CN108287204A - The remaining analysis method of piperazine in a kind of efficient detection chicken tissues, egg and pork - Google Patents
The remaining analysis method of piperazine in a kind of efficient detection chicken tissues, egg and pork Download PDFInfo
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- CN108287204A CN108287204A CN201810072291.3A CN201810072291A CN108287204A CN 108287204 A CN108287204 A CN 108287204A CN 201810072291 A CN201810072291 A CN 201810072291A CN 108287204 A CN108287204 A CN 108287204A
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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
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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
- G01N2030/022—Column chromatography characterised by the kind of separation mechanism
- G01N2030/027—Liquid chromatography
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Abstract
The present invention relates to field of veterinary drug residue detection, and in particular to the remaining analysis method of piperazine in a kind of efficient detection chicken tissues, egg and pork.This method is to extract chicken tissues, egg or pork sample, after purification by accelerated solvent extraction and solid phase extraction method, is derived through dansyl Cl, then detected with ultra performance liquid chromatography fluorescence detection.This method for other detection methods, have analysis efficiency higher, mobile phase consumption less, the rate of recovery, accuracy and high sensitivity, the advantages of favorable reproducibility.
Description
Technical field
The present invention relates to field of veterinary drug residue detection, and in particular to piperazine in a kind of efficient detection chicken tissues, egg and pork
The remaining analysis method of piperazine.
Background technology
Currently, piperazine detection method has gas chromatography, high performance liquid chromatography, gas chromatography tandem mass spectrometry both at home and abroad
Method, high performance liquid chromatography-tandem mass, but column front derivation-ultra performance liquid chromatography fluorescence detection (UPLC-FLD) detection is dynamic
Material resource tissue has not been reported with the remaining method of piperazine in food.Therefore, the present invention establish for the first time chicken tissues, egg and
Piperazine remains column front derivation-ultra performance liquid chromatography fluorescence detection in pork.This method elution program is simple, solvent consumption
Few, analysis efficiency higher, sensitivity and precision are more preferable, are more suitable for applying and popularization in batch samples are analyzed.
Invention content
In order to which efficient, accurate detection piperazine is in chicken tissues (muscle, kidney, liver), egg (shell egg, egg white, egg
It is yellow) and pork in residual, the present invention provides a kind of column front derivation-ultra performance liquid chromatography fluoroscopic examination (UPLC-FLD) sides
Method.This method can efficiently, accurately detect the residual of piperazine in chicken tissues, egg and pork, and meet the Ministry of Agriculture, European Union
(EU) requirement of detection of veterinary drugs in food method.
Chicken tissues (muscle, kidney, liver), egg (shell egg, egg white, yolk) and pork sample are passed through into accelerated solvent extraction
It is derivative through dansyl Cl (DNS-Cl) after taking the extraction of (ASE) and Solid Phase Extraction (SPE) technology, purification, then with ultra high efficiency liquid phase color
Fluorescence detection (UPLC-FLD) is composed to detect.Chromatographic condition：It is with ACQUITY UPLC HSS T3 (2.1 × 100mm, 1.8 μm)
Chromatographic column；Water-acetonitrile (15: 85, V: V) system is mobile phase；Detector is fluorescence detector, excitation wavelength 330nm, transmitted wave
Long 531nm；Flow velocity is 0.2mL/min；Sampling volume is 10 μ L；Column temperature is 25 DEG C；Quantified by external standard method.
In the present invention use ACQUITY UPLC HSS T3 (2.1 × 100mm, 1.8 μm) chromatographic column, with water-acetonitrile (15:
85, V: V) system is mobile phase, and flow velocity 0.2mL/min, chromatographic peak peak type is sharp (i.e. high sensitivity), analyte retention time
It is moderate, no other impurity peaks interference.
The present invention is in analysis efficiency, solvent consumption, the rate of recovery, precision, sensitivity and reproducibility angle, with other detections
Method is compared, find this method analysis efficiency higher, mobile phase consumption less, the rate of recovery, accuracy and high sensitivity, reappear
Property is good.
Description of the drawings
Fig. 1 dansyl Cl standard items ultra performance liquid chromatography figures.
