 to be fixed on
In same sleeve, interior 101 outlet opening of barrel is circular hole, and outer 102 outlet opening of barrel is the annulus hole of concentric, is prepared above-mentioned
Include to mix europium naphthalenedicarboxylic acid MOFs material hydrogel precursor A to be injected into interior barrel 101, hydrogel precursor B is infused
Enter into outer barrel 102；Using extrusion molding or biomaterial 3D printer is used, applies pressure, outlet to coaxial double cartridge
The hydrogel precursor of circle stock core pack arrangement is squeezed out at hole, interior cartridge outlet hole 103 is extruded as the inner core of hydrogel precursor A
Layer, outer cartridge outlet hole 104 is extruded as the surrounding layer of hydrogel precursor B；One section of common silica fibre is taken, coating is removed in one end
Layer and by its end face chamfer 8 ° of angles, be co-axially inserted 1 ~ 3cm of length to the above-mentioned circle stock core pack arrangement water being prepared along axial direction
It in the inner sandwich layer of Gel Precursor, is placed under the ultraviolet light of 365nm and radiates, ultraviolet radiation energy density is 5mW/cm2, ultraviolet
It forms within solidification 1 ~ 5 minute, the common silica fibre tail optical fiber of the other end is used for welding.
As shown in Fig. 2, to be prepared in embodiment one based on mixing europium naphthalenedicarboxylic acid MOFs Material cladding hydrogel light
Fine pictorial diagram.
Based on the sensing device of luminous MOFs material hydrogel optical fiber, as shown in figure 3, including exciting light sources 1, Y type light
Fibre 2, delay optical fiber 3, optical fiber junction 4, hydrogel optical fiber 5, environment to be measured 6, long pass filter piece 7, Fluorescence Spectrometer 8, signal
Processing unit 9.The Connection Step of the sensing device is as follows:
(a) by the first port of the optical fiber output interface connection 2 both-end side of y-type optical fiber of the exciting light sources 1 exported with tail optical fiber
201；
(b) it after the delay optical fiber 3 that the single-ended side output port 201 of y-type optical fiber 2 is connected to a segment length, and is made in above-mentioned steps
Output end of the silica fibre tail optical fiber of standby obtained 5 sensing head of integrated water gel optical fiber in optical fiber junction 4 and delay optical fiber 3
Docking, and hydrogel fiber section is submerged or is all immersed in practical water and is sensed in environment 6 to be measured；
(c) at the second port 203 of 2 dual-port side of y-type optical fiber, long pass filter piece 7 is accessed, the scattering filtered out in reflected light swashs
Shining influences, and the reflected light signal generated in hydrogel optical fiber 5 is via backtracking to 2 both-end side of y-type optical fiber.
(d) long pass filter piece 7 is connect with Fluorescence Spectrometer 8 again, filter out obtain after the scattering light of wherein exciting light it is glimmering
Optical signal is injected into Fluorescence Spectrometer 8, measures fluorescence spectrum in real time through Fluorescence Spectrometer, and measurement data is input to signal processing
Unit 9 demodulates the concentration levels of determinand according to real-time fluorescence spectrum, based on photoluminescence spectrum intensity or fluorescence lifetime
The calibration and Application in Sensing of extraneous testing concentration are realized in variation.
The exciting light sources 1 select the LED light source of 365nm, output power 10mW, band optical fiber output interface.
The y-type optical fiber 2 selects uvioresistant quartz y-type optical fiber, the port 201 of both-end side and exciting light sources optical fiber
It exports end interface to be connected, the importing of exciting light is realized in the port 202 of single-ended side, and reflected fluorescent light is realized in the port 203 of both-end side
It collects.
The delay optical fiber 3, using quartzy multimode fibre, fibre core and cladding diameter size are respectively 400 μm and 440 μm,
1 m of length realizes the low-loss optically conveying of longer range and collects.
The optical fiber junction 4 will postpone the quartz of the output end and hydrogel optical fiber of optical fiber 3 using optical fiber splicer
Optical fiber pigtail is welding together, and realizes the connection of optical path.
The hydrogel optical fiber 5 is reflection-type fibre fluorescent optical sensor, with the stone completely the same with delay 3 model of optical fiber
English tail optical fiber.
The environment to be measured 6, it is molten for culture dish in the present embodiment for the simulated environment of hydrogel Fibre Optical Sensor test
The concentration for being stepped up 2,4,6- trinitrophenol of explosive is added in liquid wherein.
