CN1815223A - Method for detecting tertiary butylhydro quinone in edible vegetable oil by liquid chromatography-iontrap mass spectrometry combination - Google Patents
Method for detecting tertiary butylhydro quinone in edible vegetable oil by liquid chromatography-iontrap mass spectrometry combination Download PDFInfo
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- CN1815223A CN1815223A CN 200610001897 CN200610001897A CN1815223A CN 1815223 A CN1815223 A CN 1815223A CN 200610001897 CN200610001897 CN 200610001897 CN 200610001897 A CN200610001897 A CN 200610001897A CN 1815223 A CN1815223 A CN 1815223A
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Abstract
Present invention refers to using liquid chromatography-ion trap mass spectra combination to detect tertiary butylhydroquinone TBHQ in edible vegetable oil. Said invention uses ethanol as extraction agent, supernatant fluid extracted from edible vegetable oil to be quantify detected to TBHQ utilizing two stages mass spectra main fragment ion m/z 149, under analysis condition of C18 chromatographic column, methanol/water mobile phase, electricity spray (ESI) ion source , and negative ion modal liquid phase chromatography-ion trap mass spectrum combination. Said invention has high sensitivity, fine selectivity, fast speed, and innocuity of extraction agent.
Description
Technical field
The present invention relates to food safety detection, particularly relate in foreign trade and food safety supervision management process, utilization liquid chromatography-ion trap mass spectrometry coupling instrument detects synthetic phenol antioxidant TBHQ (tertiary butylhydroquinone, method TBHQ) in the edible vegetable oil.
Background technology
Edible vegetable oil is in the process of producing, processing and storing; usually can add synthetic phenol antioxidant such as butylhydroxy anisole (Butylated Hydroxyanisole; BHA), BHT (BulylatedHydroxytoluene; BHT), n-propyl gallate (Propyl Gallate, PG) and TBHQ etc. to hinder slow its oxidation deterioration.That be most widely used at present is TBHQ (Fig. 1).The U.S. uses TBHQ in approval in 1972.FAO/WHO (1995) is to its tentative acceptable daily intake (acceptable daily intake, ADI) be 0～0.7mg/kg body weight, allow to use in 26 kinds of based foods, (theoreticalmaximum daily intake TMDI) is 200mg/kg to the theoretical maximum intake.China uses in approval in 1991, and state food adjuvant use hygienic standard regulation (GB2760-1996) maximum is used to limit the quantity of and is 200mg/kg, allows to use in 9 kinds of food such as edible oil and fat, fried food, biscuit, canned sundry fruit.Yet the toxicological evaluation conclusion for TBHQ still there is much controversy in recent years, and European Union, Japan and other countries are thought still do not allow its toxicological test data imperfection to use in food.
Edible vegetable oil is one of main source of human diet basis nutrient.From the progressively process of cognition to synthetized oxidation preventive agent, people more and more have doubt to its security, when selecting edible vegetable oil, all wish to select the product that does not have synthetized oxidation preventive agent, require the detection of food supervisory and management department reinforcement to TBHQ in the commercially available prod.In addition, in external food trade, because the difference of trade both sides national food hygienic standard, the content of TBHQ also is strict with the index of carrying out check and analysis often.For example, China's export to Japan food in 2004 have 7 batches defective because of detecting TBHQ, if Japanese MHLW implements new detection method (detecting sensitivity 1ppm), will have more defective batch.Yet China does not still have the standard detecting method of TBHQ in the edible vegetable oil at present, and existing inspection and quarantine industry standard SN/T1050-2002 " imports and exports the mensuration-liquid phase chromatography of antioxidant in the grease " detecting of TBHQ is limited to 2ppm.Therefore, it is also extremely urgent to set up quick, accurate, highly sensitive TBHQ standard detecting method in China.
At present, sample-pretreating method mainly comprises direct organic solvent extraction, Solid-Phase Extraction and derivatization.Three kinds of sample-pretreating methods cut both ways.Directly organic solvent extractionprocess is simple to operate, but the impurity serious interference.Though solid phase extraction and derivatization method selectivity are good, treatment step is often comparatively complicated, length consuming time.In addition, these sample-pretreating methods often comprise concentration step, the most of the time of the whole check and analysis process that accounted for.
