CN102680590A - Two-dimensional liquid chromatogram (LC)-tandem mass spectrometry method for detecting four amine substances in water - Google Patents
Two-dimensional liquid chromatogram (LC)-tandem mass spectrometry method for detecting four amine substances in water Download PDFInfo
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Abstract
The invention discloses a two-dimensional LC-tandem mass spectrometry method for detecting four amine substances in water. The method comprises the following steps: (1) installing detecting devices, installing a common C18 chromatographic column in a column temperature tank of an ultrahigh performance liquid chromatography (UPLC), connecting a hydrophilic interaction chromatography (HILIC) column in series at the back of the C18 chromatographic column, and the outlet of the HILIC column is connected with the sample inlet of a tandem mass spectrometer; (2) preprocessing obtained water samples; and (3) analyzing and detecting the processed water samples through the detecting devices. The two-dimensional LC-tandem mass spectrometry method for detecting the four amine substances in the water has the advantages that the joint detection of the four amine substances is achieved through connection of the two chromatographic columns with different properties in series, the detection sensitivity is high, the analysis speed is high, the selectivity of the method is high, the pollution is small, the operation is simple, and the like.
Description
Technical field
The present invention relates in the water detection method that four kinds of amine substances comprise acrylic amide, caprolactam, biphenylamine and aniline, specifically be used for detecting the two-dimensional liquid chromatography-tandem mass spectrum method of four kinds of amines of water.
Background technology
Four kinds of amine substances that this method relates to comprise acrylic amide, caprolactam, biphenylamine and aniline, and wherein acrylic amide is the emphasis of food security area research in recent years.In the starch food products of fried and barbecue, can produce the acrylic amide with potential neurotoxicity, genetoxic and carcinogenicity, this makes the FAO (Food and Agriculture Organization of the United Nation) (FAO) and the combination food adjuvant Committee of Experts of The World Health Organization (WHO) (JECFA) carry out the risk assessment of system to the acrylic amide in the food; Acrylic amide is very big as the raw material production amount of producing polyacrylamide simultaneously, and only the city annual production in Ningbo is promptly above 120,000 tons.Caprolactam is a main raw material of producing polyamide, is mainly used in synthetic plastic, film and electronic industry and field of vehicles, and world's annual production in 2004 is promptly above 4,000,000 tons.Aniline and biphenylamine belong to the aromatic amine material; It is the primary raw material of producing many chemicals such as dyestuff, polymkeric substance, rubber, pesticide, cosmetics, medicine; Though the Direct Production and the use of aromatic amine are limited, in the production run of above-mentioned chemicals, still there is a large amount of aromatic amines to be created as accessory substance.Amine substance possibly be discharged in the environment in the production of chemicals, use, thereby forms an important pollutant in the environment.Amine substance is owing to having stronger polarity, and is very easily water-soluble like acrylic amide, caprolactam etc., tends to cause surface water, phreatic pollution in case be discharged in the environment through migration.The acute toxicity and the biologically active of amine substance are stronger, and aromatic amine and acrylic amide etc. have extremely strong carcinogenicity.
Because the huge use amount and the toxic hazard thereof of amine substance, countries in the world comprise China, the U.S. etc. and all it are classified as the pollutant scope of routine monitoring and preferential monitoring.Amine analytical approach commonly used at present is a vapor-phase chromatography, as the middle liquid-liquid extraction of stipulating of China's " drinking water standard method of inspection "-the gaschromatographic mass spectrometry method detects biphenylamine, derivatization liquid-liquid extraction-vapor-phase chromatography detects acrylic amide etc.These methods need complicated pretreatment technology, and can't directly detect and need to increase the derivatization process for acrylic amide, caprolactam gas chromatography.The instrument detecting aspect; Every kind of pollutant all needs independently a kind of detection method, and for same testing sample, four kinds of amine substances promptly need four kinds of detection methods; Carrying out 4 different pretreatment processes, all is huge wastes for costs such as reagent, time, manpowers.
