CN116908273B - Method for rapidly detecting harmful substances in food - Google Patents
Method for rapidly detecting harmful substances in food Download PDFInfo
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- CN116908273B CN116908273B CN202311185808.7A CN202311185808A CN116908273B CN 116908273 B CN116908273 B CN 116908273B CN 202311185808 A CN202311185808 A CN 202311185808A CN 116908273 B CN116908273 B CN 116908273B
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- 239000000126 substance Substances 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims description 18
- 229920001661 Chitosan Polymers 0.000 claims abstract description 88
- 229910021397 glassy carbon Inorganic materials 0.000 claims abstract description 83
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims abstract description 61
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims abstract description 61
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims abstract description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 34
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 34
- 230000004048 modification Effects 0.000 claims abstract description 28
- 238000012986 modification Methods 0.000 claims abstract description 28
- 238000001514 detection method Methods 0.000 claims abstract description 26
- 238000002484 cyclic voltammetry Methods 0.000 claims abstract description 13
- 230000004044 response Effects 0.000 claims abstract description 11
- 238000002791 soaking Methods 0.000 claims abstract description 11
- 238000004537 pulping Methods 0.000 claims abstract description 5
- 239000006228 supernatant Substances 0.000 claims abstract description 5
- 238000011415 microwave curing Methods 0.000 claims abstract description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 54
- 238000010438 heat treatment Methods 0.000 claims description 47
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- 239000000725 suspension Substances 0.000 claims description 17
- 239000003999 initiator Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 13
- 229910017604 nitric acid Inorganic materials 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000007853 buffer solution Substances 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 238000002715 modification method Methods 0.000 claims description 6
- 239000008363 phosphate buffer Substances 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 238000001723 curing Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 229940005654 nitrite ion Drugs 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 230000027756 respiratory electron transport chain Effects 0.000 claims description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 3
- 239000003115 supporting electrolyte Substances 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 238000010998 test method Methods 0.000 claims 3
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- 238000009792 diffusion process Methods 0.000 abstract description 6
- 230000001737 promoting effect Effects 0.000 abstract description 5
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 9
- 238000003487 electrochemical reaction Methods 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 230000000711 cancerogenic effect Effects 0.000 description 2
- 231100000357 carcinogen Toxicity 0.000 description 2
- 239000003183 carcinogenic agent Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000000835 electrochemical detection Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
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- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
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- 238000010168 coupling process Methods 0.000 description 1
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- 238000006193 diazotization reaction Methods 0.000 description 1
- 210000002249 digestive system Anatomy 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- LECSHJWIACEDPZ-UHFFFAOYSA-N ethane-1,2-diamine naphthalene hydrochloride Chemical compound C(CN)N.C1=CC=CC2=CC=CC=C12.Cl LECSHJWIACEDPZ-UHFFFAOYSA-N 0.000 description 1
- ZHNUHDYFZUAESO-UHFFFAOYSA-N formamide Substances NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 1
- XKLJHFLUAHKGGU-UHFFFAOYSA-N nitrous amide Chemical compound ON=N XKLJHFLUAHKGGU-UHFFFAOYSA-N 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
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Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
Abstract
The invention discloses a rapid detection method of harmful substances in food, which comprises the following steps: s1, using a three-electrode system; the surface of the modified glassy carbon electrode is provided with a porous modification layer formed by chitosan grafted with itaconic acid and carbon nanotube sol after microwave curing; s2, preparing a reference response curve of peak current-nitrite concentration by using the cyclic voltammetry scanning of the modified glassy carbon electrode in the S1; s3, crushing and pulping the food to be detected, soaking, centrifuging to obtain supernatant, performing cyclic voltammetry scanning by using a modified glassy carbon electrode to obtain peak current, and calculating and determining the nitrite concentration in the food to be detected according to the peak current obtained in the S3 corresponding to the reference response curve obtained in the S2; according to the invention, the platinum carbon electrode porous modification layer is used for increasing the active site of nitrite, promoting the diffusion of nitrite, simultaneously effectively transmitting electrons by matching with a conductive network, reducing mass transfer control and improving the detection stability.
