CN103995075A - High performance liquid chromatography-tandem mass spectrometry detection method of plasticizer in sugar - Google Patents
High performance liquid chromatography-tandem mass spectrometry detection method of plasticizer in sugar Download PDFInfo
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Abstract
The invention discloses a high performance liquid chromatography-tandem mass spectrometry detection method of a plasticizer in sugar, comprising the following steps: (1) preparing a standard solution and detecting by high performance liquid chromatography-tandem mass spectrometry to obtain retention time and standard spectrum diagram; (2) making relationship curves between concentration and chromatographic peak area according to varieties of phthalates from the standard spectrum diagram; (3) carrying out pretreatment of a sugar sample and detecting by high performance liquid chromatography-tandem mass spectrometry to obtain a sample spectrum diagram; and (4) comparing a detection result obtained from the step (3) with the standard curve obtained from the step (2), and calculating to determine the content of the plasticizer in sugar. The method provided by the invention has advantages of simple detection step and fast detection time. A simple and feasible detection method of a plasticizer can be provided for a food production enterprise or food inspection institution. Detection of the content of a plasticizer in sugar can be realized. In particular, high sensitivity detection of DINP can be realized.
Description
Technical field
The present invention relates to a kind of method that detects plasticiser, particularly relate to a kind of method that detects the using high performance liquid chromatography tandem mass spectrum of plasticiser in sugar.
Background technology
Plasticiser, claims again plastifier, is widely used in commercial production, and with plasticity and the pliability of reinforcing material, conventional plasticiser is mainly phthalate material (Phthalate Acid Esters, abbreviation PAEs).Plasticiser is applied in various plastic products at large, and very easily from various plastic products, moves to environment even in varieties of food items, to human body there is anxious toxicity, cause hormonal imbalance and carcinogenic, teratogenesis, the damaging effect such as mutagenicity.Therefore, strict supervision has all been done to Phthalic Acid Esters in Food class material residual in countries in the world.In China, phthalate material by clearly for the non-edible material from soybeans of violated interpolation is forbidden using in food, the Ministry of Public Health has also issued the limit standard of part phthalic ester specially.According to (defend and do supervision letter [2011] No. 551) regulation, (2-ethyl) the own ester of the phthalic acid two in food (DEHP), diisononyl phthalate (DINP) and n-butyl phthalate (DBP) maximum residue limit are respectively 1.5 mg/kg, 9.0 mg/kg and 0.3 mg/kg.
Sugar is as the important source material of food and food industry, and its quality safety is being related to the quality safety of numerous relevant food.In the production of sugar, there is the packing of product link in link, the especially later stage touch plastic products, produce thus the migration of plasticizer to the risk in sugar.Therefore, detect the residual quantity of phthalate material in sugar, to grasping and control sugar quality level, seem very important.
At present, in food, the detection method of plasticiser is mainly GC-MS, as domestic, promulgated the mensuration > > detection method of GB/T21911-2008 < < Phthalic Acid Esters in Food, the method is mainly to utilize GC-MS to detect 16 kinds of plasticisers, and in milk powder, the gaschromatographic mass spectrometry detection method of plasticiser also has patent report (publication No. CN 103091418 A).GC-MS has higher sensitivity when detecting the lower plasticiser of boiling point, and detecting the higher plasticiser (as dinonyl phthalate DNP, diisononyl phthalate DINP, the different certain herbaceous plants with big flowers ester of phthalic acid two DIDP etc.) of boiling point, its detection sensitivity significantly declines.As the mensuration gas chromatography-mass spectrography > > of plastifier in standard SN/T 2250-2009 < < plastic raw materials and goods thereof shows, the total ion current chromatographic peak profile of DINP is one group of multiplet, and DINP detects and is limited to 10 mg/L.This is obviously difficult to meet the needs that the Ministry of Public Health limits the quantity of and supervises DINP.Using high performance liquid chromatography tandem mass spectrum method has advantages of that in the detection of plasticiser detection time is shorter, detection sensitivity is higher, especially for high boiling plasticisers such as DINP, also can obtain higher detection sensitivity, meet the detection needs that plasticiser residual quantity is lower.At present, in sugar, plasticiser using high performance liquid chromatography tandem mass spectrum detection method has no report.
Summary of the invention
The using high performance liquid chromatography tandem mass spectrum detection method that the object of this invention is to provide plasticiser in a kind of sugar, the needs that it can meet plasticiser trace detection in sugar, have the advantages that detection time is short, detection sensitivity is high.
