CN111089917A - Method for measuring residual quantity of plant growth regulator in melons and fruits - Google Patents

Method for measuring residual quantity of plant growth regulator in melons and fruits Download PDF

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CN111089917A
CN111089917A CN201911341171.XA CN201911341171A CN111089917A CN 111089917 A CN111089917 A CN 111089917A CN 201911341171 A CN201911341171 A CN 201911341171A CN 111089917 A CN111089917 A CN 111089917A
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sample
solution
plant growth
magnetic adsorbent
eluent
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李樱红
章虎
陈丽萍
徐明飞
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ZHEJIANG INSTITUTE FOR FOOD AND DRUG CONTROL
Zhejiang Academy of Agricultural Sciences
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ZHEJIANG INSTITUTE FOR FOOD AND DRUG CONTROL
Zhejiang Academy of Agricultural Sciences
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • G01N30/14—Preparation by elimination of some components
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N2030/022—Column chromatography characterised by the kind of separation mechanism
    • G01N2030/027—Liquid chromatography
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • G01N2030/062—Preparation extracting sample from raw material

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • Pathology (AREA)
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Abstract

A method for measuring the residual quantity of plant growth regulators in melons and fruits, in particular to the field of medicine residue detection, which comprises the following steps: homogenizing a sample to be detected, adding an extracting agent, and uniformly stirring to obtain sample slurry; adding a pigment precipitator and a matrix preservative into the sample slurry, uniformly mixing, and centrifuging to obtain a supernatant and residues; after the supernatant is steamed to be dry, re-dissolving the supernatant in purified water to obtain a sample solution; adding a magnetic adsorbent into the sample solution, centrifugally oscillating, and desorbing to obtain the magnetic adsorbent attached with adsorbate and a residual solution; eluting the magnetic adsorbent by an eluent to obtain an eluent and the desorbed magnetic adsorbent; blowing the eluent to be dry by nitrogen, re-dissolving by adopting acetonitrile-formic acid aqueous solution, and filtering by a membrane to obtain an upper computer analysis solution; and analyzing and determining the upper computer analysis liquid by a high performance liquid chromatography-tandem mass spectrometry method to obtain the recovery rate of each plant growth regulator. The method has the advantages of high accuracy and simplicity in operation.

