CN105424855B - The method of anthraquinone residual quantity in gaschromatographic mass spectrometry/mass spectroscopy tealeaves - Google Patents

The method of anthraquinone residual quantity in gaschromatographic mass spectrometry/mass spectroscopy tealeaves Download PDF

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CN105424855B
CN105424855B CN201510821776.4A CN201510821776A CN105424855B CN 105424855 B CN105424855 B CN 105424855B CN 201510821776 A CN201510821776 A CN 201510821776A CN 105424855 B CN105424855 B CN 105424855B
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sample
anthraquinone
mass
solution
tealeaves
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CN105424855A (en
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谢文
陈丽
黄超群
申屠炎
楼成杰
侯建波
谢韵第
陈安
邓晓军
于卓然
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TECHNICAL CENTER FOR ANIMAL PLANT AND FOOD INSPECTION AND QUARANTINE SHANGHAI ENTRY-EXIT INSPECTION AND QUARANTINE BUREAU
ZHEJIANG ENTRY-EXIT INSPECTION AND QUARANTINE BUREAU
Inspection & Quarantine Technology Center Of Zhejiang Entry-Exit Inspection & Quarantine Bureau
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TECHNICAL CENTER FOR ANIMAL PLANT AND FOOD INSPECTION AND QUARANTINE SHANGHAI ENTRY-EXIT INSPECTION AND QUARANTINE BUREAU
ZHEJIANG ENTRY-EXIT INSPECTION AND QUARANTINE BUREAU
Inspection & Quarantine Technology Center Of Zhejiang Entry-Exit Inspection & Quarantine Bureau
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    • 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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Abstract

The present invention relates to it is a kind of determine tealeaves in pollutant residual quantity method, more particularly in a kind of gaschromatographic mass spectrometry/mass spectroscopy tealeaves anthraquinone residual quantity method.The method of anthraquinone residual quantity in gaschromatographic mass spectrometry/mass spectroscopy tealeaves, the method comprises the following steps：1) sample treatment, 2) determine：Standard working solution and the sample solution sample introduction under the gaschromatographic mass spectrometry/Mass Spectrometry Conditions of setting., using anthraquinone residual quantity in gaschromatographic mass spectrometry/mass spectrometric determination tealeaves, method is easy, quick, accurate, reliable, and test limit, the rate of recovery and precision meet the requirements for assay method of the invention.

Description

The method of anthraquinone residual quantity in gas chromatography-mass spectrum/mass spectroscopy tealeaves
Technical field
The present invention relates to a kind of method for determining pollutant residual quantity in tealeaves, a kind of more particularly to gas chromatography-mass spectrum/ The method of anthraquinone residual quantity in mass spectroscopy tealeaves.
Background technology
Anthraquinone (Anthraquinone AQ, CAS No 84-65-1, C14H8O2) it is a kind of widely used chemical products. Used as the parent of dyes of anthraquinone, 9,10- anthraquinones are synthesis disperse dyes, acid dyes, reducing dye and reactive dye Parent；Used as the additive of paper-making process, 9,10- anthraquinones can accelerate the speed of delignification, improve paper pulp yield；In agricultural side Face, anthraquinone was once used as bird repellent and was applied to rice field and oil crops growing area, and current 9,10- anthraquinones are in European Union or other countries There is not registration again for agricultural production.In China, anthraquinone is also registered not on China tea tree and on other crops and used.Although AQ is considered as low toxicity, but EFSA (European Food Safety Authority) points out that AQ can in reevaluating report Can there is carcinogenic risk.Its molecular structural formula is as follows：
European Union specifies MRL (MRL) standard of anthraquinone in tealeaves for 0.02mg/kg, and China does not specify anthraquinone MRL in tealeaves.Document has no report to anthraquinone in tealeaves.
The content of the invention
In order to solve above-mentioned technical problem, the present invention provides anthraquinone in a kind of gas chromatography-mass spectrum/mass spectroscopy tealeaves The method of residual quantity, the method is easy, stabilization, and measure lower bound is 0.02mg/kg, and fully meets relevant regulation pair both at home and abroad The requirement of anthraquinone residual in tealeaves, can provide technical support for the supervision of tealeaves anthraquinone residual.