Object of the present invention can realize by the following technical solutions:
In sugar, a using high performance liquid chromatography tandem mass spectrum detection method for plasticiser, comprises the following steps.
(1) preparation standard solution carry out using high performance liquid chromatography tandem mass spectrum detection
The standard reserving solution of the phthalic ester of required test is diluted to respectively to the mixed standard solution of at least 5 kinds of variable concentrations with methyl alcohol, the mixed standard solution of variable concentrations is carried out to using high performance liquid chromatography tandem mass spectrum detection and obtains standard spectrogram, in standard spectrogram, retention time is determined the kind of phthalic ester, and chromatographic peak area has functional relation with corresponding phthalic ester concentration.
(2) standard spectrogram step 1 being obtained is made respectively concentration and chromatographic peak area graph of relation by phthalic ester kind.
(3) pre-service of sugar sample and using high performance liquid chromatography tandem mass spectrum detect
Take the sugar sample of having pulverized and join in glass centrifuge tube, add methyl alcohol, vortex mixed 2～3 min, then ultrasonic extraction; Centrifugal 5～10 min, get the rear filtering membrane of supernatant dilution and filter, and get filtrate and utilize using high performance liquid chromatography tandem mass spectrum instrument to detect under the condition identical with step 1, obtain sample spectrogram.
(4) each phthalic acid ester content in sugar determines
The retention time of the sample spectrogram obtaining in step 3 determined to phthalic ester kind and the typical curve of its chromatographic peak area phthalic ester kind corresponding with step 2 is compared, by insertion, determining the content of each phthalic ester in sample.
The testing conditions of using high performance liquid chromatography tandem mass spectrum is:
Chromatographic condition:
A) chromatographic column, chromatographic column: Restek Ultra AQ C18 (100 * 2.1 mm * 3 μ m);
B) mobile phase and condition of gradient elution:
0 ~ 3 min, mobile phase 0.1% formic acid water 50%, mobile phase methanol 50%;
3 ~ 7 min, mobile phase 0.1% formic acid water from 50% to 20%, mobile phase methanol from 50% to 80%;
7 ~ 8 min, mobile phase 0.1% formic acid water from 20% to 2%, mobile phase methanol from 80% to 98%;
8 ~ 10 min, mobile phase 0.1% formic acid water 2%, mobile phase methanol 98%;
10 ~ 13 min, mobile phase 0.1% formic acid water 2% to 50%, mobile phase methanol 98% to 50%;
C) sample size: 5 ~ 20 μ L;
D) column temperature: 30 ~ 40 ℃;
E) flow velocity: 0.4 mL/min.
Mass spectrum condition:
A) ionization pattern: ESI+;
B) gas curtain atmospheric pressure 344.5 kPa, collision atmospheric pressure is middle-grade, ionspray voltage 5500 V, 550 ℃ of ion source temperatures, atomization gas pressure 344.5 kPa, auxiliary heating atmospheric pressure 344.5 kPa, interface well heater is for opening;
C) drainage pattern: many reaction detection (MRM) pattern.
The present invention has following outstanding substantive distinguishing features and marked improvement:
Detecting step of the present invention is simple, detection time is fast, can be the food enterprises or food inspection mechanism a kind of simple and feasible detection plasticiser method is provided, by enforcement of the present invention, can realize the detection of content of plasticizing agent in sugar, especially realize the high-sensitivity detection of DINP.
Accompanying drawing explanation
Fig. 1 is 16 kinds of plasticiser mixed standard solutions (0.5 mg/L) liquid chromatography mass figure.
Fig. 2 is the canonical plotting (concentration and chromatographic peak area graph of a relation) of 16 kinds of plasticiser mixed standard solutions.
Fig. 3 is the liquid chromatography mass figure of white granulated sugar blank sample.
Fig. 4 is the liquid chromatography mass figure that adds 16 kinds of plasticiser mixed standard solutions (adding scalar is 0.1 mg/kg) in white granulated sugar.
Fig. 5 is the liquid chromatography mass figure that rock sugar sample plasticiser detects.
Embodiment
Below by instantiation, the present invention will be further described, and these descriptions are not that content of the present invention is further limited.One skilled in the art will understand that content of the present invention is done be equal to replacement or improve accordingly, within still belonging to protection scope of the present invention.
