CN110018142A - Composite fluorescence substrate, the preparation method and application of composite fluorescence substrate - Google Patents
Composite fluorescence substrate, the preparation method and application of composite fluorescence substrate Download PDFInfo
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- CN110018142A CN110018142A CN201910213982.5A CN201910213982A CN110018142A CN 110018142 A CN110018142 A CN 110018142A CN 201910213982 A CN201910213982 A CN 201910213982A CN 110018142 A CN110018142 A CN 110018142A
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- 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
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Abstract
The invention discloses composite fluorescence substrates, the preparation method and application of composite fluorescence substrate.The composite fluorescence substrate includes the molecularly imprinted polymer material of gel with the pore surface for being attached to the gel.Gel has tridimensional network, is capable of providing biggish specific surface area to adhere to MIP material；Since substrate has gel, gel has viscosity and is solid fraction, when gel and MIP material act synergistically, it can not only be used as needed by way of cutting, and can also by way of wiping sample to be tested surface fast enriching object, and can directly measure using Solid surface fluorescence the advantage of solid sample, fast sampling and test, compared with prior art, the quick detection to object can be realized without carrying out complicated pretreatment to sample.
Description
Technical field
The present invention relates to the technologies of the detection of the technical field of additive illegal in food detection more particularly to rhodamine B
Field, in particular to composite fluorescence substrate, the preparation method and application of composite fluorescence substrate.
Background technique
Nowadays the instrument analysis technology for additive detection illegal in food mainly has a spectral technique, including ultraviolet-can
See absorption spectrometry (μ V-Vis), atomic absorption spectrography (AAS) (AAS) etc.；The most commonly used is efficient liquid phases, gas phase color for chromatography
Spectrometry, gas chromatography and mass spectromentry joint technology (GC-MS)；Electrochemical techniques master to be applied is high performance capillary electrophoresis
(CE).The precision of these methods can satisfy the requirement of experiment, and minimum detection limit can also meet trace analysis needs, still
But there is narrow application range, equipment is expensive, complicated for operation, at high cost the problems such as；And most of chromatography need special
Detecting instrument, the requirement to testing staff is also high, thus be not suitable for mass field quickly detect.In quick context of detection,
The fast detection method that with good grounds Solid Phase Extraction principle developed, but the method is mainly that basis visually observes on solid-phase extraction column
Red stripes judged false positive easily occur, accuracy is low, and detection sensitivity is not also high.Therefore, it is established in food
It is a kind of that can be carried out fast and reliable novel detection method to illegal additive most important.
Molecularly imprinted polymer (Molecularly Imprinted Polymer, abbreviation MIP) is with specific recognition
With the polymer of selective absorption.Molecular engram solid phase extraction (Molecularly Imprinted SolidPhase
Extraction, abbreviation MISPE) it is a kind of novel sample pretreatment that developed recently gets up, it is special using MIP's
Selective absorption mechanism prepares solid phase extraction material, since MIP has specific selectivity and affinity to template molecule, and
It can be overcome food samples system complexity, pretreatment journey by the such environmental effects very little such as acid, alkali, organic solvent and heating
The unfavorable factors such as sequence is loaded down with trivial details realize the separation and concentration of low concentration intentional object in complicated food samples matrix, improve Solid Phase Extraction
The sensitivity and accuracy of clean-up effect and analyzing detecting method.
It pre-processes, i.e., is dissolved by solvent first firstly the need of to sample when being detected using MIP to object
The object of sample surfaces, filtered, be centrifuged after extracted, obtain the organic liquor containing object, then lead to organic liquor
The solid phase flowing column filled with MIP material is crossed then to be detected so that the object in organic liquor is adsorbed by MIP material.
As it can be seen that carrying out detection to object using MIP needs a large amount of pretreatment time, and preprocessing process is complicated for operation, reproducibility
Difference.
Summary of the invention
The main purpose of the present invention is to provide composite fluorescence substrate, the preparation method and application of composite fluorescence substrate,
It is too long to the pretreatment time of sample and pre- when solving the object in molecularly imprinted polymer test sample in the prior art
The technical issues of complex disposal process.
To achieve the goals above, according to an aspect of the invention, there is provided a kind of composite fluorescence substrate.This is compound glimmering
Light substrate includes the molecularly imprinted polymer material of gel with the pore surface for being attached to the gel.