In order to realize above-mentioned purpose, present invention employs following technical scheme：
The method of anthraquinone residual quantity in gas chromatography-mass spectrum/mass spectroscopy tealeaves, the method comprises the following steps：
1) sample treatment
Tealeaves sample 2g is weighed, in 50mL centrifuge tubes, 0.5mL0.2 μ g/mL anthraquinone-D8 solution is added, 20mL is added N-hexane-acetone soln, n-hexane-acetone volume ratio is 1：1, with 10 000r/min homogeneous 0.5min, 2g sodium chloride is added, Vortex 1min, 3min is centrifuged with 4 000r/min, upper strata extraction solution is transferred in concentrate bottle, with 20mL n-hexanes-acetone Solution cleans homogenizer cutter head, and this extract solution is poured into residue, vortex 1min, and 3min is centrifuged with 4 000r/min, merges Extract solution, water-bath is concentrated under reduced pressure near dry below 45 DEG C, and with 3mL n-hexane dissolution residues, and it is net to be transferred to florisil silica Change post, generally eluted with 50mL n-hexanes-ether mixed solvent again, n-hexane-ether volume ratio 8:2, flow velocity is 3mL/min, Whole eluents are collected, water-bath is concentrated under reduced pressure near dry, addition 2.0mL acetone solution residues below 45 DEG C, crosses 0.22 μm of filter Film, determines for gas chromatography-mass spectrum/mass spectrograph；
2) determine
Standard working solution and the sample solution sample introduction under the gas chromatography-mass spectrum/Mass Spectrometry Conditions of following setting：
1. mass spectrometry parameters of anthraquinone
Wherein * represents quota ion；
2. gas chromatography-mass spectrum/mass spectrographic instrument condition parameter
Gas-chromatography：
Chromatographic column：HP-5MS, 30m length × 0.25mm internal diameter × 0.25 μm thickness
Program column temperature：100 DEG C of holding 1min, 300 DEG C are warming up to the speed of 20 DEG C/min, keep 10min
Flow velocity：1.0mL/min
Sample size：1μL
Injection port temperature：300℃
Input mode Splitless injecting samples；
Mass Spectrometry Conditions：
Ionization mode：EI
Ionizing energy：70eV
Ion source temperature：280℃
Level Four bar temperature：Do not heat
Interface temperature：300℃
Mensuration mode：Selective reaction monitoring pattern (SRM)；
With respect to the maximum allowable offset of abundance of ions during qualitative confirmation：
Relative ion abundance ＞ 50%, it is allowed to relative deviation ± 20%
Relative ion abundance ＞ 20%~50%, it is allowed to relative deviation ± 25%
Relative ion abundance ＞ 10%~20%, it is allowed to relative deviation ± 30%
Relative ion abundance≤10%, it is allowed to relative deviation ± 50%；
3) blank test
In addition to sample is not added with, by above-mentioned steps 1), step 2) operating procedure carries out；
4) result is calculated and stated
The content of anthraquinone in sample is calculated with chromatographic data processor or as follows, and result of calculation must deduct blank Value：
In formula：
Xi-- the residual quantity of anthraquinone in sample, unit for milligrams per kilogram；
ci-- the solution concentration of anthraquinone is obtained from standard curve, unit is micrograms per millilitre；
V -- the final constant volume of sample liquid, unit is milliliter；
M -- the sample mass representated by final sample liquid, unit for gram；
5) judge
With mass concentration X as abscissa, peak area ratio Y is ordinate, draws 5 standard working curves, uses standard work Make curve to quantify sample, the response of medicine should be in the range of linearity of instrument detection in sample solution；In above-mentioned color Under spectral condition, with the presence or absence of corresponding measured object, it is necessary to meet following condition in judgement sample：The quality occurred in sample solution Chromatographic peak retention time is consistent with hybrid standard working solution, it is allowed to which deviation is less than ± 0.5%, and the medicine corresponding to the chromatographic peak exists The relative abundance of the relative abundance of the mass spectrometry ion mixed-matrix standard working solution suitable with concentration is consistent, and relative abundance is inclined Difference is no more than above-mentioned regulation, then can determine that and contain the medicine.
