CN109061003A - The measuring method of alkyl phenol polyoxyethylene ether content in a kind of liquid tea product - Google Patents
The measuring method of alkyl phenol polyoxyethylene ether content in a kind of liquid tea product Download PDFInfo
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Abstract
The measuring method of alkyl phenol polyoxyethylene ether content, belongs to detection technique field in a kind of liquid tea product.Method includes the following steps: 1) sample preparation；2) example enrichment and purification；3) UPLC-MS/MS is measured；4) blank test；5) result is calculated and is stated；6) judge.Measuring method of the invention has the advantage that the solid phase extraction of alkyl phenol polyoxyethylene ether content in the detection liquid tea product of the invention designed, and method is reliable and stable, and organic reagent dosage is few, it is wide to measure polymerization scope.
Description
Technical field
The invention belongs to detection technique fields, and in particular to alkyl phenol polyoxyethylene ether content in a kind of liquid tea product
Measuring method.
Background technique
Alkyl phenol polyoxyethylene ether (Alkylphenol ethoxylates, APEOs) is a kind of non-ionic surface active
Insecticides adjuvant is also made in agent, is applied to insecticide, fungicide and herbicide.APEOs mainly includes nonylphenol polyoxyethylene ether
(Nonylphenol ethoxylates, NPEOs) and octyl phenol polyoxyethylene ether (Octylphenol ethoxylates,
OPEOs) two substance.The catabolite of NPEOs and OPEOs is respectively nonyl phenol (Nonylphenol, NP) and octyl phenol
(Octylphenol, OP) all has environmental estrogens effect, and metabolite residue is lasting.2003/53/EC regulation strictly limits
The use of APEOs；2010, NP and NPEOs were put into " the toxic chemical catalogue of the stringent restraint on export and import of China "；2015
Year, NP and NPEOs are included in and " limit notice with list > (exposure draft) opinion about < insecticides adjuvant is solicited " list.Mesh
Before, have using QuEChERS method measurement the solid matrixs such as honey and its product, leaf vegetables in APEOs, and using from
The report of APEOs in sub- chromatography, liquid chromatogram measuring articles for washing and daily necessities.But for liquid tea product QuEChERS method
It is not able to satisfy rate of recovery requirement, false positive easily occurs in liquid chromatogram.
Summary of the invention
In view of the problems of the existing technology, it is an object of the invention to design to provide alkyl phenol in a kind of liquid tea product
The technical solution of the measuring method of polyethenoxy ether content.
The measuring method of alkyl phenol polyoxyethylene ether content in a kind of liquid tea product, it is characterised in that including with
Lower step:
1) sample preparation
Filtered after taking tealeaves boiling water to brew, cooling obtains millet paste, then methanol is added in millet paste, is vortexed and mixes, obtain to
Scavenging solution；
2) example enrichment and purification
2mL methanol and 4mL water elute Oasis HLB solid-phase extraction column in advance, and liquid to be clean is passed through with the speed of 1mL/min
It is drained after Oasis HLB solid-phase extraction column, discards efflux；Methanol of the 2mL containing methylene chloride elutes determinand, collects outflow
Liquid, 40 DEG C of rotary evaporations are done to close, and 1mL methanol constant volume is used after drying, 0.22 μm of organic filter membrane is crossed, for ultra performance liquid chromatography-
Tandem mass spectrum test；
3) UPLC-MS/MS is measured
Matrix matching standard solution and sample solution sample introduction under conditions of following setting:
A) UPLC-MS/MS instrument parameter:
Liquid phase chromatogram condition: chromatographic column: ACQUITYBEH C18 chromatographic column 2.1 × 100mm, 1.7 μm；Flowing
Phase A is the water of ammonium acetate containing 2mmol/L, and Mobile phase B is acetonitrile, flow velocity 0.25mL/min；Mobile phase elution program: 0~1min,
60%A~50%A；1~4min, 50%A~15%A；4~8min, 15%~1%A；8~8.7min, 1%A~1%A；8.7
~9.2min, 1%A~60%A；Sampling volume be 5 μ L, 40 DEG C of column temperature；
Mass Spectrometry Conditions: ion source module ESI+, capillary voltage 3.5kV, 150 DEG C of ion source temperature, desolvation temperature