Firstly, composite fluorescence substrate of the invention has simple and quick, clever for carrying out Solid surface fluorescence spectral detection
The high advantage of sensitivity.Secondly, the feature strong using MIP material specificity, solving that fluorescence spectra is wider can not accurately really
Surely the shortcomings that being which kind of substance, sample to be tested can be carried out more be enriched with during atual detection.Furthermore anti-interference
Can be relatively strong, trace qualitative detection rapidly can be carried out to sample to be tested.Meanwhile gel has tridimensional network, Neng Gouti
Adhere to MIP material for biggish specific surface area；Since substrate has gel, and gel has viscosity and is solid fraction, works as gel
, can not only be used as needed by way of cutting when acting synergistically with MIP material, and can also be by wiping sample to be tested
The mode fast enriching object on surface, and can directly measure using Solid surface fluorescence the advantage of solid sample, fast sampling
And the quick detection to object can be realized without carrying out complicated pretreatment to sample compared with prior art in test.
Further, the gel is PVA gel；The molecularly imprinted polymer is rhodamine B molecular engram polymer.
PVA (polyvinyl alcohol) gel easily obtains and in stable condition, hereby it is achieved that the quick of rhodamine B (being expressed as RhB, similarly hereinafter)
Detection.
Further, the mass ratio of the rhodamine B molecular engram polymer and PVA are (0.05-1): (0.2-1)；Also
Including sodium tetraborate (molecular formula: Na2B4O7·10H2O).The too high levels of rhodamine B molecular engram polymer, may shadow
Ring the stability of PVA gel；Rhodamine B molecular engram polymer is too low, then the ability for being enriched with object is poor.Luo Dan as a result,
Bright B molecularly imprinted polymer is evenly distributed in PVA gel and gained composite fluorescence substrate is strong to the accumulation ability of object.
It uses sodium tetraborate for flocculation aid, stable PVA gel can be quickly obtained.
Further, the mass ratio of PVA and sodium tetraborate is (1-5): (0.4-2).It is verified, as PVA and sodium tetraborate
Mass ratio be (1-5): when (0.4-2), the fluorescence signal of gained composite fluorescence substrate is best.
To achieve the goals above, according to another aspect of the present invention, a kind of system of composite fluorescence substrate is additionally provided
Preparation Method, comprising the following steps:
(1) mixed solution including Gel Precursor and molecularly imprinted polymer material is obtained；
(2) flocculation aid for making Gel Precursor gel chemical conversion gel is added, stirring arrives composite fluorescence to gel is formed
Substrate.
The technique of the preparation method of composite fluorescence substrate of the invention is very simple, and required generated time is short, and gained is compound
Fluorescent base bottom stability is good, has suitable hardness and viscosity, can fast sampling and test, it is complicated without being carried out to sample
The quick detection to object can be realized in pretreatment.
Further, the gel is PVA gel, and the flocculation aid is sodium tetraborate；The molecularly imprinted polymer is
Rhodamine B molecular engram polymer.
Further, step (1) specifically includes: acquisition PVA solution first, then by rhodamine B molecular engram polymer
It is added in the PVA solution；The mass fraction of PVA is 4%-10% in the PVA solution；PVA's is abundant in mixed solution
Dissolution and the evenly dispersed gel for facilitating PVA lead to compared with the technique that PVA and molecularly imprinted polymer material are directly blended
It crosses and first first obtains PVA solution, rear dispersing molecule imprinted polymer, it can be to avoid molecularly imprinted polymer to the shadow of PVA solubility
It rings, is quickly obtained stable gel to obtain.
Further, the sodium tetraborate is added in PVA solution after being configured to solution, the matter of PVA and sodium tetraborate
Amount is than being (1-5): (0.4-2).By adding after dissolving sodium tetraborate, sodium tetraborate can be made quickly and evenly to be distributed
In PVA solution, facilitates acquisition and be quickly obtained the consistent substrate of performance everywhere.