Description

Method for measuring residual quantity of plant growth regulator in melons and fruits
Technical Field
The invention relates to the field of medicine residue detection, in particular to a method for determining the residual quantity of a plant growth regulator in melons and fruits.
Background
Plant growth regulators are a class of substances that have similar physiological and biological effects as plant hormones. It has been found that the substances having the function of regulating and controlling the growth and development of plants include diethyl aminoethyl hexanoate, forchlorfenuron, compound sodium nitrophenolate, auxin, gibberellin, ethylene, cytokinin, abscisic acid, brassinolide, salicylic acid, jasmonic acid, paclobutrazol, polyamine and the like, and the substances used as plant growth regulators in agricultural production are mainly the first 9 types.
When the plant growth regulator is applied to crops according to the specified application dosage, period and method, the plant growth regulator does not cause harm to human health. If the use is not standard, the quality of agricultural products is influenced to a certain extent, and the edible food is harmful to human health.
The difficulty of measuring the PGRs in the plant with more residues is that the PGRs have more types, larger property difference, low concentration, serious matrix interference and the like, and the requirement on a pretreatment method is higher. Therefore, the establishment of a set of efficient and accurate method for measuring the residual quantity of the plant growth regulator is an urgent problem to be solved.
Disclosure of Invention
The invention provides a method for measuring the residual quantity of a plant growth regulator in melons and fruits, which has the advantages of high accuracy and simplicity in operation.
In order to achieve the purpose, the invention provides the following technical scheme:
a method for measuring the residual quantity of plant growth regulator in melons and fruits comprises the following steps:
and S01, homogenizing the sample to be detected, adding the extracting agent, and stirring uniformly to obtain sample slurry.
And S02, adding a pigment precipitator and a matrix preservative into the sample slurry, uniformly mixing, and centrifuging to obtain a supernatant and a residue.
And S03, performing rotary evaporation on the supernatant until the supernatant is dried, and re-dissolving the supernatant with purified water to obtain a sample solution.
And S04, adding a magnetic adsorbent into the sample solution, centrifuging, oscillating, and desorbing to obtain the magnetic adsorbent attached with adsorbate and a residual solution.
S05, eluting the magnetic adsorbent attached with the adsorbate by using an eluant to obtain an eluent and the desorbed magnetic adsorbent; the remaining liquid is discarded.
And S06, blowing the eluent to be dry through nitrogen, redissolving the eluent by adopting an acetonitrile-formic acid aqueous solution, and filtering the redissolved solution by a membrane to obtain the upper computer analysis solution.
And S07, analyzing and determining the upper computer analysis liquid by a high performance liquid chromatography-tandem mass spectrometry to obtain the recovery rate of each plant growth regulator.
Preferably, in step S01, the extractant is selected from: any one of a mixed solution of formic acid and acetonitrile, a mixed solution of sodium hydroxide and acetonitrile; wherein, in the mixed solution of formic acid and acetonitrile, the mass fraction of formic acid is 0.5-2%; in the mixed solution of sodium hydroxide and acetonitrile, the mass fraction of sodium hydroxide was 2%.
Preferably, in step S02, the pigment precipitating agent is calcium hydroxide. When the matrix of the melon and fruit is contacted with carbon dioxide in the air, calcium hydroxide reacts with the matrix to form calcium carbonate precipitate. The calcium carbonate precipitates can adsorb pigments in melon and fruit matrixes in the flocculation process, so that the purification effect is achieved, and the precipitates can be removed through centrifugal operation and filtering operation.
Preferably, in step S02, the matrix preservative is an inclusion of photocatalyst-hydroxymethylchitosan. When the number of samples to be treated by an experimenter is too large, the embedding substance of the photocatalyst-hydroxymethyl chitosan can inhibit the breeding of microorganisms in the matrix (change the acid-base system of the matrix and further destroy the structure of the plant growth regulator), can also play a role in slowly releasing the photocatalyst, and can prevent the sample slurry to be detected from being degraded due to long-time untreated.
Preferably, between step S01 and step S02, a step S01.1 is further included, the step S01.1 including:
(1) adding a lytic enzyme into the sample slurry, mixing, reacting, and filtering after the reaction is finished to obtain primary filtrate and primary filter residue.