350 DEG C, cone hole backflow airflow amount 50L/Hr, desolventizing gas flow 650L/Hr；Mensuration mode: reaction of high order monitoring pattern；It is qualitative
With respect to the maximum allowable offset of abundance of ions when confirmation: relative ion abundance > 50%, relative deviation ± 20% of permission；Relatively
Abundance of ions > 20%~50%, relative deviation ± 25% of permission；Relative ion abundance > 10%~20%, permission it is opposite
Deviation ± 30%；Relative ion abundance≤10%, relative deviation ± 50% of permission；
B) octyl phenol polyoxyethylene ether and nonylphenol polyoxyethylene ether mass spectrometry parameters are as shown in table 1；
4) blank test
By above-mentioned steps 1), step 2), step 3) operation carry out, but do not add standard solution；
5) result is calculated and is stated
The mass concentration of alkyl phenol polyoxyethylene ether in sample is calculated according to the following formula, processing result must deduct blank value,
In formula:
Xi-- the residual quantity of alkyl phenol polyoxyethylene ether in sample, unit are micro- gram per liter；
Ci-- the solution concentration of alkyl phenol polyoxyethylene ether is obtained from standard curve, unit is micro- gram per liter；
V -- the final constant volume of sample liquid, unit are milliliter；
Vi-- volume of sample representated by final sample liquid, unit is milliliter；
6) judge
Using mass concentration x as abscissa, peak area y is ordinate, draws 5 standard working curves, is worked with standard bent
Line quantitative determines sample, and the response of determinand meets the range of linearity of instrument detection in sample solution；It is quantitative and fixed
Property ion pair exists simultaneously, and signal-to-noise ratio >=3；The chromatographic peak retention time and matrix matching mark that determinand occurs in sample solution
Quasi- solution is consistent, and tolerance is less than ± 0.5%, it is determined that contains the object.
The measuring method of alkyl phenol polyoxyethylene ether content in a kind of liquid tea product, it is characterised in that described
In millet paste, 3:2 is mixed step 1) by volume with methanol.
The measuring method of alkyl phenol polyoxyethylene ether content in a kind of liquid tea product, it is characterised in that described
Step 2) elutes determinand using the methanol solution containing 5% methylene chloride.
The detection method that the present invention establishes, the measurement of APEOs suitable for liquid tea product have accuracy and accuracy
Height, the rate of recovery is good, organic reagent dosage is few, can measure the wide (OPEO of polymerization scopeN=3-20And NPEON=3-15) etc. advantage, can
Assay for APEOs in the liquid tea product such as millet paste, tea beverage provides technical support.
Measuring method of the invention has the advantage that alkyl phenol polyoxy second in the detection liquid tea product of the invention designed
The solid phase extraction of alkene ether content, method is reliable and stable, and organic reagent dosage is few, it is wide to measure polymerization scope.
Detailed description of the invention
Fig. 1 is NPEON=3-15And OPEON=3-20Standard specimen sweeps mass spectrogram A entirely) NPEO4 (n=3-11)；B)NPEO9-10 (n=3-15)；C)
OPEO9-10 (n=3-15)；D)OPEO16 (n=9-20)。
Fig. 2 is influence of the methylene chloride content to the rate of recovery in eluting solvent.
Fig. 3 is influence of the mixed proportion of millet paste and methanol to the rate of recovery.
Specific embodiment
Further illustrate the present invention with reference to embodiments.
Embodiment one: the foundation of Mass Spectrometry Conditions
The characteristic ion that OPEOs and NPEOs are obtained by full scan mode selects the highest ion of abundance of ions as mother
Ion；By increasing cracking voltage step by step, the optimal cracking voltage of effect is selected；Increase collision energy step by step, obtains two groups of spies
Daughter fragment ion and optimal collision energy are levied, mass spectrum is selected to respond higher ion channel as quota ion pair, another group of work
For qualitative ion pair.APEOs is in liquid chromatography mass ionization process in combination with [H]+、[Na]+、[K]+、[NH4]+Deng generation
A variety of adduction ions, add ammonium acetate in mobile phase, are remarkably improved [NH4]+Response.As shown in Figure 1, NPEON=3-15?