Further, the preparation of the rhodamine B molecular engram polymer is with SiO2It (is indicated for carrier, methacrylic acid
Are as follows: MAA, similarly hereinafter) be function monomer, ethyleneglycol dimethacrylate (indicating are as follows: EGDMA, similarly hereinafter) is crosslinking agent, acetonitrile is
Pore-foaming agent and 2, and 2 '-azodiisobutyronitriles (it indicates are as follows: AIBN, similarly hereinafter) it is initiator.It is obviously high that imprinted sites are obtained as a result,
In molecular imprinted polymer on surface material (the Surface Molecular Imprinted of conventional molecular imprinted polymer
Polymer, abbreviation SMIP).
To achieve the goals above, according to another aspect of the present invention, a kind of detection side of rhodamine B is additionally provided
Method, comprising steps of
(1) composite fluorescence substrate is cut, the composite fluorescence substrate is above-mentioned composite fluorescence substrate or uses above-mentioned
The composite fluorescence substrate that preparation method is prepared, the molecularly imprinted polymer are rhodamine B molecular engram polymer；
(2) the composite fluorescence substrate cut wipes sample to be tested surface；
(3) Solid surface fluorescence detection is carried out to get sieve for arriving sample to be tested surface to the composite fluorescence substrate after wiping
Red bright B concentration.
As it can be seen that the fluorescent base bottom being prepared using composite fluorescence substrate of the invention or preparation method of the invention, is led to
Cross wiping mode can object in fast enriching sample to be tested, then can quickly be detected by native place fluorescence spectrum
The target concentration on sample to be tested surface out, is compared with the traditional method, real without carrying out complicated pretreatment to sample to be tested
Now quickly, efficiently, accurately detect.
Further, detailed process is as follows for the wiping: spraying solvent on sample to be tested surface first, then makes described
Composite fluorescence substrate is wiped across dust-free paper on sample to be tested surface.As a result, not only can with fast enriching object, and
And also it is avoided that impurity has an impact test result.
As it can be seen that composite fluorescence substrate of the invention, the preparation method of composite fluorescence substrate and application can quickly take
The quick detection to object can be realized without carrying out complicated pretreatment to sample in sample and test.
The present invention is described further with reference to the accompanying drawings and detailed description.The additional aspect of the present invention and excellent
Point will be set forth in part in the description, and partially will become apparent from the description below, or practice through the invention
It solves.
Detailed description of the invention
The attached drawing for constituting a part of the invention is used to assist the understanding of the present invention, content provided in attached drawing and its
Related explanation can be used for explaining the present invention in the present invention, but not constitute an undue limitation on the present invention.In the accompanying drawings:
Fig. 1 is the fluorescence of the composite fluorescence substrate (being expressed as RhB-SMIPs-PVA gel base, similarly hereinafter) of embodiment 1-5
Test result.
Fig. 2 be embodiment 3, embodiment 6-8 RhB-SMIPs-PVA gel base fluorometric investigation result.
Fig. 3 be embodiment 3, embodiment 9-12 RhB-SMIPs-PVA gel base fluorometric investigation result.
Fig. 4 be the RhB-SMIPs-PVA gel base of embodiment 3 to the fluorometric investigation of the RhB solution of various concentration as a result,
Wherein, curve a-k correspond respectively to 10mg/L, 8mg/L, 6mg/L, 4mg/L, 2mg/L, 1mg/L, 0.8mg/L, 0.6mg/L,
The RhB solution of 0.4mg/L, 0.2mg/L, 0.1mg/L.
Fig. 5 is the RhB-SMIPs-PVA gel base of embodiment 3 and the PVA gel base of reference examples 1 to various concentration
The fluorometric investigation result of RhB solution.
Fig. 6 is the RhB-SMIPs-PVA gel base of embodiment 3 and the PVA gel base of reference examples 1 to various concentration
The fluorometric investigation result of Rh6G solution.
Fig. 7 is fluorometric investigation result of the RhB-SMIPs-PVA gel base to different pigments of embodiment 3.
Fig. 8 is that the RhB-SMIPs-PVA gel base of embodiment 3 detects the testing result of chilli powder surface RhB, wherein
Curve a-e be respectively 0.5mg/LRhB impregnate chilli powder, 1mg/LRhB impregnate chilli powder, 5mg/LRhB impregnate capsicum,
Chilli powder, the unsoaked chilli powder of 10mg/LRhB immersion.
Fig. 9 is SiO2The SEM photograph of-KH570, built-in figure are partial enlarged view.