(2) Weighing the filter residue, adding alcohol for redissolving, adding the decomposition enzyme again, mixing, reacting, and filtering after the reaction is finished to obtain secondary filtrate and secondary filter residue.
(3) And (3) repeating the step (2) until the quality of the filter residue is unchanged, and mixing the filter liquor obtained by the last filtration with the filter residue to obtain the sample slurry in the step S02.
Preferably, in step (1), the lytic enzyme is pectinase and cellulase.
Preferably, in step S04, the magnetic adsorbent is selected from a composite material made of magnetic graphene and β -cyclodextrin, a composite material made of chitosan and ferroferric oxide, and Fe3O4-dopamine, Fe3O4-SiO 2-chitosan graphene oxide, Fe3O4-nitrogen doped graphene, Fe3O4- β at least one of cyclodextrin-carboxymethylcellulose.
Preferably, in step S05, the eluent is selected from any one of methanol, ethyl acetate, acetonitrile and dichloromethane.
Preferably, in step S05, the magnetic adsorbent having the adsorbate attached thereto is repeated three times with the eluent, and the resulting solutions are combined three times, that is, the eluents in step S05.
The invention has the beneficial effects that:
(1) when the plant growth regulator in the melon and fruit is measured, pigments in the melon and fruit can be adsorbed by the adsorbent, so that the adsorption of the magnetic adsorbent to the plant growth regulator is influenced. The scheme can remove pigments in melon and fruit matrixes through the pigment precipitator, and avoids interference on adsorption of the plant growth regulator.
(2) By using the matrix preservative, part of sample liquid which cannot be detected can be prevented from being degraded, and substances which interfere with the detection of the plant growth regulator are prevented from being generated after the quality of the matrix of the melons and fruits is degraded.
(3) The magnetic solid-phase extraction technology combines the characteristics of simple magnetic extraction operation, time saving and rapidness, and the graphene has an ultra-large specific surface area, better chemical stability and strong pi-pi interaction on organic compounds, and a certain progress is made in the aspect of sample pretreatment, moreover, the β -cyclodextrin modified magnetic graphene is utilized to prepare the nano modified material, so that the inherent properties of β -cyclodextrin and magnetic graphene are kept, and the effect of enhancing the water solubility of the magnetic graphene and preventing the self-aggregation of the magnetic graphene is also achieved.
Detailed Description
Example 1
The embodiment provides a technical scheme:
a method for measuring the residual quantity of plant growth regulator in melons and fruits comprises the following steps:
and S01, homogenizing the sample to be detected, adding the extracting agent, and stirring uniformly to obtain sample slurry.
And S02, adding a lytic enzyme into the sample slurry, mixing, reacting, and filtering after the reaction is finished to obtain primary filtrate and primary filter residue.
S03, weighing the filter residue, adding alcohol for redissolving, adding the lyase again, mixing for reaction, and filtering after the reaction is finished to obtain secondary filtrate and secondary filter residue.
And S04, repeating the step S03 until the quality of filter residue is unchanged, and mixing the filter liquor obtained by the last filtration with the filter residue to obtain the sample slurry in the step S05.
And S05, adding calcium hydroxide and an embedding substance of photocatalyst-hydroxymethyl chitosan into the sample slurry, uniformly mixing, and centrifuging to obtain a supernatant and residues.
And S06, performing rotary evaporation on the supernatant until the supernatant is dried, and re-dissolving the supernatant with purified water to obtain a sample solution.
And S07, adding a magnetic adsorbent into the sample solution, centrifuging, oscillating, and desorbing to obtain the magnetic adsorbent attached with adsorbate and a residual solution.
S08, eluting the magnetic adsorbent attached with the adsorbate by using an eluant to obtain an eluent and the desorbed magnetic adsorbent; the remaining liquid is discarded.
And S09, blowing the eluent to be dry through nitrogen, redissolving the eluent by adopting an acetonitrile-formic acid aqueous solution, and filtering the redissolved solution by a membrane to obtain the upper computer analysis solution.
And S010, analyzing and determining the upper computer analysis liquid by using a high performance liquid chromatography-tandem mass spectrometry to obtain the recovery rate of each plant growth regulator.
Test example 1:
the test example applied the above experimental steps, and detected the plant growth regulators in apples, watermelons and strawberries, and obtained the recovery rates of different types of melons and fruits and different types of plant growth regulators are as follows:
Figure BDA0002332303680000061