Description
Technical Field
The invention relates to the technical field of food detection, in particular to a rapid detection method for harmful substances in food.
Background
Nitrite is a strong carcinogen, combines with secondary amine to form nitrosamine, induces digestive system canceration, and threatens human health. Nitrite is a highly toxic substance, and can cause poisoning after being taken by 0.2-0.5 g by adults, and can cause death after 3 g. Nitrite is also a carcinogen. The detection methods commonly used for nitrite mainly comprise diazo coupling colorimetry, ion chromatography, spectrophotometry and the like, and the methods generally require complex sample pretreatment and have the disadvantages of long time consumption, complex operation and the like.
The main inventive concept of the reagent and the method for detecting nitrate rapidly is to adopt PVP to reduce the contact between cadmium powder and other substances, ensure the sufficient reduction and diazotization of the cadmium powder, and then adopt naphthalene ethylenediamine hydrochloride in the reagent II to carry out coupling color reaction, thereby shortening the color reaction time, enabling the absorbance to be rapidly stable and obviously improving the controllability of the reaction. However, the toxicity and difficult recovery characteristics of cadmium limit its application in nitrate detection.
Disclosure of Invention
The invention aims to provide a rapid detection method for harmful substances in food, which utilizes a porous structure layer to modify a platinum carbon electrode, increases the active site of nitrite, promotes the diffusion of nitrite, reduces mass transfer control and improves the detection speed.
In order to solve the technical problem, the technical scheme of the invention is as follows: a rapid detection method of harmful substances in food comprises the following steps:
s1, using a three-electrode system, wherein Ag/AgCl is used as a reference electrode, a modified glassy carbon electrode is used as a working electrode, a platinum electrode is used as an auxiliary electrode, and phosphate buffer PBS is used as a supporting electrolyte, wherein the concentration of the phosphate buffer is 0.1M, and pH=7.0;
the surface of the modified glassy carbon electrode is provided with a porous modification layer formed by chitosan grafted with itaconic acid and carbon nanotube sol after microwave curing;
s2, respectively circularly voltammetrically scanning a buffer solution containing nitrite with the concentration of 0.1 mu mol/L to 10 mu mol/L by using the glassy carbon electrode modified in the S1, and recording peak current;
then, the nitrite ion concentration is taken as an abscissa, and the peak current is taken as an ordinate, so that a reference response curve of the peak current-nitrite concentration is prepared;
the scanning voltage ranges from 0.4V to 1.2V, and the scanning speed ranges from 50mV/s to 200mV/s;
s3, crushing and pulping the food to be detected, soaking, centrifuging to obtain supernatant, performing cyclic voltammetry scanning by using a modified glassy carbon electrode to obtain peak current, and calculating and determining the nitrite concentration in the food to be detected according to the peak current obtained in the S3 corresponding to the reference response curve obtained in the S2;
in the cyclic voltammetry scanning process, nitrite in the buffer solution is distributed on the porous modification layer under the electrostatic adsorption effect of chitosan and is matched with carbon nano tubes in the porous modification layer for electron transfer.