(1) instrument and reagent
Various phthalic ester standard reserving solutions (1000 mg/L); Methyl alcohol (chromatographically pure), it is pure that all the other reagent are analysis;
Using high performance liquid chromatography tandem mass spectrum instrument, electronic balance (being accurate to 0.1 mg), vortex oscillator, supercentrifuge, glassware is commonly used (after glassware used is clean, with distilled water drip washing three times in laboratory, acetone soaks 1 hour, toasts 2 hours at 250 ℃, is cooled to room temperature standby).
(2) testing conditions
Chromatographic condition:
A) chromatographic column, chromatographic column: Restek Ultra AQ C18 (100 * 2.1 mm * 3 μ m);
B) mobile phase and condition of gradient elution:
0 ~ 3 min, mobile phase 0.1% formic acid water 50%, mobile phase methanol 50%;
3 ~ 7 min, mobile phase 0.1% formic acid water from 50% to 20%, mobile phase methanol from 50% to 80%;
7 ~ 8 min, mobile phase 0.1% formic acid water from 20% to 2%, mobile phase methanol from 80% to 98%;
8 ~ 10 min, mobile phase 0.1% formic acid water 2%, mobile phase methanol 98%;
10 ~ 13 min, mobile phase 0.1% formic acid water 2% to 50%, mobile phase methanol 98% to 50%;
C) sample size: 5 μ L;
D) column temperature: 40 ℃;
E) flow velocity: 0.4 mL/min.
Mass spectrum condition:
A) ionization pattern: ESI+;
B) gas curtain atmospheric pressure 344.5 kPa, collision atmospheric pressure is middle-grade, ionspray voltage 5500 V, 550 ℃ of ion source temperatures, atomization gas pressure 344.5 kPa, auxiliary heating atmospheric pressure 344.5 kPa, interface well heater is for opening;
C) drainage pattern: many reaction detection (MRM) pattern.
(3) checkout procedure
Step (1): standard solution preparation
It is 0.5 mg/L that the standard reserving solution of the phthalic ester of required test is diluted to concentration with methyl alcohol, 0.2 mg/L, 0.1 mg/L, 0.05 mg/L, the standard solution of 0.02 mg/L series;
Standard spectrogram is measured and obtained to the standard solution of 16 kinds of prepared phthalic esters under above-mentioned instrument condition, and in standard spectrogram, retention time is determined the kind (table 1) of phthalic ester.
Table 1 plasticiser retention time and multiple-reaction monitoring condition
Chromatographic peak area (in Table 2) in the standard spectrogram of the variable concentrations of phthalic ester, chromatographic peak area has functional relation with the concentration of corresponding phthalic ester; Related coefficient and method detection limit are as shown in table 3, and the using high performance liquid chromatography tandem mass spectrum figure of the standard solution of 0.5 mg/L as shown in Figure 1.
Chromatographic peak area list under table 2 phthalic ester variable concentrations
Note: * 1.04E+04 represents 1.04 * 10
4.
Step (2): press concentration and the chromatographic peak area of each standard items in table 2, take response as ordinate, concentration is horizontal ordinate, drawing standard curve (Fig. 2) obtains typical curve equation (in Table 3).
Typical curve equation, related coefficient and the detection limit of table 3 plasticiser
Step (3): the pre-service of sugar sample and using high performance liquid chromatography tandem mass spectrum detect
Take white granulated sugar sample 2.0 g, add 5 mL methyl alcohol, be placed in centrifuge tube mesoscale eddies and mix 2 min, ultrasonic extraction 15 min; Then by centrifuge tube with centrifugal 5 min of 5000 r/min, get supernatant and carry out upper machine testing and obtain sample spectrogram (Fig. 3).
Step (4): the determining of each phthalic acid ester content in sugar
The retention time of the sample spectrogram obtaining in step 3 determined to phthalic ester kind and the typical curve of its chromatographic peak area phthalic ester kind corresponding with step 2 is compared, by insertion, determining the content of each FOS in sample.
(4) computation process
Content of plasticizing agent in sample calculates and obtains by instrument software or by formula (1):
………………………（1）
In formula:
x i ---plasticiser content (i) in sample, unit is milligrams per kilogram (mg/kg);
C
i---(i) concentration corresponding to response of plasticiser in sample, unit is milligrams per liter (mg/L);
C
0---plasticiser concentration (i) in blank sample, unit is milligrams per liter (mg/L);
v---sample constant volume, unit is milliliter (mL);
m---the quality of sample, unit is gram (g);
f---extension rate.
Plasticiser in sample solution (
x i ) response should be in the typical curve range of linearity, sample introduction analysis again after surpassing the range of linearity and should diluting.
