CN105738455A - Method for analyzing polycyclic aromatic hydrocarbon by using micellar electrokinetic capillarychromatography - Google Patents
Method for analyzing polycyclic aromatic hydrocarbon by using micellar electrokinetic capillarychromatography Download PDFInfo
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- CN105738455A CN105738455A CN201410764505.5A CN201410764505A CN105738455A CN 105738455 A CN105738455 A CN 105738455A CN 201410764505 A CN201410764505 A CN 201410764505A CN 105738455 A CN105738455 A CN 105738455A
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Abstract
The invention provides a method for measuring a polycyclic aromatic hydrocarbon neutral molecule in cosmetics by using a Large Volume Sample Stacking-pH Dynamic link-micellar electrokinetic capillarychromatography (LVSS-DypH-MEEKC). The method employs the LVSS-DypH-MEEKC to analyze and detect a cosmetic extract, and obtains electrophoresis spectrograms of polycyclic aromatic hydrocarbon compounds of benzo[g, h, i]erylenesolution, dibenzo[a,h]anthracene, benzo[a]erylenesolution, benzo[b]fluoranthene, benzo[a]anthracene, and fluoranthene. The concentrations of the six substances are obtained according to a correction curvilinear equation. According to the invention, the concentrations of the benzo[g, h, i]erylenesolution, the dibenzo[a,h]anthracene, the benzo[a]erylenesolution, the benzo[b]fluoranthene, the benzo[a]anthracene, and the fluoranthene in the cosmetics can be analyzed and measured simultaneously. The method for analyzing polycyclic aromatic hydrocarbon by using micellar electrokinetic capillarychromatography can be used for detecting the polycyclic aromatic hydrocarbons and provides an effective reference for separation and enrichment of other neutral compounds with the same structure and property. The method is simple, rapid and high efficient. A buffer solution used in the method is mainly an aqueous solution without a large amount of organic solvents, has small pollution, and is environment friendly. The amount of requirement solvents and samples are small. The price of used hollow capillary columns is low, and the analysis cost is low.
Description
Technical field
The invention belongs to technical field of analysis and detection, disclose the use of the method that large volume sample injection-pH Dynamic link library-sweep collection microemulsions polymerization (LVSS-DypH-MEEKC) measures polycyclic aromatic hydrocarbons in cosmetics neutral molecule.
Background technology
The neutral molecule that polycyclic aromatic hydrocarbon (PAHs) mostly is fat-soluble height, hydrophobicity is strong, can bring out skin carcinoma, carcinoma of scrotum and pulmonary carcinoma, is important environment and food contaminant." cosmetics health specification " specifies, benzo [g, h, i] pyrene, dibenzo [a, h] anthracene, benzo [a] pyrene, benzo [b] fluoranthene, benzo [a] polycyclic aromatic hydrocarbon compounds such as anthracene, fluoranthene are banned substance in cosmetics.At present, the Principle analytical techniques of PAHs has high performance liquid chromatography (HPLC) gas chromatography (GC).Some PAHs can not use GC direct analysis.And for the similar PAHs of structure, utilizing HPLC to analyze, sensitivity and separating degree are all relatively low.Capillary electrophoresis method has that instrument is simple, easy to operate, separation efficiency is high, analyzes the features such as speed is fast, operator scheme is many, is applied to the analysis of all kinds of sample more and more widely.Having some at present utilizes Micellar Capillary Electrophoresis (MEKC) and filled capillary pipe chromatograph (CEC) to be successfully separated the example of PAHs.But the detection sensitivity of conventional capillary electrophoresis method is relatively low, it is impossible to meet quality monitoring requirement.On-line concentration only by regulating and controlling just to be remarkably improved detection sensitivity to buffer composition and injection procedure, becomes the study hotspot in capillary electrophoresis analysis field in recent years.On-line concentration is broadly divided into sample stacking technology, sweeps collection art, isotachophoresis etc., and technology of wherein piling up often realizes when sample introduction, with rear several technology couplings, can improve sensitivity further.
It is a kind of specific form of conventional electricity accumulation mode that large volume sample injection pile amasss, and can pile up the restriction of technology sampling volume efficiently against routine, make detection sensitivity improve more than two orders of magnitude.In MEEKC method, sample strengthens with the effect containing the more microemulsion particle of the high power capacity factor, and concentrating degree increases, and makes detection sensitivity significantly improve.
