CN109342527B - Preparation method of electrode for measuring phenylethylamine - Google Patents

Preparation method of electrode for measuring phenylethylamine Download PDF

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CN109342527B
CN109342527B CN201811417319.9A CN201811417319A CN109342527B CN 109342527 B CN109342527 B CN 109342527B CN 201811417319 A CN201811417319 A CN 201811417319A CN 109342527 B CN109342527 B CN 109342527B
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黄德乾
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Haicheng Leach Carbon Materials Co ltd
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Abstract

The invention discloses a preparation method of an electrode for measuring phenylethylamine, and relates to the technical field of electroanalytical chemistry. The preparation method comprises the following steps: of flexible graphiteModified CeO2Preparation, loading, dispersion and preparation; the invention adopts the modified flexible graphite modified CeO2As a sensor sensitive material, the material has the advantages of simple preparation, low cost, accurate detection, large specific surface area, good conductivity and strong enrichment capacity; the active auxiliary agent synthesized by taking sarcosine and sorbitol as raw materials through an esterification reaction can improve the activity of a sensor electrode, can obviously improve the electrochemical response signal of phenylethylamine, and has high analysis sensitivity and high analysis speed.

Description

Preparation method of electrode for measuring phenylethylamine
The technical field is as follows:
the invention relates to the technical field of electroanalytical chemistry, in particular to a preparation method of an electrode for measuring phenylethylamine.
Background art:
patent application publication No. CN106198661A discloses an electrochemical determination method of phenylethylamine, and biogenic amine is a general name of a class of nitrogen-containing small molecular weight compounds. They can be classified into 3 major classes according to their structural features: (1) aliphatic, such as cadaverine, putrescine, spermidine, spermine, and the like; (2) aromatic compounds such as phenethylamine, tyramine, and the like; (3) heterocyclic ring families, such as tryptamine, histamine, and the like. Biogenic amines are present in various animal and plant tissues, are normally active ingredients in biological organisms, and play important physiological roles in animal and plant organisms. For example, spermine, spermidine, putrescine, cadaverine, and the like are indispensable parts of biologically active cells, and play a key role in regulating the synthesis of proteins and nucleic acids and the stability of biological membranes. In addition, biogenic amines are also widely present in a variety of food products, especially fermented and protein-rich food products. Such as: meat products, aquatic products, cheese, sausage, beer, wine, etc. The main biogenic amines in food products include: and a plurality of monoamine and polyamine substances such as histamine, tyramine, beta-phenylethylamine, cadaverine, putrescine, tryptamine, spermine and spermidine. In foods with rich protein content such as meat products, aquatic products and the like, the enzyme generated by related microorganisms can catalyze and remove carboxyl of free amino acid to generate biogenic amine, so the content of the biogenic amine is closely related to the quality of the biogenic amine.
Phenylethylamine is also called 2-phenylethylamine or β -phenylethylamine, and its molecular formula is C8H11In human body, phenylethylamine is an alkaloid and monoamine neurotransmitter, can raise dopamine level in extracellular fluid, and can inhibit dopamine nerve activation, and can be used for curing depression, in human brain, β -phenylethylamine has the action of nerve regulating substance, neurotransmitter and tracer amineA stimulant, an appetite-reducing agent, a bronchodilator and the like. Phenylethylamine is a pharmacologically important drug, but if it is present in food in excess, it will cause some physical damage. Therefore, it is important to detect the content of biogenic amine in food such as fermented food, animal-derived food, and wine.
The invention content is as follows:
the invention aims to solve the technical problem of providing a preparation method for measuring phenethylamine electrode, which has simple operation, accurate detection and high sensitivity.
