CN106248834A - The UPLC MS/MS detection method of paraben preservative concentration in Urina Hominis - Google Patents
The UPLC MS/MS detection method of paraben preservative concentration in Urina Hominis Download PDFInfo
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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Abstract
The present invention provides the UPLC MS/MS detection method of paraben preservative concentration in Urina Hominis, comprise the following steps: (1) sample treatment: take urine sample to be measured in test tube or centrifuge tube, the water of 1/10 times of volume of sample-adding, it is subsequently adding β glucose glycuronide enzyme, shake up and seal, put into and 37 DEG C of water-baths are heated to reaction completely, take a certain amount of reactant liquor, add precipitant (methanol/acetonitrile=1:1) protein precipitation of 3 times amount, after vortex mixing, 15000rpm is centrifuged 10min, takes supernatant 5 10 μ L and carries out sample analysis；(2) sample introduction, carries out UPLC MS/MS detection according to certain condition；(3) according in the peak area of sample and the regression equation of standard curve, the concentration of paraben preservative in urine is calculated.The invention has the beneficial effects as follows the method simple and fast, highly sensitive, capacity of resisting disturbance is strong, and qualitative and quantitative detection while anticorrosive additive in applicable urine, the food of excess preservative can be detected in urine by metabolism.
Description
Technical field
The invention belongs to field of bioanalysis, especially relate to paraben preservative concentration in a kind of Urina Hominis
UPLC-MS/MS detection method.
Background technology
P-Hydroxybenzoate has another name called Nipagin ester, is clear crystal or crystalline powder, includes it under normal temperature condition
Methyl ester, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester etc., as a rule, along with the increase of its alkyl carbon chain, its toxicity reduces,
Antibacterial action strengthens.Hydroxybenzoate water solublity is poor, can improve its water solublity by synthesizing its sodium salt.
Methyl parahydroxybenzoate, also referred to as methyl hydroxybenzoate or methyl hydroxybenzoate, white crystalline powder or colourless crystallization, readily soluble
In alcohol, ether and acetone, the atomic water that is dissolved in, boiling point 270-280 DEG C.It is mainly used as organic synthesis, food, cosmetics, medical killing
Bacterium preservative, also serves as in feed anticorrosion agent.Methyl parahydroxybenzoate preservative is mainly added in food, if the biggest
The edible methyl parahydroxybenzoate of amount, is likely to result in gastrointestinal upset, skin, mucosa inflammation and generation estrogen.
Ethylparaben is relatively strong to the Antifungal activity of mycete, also has certain inhibitory action to antibacterial.At medicament
In be used as bacteriostatic preservative, be widely used in liquid preparation, semi-solid preparation.This product has phase in food industry and daily chemical industry
As purposes, be widely used in the anticorrosion of foods and cosmetics.Human body the most also can be caused intestinal by ethylparaben dose
The discomforts such as stomach.
Propyl p-hydroxybenzoate has another name called propylparaben, to Para Hydroxy Benzoic Acid propyl ester.Mycete, yeast are had with antibacterial
Antibacterial action widely, its antibacterial action is more than ethyl hydroxybenzoate.Once the food preservative in soy sauce, pickles produce.Strong
Health endangers: sucks, take in or is harmful to health through skin absorption.Eye, mucosa and upper respiratory tract and skin there is stimulation.
Butyl p-hydroxybenzoate has another name called butoben；For the antibacterial of medicine, cosmetics and food and anticorrosion.To ferment
Female and mycete has the strongest inhibitory action.
Paraben preservative extensively detects in blood of human body and urine, main with metabolism in human body
Presented in thing P-hydroxybenzoic acid.Research shows, such preservative may be relevant with the morbidity of breast carcinoma, zoopery table
Such preservative bright is likely to be of estrogen activity, therefore its residual, pollution and toxicity in surrounding medium and tissue
Receive significant attention.
Summary of the invention
It is an object of the invention to provide a kind of simple to operate, detection efficiency is high, the methyl parahydroxybenzoate of low cost, second
Ester, propyl ester, butyl ester concentration detection method, be especially suitable for methyl parahydroxybenzoate, ethyl ester, propyl ester, butyl ester concentration in urine
Detection.
The technical scheme is that
The UPLC-MS/MS detection method of paraben preservative concentration in Urina Hominis in Urina Hominis, including following step
Rapid:
1) sample treatment: take urine sample to be measured in test tube or centrifuge tube, the water of 1/10 times of volume of sample-adding, it is subsequently adding
β-glucose glycuronide enzyme, shakes up and seals, and puts into and is heated to reaction in 37 DEG C of water-baths completely, take a certain amount of reactant liquor, adds 3
Precipitant (methanol/acetonitrile=1:1) protein precipitation of times amount, after vortex mixing, 15000rpm is centrifuged 10min, takes supernatant 5-10 μ
L carries out sample analysis.