Summary of the invention
In order to solve above-mentioned the deficiencies in the prior art part, the primary and foremost purpose of the present invention be in that by large volume sample injection, pH Dynamic link library and sweep collection phase coupling mode PAHs is carried out concentration and separation, by changing the migration velocity carrying the microemulsion particle that analyte is advanced, connect at pH and zone produces pile up, polarity need not be changed and just can realize large volume sample injection accumulation, it is achieved the Sensitive Detection to PAHs.
The purpose of the present invention is realized by following technical scheme: under backward voltage, utilizes suitable LVSS-DypH-sweep system to concurrently separate six kinds strong lipophilic polycyclic aromatic hydrocarbon neutral molecules of analysis, reaches the purpose simultaneously detected.The detecting step of this present invention is as follows:
(1) accurately weigh six standard substance, dissolve constant volume in the volumetric flask of 5mL with dichloromethane and ethanol, be made into the stock solution of 2g/L, keep in Dark Place at-18 DEG C.
(2) under backward voltage, adopt large volume sample injection-pH Dynamic link library-sweep collection microemulsions polymerization (LVSS-DypH-MEEKC) to measure 6 kinds of polycyclic aromatic hydrocarbons, obtain the forward MEEKC electrophoretic image of the standard substance of 6 kinds of PAHs
(3) adopt LVSS-DypH-sweep system, utilize microemulsion Electrokinetic Chromatography method, under optimal detection condition, the extracting solution of sample is analyzed, it is thus achieved that the capillary electrophoresis figure of sample.
(4) the calibration trace equation according to six kinds of polycyclic aromatic hydrocarbons, the content of the polycyclic aromatic hydrocarbon calculated in step (3) in cosmetic sample.
The optimal detection condition that the present invention adopts is:
Consisting of of microemulsion: SDS2.4% (w/w), normal octane 0.6% (w/w), n-butyl alcohol 6.6% (w/w), 20mmol/LNaH2PO4Buffer (pH2.2).
Height is led buffer (HCB) and is consisted of: 20mmol/LNaH2PO4(pH2.2)-acetonitrile (80:20v/v).
Sample substrate is: SDS2.4% (w/w)-n-butyl alcohol 6.6% (w/w)-normal octane 0.6% (w/w), 0.2mmol/L borate buffer solution (pH7.8)-20% acetonitrile.
Ultraviolet detection wavelength is 280nm, and working voltage is-20kV, and temperature is 20 DEG C.
The described sample extracting solution of step (3) adopts following steps to obtain, and in a certain amount of sample, adds 10mL normal hexane-acetone (1:1；V/v) solution, after ultrasonic 20min, high speed centrifuge is utilized to be centrifuged 5min, taking supernatant, add 10mL normal hexane-acetone (1:1v/v) solution in lower floor's residue, operational approach is ibid, repeat to extract three times, merging supernatant, cream kind cosmetics repeat twice supernatant of extraction on the basis of the above-described procedure, merge supernatant.Supernatant is put into the freezing 5min of refrigerator；Extracting solution after freezing filters with 0.45 μm of filter membrane after taking out, and constant volume is in 50mL volumetric flask.By filtrate again with dichloromethane liquid-liquid extraction 4 times, each 10mL, merge upper strata hexamethylene phase, be concentrated into about 2mL.
Under best testing conditions, six kinds of polycyclic aromatic hydrocarbons reached baseline separation in 9 minutes, it is shown that good separation selectivity and sensitivity.Six materials are in the range of linearity respectively 50-4.0 × 10 of the method3Ng/mL, 15-1.5 × 102Ng/mL, 10-1.0 × 104Ng/mL, 50-4.0 × 103Ng/mL, 1.0 × 102-1.0×104Ng/mL, 87.5-7.0 × 104ng/mL.Detection is limited to 38.0ng/mL, 8.75ng/mL, 57.5ng/mL, 23.6ng/mL, 84.0ng/mL, 48.6ng/mL (S/N=3), and the relative standard deviation (RSD) of peak area is less than 5.1%.