Preferably, the modification method of the glassy carbon electrode in the step S1 comprises the following steps:
s11, placing the glassy carbon electrode in concentrated sulfuric acid, heating and soaking to oxidize the surface of the glassy carbon electrode to obtain carboxyl;
s12, uniformly mixing the chitosan grafted with the itaconic acid with the carbon nano tube to obtain suspension sol, coating, and heating by microwaves, drying and curing;
in the microwave heating process, itaconic acid grafted on chitosan is subjected to self-polymerization to form a network, and simultaneously hydroxyl of the chitosan is esterified with carboxyl on the surface of the glassy carbon electrode to form chemical bond connection; meanwhile, water molecules are separated from the modification layer to form a porous structure. Compared with the prior art, the modified layer is directly dripped on the surface of the glassy carbon electrode and then naturally dried, the combination between the modified layer and the glassy carbon electrode is relatively weak, in the invention, the sol which is uniformly mixed with the itaconic acid and is grafted on the surface of the glassy carbon electrode is solidified on the surface of the glassy carbon electrode in a microwave drying mode, on one hand, the hydroxyl on the surface of the chitosan, the carboxyl on the surface of the glassy carbon electrode, the carboxyl on the surface of the carbon nanotube and the carboxyl of the itaconic acid all form ester bonds, the amino on the surface of the chitosan and the carboxyl on the surface of the carbon nanotube form amide bonds, and self-aggregation can also occur between the itaconic acid, so that in the microwave solidification process, the modified layer structure forms chemical bond connection in a three-dimensional space, the combination of the modified layer and the glassy carbon electrode is stable, and the material in the layer is also stably connected through the chemical bond, so that the modified glassy carbon electrode can be repeatedly used in the detection of nitrite.
Preferably, dissolving the chitosan modified by itaconic acid by deionized water, adding dilute nitric acid, mixing, performing ultrasonic treatment, adding carbon nano tubes with oxygen-containing groups on the surfaces, and vigorously stirring to obtain suspension sol;
the dosage ratio of chitosan to deionized water is 1g: (30 ml to 40 ml); the mass ratio of the chitosan to the carbon nano tube is 1: (0.05 to 0.10); the pH value of the material system is adjusted to 3 to 4 by adding dilute nitric acid. The invention utilizes sol to be matched with microwave drying, promotes uniform dispersion of chitosan relative to the carbon nano tube, and further utilizes microwave drying to promote water separation, thereby constructing the porous structure of the modification layer.
The preferred method for modifying chitosan using itaconic acid is as follows:
s21, heating and dissolving chitosan by using acetic acid solution;
s22, introducing nitrogen for protection, keeping heating and stirring, dropwise adding an itaconic acid aqueous solution and an initiator into the mixed solution of S21, and heating and stirring part of itaconic acid-COOH and chitosan-NH under stirring 2 generating-CONH-by reaction to form branch connection; obtaining itaconic acid modified chitosan. The invention uses itaconic acid to modify chitosan, on one hand, itaconic acid is self-polymerized and effectively connectedThe chitosan is connected, on the other hand, the carbon-carbon double bond of the itaconic acid is ring-opened and self-polymerized, and the self-polymerization reaction formula is as follows:
. Therefore, the itaconic acid is used as a catalyst in a sol state to effectively promote the stable connection between chitosan and the glassy carbon electrode in the modification layer, and simultaneously, the stability of the film layer is enhanced.
Preferably, the dosage ratio of chitosan to acetic acid solution in S21 is 1g: (80 ml to 100 ml);
the mass fraction of the acetic acid solution is 1.5% to 2.5%.
The preferred process conditions for the itaconic acid modified chitosan reaction are as follows: the reaction temperature is 60 ℃ to 70 ℃ and the reaction time is 2 hours to 3 hours.
Preferably, the mass ratio of chitosan to itaconic acid in S22 is 1 (0.2 to 0.3);
the concentration of the dropwise addition initiator is 2.0X10 -2 mol/L to 3.0X10 -2 mol/L；
The initiator is H 2 O 2 。
Preferably, the process parameters of the S12 microwave heating are as follows:
heating to 100-120 ℃; heating time is 5min to 8min.
Preferably, the diameter of the unmodified glassy carbon electrode is 4mm; the suspension sol was coated in S12 in 5 μl to 8 μl.