And carry out quantitative detection method, mainly comprise liquid phase chromatography and vapor-phase chromatography.The selectivity of these analytical approachs is good inadequately, can separate well with impurity for making component, often surpasses 20min analysis time.For example, for liquid chromatography, need to adopt linear gradient elution method consuming time usually; And, then need to realize the separation of component by temperature programme for gas chromatography.In addition, these Sensitivity of Analytical Method are not high enough, and detection limit all is the ppm level, can not satisfy present detection requirement.
The research of liquid chromatography/mass spectrometry coupling technique starts from the seventies in 20th century, will be strong at boiling point height, polarity, liquid chromatography that heat-labile compound separates and highly sensitive, detection limit is low, can provide the mass spectrum of compound structure information to be chained together.Ion trap mass spectrometer (ITMS) is a kind of novel mass spectrometer that grows up the eighties in 20th century, and it is little, simple in structure to have a volume, good with the various ion gun compatibility in outside, characteristics such as long and quality selection storage of ion storage time.At present, liquid chromatography/ion trap mass spectrometry coupling has developed into a kind of important analytical technology, application in many research fields such as food medicine, environmental chemistry, biological chemistry launches gradually, but is applied to still do not have bibliographical information in the synthetic phenol antioxidant detection.
Summary of the invention
The objective of the invention is to overcome weak point in the prior art, and provide a kind of and simplify the sample pre-treatments step, shorten analysis time and reduce the method for TBHQ in the detection edible vegetable oil of detection limit.
The object of the invention can realize by the following method: the present invention detects the method for the TBHQ in the edible vegetable oil, be that edible vegetable oil is after extraction, centrifugal layering, pipette upper layer of extraction liquid, re-extract 2～3 times, the extract that merges pipettes supernatant to the sample introduction bottle after centrifugal layering, in chromatographic column is the C18 post, moving phase is methanol, electron spray (ESI) ion gun, under the liquid chromatography of negative ion mode-ion trap mass spectrometry coupling analysis condition, utilize 149 couples of T BHQ of the main fragmention m/z of second order ms to carry out detection by quantitative.Concrete steps are as follows:
At first, pipette 0.1～0.3mL edible vegetable oil in the glass centrifuge tube, add 1.5～2.5mL ethanol, oscillation extraction 3～5min on micro-mixer is after the centrifugal 4～8min of 3000～4000r/min, pipette upper layer of extraction liquid to the glass centrifuge tube, re-extract 2～3 times, combining extraction liquid pipettes supernatant to the sample introduction bottle behind the centrifugal 4～8min of 3000～4000r/min; Then, in chromatographic column is C18 (2.1mm * 150mm, 0.5 μ m), 25～35 ℃ of column temperatures, moving phase is methanol, flow velocity 0.15～0.40mL/min, sampling volume 5～20 μ L detect wavelength 280nm, electric spray ion source, negative ion mode, atomization gas (nitrogen) 30～40psi, dry gas (nitrogen) 8～12L/min, 160～280 ℃, broken voltage 1.6～1.8V (broken cutoff m/z 80) under the liquid chromatography of mass scanning scope m/z 50～300-ion trap mass spectrometry coupling analysis condition, utilizes 149 couples of TBHQ of the main fragmention m/z of second order ms to carry out detection by quantitative.
The organic solvent bibliographical information that can be used as extractant has a lot, as acetonitrile, methyl alcohol, and sherwood oil, ethanol etc., because with respect to other organic solvents, ethanol is nontoxic, wide material sources, cheap, therefore, preferred alcohol of the present invention is as extractant.
Can pass through liquid chromatography-mass spectrometric hyphenated technique, realize reduction detection limit, the purpose that strengthens selectivity, shortens analysis time, key be the optimized choice of mass spectrum condition, as flow velocity and temperature, the broken voltage etc. of atomization gas pressure, dry gas.
Atomization gas (nitrogen) enters in the sample flow with certain pressure through atomization needle, and the component of separating through liquid chromatography is atomized.The pressure of atomization gas is to influence atomizing effect and the stable key factor of sample flow.The too low atomizing requirement that can not satisfy sample of atomization gas pressure too highly then causes the instability of sample flow and influences the detection effect, and being suitable for atomization gas pressure of the present invention is 30～40psi.