2) HPLC-MS/MS analyzes: the sample after processing, with triple level Four bar LC-MS instrument, enters under the following conditions
Row analyzes liquid-phase condition: flow phase: A:0.1% aqueous formic acid, B: acetonitrile；Flow velocity: 0.3ml/min；Sample size: 5 μ L；Post
Temperature: 45 DEG C；Chromatographic column: Waters ACQUITYBEH C18,1.7μm,2.1*50mm Column
Table 1. gradient elution program
| Time/min | A% | B% |
| 0 | 95 | 5 |
| 2.0 | 70 | 30 |
| 5.0 | 60 | 40 |
| 7.0 | 10 | 90 |
| 8.0 | 10 | 90 |
| 8.1 | 95 | 5 |
| 10.0 | 95 | 5 |
Table 2. Mass Spectrometry Conditions
Other mass spectrometry parameters:
Capillary voltage (kV): 3.2kV；Source temperature (DEG C): 120；
Desolventizing temperature (DEG C): 350；Desolventizing throughput (L/Hr): 800；
Gas curtain throughput (L/Hr): 50；Residence time (s): 0.1s
3) according in the peak area of sample and the regression equation of standard curve, calculate methyl parahydroxybenzoate in urine,
Ethyl ester, propyl ester, the concentration of butyl ester.
Further, step (1) sample treatment is: take 500 μ L urines, adds 50 μ L water, the β glucose glycuronide enzyme of 50 μ L
(80U/mL), shake up and seal, put into heating 120min in 37 DEG C of water-baths.After reaction terminates, extract reaction solution 100 μ L, add 300
μ L precipitant (methanol/acetonitrile=1:1) protein precipitation, after vortex mixing, 15000rpm is centrifuged 10min, takes supernatant 5 μ L sample introduction and divides
Analysis.
The manufacturing process of above method step (3) standard curve:
A. standard substance process: take 500 μ L urines, add 50 μ L standard solution, be configured to be equivalent to plasticiser in urine each
Constituent concentration is: the serial solution of 5,10,25,50,100,250,500ng/ml, adds the β glucose glycuronide enzyme of 50 υ Λ
(80U/mL), shake up and seal, put into heating 120min in 37 DEG C of water-baths.After reaction terminates, extract reaction solution 100 μ L, add 300
μ L precipitant (methanol/acetonitrile=1:1) protein precipitation, after vortex mixing, 15000rpm is centrifuged 10min, takes supernatant 5 μ L sample introduction and divides
Analysis.
B. standard curve making: with testing concentration as abscissa, determinand peak area corresponding to urine sample become swarming
The difference of area is vertical coordinate, makes standard curve.
When HPLC-MS analyzes, conventionally draw the standard curve of 4 kinds of paraben preservatives,
4 kinds of paraben preservative linear equation, correlation coefficient, detection limit and quantitatively is may determine that according to its standard curve
Limit, is specifically shown in Table 3.
Table 3HPLC-MS/MS measures the linear equation of paraben preservative, correlation coefficient, detection limit LOD
With quantitative limit LOQ
The present invention has the advantage that with good effect: P-hydroxybenzoic acid in UPLC-MS/MS detection method detection Urina Hominis
Esters concentration, simple and fast, highly sensitive, capacity of resisting disturbance is strong, is suitable for qualitative, quantitative inspection while anticorrosive additive in urine
Surveying, the food of excess preservative can be detected in urine by metabolism, carries for the supervision of anticorrosive additive in food in food service industry
Supply technical support.
Accompanying drawing explanation
Fig. 1 is canonical plotting (A: the methyl parahydroxybenzoate of four kinds of parabenses of the present invention；B: right
Nipagin A；C: propyl p-hydroxybenzoate；D: butyl p-hydroxybenzoate).
Fig. 2 is minimum quantitative limit (5ng/ml) concentration hybrid standard product chromatogram ((A: methyl parahydroxybenzoate；B: right
Nipagin A；C: propyl p-hydroxybenzoate；D: butyl p-hydroxybenzoate).
