CN101726533B - Rapid and sensitive method for detecting melamine - Google Patents

Rapid and sensitive method for detecting melamine Download PDF

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Publication number
CN101726533B
CN101726533B CN 200810228131 CN200810228131A CN101726533B CN 101726533 B CN101726533 B CN 101726533B CN 200810228131 CN200810228131 CN 200810228131 CN 200810228131 A CN200810228131 A CN 200810228131A CN 101726533 B CN101726533 B CN 101726533B
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China
Prior art keywords
melamine
sample
sample introduction
injection port
thin slice
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CN 200810228131
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Chinese (zh)
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CN101726533A (en
Inventor
李海洋
仓怀文
董璨
徐秀明
杜永斋
王贞鑫
鞠帮玉
王海龙
丛润滋
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中国科学院大连化学物理研究所
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Abstract

The invention discloses a new method for detecting melamine. Based on an ion mobility spectrometry technology, by using the ion mobility spectrometry as a detection means and combining a simple solvent extraction pretreatment method, the method has high detection speed and sensitivity and needs only 0.5 minute for analysis and less than 5 minutes for pretreatment; and the detection limit can reach 50ppb.

Description

A kind of method of quick, sensitive detection melamine
Technical field
The present invention relates to the melamine detection method, specifically a kind of method of quick, sensitive detection melamine newly, this method is the basis with the ion mobility spectrometry technology; Utilize ionic migration spectrometer as analysis means, utilize simple solvent extraction pretreatment technology, detection speed is fast; Only want 0.5 minute analysis time; Time for sample pretreatment is less than 5 minutes, and is highly sensitive, and detectability can reach 50ppb.
Background technology
Melamine (English name Melamine) is called for short triamine, is a kind of triazines nitrogen heterocyclic ring organic compound, important azacyclo-Organic Chemicals.Proterties is pure white monoclinic prism body, and is tasteless, density 1.573g/cm 3(16 ℃).354 ℃ of normal pressure fusing points (decomposition); The Fast Heating distillation, 300 ℃ of sublimation temperatures.Be dissolved in hot water, water-soluble 3G/L (20 & ordm; C), be slightly soluble in cold water, the atomic hot ethanol that is dissolved in is insoluble to ether, benzene and phenixin, dissolves in methyl alcohol, formaldehyde, acetate, hot monoethylene glycol, glycerine, pyridine etc.Low toxicity.More stable in the ordinary course of things, emit prussiate but at high temperature may decompose.
Melamine is a kind of broad-spectrum basic organic chemical industry's intermediate product, and topmost purposes is as the raw material of producing melamine formaldehyde resin (MF).Melamine can also be made fire retardant, water reducer, formaldehyde detersive etc.This resin hardness ratio Lauxite is high; Nonflammable; Water-fast, heat-resisting, ageing-resistant, anti-electric arc, resistance to chemical attack, good insulation performance performance, glossiness and physical strength are arranged, extensively apply to industries such as timber, plastics, coating, papermaking, weaving, leather, electric, medicine.
Melamine is a kind of industrial chemicals of low toxicity.Zoopery is the result show, its in animal body metabolism can retain very soon and not, mainly influence urinary system.In recent years, because the defective of food and feed industry protein content method of testing, melamine often is used as food additives by illegal businessman, and with the protein content index in the lifting food inspection, so melamine also is " extract of protein " by person.2007, the contaminated incident of U.S.'s outburst pet food.Post-survey shows: mixed≤gluten powder of 6.6% melamine is that pet food causes the reason of poisoning.In September, 2008, the contaminated incident of China's outburst Sanlu baby milk powder, the infant who has caused eating contaminated milk powder produces the kidney stone illness, and its reason also is to contain melamine in the milk powder.State General Administration for Quality Supervision has promptly carried out the special examination of baby milk powder content of melamine recently in the whole nation.Special examination is this time investigated all the other 109 tame enterprises, has checked 491 batch products of these enterprises altogether.Interim check result shows, has 69 batch products of 22 tame baby milk powder manufacturing enterprises to detect the different melamine of content.Therefore quick, the sensitive detection of melamine is extremely urgent.
The method of existing detection melamine mainly comprises LC/MS, SPE and high performance liquid chromatography coupling method, high performance liquid chromatography-diode array etc.These methods need loaded down with trivial details sample pre-treatments program, waste time and energy, and can not realize express-analysis, and detection sensitivity not high enough (2
