CN104111281A - Method for rapidly analyzing plasticizer in wine - Google Patents
Method for rapidly analyzing plasticizer in wine Download PDFInfo
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- CN104111281A CN104111281A CN201310136590.6A CN201310136590A CN104111281A CN 104111281 A CN104111281 A CN 104111281A CN 201310136590 A CN201310136590 A CN 201310136590A CN 104111281 A CN104111281 A CN 104111281A
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Abstract
The invention discloses a new simple method for rapidly sensitively detecting a plasticizer (phthalates) in wine. An ion migration spectrum technology is taken as the basis, and an ion migration spectrometer is utilized as the analysis detection means. No complex pretreatment on a wine sample is needed. Liquid compositions in the wine sample can be volatilized through heating (40-80 DEG C) of a self-prepared thermal-desorption heater. The method is rapid in detection speed, the sampling analysis time of a sample is less than 10 s, the detection sensitivity is high, and the detection limit can reach 0.1 mg/Kg. The measure method is low in sample pretreatment condition requirements, simple and rapid for operation, good in reliability, and suitable for qualitative and quantitative analysis on a plasticizer in the wine sample.
Description
Technical field
The present invention relates to the detection method of plasticiser in wine, the specifically rapid analysis of plasticiser in a kind of new quick, sensitive detection wine, this method is taking Ion mobility spectrometry as basis, utilize ion mobility spectrometry fast detector as analysis means, wine sample, without complicated pre-treatment, only need be analysed well heater heating (40-80 DEG C) with pyrolysis and volatilize liquid component in wine sample.Detection speed is fast, and sample feeding is less than 10 seconds analysis time, highly sensitive, and detectability can reach 0.1mg/kg.
Background technology
Dibutyl phthalate (DBP) is the most frequently used plasticiser of Polyvinylchloride, can make plastic products have good flexibility, but volatility and water extractable are larger, thereby poor durability.Dibutyl phthalate is the good plasticiser of NC Nitroncellulose, and gelatinisation ability is strong, for NC Nitroncellulose coating, has good emollescence.Stability, resistance to deflection, cohesiveness and water proofing property are all better than other plasticisers.Plasticiser (DEHP), refers to " phthalic acid (2-ethylhexyl) diester ", is a kind of poisonous chemical industry plastics softening agent.Belong to colourless, liquid with no taste, the raw material of Chang Zuowei sofa, automotive seat, rubber tube, cosmetics and toy.A large amount of eating may affect liver and kidney, even carcinogenic.Diisobutyl phthalate (DIBP), DIBP is one of conventional plasticiser.Can be used as the plasticiser of celluosic resin, vinylite, butyronitrile rubber and chlorinated rubber etc.Plasticising usefulness and DBP are similar, have good dissolubility, dispersiveness and stickability.Have reproductive system toxicity, external multiple companies and tissue use as Miles etc. has forbidden adding at present.Plasticiser is illegally widely used in food, medicine for many years, is called as " reprint melamine ".
Recently the Jiu Gui Jiu of quoting is on the net not case containing plasticiser, and in fact it is only the tip of the iceberg of liquor industry.Increase wine turbidity, stablize wine system, when plasticiser is joined in wine, the mechanism of action of plasticiser is that plasticiser molecule is inserted between polymer molecular chain, weaken the stress of polymer molecule interchain, result increased polymer molecular chain movability, reduced the crystallinity of polymer molecular chain, the plasticity of polymkeric substance is increased, thereby improve the mouthfeel of wine.Plasticiser main source in Liquor Products is that plastics connect fat, finished wine Plastic Drum packaging etc.
The harm of plasticiser is self-evident, and on June 1st, 2012, the Ministry of Public Health once promptly made an announcement, and plasticiser is listed in to " the non-edible material from soybeans of the illegal interpolation of possibility and the food additives list of easy abuse in the 6th batch of food ".Detection method has GC-MS and HPLC-MS.But its detection method sample pre-treatments complexity, consuming time.In ion mobility spectrometry detection wine, plasticiser method sample pre-treatments conditional request is low, easy and simple to handle, quick, good reliability.Be applicable to very much drinks processing factory, each quality inspection unit, the fast detecting analysis of Ge great marketing unit.
