CN107353369B - A kind of photonic crystal sensor material and its preparation method and application - Google Patents
A kind of photonic crystal sensor material and its preparation method and application Download PDFInfo
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- CN107353369B CN107353369B CN201710557860.9A CN201710557860A CN107353369B CN 107353369 B CN107353369 B CN 107353369B CN 201710557860 A CN201710557860 A CN 201710557860A CN 107353369 B CN107353369 B CN 107353369B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/06—Oxidation
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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
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/47—Scattering, i.e. diffuse reflection
- G01N21/4788—Diffraction
Abstract
The invention discloses a kind of photonic crystal sensor materials and its preparation method and application, the preparation method include: (1) in the presence of an inert gas, compound shown in compound shown in formula I, formula II, water and initiator are contacted, emulsifier-free emulsion polymerization reaction is carried out, polymer microballoon is obtained；(2) by the polymer microballoon and H2O2With HRP haptoreaction, PMD microballoon is obtained；(3) suspension of the PMD microballoon is dispersed to and stood heap base, the photonic crystal sensor material is made；Photonic crystal sensor material preparation process of the invention is simple, and when for detecting, detection is easy to operate, and response is rapid, high sensitivity, and detection range is wide；Wherein, R is the group containing alkylene, alkynes base, olefin amide base or alkene ester group.
Description
Technical field
The present invention relates to field of food safety, more particularly, to a kind of photonic crystal sensor material and preparation method thereof
And application.
Background technique
Ciprofloxacin [fluoro- 1,4- dihydro -4- oxo -7- (piperazinyl) quinolone -3- carboxylic acid of 1- cyclopropyl -6-]
(Ciprofloxacin, CF) belongs to fluoroquinolones, it is the synthetic antibiotic with broad-spectrum antimicrobial effect, sterilization
One of effect is good and cheap, therefore become the most common antibiotic of fish culture.But a large amount of uses of CF, it can lead to it in ring
A large amount of residuals in border and relevant food, especially in fish culture waters and the flesh of fish, these can not only promote bacterial drug resistance
Generation, can also CF be made to enter human body by food chain, endanger people's health.Therefore, there is an urgent need to monitor the residual of CF,
With guarantee environment and food safety.
So far, there are many methods to monitor the CF content in cultivation fish and water, including high performance liquid chromatography
(HPLC), fluorescence spectrum, enzyme linked immunosorbent assay (ELISA) (ELISA), micro-biological process, Capillary Electrophoresis and various spectrophotometrics
Method.But these methods need professional to operate, and need the pretreatment of complicated and time consumption.
Photonic crystal (PC), be exactly by the dielectric material of differing dielectric constant in space according to certain cycle sequences into
The orderly periodic structure material with optical wavelength magnitude is formed after row arrangement.When light is propagated in the photonic crystal, it may occur that cloth
Glug diffraction, diffraction wavelength follow following law: m λ=2ndsin θ, and exactly this diffraction makes photonic crystal have unique knot
Structure color.If the lattice parameter of photonic crystal changes, the change of diffraction wavelength can be caused, therefore, photonic crystal is as one
Kind sensing material, may be implemented no reagent, unmarked quick detection.
Holtz et al. is prepared for a kind of photonic crystal that response can be generated to metal ion.Firstly, will be with bases such as crown ethers
The latex particle of the monodisperse electrification of group is dispersed in the monomer solution of acrylic amide, forms the composite junction of high-sequential
Then structure carries out initiation polymerization, finally obtain the colloid array of ordered structure.Crown ether functional group selectivity in colloid array
It is chelated with metal ion, increases colloid array osmotic pressure, volume sweell(ing), spacing of lattice increases, and finally makes Prague
Diffraction maximum red shift.The suction-operated is reversible, and the colloid array of swollen state is immersed in deionized water, colloid array
Internal penetration pressure can reduce again, and Bragg diffraction peak is returned to home position again.Phenyl boric acid group is introduced photon by Asher et al.
Detection in crystal array, for glucose.The photon crystal material can under low ionic strength respond various saccharides.
It can be to Na in addition, being developed there are also researcher+、K+、Pb2+, pH value, temperature, illumination, the photon of the generations response such as mechanical force it is brilliant
Body.