Figure 10 is the SEM photograph of the RhB-SMIPs before elution.
Figure 11 is the SEM photograph for washing off the RhB-SMIPs after template molecule RhB, and built-in figure is partial enlarged view.
Figure 12 is the SEM photograph of the PVA gel base of reference examples 1.
Figure 13 is the SEM photograph of the RhB-SMIPs-PVA gel base of embodiment 3, and built-in figure is partial enlarged view.
Specific embodiment
Clear, complete explanation is carried out to the present invention with reference to the accompanying drawing.Those of ordinary skill in the art are being based on these
The present invention will be realized in the case where explanation.Before in conjunction with attached drawing, the present invention will be described, of particular note is that:
The technical solution provided in each section including following the description and technical characteristic in the present invention are not rushing
In the case where prominent, these technical solutions and technical characteristic be can be combined with each other.
In addition, the embodiment of the present invention being related in following the description is generally only the embodiment of present invention a part, and
The embodiment being not all of.Therefore, based on the embodiments of the present invention, those of ordinary skill in the art are not making creation
Property labour under the premise of every other embodiment obtained, should fall within the scope of the present invention.
About term in the present invention and unit.Term in description and claims of this specification and related part
" comprising ", " having " and their any deformation, it is intended that cover and non-exclusive include.
Embodiment 1
The PVA for weighing 0.2g, which is dissolved in, obtains the PVA solution that mass fraction is 2% in 10ml ultrapure water, then weigh 0.05g
Rhodamine B molecular engram polymer (RhB-SMIPs) powder be added in 1mLPVA solution, stirring keep its evenly dispersed, obtain
To mixed solution.Then the sodium tetraborate for weighing 0.4g, which is dissolved in 10mL ultrapure water, obtains sodium tetraborate solution.Take 1mL's
The mixed solution of RhB-SMIPs and PVA is mixed with the sodium tetraborate solution of 0.4mL, and the PVA of the mass ratio is found through experiments that
Solution can not plastic after mixing with sodium tetraborate solution.
Embodiment 2
The PVA for weighing 0.4g, which is dissolved in, obtains the PVA solution that mass fraction is 4% in 10ml ultrapure water, then weigh 0.05g
RhB-SMIPs powder be added in 1mLPVA solution, stirring keep its evenly dispersed, obtain mixed solution.Then 0.4g is weighed
Sodium tetraborate be dissolved in 10mL ultrapure water and obtain sodium tetraborate solution.Take RhB-SMIPs the and PVA mixed solution of 1mL with
The sodium tetraborate solution of 0.4mL mixes, and is stirred with glass bar until being formed has the gel of good deformable function to get arriving
RhB-SMIPs-PVA gel base.
Embodiment 3
The PVA for weighing 0.6g, which is dissolved in, obtains the PVA solution that mass fraction is 6% in 10ml ultrapure water, then weigh 0.05
RhB-SMIPs powder be added in 1mLPVA solution, stirring keep its evenly dispersed, obtain mixed solution.Then 0.4g is weighed
Sodium tetraborate be dissolved in 10mL ultrapure water and obtain sodium tetraborate solution.Take the mixed solution of the RhB-SMIPs and PVA of 1mL with
The sodium tetraborate solution of 0.4mL mixes, and is stirred with glass bar until being formed has the gel of good deformable function to get arriving
RhB-SMIPs-PVA gel base.
Embodiment 4
The PVA for weighing 0.8g, which is dissolved in, obtains the PVA solution that mass fraction is 8% in 10ml ultrapure water, then weigh 0.05g
RhB-SMIPs powder be added in 1mLPVA solution, stirring keep its evenly dispersed, obtain mixed solution.Then 0.4g is weighed
Sodium tetraborate be dissolved in 10mL ultrapure water and obtain sodium tetraborate solution.Take the mixed solution of the RhB-SMIPs and PVA of 1mL with
The sodium tetraborate solution of 0.4mL mixes, and is stirred with glass bar until being formed has the gel of good deformable function to get arriving
RhB-SMIPs-PVA gel base.