Fig. 2 piperazines standard items (50 μ g/kg) ultra performance liquid chromatography figure.
Fig. 3 blank chicken muscle derivative products ultra performance liquid chromatography figures.
50 μ g/kg piperazine standard items derivative products ultra performance liquid chromatography figures are added in Fig. 4 chicken muscles.
Fig. 5 blank chicken kidney derivative products ultra performance liquid chromatography figures.
50 μ g/kg piperazine standard items derivative products ultra performance liquid chromatography figures are added in Fig. 6 chicken kidneys.
Fig. 7 blank chicken liver derivative products ultra performance liquid chromatography figures.
50 μ g/kg piperazine standard items derivative products ultra performance liquid chromatography figures are added in Fig. 8 chicken livers.
Fig. 9 blank chicken shell egg derivative products ultra performance liquid chromatography figures.
50 μ g/kg piperazine standard items derivative products ultra performance liquid chromatography figures are added in Figure 10 chicken shell eggs.
Figure 11 blank egg white derivative products ultra performance liquid chromatography figures.
50 μ g/kg piperazine standard items derivative products ultra performance liquid chromatography figures are added in Figure 12 egg whites.
Figure 13 blank egg yolk derivative products ultra performance liquid chromatography figures.
50 μ g/kg piperazine standard items derivative products ultra performance liquid chromatography figures are added in Figure 14 egg yolks.
Figure 15 blank pork derivative products ultra performance liquid chromatography figures.
50 μ g/kg piperazine standard items derivative products ultra performance liquid chromatography figures are added in Figure 16 porks.
Piperazine standard curve (n=7) is added in Figure 17 blank chicken muscle matrix.
Piperazine standard curve (n=7) is added in Figure 18 blank chicken kidney matrix.
Piperazine standard curve (n=7) is added in Figure 19 blank chicken liver matrix.
Piperazine standard curve (n=7) is added in Figure 20 blank chicken shell egg matrix.
Piperazine standard curve (n=7) is added in Figure 21 blank egg white matrix.
Piperazine standard curve (n=7) is added in Figure 22 blank egg yolk matrix.
Piperazine standard curve (n=7) is added in Figure 23 blank pork matrix.
Specific implementation mode
Term as used in the present invention generally has those of ordinary skill in the art usual unless otherwise specified
The meaning of understanding.
The present invention is described in further detail with reference to specific embodiment, and with reference to data.These embodiments only be
It illustrates the present invention, rather than limits the scope of the invention in any way.
Below in an example, the various processes and method not being described in detail are conventional methods as known in the art.
The source of agents useful for same, trade name and it is necessary to list its constituent person, are indicated, thereafter phase used on the first appearance
Unless otherwise specified with reagent, identical with the content indicated for the first time.
1. testing raising and the sample collection of poultry
This experiment randomly selects the yellow chicken (Jiangsu Jinghai Poultry Group Co., Ltd.) 12 in 112 age in days capital sea, and (male and female is each
Half), the yellow chicken laying hen (Jiangsu Jinghai Poultry Group Co., Ltd.) in capital sea 20 of 196 ages in days and 180 age in days ternarys (Du ×
Long × about) hybridized pig (Changzhou health and happiness Farming Ltd.) 12 (male and female is fifty-fifty), single cage or separated raisings, feeding, which is free of, appoints
The complete feed (Jiangsu Jinghai Poultry Group Co., Ltd.'s feed factory and Yangzhou are raised big feed factory and provided) of what drug, freely drinks
Water.
It butchers, takes respectively for trying the muscle of the muscle of chicken, liver, kidney and examination pig as blank sample after raising 2 weeks,
It is placed in -35 DEG C and preserves.In addition, the yellow chicken in capital sea laid eggs fowl raising after 2 weeks, and it is continuous to collect 10d eggs, it is placed in 4 DEG C of refrigerators temporarily
Shi Baocun is dispensed after taking shell egg, egg white, yolk homogenate after sample collection respectively, respectively as blank sample, is placed in -35 DEG C
It preserves.
