CN109725036A - Electrochemical sensor and its detection method a kind of while that detect sulphadiazine and paracetamol - Google Patents
Electrochemical sensor and its detection method a kind of while that detect sulphadiazine and paracetamol Download PDFInfo
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- CN109725036A CN109725036A CN201910162759.2A CN201910162759A CN109725036A CN 109725036 A CN109725036 A CN 109725036A CN 201910162759 A CN201910162759 A CN 201910162759A CN 109725036 A CN109725036 A CN 109725036A
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Abstract
The invention discloses a kind of electrochemical sensors and its detection method for detecting sulphadiazine and paracetamol simultaneously, and the electrochemical sensor is using GO@COF composite material and the dual modified electrode of MIP as working electrode；Using saturated calomel electrode as reference electrode；Using platinum electrode as auxiliary electrode, three-electrode system is constructed, using the electro-chemical activity of sulphadiazine and paracetamol, establishes the rapid sensitive detection method to sulphadiazine and paracetamol simultaneously with extensive detection range.The present invention is low in cost, and experimental implementation is simple, high sensitivity, and sulphadiazine and paracetamol while are detected suitable for various food.
Description
Technical field
The present invention relates to the detection methods of sulphadiazine and paracetamol, detect sulfanilamide (SN) simultaneously more particularly to a kind of
The electrochemical sensor and its detection method of pyrimidine and paracetamol, belong to technical field of food safety detection.
Background technique
Sulphadiazine (SDZ) is a kind of current China clinically common sulfamido anti-infectives.By interfering folic acid
Metabolism inhibit bacterial growth.Since the features such as it is efficient, cheap, property is stablized, is widely used in all kinds of animal derived foods
In product process.Also just because of it is widely used, abuse phenomenon is on the rise, and sulfadiazine residue makes under the physical function of people
Drop causes have a stomach upset sense, anemia, concurrent kidney trouble and hematologic disease, and has potential toxicity and carcinogenicity.China
The Ministry of Agriculture, people's republic provides that maximum allowable residue limits of the sulfa drugs in animal derived food are 100 μ gkg-1。
Paracetamol (AP) is most widely used analgesic-antipyretic in current world wide.It is commonly used for head
Bitterly, the treatment of the diseases such as fever, toothache, is a kind of effective alternative medicine of aspirin.Using not in regulation limitation range
Serious side effect can be generated.But excessively it can cause the damage of liver and kidney very using the accumulation that will lead to toxic metabolites
To causing body dead.
Liquid chromatography is mostly used in relation to sulphadiazine in food and paracetamol detection method both at home and abroad at present
Or liquid phase, the method for internal standard method for gas chromatography carry out qualitative, quantitative detection, but used in above-mentioned several detection methods
Equipment price is expensive, and analysis time is long, needs complicated Sample Pretreatment Technique；Moreover, sulphadiazine and paracetamol
Different sample-pretreating methods is needed before detection, it is difficult to be detected while realization to sulphadiazine and paracetamol.
Therefore researching and developing method that is quick, accurate, sensitive and can measuring sulphadiazine and paracetamol simultaneously has important meaning
Justice.
Summary of the invention
For the problems of above-mentioned prior art, the object of the present invention is to provide it is a kind of detect simultaneously sulphadiazine and
The electrochemical sensor of paracetamol.Electrochemical sensor of the invention can simultaneously, quickly, Sensitive Detection sulphadiazine
And paracetamol, sample pre-treatments are simple, detection sensitivity is high, analysis time is short, experimental implementation is simple, are suitable for each
Sulphadiazine and paracetamol while, are quickly detected in kind of food.