Embodiment 5
The PVA for weighing 1g, which is dissolved in, obtains the PVA solution that mass fraction is 10% in 10ml ultrapure water, then weigh 0.05g
RhB-SMIPs powder be added in 1mLPVA solution, stirring keep its evenly dispersed, obtain mixed solution.Then 0.4g is weighed
Sodium tetraborate be dissolved in 10mL ultrapure water and obtain sodium tetraborate solution.Take the mixed solution of the RhB-SMIPs and PVA of 1mL with
The sodium tetraborate solution of 0.4mL mixes, and is stirred with glass bar until being formed has the gel of good deformable function to get arriving
RhB-SMIPs-PVA gel base.
It is respectively configured the RhB standard solution of 0.5mg/L, 1mg/L, 5mg/L, is dripped in embodiment 1-5 to get arriving
Fluorescence detection is carried out after on RhB-SMIPs-PVA gel base, test results are shown in figure 1, it can be found that working as PVA mass ratio
When being 6%, fluorescence signal is best.
Embodiment 6
The PVA for weighing 0.6g, which is dissolved in, obtains the PVA solution that mass fraction is 6% in 10ml ultrapure water, then weigh
The RhB-SMIPs powder of 0.005g is added in 1mL PVA solution, and stirring keeps its evenly dispersed, obtains mixed solution.Then
The sodium tetraborate for weighing 0.4g, which is dissolved in 10mL ultrapure water, obtains sodium tetraborate solution.Take mixing for the RhB-SMIPs and PVA of 1mL
It closes solution to mix with the sodium tetraborate solution of 0.4mL, the gel up to being formed with good deformable function is stirred with glass bar,
Obtain RhB-SMIPs-PVA gel base.
Embodiment 7
The PVA for weighing 0.6g, which is dissolved in, obtains the PVA solution that mass fraction is 6% in 10ml ultrapure water, then weigh 0.01g
RhB-SMIPs powder be added in 1mL PVA solution, stirring keep its evenly dispersed, obtain mixed solution.Then it weighs
The sodium tetraborate of 0.4g, which is dissolved in 10mL ultrapure water, obtains sodium tetraborate solution.Take the mixing of the RhB-SMIPs and PVA of 1mL molten
Liquid is mixed with the sodium tetraborate solution of 0.4mL, is stirred with glass bar until forming the gel with good deformable function, i.e.,
Obtain RhB-SMIPs-PVA gel base.
Embodiment 8
The PVA for weighing 0.6g, which is dissolved in, obtains the PVA solution that mass fraction is 6% in 10ml ultrapure water, then weigh 0.1g
RhB-SMIPs powder be added in 1mLPVA solution, stirring keep its evenly dispersed, obtain mixed solution.Then 0.4g is weighed
Sodium tetraborate be dissolved in 10mL ultrapure water and obtain sodium tetraborate solution.Take the mixed solution of the RhB-SMIPs and PVA of 1mL with
The sodium tetraborate solution of 0.4mL mixes, and is stirred with glass bar until being formed has the gel of good deformable function to get arriving
RhB-SMIPs-PVA gel base.
It is respectively configured the RhB standard solution of 0.5mg/L, 1mg/L, 5mg/L, is dripped in embodiment 3, embodiment 6-8
Fluorescence detection is carried out after RhB-SMIPs-PVA gel base, test results are shown in figure 2, it can be found that working as RhB-SMIPs powder
When last additive amount is 0.05g, fluorescence signal is best.
Embodiment 9
The PVA for weighing 0.6g, which is dissolved in, obtains the PVA solution that mass fraction is 6% in 10ml ultrapure water, then weigh 0.05g
RhB-SMIPs powder be added in 1mL PVA solution, stirring keep its evenly dispersed, obtain mixed solution.Then it weighs
The sodium tetraborate of 0.4g, which is dissolved in 10mL ultrapure water, obtains sodium tetraborate solution.Take the mixing of the RhB-SMIPs and PVA of 1mL molten
Liquid is mixed with the sodium tetraborate solution of 0.2mL, is stirred with glass bar until forming the gel with good deformable function, i.e.,
Obtain RhB-SMIPs-PVA gel base.