Currently, there has been no the photonic crystal of detection Ciprofloxacin, also, above-mentioned these photon crystal materials preparation process is multiple
It is miscellaneous, it needs to prepare microballoon and is dispersed in gel and be fixed；Some then needs first to prepare opal template, then in mould
Polymer is poured into plate stitch gap, then etches away opal template.
Therefore, it is necessary to a kind of preparation method of photonic crystal sensor material for detecting Ciprofloxacin is provided, meanwhile, overcome
The problems such as photon crystal material preparation process is complicated at present, preparation cost is high.
Summary of the invention
The object of the present invention is to provide a kind of photonic crystal sensor material and its preparation method and application, which is passed
Sense material is able to detect Ciprofloxacin, and preparation process is simple, preparation cost is low.
To achieve the goals above, the first aspect of the present invention provides a kind of preparation side of photonic crystal sensor material
Method, the preparation method include:
(1) in the presence of an inert gas, compound shown in compound, Formula II shown in Formulas I, water and initiator are contacted, into
The reaction of row emulsifier-free emulsion polymerization, obtains polymer microballoon；
Wherein, R is the group containing alkylene, alkynes base, olefin amide base or alkene ester group；
(2) by the polymer microballoon and H2O2With HRP haptoreaction, PMD microballoon is obtained；
(3) suspension of the PMD microballoon is dispersed to and stood heap base, the photonic crystal sensor material is made.
The second aspect of the present invention provides photonic crystal sensor material made from preparation method described in one kind.
The third aspect of the present invention is the photonic crystal sensor material as dinitrogen heterocyclic compound detection reagent
Using, wherein the dinitrogen heterocyclic compound is the compound with group shown in formula IV,
Technical solution of the present invention has the advantages that
(1) photonic crystal sensor material preparation process of the invention is simple, it is only necessary to by prepare microballoon by oxidation and heap
Base can be obtained photonic crystal sensor material；
(2) condition of heap of the invention base photonic crystal is simpler, and the heap base of microballoon can be realized by a conventional oven,
Greatly reduce photonic crystal sensor material prepares threshold and cost；
(3) using photonic crystal sensor material of the invention to containing the structure containing hydrogen on dinitrogen heterocycle and a nitrogen
Compound it is easy to detect, it is easy to operate, be not necessarily to any pre-treatment, and respond rapidly, high sensitivity, detection range is wide, benefit
It is detected with photonic crystal sensor material of the invention, 15min can be obtained stable response signal, and detection range is 2 μ g/L-
512 μ g/L, lowest detection are limited to 0.76 μ g/L.
Other features and advantages of the present invention will then part of the detailed description can be specified.
Detailed description of the invention
Exemplary embodiment of the invention is described in more detail in conjunction with the accompanying drawings, it is of the invention above-mentioned and its
Its purpose, feature and advantage will be apparent, wherein in exemplary embodiment of the invention, identical reference label
Typically represent same parts.
Fig. 1 a and Fig. 1 b respectively illustrate glucose responding mechanism in the prior art and increase spreading out for PC with concentration of glucose
Penetrate peak red shift.
Fig. 2 shows the preparation of PMMA-DMA PC according to the present invention and detection process schematic diagrams.
Specific embodiment
The preferred embodiment that the present invention will be described in more detail below with reference to accompanying drawings.Although showing the present invention in attached drawing
Preferred embodiment, however, it is to be appreciated that may be realized in various forms the present invention without the embodiment party that should be illustrated here
Formula is limited.On the contrary, thesing embodiments are provided so that the present invention is more thorough and complete, and can will be of the invention
Range is completely communicated to those skilled in the art.
The first aspect of the present invention provides a kind of preparation method of photonic crystal sensor material, which includes:
(1) in the presence of an inert gas, compound shown in compound, Formula II shown in Formulas I, water and initiator are contacted, into
The reaction of row emulsifier-free emulsion polymerization, obtains polymer microballoon；
Wherein, R is the group containing alkylene, alkynes base, olefin amide base or alkene ester group；
(2) by the polymer microballoon and H2O2With HRP haptoreaction, PMD microballoon is obtained；
(3) suspension of the PMD microballoon is dispersed to and stood heap base, the photonic crystal sensor material is made.
In accordance with the present invention it is preferred that compound of formula I is compound shown in formula III,
Wherein, m is the integer of 2-10, R1For covalent bond ,-NHCO (CH2)pOr-COO (CH2)q, p and q are each independently
For the integer of 0-10, R2For C1-C10Alkyl.