2. present invention extraction and purifying step
1) it accurately weighs the good blank sample of (2.0 ± 0.02) g homogeneous to be put in mortar, and 4.0g diatomite is added and grinds
Mill, in order to reach best extraction efficiency, sample is ground into little particle as far as possible, is fitted into the abstraction pool of 22mL, with ASE into
Row extraction；
2) at 1500psi, 80 DEG C of extraction conditions, each abstraction pool uses n-hexane static extracting 1 time first, discards extraction
Liquid；Again with 2% formic acid acetonitrile static extracting 2 times, it is for use to collect extract liquor.15~20min of each extraction process；
3) extract liquor for collecting above-mentioned extraction is through the small column purifications of Strata-X-C, chicken tissues, pork 60mg/3mL
Strata-X-C column purifications (decontamination procedure is shown in Table 1), with 100mg/3mL Strata-X-C column purifications, (decontamination procedure is shown in Table egg
2).Above-mentioned eluent 15mL centrifuge tubes are collected, eluent is placed in nitrogen evaporator and dries up, for use；
4) sample after blowing nitrogen is redissolved with 1.0mL acetonitriles, and ultrasonic 10min shakes up, and pipettes 100 μ L0.12% triethylamines
With 600 μ L 1.0mg/mL solution of dansyl chloride, it is settled to 2.0mL with acetonitrile, is placed under 50 DEG C of environment and is protected from light 20min, wait for
After reaction, vortex 1min, crosses 0.22 μm of organic phase pin type filter, and filtrate is detected for UPLC-FLD.
1 chicken tissues of table and pork sample Solid Phase Extraction program
2 egg sample Solid Phase Extraction program of table
3 experimental conditions
Chromatographic column：ACQUITY UPLC HSS T3,2.1×100mm,1.8μm；Mobile phase A：Ultra-pure water；Mobile phase B：Second
Nitrile, its ratio be 15: 85 (V: V)；Detector：Fluorescence detector, excitation wavelength 330nm, launch wavelength 531nm；Flow velocity：
0.2mL/min；Sampling volume：10μL；Column temperature：25℃.
4 quantitative approach
The drafting of 4.1 standard curves
It is complete that the homogeneous good chicken muscles of 10 parts of (2.0 ± 0.02) g, chicken kidney, chicken liver, pork and chicken are accurately weighed respectively
Egg, egg white, yolk blank sample carry out pre-treatment to above-mentioned blank sample by the method in 2, prepare bare substrate extracting solution,
It is spare.
Suitable blank chicken muscle, chicken kidney, chicken liver and pork matrix extracting solution are pipetted respectively, and standard working solution is dilute
A series of concentration are interpreted into, are derived by the method in 2 so that is final corresponding in blank chicken muscle, chicken kidney, chicken liver and pig
The addition of piperazine a concentration of LOQ, 5.0,10.0,50.0,100.0,150.0,200.0 μ g/kg in meat.
Pipette respectively appropriate blank chicken shell egg, egg white and yolk matrix extracting solution standard working solution is diluted to it is a series of dense
Degree, is derived by the method in 2 so that the addition concentration of the final corresponding piperazine in blank chicken shell egg, yolk, egg white sample
For the μ g/kg of LOQ, 10.0,20.0,50.0,100.0,150.0,200.0.
Each concentration samples of above-mentioned processing are analyzed under the HPLC-FLD methods optimized.It is worked with piperazine standard
Liquid adds a concentration of independent variable (x) in different bare substrates, using piperazine derivatives peak areas as dependent variable (y), is made with this
Make standard curve.
The piperazine range of linearity, regression equation and the coefficient of determination in 3 chicken tissues of table, egg and pork
By table 3 and attached drawing 17~23 as it can be seen that piperazine adds in blank chicken tissues (muscle, kidney, liver) and pork matrix
Add concentration within the scope of the μ of LOQ~200.0 g/kg, piperazine derivatives peak areas is in good linear relationship with piperazine concentration；
Piperazine adds concentration within the scope of the μ of LOQ~400.0 g/kg in blank egg (shell egg, egg white, yolk) matrix, piperazine derivatives production
Object peak area is also in good linear relationship with concentration；Wherein, the range of linearity, equation of linear regression and coefficient of determination R2It is shown in Table 3.