The ppm magnitude).In the last few years, ion mobility spectrometry was because advantage such as its high sensitivity, express-analysis, portability and be used to the on-line analysis of industry and environment more and more.Therefore, the present invention just is used for melamine detection with ion mobility spectrometry, and detection speed is fast, and is highly sensitive.
Summary of the invention
The purpose of this invention is to provide a kind of method of new detection melamine, this method detection speed is fast, and only want 0.5 minute analysis time, and time for sample pretreatment is less than 5 minutes, and is highly sensitive, and detectability can reach 50ppb.
In order to realize quick, the sensitive detection of melamine, the present invention is the basis with the ion migrating technology, utilizes ionic migration spectrometer as analysis means, utilizes the solvent extraction method pretreatment technology, and detection speed is fast, and is highly sensitive.
A kind of method that detects melamine fast, delicately,
1) solvent extraction: testing sample is dissolved in the organic solvent, leaves standstill and get supernatant and supply to detect, or with the filtering with microporous membrane in following the aperture of 0.1~5 μ m, filtrating is as sample solution confession detection as sample solution;
2) sample solution of extraction 20-50mL drops on the sample introduction thin slice, utilizes ionic migration spectrometer to detect, and measures time and peak intensity that ion arrives the ionic migration spectrometer detector;
3) melamine is dissolved in the organic solvent; Melamine solution with the 0.1-10ppm standard is the standard sample solution; Extract the standard sample solution of 20-50mL, drop on the sample introduction thin slice, with step 2) under the identical condition; Utilize ionic migration spectrometer to detect, measure the reagent ion peak position that ion arrives the ionic migration spectrometer detector;
4) confirm step 2 through reagent ion peak position that step 3) obtained) peak intensity of the melamine among the result that obtains, further just can confirm the content of melamine.
The usage ratio of said testing sample and organic solvent is 1:100~4:5; Said organic solvent is for dissolving organism methyl alcohol, formaldehyde, acetate, hot monoethylene glycol, glycerine and/or the pyridine of melamine; Said sample introduction thin slice is metal grid mesh, gather tetrafluoro sheet or sample introduction paper.
Said ionic migration spectrometer is traditional uniform field migration spectrum; Mainly comprise sampling device, ionization source, reaction zone, ion gate, migration area, signal reception and detection system and gas circuit drying system; Said sampling device is made up of injection port and the carrier gas transfer pipeline that is arranged at the injection port outside; Around the outside of injection port, be provided with hot parser; The hot parser inboard is provided with heating rod or heating tape, is inserted in the injection port during said sample introduction thin slice sample introduction.
The inboard of said hot parser is provided with temperature controller, and it is connected with heating rod or heating tape circuit; Said carrier gas transfer pipeline is processed by four fluorine tube or metal tube, and the carrier gas transfer pipeline is provided with flowmeter.
Advantage of the present invention is following:
Compare with traditional gas chromatography, liquid phase chromatogram-mass spectrometry combination method; The means of ion mobility spectrometry as analyzing melamine are had the following advantages: the whole instrument total amount is easy to carry less than 15kg; The instrument independent operating; Do not need computer and external source of the gas and liquid, be fit to on-the-spot the use, the instrument advantages of small volume is portable; Measuring amount speed is fast, is generally less than 0.5 minute analysis time; Sample pre-treatments is required very low, the equipment that pre-treatment needs and time few (pre-service averaging time less than 8 minutes), be fit to very much the on-site quick screening of each flow process of dairy produce production; The operating cost of instrument is very low, and consumables mainly are the required organic solvents of pre-treatment, measures the solvent that single sample consumes 25mL approximately, and its cost is lower than 1 yuan; The cost performance of instrument is high, and analysis speed is more suitable for the analysis of sample in batches than fast 10 times of HPLC-UV and GC-MS etc.
Description of drawings
Below in conjunction with accompanying drawing and embodiment the present invention is done further detailed explanation:
Fig. 1 measures the ion mobility spectrometry structural representation of melamine.