To achieve the above object, the present invention adopts the following technical scheme:
The first aspect of the present invention provides a kind of highly sensitive electrochemical sensor, and the electrochemical sensor is with GO@
COF composite material and the dual modified electrode of MIP are working electrode；The working electrode is prepared by the following method:
GO COF composite material sol drop is coated onto bare glassy carbon electrode surface, is dried, the GO COF/GCE after being modified
Electrode；
The immersion of GO@COF/GCE electrode is contained into sulphadiazine, paracetamol, pyrroles and tetrabutylammonium perchlorate
Electrochemical polymerization is carried out in acetonitrile solution, using cyclic voltammetry with 100mVs in -0.6V-+1.2V potential range-1Speed
3~8 circle of rate scanning；Then electrode is immersed concentration again is 0.5~1.0molL-1In NaOH solution using cyclic voltammetry-
With 50mVs in 0.6V-+1.2V potential range-1Rate scanning 10~20 enclose, obtain by GO@COF compound and MIP be dual repairs
Adorn electrode MIP/GO@COF/GCE, as working electrode.
Preferably, the concentration of the GO COF composite material solution is 1-2mg/mL.
The GO@COF composite material is that method prepares (Sun J, Klechikov A, Moise C, et according to the literature
al.Molecular pillar approach to grow vertical covalent organic framework
nanosheets on graphene:new hybrid materials for energy storage[J].Angewandte
Chemie,2017.)。
Preferably, in the acetonitrile solution, the concentration of sulphadiazine and paracetamol is 5mM, pyrroles and four fourths
The concentration of base ammonium perchlorate is 0.1M.
Further, in the electrochemical sensor further include: reference electrode and auxiliary electrode.
Preferably, the reference electrode is saturated calomel electrode；The auxiliary electrode is platinum electrode.
The second aspect of the present invention provides above-mentioned electrochemical sensor and detects sulphadiazine and paracetamol at the same time
In application.
The third aspect of the present invention provides and a kind of using above-mentioned electrochemical sensor while detecting sulphadiazine and to acetyl
The method of amino phenols, comprising the following steps:
(1) working electrode, reference electrode and the auxiliary electrode in electrochemical sensor are constituted into three-electrode system, utilizes difference
Divide pulse voltammetry within the scope of potential window 0.25-1.6V, working electrode immersion phosphate buffer solution is prepared not
With being incubated in concentration sulphadiazine and paracetamol standard solution, corresponding current value I is recordedP；Respectively with sulphadiazine and
Paracetamol concentration of standard solution C is abscissa, current value IPFor ordinate, I is drawnP- C working curve；
(2) I drawn using step (1)P- C working curve is to the sulphadiazine in the determinand through pre-treatment and to second
The content of acylamino- phenol is detected.
Preferably, in step (1), the concentration of the phosphate buffer solution is 0.2molL-1, pH value 7.0.
Preferably, in step (2), the pre-treating method of the determinand are as follows: by determinand ethyl acetate vortex centrifugal
It repeats to extract 2-4 times, combined extract and with being dried with nitrogen.
It is furthermore preferred that the determinand and the ratio of ethyl acetate additional amount are 1g:(1-5) mL.
Beneficial effects of the present invention:
(1) for the electrode of the invention modified jointly using GO@COF composite material and MIP as working electrode, constructing can be same
When the electrochemical sensor of Sensitive Detection is carried out to sulphadiazine and paracetamol, wherein GO@COF composite material has
Biggish specific surface area, the advantages that conducting electricity very well, can significantly increase current signal strength.MIP modified electrode can be realized electricity
Specific recognition of the chemical sensor to sulphadiazine and paracetamol.Using electrochemical sensor of the invention to sulfanilamide (SN)
The minimum detectability of pyrimidine and paracetamol is respectively 48.0 μ g/kg and 4.8 μ g/kg, can satisfy detection needs, analysis
Time shortens 1.0h or so than traditional detection method, is suitable for simultaneously quickly detection sulphadiazine and paracetamol.
(2) cost is relatively low for electrochemical sensor prepared by the present invention, and pre-treatment is simple, high sensitivity, analysis time
It is short, experimental implementation is simple, sulphadiazine and paracetamol while, are quickly detected suitable for various food.
The present invention is compared with other existing detection methods:
Detailed description of the invention
Fig. 1: the sulphadiazine of various concentration and the DPV curve of paracetamol.