Embodiment 1: recovery testu in white granulated sugar
Getting a white granulated sugar sample processes according to above-mentioned experimental procedure, the content of plasticizing agent of sample detection sample, its result as shown in Figure 3, result shows to occur except DEHP has faint peak shape, other plasticisers all do not detect, substitution typical curve calculates, and the testing result of DEHP, lower than detection limit scope, shows and do not detect.
On this basis, we have done the recovery of standard addition experiment of 16 kinds of plasticisers in white granulated sugar, add scale value and are respectively 0.05 mg/L, 0.1 mg/L and 0.5 mg/L, and each adds scale value and does 6 parallel laboratory tests.Experimental result is as shown in Fig. 4 (mark-on 0.1 mg/kg), table 4, and three mark-on levels, the standard deviation value scope of 81.6% ~ 110%, 6 groups of parallel laboratory test results of recovery of standard addition scope is 0.52% ~ 4.9%.
The recovery of standard addition of 16 kinds of plasticisers in table 4 white granulated sugar
Above-mentioned experimental result shows, this analytical approach recovery of standard addition is high, and experiment precision is good, substantially can meet the needs that in white granulated sugar, various plasticisers detect.
Embodiment 2: the detection of plasticiser in rock sugar
Getting a rock sugar sample pulverizes as after Powdered, according to above-mentioned experimental procedure, process, the content of plasticizing agent of sample detection sample, its result as shown in Figure 5, testing result is that DEHP detects, detected value is 0.095 mg/L, and the DEHP content calculating in substitution formula (1) in rock sugar sample is 0.238 mg/kg.This result shows to have a small amount of DEHP residual in rock sugar, and its reason may be that crystal sugar production technique is the dissolving crystallized again of white granulated sugar, and technique is more complicated than white granulated sugar, and the possibility that touches plastic products increases, and causes the introducing of DEHP; Or in later stage packaging process, used the higher plastic package material of DEHP content, the migration of plasticiser to cause that DEHP's is residual.This result also points out sugar enterprise in production procedure, should note avoiding contacting all types of plastic goods, to plastic package material, will have strict quality control, to avoid residual at sugar product of plasticiser.
Claims (2)
1. a using high performance liquid chromatography tandem mass spectrum detection method for plasticiser in sugar, is characterized in that comprising the steps:
(1) preparation standard solution carry out using high performance liquid chromatography tandem mass spectrum detection
The standard reserving solution of the phthalic ester of required test is diluted to respectively to the mixed standard solution of at least 5 kinds of variable concentrations with methyl alcohol, the mixed standard solution of variable concentrations is carried out to using high performance liquid chromatography tandem mass spectrum detection and obtains standard spectrogram, in standard spectrogram, retention time is determined the kind of phthalic ester, and chromatographic peak area has functional relation with corresponding phthalic ester concentration;
(2) standard spectrogram step 1 being obtained is made respectively concentration and chromatographic peak area graph of relation by phthalic ester kind;
(3) pre-service of sugar sample and using high performance liquid chromatography tandem mass spectrum detect
Take the sugar sample of having pulverized and join in glass centrifuge tube, add methyl alcohol, vortex mixed 2～3 min, then ultrasonic extraction; Centrifugal 5～10 min, get the rear filtering membrane of supernatant dilution and filter, and get filtrate and utilize using high performance liquid chromatography tandem mass spectrum instrument to detect under the condition identical with step (1), obtain sample spectrogram;
(4) each phthalic acid ester content in sugar determines
Retention time in the sample spectrogram obtaining in step 3 determined to phthalic ester kind and the typical curve of its chromatographic peak area phthalic ester kind corresponding with step 2 is compared, by insertion, determining the content of each phthalic ester in sample.