Preferably, described florisil silica decontaminating column selects 200mm × 15mm internal diameter glass columns, bottom pad about 5mm Absorbent cotton high and about 10mm anhydrous sodium sulfate high, 10g florisil silicas, 75 μm~150 μm, 650 DEG C of the granularity of florisil silica Calcination 4h, is cooled to room temperature, the water deactivation for plus 2% using 130 DEG C of activation 4h in drier；Top adds about 10mm anhydrous sulphur high Sour sodium, uses n-hexane wet method dress post, discards leacheate.
Assay method of the invention is using anthraquinone residual quantity in gas chromatography-mass spectrum/mass spectrometric determination tealeaves, method letter Just, quickly, accurately, reliably, test limit, the rate of recovery and precision meet the requirements.
Assay method of the invention has following technique effect：
1) method that gas chromatography-mass spectrum/mass spectrography determines anthraquinone residual quantity in tealeaves simultaneously is developed first, is filled up Technological gap；
2) there is provided the optimal conditions of anthraquinone residual quantity in gas chromatography-mass spectrum/mass spectrometric determination cotton.
Brief description of the drawings
Fig. 1 is the selective ion flow graph of anthraquinone and anthraquinone-D8 mixed standard solutions.
Fig. 2 is the selective ion flow graph of blank Tea Samples and anthraquinone-D8 mixed solutions.
Fig. 3 is the selective ion that blank Tea Samples add anthraquinone and anthraquinone-D8 mixed standard solutions (0.02mg/kg) Flow graph.
Specific embodiment
1st, reagent and material
1.1 n-hexanes：Chromatographically pure.
1.2 acetone：Chromatographically pure.
1.3 ether：Chromatographically pure.
1.4 sodium chloride：Pure, 650 DEG C of calcination 4h are analyzed, room temperature is cooled in drier, stored in standby in air-tight bottle.
1.5 anhydrous sodium sulfates：Pure, 650 DEG C of calcination 4h are analyzed, room temperature is cooled in drier, stored in standby in air-tight bottle With.
1.6 anthraquinones, anthraquinone-D8 standard substances (Anthraquinone, CAS:84-65-1, C14H8O2； Anthraquinone-D8,,CAS:10439-39-1)：Purity is more than or equal to 99%.
1.7 Standard Stock solutions：Accurately weigh through appropriate standard substance (1.6), the mark of 0.4mg/mL is configured to acetone Quasi- storing solution, stores, the term of validity 6 months in lucifuge in 0 DEG C~4 DEG C refrigerators.
1.8 anthraquinone-D8 Standard Stock solutions：Accurately weigh through appropriate standard items (1.6), 0.4mg/mL is configured to acetone Standard reserving solution, stored in lucifuge in 0 DEG C~4 DEG C refrigerators, the term of validity 6 months.
The preparation of interstitial fluid in 1.9 standards：The accurate standard reserving solution that pipettes is appropriate (1.7), is configured to 10 μ g/mL's with acetone Standard liquid；The accurate standard reserving solution that pipettes is appropriate (1.8), and the mixed standard solution of 0.2 μ g/mL is configured in 0 DEG C with acetone Lucifuge storage, the term of validity 3 months in~4 DEG C of refrigerators.
The preparation of 1.10 standard working solutions：Standard intermediate solution (1.9) is diluted to acetone as needed appropriate dense The standard working solution of degree.
1.11 florisil silicas：75 μm~150 μm of granularity (100 mesh~200 mesh), 650 DEG C of calcination 4h use 130 DEG C of work Change 4h and room temperature is cooled in drier, the water deactivation for plus 2% is standby.
1.12 decontaminating columns：200mm × 15mm (internal diameter) glass column, bottom pad about 5mm absorbent cotton high and about 10mm are high anhydrous Sodium sulphate, 10g florisil silicas (1.11), top adds about 10mm anhydrous sodium sulfates high, uses n-hexane wet method dress post, discards drip washing Liquid (need to first do elution curve before).
1.13 miillpore filters：0.22 μm, organic facies pattern.
2nd, instrument and equipment
2.1 gas chromatography-mass spectrums/mass spectrograph：Equipped with (EI) ion gun；
2.2 assay balances：The 1g of sensibility reciprocal 0.000 and 0.01g；
2.3 turbine mixers；
2.4 homogenizers；
2.5 oscillators；
2.6 centrifuges：The 000r/min of maximum (top) speed 4；
2.7 Rotary Evaporators；
2.8 pulverizers.