In addition; Up to the present still do not utilize liquid chromatography-tandem mass spectrometry to detect the method for multiple amine substance in the water simultaneously, main cause is: at first, amine substance has extremely strong polarity; Though in common C18 chromatographic column, can realize the separation of four kinds of amine substances; But each material peak shape is relatively poor, even hangover or bimodal phenomenon occur, therefore is difficult to realize effective reservation; In hydrophilic Interaction Chromatography (HILIC); Amine substance can keep good peak shape, but because four kinds of amine substance character are close, almost goes out the peak at one time; Serious competition ionization phenomena appears in the meeting of ionization simultaneously in the mass spectrum ionization source, thereby can't carry out simultaneously quantitatively a plurality of materials.
Summary of the invention
Technical matters to be solved by this invention is to above-mentioned technical barrier; Be provided for detecting the two-dimensional liquid chromatography-tandem mass spectrum method of four kinds of amines in the water; In Ultra Performance Liquid Chromatography-use the mode of two kinds of chromatographic columns series connection of different nature to detect four kinds of amine substances simultaneously in the tandem mass spectrum technology; Solve the problem that amine substance can't keep on the one hand in common C18 chromatographic column, solve the problem that amine substance can't separate on the other hand in hydrophilic Interaction Chromatography (HILIC) post.The present invention both can realize the joint-detection of four kinds of amine substances, had characteristics such as highly sensitive, that analysis speed fast, the method selectivity is strong, simple to operate again, had practiced thrift costs such as reagent, time, manpower greatly.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: be used for detecting the two-dimensional liquid chromatography-tandem mass spectrum method of four kinds of amines of water, may further comprise the steps:
Step 1, installation and measuring equipment: a common anti-phase C18 chromatographic column is installed in the column oven of Ultra Performance Liquid Chromatography appearance, and a hydrophilic Interaction Chromatography (HILIC) post of connecting thereafter, outlet connects the injection port of tandem mass spectrometer;
Step 2, the water sample of gained is carried out pre-treatment;
Step 3, the water sample of handling well is carried out assay determination through above-mentioned checkout equipment.
For optimizing technique scheme, the measure of taking also comprises:
Above-mentioned tandem mass spectrum instrument is the triple level Four bar of a Waters Quattro Premier XE tandem mass spectrometer, and used Ultra Performance Liquid Chromatography is a Waters Acquity UPLC system.
In the above-mentioned step 1, the common C18 chromatographic column of using is Acquity UPLC BEH C18 chromatographic column, and the hydrophilic Interaction Chromatography of using (HILIC) post is Acquity UPLC BEH HILIC chromatographic column.Common C18 chromatographic column chromatographic column is installed in the column oven that the Ultra Performance Liquid Chromatography appearance carries; The hydrophilic Interaction Chromatography post that is in series is installed in independently in the column oven, and with the stainless steel guide pillar endpiece of hydrophilic Interaction Chromatography post and the injection port of tandem mass spectrometer is connected to a fixed.
In the above-mentioned step 2, pre-treatment comprises with disposable needle injector gets the 1mL water sample, gets in the brown liquid phase sample introduction bottle after filtering with 0.2 μ m water pin type filter, to be analyzed.
The service condition of above-mentioned liquid chromatography instrument is: column temperature: 40 ℃; Moving phase: methyl alcohol/0.1% aqueous formic acid, be initially 50:50, to 90:10, continue to 1.5 minutes through linear gradient 1.1 minutes, again through linear gradient 4 minutes to 50:50, continue to 6 minutes, single injected sampling finishes; Flow velocity: 0.18mL/min; Sample size: 5 μ L.
The service condition of above-mentioned tandem mass spectrum instrument is: ion gun: electron spray ionisation ESI; Scan mode: positive ion scanning; Detection mode: many reaction detection; Capillary voltage: 3.0Kv; Taper hole voltage: aniline is 50v, and acrylic amide is 25v, and caprolactam is 35V, and biphenylamine is 60V; Source temperature: 100 ℃; The temperature of desolvating: 400 ℃; Flow velocity desolvates: 700L/hr; Taper hole gas velocity: 50L/hr; Collision energy: aniline is 17ev, and acrylic amide is 10ev, and caprolactam is 17ev, and biphenylamine is 26ev; Residence time: 0.2s; Ion channel: aniline is 94>77, and acrylic amide is 72>55, and caprolactam is 113.5>69, and biphenylamine is 185>167.