[M+NH is formed under the conditions of the mobile phase of setting4]+Molecular ion peak (Figure 1A and Figure 1B)；OPEOs is in low degree, that is, n=
[M+NH under the conditions of 3-144]+Relative abundance is higher (Fig. 1 C), in higher degrees of polymerization n >=15, the double charge [M+2NH of OPEOs4
]2+Mass spectrum response be higher than [M+NH4]+(Fig. 1 D).
Embodiment two: eluting solvent blend proportion optimization
Fig. 2 is shown in influence of the methylene chloride content to the APEOs rate of recovery in methanol.When methylene chloride content is respectively in methanol
5%, 25%, 50%, the rate of recovery of 80%, APEOs is respectively 80~90%, 75~90%, 80~90% and 80~110%,
Four groups of processing rate of recovery are not much different, it is contemplated that the toxicity of methylene chloride, methanol solution of the final choice containing 5% methylene chloride are made
Eluting solvent.
Embodiment three: millet paste and methanol blend proportion optimization
As shown in figure 3,6mL millet paste+4mL methanol, 7mL millet paste+3mL methanol, 8mL millet paste+2mL methanol, 9mL millet paste+
Under the conditions of 1mL methanol and 10mL millet paste upper prop, with the increase of millet paste ratio, the APEOs rate of recovery is gradually decreased；In millet paste and first
When alcohol mixed proportion is V+V=3+2, the APEOs rate of recovery is 80~110%, meets the requirement of retention analysis.Therefore selection 6mL
The mixed proportion of millet paste+4mL methanol.
Example IV: the measuring method of alkyl phenol polyoxyethylene ether content in liquid tea product
1, reagent and material
1.1 methanol: pure, chromatographically pure is analyzed.
1.2 methylene chloride: analysis is pure.
1.3 acetonitriles: chromatographically pure.
1.4 ammonium acetates: chromatographically pure.
1.5 pure water.
1.6Waters Oasis HLB solid phase extraction column (3cc/60mg).
1.7 standard substances: NPEO4 (n=3-11)、NPEO9-10 (n=3-15)、OPEO9-10 (n=3-15)And OPEO16 (n=9-20)。
1.8 Standard Stock solutions prepare: accurately weigh respectively 1.7 standard substance 0.005g (being accurate to 0.0001g) in
In 25mL volumetric flask, with acetonitrile constant volume, it is configured to 200mg/L Standard Stock solutions, -20 DEG C of preservations.
1.9 standard working solutions are prepared: it is appropriate accurately to pipette 1.8 standard reserving solutions respectively, is configured to 10mg/L with acetonitrile
Mixed standard solution.The mixed standard solution of 10mg/L is diluted step by step with methanol into required standard working solution, is protected from light storage
It is stored in -20 DEG C of refrigerators.
1.10 miillpore filters: 0.22 μm, organic phase.
2, instrument and equipment
2.1 ultra performance liquid chromatography chromatography-mass spectroscopies/mass spectrograph: it is furnished with (ESI) ion source.
2.2 assay balances: sensibility reciprocal 0.00001g and 0.01g.
2.3 multitube vortex mixed instrument.
2.4 Rotary Evaporators.
3, determination step
3.1 sample preparations and purification
1) sample preparation
From tea beverage as typical liquid tea product, that is, tealeaves 1.0g is weighed in 100mL beaker, boiling water 50mL is brewed
5min, filter, be cooled to room temperature it is spare.4mL methanol is added in 6mL millet paste, is vortexed and mixes 1min, it is to be clean.
2) example enrichment and purification: 2mL methanol and 4mL water elute Oasis HLB solid-phase extraction column in advance, by liquid to be clean with
The speed of 1mL/min is drained after passing through Oasis HLB solid-phase extraction column, discards efflux；2mL contains the methanol of 5% methylene chloride
Determinand is eluted, efflux is collected, 40 DEG C of rotary evaporations are done to close, 1mL methanol constant volume are used after drying, crossing 0.22 μm has machine filter
Film is tested for ultra performance liquid chromatography-tandem mass spectrum (UPLC-MS/MS).
