CN106841481A - The method that solid phase dispersion purification techniques quickly determines 9,10 anthraquinone residual quantities in tealeaves - Google Patents
The method that solid phase dispersion purification techniques quickly determines 9,10 anthraquinone residual quantities in tealeaves Download PDFInfo
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Abstract
The method that solid phase dispersion purification techniques quickly determines 9,10 anthraquinone residual quantities in tealeaves, belongs to detection technique field.It is comprised the following steps：1）Sample extraction；2）Sample purification；3）GC MS/MS are determined；4）Blank test；5）Result is calculated and stated；6）Judge.Assay method of the invention has the advantages that：The method that solid phase dispersion purification techniques quickly determines 9,10 anthraquinone residual quantities in tealeaves is developed, laboratory operating procedures are simplified, time cost is reduced；Experimentation is not related to column purification step, reduces organic solvent usage amount, reduces environmental pressure.
Description
Technical field
The invention belongs to detection technique field, and in particular to solid phase dispersion purification techniques quickly determines 9,10- anthracenes in tealeaves
The method of quinone residual quantity.
Background technology
9,10- anthraquinones（Anthraquinone, CAS No 84-65-1）It is a kind of emerging pollutant of appearance in tealeaves,
European Union specifies its MRL in tealeaves（MRL）It is 0.02 mg/kg.2012, European Union circulated a notice of Chinese tea first
9,10- anthraquinones are exceeded in leaf；China 9,10- anthraquinones in 2014 are located in European Union's tealeaves first of the exceeded circular of pollutant.At present, it is right
The detection method research of 9,10- anthraquinones is less in tealeaves.Passing through gel chromatography, TPT or laboratory existing document report more
Self-control glass column purification, experimental procedure is cumbersome, and consumption of organic solvent is big, causes experimental period high cost, and environmental pressure is high.
9,10- anthraquinone molecular structural formulas are as follows：
。
The content of the invention
For the problem that prior art is present, a kind of solid phase dispersion purification techniques is provided present invention aim at design quick
The method for determining 9,10- anthraquinone residual quantities in tealeaves.The solid phase dispersion that the method passes through florisil silica, effectively simplifies experiment
Step and reduction organic solvent usage amount.The method is easy to operate quick, and consumption of organic solvent is few, the rate of recovery, detection limit and
The aspects such as precision can meet residue limits requirement in domestic and international tealeaves, can be tealeaves 9, and the measure of 10- anthraquinone residual quantities is carried
For technical support.
The method that described solid phase dispersion purification techniques quickly determines 9,10- anthraquinone residual quantities in tealeaves, it is characterised in that
Comprise the following steps：
1）Sample extraction
The g of pulverizing tea sample 2 is taken in 50 mL polytetrafluoroethylene (PTFE) centrifuge tubes, 2 mL distilled water are added, fully 30 is soaked after wetting
min；It is 4 to add 10 mL volume ratios：1 n-hexane and acetone mixed solution, the min of ultrasonic extraction 30；Add the anhydrous sulphur of 2 g
Sour magnesium shakes up cooling, and be vortexed 30 s, and 5 min are centrifuged with 6000 r/min；5 mL supernatants are taken in heart bottle, 35 DEG C of rotations are steamed
It is sent to and closely does, is 39 with 5 mL volume ratios:1 n-hexane and acetone mixed solution dissolved residue, it is to be clean；
2）Sample purification
Liquid to be clean is taken in 10 mL centrifuge tubes, add 0.7 g to add water deactivation florisil silica, be vortexed 1 min, 6000 r/
Min is centrifuged 5 min；4 mL supernatants are pipetted in heart bottle, 35 DEG C of rotary evaporations are done near, nitrogen drying；0.8 mL contains
The deuterated anthraquinone volume ratio of internal standard is 39:1 n-hexane and acetone mixed solution constant volume, adds 0.8 mL acetonitrile liquid liquid quiet after distributing
Put, take acetonitrile layer solution and cross 0.22 μm of organic film, for GC-MS/MS tests；
3）GC-MS/MS is determined