The technical problem to be solved by the invention is realized by adopting the following technical scheme:
a preparation method of an electrode for measuring phenylethylamine comprises the following steps:
(1) modification of flexible graphite: adding flexible graphite into deionized water, refluxing and stirring for 10-30min, then adding titanate coupling agent and chain extender, and continuing to reflux and stir for 0.5-2 h;
(2)CeO2the preparation of (1): adding citric acid into deionized water, stirring, and adding Ce (NO)3)3·6H2Stirring for 10-30min at 35 ℃, transferring to a reaction kettle, sealing and reacting for 8-10h at 150 ℃ in 140-;
(3) loading: adding CeO into the solution in the step 12Refluxing and stirring for 0.5-4h, cooling to 70-75 ℃, adding castor oil and active auxiliary agent, continuously stirring for 20-40min, filtering while hot, washing the solid with deionized water to remove impurities, and drying in vacuum at 50 ℃ to constant weight;
(4) dispersing: adding the solid obtained in the step 3 into absolute ethyl alcohol, and performing ultrasonic dispersion for 1-2 hours to obtain a dispersion liquid;
(5) preparation: and (4) dropwise coating the dispersed liquid obtained in the step (4) on the surface of a glassy carbon electrode, and evaporating and drying to obtain the electrode for measuring phenylethylamine.
An electrochemical sensor for detecting phenylethylamine comprises a working electrode, a reference electrode,A counter electrode; the method is characterized in that: the working electrode is CeO with the surface coated with flexible graphite2A thin film glassy carbon electrode.
The citric acid, deionized water and Ce (NO)3)3·6H2The mass ratio of O is 5-10: 50-80: 5-10.
The flexible graphite, titanate coupling agent, chain extender and CeO2The mass of the castor oil and the active auxiliary agent is 20-30: 6-10: 0.1-0.2: 6-8: 0.1-0.5: 1-2.
The preparation method of the active auxiliary agent comprises the following steps: adding sarcosine into deionized water, stirring at 40 deg.C for 10min, adding sorbitol and tetraethyl titanate, heating to reflux state, stirring at constant temperature for 0.5-4h, adding corn oil, stirring at 70-80 deg.C for 30-40min, filtering, washing the obtained solid with deionized water to remove impurities, and vacuum drying at 50 deg.C to constant weight.
The mass ratio of the sarcosine to the sorbitol to the tetraethyl titanate to the corn oil is 6-8: 10-15: 0.05: 0.5-2.
The flexible graphite as one new kind of functional carbon material is one kind of loose and porous vermicular matter obtained through intercalation, water washing, drying and high temperature puffing of natural graphite flake. The flexible graphite has excellent performances of cold and heat resistance, corrosion resistance, self-lubrication and the like of natural graphite, and also has the characteristics of softness, compression resilience, adsorbability, ecological environment harmony, biocompatibility, radiation resistance and the like which are not possessed by the natural graphite.
CeO2 is an important rare earth oxide, has attracted great research interest due to its special structure and morphology, and is widely used in the fields of medicine, materials, chemistry, biology and environmental engineering.
The invention has the beneficial effects that:
(1) the invention adopts the modified flexible graphite modified CeO2As a sensor sensitive material, the material has the advantages of simple preparation, low cost, accurate detection, large specific surface area, good conductivity and strong enrichment capacity;
(2) the active auxiliary agent synthesized by taking sarcosine and sorbitol as raw materials through an esterification reaction can improve the activity of a sensor electrode, can obviously improve the electrochemical response signal of phenylethylamine, and has high analysis sensitivity and high analysis speed.
The specific implementation mode is as follows:
in order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the invention is further described with the specific embodiments.