By adopting the technical scheme, the invention has the beneficial effects that:
crushing and pulping food to be detected, soaking, centrifuging to obtain supernatant, performing cyclic voltammetry scanning by using a modified glassy carbon electrode to obtain peak current, and comparing response curves obtained by the modified glassy carbon electrode to determine nitrite concentration in the food to be detected; the hydroxyl of chitosan in the modification layer on the surface of the glassy carbon battery and the carboxyl on the surface of the glassy carbon battery are subjected to esterification reaction under the catalysis of itaconic acid to form the modification layer, namely the itaconic acid modified chitosan/carbon nanotube composite layer is connected with the glassy carbon electrode through chemical bonds, so that the bonding force between the modification layer and the surface of the glassy carbon electrode is remarkably improved, and the stability of the modified glassy carbon electrode in a test is improved on the structure of the glassy carbon electrode and the modification layer; meanwhile, in the microwave heating process, further chemical bonding can be generated between the itaconic acid grafted chitosan and the carbon nano tube and between the itaconic acid, for example, the hydroxyl of the chitosan reacts with the carboxyl on the surface of the carbon nano tube to form an ester bond, and the amino on the surface of the chitosan reacts with the carboxyl on the surface of the carbon nano tube to form an amide bond, so that a stable modification layer structure is formed; in the microwave heating process, the obtained modification layer is dehydrated to form a porous structure in the microwave heating process, and the porous structure is matched with chitosan and carbon nanotubes to form nitrite detection active sites, so that the existence and uniform dispersion of the carbon nanotubes effectively ensure the transfer of electrons and provide current for the electrochemical reaction of nitrite; on the other hand, the porous-structure modified membrane is beneficial to constructing a rich diffusion layer, promoting mass transfer in electrochemical reaction, reducing nitrite diffusion and limitation of mass transfer on electrochemical reaction, effectively promoting electrochemical conversion of nitrite, and has sensitive electrochemical detection in the electrochemical detection process and difficult pollution and poisoning.
Drawings
FIG. 1 is an SEM image of a modified layer of a glassy carbon electrode according to example 3 of the present invention;
FIG. 2 is an infrared spectrum of itaconic acid grafted chitosan for forming a modified layer according to example 3 of the present invention, wherein A is itaconic acid and B is itaconic acid grafted chitosan;
FIG. 3 is a cyclic voltammogram of a modified glassy carbon electrode at different scan rates for example 3 of the present invention where A-50mV/s; b-100 mV/s; c-200 mV/s;
FIG. 4 is a reference response curve of peak current versus nitrite concentration for a modified glass carbon electrode in accordance with example 3 of the present invention, wherein the peak current is ipa (mA/cm 2 ) Nitrite concentration was C (mmol/L).
Detailed Description
In order to further explain the technical scheme of the invention, the invention is explained in detail by specific examples.
Example 1
The embodiment discloses a modified glassy carbon electrode applied to a rapid detection method of harmful substances in food, wherein the modification method of the glassy carbon electrode comprises the following steps:
s11, placing the glassy carbon electrode in concentrated sulfuric acid, heating and soaking to oxidize the surface of the glassy carbon electrode to obtain carboxyl, and cleaning and drying the glassy carbon electrode for later use;
s12, uniformly mixing the chitosan grafted with the itaconic acid with the carbon nano tube to obtain suspension sol, coating, and heating by microwaves, drying and curing;
the technological parameters of microwave heating are as follows:
the target temperature is 120 ℃; heating time is 5min.
The diameter of the unmodified glassy carbon electrode is 4mm; the suspension was coated with 5. Mu.L in S12.
In the microwave heating process, itaconic acid grafted on chitosan is subjected to self-polymerization to form a network, and simultaneously hydroxyl of the chitosan is esterified with carboxyl on the surface of the glassy carbon electrode to form chemical bond connection; meanwhile, water molecules are separated from the modification layer to form a porous structure.
In the embodiment, the chitosan modified by itaconic acid is dissolved by deionized water, diluted nitric acid is added for mixing, ultrasound is carried out, carbon nano tubes with oxygen-containing groups on the surfaces are added, and the suspension sol is obtained by intense stirring;
the dosage ratio of chitosan to deionized water is 1g:30ml; the mass ratio of the chitosan to the carbon nano tube is 1:0.05; and adding dilute nitric acid to adjust the pH value of the material system to 3.3, wherein the mass fraction of the dilute nitric acid is 5%.