Summary of the invention
The object of this invention is to provide the method for plasticiser (phthalate) in a kind of new detection wine, this method wine sample is without complicated pre-treatment
1) standard detection: get the alcohol of plasticiser standard model of concentration 0.1-100mg/kg and/or aqueous solution, 5-50 μ L in clean sample introduction sheet surface sampling place, analyse well heater heating with pyrolysis and volatilize wherein liquid component, then analyse injector by ion mobility spectrometry pyrolysis and detect analysis; Obtain transit time and the signal peak strength value of the ion analysis detection of plasticiser standard model;
2) testing sample detects: get 5-50 μ L wine sample to be measured in clean sample introduction sheet surface sampling place, analyse well heater heating volatilize liquid component in wine sample with pyrolysis; Taking ionic migration spectrometer as detecting instrument, the pyrolysis of sample introduction thin slice insertion ion mobility spectrometry is analysed injector and is detected analysis; Obtain transit time and signal peak strength value that ion analysis detects;
3) by step 2) ion analysis of the plasticiser standard model that obtains of the transit time that obtains and signal peak strength value and the step 1) transit time and the contrast of signal peak strength value that detect;
Determine in wine sample to be measured whether contain the plasticiser described in plasticiser standard model according to transit time; If the plasticiser that contains plasticiser standard model, can determine its kind, and then determine the content of plasticiser in wine sample to be measured according to corresponding signal peak strength.
Plasticiser standard model is the plasticiser in national examination criteria, comprising: repefral (DMP); Diethyl phthalate (DEP); Dipropyl phthalate (DPRP); Phthalic acid fourth Bian ester (BBP); Diisobutyl phthalate (DIBP) or n-butyl phthalate (DBP); Diamyl phthalate (DPP); Dicyclohexyl phthalate (DCHP); Dihexylphthalate (DNP); Diphenyl phthalate (DPHP); Dioctyl adipate (DEHA); Diisooctyl phthalate (DIOP); Phthalic acid two (2-ethyl hexyl) ester (DEHP); Di-n-octyl phthalate (DNOP); Diisononyl phthalate (DINP) or dinonyl phthalate (DNP); One or two or more kinds mixing in the different certain herbaceous plants with big flowers ester of phthalic acid two (DIDP).
The pyrolysis using in test is analysed heter temperature and is chosen in adjusting between 40-80 DEG C, volatilizes liquid component, adopts 40-80 DEG C of low-temperature heat process to reduce plasticiser loss.
Sample introduction thin slice is metal grid mesh, tetrafluoro plate or teflon high temperature cloth.
In test, to analyse injector be that injector is analysed in stepper motor pyrolysis, injector is analysed in solenoid valve pyrolysis or injector is analysed in Halogen lamp LED pyrolysis in pyrolysis.
Described ion mobility spectrometry is uniform field ion mobility spectrometry, and detecting pattern is positive ion high pressure mode.
Ion mobility spectrometry, comprise sampling device, ionization source, reaction zone, ion gate, migration area, signal reception and detection system and gas circuit drying system, it is characterized in that: described sampling device is made up of injection port and the carrier gas transfer pipeline that is arranged at injection port outside, be externally connected with pyrolysis at injection port and analyse injector, pyrolysis eutectoid temperature, between 150-250 DEG C, is placed in injection port when described sample introduction thin slice sample introduction.
The Ministry of Public Health's current finite quantity regulation be three kinds: phthalic acid two (α-ethylhexyl ester) (DEHP), diisononyl phthalate (DINP), n-butyl phthalate (DBP).Maximum residue limit is respectively 1.5mg/kg, 9.0mg/kg and 0.3mg/kg, and this method meets analyzing and testing requirement.