Matrix matching standard liquid and the sample solution sample introduction under the gas chromatography-mass spectrum/Mass Spectrometry Conditions of following setting：
A）Gas chromatography-mass spectrum/mass spectrometer parameter：
Gas-chromatography：Chromatographic column：VF-5ms, m × 0.25 mm × 0.25 μm of specification 30；Program column temperature：80 DEG C of holding 1min,
240 DEG C are warming up to the speed of 15 DEG C/min, then 280 DEG C are warming up to 25 DEG C/min, keep 5min；Carrier gas：Helium, purity
99.999%, the mL/min of flow velocity 1.0；Injector temperature：250℃；Input mode：Splitless injecting samples；
Mass Spectrometry Conditions：Ionization mode：EI；Collision gas:Argon gas, purity 99.999%, 2.0 mTorr；
Ionizing energy：70eV；Ion source temperature：210℃；Transmission line temperature：280℃；Mensuration mode：Reaction of high order detects mould
Formula；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%,
Relative deviation ± 30% of permission；Relative ion abundance≤10%, it is allowed to relative deviation ± 50%；
B）9,10- anthraquinone mass spectrometry parameters
4）Blank test
In addition to sample is not added with, by above-mentioned steps 1）, step 2）, step 3）Operation is carried out；
5）Result is calculated and stated
The mass concentration of anthraquinone in sample is calculated as follows, and result must deduct blank value：
In formula：
Xi-- the residual quantity of anthraquinone in sample, unit for milligrams per kilogram；
Ci-- obtain the solution concentration of anthraquinone from standard curve, unit for milligrams per liter；
V -- the final constant volume of sample liquid, unit is milliliter；
M -- the sample mass representated by final sample liquid, unit for gram；
6）Judge
With mass concentration X as abscissa, peak area ratio Y is ordinate, draws 5 standard working curves, works bent with standard
Line is quantitative determined to sample, and the response of determinand meets the range of linearity of instrument detection in sample solution；It is quantitative and fixed
Property ion pair exist simultaneously, and signal to noise ratio >=3；The chromatographic peak retention time that determinand occurs in sample solution and matrix matching mark
Quasi- solution is consistent, it is allowed to which deviation is less than ± 0.5%, then can determine that and contain the medicine.
The quick method for determining 9,10- anthraquinone residual quantities in tealeaves of described solid phase dispersion purification, it is characterised in that：Not sieve
In dry 4 h under the conditions of 500 DEG C of tripoli, in room temperature is cooled in drier, add 7% water w/w deactivations.
The present invention quickly determines 9,10- anthraquinone residual quantities in tealeaves using solid phase dispersion purification techniques, easy to operate quick,
Consumption of organic solvent is few.The residue limits requirement in the aspects such as the rate of recovery, detection limit and precision can meet domestic and international tealeaves.
Assay method of the invention has the advantages that：
The method that solid phase dispersion purification techniques quickly determines 9,10- anthraquinone residual quantities in tealeaves is developed, experimental implementation is simplified
Step, reduces time cost；Experimentation is not related to column purification step, reduces organic solvent usage amount, reduces environment and bears
Load.
Brief description of the drawings
Fig. 1 is 9,10- anthraquinones（0.01mg/L）With deuterated-anthraquinone（0.04 mg/L）Standard specimen mass spectrogram；
Fig. 2 is that Extraction solvent difference content of acetone influences on 9,10- anthraquinones extraction efficiency；
Fig. 3 is influence of the florisil silica water content to 9,10- anthraquinone extraction efficiencies；
Fig. 4 is influence of the florisil silica amount to the 9,10- anthraquinone rate of recovery.
Specific embodiment
Further illustrate the present invention with reference to embodiments.
Embodiment one：The foundation of Mass Spectrometry Conditions
Full scan mode obtains 9,10- anthraquinone characteristic ions m/z 208,180 and 152, the conduct of selection abundance of ions highest 208
Parent ion.Increase collision energy step by step, obtain feature daughter ion 180 and 152 and optimal collision energy, tealeaves base is not received in selection
The m/z 208 of matter interference>152 ion channels are used as quota ion pair, m/z 208>180 used as qualitative ion pair.Same side
Formula optimizes deuterated-the qualitative, quantitative ion pair of anthraquinone.Mass spectrogram is shown in Fig. 1.