The method for modifying chitosan by using itaconic acid in the embodiment is as follows:
s21, heating and dissolving chitosan by using acetic acid solution; the dosage ratio of chitosan to acetic acid solution is 1g: 80ml; the mass fraction of the acetic acid solution was 2.5%.
S22, introducing nitrogen for protection, keeping heating and stirring, and dropwise adding an itaconic acid aqueous solution and an initiator into the mixed solution of S21, wherein the mass ratio of chitosan to itaconic acid in S22 is 1:0.2; the concentration of the dropwise addition initiator is 2.0X10 -2 mol/L; the initiator is H 2 O 2 。
Heating and stirring part of itaconic acid-COOH and chitosan-NH 2 Reaction to produce-CONH-forming a graft; the technological conditions of the itaconic acid modified chitosan reaction are as follows: the reaction temperature is 60 ℃ and the reaction time is 2 hours, so that the itaconic acid modified chitosan is obtained.
Example 2
The embodiment discloses a modified glassy carbon electrode applied to a rapid detection method of harmful substances in food, wherein the modification method of the glassy carbon electrode comprises the following steps:
s11, placing the glassy carbon electrode in concentrated sulfuric acid, heating and soaking to oxidize the surface of the glassy carbon electrode to obtain carboxyl, and cleaning and drying the glassy carbon electrode for later use;
s12, uniformly mixing the chitosan grafted with the itaconic acid with the carbon nano tube to obtain suspension sol, coating, and heating by microwaves, drying and curing;
the technological parameters of microwave heating are as follows:
target temperature 100 ℃; heating time is 8min.
The diameter of the unmodified glassy carbon electrode is 4mm; the suspension was coated with 8. Mu.L in S12.
In the microwave heating process, itaconic acid grafted on chitosan is subjected to self-polymerization to form a network, and simultaneously hydroxyl of the chitosan is esterified with carboxyl on the surface of the glassy carbon electrode to form chemical bond connection; meanwhile, water molecules are separated from the modification layer to form a porous structure.
In the embodiment, the chitosan modified by itaconic acid is dissolved by deionized water, diluted nitric acid is added for mixing, ultrasound is carried out, carbon nano tubes with oxygen-containing groups on the surfaces are added, and the suspension sol is obtained by intense stirring;
the dosage ratio of chitosan to deionized water is 1g:35ml; the mass ratio of the chitosan to the carbon nano tube is 1: 0.08; and adding dilute nitric acid to adjust the pH value of the material system to 3.4, wherein the mass fraction of the dilute nitric acid is 5%.
The method for modifying chitosan by using itaconic acid in the embodiment is as follows:
s21, heating and dissolving chitosan by using acetic acid solution; the dosage ratio of chitosan to acetic acid solution is 1g: 90ml; the mass fraction of the acetic acid solution was 2.0%.
S22, introducing nitrogen for protection, keeping heating and stirring, and dropwise adding the itaconic acid aqueous solution and the initiator into the mixed solution of S21The mass ratio of chitosan to itaconic acid in S22 is 1:0.3; the concentration of the dropwise addition initiator is 2.0X10 -2 mol/L; the initiator is H 2 O 2 。
Heating and stirring part of itaconic acid-COOH and chitosan-NH 2 generating-CONH-by reaction to form branch connection; the technological conditions of the itaconic acid modified chitosan reaction are as follows: the reaction temperature is 70 ℃ and the reaction time is 2 hours, so that the itaconic acid modified chitosan is obtained.
Example 3
The embodiment discloses a modified glassy carbon electrode applied to a rapid detection method of harmful substances in food, wherein the modification method of the glassy carbon electrode comprises the following steps:
s11, placing the glassy carbon electrode in concentrated sulfuric acid, heating and soaking to oxidize the surface of the glassy carbon electrode to obtain carboxyl, and cleaning and drying the glassy carbon electrode for later use;
s12, uniformly mixing the chitosan grafted with the itaconic acid with the carbon nano tube to obtain suspension sol, coating, and heating by microwaves, drying and curing;
the technological parameters of microwave heating are as follows:
target temperature 110 ℃; heating time is 6min.