Advantage of the present invention is as follows:
Compared with traditional gas chromatography, liquid phase chromatogram-mass spectrometry combination method, the means of ion mobility spectrometry plasticiser in analyzing wine are had the following advantages: it is easy to carry that whole instrument total amount is less than 15kg, instrument independent operating, is applicable to on-the-spot use; Measuring speed is fast, is generally less than 10 seconds analysis time; Very low to sample pre-treatments requirement, be applicable to very much on-site quick screening; The operating cost of instrument is very low, and cost performance is high, and analysis speed is faster more than 10 times than HPLC-UV and GC-MS etc., is more suitable for the analysis of batch sample; Can realize polycomponent on-line analysis simultaneously, can greatly reduce inspection and drop into.
Brief description of the drawings
Fig. 1 is the ion mobility spectrometry structural principle schematic diagram that detects plasticiser in wine;
Fig. 2 is the ion mobility spectrometry figure that detects 20mg/kg, 10 μ LDBP standard models with ion mobility spectrometry;
Fig. 3 is the canonical plotting that detects DBP standard model with ion mobility spectrometry;
Fig. 4 (a) is the ion mobility spectrometry figure that detects wine sample 1 with ion mobility spectrometry;
Fig. 4 (b) is the ion mobility spectrometry figure that detects wine sample 2 with ion mobility spectrometry.
Embodiment
Described ionic migration spectrometer: taking ionization source as radioactivity
63ni source, ultraviolet light ionization source and discharge ionization source.Ionic migration spectrometer adopts traditional uniform field migration spectrum, and its structural representation is as Fig. 1.This instrument mainly comprises following components: sampling device 1, ionization source 2, reaction zone 3, ion gate 4, migration tube 5, make-up gas 6 and signal receive and detection system 7,8,9,10.Wherein, 7 is Faraday cylinder, and 8 is amplifier, and 9 is A/D converter, and 10 is data handling system, and 11 is pressurized air.Sampling device is mainly made up of hot parser, sample introduction thin slice and carrier gas transfer pipeline, wherein hot parser is mainly made up of injection port, heating rod and temperature controller, sample introduction thin slice can be metal grid mesh or polytetrafluoro sheet, and carrier gas transfer pipeline is made up of four fluorine tube or metal tube and flowmeter.
The detection of the method is limited to 3 times of 0.1mg/kg(noise signal intensity and is defined as minimum detectable level);
Fig. 2-4 provided some experiment spectrograms to the present invention give with explanation.The experiment condition of these spectrograms is: when experiment, migration tube temperature is maintained at about 100 DEG C, and injector temperature remains on 180 DEG C.
In order to realize quick, the Sensitive Detection of plasticiser in wine, the present invention uses ion mobility spectrometry as analysis means;
Detailed process is as follows: get the wine liquid sample of 10 μ L, drop in sampling place on clean sample introduction thin slice, analyse well heater heating (40-80 DEG C) volatilize liquid component in wine sample, the then injection port of inserting instrument with pyrolysis.Sample is by a built-in hot parser fast vaporizing, and the temperature of hot parser is at 180 DEG C; The ionized region of ion mobility spectrometry is analysed the sample gas obtaining and is brought into by carrier gas in pyrolysis, and the flow of carrier gas is in 400sccm left and right; Sample is ionized to negative ions in ionized region, and the ion gate of opening by periodicity enters the drift region being made up of uniform electric field, obtains separating and detect in drift region.The mobility constant of different compounds is variant, the speed difference moving in drift region, the asynchronism(-nization) of their arrival detecting devices.Measure time and peak intensity that ion arrives detector, just can confirm the kind of plasticiser, and determine its concentration in conjunction with graticule equation.
Special the pointing out of the present invention's palpus: all tests must complete in glass apparatus.
Embodiment 1
The DBP standard model of getting 20mg/kg, 10 μ L, drops in sampling place on clean sample introduction thin slice, analyses well heater heating (70 DEG C) volatilize liquid component, the then injection port of inserting instrument with pyrolysis.As shown in Figure 2, the quasi-molecular ions of reagent is at about 5.4ms for testing result, and the characteristic peak of DBP standard items is at 7.56ms.