Fig. 1 a sampling device structural representation;
Fig. 2 detects the migration spectrogram of pure article melamine with ion mobility spectrometry.
Fig. 3 detects the migration spectrogram of milk sample with ion mobility spectrometry.
Fig. 4 detects the migration spectrogram of powdered milk sample with ion mobility spectrometry.
Embodiment
In order to realize quick, the sensitive detection of melamine, the present invention with ion mobility spectrometry as analysis means and the coupling of this simple sample pre-treatments technology of solvent extraction.
Ionic migration spectrometer adopts traditional uniform field migration spectrum, and its structural representation is seen 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.Wherein, 8 is Faraday cylinder, and 9 is amplifier, and 10 is A/D converter, and 11 is pressurized air, and 12 is data handling system (like oscillograph).
As shown in Figure 2; Said sampling device is made up of injection port 16 and the carrier gas transfer pipeline 15 that is arranged at the injection port outside; Around the outside of injection port, be provided with hot parser 13; Hot parser 13 inboards are provided with sample introduction thin slice 14 and heating rod or heating tape 17, place injection port 16 places during said sample introduction thin slice 14 sample introductions, and the carrier gas of carrier gas transfer pipeline 15 outlets purges on sample introduction thin slice 14.
The inboard of said hot parser 13 is provided with temperature controller 18, and it is connected with heating rod or heating tape circuit; Said sample introduction thin slice is metal grid mesh, gather tetrafluoro sheet and/or sample introduction paper; Said carrier gas transfer pipeline is processed by four fluorine tube or metal tube 19, and the carrier gas transfer pipeline is provided with flowmeter 20;
Utilize the process of this instrument detecting melamine following: to extract the organic solvent extraction milk of 20-50mL and the supernatant after the milk powder, drop on the sample introduction paper, insert the injection port 16 of instrument then.The sample that contains melamine is vaporized by a built-in hot parser 13 fast, and the temperature of hot parser is by temperature controller 18 controls, about 200 ℃; Pyrolysis is analysed the sample gas that obtains and is got into the general ionized region 2 of ion migration by the carrier gas carrier band of being carried by carrier gas transfer pipeline 15, and the flow of carrier gas is by flowmeter 18 controls, about 300sccm; Sample is ionized to negative ions at ionized region, and the ion gate 4 through the cycle opens gets into the drift region 5 that is made up of uniform electric field, obtains in the drift region separating and detects.The mobility constant of different compounds is variant, and the speed that moves in the drift region is different, and they arrive the asynchronism(-nization) of detecting device.Measure time and peak intensity that ion arrives detector, just can confirm classes of compounds, and measure its content.
This method requires low to sample pre-treatments, as long as with organic solvent extraction, concrete steps are following: take by weighing the volumetric flask that milk powder or fresh milk 0.5g place 25mL, and with analytically pure organic solvent constant volume, ultrasonic 2 minutes, with the organic membrane filtration of 0.45m.Wherein organic solvent comprises methyl alcohol, formaldehyde, acetate, hot monoethylene glycol, glycerine and pyridine etc. for dissolving the compound of melamine.
Fig. 2-4 has provided some experiment spectrograms the present invention has been given and explanation.The experiment condition of these spectrograms is: migration tube length is 6.6cm, and migration electric field intensity is 500V/cm, and the ion gate time of opening the door is 0.2ms; Cycle is 40ms; Float gas and the sample carrier gas is the pressurized air through silica gel and charcoal treatment, float gas velocity 400sccm, flow rate of carrier gas 300sccm; The migration tube temperature remains on about 130 ℃ during experiment, and the injector temperature remains on about 200 ℃.
Embodiment 1
Fig. 2 has provided the migration spectrogram that detects pure article melamine with ion mobility spectrometry, and as can be seen from the figure, melamine is well detected, and the reagent ion peak is at 4.34ms, and the characteristic peak of melamine is at 8.48ms.
Embodiment 2
What Fig. 3 provided is the migration spectrogram that detects milk sample with ion mobility spectrometry.Can find out that from the comparison of two figure (Fig. 2 and 3) this method can detect the melamine in the milk sample delicately.
Embodiment 3
What Fig. 4 provided is the migration spectrogram that detects powdered milk sample with ion mobility spectrometry.Can find out that from the comparison of two figure (Fig. 2 and 4) this method also can detect the melamine in the milk sample delicately.