Preferably, m is the integer of 2-5, R1For-NHCO (CH2)p, R2For C1-C5Alkyl.It is further preferred that
Compound shown in the formula III is 3- Methacrylamide base dopamine.
In accordance with the present invention it is preferred that relative to compound shown in formula I described in every gram, the use of compound shown in the formula II
Amount is 0.1-0.2L, and the dosage of the initiator is 2-5g.
In accordance with the present invention it is preferred that the temperature of the polymerization reaction is 70-90 DEG C, the time of polymerization reaction is 80-
120min。
In accordance with the present invention it is preferred that the initiator is KPS or APS (ammonium persulfate).
Under the relative usage and polymerization reaction time of above-mentioned preferred DMA and MMA, the spherical shape of PMD microballoon preferably, is responded
Rapidly.
In accordance with the present invention it is preferred that the method for step (1) includes: by compound, water shown in compound shown in formula I, formula II
Then ultrasonic deoxygenation after mixing under inert gas protection, stirs and is heated to 70-90 DEG C, carry out finally, initiator is added
Emulsifier-free emulsion polymerization reaction.
In accordance with the present invention it is preferred that step (3) includes: to collect the product centrifugation washing after step (2) reaction intermediate
Layer product is simultaneously diluted to mass concentration as 0.1%-5%, and heap is poured into after ultrasonic disperse and is built in container, 30-50 DEG C of baking oven is placed in
The photonic crystal sensor material is made in middle standing.
The heap base of photonic crystal sensor material is carried out in special instrument-climatic chamber at present, a constant temperature
Constant humidity cabinet price 7000 rises；However the heap that the present invention is the progress photonic crystal sensor material in a conventional oven is built, therefore significantly
It reduces and prepares threshold and cost.
The second aspect of the present invention provides a kind of photonic crystal sensor material as made from above-mentioned preparation method.
The third aspect of the present invention is the photonic crystal sensor material as dinitrogen heterocyclic compound detection reagent
Using, wherein the dinitrogen heterocyclic compound is the compound with group shown in formula IV,
Preferably, photonic crystal sensor material provided by the invention can as Ciprofloxacin, Norfloxacin and
The detection reagent of Enoxacin.
As shown in Fig. 2, the piperazinyl group (containing there are two that of N rings) of Ciprofloxacin (CF), it can be under weak basic condition
Michael addition reaction occurs with quinone, can then be connected on photon crystal micro-ball, change the refractive index of photonic crystal, to draw
Play the decline of diffraction peak intensity.
When detecting, by optimizing detection system, the PBS buffer solution of preferably pH=7.4 is brilliant by photon of the invention
Body sensing material immerses in above-mentioned buffer solution up to after stablizing, and the Ciprofloxacin standard that various concentration is successively added from low to high is molten
Liquid, the i.e. concentration of Ciprofloxacin standard solution are 0.01 μ g/L-2896 μ g/L, by the change for observing photonic crystal diffraction peak intensity
Change, obtaining detection and marking curvilinear range is 2 μ g/L-512 μ g/L, and lowest detection is limited to 0.76 μ g/L.
The detection range of prior art HPLC-MS method (LC-MS) is 5 μ g/L-60 μ g/L, thus, it can be known that of the invention
Detection range it is wider, sensitivity is higher；Moreover, the detection for actual sample fishpond water, without carrying out any pre-treatment, directly
It connects and detection architecture is added, 15min can get stabilization signal, and easy to operate, response is rapid.
The present invention is further illustrated by the following examples.
Embodiment 1
20mg 3- Methacrylamide base dopamine (DMA) is dissolved in compound shown in 3mL formula II (MMA), then
The solution is added in 25.5mL deionized water, ultrasonic deoxygenation 10min；Mechanical stirring, bath temperature 80 are carried out with 370rpm
DEG C, while logical nitrogen protection, after system temperature up to after 80 DEG C, initiator KPS is added, and (60mg KPS is dissolved in 1.5mL deionization
In water), the reaction was continued 90min；After centrifugation removal supernatant, 1mL 0.1mM H is added into microballoon2O2And HRP (10.0mgHPR
It is dissolved in 0.50mL 0.10M PBS, pH 7.00), it is sufficiently mixed, ambient temperature overnight；It is then centrifuged for, washes, be centrifuged in 4000rpm
10min, removal supernatant precipitating, only collects middle layer, i.e. acquisition PMD microballoon；
Obtained PMD microballoon is diluted to the suspension that mass fraction is 1% with deionized water, is delayed after abundant ultrasonic disperse
Slowly it pours into horizontal exhibition cylinder, is subsequently placed in 40 DEG C of baking ovens, stand 5-6 days, that is, obtaining, there is the photonic crystal of green gloss to pass
Feel material.