The diameter of the unmodified glassy carbon electrode is 4mm; the suspension was coated with 8. Mu.L in S12.
In the microwave heating process, itaconic acid grafted on chitosan is subjected to self-polymerization to form a network, and simultaneously hydroxyl of the chitosan is esterified with carboxyl on the surface of the glassy carbon electrode to form chemical bond connection; meanwhile, the water molecules are separated from the modification layer to form a porous structure, as shown in fig. 1.
In the embodiment, the chitosan modified by itaconic acid is dissolved by deionized water, diluted nitric acid is added for mixing, ultrasound is carried out, carbon nano tubes with oxygen-containing groups on the surfaces are added, and the suspension sol is obtained by intense stirring;
the dosage ratio of chitosan to deionized water is 1g:40ml; the mass ratio of the chitosan to the carbon nano tube is 1: 0.10; and adding dilute nitric acid to adjust the pH value of the material system to 3.6, wherein the mass fraction of the dilute nitric acid is 5%.
The method for modifying chitosan by using itaconic acid in the embodiment is as follows:
s21, heating and dissolving chitosan by using acetic acid solution; the dosage ratio of chitosan to acetic acid solution is 1g:100ml; the mass fraction of the acetic acid solution is 1.5%.
S22, introducing nitrogen for protection, keeping heating and stirring, and dropwise adding an itaconic acid aqueous solution and an initiator into the mixed solution of S21, wherein the mass ratio of chitosan to itaconic acid in S22 is 1:0.2; the concentration of the dropwise addition initiator is 3.0X10 -2 mol/L; the initiator is H 2 O 2 。
Heating and stirring part of itaconic acid-COOH and chitosan-NH 2 generating-CONH-by reaction to form branch connection; the technological conditions of the itaconic acid modified chitosan reaction are as follows: the reaction temperature is 60 ℃ and the reaction time is 3 hours, so that the itaconic acid modified chitosan is obtained. In this example, the IR spectrum of itaconic acid grafted chitosan in the film-forming material of the porous modification layer is shown in FIG. 2, and it can be seen that-OH, -NH and-CH are present 2 The stretching vibration absorption peak of (C) moves in the homogeneous long wave direction at 1725cm -1 Near the peak of the stretching vibration absorption of-C=O, the peak of the bending vibration absorption in the methyl C-H plane falls at 1383cm -1 ，1628 cm -1 Near the vibration peak with amide bond expansion and contraction, 3300 and 3300 cm -1 To 3500 cm -1 The expansion vibration peak of C-N in the amide bond is also formed between the chitosan and the itaconic acid, so that the grafting reaction of the chitosan and the itaconic acid is known.
Comparative example
The comparative example discloses a modified glassy carbon electrode applied to a rapid detection method of harmful substances in food, and the modification method of the glassy carbon electrode comprises the following steps:
s11, placing the glassy carbon electrode in concentrated sulfuric acid, heating and soaking to oxidize the surface of the glassy carbon electrode to obtain carboxyl, and cleaning and drying the glassy carbon electrode for later use;
s12, heating and dissolving chitosan by using acetic acid solution; the dosage ratio of chitosan to acetic acid solution is 1g:100ml; the mass fraction of the acetic acid solution is 1.5%, and the mass ratio of chitosan to carbon nano tube is 1:0.10. Uniformly mixing chitosan and carbon nano tubes to obtain suspension sol, coating, and naturally drying to obtain the modified glassy carbon electrode.
The diameter of the unmodified glassy carbon electrode is 4mm; the suspension was coated with 8. Mu.L in S12.