Dry gas (nitrogen) is in order to realize the desolvation of sample, and the flow velocity of dry gas and temperature are the principal elements that influences sample desolvation effect.The dry gas flow velocity is big more, and the desolvation effect is good more, is detecting under the more excellent situation of effect, and for saving nitrogen, being suitable for dry gas flow velocity of the present invention is 8～12L/min.The dry gas temperature is low excessively, and the desolvation effect of sample is undesirable; The dry gas temperature is too high, then often causes the thermal decomposition of sample molecule.Being suitable for dry gas temperature of the present invention is 160～280 ℃.
Under reaction of high order mass spectrum (MRM) pattern, the key factor that broken voltage influence second order ms detects.Broken magnitude of voltage is low excessively, and parent ion m/z 165 can not be able to fragmentation well, and the fragmention abundance of formation is low; Broken magnitude of voltage is too high, and parent ion m/z 165 is broken fully, but fragmention m/z 149 can not stablize and reside in the ion trap, causes detected fragmention abundance not high.Being suitable for broken voltage of the present invention is 1.6～1.8V, and this moment, most of parent ion was broken, and the fragmention peak area maximum that forms.
The present invention adopts liquid chromatography-ion trap mass spectrometry coupling method through facts have proved in a large number, is extractant with ethanol, the range of linearity 0～4542.5 μ g/L, R
2=0.9990, detect and be limited to 0.3mg/kg, quantitatively be limited to 1mg/kg, the recovery can reach 81.9%～109.6%, relative standard deviation≤5.3%, compare with existing inspection and quarantine industry standard SN/T1050-2002 " mensuration-liquid phase chromatography of antioxidant in the import and export grease " (detecting of TBHQ is limited to 2mg/kg), this method can satisfy the detection requirement fully, and this method can further reduce the detection limit of method by the mode that increases sample size.
The present invention compared with prior art has following advantage:
At first, the selectivity that TBHQ ion trap second order ms detects is good, has reduced the requirement for liquid chromatography component separating effect, can finish detection in the 10min.Secondly, it is highly sensitive that TBHQ ion trap second order ms detects, and makes the pre-treatment process of sample save concentration step consuming time.This two promise the whole detection method of TBHQ analysis time of having liquid phase chromatography and the incomparable low detection limit of vapor-phase chromatography, simple sample pre-treatments and shortening greatly, this is the characteristics of this method.The 3rd, with ethanol as extractant recovery height, and ethanol nontoxic, with low cost, be easy to obtain.
Description of drawings
Fig. 1-a is that TBHQ second order ms extraction ion flow graph, Fig. 1-b are that mass spectrogram and Fig. 1-c are the cleavage of mass spectrum modes
Fig. 2 is the chemical structural formula of TBHQ
Embodiment
Below in conjunction with accompanying drawing, enumerate 1 embodiment, the present invention is further specified, but the present invention is not only limited to this embodiment.
Pipette 0.2mL edible vegetable oil in 10mL glass centrifuge tube, add 2mL ethanol, oscillation extraction 5min on micro-mixer is after the centrifugal 5min of 4000r/min, pipette upper layer of extraction liquid to 10mL glass centrifuge tube, re-extract 3 times, combining extraction liquid pipettes 0.8mL to 1.5mL sample introduction bottle and carries out liquid chromatography/ion trap mass spectrometry coupling analysis behind the centrifugal 5min of 4000r/min.
The LC-MS analysis condition of TBHQ is as follows.[chromatographic condition] chromatographic column is ZORBAX Eclipse XDB-C18 (2.1mm * 150mm, 0.5 μ m); 35 ℃ of column temperatures; Moving phase is methanol (50: 50), flow velocity 0.4mL/min; Sampling volume 5 μ L; Detect wavelength 280nm.[mass spectrum condition] electron spray (ESI) ion gun; Negative ion mode; Parent ion m/z 165; Main fragmention m/z 149; Atomization gas (nitrogen) 30.0psi; Dry gas (nitrogen) 10.0L/min, 160 ℃; Broken cutoff m/z 80; Broken voltage 1.7V; Mass scanning scope m/z 50～300.
The content of TBHQ is according to the typical curve range of linearity (0～4542.5 μ g/L, the R of the main fragmention m/z 149 of second order ms
2=0.9990) tries to achieve.
The concentration of TBHQ is calculated as follows in the edible vegetable oil:
The present invention carries out check and analysis (table 1) to 10 kinds of commercially available edible vegetable oils in Beijing, and the recovery is 81.9～109.6%, and (RSD %)≤5.3, can satisfy the requirement of quantitative test to relative standard deviation fully.