Embodiment 2
Get 0.1,0.5,1.25,5,7.5,10, the DBP standard model of 12.5mg/kg, 10 μ L, drop in sampling place on clean sample introduction thin slice, analyse well heater heating (70 DEG C) with pyrolysis and volatilize liquid component, then the injection port of inserting instrument detects and analyzes.Three tests repeat, and get its mean value and draw graticule equation; As shown in Figure 3, graticule equation is Y=22.94178+6.12287X to result.
Embodiment 3
Get all product of 10 μ L wine to be measured, drop in sampling place on clean sample introduction thin slice, analyse well heater heating (70 DEG C) with pyrolysis and volatilize liquid component, the then injection port of inserting instrument.Testing result, as Fig. 4 (a), Fig. 4 (b), is respectively the ion mobility spectrometry figure of ion mobility spectrometry detection wine sample 1 and 2; Wine sample 1DBP plasticiser concentration is 2mg/kg; Wine sample 2DBP plasticiser concentration is 17mg/kg.Test is taked to repeat for three times, gets its mean value as analysis result.
The present invention, taking Ion mobility spectrometry as basis, utilizes ion mobility spectrometry as analyzing and testing means.Wine sample, without complicated pre-treatment, only need be analysed well heater heating (40-80 DEG C) with self-control pyrolysis and volatilize liquid component in wine sample.The method detection speed is fast, and sample feeding is less than 10 seconds analysis time, and detection sensitivity is high, and detectability can reach 0.1mg/kg.This measuring method sample pre-treatments conditional request is low, easy and simple to handle, quick, and good reliability is applicable to plasticiser in wine sample to carry out qualitative and quantitative analysis.
Claims (7)
1. a method for plasticiser in express-analysis wine, is characterized in that:
1) standard detection: get the alcohol of plasticiser standard model of concentration 0.1-100mg/kg and/or aqueous solution, 5-50 μ L in clean sample introduction sheet surface sampling place, analyse well heater heating with pyrolysis and volatilize wherein liquid component, then analyse injector by ion mobility spectrometry pyrolysis and detect analysis; Obtain transit time and the signal peak strength value of the ion analysis detection of plasticiser standard model;
2) testing sample detects: get 5-50 μ L wine sample to be measured in clean sample introduction sheet surface sampling place, analyse well heater heating volatilize liquid component in wine sample with pyrolysis; Taking ionic migration spectrometer as detecting instrument, the pyrolysis of sample introduction thin slice insertion ion mobility spectrometry is analysed injector and is detected analysis; Obtain transit time and signal peak strength value that ion analysis detects;
3) by step 2) ion analysis of the plasticiser standard model that obtains of the transit time that obtains and signal peak strength value and the step 1) transit time and the contrast of signal peak strength value that detect;
Determine in wine sample to be measured whether contain the plasticiser described in plasticiser standard model according to transit time; If the plasticiser that contains plasticiser standard model, can determine its plasticiser kind, and then determine the content of plasticiser in wine sample to be measured according to corresponding signal peak strength.
2. method according to claim 1, is characterized in that: described plasticiser standard model is the plasticiser in national examination criteria, comprising: repefral (DMP); Diethyl phthalate (DEP); Dipropyl phthalate (DPRP); Phthalic acid fourth Bian ester (BBP); Diisobutyl phthalate (DIBP) or n-butyl phthalate (DBP); Diamyl phthalate (DPP); Dicyclohexyl phthalate (DCHP); Dihexylphthalate (DNP); Diphenyl phthalate (DPHP); Dioctyl adipate (DEHA); Diisooctyl phthalate (DIOP); Phthalic acid two (2-ethyl hexyl) ester (DEHP); Di-n-octyl phthalate (DNOP); Diisononyl phthalate (DINP) or dinonyl phthalate (DNP); One or two or more kinds mixing in the different certain herbaceous plants with big flowers ester of phthalic acid two (DIDP).
3. method according to claim 1, is characterized in that: the pyrolysis using in described test is analysed heter temperature and is chosen in adjusting between 40-80 DEG C, volatilizes liquid component, adopts 40-80 DEG C of low-temperature heat process to reduce plasticiser loss.
4. method according to claim 1, is characterized in that: described sample introduction thin slice is metal grid mesh, tetrafluoro plate or teflon high temperature cloth.