3.2UPLC-MS/MS measurement
Matrix matching standard solution and sample solution sample introduction under conditions of following setting:
A) UPLC-MS/MS instrument parameter:
Liquid phase chromatogram condition: chromatographic column: ACQUITYBEH C18 chromatographic column (2.1 × 100mm, 1.7 μm)；
Mobile phase A is the water of ammonium acetate containing 2mmol/L, and Mobile phase B is acetonitrile, flow velocity 0.25mL/min.Mobile phase elution program: 0~
1min, 60%A~50%A；1~4min, 50%A~15%A；4~8min, 15%~1%A；8~8.7min, 1%A~1%
A；8.7~9.2min, 1%A~60%A；Sampling volume be 5 μ L, 40 DEG C of column temperature.Mass Spectrometry Conditions: ion source module ESI+, capillary
Tube voltage 3.5kV, 150 DEG C of ion source temperature, 350 DEG C of desolvation temperature, cone hole backflow airflow amount 50L/Hr, desolventizing air-flow
Measure 650L/Hr.
B)OPEON=3-20And NPEON=3-15Mass spectrometry parameters are shown in Table 1.
4, blank test
It is carried out by above-mentioned steps 1, step 2, step 3 operation, but is not added standard solution.
5, result is calculated and is stated
The mass concentration of alkyl phenol polyoxyethylene ether in sample is calculated according to the following formula, processing result must deduct blank value.
In formula:
Xi-- the residual quantity of alkyl phenol polyoxyethylene ether in sample, unit are micro- gram per liter；
Ci-- the solution concentration of alkyl phenol polyoxyethylene ether is obtained from standard curve, unit is micro- gram per liter；
V -- the final constant volume of sample liquid, unit are milliliter；
Vi-- volume of sample representated by final sample liquid, unit is milliliter.
The content of alkyl phenol polyoxyethylene ether in liquid tea product is measured, by UPLC-MS/MS with OPEO11For, respectively
Measure 1.3 μ g/L of matrix standard specimen, 2.5 μ g/L, 12.5 μ g/L, 63.0 μ g/L and 125.4 μ g/L peak area be 32609.7,
124204.7,619254.2,2538049.1 and 4468542.3, with response to OPEO11Content draws standard curve y=3.6E
+07x+9.7E+04(R2=0.9950), sample to be tested peak area is 1.0E+06, brings standard curve calculating, C intoiFor 25.3 μ g/
L, V 1mL, ViFor 6mL, formula calculating, X are brought intoi=4.2 μ g/L.
6, method is confirmed
Under determining experiment condition, 1.10 standard working solutions and extraction standard working solution are measured, is cross with concentration
Coordinate x, peak area are that ordinate y draws standard curve, and calculates matrix effect (ME%).Rate of recovery experiment three additions of setting
Concentration, each five groups of addition concentration parallel, using minimum addition concentration as method LOQ.The rate of recovery and LOQ etc. are shown in Table 2, linear side
Journey and related coefficient etc. are shown in Table 3.As seen from table, the pitch-based sphere of APEOs be 0.00047~15 μ g/L, the rate of recovery be 88~
110%, RSD% are that 1~17%, LOQ is 0.00047~0.15 μ g/L；The range of linearity of APEOs is 0.00047~15 μ g/L,
The R of extraction standard working solution2It is -9.3~-0.1% for 0.9900~0.9987, ME%.