Claims (5)

1. method that detects melamine fast, delicately is characterized in that:
1) solvent extraction: testing sample is dissolved in the organic solvent, leaves standstill and get supernatant as sample solution confession detection;
2) sample solution of extraction 20-50mL drops on the sample introduction thin slice, utilizes ionic migration spectrometer to detect, and measures time and peak intensity that ion arrives the ionic migration spectrometer detector;
3) melamine is dissolved in the organic solvent; Melamine solution with the 0.1-10ppm standard is the standard sample solution; Extract the standard sample solution of 20-50mL, drop on the sample introduction thin slice, with step 2) under the identical condition; Utilize ionic migration spectrometer to detect, measure the reagent ion peak position that ion arrives the ionic migration spectrometer detector;
4) confirm step 2 through reagent ion peak position that step 3) obtained) peak intensity of the melamine among the result that obtains, further just can confirm the content of melamine;
Said organic solvent is for dissolving organism methyl alcohol, formaldehyde, acetate, hot monoethylene glycol, glycerine and/or the pyridine of melamine.
2. method according to claim 1 is characterized in that: the usage ratio of said testing sample and organic solvent is 1: 100~4: 5.
3. method according to claim 1 is characterized in that: said sample introduction thin slice is metal grid mesh, gather tetrafluoro sheet or sample introduction paper.
4. method according to claim 1, said ionic migration spectrometer are traditional uniform field migration spectrum; 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: said sampling device is made up of injection port and the carrier gas transfer pipeline that is arranged at the injection port outside; Around the outside of injection port, be provided with hot parser; The hot parser inboard is provided with heating rod or heating tape, places injection port during said sample introduction thin slice sample introduction.
5. method according to claim 4 is characterized in that: the inboard of said hot parser is provided with temperature controller, and it is connected with heating rod or heating tape circuit; Said carrier gas transfer pipeline is processed by four fluorine tube or metal tube, and the carrier gas transfer pipeline is provided with flowmeter.
CN 200810228131 2008-10-17 2008-10-17 Rapid and sensitive method for detecting melamine CN101726533B (en)

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CN102323329A (en) * 2011-07-15 2012-01-18 武汉矽感科技有限公司 Method for acquiring sample molecules in object to be detected and sample introduction mechanism of ion migration spectrometer
CN103134848A (en) * 2011-12-01 2013-06-05 中国科学院大连化学物理研究所 Qualitative and semi-quantitative analysis method for sample detection by ion mobility spectrometry
CN103512949A (en) * 2012-06-29 2014-01-15 中国科学院大连化学物理研究所 Method for detecting bisphenol A in plastic product
CN103675080A (en) * 2012-09-13 2014-03-26 中国科学院大连化学物理研究所 Headspace sampler and ion mobility spectrometry combined system
CN104111284A (en) * 2013-04-18 2014-10-22 中国科学院大连化学物理研究所 Method for rapidly sensitively detecting sodium valproate in blood
CN103499633B (en) * 2013-10-15 2015-10-21 无锡艾科瑞思产品设计与研究有限公司 Based on the method for quick of melamine in the milk powder of saturated milk solution
CN105510113A (en) * 2014-09-25 2016-04-20 中国科学院大连化学物理研究所 Method for improving thermal desorption efficiency of to-be-detected sample
CN105738459B (en) * 2014-12-08 2019-09-06 中国科学院大连化学物理研究所 A kind of method of sodium vedproate detection sensitivity in raising blood
CN106198702B (en) * 2015-05-06 2019-01-25 中国科学院大连化学物理研究所 A kind of method of drugs in quick detection saliva

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