3rd, determination step
3.1 sample pre-treatments
Tealeaves sample 2g (being accurate to 0.01g) is weighed in 50mL centrifuge tubes, 0.5mL anthraquinones-D8 (0.2 μ g/mL) are added, 20mL n-hexanes-acetone (1+1, volume ratio) is added, with 10 000r/min homogeneous 0.5min, 2g sodium chloride is added, is vortexed 1min, with 4 000r/min be centrifuged 3min, by upper strata extraction solution be transferred in concentrate bottle, with 20mL n-hexanes-acetone (1+1, Volume ratio) cleaning homogenizer cutter head, and this extract solution is poured into residue, vortex 1min, 3min is centrifuged with 4 000r/min, close And extract solution, water-bath is concentrated under reduced pressure near dry below 45 DEG C, with 3mL n-hexane dissolution residues, and is transferred to florisil silica Decontaminating column (1.12), generally uses 50mL n-hexanes-ether (8+2, volume ratio) mixed solvent again, and flow velocity is 3mL/min, collects complete Portion's eluent, water-bath is concentrated under reduced pressure near dry, addition 2.0mL acetone solution residues below 45 DEG C, crosses 0.22 μm of filter membrane, supply Phase chromatography-mass spectroscopy/mass spectrograph is determined.
3.2 determine
By test condition depends on used instrument, therefore the universal parameter of chromatography can not possibly be provided.Using Following operating conditions have been demonstrated that to test be suitable.Design parameter is shown in Table 2, table 3.
The gas chromatograph parameters of table 2
Chromatographic column HP-5MS, 30m (length) × 0.25mm (internal diameter) × 0.25 μm (thickness)
Program column temperature 100 DEG C of holding 1min, 300 DEG C are warming up to the speed of 20 DEG C/min, keep 10min
Flow velocity 1.0mL/min
Sample size 1μL
Injection port temperature 300℃
Input mode Splitless injecting samples
The Mass Spectrometry Conditions parameter of table 3
Ionization mode EI
Ionizing energy 70eV
Ion source temperature 280℃
Level Four bar temperature Do not heat
Interface temperature 300℃
Mensuration mode Selective reaction monitoring pattern (SRM)
4 blank tests
In addition to sample is not added with, carried out by aforesaid operations step.
5 results are calculated and stated
The content of anthraquinone in sample is calculated with chromatographic data processor or by formula (1), result of calculation must deduct blank value：
In formula：
Xi-- the residual quantity of anthraquinone in sample, unit is milligrams per kilogram (mg/kg)；
ci-- the solution concentration of the anthraquinone obtained from standard curve, unit is micrograms per millilitre (μ g/mL)；
V -- the final constant volume of sample liquid, unit is milliliter (mL)；
M -- the sample mass representated by final sample liquid, unit is gram (g)；
6 determine lower bound
The measure lower bound of this method is 0.02mg/kg.
7 rate of recovery
The experiment of this method rate of recovery sets three addition concentration, and the experiment condition as determined by this method adds to each Plus concentration carries out 6 experiments, the rate of recovery and precision the results are shown in Table 4.