The present invention, relative to prior art, has such advantages as and beneficial effect: the quality control that (1) present invention is cosmetics provides technical support, and detection is quickly；(2) environmental friendliness, economic and environment-friendly, buffer used mostly is aqueous phase, it is not necessary to consumes substantial amounts of organic solvent, ratio liquid chromatograph more environmental protection, is more beneficial for the healthy of tester；(3) analysis cost is low, and required sample and solvent are all little, detects the buffer solution of a sample consumption less than 1mL, and chromatographic column that need not be special, only uses common open hole capillary column, and price is lower than general chromatographic column several times.(4) the method can be not only used for the detection of polycyclic aromatic hydrocarbon, and the separation and concentration for comparatively close other neutral compound of structure and character provides an effective reference.
Accompanying drawing explanation
Fig. 1 is LVSS-DypH-sweep schematic diagram.Wherein (A) large volume sample injection；(B) dynamic pH junction；(C) collection is swept；(D) MEEKC modal cutoff.
The LVSS-DypH-sweep electrophoretic image of Fig. 2 standard substance.Wherein 1. benzos [g, h, i] pyrene, 2. dibenzo [a, h] anthracene, 3. benzo [a] pyrene, 4. benzo [b] fluoranthene, 5. benzo [a] anthracene, 6. fluoranthene.
Specific embodiments
Embodiment:
1, materials and methods
(1) test material:
Emulsion in certain branding cosmetic.
(2) instrument and chromatographic condition:
TH-3100 efficient capillary electrophoresis apparatus.
(total length is 65cm to adopt non-coating quartz capillary, effective length 50cm, column internal diameter is 50 μm) for split tunnel, in the way of 20s/16Kpa, enter height lead zone (HCB), then 80s/16Kpa mode sample introduction, ultraviolet detection wavelength 280nm, working voltage-20kV, temperature 20 DEG C.
(3) preparation of polycyclic aromatic hydrocarbon standard solution:
Accurately weigh six standard substance, dissolve constant volume in the volumetric flask of 5mL with dichloromethane and ethanol, be made into the stock solution of 2g/L, keep in Dark Place at-18 DEG C.
(4) prepared by sample solution:
Accurately weigh 2.00g cosmetics to be measured, add 10mL normal hexane-acetone (1:1；V/v) solution, after ultrasonic 20min, high speed centrifuge is utilized to be centrifuged 5min, taking supernatant, add 10mL normal hexane-acetone (1:1v/v) solution in lower floor's residue, operational approach is ibid, repeat to extract three times, merging supernatant, cream kind cosmetics repeat twice supernatant of extraction on the basis of the above-described procedure, merge supernatant.Supernatant is put into the freezing 5min of refrigerator；Extracting solution after freezing filters with 0.45 μm of filter membrane after taking out, and constant volume is in 50mL volumetric flask.By filtrate again with dichloromethane liquid-liquid extraction 4 times, each 10mL, merge upper strata hexamethylene phase, be concentrated into about 2mL.
(5) microemulsion runs the preparation of liquid:
0.024g/mL sodium lauryl sulphate SDS, 0.066g/mL n-butyl alcohol, 0.006g/mL normal octane, the phosphate sodium dihydrogen buffer solution of 20mmol/LpH2.2, ultrasonic 30min.Through 0.45 μm of membrane filtration before using, and ultrasonic degassed 10min.
(6) mensuration of polycyclic aromatic hydrocarbons in cosmetics content:
Under the experiment condition optimized, cosmetics extracting solution sample introduction on efficient capillary electrophoresis apparatus, parallel assay 3 times.
(7) sample recovery rate measures:
Corresponding cosmetics add the standard solution of a certain amount of corresponding polycyclic aromatic hydrocarbon, fully mixes, with respective sample same process, gained extracting solution sample introduction on efficient capillary electrophoresis apparatus, same parallel assay 3 times simultaneously.
2, measurement result
(1) polycyclic aromatic hydrocarbon separating resulting (as shown in Figure 2)
(2) polycyclic aromatic hydrocarbon measurement result:
The range of linearity of 6 kinds of polycyclic aromatic hydrocarbons, regression equation and correlation coefficient, detection limit are shown in Table 1.
Sample determination result and recovery of standard addition are in Table 2.
The regression equation of 1 six kinds of PAHs of table, the range of linearity and detection limit
(enrichment times: the peak area of the peak area of extension rate × LVSS-DypH-sweep/positive MEEKC)
The measurement result of six kinds of polycyclic aromatic hydrocarbons and response rate experiment in table 2 sample
Note: N.F refers to not detect.