The recovery of standard addition and precision of alkyl phenol polyoxyethylene ether in 2 millet paste of table
The standard curve and matrix effect of 3 alkyl phenol polyoxyethylene ether of table
Claims (3)
1. the measuring method of alkyl phenol polyoxyethylene ether content in a kind of liquid tea product, it is characterised in that the following steps are included:
1) sample preparation
Filtering, cooling obtain millet paste, then methanol are added in millet paste after taking tealeaves boiling water to brew, and are vortexed and mix, obtain to be clean
Liquid；
2) example enrichment and purification
2mL methanol and 4mL water elute Oasis HLB solid-phase extraction column in advance, and liquid to be clean is passed through with the speed of 1mL/min
It is drained after Oasis HLB solid-phase extraction column, discards efflux；Methanol of the 2mL containing methylene chloride elutes determinand, collects outflow
Liquid, 40 DEG C of rotary evaporations are done to close, and 1mL methanol constant volume is used after drying, 0.22 μm of organic filter membrane is crossed, for ultra performance liquid chromatography-
Tandem mass spectrum test；
3) UPLC-MS/MS is measured
Matrix matching standard solution and sample solution sample introduction under conditions of following setting:
A) UPLC-MS/MS instrument parameter:
Liquid phase chromatogram condition: chromatographic column: ACQUITYBEH C18 chromatographic column 2.1 × 100mm, 1.7 μm；Mobile phase A
For the water of the ammonium acetate containing 2mmol/L, Mobile phase B is acetonitrile, flow velocity 0.25mL/min；Mobile phase elution program: 0~1min,
60%A~50%A；1~4min, 50%A~15%A；4~8min, 15%~1%A；8~8.7min, 1%A~1%A；8.7
~9.2min, 1%A~60%A；Sampling volume be 5 μ L, 40 DEG C of column temperature；
Mass Spectrometry Conditions: ion source module ESI+, capillary voltage 3.5kV, 150 DEG C of ion source temperature, 350 DEG C of desolvation temperature,
Cone hole backflow airflow amount 50L/Hr, desolventizing gas flow 650L/Hr；Mensuration mode: reaction of high order monitoring pattern；When qualitative confirmation
The maximum allowable offset of relative ion abundance: relative ion abundance > 50%, relative deviation ± 20% of permission；Relative ion is rich
Spend > 20%~50%, relative deviation ± 25% of permission；Relative ion abundance > 10%~20%, the relative deviation of permission ±
30%；Relative ion abundance≤10%, relative deviation ± 50% of permission；
B) octyl phenol polyoxyethylene ether and nonylphenol polyoxyethylene ether mass spectrometry parameters are as shown in table 1:
1 octyl phenol polyoxyethylene ether (OPEO of table3-20) and nonylphenol polyoxyethylene ether (NPEO3-15) mass spectrometry parameters
* quota ion
4) blank test
By above-mentioned steps 1), step 2), step 3) operation carry out, but do not add standard solution；
5) result is calculated and is stated
It is calculated according to the following formula the mass concentration of alkyl phenol polyoxyethylene ether in sample, processing result must deduct blank value, in formula:
Xi-- the residual quantity of alkyl phenol polyoxyethylene ether in sample, unit are micro- gram per liter；
Ci-- the solution concentration of alkyl phenol polyoxyethylene ether is obtained from standard curve, unit is micro- gram per liter；
V -- the final constant volume of sample liquid, unit are milliliter；
Vi-- volume of sample representated by final sample liquid, unit is milliliter；
6) judge
Using mass concentration x as abscissa, peak area y is ordinate, 5 standard working curves is drawn, with standard working curve pair
Sample is quantitative determined, and the response of determinand meets the range of linearity of instrument detection in sample solution；Qualitatively and quantitatively from
Son is to existing simultaneously, and signal-to-noise ratio >=3；The chromatographic peak retention time and matrix matching standard that determinand occurs in sample solution are molten
Liquid is consistent, and tolerance is less than ± 0.5%, it is determined that contains the object.
2. the measuring method of alkyl phenol polyoxyethylene ether content in a kind of liquid tea product according to claim 1, special
Sign is that 3:2 is mixed the step 1) by volume with methanol in millet paste.