, need to be by the concentration dilution of analysis within the scope of this if the concentration of analysis is more than the range of linearity of sample, the result detected multiplies
The concentration of raw sample is obtained with extension rate.
4.2 the measurement of the rate of recovery and precision
The homogeneous good blank samples of (2.0 ± 0.02) g are accurately weighed, bare substrate extracting solution is produced by the method in 2.Point
Appropriate piperazine standard working solution bare substrate extracting solution dilution series concentration is not taken, is derived by the method in 2, makes it most
A concentration of LOQ, 0.5MRL, 1.0MRL, 2.0MRL are added in each blank sample eventually, it is each add concentration set 6 it is parallel, then supply
UPLC-FLD is detected；Wherein, shell egg, egg white, yolk sample are both needed to extracting solution before derivative and dilute 20 times of (guarantors in addition to LOQ is horizontal
The detectable concentration of sample is demonstrate,proved in the standard curve range of linearity)；Finally testing result is brought into and acquires concentration in standard curve, with
The concentration of the analyte of actual interpolation is compared and acquires TIANZHU XINGNAO Capsul.
Dansyl Cl standard items ultra performance liquid chromatography figure is shown in Fig. 1；Piperazine standard items (50 μ g/kg) ultra performance liquid chromatography
Figure is shown in Fig. 2；Blank chicken muscle derivative products ultra performance liquid chromatography figure is shown in Fig. 3；50 μ g/kg piperazine standard items are added in chicken muscle
Derivative products ultra performance liquid chromatography figure is shown in Fig. 4；Blank chicken kidney derivative products ultra performance liquid chromatography figure is shown in Fig. 5；Chicken kidney
50 μ g/kg piperazine standard items derivative products ultra performance liquid chromatography figures of middle addition are shown in Fig. 6；Blank chicken liver derivative products ultra high efficiency
Liquid chromatogram is shown in Fig. 7；50 μ g/kg piperazine standard items derivative products ultra performance liquid chromatography figures are added in chicken liver sees Fig. 8；It is empty
Cold boiled chicken shell egg derivative products ultra performance liquid chromatography figure is shown in Fig. 9；It is super that 50 μ g/kg piperazine standard items derivative products are added in chicken shell egg
High-efficient liquid phase chromatogram is shown in Figure 10；Blank egg white derivative products ultra performance liquid chromatography figure is shown in Figure 11；50 μ are added in egg white
G/kg piperazine standard items derivative products ultra performance liquid chromatography figures are shown in Figure 12；Blank egg yolk derivative products ultra performance liquid chromatography
Figure is shown in Figure 13；50 μ g/kg piperazine standard items derivative products ultra performance liquid chromatography figures are added in egg yolk sees Figure 14；Blank pork
Derivative products ultra performance liquid chromatography figure is shown in Figure 15；50 μ g/kg piperazine standard items derivative products ultra high efficiency liquid phases are added in pork
Chromatogram is shown in Figure 16.
Withinday precision：Above-mentioned 4 are added in same instrument of different time points on the same day and same standard curve
Concentration is measured, it is each add concentration set 6 it is parallel, find out in a few days RSD.
Day to day precision：In 7 days not on the same day, same instrument pair of various criterion curve (all drawing standard curve daily)
Above-mentioned 4 additions concentration is measured, it is each add concentration set 6 it is parallel, find out RSD in the daytime.
With this condition, in the method for the present invention extraction chicken tissues, egg and pork piperazine TIANZHU XINGNAO Capsul and precision
It is shown in Table 4.
Piperazine TIANZHU XINGNAO Capsul and precision (n=6) in 4 blank chicken tissues of table, egg and pork
Note：α maximum residue limit
The determination of 4.3 detection limits and quantitative limit
The homogeneous good blank samples of (2.0 ± 0.02) g are accurately weighed, bare substrate extracting solution is produced by the method in 2.With
Bare substrate extracting solution dilutes the piperazine standard working solution of low concentration step by step, derives by the method in 2, then detect, repeats sample introduction 6
It is secondary, calculate signal-to-noise ratio (S/N).As S/N >=3, corresponding piperazine concentration is to detect limit (LOD), corresponding as S/N >=10
Piperazine concentration, and meet accuracy and the requirement of precision under the concentration and (generally require the rate of recovery to be more than 70%, relative standard is inclined
Poor RSD≤20%) it is quantitative limit (LOQ).