Fig. 3 is graticule (25ng/ml) concentration hybrid standard product chromatogram ((A: methyl parahydroxybenzoate；B: para hydroxybenzene
Ethyl formate；C: propyl p-hydroxybenzoate；D: butyl p-hydroxybenzoate)
Detailed description of the invention
Embodiment 1
Detection (its sample treatment of parabens concentration in sample 1, sample 2, sample 3, sample 4, sample 5
Method is identical with testing conditions):
(1) standard substance process: take 500uL urine, add 50uL standard solution, are configured to be equivalent to plasticiser in urine each
Constituent concentration is: the serial solution of 5,10,25,50,100,250,500ng/ml.Add the β glucose glycuronide enzyme (80U/ of 50uL
ML), shake up and seal, put into heating 120min in 37 DEG C of water-baths.After reaction terminates, extract reaction solution 100uL, add 300uL and sink
Shallow lake agent (methanol/acetonitrile=1:1) protein precipitation, after vortex mixing, 15000rpm is centrifuged 10min, takes supernatant 5uL and carries out sample and divide
Analysis.
(2) standard curve making: with testing concentration as abscissa, determinand peak area corresponding to urine sample become swarming
The difference of area is vertical coordinate, makes standard curve.Standard curve is shown in Fig. 1.
(3) sample treatment: take 500uL urine, adds 50uL water, β glucose glycuronide enzyme (80U/mL) of 50uL, shakes up and close
Envelope, puts into heating 120min in 37 DEG C of water-baths.After reaction terminates, extract reaction solution 100uL, add 300uL precipitant (methanol/second
Nitrile=1:1) protein precipitation, after vortex mixing, 15000rpm is centrifuged 10min, takes supernatant 5uL and carries out sample analysis.
(4) testing conditions is: triple level Four bar LC-MS instrument, liquid-phase condition: flowing phase: A:0.1%FA aqueous solution, B:
Acetonitrile；
Flow velocity: 0.3ml/min；Sample size: 5uL；Column temperature: 45 DEG C；
Chromatographic column: Waters ACQUITYBEH C18,1.7μm,2.1*50mm Column
Gradient elution program is identical with table 1
Mass Spectrometry Conditions: identical with table 2
Other mass spectrometry parameters:
Capillary voltage (kV): 3.2kV；Source temperature (DEG C): 120；
Desolventizing temperature (DEG C): 350；Desolventizing throughput (L/Hr): 800；
Gas curtain throughput (L/Hr): 50；Residence time (s): 0.1s
(5) according in the peak area of sample and the regression equation of standard curve, 4 kinds of p-Hydroxybenzoates in urine are calculated
The concentration (the results are shown in Table 4) of class preservative.
The concentration of 4 kinds of p-Hydroxybenzoates in table 4 sample 1-5
Embodiment 2
2.1 method response rate experiments
Taking six parts of need testing solutions, add equal-volume 10, each composition reference substance solution of 100,800ng/ml respectively, mixing is all
Even, it is configured to 5, each composition reference substance solution of 50,400ng/ml, sample introduction, every sample operation repetitive six parts, calculate the response rate.
The results detailed in Table 5.
Table 5 response rate test result
2.2 method precision experiments
It is configured to 5 by QC sample preparation method, each ingredient solution of 50,400ng/ml, sample introduction, every sample operation repetitive six
Part, investigate the precision of method.The results detailed in Table 6.
Table 6 method precision result of the test
2.3 solution stability testing
It is configured to 5 by QC sample preparation method, each ingredient solution of 50,400ng/ml, sample introduction, every sample operation repetitive three
Part, investigate 100% sample-adding solution rule over time.100% sample-adding solution room temperature is placed and is investigated each chemical combination after 4 hours
The situation of change of substrate concentration, it is desirable to: the RSD of compound should be not more than 10.0%.If meeting proof scheme requirement, then comparison is described
It is stable that product solution was placed within this time period, provides foundation for the time limit of test solution standing time during later detection.Knot
Fruit refers to table 7.
Table 7 stability test result
Embodiment 3
The preparation of minimum quantitative limit (5ng/ml) concentration hybrid standard product and graticule (25ng/ml) concentration hybrid standard product and
Testing conditions:
(1) standard substance process: take 500uL urine, add 50uL standard solution, are configured to be equivalent to plasticiser in urine each
Constituent concentration is: the serial solution of 5,10,25,50,100,250,500ng/ml.Add the β glucose glycuronide enzyme (80U/ of 50uL
ML), shake up and seal, put into heating 120min in 37 DEG C of water-baths.After reaction terminates, extract reaction solution 100uL, add 300uL and sink
Shallow lake agent (methanol/acetonitrile=1:1) protein precipitation, after vortex mixing, 15000rpm is centrifuged 10min, takes supernatant 5uL and carries out sample and divide
Analysis.
(2) standard curve making: with testing concentration as abscissa, determinand peak area corresponding to urine sample become swarming
The difference of area is vertical coordinate, makes standard curve.Standard curve is shown in Fig. 1.