Fig. 2: sulphadiazine (A) and paracetamol (B) standard curve.
As shown in Figure 1, sulphadiazine and the paracetamol range of linearity are 5.0 × 10 respectively in this method-7-2.0
×10-4Mol/L and 5.0 × 10-8-2.0×10-5Mol/L, minimum detectability are 1.6 × 10-7Mol/L (48.0 μ g/kg) and 3.2
×10-8mol/L(4.8μg/kg)。
Specific embodiment
It is noted that following detailed description is all illustrative, it is intended to provide further instruction to the application.Unless another
It indicates, all technical and scientific terms used herein has usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
" room temperature " mentioned in the present invention refers to that temperature is 15-30 DEG C.
As background technology part is introduced, related sulphadiazine in food and paracetamol inspection both at home and abroad at present
Survey method mostly uses liquid chromatography or liquid phase, the method for internal standard method for gas chromatography to carry out qualitative, quantitative detection, but
Equipment price used in above-mentioned several detection methods is expensive, and analysis time is long, needs complicated Sample Pretreatment Technique；And
And sulphadiazine and paracetamol need different sample-pretreating methods before detection, it is difficult to realize to sulphadiazine
It is detected while with paracetamol.Based on this, the object of the present invention is to provide one kind can detect simultaneously sulphadiazine and
The electrochemical sensor and its detection method of paracetamol.
To realize while detecting sulphadiazine and paracetamol, the present invention is to be total to GO@COF composite material and MIP
Same modified electrode, wherein electrode is modified using GO@COF composite material, current signal strength can be enhanced；Utilize MIP
Electrode is modified, electrochemical sensor may be implemented to the specific recognition of sulphadiazine and paracetamol.To
Establishing has highly sensitive rapid detection method to sulphadiazine and paracetamol.
In one embodiment of the present invention, the method for the GO@COF composite material and the common modified electrode of MIP are as follows:
It is 1.5mg mL by 5~10 μ L concentration-1GO@COF composite material sol drop-coated in bare glassy carbon electrode surface, room temperature
Under dry, the GO@COF/GCE electrode after being modified；GO@COF/GCE electrode is immersed in containing 5mM sulphadiazine and to second
Electrochemical polymerization is carried out in the acetonitrile solution of acylamino- phenol, 0.1M pyrroles and 0.1M tetrabutylammonium perchlorate.Utilize cyclic voltammetric
Method is in -0.6V-+1.2V potential range with 100mVs-1Rate scanning 3~8 enclose.Then this electrode will be immersed concentration is
0.5~1.0molL-1Utilize cyclic voltammetry in -0.6V-+1.2V potential range with 50mVs in NaOH solution-1Rate
10~20 circle of scanning, obtains by GO@COF compound and the dual modified electrode of MIP (MIP/GO@COF/GCE).
In another embodiment of the invention, it gives using electrochemical sensor of the invention while detecting sulfanilamide (SN)
The method of pyrimidine and paracetamol, specific as follows:
(1) using saturated calomel electrode and platinum electrode as reference electrode and auxiliary electrode, GO@COF compound and MIP
Dual modified electrode (MIP/GO@COF/GCE) constitutes three-electrode system as working electrode, using differential pulse voltammetry in electricity
Within the scope of the window 0.25-1.6V of position, 0.2molL is used into working electrode immersion-1The phosphate buffer solution of pH 7.0 is prepared not
With being incubated in concentration sulphadiazine and paracetamol standard solution, corresponding current value I is recordedP。
(2) respectively using sulphadiazine and paracetamol concentration of standard solution C as abscissa, current value is ordinate,
Draw IP- C working curve.Sulphadiazine is calculated separately in the corresponding sample of different current values according to the following formula and to acetyl ammonia
The content of base phenol:
Ip (- μ A)=0.058C [SDZ] (μM) ﹢ 0.021 (1)
Ip (- μ A)=0.565C [AP] (μM) ﹢ 0.016 (2)
(3) volume ratio (g/mL) 1:1 by weight is added ethyl acetate solution vortex centrifugal and repeats extraction three times in analyte,
Combined extract is with being dried with nitrogen.With 5mL 0.2molL-1The phosphate buffer solution dissolved nitrogen of pH 7.0 obtains surplus after blowing
Excess, 0.22 μm of membrane filtration obtain sample extracting solution；Replace sulphadiazine and paracetamol standard molten sample extracting solution
Liquid repeats step 2) operation, calculates separately out sulphadiazine and acetparaminosalol in analyte by standard curve according to current value
Phenol content.