According to the addition recovery test of above-mentioned 6 parallel blank samples, obtain under existence conditions, piperazine chicken muscle,
LOD in chicken kidney, chicken liver, chicken shell egg, egg white, egg yolk is respectively 0.50,1.20,0.80,1.25,1.40,1.05,
0.62 μ g/kg, LOQ is respectively 1.80,3.50,2.40,3.50,4.20,3.50,1.85 μ g/kg.
4.4 repetitive test
100 6 parts of μ L piperazines standard working solutions (1.0 μ g/mL) are taken, are respectively placed in 10mL centrifuge tubes, are added 0.12% 3
100 μ L, 1.0mg/mL dansyl Cl of ethamine, 600 μ L, are settled to 2.0mL with acetonitrile, are placed under 50 DEG C of environment and are protected from light respectively
20min restores to room temperature, vortex 1min after reaction, is detected for HPLC-FLD, obtain retention time and peak area, calculate
The RSD values of retention time and peak area.
The reproducibility (n=6) of 5 retention time of table and peak area
As shown in Table 5, in 6 measurement results, the RSD of piperazine derivatives product retention time is 0.10%, peak area
RSD is 0.18%.
Claims (2)
1. the remaining analysis method of piperazine in a kind of efficient detection chicken tissues, egg and pork, which is characterized in that by chicken tissues,
After egg or pork sample are by accelerated solvent extraction and solid phase extraction method extraction, purification, derive through dansyl Cl, then with surpassing
High Performance Liquid Chromatography with Fluorescence Detection detects.
2. according to the method required described in 1, which is characterized in that the chromatographic condition of ultra performance liquid chromatography fluoroscopic examination is：With
ACQUITY UPLC HSS T3,2.1 × 100mm, 1.8 μm are chromatographic column；Water-acetonitrile system of volume ratio 15: 85 is flowing
Phase；Detector is fluorescence detector, excitation wavelength 330nm, launch wavelength 531nm；Flow velocity is 0.2mL/min；Sampling volume is
10μL；Column temperature is 25 DEG C；Quantified by external standard method.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110596293A (en) * | 2019-10-18 | 2019-12-20 | 山东威高药业股份有限公司 | High performance liquid detection method for homopiperazine |
| CN111693639A (en) * | 2020-06-12 | 2020-09-22 | 扬州大学 | Confirmation analysis method for detecting penicillin G residue in poultry tissue, poultry egg or pork |
| CN115112800A (en) * | 2022-07-01 | 2022-09-27 | 河南润弘制药股份有限公司 | Improved detection method for high piperazine in fasudil hydrochloride injection |
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| CN104807906A (en) * | 2015-05-07 | 2015-07-29 | 扬州大学 | Method for detecting piperazine residue in poultry with high efficiency |
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2018
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104807906A (en) * | 2015-05-07 | 2015-07-29 | 扬州大学 | Method for detecting piperazine residue in poultry with high efficiency |
Non-Patent Citations (2)
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| 周东庆: "鸡肉和猪组织中哌嗪残留高效液相色谱检测方法的建立", 《中国优秀硕士学位论文全文数据库》 * |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110596293A (en) * | 2019-10-18 | 2019-12-20 | 山东威高药业股份有限公司 | High performance liquid detection method for homopiperazine |
| CN111693639A (en) * | 2020-06-12 | 2020-09-22 | 扬州大学 | Confirmation analysis method for detecting penicillin G residue in poultry tissue, poultry egg or pork |
| CN115112800A (en) * | 2022-07-01 | 2022-09-27 | 河南润弘制药股份有限公司 | Improved detection method for high piperazine in fasudil hydrochloride injection |
| CN115112800B (en) * | 2022-07-01 | 2023-07-07 | 河南润弘制药股份有限公司 | Improved detection method for homopiperazine in fasudil hydrochloride injection |
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