(3) sample treatment: take 500uL urine, adds 50uL water, β glucose glycuronide enzyme (80U/mL) of 50uL, shakes up and close
Envelope, puts into heating 120min in 37 DEG C of water-baths.After reaction terminates, extract reaction solution 100uL, add 300uL precipitant (methanol/second
Nitrile=1:1) protein precipitation, after vortex mixing, 15000rpm is centrifuged 10min, takes supernatant 5uL and carries out sample analysis.
(4) testing conditions is: triple level Four bar LC-MS instrument, liquid-phase condition: flowing phase: A:0.1%FA aqueous solution, B:
Acetonitrile；
Flow velocity: 0.3ml/min；Sample size: 5uL；Column temperature: 45 DEG C；
Chromatographic column: Waters ACQUITYBEH C18,1.7μm,2.1*50mm Column
Gradient elution program is identical with table 1
Mass Spectrometry Conditions: identical with table 2
Other mass spectrometry parameters:
Capillary voltage (kV): 3.2kV；Source temperature (DEG C): 120；
Desolventizing temperature (DEG C): 350；Desolventizing throughput (L/Hr): 800；
Gas curtain throughput (L/Hr): 50；Residence time (s): 0.1s
The chromatogram of testing result is shown in Fig. 2 and Fig. 3 respectively.
Above one embodiment of the present of invention is described in detail, but described content has been only the preferable enforcement of the present invention
Example, it is impossible to be considered the practical range for limiting the present invention.All impartial changes made according to the present patent application scope and improvement
Deng, within all should still belonging to the patent covering scope of the present invention.
Claims (6)
1. the UPLC-MS/MS detection method of paraben preservative concentration in Urina Hominis, it is characterised in that: include with
Lower step:
1) sample treatment: take urine sample to be measured in test tube or centrifuge tube, the water of 1/10 times of volume of sample-adding, it is subsequently adding β-Portugal
Sugar glycuronide enzyme, shakes up and seals, and puts into and is heated to reaction in 37 DEG C of water-baths completely, takes a certain amount of reactant liquor, add 3 times amount
Precipitant (methanol/acetonitrile=1:1) protein precipitation, vortex mixing after, 15000rpm is centrifuged 10min, takes supernatant 5-10 μ L and enters
Sample is analyzed；
2) HPLC-MS/MS analyzes: the sample after processing with triple level Four bar LC-MS instrument, is carried out point under the following conditions
Analysis liquid-phase condition: flowing phase: A:0.1% aqueous formic acid, B: acetonitrile；Flow velocity: 0.3ml/min；Sample size: 5 μ L；Column temperature: 45
℃；Chromatographic column: Waters ACQUITYBEH C18,1.7μm,2.1*50mm Column
Gradient elution program
Mass Spectrometry Conditions
Other mass spectrometry parameters:
Capillary voltage (kV): 3.2kV；Source temperature (DEG C): 120；
Desolventizing temperature (DEG C): 350；Desolventizing throughput (L/Hr): 800；
Gas curtain throughput (L/Hr): 50；Residence time (s): 0.1s
3) according in the peak area of sample and the regression equation of standard curve, methyl parahydroxybenzoate in urine is calculated, to hydroxyl
Yl benzoic acid ethyl ester, propyl p-hydroxybenzoate, the concentration of butyl p-hydroxybenzoate.
The UPLC-MS/MS detection side of paraben preservative concentration in Urina Hominis the most according to claim 1
Method, it is characterised in that: step (1) sample treatment is: take 500 μ L urines, adds 50 μ L water, the β glucose glycuronide enzyme of 50 μ L
(80U/mL), shake up and seal, put into heating 120min in 37 DEG C of water-baths, after reaction terminates, extract reaction solution 100 μ L, add 300
μ L precipitant (methanol/acetonitrile=1:1) protein precipitation, after vortex mixing, 15000rpm is centrifuged 10min, takes supernatant 5 μ L and carries out sample
Analyze.
The UPLC-MS/MS detection side of paraben preservative concentration in Urina Hominis the most according to claim 1
Method, it is characterised in that: the manufacturing process of step (3) standard curve:
A. standard substance process: take 500 μ L urines, add 50 μ L standard solution, are configured to be equivalent to each composition of plasticiser in urine
Concentration is: the serial solution of 5,10,25,50,100,250,500ng/ml, adds β glucose glycuronide enzyme (80U/mL) of 50 μ L,
Shake up and seal, put into heating 120min in 37 DEG C of water-baths, after reaction terminates, extract reaction solution 100 μ L, add 300 μ L precipitant
(methanol/acetonitrile=1:1) protein precipitation, after vortex mixing, 15000rpm is centrifuged 10min, takes supernatant 5 μ L sample introduction analysis；
B. standard curve making: with testing concentration as abscissa, determinand peak area Component peak area corresponding to urine sample
Difference be vertical coordinate, make standard curve.