In order to enable those skilled in the art can clearly understand the technical solution of the application, below with reference to tool
The technical solution of the application is described in detail in the embodiment of body.
The test material that test material is this field routine is not specifically described used in the embodiment of the present invention,
It can be commercially available by commercial channel.
Embodiment 1:
1. electrochemical sensor electrodes are modified:
It is 1.5mgmL by 8 μ L concentration-1GO@COF composite material sol drop-coated in bare glassy carbon electrode surface, at room temperature
It dries.GO@COF/GCE electrode after being modified；GO@COF/GCE electrode is immersed in containing 5mM sulphadiazine and to acetyl
Electrochemical polymerization is carried out in the acetonitrile solution of amino phenols, 0.1M pyrroles and 0.1M tetrabutylammonium perchlorate.Utilize cyclic voltammetry
With 100mVs in -0.6V-+1.2V potential range-1Rate scanning 5 enclose.Then this electrode will be immersed concentration is
1.0molL-1Utilize cyclic voltammetry in -0.6V-+1.2V potential range with 50mVs in NaOH solution-1Rate scanning 15
Circle, obtains by GO@COF compound and the dual modified electrode of MIP (MIP/GO@COF/GCE).
2. resulting after this experiment modification using saturated calomel electrode and platinum electrode as reference electrode and auxiliary electrode
Electrode MIP/GO@COF/GCE constitutes three-electrode system as working electrode, using differential pulse voltammetry in potential window
Within the scope of 0.25-1.6V, 0.2molL is used into working electrode immersion-1The concentration difference that the phosphate buffer solution of pH7.0 is prepared
For 0.5,5,10,20,50,100 and 200 μm of ol L-1Sulphadiazine and 0.05,0.5,1,2,5,10 and 20 μm of olL-1To second
It is incubated in acylamino- phenol standard solution, records corresponding current value I respectivelyP(Fig. 1).
3. current value is ordinate using sulphadiazine and paracetamol concentration of standard solution C as abscissa, draw
IP- C working curve.Containing for sulphadiazine and paracetamol in the corresponding sample of different current values is calculated according to the following formula
Amount:
Ip (- μ A)=0.058C [SDZ] (μM) ﹢ 0.021 (1)
Ip (- μ A)=0.565C [AP] (μM) ﹢ 0.016 (2)
4. accurately weighing chicken 5g, 20mL ethyl acetate solution vortex centrifugal is added, repeats to extract three times, combined extract
With being dried with nitrogen.With 5mL 0.2molL-1The residue that the phosphate buffer solution dissolved nitrogen of pH 7.0 obtains after blowing is used
0.22 μm of membrane filtration obtains sample extracting solution.
5. sample extracting solution is replaced standard sample dilution liquid, step 2 operation is repeated, middle sulfanilamide (SN) is obtained according to above-mentioned calculation formula
Pyrimidine and paracetamol extract concentration are respectively 3.3 × 10-6molL-1With 2.0 × 10-7molL-1, calculate in chicken
Sulphadiazine and Determination Paracetamol in Paracetamol are respectively 835 μ g kg-1With 29.7 μ g kg-1。
The foregoing is merely preferred embodiment of the present application, are not intended to limit this application, for the skill of this field
For art personnel, various changes and changes are possible in this application.Within the spirit and principles of this application, made any to repair
Change, equivalent replacement, improvement etc., should be included within the scope of protection of this application.