Compared with prior art, the two-dimensional liquid chromatography-tandem mass spectrum method that is used for detecting four kinds of amines of water of the present invention has the following advantages:
1, compares with the method for the gas chromatographic detection amine of stipulating in the national standard method; This method need not to use complicated and unmanageable derivatization technology; Need not pre-treatment flow process through labor reagent, time, manpower, thereby environmental protection more, economy.Simultaneously, thus owing to use the sensitivity of tandem mass spectrum technology method higher, selectivity is better.
2, compare with external each liquid matter method that detects a kind of amine substance, this method detects four kinds of amine substances simultaneously, has realized the integration utilization of resource, has realized the cost compression on reagent, time, the manpower.
3, the initiative use of this method the methods of two kinds of heterogeneity chromatographic column series connection; In fact used simple two-dimensional liquid chromatography principle; First root chromatogram column is used for the separation of amine substance; Second root chromatogram column is applied to the reservation enrichment of amine substance, thus the separation of the very close amine substance of the multiple character that has realized on common liquid-phase chromatographic column, can't keeping.
4, highly sensitive, the good reproducibility of this method, the recovery are high, satisfy the Quality Control requirement of trace analysis fully.The method detectability of four kinds of amine substances is respectively acrylic amide: 1.0ng/mL; Caprolactam: 5.0ng/mL; Biphenylamine: 0.5 ng/mL; Aniline: 0.1 ng/mL.The actual water sample of four kinds of amine substances and 7 replication relative standard deviations of actual mark-on water sample are in 2.66～7.60%, and recovery of standard addition is between 87.0～94.8%.
Description of drawings
Fig. 1 detects the actual chromatogram of four kinds of amine substances simultaneously for using self-control two-dimensional liquid chromatography-tandem mass spectrum technology;
Fig. 2 is the typical curve that four kinds of amine substances obtain through instrumental analysis;
Fig. 3 is the self-control rough schematic that two-dimensional liquid chromatography-the tandem mass spectrum technical point leaves.
Embodiment
Below in conjunction with accompanying drawing embodiments of the invention are described in further detail.
Fig. 1 is extremely shown in Figure 3 to be detection synoptic diagram of the present invention.
Fig. 1 detects the actual chromatogram of four kinds of amine substances simultaneously for using self-control two-dimensional liquid chromatography-tandem mass spectrum technology.Visible by figure, under the situation of using two kinds of chromatographic column series connection, four kinds of amine substances have obtained separating preferably in chromatogram, can satisfy the needs of actual detected.
Fig. 2 is the typical curve that four kinds of amine substances of 5 concentration of 5 μ g/L, 10 μ g/L, 20 μ g/L, 50 μ g/L, 100 μ g/L pass through instrumental analysis.Visible by figure, the typical curve that uses this method to obtain is linear good.
Fig. 3 is self-control rough schematic that two-dimensional liquid chromatography-the tandem mass spectrum technical point leaves, has illustrated the instrument connected mode of detection technique.
Detecting instrument: the Ultra Performance Liquid Chromatography instrument that uses in this experiment is Acquity UPLC system, and the tandem mass spectrum instrument that uses is the triple level Four bar of Quattro Premier XE tandem mass spectrum.
The present invention is used for detecting the two-dimensional liquid chromatography-tandem mass spectrum method of four kinds of amines of water, may further comprise the steps:
Step 1, installation and measuring equipment: a common anti-phase C18 chromatographic column is installed in the column oven of Ultra Performance Liquid Chromatography appearance, and the hydrophilic Interaction Chromatography post of connecting thereafter, the outlet of hydrophilic Interaction Chromatography post connects the injection port of tandem mass spectrometer;
Step 2, the water sample of gained is carried out pre-treatment;
Step 3, the water sample of handling well is carried out assay determination through above-mentioned checkout equipment.