The long pass filter piece 7 is optical fiber integrated optical wave plate, and fluorescence of the wavelength higher than 500 nm can pass through, wave
The long exciting light scattering lower than 500 nm is ended, and is reduced by 365 nm wavelength dispersion light of exciting light and is interfered the measurement of fluorescence.
The Fluorescence Spectrometer 8, there is optical fiber input interface, realizes the measurement of fluorescence spectrum.
The signal processing unit 9 is the fluorescence monitoring processing unit of fibre optical sensor, according to real-time fluorescence spectrum, solution
Recall the concentration levels of explosive 2,4,6- trinitrophenol to be measured.
In the present embodiment one, the first port of the optical fiber output interface connection 2 both-end side of y-type optical fiber of exciting light sources 1
201, the port 202 of the single-ended side of y-type optical fiber 2 is connect with delay optical fiber 3, postpones the output end of optical fiber 3 and the stone of hydrogel optical fiber 5
English optical fiber pigtail 501 is connected in 4 welding of optical fiber junction, and hydrogel optical fiber 5 is placed in environment 6 to be measured as sensing unit, water
The reflected light signal generated in gel optical fiber 5 is via backtracking to y-type optical fiber 2, the second port 203 of 2 both-end side of y-type optical fiber
Export reflected light signal is connected to long pass filter piece 7, filters out the fluorescence signal obtained after exciting light scattering light therein and is connected to
The optical fiber input interface of Fluorescence Spectrometer 8 measures fluorescence spectrum through Fluorescence Spectrometer 8 in real time, and related measurement data is input to letter
Number processing unit 9 demodulates 2,4, the 6- trinitro- of explosive to be measured as shown in Fig. 4 a, Fig. 4 b according to real-time fluorescence spectrum
The concentration levels of phenol.As 2,4,6- trinitrophenol concentration are stepped up from 0 μ L to 140 μ L, fluorescence can be with concentration
Increase and be gradually quenched, in fluorescence spectra as shown in fig. 4 a, takes the peak strength of fluorescence spectrum for testing concentration association
The concentration of value, fluorescence intensity and 2,4,6- trinitrobenzen of explosive to be measured is inversely proportional, and fitting obtains concentration as shown in Figure 4 b
With intensity variation curve, it can be found that the concentration with 2,4,6- trinitrobenzen of explosive to be measured increases, fluorescence intensity is linear
Weaken.
Since two double methacrylate hydrogel material of polyethylene glycol has good light conductivity, ion permeability and biofacies
Capacitive is mixed europium naphthalenedicarboxylic acid MOFs granular materials and is integrated into for the highly selective fluorescence of 2,4,6- trinitrophenol of explosive
In 5 fibre core of hydrogel optical fiber, explosive 2,4,6- trinitrophenol molecule enters fibre core by osmosis and is fixed on it
In it is luminous mix europium naphthalenedicarboxylic acid MOFs particle and have an effect cause the concentration correlation of fluorescence to quench, this MOFs integrated hydrogel
Optical fiber greatly strengthens the mechanical bond of luminous MOFs material and optical fiber, by being fastened on 5 tail end of hydrogel optical fiber
Common silica fibre can efficiently realize the importing of exciting light and the collection of fluorescence, effectively realize and be directed to explosive 2,4,6- tri-
The in situ, real-time of nitrophenol, remote fluorescence monitoring and Application in Sensing.The present embodiment uses all optical fibre structure, and structure is simple, at
This is low, is easy to existing fibre system and integrates, further the large-scale optical fiber sensing monitoring network of building.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (7)
1. a kind of preparation method of the hydrogel optical fiber based on MOFs, which comprises the following steps:
(1) hydrogel precursor A and hydrogel precursor B is prepared respectively, and two kinds of hydrogel precursors are by hydrogel monomer, light
Initiator and deionized water mixing composition, wherein concentration range shared by hydrogel monomer is 0.4 ~ 0.7 in hydrogel precursor A
Concentration range shared by hydrogel monomer is 0.3 ~ 0.6 g/ml, water in hydrogel precursor A in g/ml, hydrogel precursor B
0.05 ~ 0.15 g/ml higher than hydrogel B of concentration shared by gel monomers；
(2) Metal-organic frame (MOFs) the particle blending after grinding into hydrogel precursor A and is injected into coaxial double
The interior barrel of barrel, hydrogel precursor B are injected into the outer barrel of coaxial double cartridge；Using extrusion molding or use biomaterial 3D
Printer applies pressure to coaxial double cartridge, the mixing forerunner of circle stock core pack arrangement is squeezed out at the outlet opening of coaxial double cartridge
Body；The core pack arrangement includes: the surrounding layer that the inner sandwich layer that hydrogel precursor A is constituted and hydrogel precursor B are constituted；By stone
English optical fiber one end is co-axially inserted one section to inner sandwich layer structure along axial direction, is placed under ultraviolet light radiation curing into hydrogel optical fiber.