Claims (10)
1. a kind of electrochemical sensor, which is characterized in that the electrochemical sensor is with GO@COF composite material and MIP is dual repairs
Decorations electrode is working electrode；The working electrode is prepared by the following method:
GO COF composite material sol drop is coated onto bare glassy carbon electrode surface, is dried, the GO COF/GCE electrode after being modified；
The immersion of GO@COF/GCE electrode is contained into sulphadiazine, paracetamol, pyrroles and the acetonitrile of tetrabutylammonium perchlorate
Electrochemical polymerization is carried out in solution, using cyclic voltammetry with 100mVs in -0.6V-+1.2V potential range-1Rate sweep
Retouch 3~8 circles；Then electrode is immersed concentration again is 0.5~1.0molL-1Using cyclic voltammetry in -0.6V- in NaOH solution
With 50mVs in+1.2V potential range-1Rate scanning 10~20 enclose, obtain by GO@COF compound and the dual modified electrode of MIP
MIP/GO@COF/GCE, as working electrode.
2. electrochemical sensor according to claim 1, which is characterized in that the concentration of the GO COF composite material solution
For 1-2mg/mL.
3. electrochemical sensor according to claim 1, which is characterized in that in the acetonitrile solution, sulphadiazine and right
The concentration of Paracetamol is 5mM, and the concentration of pyrroles and tetrabutylammonium perchlorate are 0.1M.
4. electrochemical sensor according to claim 1-3, which is characterized in that in the electrochemical sensor also
It include: reference electrode and auxiliary electrode.
5. electrochemical sensor according to claim 4, which is characterized in that the reference electrode is saturated calomel electrode；
The auxiliary electrode is platinum electrode.
6. the described in any item electrochemical sensors of claim 1-5 detect in sulphadiazine and paracetamol at the same time
Using.
7. a kind of detect sulphadiazine and acetparaminosalol using the described in any item electrochemical sensors of claim 1-5 simultaneously
The method of phenol, comprising the following steps:
(1) working electrode, reference electrode and the auxiliary electrode in electrochemical sensor are constituted into three-electrode system, utilizes difference arteries and veins
Voltammetry is rushed within the scope of potential window 0.25-1.6V, the difference that working electrode immersion is prepared with phosphate buffer solution is dense
It is incubated in degree sulphadiazine and paracetamol standard solution, records corresponding current value IP；Respectively with sulphadiazine and to second
Acylamino- phenol concentration of standard solution C is abscissa, current value IPFor ordinate, I is drawnP- C working curve；
(2) I drawn using step (1)P- C working curve is to the sulphadiazine and acetparaminosalol in the determinand through pre-treatment
The content of phenol is detected.
8. the method according to the description of claim 7 is characterized in that in step (1), the concentration of the phosphate buffer solution is
0.2molL-1, pH value 7.0.
9. the method according to the description of claim 7 is characterized in that in step (2), the pre-treating method of the determinand are as follows:
Determinand is repeated to extract 2-4 times with ethyl acetate vortex centrifugal, combined extract and with being dried with nitrogen.
10. according to the method described in claim 9, it is characterized in that, the determinand and the ratio of ethyl acetate additional amount are 1g:
(1-5)mL。
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| CN112858407A (en) * | 2021-01-19 | 2021-05-28 | 山东农业大学 | Electrochemical sensor for detecting ciprofloxacin and detection method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107970894A (en) * | 2017-12-11 | 2018-05-01 | 哈尔滨理工大学 | A kind of preparation method and application of COF/GO adsorbents |
Non-Patent Citations (2)
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| LIXIAO CHEN ET AL.: "Applications of covalent organic frameworks in analytical chemistry", 《TRENDS IN ANALYTICAL CHEMISTRY》 * |
| 时作龙等: "分子印迹化学发光传感器在线检测牛肉与鸡肉组织中残留的磺胺嘧啶", 《分析试验室》 * |
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| CN112858407A (en) * | 2021-01-19 | 2021-05-28 | 山东农业大学 | Electrochemical sensor for detecting ciprofloxacin and detection method thereof |
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