Embodiment two：The optimization of Extraction solvent
Fig. 2 is shown in influence of the mixed proportion of acetone and n-hexane to the 9,10- anthraquinone rate of recovery.When volume of the acetone in n-hexane
When fraction is less than 10%, average recovery rate is less than 70%；Increase Extraction solvent in content of acetone to 20% and more than, the rate of recovery is basic
Stabilization meets the requirement of retention analysis in 80-90%.The common extraction of polar substances in tealeaves can be increased due to content of acetone increase,
Therefore final choice acetone+n-hexane（V/V = 1+4）As Extraction solvent.
Embodiment three：Florisil silica uses screening
1）Water content is 1%, 3%, 5%, 7%, 10% in setting florisil silica, and 12% different disposal is found with water content
Increase, 9, the 10- anthraquinone rate of recovery are improved（Fig. 3）, when water content is more than 5%, rate of recovery stabilization is 80% or so.With amount of water
Increase, the color burn of extract solution, therefore 7% water content of selection is used as the activation condition of florisil silica adsorbent.
2）Optimize influence of the florisil silica addition to the rate of recovery（Fig. 4）.Increase the amount of florisil silica, Ke Yiyou
Effect improves clean-up effect.But due to the suction-operated of florisil silica, the addition of florisil silica and returning for 9,10- anthraquinones
Yield is in obvious negative correlativing relation, and is declined significantly when the rate of recovery of 9,10- anthraquinones is in 0.7 more than g, therefore Fu Luoli
The consumption of tripoli selects 0.7 g.
Embodiment five：The method that solid phase dispersion purification techniques quickly determines 9,10- anthraquinone residual quantities in tealeaves
1st, reagent and material
1.1 n-hexanes：Chromatographically pure.
1.2 acetone：Chromatographically pure.
1.3 acetonitriles：Chromatographically pure.
1.4 anhydrous magnesium sulfates：Pure, 650 DEG C of calcination 4h are analyzed, room temperature is cooled in drier, in storing in air-tight bottle
It is standby.
1.5 9,10- anthraquinones standard substances (Anthraquinone, CAS:84-65-1, C14H8O2) ：Purity 99.0%.
1.6 deuterated-anthraquinone standard substance (D8-Anthraquinone,CAS:10439-39-1) ：Purity 98.6%.
1.7 Standard Stock solutions：Accurately weigh the g of standard substance (1.5) 0.010（It is accurate to 0.0001 g）In 50 mL
In volumetric flask, with acetone constant volume, 100 mg/L stock standard solutions are configured to, in -20 DEG C of preservations.
1.8 D8- anthraquinone Standard Stock solutions：Accurately weigh the g of standard items (1.6) 0.010（It is accurate to 0.0001 g）In
In 50 mL volumetric flasks, with acetone constant volume, 100 mg/L stock standard solutions are configured to, in -20 DEG C of preservations.
The preparation of interstitial fluid in 1.9 standards：The accurate standard reserving solution that pipettes is appropriate (1.7), with acetontrile into 10 mg/L
Standard liquid；It is accurate to pipette that standard reserving solution is appropriate (1.8), with acetontrile into 4mg/L mixed standard solution in -20
Lucifuge storage in DEG C refrigerator.
The preparation of 1.10 standard working solutions：As needed by standard intermediate solution (1.9) with dilution in acetonitrile into appropriate
The standard working solution of concentration.
1.11 florisil silicas：150-250 μm, 4 h are dried under the conditions of 500 DEG C, add 7% water（w/w）Activation, it is standby
With.
1.12 miillpore filters：0.22 μm, organic phase.
2nd, instrument and equipment
2.1 gas chromatography-mass spectrums/mass spectrograph：Equipped with (EI) ion gun.
2.2 assay balances：Sensibility reciprocal 0.00001g and 0.01g.
2.3 vortex instrument.
2.4 solid sample pulverizers.
2.5 centrifuges.