Claims (9)

1. a method for measuring the residual quantity of plant growth regulators in melons and fruits is characterized by comprising the following steps:
s01, homogenizing the sample to be detected, adding an extracting agent, and uniformly stirring to obtain sample slurry;
s02, adding a pigment precipitator and a matrix preservative into the sample slurry, uniformly mixing, and centrifuging to obtain a supernatant and residues;
s03, performing rotary evaporation on the supernatant until the supernatant is dried, and re-dissolving the supernatant in purified water to obtain a sample solution;
s04, adding a magnetic adsorbent into the sample solution, centrifugally oscillating, and desorbing to obtain the magnetic adsorbent attached with adsorbate and a residual solution;
s05, eluting the magnetic adsorbent attached with the adsorbate by using an eluant to obtain an eluent and the desorbed magnetic adsorbent;
discarding residual liquid;
s06, blowing the eluent to be dry through nitrogen, re-dissolving the eluent by adopting an acetonitrile-formic acid aqueous solution, and filtering a membrane to obtain an upper computer analysis solution;
and S07, analyzing and determining the upper computer analysis liquid by a high performance liquid chromatography-tandem mass spectrometry to obtain the recovery rate of each plant growth regulator.
2. The method of claim 1, wherein in step S01, the extraction agent is selected from the group consisting of: any one of a mixed solution of formic acid and acetonitrile, a mixed solution of sodium hydroxide and acetonitrile;
wherein, in the mixed solution of formic acid and acetonitrile, the mass fraction of formic acid is 0.5-2%; in the mixed solution of sodium hydroxide and acetonitrile, the mass fraction of sodium hydroxide was 2%.
3. The method of claim 1, wherein in step S02, the pigment-precipitating agent is calcium hydroxide.
4. The method of claim 1, wherein in step S02, the matrix preservative is an inclusion compound of photocatalyst-hydroxymethyl chitosan.
5. The method of claim 1, further comprising a step S01.1 between the step S01 and the step S02, wherein the step S01.1 comprises:
(1) adding a lytic enzyme into the sample slurry, mixing, reacting, and filtering after the reaction is finished to obtain primary filtrate and primary filter residue;
(2) weighing the filter residue, adding alcohol for redissolving, adding the decomposition enzyme again, mixing, reacting, and filtering after the reaction is finished to obtain secondary filtrate and secondary filter residue;
(3) and (3) repeating the step (2) until the quality of the filter residue is unchanged, and mixing the filter liquor obtained by the last filtration with the filter residue to obtain the sample slurry in the step S02.
6. The method for determining the residual amount of plant growth regulator in melon and fruit according to claim 4, wherein in step (1), the degrading enzymes are pectinase and cellulase.
7. The method for determining the residual amount of plant growth regulator in melon and fruit according to claim 1, wherein in step S04, the magnetic adsorbent is selected from the group consisting of a composite material of magnetic graphene and β -cyclodextrin, a composite material of chitosan and ferroferric oxide, and Fe3O4-dopamine, Fe3O4-SiO 2-chitosan graphene oxide, Fe3O4-nitrogen doped graphene, Fe3O4- β at least one of cyclodextrin-carboxymethylcellulose.
8. The method of claim 1, wherein in step S05, the eluent is selected from the group consisting of methanol, ethyl acetate, acetonitrile, and dichloromethane.
9. The method of claim 1, wherein the step S05 is performed by repeating the elution with the magnetic adsorbent having the adsorbate attached thereto three times and combining the three eluents, i.e., the eluents obtained in step S05.
CN201911341171.XA 2019-12-23 2019-12-23 Method for measuring residual quantity of plant growth regulator in melons and fruits Pending CN111089917A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101504410A (en) * 2009-03-17 2009-08-12 中国检验检疫科学研究院 Blood serum sample treatment preparation used for protein suspending chip detection
CN108802223A (en) * 2018-06-13 2018-11-13 绿城农科检测技术有限公司 A kind of method of 9 plant growth regulators residual quantities in measurement melon and fruit
CN109738265A (en) * 2019-02-20 2019-05-10 浙江省食品药品检验研究院 The preprocess method of plant growth regulator residual quantity in a kind of measurement melon and fruit

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101504410A (en) * 2009-03-17 2009-08-12 中国检验检疫科学研究院 Blood serum sample treatment preparation used for protein suspending chip detection
CN108802223A (en) * 2018-06-13 2018-11-13 绿城农科检测技术有限公司 A kind of method of 9 plant growth regulators residual quantities in measurement melon and fruit
CN109738265A (en) * 2019-02-20 2019-05-10 浙江省食品药品检验研究院 The preprocess method of plant growth regulator residual quantity in a kind of measurement melon and fruit

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
WEBSTER, BARBARA. I.: "Extraction and purification procedures in the determination of residues of DDT and related pesticides on plant material" *
张雁,蔡妙颜,李琳,郭祀远: "磷酸钙沉降和浮升吸附脱色效果的对比研究" *
闫加磊;孙妍;石亮;周宜君;陈慧英;: "羧甲基壳聚糖/Ce~(3+)掺杂TiO_2复合抗菌材料的研究" *

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