3. the measuring method of alkyl phenol polyoxyethylene ether content in a kind of liquid tea product according to claim 1, special
Sign is the step 2) using the methanol solution elution determinand containing 5% methylene chloride.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109884208A (en) * | 2019-03-18 | 2019-06-14 | 珠海格力电器股份有限公司 | Method for detecting 4-nonylphenol ethoxylate by using ultra-high performance liquid chromatography-PDA (personal digital Assistant) |
| CN112362768A (en) * | 2020-10-23 | 2021-02-12 | 北京民海生物科技有限公司 | Method for measuring content of Berol 185 in sample by using liquid chromatography tandem mass spectrometry |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003101611A1 (en) * | 2002-05-31 | 2003-12-11 | Japan Envirochemicals, Ltd. | Isolation material for hormone disrupting substance, method of concentrating and method of clean-up |
| CN103175933A (en) * | 2013-02-20 | 2013-06-26 | 广州市质量监督检测研究院 | Method for quantitatively detecting alkylphenol polyoxyethylene in daily chemical products |
| CN104090048A (en) * | 2014-07-31 | 2014-10-08 | 国家烟草质量监督检验中心 | Method for measuring contents of octylphenol polyoxyethylene ether and nonylphenol polyoxyethylene ether in paper |
| CN104133017A (en) * | 2014-07-31 | 2014-11-05 | 国家烟草质量监督检验中心 | Determination method for content of polyoxyethylene octylphenol ether and polyoxyethylene nonyl phenyl ether in water-based adhesive |
| CN107436334A (en) * | 2017-09-30 | 2017-12-05 | 山东出入境检验检疫局检验检疫技术中心 | The method of APES in rapid screening and accurate confirmation textile |
-
2018
- 2018-09-19 CN CN201811091173.3A patent/CN109061003A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003101611A1 (en) * | 2002-05-31 | 2003-12-11 | Japan Envirochemicals, Ltd. | Isolation material for hormone disrupting substance, method of concentrating and method of clean-up |
| EP1514597A1 (en) * | 2002-05-31 | 2005-03-16 | Japan Envirochemicals, Ltd. | Isolation material for hormone disrupting substance, method of concentrating and method of clean-up |
| CN103175933A (en) * | 2013-02-20 | 2013-06-26 | 广州市质量监督检测研究院 | Method for quantitatively detecting alkylphenol polyoxyethylene in daily chemical products |
| CN104090048A (en) * | 2014-07-31 | 2014-10-08 | 国家烟草质量监督检验中心 | Method for measuring contents of octylphenol polyoxyethylene ether and nonylphenol polyoxyethylene ether in paper |
| CN104133017A (en) * | 2014-07-31 | 2014-11-05 | 国家烟草质量监督检验中心 | Determination method for content of polyoxyethylene octylphenol ether and polyoxyethylene nonyl phenyl ether in water-based adhesive |
| CN107436334A (en) * | 2017-09-30 | 2017-12-05 | 山东出入境检验检疫局检验检疫技术中心 | The method of APES in rapid screening and accurate confirmation textile |
Non-Patent Citations (4)
| Title |
|---|
| P.M. NAGARNAIK 等: "Concentrations and mass loadings of hormones, alkylphenols, and alkylphenol ethoxylates in healthcare facility wastewaters", 《CHEMOSPHERE》 * |
| PATRICK D. DEARMOND 等: "Rapid liquid chromatography–tandem mass spectrometry-based method for the analysis of alcohol ethoxylates and alkylphenol ethoxylates in environmental samples", 《JOURNAL OF CHROMATOGRAPHY A》 * |
| 江泽军 等: "液体农药制剂中烷基酚及其聚氧乙烯醚类助剂的高效液相色谱分析", 《农药学学报》 * |
| 郭文建 等: "固相萃取-液相色谱/荧光检测法同时测定水中8 种烷基酚和烷基酚聚氧乙烯醚", 《环境化学》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109884208A (en) * | 2019-03-18 | 2019-06-14 | 珠海格力电器股份有限公司 | Method for detecting 4-nonylphenol ethoxylate by using ultra-high performance liquid chromatography-PDA (personal digital Assistant) |
| CN112362768A (en) * | 2020-10-23 | 2021-02-12 | 北京民海生物科技有限公司 | Method for measuring content of Berol 185 in sample by using liquid chromatography tandem mass spectrometry |
| CN112362768B (en) * | 2020-10-23 | 2023-09-08 | 北京民海生物科技有限公司 | Method for measuring Berol 185 content in sample by utilizing liquid chromatography-tandem mass spectrometry |
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