2.6 Ultrasound Instruments.
2.7 Nitrogen evaporators.
3rd, determination step
3.1 sample extractions
The g of pulverizing tea sample 2 is taken in 50 mL polytetrafluoroethylene (PTFE) centrifuge tubes, 2 mL distilled water are added, fully 30 is soaked after wetting
min；Add 10 mL n-hexanes and acetone mixed solution（Volume ratio 4：1）, the min of ultrasonic extraction 30；Add 2 g anhydrous slufuric acids
Magnesium shakes up cooling, and be vortexed 30 s, and 5 min are centrifuged with 6000 r/min；5 mL supernatants are taken in heart bottle, 35 DEG C of rotary evaporations
To near dry, with 5 mL n-hexanes and acetone mixed solution（Volume ratio 39:1）Dissolved residue, it is to be clean.
3.2 sample purifications
Liquid to be clean is taken in 10 mL centrifuge tubes, add 0.7 g to add water deactivation florisil silica, be vortexed 1 min, 6000 r/
Min is centrifuged 5 min；4 mL supernatants are pipetted in heart bottle, 35 DEG C of rotary evaporations are done near, nitrogen drying；0.8 mL is just
Hexane and acetone mixed solution（Volume ratio 39:1, the deuterated anthraquinone of containing the internal standard）0.8 mL is settled to, 0.8 mL acetonitrile liquid liquid is added
After distribution, stand, take acetonitrile layer solution and cross 0.22 μm of organic film, for GC-MS/MS tests.
3.3 determine
By test condition depends on used instrument, therefore the universal parameter of chromatography can not possibly be provided.Using following
Operating condition has been demonstrated that to test be suitable.Design parameter is shown in Table 2, table 3.
The gas chromatograph parameters of table 2
The Mass Spectrometry Conditions parameter of table 3
4th, blank test
In addition to sample is not added with, carried out by above-mentioned steps；
5th, result is calculated and stated
The content of anthraquinone in sample is calculated as follows, and result must deduct blank value：
In formula：
Xi-- the residual quantity of anthraquinone in sample, unit for milligrams per kilogram；
Ci-- obtain the solution concentration of anthraquinone from standard curve, unit for milligrams per liter；
V -- the final constant volume of sample liquid, unit is milliliter；
M -- the sample mass representated by final sample liquid, unit for gram.
The content of anthraquinone in tealeaves is determined by GC-MS/MS, standard curve making determines standard specimen 0.008mg/L respectively,
The peak area ratio of 0.016mg/L, 0.04mg/L, 0.16mg/L, 0.8mg/L（AQ/d8-AQ）It is 0.26,0.61,1.6,
6.80,36.80, standard curve y=46.222x -0.2461 (R are drawn to 9,10- anthraquinone contents with response2 =
0.9998), testing sample peak area ratio is 10, brings standard curve calculating, C intoiIt is 0.22mg/L, V is 0.8 mL, and m is
1g, brings formula calculating, X intoi=0.18mg/L。
6th, lower bound is determined
The measure lower bound of this method is 0.02 mg/kg.