2. a kind of preparation method of hydrogel optical fiber based on luminous MOFs according to claim 1, which is characterized in that institute
Stating hydrogel monomer can be polyethyleneglycol diacrylate, polyvinyl alcohol, poly lactide-glycolide acid, poly- methyl-prop
E pioic acid methyl ester, alginic acid.
3. a kind of preparation method of hydrogel optical fiber based on MOFs according to claim 1, which is characterized in that the gold
Belonging to organic framework (MOFs) is carboxylate ligand figure MOFs, zirconium base porphyrin MOFs, containing n-donor ligand type MOFs, class zeolite imidazole type
MOFs, it is fluorinated MOFs and mixes europium naphthalenedicarboxylic acid MOFs.
4. a kind of preparation method of hydrogel optical fiber based on MOFs according to claim 1, which is characterized in that the gold
Belong to organic framework (MOFs) and is ground to after sub-micrometer scale blending again into hydrogel precursor A.
5. a kind of sensing device using the hydrogel optical fiber based on MOFs described in any one of claim 1 ~ 4, which is characterized in that
Including exciting light sources, y-type optical fiber, delay optical fiber, optical fiber junction, hydrogel optical fiber, long pass filter piece, Fluorescence Spectrometer,
Signal processing unit；The first port of the optical fiber output interface connection y-type optical fiber both-end side of the exciting light sources, y-type optical fiber
The port of single-ended side is connect with delay optical fiber, and the silica fibre tail optical fiber of the output end and hydrogel optical fiber that postpone optical fiber connects in optical fiber
Place's docking is connect, hydrogel optical fiber is placed in environment to be measured as sensing unit, the reflected light signal warp generated in hydrogel optical fiber
By backtracking to y-type optical fiber both-end side, the second port of y-type optical fiber both-end side is connected to long pass filter piece, filters out exciting light
Scattering light after the fluorescence signal that obtains be connected to Fluorescence Spectrometer, measure fluorescence spectrum in real time through Fluorescence Spectrometer, will measure
Data are input to signal processing unit, according to real-time fluorescence spectrum, demodulate the concentration levels of determinand.
6. sensing device according to claim 5, which is characterized in that the exciting light sources are LED light source, semiconductor swashs
Light device or optical fiber laser, the outgoing wavelength of exciting light sources excitation wave appearance corresponding with Metal-organic frame (MOFs)
Together.
7. sensing device according to claim 5, which is characterized in that the cutoff wavelength of the long pass filter is greater than excitation
The wavelength of radiant, and it is less than the wavelength of fluorescence that Metal-organic frame (MOFs) is emitted.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109912817A (en) * | 2019-03-08 | 2019-06-21 | 苏州大学 | Hydrogel nanoparticles and preparation method thereof for measuring ionizing radiation dose |
| CN109916870A (en) * | 2019-03-30 | 2019-06-21 | 华南理工大学 | Composite fiber and preparation method based on luminescent metal organic framework materials be applied to many reference amounts distribution type fiber-optic fluorescence sense system |
| CN110724293A (en) * | 2019-09-10 | 2020-01-24 | 上海电力大学 | Preparation method of hydrogel optical fiber cladding |
| CN111205467A (en) * | 2020-01-08 | 2020-05-29 | 东华大学 | Preparation method of lanthanide metal organic framework material with controllable fluorescence property |
| CN113174652A (en) * | 2021-04-30 | 2021-07-27 | 安徽大学 | Method for coaxially printing quantum dot hydrogel optical fiber and multi-parameter sensing application |
| CN113502155A (en) * | 2020-12-14 | 2021-10-15 | 广东石油化工学院 | Fluorescent probe for visually detecting doxycycline and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070215816A1 (en) * | 2006-03-16 | 2007-09-20 | Rongqing Hui | Laser system for photonic excitation investigation |