The UPLC-MS/MS detection side of paraben preservative concentration in Urina Hominis the most according to claim 1
Method, it is characterised in that: methyl parahydroxybenzoate in the method, ethylparaben, propyl p-hydroxybenzoate, to hydroxyl
The detection limit of yl benzoic acid butyl ester is: 2ng/ml.
The UPLC-MS/MS detection side of paraben preservative concentration in Urina Hominis the most according to claim 1
Method, it is characterised in that: methyl parahydroxybenzoate, ethylparaben, propyl p-hydroxybenzoate, fourth pair in the method
The quantitative limit of hydroxybenzoate is: 5ng/ml.
The UPLC-MS/MS detection side of paraben preservative concentration in Urina Hominis the most according to claim 1
Method, it is characterised in that: the detection range of the method: methyl parahydroxybenzoate in the method, ethylparaben, to hydroxyl
Yl benzoic acid propyl ester, the detection range of fourth p-Hydroxybenzoate are 5-500ng/ml.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106680401A (en) * | 2017-03-20 | 2017-05-17 | 河南师范大学 | Quantitative method for testing p-hydroxybenzoate alkyl ester compounds in sediment |
| CN106680394A (en) * | 2017-01-05 | 2017-05-17 | 上海迪安医学检验所有限公司 | Kit for determining content of 14 environmental hormones in urine in liquid chromatography tandem mass spectrometry |
| CN106680393A (en) * | 2017-01-05 | 2017-05-17 | 上海迪安医学检验所有限公司 | Method for determining contents of 14 types of environmental hormones in urea through liquid chromatography-tandem mass spectrometry |
| CN108445096A (en) * | 2018-02-08 | 2018-08-24 | 河南中烟工业有限责任公司 | The detection method of benzoates plasticizer content in a kind of essence spice for cigarette |
| CN108562659A (en) * | 2018-02-08 | 2018-09-21 | 河南中烟工业有限责任公司 | The detection method of benzoates plasticizer content in a kind of cigarette paper wrapper |
| CN109507335A (en) * | 2018-12-29 | 2019-03-22 | 上海交通大学医学院附属新华医院 | Utilize the method for a variety of different type environmental contaminants in LC-MS-MS high throughput detection urine |
| CN113671093A (en) * | 2020-05-13 | 2021-11-19 | 上海大学 | Method for rapidly detecting p-hydroxybenzoic acid substances in human urine |
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2016
- 2016-09-23 CN CN201610853885.9A patent/CN106248834A/en active Pending
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|---|---|---|---|---|
| CN106680394A (en) * | 2017-01-05 | 2017-05-17 | 上海迪安医学检验所有限公司 | Kit for determining content of 14 environmental hormones in urine in liquid chromatography tandem mass spectrometry |
| CN106680393A (en) * | 2017-01-05 | 2017-05-17 | 上海迪安医学检验所有限公司 | Method for determining contents of 14 types of environmental hormones in urea through liquid chromatography-tandem mass spectrometry |
| CN106680394B (en) * | 2017-01-05 | 2019-03-08 | 上海迪安医学检验所有限公司 | Liquid Chromatography-Tandem Mass Spectrometry measures the kit of 14 kinds of Environmental Hormone contents in urine |
| CN106680401A (en) * | 2017-03-20 | 2017-05-17 | 河南师范大学 | Quantitative method for testing p-hydroxybenzoate alkyl ester compounds in sediment |
| CN106680401B (en) * | 2017-03-20 | 2019-09-24 | 河南师范大学 | The quantitative approach of parabens compound in a kind of measurement deposit |
| CN108445096A (en) * | 2018-02-08 | 2018-08-24 | 河南中烟工业有限责任公司 | The detection method of benzoates plasticizer content in a kind of essence spice for cigarette |
| CN108562659A (en) * | 2018-02-08 | 2018-09-21 | 河南中烟工业有限责任公司 | The detection method of benzoates plasticizer content in a kind of cigarette paper wrapper |
| CN109507335A (en) * | 2018-12-29 | 2019-03-22 | 上海交通大学医学院附属新华医院 | Utilize the method for a variety of different type environmental contaminants in LC-MS-MS high throughput detection urine |
| CN113671093A (en) * | 2020-05-13 | 2021-11-19 | 上海大学 | Method for rapidly detecting p-hydroxybenzoic acid substances in human urine |
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