Embodiment 10
The PVA for weighing 0.6g, which is dissolved in, obtains the PVA solution that mass fraction is 6% in 10ml ultrapure water, then weigh 0.05g
RhB-SMIPs powder be added in 1mL PVA solution, stirring keep its evenly dispersed, obtain mixed solution.Then it weighs
The sodium tetraborate of 0.4g, which is dissolved in 10mL ultrapure water, obtains sodium tetraborate solution.Take the mixing of the RhB-SMIPs and PVA of 1mL molten
Liquid is mixed with the sodium tetraborate solution of 0.6mL, is stirred with glass bar until forming the gel with good deformable function, i.e.,
Obtain RhB-SMIPs-PVA gel base.
Embodiment 11
The PVA for weighing 0.6g, which is dissolved in, obtains the PVA solution that mass fraction is 6% in 10ml ultrapure water, then weigh 0.05g
RhB-SMIPs powder be added in 1mL PVA solution, stirring keep its evenly dispersed, obtain mixed solution.Then it weighs
The sodium tetraborate of 0.4g, which is dissolved in 10mL ultrapure water, obtains sodium tetraborate solution.Take the mixing of the RhB-SMIPs and PVA of 1mL molten
Liquid is mixed with the sodium tetraborate solution of 0.8mL, is stirred with glass bar until forming the gel with good deformable function, i.e.,
Obtain RhB-SMIPs-PVA gel base.
Embodiment 12
The PVA for weighing 0.6g, which is dissolved in, obtains the PVA solution that mass fraction is 6% in 10ml ultrapure water, then weigh 0.05g
RhB-SMIPs powder be added in 1mL PVA solution, stirring keep its evenly dispersed, obtain mixed solution.Then it weighs
The sodium tetraborate of 0.4g, which is dissolved in 10mL ultrapure water, obtains sodium tetraborate solution.Take the mixing of the RhB-SMIPs and PVA of 1mL molten
Liquid is mixed with the sodium tetraborate solution of 1mL, stirred with glass bar until formed have the gel of good deformable function to get
To RhB-SMIPs-PVA gel base.
The RhB standard solution of 0.5mg/L, 1mg/L, 5mg/L is respectively configured, is dripped in embodiment 3, embodiment 9-12
RhB-SMIPs-PVA gel base on after carry out fluorescence detection, test results are shown in figure 3.Abscissa in Fig. 3 is PVA
The volume ratio of solution and sodium tetraborate solution, corresponding mass ratio are respectively 3:0.4,3:0.8,3:1.2,3:1.6,3:2.From
Fig. 3 can be seen that the volume ratio of PVA solution and sodium tetraborate solution when being 10:4 (mass ratio 3:0.8), and fluorescence signal is most
It is good.
In order to detect RhB-SMIPs-PVA gel base of the invention to the minimum detectability of RhB, it is configured with 0.1-
The RhB solution of 10mg/L concentration gradient takes the 5uL solution to be added dropwise respectively and coagulates in the RhB-SMIPs-PVA of the embodiment 3 of 0.03g
On matrix bottom, it is to be adsorbed completely after, carry out fluorescence detection.Testing result is as shown in Figure 4, it can be seen that the RhB-SMIPs-PVA
Gel base can detect the RhB in the RhB solution that concentration is 0.1mg/L.Compare rhodamine B prepared by Zhao Chen et al.
(Zhao Chen, Jia Guangfeng, Lu Wenzong wait the preparation of rhodamine B molecular imprinted polymer on surface and its fluorescence inspection to molecularly imprinted polymer
Survey [J] Food Science, 2014,35 (20): 236-241) minimum concentration that can detect also be 0.1mg/L RhB, it is seen then that this
Gel is not only without influencing the specificity of RhB-SMIPs in the RhB-SMIPs-PVA gel base of invention, but also is obviously improved
Detection speed.
In order to verify the specificity that RhB-SMIPs-PVA gel base adsorbs RhB, we are had chosen and RhB structure class
As dyestuff, i.e., rhodamine 6G (Rh6G) as control.Since the molecular structure and RhB of Rh6G are closely similar, in aqueous solution
In all have strong fluorescence, fluorescent wavelength ranges are also close to RhB, so often interfering to the detection of RhB.Tool
Body process is as follows:
The reference examples of embodiment 3, i.e. reference examples 1 are carried out first, and difference is in reference examples 1 without containing RhB-SMIPs.It connects
Go the adsorption concentration to be respectively with the RhB-SMIPs-PVA gel base of the PVA gel base of reference examples 1 and embodiment 3 respectively
RhB the and Rh6G solution of 10mg/L, 20mg/L, 40mg/L, 50mg/L, 80mg/L, finally carry out fluorescence detection, testing result
As shown in Figure 5 and Figure 6.