| US20090201953A1 (en) * | 2005-05-03 | 2009-08-13 | The Arizona Bd Of Reg On Behalf Of The University Az | Microstructured optical fibers and manufacturing methods thereof |
| CN101735798A (en) * | 2009-11-26 | 2010-06-16 | 华南理工大学 | Rare earth organic framework material having sensing function to acetone, preparation method and application thereof |
| EP2500314A1 (en) * | 2011-03-14 | 2012-09-19 | Nederlandse Organisatie voor toegepast -natuurwetenschappelijk onderzoek TNO | Photonic crystal sensor |
| US20140315321A1 (en) * | 2011-11-15 | 2014-10-23 | Shenzhen University | Chloride Ion Fluorescence Detection Method and Device, and Use Thereof |
| CN105842196A (en) * | 2016-05-16 | 2016-08-10 | 山东大学 | Monolayer colloidal crystal (MCC) steam sensor with surface wrapped by ultrathin metal organic framework material, preparation method and application |
| CN108246271A (en) * | 2018-02-23 | 2018-07-06 | 合肥学院 | The preparation method for the molecular blotting polymer microsphere that one kind detects for 2,4,6- trinitrophenols |
| CN108490534A (en) * | 2018-05-24 | 2018-09-04 | 重庆邮电大学 | A kind of temperature-insensitive Polarization filter based on circular hole mixed type microstructured optical fibers |
-
2018
- 2018-09-27 CN CN201811133196.6A patent/CN109211859B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090201953A1 (en) * | 2005-05-03 | 2009-08-13 | The Arizona Bd Of Reg On Behalf Of The University Az | Microstructured optical fibers and manufacturing methods thereof |
| US20070215816A1 (en) * | 2006-03-16 | 2007-09-20 | Rongqing Hui | Laser system for photonic excitation investigation |
| CN101735798A (en) * | 2009-11-26 | 2010-06-16 | 华南理工大学 | Rare earth organic framework material having sensing function to acetone, preparation method and application thereof |
| EP2500314A1 (en) * | 2011-03-14 | 2012-09-19 | Nederlandse Organisatie voor toegepast -natuurwetenschappelijk onderzoek TNO | Photonic crystal sensor |
| US20140315321A1 (en) * | 2011-11-15 | 2014-10-23 | Shenzhen University | Chloride Ion Fluorescence Detection Method and Device, and Use Thereof |
| CN105842196A (en) * | 2016-05-16 | 2016-08-10 | 山东大学 | Monolayer colloidal crystal (MCC) steam sensor with surface wrapped by ultrathin metal organic framework material, preparation method and application |
| CN108246271A (en) * | 2018-02-23 | 2018-07-06 | 合肥学院 | The preparation method for the molecular blotting polymer microsphere that one kind detects for 2,4,6- trinitrophenols |
| CN108490534A (en) * | 2018-05-24 | 2018-09-04 | 重庆邮电大学 | A kind of temperature-insensitive Polarization filter based on circular hole mixed type microstructured optical fibers |
Non-Patent Citations (1)
| Title |
|---|
| 陆颖;姚建铨;毕卫红;齐跃峰;: "新型光子晶体光纤传感器的基础研究" * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109912817A (en) * | 2019-03-08 | 2019-06-21 | 苏州大学 | Hydrogel nanoparticles and preparation method thereof for measuring ionizing radiation dose |
| CN109912817B (en) * | 2019-03-08 | 2021-05-18 | 苏州大学 | Hydrogel nanoparticles for measuring ionizing radiation dose and preparation method thereof |
| CN109916870A (en) * | 2019-03-30 | 2019-06-21 | 华南理工大学 | Composite fiber and preparation method based on luminescent metal organic framework materials be applied to many reference amounts distribution type fiber-optic fluorescence sense system |
| CN110724293A (en) * | 2019-09-10 | 2020-01-24 | 上海电力大学 | Preparation method of hydrogel optical fiber cladding |
| CN111205467A (en) * | 2020-01-08 | 2020-05-29 | 东华大学 | Preparation method of lanthanide metal organic framework material with controllable fluorescence property |
| CN113502155A (en) * | 2020-12-14 | 2021-10-15 | 广东石油化工学院 | Fluorescent probe for visually detecting doxycycline and preparation method thereof |
| CN113502155B (en) * | 2020-12-14 | 2024-01-30 | 广东石油化工学院 | Fluorescent probe for visually detecting doxycycline and preparation method thereof |
| CN113174652A (en) * | 2021-04-30 | 2021-07-27 | 安徽大学 | Method for coaxially printing quantum dot hydrogel optical fiber and multi-parameter sensing application |
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