The addition concentration and rate of recovery scope of the sample of table 4

Claims (2)

1. in gas chromatography-mass spectrum/mass spectroscopy tealeaves anthraquinone residual quantity method, it is characterised in that the method include it is following Step：
1) sample treatment
Weigh tealeaves sample 2g, in 50mL centrifuge tubes, add 0.5mL0.2 μ g/mL anthraquinone-D8 solution, add 20mL just oneself Alkane-acetone soln, n-hexane-acetone volume ratio is 1：1, with 10 000r/min homogeneous 0.5min, 2g sodium chloride is added, it is vortexed 1min, 3min is centrifuged with 4 000r/min, upper strata extraction solution is transferred in concentrate bottle, with 20mL n-hexanes-acetone soln Cleaning homogenizer cutter head, and this extract solution is poured into residue, vortex 1min, 3min is centrifuged with 4 000r/min, merge and extract Liquid, water-bath is concentrated under reduced pressure near dry below 45 DEG C, with 3mL n-hexane dissolution residues, and is transferred to florisil silica decontaminating column, Eluted with 50mL n-hexanes-ether mixed solvent again, n-hexane-ether volume ratio 8:2, flow velocity is 3mL/min, collects and all washes De- liquid, water-bath is concentrated under reduced pressure near dry, addition 2.0mL acetone solution residues below 45 DEG C, crosses 0.22 μm of filter membrane, supplies phase color Spectrum-mass spectrum/mass spectrograph is determined；
2) determine
Standard working solution and the sample solution sample introduction under the gas chromatography-mass spectrum/Mass Spectrometry Conditions of following setting：
1. mass spectrometry parameters of anthraquinone
Wherein * represents quota ion；
2. gas chromatography-mass spectrum/mass spectrographic instrument condition parameter
Gas-chromatography：
Chromatographic column：HP-5MS, 30m length × 0.25mm internal diameter × 0.25 μm thickness
Program column temperature：100 DEG C of holding 1min, 300 DEG C are warming up to the speed of 20 DEG C/min, keep 10min
Flow velocity：1.0mL/min
Sample size：1μL
Injection port temperature：300℃
Input mode Splitless injecting samples；
Mass Spectrometry Conditions：
Ionization mode：EI
Ionizing energy：70eV
Ion source temperature：280℃
Level Four bar temperature：Do not heat
Interface temperature：300℃
Mensuration mode：Selective reaction monitoring pattern (SRM)；
With respect to the maximum allowable offset of abundance of ions during qualitative confirmation：
Relative ion abundance>50%, it is allowed to relative deviation ± 20%
Relative ion abundance>20%~50%, it is allowed to relative deviation ± 25%
Relative ion abundance>10%~20%, it is allowed to relative deviation ± 30%
Relative ion abundance≤10%, it is allowed to relative deviation ± 50%；
3) blank test
In addition to sample is not added with, by above-mentioned steps 1), step 2) operating procedure carries out；
4) result is calculated and stated
The content of anthraquinone in sample is calculated with chromatographic data processor or as follows, and result of calculation must deduct blank value：
X i = c i × V × 1000 m × 1000
In formula：
Xi-- the residual quantity of anthraquinone in sample, unit for milligrams per kilogram；
ci-- the solution concentration of anthraquinone is obtained from standard curve, unit is micrograms per millilitre；
V -- the final constant volume of sample liquid, unit is milliliter；
M -- the sample mass representated by final sample liquid, unit for gram；
5) judge
With mass concentration X as abscissa, peak area ratio Y is ordinate, draws 5 standard working curves, works bent with standard Line is quantified to sample, and the response of medicine should be in the range of linearity of instrument detection in sample solution；In above-mentioned chromatostrip Under part, with the presence or absence of corresponding measured object, it is necessary to meet following condition in judgement sample：The mass chromatography occurred in sample solution Peak retention time is consistent with hybrid standard working solution, it is allowed to which deviation is less than ± 0.5%, and the medicine corresponding to the chromatographic peak is in mass spectrum The relative abundance of the relative abundance of the qualitative ion mixed-matrix standard working solution suitable with concentration is consistent, and relative abundance deviation is not More than above-mentioned regulation, then can determine that and contain the medicine.
2. in gas chromatography-mass spectrum according to claim 1/mass spectroscopy tealeaves anthraquinone residual quantity method, its feature It is：Florisil silica decontaminating column selects 200mm × 15mm internal diameter glass columns, bottom pad about 5mm absorbent cotton high and about 10mm is high Anhydrous sodium sulfate, 10g florisil silicas, 75 μm~150 μm of the granularity of florisil silica, 650 DEG C of calcination 4h use 130 DEG C of work Change 4h and room temperature is cooled in drier, the water deactivation for plus 2%；Top adds about 10mm anhydrous sodium sulfates high, uses n-hexane wet method Dress post, discards leacheate.
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CN108414652B (en) * 2018-02-09 2021-06-25 中国农业科学院茶叶研究所 Method for detecting content of anthracene and anthraquinone and anthrone oxides thereof in multi-medium environment
CN108680669A (en) * 2018-05-08 2018-10-19 江苏安舜技术服务有限公司 The test method of anthraquinone in a kind of plant-derived product and food
CN115261170A (en) * 2022-09-05 2022-11-01 惠风酒业发展(上海)有限公司 Distiller's yeast and health rice wine
CN117420256B (en) * 2023-10-16 2024-06-04 上海国齐检测技术有限公司 Method for detecting anthraquinone compounds and application thereof

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