For optimizing technique scheme, the measure of taking also comprises:
Above-mentioned tandem mass spectrum instrument is the triple level Four bar of a Waters Quattro Premier XE tandem mass spectrometer.
In the above-mentioned step 1, a common anti-phase C18 chromatographic column is installed in the column oven of Ultra Performance Liquid Chromatography appearance, and a hydrophilic Interaction Chromatography (HILIC) post of connecting thereafter, outlet connects the injection port of tandem mass spectrometer.
In the above-mentioned step 2, pre-treatment comprises with disposable needle injector gets the 1mL water sample, gets in the brown liquid phase sample introduction bottle after filtering with 0.2 μ m water pin type filter, to be analyzed.
The service condition of above-mentioned liquid chromatography instrument is: column temperature: 40 ℃; Moving phase condition such as table 1: methyl alcohol/0.1% aqueous formic acid, be initially 50:50, to 90:10, continue to 1.5 minutes through linear gradient 1.1 minutes, again through linear gradient 4 minutes to 50:50, continue to 6 minutes, single injected sampling finishes; Flow velocity: 0.18mL/min; Sample size: 5 μ L.
The service condition of above-mentioned tandem mass spectrum instrument is: ion gun: electron spray ionisation ESI; Scan mode: positive ion scanning; Detection mode: many reaction detection; Capillary voltage: 3.0Kv; Taper hole voltage: aniline is 50v, and acrylic amide is 25v, and caprolactam is 35V, and biphenylamine is 60V; Source temperature: 100 ℃; The temperature of desolvating: 400 ℃; Flow velocity desolvates: 700L/hr; Taper hole gas velocity: 50L/hr; Collision energy: aniline is 17ev, and acrylic amide is 10ev, and caprolactam is 17ev, and biphenylamine is 26ev; Residence time: 0.2s; Ion channel: aniline is 94>77, and acrylic amide is 72>55, and caprolactam is 113.5>69, and biphenylamine is 185>167.
The present invention is used for detecting the two-dimensional liquid chromatography-tandem mass spectrum method of four kinds of amines of water owing to used tandem mass spectrum as detecting device, on selective power, is greatly improved, and is suitable for the joint-detection of multiple pollutant.And because its high sensitivity, for cleaning water samples such as surface water, underground water, using very usually, simple filtering step gets final product direct injected.One aspect of the present invention has solved the problem that amine substance can't keep in common C18 chromatographic column, solved the problem that amine substance can't separate in the hydrophilic Interaction Chromatography post on the other hand.The present invention both can realize the joint-detection of four kinds of amine substances, had characteristics such as highly sensitive, that analysis speed fast, the method selectivity is strong, simple to operate again, had practiced thrift costs such as reagent, time, manpower greatly.
Table 1 eluent gradient
| Time (min) | A% (methyl alcohol) | B% (0.1% aqueous formic acid) | Curve |
| initial | 50 | 50 | initial |
| 1.1 | 90 | 10 | 6 |
| 1.5 | 90 | 10 | 1 |
| 4 | 50 | 50 | 6 |
| 6 | 50 | 50 | 1 |
The service condition of tandem mass spectrum instrument is in the above-mentioned steps 3: ion gun: electron spray ionisation ESI; Scan mode: positive ion scanning; Detection mode: many reaction detection; Actual conditions is seen table 2, table 3.
Table 2 mass spectrum condition
| The mass spectrum parameter | Optimal value |
| Capillary voltage (V) | 3.0 |
| The source temperature (℃) | 100 |
| Desorption temperature degree (℃) | 400 |
| Desorption gas velocity (L/h) | 700 |
| Taper hole gas velocity (L/h) | 50 |
| Collision gas velocity (mL/min) | 0.8 |
Table 3 quality analysis parameter
| Title | Taper hole voltage (V) | Collision energy (eV) | The residence time (S) | Parent ion/daughter ion |
| Biphenylamine | 60 | 26 | 0.2 | 185>;167 |
| Aniline | 50 | 17 | 0.2 | 94>;77 |
| Acrylic amide | 25 | 10 | 0.2 | 72>;55 |
| Caprolactam | 35 | 17 | 0.2 | 113.5>;69 |
Result of calculation, quantitative with the external standard curve method, on typical curve, directly find the concentration of amine substance in the water sample according to the peak area response of quota ion.Computing formula is following:
C=(A—b)/a (1)
Wherein: the concentration of C-amine substance, μ g/L;
The peak area of A-quota ion;
The intercept of b-typical curve;
The slope of a-typical curve.