7th, the rate of recovery
The experiment of this method rate of recovery sets four addition concentration, and the experiment condition as determined by this method is dense to each addition
Degree carries out 5 experiments, and 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. the method that solid phase dispersion purification techniques quickly determines 9,10- anthraquinone residual quantities in tealeaves, it is characterised in that including following
Step：
1）Sample extraction
The g of pulverizing tea sample 2 is taken in 50 mL polytetrafluoroethylene (PTFE) centrifuge tubes, 2 mL distilled water are added, fully 30 is soaked after wetting
min；It is 4 to add 10 mL volume ratios：1 n-hexane and acetone mixed solution, the min of ultrasonic extraction 30；Add the anhydrous sulphur of 2 g
Sour magnesium shakes up cooling, and be vortexed 30 s, and 5 min are centrifuged with 6000 r/min；5 mL supernatants are taken in heart bottle, 35 DEG C of rotations are steamed
It is sent to and closely does, is 39 with 5 mL volume ratios:1 n-hexane and acetone mixed solution dissolved residue, it is to be clean；
2）Sample purification
Liquid to be clean is taken in 10 mL centrifuge tubes, add 0.7 g to add water deactivation florisil silica, be vortexed 1 min, 6000 r/
Min is centrifuged 5 min；4 mL supernatants are pipetted in heart bottle, 35 DEG C of rotary evaporations are done near, nitrogen drying；0.8 mL contains
The deuterated anthraquinone volume ratio of internal standard is 39:1 n-hexane and acetone mixed solution constant volume, adds 0.8 mL acetonitrile liquid liquid quiet after distributing
Put, take acetonitrile layer solution and cross 0.22 μm of organic film, for GC-MS/MS tests；
3）GC-MS/MS is determined
Matrix matching standard liquid and the sample solution sample introduction under the gas chromatography-mass spectrum/Mass Spectrometry Conditions of following setting：
A）Gas chromatography-mass spectrum/mass spectrometer parameter：
Gas-chromatography：Chromatographic column：VF-5ms, m × 0.25 mm × 0.25 μm of specification 30；Program column temperature：80 DEG C of holding 1min, with
The speed of 15 DEG C/min is warming up to 240 DEG C, then is warming up to 280 DEG C with 25 DEG C/min, keeps 5min；Carrier gas：Helium, purity
99.999%, the mL/min of flow velocity 1.0；Injector temperature：250℃；Input mode：Splitless injecting samples；
Mass Spectrometry Conditions：Ionization mode：EI；Collision gas:Argon gas, purity 99.999%, 2.0 mTorr；
Ionizing energy：70eV；Ion source temperature：210℃；Transmission line temperature：280℃；Mensuration mode：Reaction of high order detects mould
Formula；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%,
Relative deviation ± 30% of permission；Relative ion abundance≤10%, it is allowed to relative deviation ± 50%；
B）9,10- anthraquinone mass spectrometry parameters
4）Blank test
In addition to sample is not added with, by above-mentioned steps 1）, step 2）, step 3）Operation is carried out；
5）Result is calculated and stated
The mass concentration of anthraquinone in sample is calculated as follows, and result must deduct blank value：
In formula：
Xi-- the residual quantity of anthraquinone in sample, unit for milligrams per kilogram；
Ci-- obtain the solution concentration of anthraquinone from standard curve, unit for milligrams per liter；
V -- the final constant volume of sample liquid, unit is milliliter；
M -- the sample mass representated by final sample liquid, unit for gram；
6）Judge
With mass concentration X as abscissa, peak area ratio Y is ordinate, draws 5 standard working curves, works bent with standard
Line is quantitative determined to sample, and the response of determinand meets the range of linearity of instrument detection in sample solution；It is quantitative and fixed
Property ion pair exist simultaneously, and signal to noise ratio >=3；The chromatographic peak retention time that determinand occurs in sample solution and matrix matching mark
Quasi- solution is consistent, it is allowed to which deviation is less than ± 0.5%, then can determine that and contain the medicine.
2. the quick method for determining 9,10- anthraquinone residual quantities in tealeaves of solid phase dispersion purification according to claim 1, its
It is characterised by：4 h are dried under the conditions of 500 DEG C of florisil silica, in room temperature is cooled in drier, 7% water w/w deactivations is added.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108414652A (en) * | 2018-02-09 | 2018-08-17 | 中国农业科学院茶叶研究所 | The detection method of anthracene and its oxide anthraquinone, anthrone content in multi-interfacial feature |
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| CN103884788A (en) * | 2014-02-26 | 2014-06-25 | 华中农业大学 | Method for detecting pesticide residues in tea by using gas chromatograph-mass spectrometry |
| CN105424855A (en) * | 2015-11-23 | 2016-03-23 | 浙江出入境检验检疫局检验检疫技术中心 | Method for measuring residual amount of anthraquinone in tea with gas chromatography-mass spectrum/mass spectrum method |
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| CN108414652A (en) * | 2018-02-09 | 2018-08-17 | 中国农业科学院茶叶研究所 | The detection method of anthracene and its oxide anthraquinone, anthrone content in multi-interfacial feature |
| 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 |
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