5. method according to claim 1, is characterized in that: in described test, to analyse injector be that injector is analysed in stepper motor pyrolysis, injector is analysed in solenoid valve pyrolysis or injector is analysed in Halogen lamp LED pyrolysis in pyrolysis.
6. method according to claim 1, is characterized in that: described ion mobility spectrometry is uniform field ion mobility spectrometry, and detecting pattern is positive ion high pressure mode.
7. method according to claim 1, it is characterized in that: described ion mobility spectrometry, mainly comprise sampling device, ionization source, reaction zone, ion gate, migration area, signal reception and detection system and gas circuit drying system, it is characterized in that: described sampling device is made up of injection port and the carrier gas transfer pipeline that is arranged at injection port outside, be externally connected with pyrolysis at injection port and analyse injector, pyrolysis eutectoid temperature, between 150-250 DEG C, is placed in injection port when described sample introduction thin slice sample introduction.
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| CN201310136590.6A CN104111281A (en) | 2013-04-18 | 2013-04-18 | Method for rapidly analyzing plasticizer in wine |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108918769A (en) * | 2018-05-18 | 2018-11-30 | 北京声迅电子股份有限公司 | A kind of hot volatilization device of trace measured object gas |
| CN110632164A (en) * | 2019-10-31 | 2019-12-31 | 大连大学 | Method for simultaneously detecting phthalate compounds in food |
| CN110646501A (en) * | 2019-10-31 | 2020-01-03 | 大连大学 | Method for detecting environmental hormone dimethyl phthalate |
| CN110907262A (en) * | 2019-12-18 | 2020-03-24 | 江苏恒顺醋业股份有限公司 | Pretreatment device and pretreatment method for detecting trimethylamine in vinegar grains |
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| CN101852767A (en) * | 2009-04-01 | 2010-10-06 | 中国科学院大连化学物理研究所 | Method for quickly detecting trace melamine |
| CN101852766A (en) * | 2009-04-01 | 2010-10-06 | 中国科学院大连化学物理研究所 | Method for detecting phthalate ester plasticizer in plastic |
| WO2011157781A1 (en) * | 2010-06-17 | 2011-12-22 | Step Sensortechnik Und Elektronik Pockau Gmbh | Method for ion mobility spectrometry |
| CN202837258U (en) * | 2012-09-10 | 2013-03-27 | 中国科学院大连化学物理研究所 | Combined type multifunctional sample injector used for ion mobility spectrometry |
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2013
- 2013-04-18 CN CN201310136590.6A patent/CN104111281A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101852767A (en) * | 2009-04-01 | 2010-10-06 | 中国科学院大连化学物理研究所 | Method for quickly detecting trace melamine |
| CN101852766A (en) * | 2009-04-01 | 2010-10-06 | 中国科学院大连化学物理研究所 | Method for detecting phthalate ester plasticizer in plastic |
| WO2011157781A1 (en) * | 2010-06-17 | 2011-12-22 | Step Sensortechnik Und Elektronik Pockau Gmbh | Method for ion mobility spectrometry |
| CN202837258U (en) * | 2012-09-10 | 2013-03-27 | 中国科学院大连化学物理研究所 | Combined type multifunctional sample injector used for ion mobility spectrometry |
Non-Patent Citations (1)
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108918769A (en) * | 2018-05-18 | 2018-11-30 | 北京声迅电子股份有限公司 | A kind of hot volatilization device of trace measured object gas |
| CN108918769B (en) * | 2018-05-18 | 2022-10-25 | 北京声迅电子股份有限公司 | Trace measured object gas heat volatilization device |
| CN110632164A (en) * | 2019-10-31 | 2019-12-31 | 大连大学 | Method for simultaneously detecting phthalate compounds in food |
| CN110646501A (en) * | 2019-10-31 | 2020-01-03 | 大连大学 | Method for detecting environmental hormone dimethyl phthalate |
| CN110907262A (en) * | 2019-12-18 | 2020-03-24 | 江苏恒顺醋业股份有限公司 | Pretreatment device and pretreatment method for detecting trimethylamine in vinegar grains |
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Application publication date: 20141022 |