Embodiment 1:
Typical curve is drawn:
Amine storing solution with 5:5 methanol solvent standard configuration 1.0 μ g/mL is subsequent use.Four kinds of amine substance standard solution that dispose 5 concentration of 5 μ g/L, 10 μ g/L, 20 μ g/L, 50 μ g/L, 100 μ g/L with 5:5 methanol solvent then carry out typical curve to be drawn, and the result is following.
Table 4 standard curve determination result
| Sequence number | The compound title | Regression equation | Related coefficient |
| 1 | Biphenylamine | Y=261.27X+623.67 | 0.9999 |
| 2 | Aniline | Y=559.9X+4654.2 | 0.9993 |
| 3 | Acrylic amide | Y=7.28X+0.1889 | 0.9994 |
| 4 | Caprolactam | Y=4.38X-17.51 | 0.9997 |
Embodiment 2:
Detection of amines in the surface water:
Get the actual surface water sample and suck about 1 mL with disposable needle injector, it is to be measured directly to inject brown liquid phase sample introduction bottle through the water pin type filter filtration back of 0.2 μ m, 7 parts of replicate determinations.Equally, other gets 7 parts of same actual water sample, and adding 10 μ L concentration respectively is the amine standard solution of 5mg/L, is settled to 1mL with actual water sample, does the mark-on recovery test.
Through Ultra Performance Liquid Chromatography-tandem mass spectrum analysis, condition determination such as method are said with testing sample.In the actual surface water sample, do not detect amine substance, the precision and the recovery of mark-on sample are seen table 5.
Table 5 actual surface water mark-on sample precision and determination of recovery rates result
From table, can know that the average recovery rate scope is 87.0-94.8%, the relative standard deviation scope is 2.66-7.60%, all can satisfy the requirement of actual detected.
Most preferred embodiment of the present invention is illustrated, and various variations or the remodeling made by those of ordinary skills can not depart from the scope of the present invention.
Claims (6)
1. be used for detecting the two-dimensional liquid chromatography-tandem mass spectrum method of four kinds of amines of water, it is characterized in that: may further comprise the steps:
Step 1, installation and measuring equipment: a common C18 chromatographic column is installed in the column oven of Ultra Performance Liquid Chromatography appearance, and the hydrophilic Interaction Chromatography post of connecting thereafter, the outlet of hydrophilic Interaction Chromatography post connects the injection port of tandem mass spectrometer;
Step 2, the water sample of gained is carried out pre-treatment;
Step 3, the water sample of handling well is carried out assay determination through above-mentioned checkout equipment.
2. two-dimensional liquid chromatography-tandem mass spectrum the method that is used for detecting four kinds of amines of water according to claim 1; It is characterized in that: described tandem mass spectrum instrument is the triple level Four bar of a Quattro Premier XE tandem mass spectrometer, and used Ultra Performance Liquid Chromatography is a Waters Acquity UPLC system.
3. two-dimensional liquid chromatography-tandem mass spectrum the method that is used for detecting four kinds of amines of water according to claim 1 and 2; It is characterized in that: in the described step 1; Common C18 chromatographic column chromatographic column is installed in the column oven that the Ultra Performance Liquid Chromatography appearance carries; The hydrophilic Interaction Chromatography post that is in series is installed in independently in the column oven, and with the stainless steel guide pillar endpiece of hydrophilic Interaction Chromatography post and the injection port of tandem mass spectrometer is connected to a fixed.