The photonic crystal sensor material is immersed in the PBS buffer solution of pH=7.4 after reaching stable, successively from low to high
The Ciprofloxacin standard solution of various concentration is added, i.e. the concentration of Ciprofloxacin standard solution is 0.01 μ g/L-2896 μ g/L, is led to
The variation of observation photonic crystal diffraction peak intensity is crossed, obtaining detection and marking curvilinear range is 2 μ g/L-512 μ g/L, and lowest detection is limited to
0.76μg/L。
The embodiment of the present invention is described above, above description is exemplary, and non-exclusive, and also not
It is limited to disclosed embodiment.Without departing from the scope and spirit of embodiment described, for the art
Those of ordinary skill for many modifications and changes are obvious.
Claims (10)
1. a kind of preparation method of photonic crystal sensor material, which is characterized in that the preparation method includes:
(1) in the presence of an inert gas, compound shown in compound, Formula II shown in Formulas I, water and initiator are contacted, carries out nothing
Soap emulsion polymerization, obtains polymer microballoon；
Wherein, R is the group containing alkylene, alkynes base, olefin amide base or alkene ester group；
(2) by the polymer microballoon and H2O2With HRP haptoreaction, PMD microballoon is obtained；
(3) suspension of the PMD microballoon is dispersed to and stood heap base, the photonic crystal sensor material is made.
2. the preparation method of photonic crystal sensor material according to claim 1, wherein compound of formula I is shown in formula III
Compound,
Wherein, m is the integer of 2-10, R1For covalent bond ,-NHCO (CH2)pOr-COO (CH2)q, p and q are each independently 0-
10 integer, R2For C1-C10Alkyl.
3. the preparation method of photonic crystal sensor material according to claim 2, wherein compound shown in the formula III
For 3- Methacrylamide base dopamine.
4. the preparation method of photonic crystal sensor material according to claim 1, wherein relative to I institute of formula described in every gram
Show compound, the dosage of compound shown in the formula II is 0.1-0.2L, and the dosage of the initiator is 2-5g.
5. the preparation method of photonic crystal sensor material according to claim 1, wherein the temperature of the polymerization reaction is
70-90 DEG C, the time of polymerization reaction is 80-120min.
6. the preparation method of photonic crystal sensor material according to claim 1, wherein the initiator be KPS or
APS。
7. the preparation method of photonic crystal sensor material according to claim 1, wherein the method for step (1) include: by
Then ultrasonic deoxygenation after compound shown in formula I, compound shown in formula II, water mixing under inert gas protection, is stirred and is added
Heat arrives 70-90 DEG C, finally, initiator, which is added, carries out emulsifier-free emulsion polymerization reaction.
8. the preparation method of photonic crystal sensor material according to claim 1, wherein step (3) includes: by step
(2) product after reacting is centrifuged washing, collects middle layer product and is diluted to mass concentration for 0.1%-5%, after ultrasonic disperse
It pours into heap to build in container, is placed in 30-50 DEG C of baking oven and stands, the photonic crystal sensor material is made.
9. photonic crystal sensor material made from preparation method described in any one of -8 according to claim 1.
10. application of the photonic crystal sensor material as claimed in claim 9 as dinitrogen heterocyclic compound detection reagent, wherein
The dinitrogen heterocyclic compound is the compound with group shown in formula IV,
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| CN105859933B (en) * | 2016-03-31 | 2018-09-21 | 北京化工大学 | A kind of response type polymer microballoon and its preparation method and application with nucleocapsid |
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| CN106929915B (en) * | 2017-04-26 | 2019-01-11 | 北京市环境保护科学研究院 | A kind of opal photonic crystal of curved-surface structure and the preparation method of molecularly imprinted polymer inverse opal film |
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