Claims (7)
1. the method for 6 kinds of polycyclic aromatic hydrocarbons in a separation determination skin-care cosmetics, it is characterized in that with large volume sample injection-pH Dynamic link library-sweep collection microemulsions polymerization (LVSS-DypH-MEEKC) method, sample is after normal hexane-acetone extraction, lead buffer (HCB) for advanced one section high, then the method utilizing large volume sample injection, sample extracting solution sample introduction to microemulsion is run on the capillary electrophoresis of liquid, separate under electrophoresis and condition determination and measure cosmetics benzo [g, h, i] pyrene, dibenzo [a, h] anthracene, benzo [a] pyrene, benzo [b] fluoranthene, benzo [a] anthracene, the content of fluoranthene.
2. method according to claim 1, is characterized in that sample extracting solution adopts following steps to obtain, in a certain amount of sample, adds 10mL normal hexane-acetone (1:1；V/v) solution, after ultrasonic 20min, high speed centrifuge is utilized to be centrifuged 5min, taking supernatant, add 10mL normal hexane-acetone (1:1v/v) solution in lower floor's residue, operational approach is ibid, repeat to extract three times, merging supernatant, cream kind cosmetics repeat twice supernatant of extraction on the basis of the above-described procedure, merge supernatant.Supernatant is put into the freezing 5min of refrigerator；Extracting solution after freezing filters with 0.45 μm of filter membrane after taking out, and constant volume is in 50mL volumetric flask.By filtrate again with dichloromethane liquid-liquid extraction 4 times, each 10mL, merge upper strata hexamethylene phase, be concentrated into about 2mL.
3. method according to claim 1, is characterized in that microemulsion runs consisting of of liquid: SDS2.4% (w/w), normal octane 0.6% (w/w), n-butyl alcohol 6.6% (w/w), 20mmol/LNaH2PO4Buffer (pH2.2).
Height is led buffer (HCB) and is consisted of: 20mmol/LNaH2PO4(pH2.2)-acetonitrile (80:20v/v).
4. method according to claim 1, sample is dissolved in sample substrate, consisting of of sample substrate: SDS2.4% (w/w)-n-butyl alcohol 6.6% (w/w)-normal octane 0.6% (w/w), 0.2mmol/L borate buffer solution (pH7.8)-20% acetonitrile.
5. method according to claim 1, is characterized in that the capillary tube that capillary electrophoresis adopts is non-coating quartz capillary, and total length is 65cm, effective length 50cm, and column internal diameter is 50 μm.
6. method according to claim 1, is characterized in that the condition of capillary electrophoresis is: sample introduction pressure 16Kpa, sample injection time 80s, and height is led zone (HCB) and entered pressure 16Kpa, entry time 20s, anti-phase working voltage-20kV, running temperature 20 DEG C.
7. method according to claim 1, is characterized in that sample extracting solution is after capillary electrophoresis separation, adopts UV-detector detection, and detection wavelength is 280nm.
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| CN112305116A (en) * | 2020-10-30 | 2021-02-02 | 上海化工研究院有限公司 | Method for determining ultra-trace polycyclic aromatic hydrocarbon in water quality |
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| CN102706971A (en) * | 2010-12-09 | 2012-10-03 | 江南大学 | A method for analysis of corticosteroids in cosmetics utilizing reverse microemulsion electrokinetic chromatography by taking an ionic liquid as an additive |
| US20130319862A1 (en) * | 2012-06-04 | 2013-12-05 | Beckman Coulter, Inc. | Leakage current sense circuit for error detection in an improved capillary electrophoresis-electrospray ionization- mass spectrometry system |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102706971A (en) * | 2010-12-09 | 2012-10-03 | 江南大学 | A method for analysis of corticosteroids in cosmetics utilizing reverse microemulsion electrokinetic chromatography by taking an ionic liquid as an additive |
| US20130319862A1 (en) * | 2012-06-04 | 2013-12-05 | Beckman Coulter, Inc. | Leakage current sense circuit for error detection in an improved capillary electrophoresis-electrospray ionization- mass spectrometry system |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112305116A (en) * | 2020-10-30 | 2021-02-02 | 上海化工研究院有限公司 | Method for determining ultra-trace polycyclic aromatic hydrocarbon in water quality |
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Application publication date: 20160706 |