The specificity of RhB-SMIPs can be determined by enhancement factor α:
α=IM/IN
In formula: IM indicates the fluorescence signal intensity that the RhB-SMIPs-PVA gel base of embodiment 3 is measured, IN expression pair
The fluorescence signal intensity that 1 PVA gel base is measured as usual.
Test result after being converted into enhancement factor is shown in Table 1.
Table 1
The α value that the α value of RhB and Rh6G can be seen that RhB from table 1 is always more than the α value of Rh6G, illustrates MIP material
The gel of absorption in to(for) RhB plays significant effect.
Simultaneously as often addition is similar to other orchils of RhB in food in the market, thus to RhB's
Detection interferes, we, which choose, is usually used in food dyeing, similar to RhB color, is interfered in RhB detection process
Sunset yellow (Sunset yellow), S Ⅰ (Sudan I), S Ⅳ (Sudan IV) are as a comparison.It shows in Fig. 7 in phase
With under concentration 10mg/L, the PVA gel base of reference examples 1 and the RhB-SMIPs-PVA gel base of embodiment 3 are to RhB, day
Fall the suction-operated of Huang, S Ⅰ, S Ⅳ.As can be seen that in the gel base for having MIP material, the signal of RhB compared to
Other three kinds of pigments have apparent enhancing.
We equally assess result by calculating enhancement factor, and the results are shown in Table 2.
Table 2
From Table 2, it can be seen that the enhancement factor highest of RhB, and the enhancement factor of other pigments is no better than 1, this meaning
Taste embodiment 3 RhB-SMIPs-PVA gel base it is very strong to the anti-interference ability of RhB.
It can apply to the detection of actual sample well to verify above-mentioned RhB-SMIPs-PVA gel base, carry out
Following test: the chilli powder for weighing 0.5g respectively, which is immersed in the RhB solution of 0.5mg/L, 1mg/L, 5mg/L, 10mg/L, to be prepared
At mark-on sample, it is dried for standby.Suitable alcohol is sprayed on sample to be tested, takes the RhB-SMIPs-PVA of the embodiment 3 of 0.03g
Gel base is wiped repeatedly across dust-free paper on sample to be tested surface, is enriched with to the RhB on sample, finally by the substrate after sampling
It is placed on solid support and carries out fluorescence detection.Test results are shown in figure 8, it can be seen that the party can detect practical sample
Most down to the RhB of 0.5mg/kg on product.Shady large spark of comparison et al. is in 2015 to rhodamine in chilli in the market and chilli powder
(shady large spark, He Weiwei, Jiang Dingguo wait the investigation of rhodamine B content in chilli and chilli powder for the investigation and analysis of B content
With analysis [J] Chinese food health magazine, 2015,27 (3): 297-301) it can be found that RhB-SMIPs-PVA of the invention
The minimum detectability of gel base is on the market in the RhB detection content range in actual sample.And compared to it with super
The cumbersome preprocess method of High Performance Liquid Chromatography/Mass Spectrometry/mass spectrometer, RhB-SMIPs-PVA gel base energy of the invention
The sampling and detection for realizing sample in a few minutes, save the plenty of time.
Above-described embodiment RhB-SMIPs's the preparation method is as follows:
Take the SiO of 1.5g2Particle and 50ml dry toluene are added in conical flask, ultrasonic 20min, at room temperature magnetic agitation
1h..Conical flask is added dropwise in 5mlKH570 (silane coupling agent), is passed through after nitrogen drains air and seals in conical flask, magnetic
Power stirs 15 hours.The modified SiO of KH570 will be passed through2It is centrifuged after being washed with dry toluene, then is washed with dehydrated alcohol
Centrifugation, obtains SiO after repeatedly2-KH570.A conical flask separately is taken, 10ml acetonitrile, 2mgRhB, 94ulMAA are added thereto,
Room temperature under nitrogen protects lower magnetic agitation 12h.It then proceedes to that 24mgSiO is added to the inside2-KH570、0.875mlEGDMA、
15mgAIBN, magnetic agitation for 24 hours, obtains RhB-SMIPs under 75 DEG C of nitrogen protections.RhB-SMIPs is washed with methanol, it is repeatedly super
Centrifugation is until RhB is washed off after sound.RhB-SMIPs drying after elution, crushed into powder shape.