Example 1
(1) Modification of flexible graphite: adding 20g of flexible graphite into deionized water, refluxing and stirring for 10min, then adding 6g of titanate coupling agent and 0.1g of chain extender, and continuing refluxing and stirring for 2 h;
(2)CeO2the preparation of (1): adding 6g citric acid into 60g deionized water, stirring well, adding 6gCe (NO)3)3·6H2Stirring for 20min at 35 ℃, transferring into a reaction kettle, sealing at 140 ℃, reacting for 8h, filtering, washing impurities of the obtained product with deionized water and absolute ethyl alcohol, drying at 60 ℃ in vacuum to constant weight, and calcining the dried solid at 320 ℃ for 1 h;
(3) loading: adding 6gCeO into the solution obtained in the step 12Refluxing and stirring for 3h, cooling to 70 ℃, adding 0.2g of castor oil and 1g of active auxiliary agent, continuously stirring for 30min, filtering while hot, washing the solid with deionized water to remove impurities, and drying in vacuum at 50 ℃ to constant weight;
(4) dispersing: adding the solid obtained in the step 3 into absolute ethyl alcohol, and performing ultrasonic dispersion for 2 hours to obtain a dispersion liquid;
(5) preparation: the dispersed liquid obtained in the step 4 is dripped on the surface of a glassy carbon electrode, and the electrode for measuring phenylethylamine is obtained after evaporation and drying;
preparation of the active assistant: adding 7g of sarcosine into deionized water, stirring at 40 ℃ for 10min, then adding 12g of sorbitol and 0.05g of tetraethyl titanate, heating to a reflux state, keeping the temperature and stirring for 4h, then adding 1g of corn oil, stirring at 75 ℃ for 40min, filtering, washing the obtained solid with deionized water to remove impurities, and drying at 50 ℃ in vacuum to constant weight.
Example 2
(1) Modification of flexible graphite: adding 25g of flexible graphite into deionized water, refluxing and stirring for 10min, then adding 7g of titanate coupling agent and 0.2g of chain extender, and continuing refluxing and stirring for 2 h;
(2)CeO2the preparation of (1): adding 8g citric acid into 80g deionized water, stirring well, adding 8gCe (NO)3)3·6H2Stirring for 20min at 35 ℃, transferring into a reaction kettle, sealing at 150 ℃, reacting for 8h, filtering, washing impurities of the obtained product with deionized water and absolute ethyl alcohol, drying at 60 ℃ in vacuum to constant weight, and calcining the dried solid at 340 ℃ for 1 h;
(3) loading: adding 6gCeO into the solution obtained in the step 12Refluxing and stirring for 3h, cooling to 70 ℃, adding 0.3g of castor oil and 1g of active auxiliary agent, continuously stirring for 30min, filtering while hot, washing the solid with deionized water to remove impurities, and drying in vacuum at 50 ℃ to constant weight;
(4) dispersing: adding the solid obtained in the step 3 into absolute ethyl alcohol, and performing ultrasonic dispersion for 2 hours to obtain a dispersion liquid;
(5) preparation: the dispersed liquid obtained in the step 4 is dripped on the surface of a glassy carbon electrode, and the electrode for measuring phenylethylamine is obtained after evaporation and drying;
preparation of the active assistant: adding 7g of sarcosine into deionized water, stirring at 40 ℃ for 10min, then adding 12g of sorbitol and 0.05g of tetraethyl titanate, heating to a reflux state, keeping the temperature and stirring for 4h, then adding 1g of corn oil, stirring at 75 ℃ for 40min, filtering, washing the obtained solid with deionized water to remove impurities, and drying at 50 ℃ in vacuum to constant weight.
Comparative example 1
(1) Modification of flexible graphite: adding 20g of flexible graphite into deionized water, refluxing and stirring for 10min, and then continuing to reflux and stir for 2 h;
(2)CeO2the preparation of (1): adding 6g citric acid into 60g deionized water, stirring well, adding 6gCe (NO)3)3·6H2Stirring at 35 deg.C for 20min, transferring into a reaction kettle, sealing at 140 deg.C, reacting for 8 hr, filtering, washing with deionized water and anhydrous ethanol to remove impurities, vacuum drying at 60 deg.C to constant weight, and calcining at 320 deg.C for 1 hrThen, the method is carried out;
(3) loading: adding 6gCeO into the solution obtained in the step 12Refluxing and stirring for 3h, cooling to 70 ℃, adding 0.2g of castor oil and 1g of active auxiliary agent, continuously stirring for 30min, filtering while hot, washing the solid with deionized water to remove impurities, and drying in vacuum at 50 ℃ to constant weight;
(4) dispersing: adding the solid obtained in the step 3 into absolute ethyl alcohol, and performing ultrasonic dispersion for 2 hours to obtain a dispersion liquid;
(5) preparation: the dispersed liquid obtained in the step 4 is dripped on the surface of a glassy carbon electrode, and the electrode for measuring phenylethylamine is obtained after evaporation and drying;
preparation of the active assistant: adding 7g of sarcosine into deionized water, stirring at 40 ℃ for 10min, then adding 12g of sorbitol and 0.05g of tetraethyl titanate, heating to a reflux state, keeping the temperature and stirring for 4h, then adding 1g of corn oil, stirring at 75 ℃ for 40min, filtering, washing the obtained solid with deionized water to remove impurities, and drying at 50 ℃ in vacuum to constant weight.