2. the method for plasticiser in detection sugar according to claim 1, is characterized in that: in step 1 and 3, the testing conditions of using high performance liquid chromatography tandem mass spectrum is:
Chromatographic condition:
A) chromatographic column, chromatographic column: Restek Ultra AQ C18 (100 * 2.1 mm * 3 μ m);
B) mobile phase and condition of gradient elution:
0 ~ 3 min, mobile phase 0.1% formic acid water 50%, mobile phase methanol 50%;
3 ~ 7 min, mobile phase 0.1% formic acid water from 50% to 20%, mobile phase methanol from 50% to 80%;
7 ~ 8 min, mobile phase 0.1% formic acid water from 20% to 2%, mobile phase methanol from 80% to 98%;
8 ~ 10 min, mobile phase 0.1% formic acid water 2%, mobile phase methanol 98%;
10 ~ 13 min, mobile phase 0.1% formic acid water 2% to 50%, mobile phase methanol 98% to 50%;
C) sample size: 5 ~ 20 μ L;
D) column temperature: 30 ~ 40 ℃;
E) flow velocity: 0.4 mL/min;
Mass spectrum condition:
A) ionization pattern: ESI+;
B) gas curtain atmospheric pressure 344.5 kPa, collision atmospheric pressure is middle-grade, ionspray voltage 5500 V, 550 ℃ of ion source temperatures, atomization gas pressure 344.5 kPa, auxiliary heating atmospheric pressure 344.5 kPa, interface well heater is for opening; C) drainage pattern: many reaction detection (MRM) pattern.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106526016A (en) * | 2016-10-28 | 2017-03-22 | 陕西科技大学 | Ultra-high performance liquid chromatography-quadrupole electrostatic field orbital ion trap mass spectrometry screening method for plasticizer in milk and dairy products |
| CN110646547A (en) * | 2019-10-16 | 2020-01-03 | 台州科技职业学院 | Method for simultaneously measuring di (2-ethyl) hexyl ortho-, meta-and terephthalate in food simulant |
| CN112305110A (en) * | 2020-10-26 | 2021-02-02 | 舟山新诺佳生物工程有限责任公司 | Detection method suitable for ethyl ester type and glyceride type fish oil product plasticizers |
| CN117347530A (en) * | 2023-12-04 | 2024-01-05 | 天津玉健生物工程有限公司 | Detection method of plasticizer in vitamin B2 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106526016A (en) * | 2016-10-28 | 2017-03-22 | 陕西科技大学 | Ultra-high performance liquid chromatography-quadrupole electrostatic field orbital ion trap mass spectrometry screening method for plasticizer in milk and dairy products |
| CN110646547A (en) * | 2019-10-16 | 2020-01-03 | 台州科技职业学院 | Method for simultaneously measuring di (2-ethyl) hexyl ortho-, meta-and terephthalate in food simulant |
| CN110646547B (en) * | 2019-10-16 | 2022-06-03 | 台州科技职业学院 | Method for simultaneously determining di (2-ethyl) hexyl ortho-, meta-and terephthalate in food simulant |
| CN112305110A (en) * | 2020-10-26 | 2021-02-02 | 舟山新诺佳生物工程有限责任公司 | Detection method suitable for ethyl ester type and glyceride type fish oil product plasticizers |
| CN112305110B (en) * | 2020-10-26 | 2022-08-12 | 舟山新诺佳生物工程有限责任公司 | Detection method suitable for ethyl ester type and glyceride type fish oil product plasticizers |
| CN117347530A (en) * | 2023-12-04 | 2024-01-05 | 天津玉健生物工程有限公司 | Detection method of plasticizer in vitamin B2 |
| CN117347530B (en) * | 2023-12-04 | 2024-02-13 | 天津玉健生物工程有限公司 | Detection method of plasticizer in vitamin B2 |
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Address after: No.10, shiliugang Road, Haizhu District, Guangzhou City, Guangdong Province 510000 Patentee after: Institute of bioengineering, Guangdong Academy of Sciences Address before: No.10, shiliugang Road, Haizhu District, Guangzhou City, Guangdong Province 510000 Patentee before: GUANGDONG PROVINCIAL BIOENGINEERING INSTITUTE (GUANGZHOU SUGARCANE INDUSTRY RESEARCH INSTITUTE) Address after: No.10, shiliugang Road, Haizhu District, Guangzhou City, Guangdong Province 510000 Patentee after: Institute of biological and medical engineering, Guangdong Academy of Sciences Address before: No.10, shiliugang Road, Haizhu District, Guangzhou City, Guangdong Province 510000 Patentee before: Institute of bioengineering, Guangdong Academy of Sciences |
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Address after: No.10, shiliugang Road, Haizhu District, Guangzhou City, Guangdong Province 510000 Patentee after: GUANGDONG PROVINCIAL BIOENGINEERING INSTITUTE (GUANGZHOU SUGARCANE INDUSTRY RESEARCH INSTITUTE) Address before: 510316, 10, pomegranate Road, Guangzhou, Guangdong, Haizhuqu District Patentee before: GUANGZHOU SUGARCANE INDUSTRY Research Institute |