4. two-dimensional liquid chromatography-tandem mass spectrum the method that is used for detecting four kinds of amines of water according to claim 3; It is characterized in that: in the described step 2; Pre-treatment comprises with disposable needle injector gets the 1mL water sample; With getting in the brown liquid phase sample introduction bottle after the filtration of 0.2 μ m water pin type filter, to be analyzed.
5. two-dimensional liquid chromatography-tandem mass spectrum the method that is used for detecting four kinds of amines of water according to claim 4, it is characterized in that: the service condition of described liquid chromatography instrument is: column temperature: 40 ℃; Moving phase: methyl alcohol/0.1% aqueous formic acid, be initially 50:50, to 90:10, continue to 1.5 minutes through linear gradient 1.1 minutes, again through linear gradient 4 minutes to 50:50, continue to 6 minutes, single injected sampling finishes; Flow velocity: 0.18mL/min; Sample size: 5 μ L.
6. two-dimensional liquid chromatography-tandem mass spectrum the method that is used for detecting four kinds of amines of water according to claim 5, it is characterized in that: the service condition of described tandem mass spectrum instrument is: ion gun: electron spray ionisation (ESI); Scan mode: positive ion scanning; Detection mode: many reaction detection; Capillary voltage: 3.0Kv; Taper hole voltage: aniline is 50v, and acrylic amide is 25v, and caprolactam is 35V, and biphenylamine is 60V; Source temperature: 100 ℃; The temperature of desolvating: 400 ℃; Flow velocity desolvates: 700L/hr; Taper hole gas velocity: 50L/hr; Collision energy: aniline is 17ev, and acrylic amide is 10ev, and caprolactam is 17ev, and biphenylamine is 26ev; Residence time: 0.2s; Ion channel: aniline is 94>77, and acrylic amide is 72>55, and caprolactam is 113.5>69, and biphenylamine is 185>167.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107271578A (en) * | 2017-03-23 | 2017-10-20 | 浙江奇彩环境科技股份有限公司 | Method for amine substance content in determination sample |
| CN107894481A (en) * | 2018-01-11 | 2018-04-10 | 南通市食品药品监督检验中心 | A kind of method of caprolactam in ultra-performance liquid chromatography measure food contact material nylon 6 |
| CN113433241A (en) * | 2021-06-28 | 2021-09-24 | 江苏新锐环境监测有限公司 | Determination of benzidine in soil by ultrasonic extraction-high performance liquid chromatography |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101949900A (en) * | 2010-08-19 | 2011-01-19 | 中国烟草总公司郑州烟草研究院 | Comprehensive two-dimensional ultrahigh pressure high performance liquid chromatography separation system |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101949900A (en) * | 2010-08-19 | 2011-01-19 | 中国烟草总公司郑州烟草研究院 | Comprehensive two-dimensional ultrahigh pressure high performance liquid chromatography separation system |
Non-Patent Citations (3)
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|---|
| STEFAN LOUW等: "Serial coupling of reversed-phase and hydrophilic interaction liquid chromatography to broaden the elution window for the analysis of pharmaceutical compounds", 《JOURNAL OF CHROMATOGRAPHY A》 * |
| TSUYOSHI MURAHASHI: "Comprehensive two-dimensional high-performance liquid chromatography for the separation of polycyclic aromatic hydrocarbons", 《ANALYST》 * |
| YANMING LIU等: "Novel two-dimensional reversed-phase liquid chromatography/hydrophilic interaction chromatography,an excellent orthogonal system for practical analysis", 《JOURNAL OF CHROMATOGRAPHY A》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107271578A (en) * | 2017-03-23 | 2017-10-20 | 浙江奇彩环境科技股份有限公司 | Method for amine substance content in determination sample |
| CN107894481A (en) * | 2018-01-11 | 2018-04-10 | 南通市食品药品监督检验中心 | A kind of method of caprolactam in ultra-performance liquid chromatography measure food contact material nylon 6 |
| CN113433241A (en) * | 2021-06-28 | 2021-09-24 | 江苏新锐环境监测有限公司 | Determination of benzidine in soil by ultrasonic extraction-high performance liquid chromatography |
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| CN102680590B (en) | 2013-09-18 |
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