The modified glassy carbon electrodes obtained in examples 1 to 3 and comparative example, respectively, were applied to the detection of harmful substances in food, more specifically nitrite concentration, and the specific method comprises the following steps:
s1, using a three-electrode system, wherein Ag/AgCl is used as a reference electrode, a modified glassy carbon electrode is used as a working electrode, a platinum electrode is used as an auxiliary electrode, and phosphate buffer PBS is used as a supporting electrolyte, wherein the concentration of the phosphate buffer is 0.1M, and pH=7.0;
the surface of the modified glassy carbon electrode is provided with a porous modification layer formed by chitosan grafted with itaconic acid and carbon nanotube sol after microwave curing;
s2, respectively circularly voltammetrically scanning a buffer solution containing nitrite with the concentration of 0.1 mu mol/L to 10 mu mol/L by using the glassy carbon electrode modified in the S1, and recording peak current;
then, the nitrite ion concentration is taken as an abscissa, and the peak current is taken as an ordinate, so that a reference response curve of the peak current-nitrite concentration is prepared;
the scanning voltage ranges from 0.4V to 1.2V, and the scanning speed ranges from 50mV/s to 200mV/s;
s3, crushing and pulping the food to be detected, soaking, centrifuging to obtain supernatant, performing cyclic voltammetry scanning by using a modified glassy carbon electrode to obtain peak current, and calculating and determining the nitrite concentration in the food to be detected according to the peak current obtained in the S3 corresponding to the reference response curve obtained in the S2;
in the cyclic voltammetry scanning process, nitrite in the buffer solution is distributed on the porous modification layer under the electrostatic adsorption effect of chitosan and is matched with carbon nano tubes in the porous modification layer for electron transfer.
Taking the modified glassy carbon electrode obtained in example 3 as an example, the electrochemical cyclic voltammetry scanning is used for constructing a reference response curve of peak current-nitrite concentration, as shown in fig. 4, and a linear equation is as follows:
i pa =0.357+0.362C;
the cyclic voltammogram of the glassy carbon electrode modified in the embodiment 3 at different scanning speeds is shown in fig. 3, and as shown in the figure, the porous structure of the porous modification layer is matched with the formation of a conductive network of the carbon nano tube, the detection active sites of the modified glassy carbon electrode nitrite are rich, and the existence and uniform dispersion of the carbon nano tube effectively ensure the transfer of electrons, so that current is provided for the electrochemical reaction of nitrite; on the other hand, the porous-structure modified membrane is beneficial to constructing a rich diffusion layer, promoting mass transfer in electrochemical reaction, reducing nitrite diffusion and limitation of mass transfer on electrochemical reaction, effectively promoting nitrite electrochemical conversion, and effectively improving detection speed by using a scanning speed of 100 mV/s.
The glassy carbon electrodes with the modification layers prepared in examples 1 to 3 and comparative example were used to test multiple times for sodium nitrite aqueous solutions of the same concentration, wherein the concentration of sodium nitrite was 1.00 μg/g; after each measurement, ultrasonically cleaning the modified glassy carbon electrode by using deionized water, and drying for next use; specific data are shown in tables 1 to 4. Wherein the modified glassy carbon electrodes prepared in examples 1-3 are soaked and washed with deionized water for several times before use, and nitrate radical affecting the test result is removed.
Table 1 test results of example 1 modified glassy carbon electrode for rapid detection of nitrite concentration
Table 2 test results of example 2 modified glassy carbon electrode for rapid detection of nitrite concentration
Table 3 test results of example 3 modified glassy carbon electrode for rapid detection of nitrite concentration
Table 4 test results of comparative example modified glassy carbon electrode for rapid detection of nitrite concentration
As can be seen from tables 1 to 4, the glassy carbon electrode with the modification layer used in the present invention has a stable structure and can be repeatedly used for a plurality of times; and the test result is stable and rapid, and the test result is composed of nonmetal and is not easy to poison and pollute.