Comparative example 2
(1) Modification of flexible graphite: adding 20g of flexible graphite into deionized water, refluxing and stirring for 10min, then adding 6g of titanate coupling agent and 0.1g of chain extender, and continuing refluxing and stirring for 2 h;
(2)CeO2the preparation of (1): adding 6g citric acid into 60g deionized water, stirring well, adding 6gCe (NO)3)3·6H2Stirring for 20min at 35 ℃, transferring into a reaction kettle, sealing at 140 ℃, reacting for 8h, filtering, washing impurities of the obtained product with deionized water and absolute ethyl alcohol, drying at 60 ℃ in vacuum to constant weight, and calcining the dried solid at 320 ℃ for 1 h;
(3) loading: adding 6gCeO into the solution obtained in the step 12Refluxing and stirring for 3h, cooling to 70 ℃, adding 1g of active auxiliary agent, continuously stirring for 30min, filtering while hot, washing the solid with deionized water to remove impurities, and drying in vacuum at 50 ℃ to constant weight;
(4) dispersing: adding the solid obtained in the step 3 into absolute ethyl alcohol, and performing ultrasonic dispersion for 2 hours to obtain a dispersion liquid;
(5) preparation: the dispersed liquid obtained in the step 4 is dripped on the surface of a glassy carbon electrode, and the electrode for measuring phenylethylamine is obtained after evaporation and drying;
preparation of the active assistant: adding 7g of sarcosine into deionized water, stirring at 40 ℃ for 10min, then adding 12g of sorbitol and 0.05g of tetraethyl titanate, heating to a reflux state, keeping the temperature and stirring for 4h, then adding 1g of corn oil, stirring at 75 ℃ for 40min, filtering, washing the obtained solid with deionized water to remove impurities, and drying at 50 ℃ in vacuum to constant weight.
Comparative example 3
(1) Modification of flexible graphite: adding 20g of flexible graphite into deionized water, refluxing and stirring for 10min, then adding 6g of titanate coupling agent and 0.1g of chain extender, and continuing refluxing and stirring for 2 h;
(2)CeO2the preparation of (1): adding 6g citric acid into 60g deionized water, stirring well, adding 6gCe (NO)3)3·6H2Stirring for 20min at 35 ℃, transferring into a reaction kettle, sealing at 140 ℃, reacting for 8h, filtering, washing impurities of the obtained product with deionized water and absolute ethyl alcohol, drying at 60 ℃ in vacuum to constant weight, and calcining the dried solid at 320 ℃ for 1 h;
(3) loading: adding 6gCeO into the solution obtained in the step 12Refluxing and stirring for 3h, cooling to 70 ℃, adding 0.2g of castor oil, continuously stirring for 30min, filtering while hot, washing the solid with deionized water to remove impurities, and drying in vacuum at 50 ℃ to constant weight;
(4) dispersing: adding the solid obtained in the step 3 into absolute ethyl alcohol, and performing ultrasonic dispersion for 2 hours to obtain a dispersion liquid;
(5) preparation: the dispersed liquid obtained in the step 4 is dripped on the surface of a glassy carbon electrode, and the electrode for measuring phenylethylamine is obtained after evaporation and drying;
example 3
Based on example 1, comparative example 1 in which a titanate coupling agent and a chain extender were not added, comparative example 2 in which castor oil was not added, and comparative example 3 in which a co-agent was not added were provided.