Fig. 9 is SiO2The SEM photograph of-KH570, it can be seen that it is modified by the surface of KH570, cover its surface
The organo-functional group of silane coupling agent.Figure 10 is the SEM photograph of the RhB-SMIPs before elution, it can be seen that by a series of
Crosslinked action, in SiO2Surface covers one layer of organic matter.Figure 11 is the SEM for washing off the RhB-SMIPs after template molecule RhB
Photo, it can be seen that form many cavitys in material, leave the binding site of RhB.
Figure 12 is the SEM photograph of the PVA gel base of reference examples 1, it can be seen that PVA gel base has reticular structure,
Very high specific surface area can be provided for the suction-operated of substrate.Figure 13 is the RhB-SMIPs-PVA gel base of embodiment 3
SEM photograph, it can be seen that RhB-SMIPs has equably been embedded in PVA gel, is played when carrying out specific adsorption to RhB
Vital effect.
Related content of the invention is illustrated above.Those of ordinary skill in the art are in the feelings illustrated based on these
The present invention will be realized under condition.Based on above content of the invention, those of ordinary skill in the art are not making creativeness
Every other embodiment obtained, should fall within the scope of the present invention under the premise of labour.
Claims (10)
1. composite fluorescence substrate, it is characterised in that: the molecular engram including gel and the pore surface for being attached to the gel is poly-
Close object material.
2. composite fluorescence substrate as described in claim 1, it is characterised in that: the gel is PVA gel；The molecular engram
Polymer is rhodamine B molecular engram polymer.
3. composite fluorescence substrate as claimed in claim 2, it is characterised in that: the rhodamine B molecular engram polymer and PVA
Mass ratio be (0.05-1): (0.2-1)；It further include sodium tetraborate.
4. composite fluorescence substrate as claimed in claim 3, it is characterised in that: the mass ratio of PVA and sodium tetraborate is (1-5):
(0.4-2)。
5. the preparation method of composite fluorescence substrate, comprising the following steps:
(1) mixed solution including Gel Precursor and molecularly imprinted polymer material is obtained；
(2) flocculation aid for making Gel Precursor gel chemical conversion gel is added, stirring arrives composite fluorescence base to gel is formed
Bottom.
6. the preparation method of composite fluorescence substrate as claimed in claim 5, it is characterised in that: the gel is PVA gel, institute
Stating flocculation aid is sodium tetraborate；The molecularly imprinted polymer is rhodamine B molecular engram polymer.
7. the preparation method of composite fluorescence substrate as claimed in claim 6, it is characterised in that: step (1) specifically includes: first
PVA solution is obtained, then rhodamine B molecular engram polymer is added in the PVA solution；PVA in the PVA solution
Mass fraction is 4%-10%；The sodium tetraborate is added in PVA solution after being configured to solution, PVA and sodium tetraborate
Mass ratio is (1-5): (0.4-2).
8. the preparation method of composite fluorescence substrate as claimed in claim 6, it is characterised in that: the rhodamine B molecular engram
The preparation of polymer is with SiO2It is function monomer for carrier, methacrylic acid, ethyleneglycol dimethacrylate is crosslinking agent, acetonitrile
It is initiator for pore-foaming agent and 2,2 '-azodiisobutyronitriles.
9. the detection method of rhodamine B, comprising steps of
(1) cut composite fluorescence substrate, the composite fluorescence substrate be composite fluorescence substrate described in one of claim 1-4 or
The composite fluorescence substrate being prepared using preparation method described in one of claim 5-8, the molecularly imprinted polymer are
Rhodamine B molecular engram polymer；
(2) the composite fluorescence substrate cut wipes sample to be tested surface；
(3) Solid surface fluorescence detection is carried out to get the rhodamine B for arriving sample to be tested surface to the composite fluorescence substrate after wiping
Concentration.
10. the detection method of rhodamine B as claimed in claim 9, it is characterised in that: detailed process is as follows for the wiping:
Solvent is sprayed on sample to be tested surface first, carries out the composite fluorescence substrate on sample to be tested surface across dust-free paper
Wiping.
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