Claims (7)
1. A rapid detection method for harmful substances in food is characterized in that: the method comprises the following steps:
s1, using a three-electrode system, wherein Ag/AgCl is used as a reference electrode, a modified glassy carbon electrode is used as a working electrode, a platinum electrode is used as an auxiliary electrode, and phosphate buffer PBS is used as a supporting electrolyte, wherein the concentration of the phosphate buffer is 0.1M, and pH=7.0;
the surface of the modified glassy carbon electrode is provided with a porous modification layer formed by chitosan grafted with itaconic acid and carbon nanotube sol after microwave curing;
s2, respectively carrying out cyclic voltammetry scanning on a buffer solution containing nitrite with the concentration of 0.1 mu mol/L and 10 mu mol/L by using the glassy carbon electrode modified in the S1, and recording peak current;
then, the nitrite ion concentration is taken as an abscissa, and the peak current is taken as an ordinate, so that a reference response curve of the peak current-nitrite concentration is prepared;
the scanning voltage ranges from 0.4V to 1.2V, and the scanning speed ranges from 50mV/s to 200mV/s;
s3, crushing and pulping the food to be detected, soaking, centrifuging to obtain supernatant, performing cyclic voltammetry scanning by using a modified glassy carbon electrode to obtain peak current, and calculating and determining the nitrite concentration in the food to be detected according to the peak current obtained in the S3 corresponding to the reference response curve obtained in the S2;
in the cyclic voltammetry scanning process, nitrite in a buffer solution is distributed on the porous modification layer under the electrostatic adsorption effect of chitosan and is matched with carbon nano tubes in the porous modification layer for electron transfer;
the modification method of the glassy carbon electrode in the S1 comprises the following steps:
s11, placing the glassy carbon electrode in concentrated sulfuric acid, heating and soaking to oxidize the surface of the glassy carbon electrode to obtain carboxyl;
s12, uniformly mixing the chitosan grafted with the itaconic acid with the carbon nano tube to obtain suspension sol, coating, and heating by microwaves, drying and curing;
s12, the technological parameters of microwave heating are as follows:
heating to 100-120 ℃; heating for 5min to 8min;
in the microwave heating process, itaconic acid grafted on chitosan is subjected to self-polymerization to form a network, and simultaneously hydroxyl of the chitosan is esterified with carboxyl on the surface of the glassy carbon electrode to form chemical bond connection; meanwhile, water molecules are separated from the modification layer to form a porous structure.
2. The rapid detection method according to claim 1, wherein: dissolving itaconic acid modified chitosan by deionized water, adding dilute nitric acid, mixing, performing ultrasonic treatment, adding carbon nano tubes with oxygen-containing groups on the surfaces, and vigorously stirring to obtain suspension sol;
the dosage ratio of chitosan to deionized water is 1g: (30 ml to 40 ml); the mass ratio of the chitosan to the carbon nano tube is 1: (0.05 to 0.10); the pH value of the material system is adjusted to 3 to 4 by adding dilute nitric acid.
3. The rapid detection method according to claim 2, wherein: the method for modifying chitosan by using itaconic acid is as follows:
s21, heating and dissolving chitosan by using acetic acid solution;
s22, introducing nitrogen for protection, keeping heating and stirring, dropwise adding an itaconic acid aqueous solution and an initiator into the mixed solution of S21, and heating and stirring part of itaconic acid-COOH and chitosan-NH under stirring 2 generating-CONH-by reaction to form branch connection; obtaining itaconic acid modified chitosan.
4. A rapid test method according to claim 3, wherein:
the dosage ratio of chitosan to acetic acid solution in S21 is 1g: (80 ml to 100 ml);
the mass fraction of the acetic acid solution is 1.5% to 2.5%.
5. A rapid test method according to claim 3, wherein:
the technological conditions of the itaconic acid modified chitosan reaction are as follows: the reaction temperature is 60 ℃ to 70 ℃ and the reaction time is 2 hours to 3 hours.
6. A rapid test method according to claim 3, wherein:
in S22, the mass ratio of chitosan to itaconic acid is 1 (0.2 to 0.3);
the concentration of the dropwise addition initiator is 2.0X10 -2 mol/L to 3.0X10 -2 mol/L；
The initiator is H 2 O 2 。
7. The rapid detection method according to claim 1, wherein:
the diameter of the unmodified glassy carbon electrode is 4mm; the suspension sol was coated in S12 in 5 μl to 8 μl.
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