The electrodes of examples 1-2 and comparative examples 1-3 were prepared and used for detecting phenylethylamine in fish sauce, and the detection results are shown in table 1.
TABLE 1 detection results of phenylethylamine in fish sauce
Figure GDA0002579391630000061
Figure GDA0002579391630000071
Sample treatment: taking a fish sauce sample, filtering with a filter membrane, adding sodium chloride to saturate the solution, measuring 10mL of saturated solution, adjusting the pH to 12.5 with NaOH solution, adding 5mL of n-butanol-trichloromethane mixed solution with the volume ratio of 1:1, shaking, centrifuging, taking an upper organic phase, repeating for 2 times, combining the organic phases, drying, adding NaOH solution with the pH value of 12.5, and dissolving to obtain the solution to be detected.
The specific detection conditions are as follows: and (3) detecting the potential: 1.1V; enrichment potential: 0.8V; differential pulse conditions: the amplitude was 0.05V, the pulse period was 0.5s, and the pulse width was 0.05 s.
The same sample is measured by High Performance Liquid Chromatography (HPLC) and is compared, and the detection result is very consistent with the result obtained by the electrode, so that the sensor can be used for measuring the actual sample, and the detection result is quick and accurate.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (5)

1. A preparation method of an electrode for measuring phenylethylamine is characterized by comprising the following steps:
(1) modification of flexible graphite: adding flexible graphite into deionized water, refluxing and stirring for 10-30min, then adding titanate coupling agent and chain extender, and continuing to reflux and stir for 0.5-2 h;
(2)CeO2the preparation of (1): adding citric acid into deionized water, stirring, and adding Ce (NO)3)3·6H2Stirring for 10-30min at 35 ℃, transferring to a reaction kettle, sealing and reacting for 8-10h at 150 ℃ in 140-;
(3) loading: adding CeO into the solution in the step 12Refluxing and stirring for 0.5-4h, cooling to 70-75 ℃, adding castor oil and active auxiliary agent, continuously stirring for 20-40min, filtering while hot, washing the solid with deionized water to remove impurities, and drying in vacuum at 50 ℃ to constant weight;
(4) dispersing: adding the solid obtained in the step 3 into absolute ethyl alcohol, and performing ultrasonic dispersion for 1-2 hours to obtain a dispersion liquid;
(5) preparation: and (4) dropwise coating the dispersed liquid obtained in the step (4) on the surface of a glassy carbon electrode, and evaporating and drying to obtain the electrode for measuring phenylethylamine.
2. The preparation method for a phenethylamine electrode according to claim 1, wherein: the citric acid, deionized water and Ce (NO)3)3·6H2The mass ratio of O is 5-10: 50-80: 5-10.
3. The preparation method for a phenethylamine electrode according to claim 1, wherein: the flexible graphite, titanate coupling agent, chain extender and CeO2The mass of the castor oil and the active auxiliary agent is 20-30: 6-10: 0.1-0.2: 6-8: 0.1-0.5: 1-2.
4. The method for preparing an electrode for measuring phenethylamine according to claim 1, wherein the method for preparing the co-agent is: adding sarcosine into deionized water, stirring at 40 deg.C for 10min, adding sorbitol and tetraethyl titanate, heating to reflux state, stirring at constant temperature for 0.5-4h, adding corn oil, stirring at 70-80 deg.C for 30-40min, filtering, washing the obtained solid with deionized water to remove impurities, and vacuum drying at 50 deg.C to constant weight.
5. The method for preparing an electrode for measuring phenethylamine according to claim 4, wherein: the mass ratio of the sarcosine to the sorbitol to the tetraethyl titanate to the corn oil is 6-8: 10-15: 0.05: 0.5-2.
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