TBHQ's detects concentration in 10 kinds of edible vegetable oils of table 1
| Edible vegetable oil | TBHQ detects concentration mg/kg | The recovery/% | Date of manufacture |
| Ready-mixed | 87.7±2.5 43.8±1.1 38.5±2.2 0.0±0.0 0.0±0.0 41.3±1.8 0.0±0.0 0.0±0.0 0.0±0.0 0.0±0.0 | 93.2±5.3 105.1±4.5 97.8±4.0 96.2±3.5 88.5±5.0 94.4±3.4 99.4±4.2 81.9±1.9 98.6±3.5 109.6±4.6 | 2003-12-25 2003-09-05 2003-11-16 2004-11-14 2004-07-17 2004-08-15 2004-06-18 2003-09-30 2004-09-03 2003-12-06 |
Claims (2)
1, liquid chromatography-ion trap mass spectrometry coupling detects the method for TBHQ in the edible vegetable oil, it is characterized in that edible vegetable oil is after extraction, centrifugal layering, pipette upper layer of extraction liquid, re-extract 2～3 times, the extract that merges pipettes supernatant to the sample introduction bottle after centrifugal layering, in chromatographic column is the C18 post, moving phase is methanol, electric spray ion source, under the liquid chromatography of negative ion mode-ion trap mass spectrometry coupling analysis condition, utilize 149 pairs of TBHQs of the main fragmention m/z of second order ms to carry out detection by quantitative.
2, the method for TBHQ in the detection edible vegetable oil according to claim 1 is characterized in that extractant is an ethanol.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101545895B (en) * | 2009-05-06 | 2010-12-08 | 河南工业大学 | Method for quickly detecting TBHQ in edible fat |
| CN103105393A (en) * | 2013-01-24 | 2013-05-15 | 昆明理工大学 | Rapid detection method of PG (propylgallate) in edible-oil-type food |
| CN105738534A (en) * | 2014-12-08 | 2016-07-06 | 中粮集团有限公司 | Method for fast detection of butylated hydroxyanisole (BHA), 2, 6-ditertbutyl-4 methylphenol (BHT) and tert-butylhydroquinone (TBHQ) of plant oil sample and pre-treatment method |
| CN111257465A (en) * | 2020-02-26 | 2020-06-09 | 成都海关技术中心 | Method for detecting content of tert-butyl hydroquinone in broad bean paste |
| CN111983065A (en) * | 2020-08-10 | 2020-11-24 | 东北农业大学 | Method for removing tert-butyl hydroquinone in edible vegetable oil |
| CN112129846A (en) * | 2020-08-14 | 2020-12-25 | 广东人人康药业有限公司 | High performance liquid chromatography for efficiently separating and detecting p-benzoquinone in hydroquinone and application thereof |
-
2006
- 2006-01-25 CN CN 200610001897 patent/CN1815223A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101545895B (en) * | 2009-05-06 | 2010-12-08 | 河南工业大学 | Method for quickly detecting TBHQ in edible fat |
| CN103105393A (en) * | 2013-01-24 | 2013-05-15 | 昆明理工大学 | Rapid detection method of PG (propylgallate) in edible-oil-type food |
| CN105738534A (en) * | 2014-12-08 | 2016-07-06 | 中粮集团有限公司 | Method for fast detection of butylated hydroxyanisole (BHA), 2, 6-ditertbutyl-4 methylphenol (BHT) and tert-butylhydroquinone (TBHQ) of plant oil sample and pre-treatment method |
| CN111257465A (en) * | 2020-02-26 | 2020-06-09 | 成都海关技术中心 | Method for detecting content of tert-butyl hydroquinone in broad bean paste |
| CN111983065A (en) * | 2020-08-10 | 2020-11-24 | 东北农业大学 | Method for removing tert-butyl hydroquinone in edible vegetable oil |
| CN112129846A (en) * | 2020-08-14 | 2020-12-25 | 广东人人康药业有限公司 | High performance liquid chromatography for efficiently separating and detecting p-benzoquinone in hydroquinone and application thereof |
| CN112129846B (en) * | 2020-08-14 | 2021-11-02 | 广东人人康药业有限公司 | High performance liquid chromatography for efficiently separating and detecting p-benzoquinone in hydroquinone and application thereof |
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