CN105974041A - Method for detecting perfluorinated compounds by using solid phase microextraction with liquid phase chromatography-tandem mass spectrum - Google Patents
Method for detecting perfluorinated compounds by using solid phase microextraction with liquid phase chromatography-tandem mass spectrum Download PDFInfo
- Publication number
- CN105974041A CN105974041A CN201610506004.6A CN201610506004A CN105974041A CN 105974041 A CN105974041 A CN 105974041A CN 201610506004 A CN201610506004 A CN 201610506004A CN 105974041 A CN105974041 A CN 105974041A
- Authority
- CN
- China
- Prior art keywords
- extraction
- solid
- sample
- solid phase
- coating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/08—Preparation using an enricher
Abstract
The invention relates to a method for detecting perfluorinated compounds by using solid phase microextraction with liquid phase chromatography-tandem mass spectrum. The method comprises the following steps: taking a polyhydric material as a solid phase microextraction coating substrate; carrying out silylation reaction on dimethyl octadecyl[3-trimethoxysilylpropyl] ammonium chloride and the substrate; preparing a novel solid phase microextraction coating with high extraction speed, high stability and high selectivity in site; and detecting the perfluorinated compounds of textile by using the novel solid phase microextraction coating. Meanwhile, solid phase microextraction is used with a liquid phase chromatography-tandem mass spectrometer, a green detecting method for the perfluorinated compounds is provided, use frequency of toxic and harmful organic solvents which pollute the environment and the waste liquid can be reduced, and extraction cost is saved; and meanwhile, high selectivity of solid phase microextraction is utilized, impurities in machine samples can be greatly reduced, the service life of a chromatographic column is prolonged, and maintenance cost is reduced.
Description
Technical field
A kind of method that the present invention relates to solid-phase microextraction and Liquid Chromatography-tandem Mass detection perfluorochemical, relates more specifically to a kind of method utilizing solid-phase micro-extraction coating and liquid chromatography-tandem mass spectrometry instrument combination detection perfluorochemical.
Background content
Perfluorochemical (PFCs) is pollutant [food and the medicine that a class has the organs official of hepatotoxicity, Cardiovascular Toxicity, development toxicity, immune system toxicity, endocrine disrupting and potential carcinogenecity, 10 (7): 66-69], human health and living environment are caused serious threat.In May, 2009, in the Stockholm conference Meeting of States Parties that Geneva, Switzerland is held, perfluoro octyl sulfonic acid and its esters (PFOS), full-fluorine octyl sulfuryl fluoride are formally listed in pact accessories B as newly-increased persistence organic pollutant to be any limitation as；The countries and regions such as the U.S., Canada, European Union have promulgated that relevant laws and regulations forbid the PFCs use in some field, in succession with the maximum allowable addition of such material of limit；In December, 2012, perfluorinated undecanoic acid (PFUdA), perfluor dodecylic acid (PFDoA), perfluor tridecanoic acid (PFTrDA), perfluor tetradecanoic acid (PFTeDA) are classified as the 8th batch by Europe chemical balance motion office and pay high attention to material (Substances of Very High Concern, SVHC)；In June, 2013, perfluoro caprylic acid (PFOA) and perfluorooctanoic acid are listed in the 9th crowd of SVHC.So far, PFOS, perfluoro-heptanoic acid (PFHpA), PFOA, perfluoro-pelargonic acid (PFNA), perfluoro decanoate (PFDA), these 9 kinds of perfluorochemicals of PFUdA, PFDoA, PFTrDA, PFTeDA have been classified as in textile by OEKO-TEX Standard 100 harmful substance and regulation Limited Doses.
At present, in textile, the research about perfluorochemical is concentrated mainly on perfluoro caprylic acid and Perfluorooctane sulfonates and its esters, domestic has SN/T 2842-2011 and two standards of GB/T 31126-2014 to the detection of perfluorochemical in textile to the perfluorocarboxylic acid of other classes and perfluorinated sulfonic acid class research are very few.SN/T 2842-2011 will treat that test sample is put in soxhlet extraction device, carry out surname extraction 6h with the methanol of 100mL, and extracting solution is examination with computer after activated-charcoal column purification, concentration.GB/T 31126-2014 40mL methanol supersound extraction 40min in ultrasonic washing unit, extracting solution is layered by centrifugation, examination with computer after concentration.Although the two standard solves the matter of great urgency of PFCs detection in textile, but pretreatment process therein has following 3 prominent shortcomings: (1) uses ultrasonic extraction or the extraction mode of soxhlet extraction, and extraction efficiency is low, the longest；(2) sample is extracted by a large amount of use organic solvents, not only endangers the health of tester but also can pollute environment further；3), during sample substrate complexity, upper machine sample can reduce detection sensitivity and infringement test instrunment with a large amount of impurity.
Solid-phase microextraction (Solid Phase Microextraction, SPME) is a kind of for assay laboratory with Sample Pretreatment Technique on-the-spot on the spot.SPME uses and a small amount of extraction phase is coated in the surface of solids equably, then the analyte being enriched with in coating is resolved by high-temperature hot or solvent eluting is resolved in analytical tool (such as gas chromatogram or liquid chromatograph) be analyzed measuring quick and completely.Its feature be integrate sample, extract, concentrate, sample introduction, sample is had the strongest enrichment, sensitivity for analysis can be greatly improved and without using solvent.
Nowadays the most existing in a large number about the document report of SPME application, its content relates to the aspects such as basis, device, coating, extraction mode, it is concentrated mainly on the application [chemical reagent of each side such as food, environmental protection, medicine, biomedicine and Analysis of Natural Products, 2008,30 (1): 13].But the application in textile analysis is only limitted to volatile organic matter, organophosphorus pesticide, forbidding azo dyes, free formaldehyde, unusual odor and the detection of antitermite agent residual.There is presently no pertinent literature and be reported in textile application SPME extraction perfluorochemical.
Meanwhile, SPME technology application major part in textile analysis is commodity in use SPME coating, and price is higher, it is difficult to be applied to the most actually detected.And, it is few to there is coat type in commercialization SPME coating type fiber, can extract the direction problem such as extensively, and lack only for the SPME coating of PFCs detection in textile.Although being prepared for a lot of new coating fiber type by sol-gel process, electrochemical method in recent years, but generally there are the drawbacks such as organic coating adsorbance little, production process requires strictly, poor repeatability, limiting the popularization of coating type solid-phase micro-extraction fibre.It is therefore desirable to the novel solid phase micro extraction coating that developing selective is strong, highly sensitive, organic solvent-resistant, extraction direction are single.
Summary of the invention
It is an object of the invention to provide a kind of method utilizing solid-phase micro-extraction coating and Liquid Chromatography-tandem Mass detection perfluorochemical.
The method that the solid-phase microextraction of the present invention detects perfluorochemical with Liquid Chromatography-tandem Mass, preparation including solid-phase micro-extraction coating, described solid-phase micro-extraction coating, with polyhydroxy material for solid-phase micro-extraction coating substrate, utilizes dimethyl stearyl [3-trimethoxy silicon propyl group] ammonium chloride to obtain with substrate generation Silanization reaction.
Above-mentioned polyhydroxy material is timber, silicon dioxide, metal-oxide (titanium dioxide TI2O, zinc oxide ZnO, aluminium oxide Al2O3Deng) in any one.
When prepared by solid-phase micro-extraction coating, use anhydrous solvent, preferably DMF (DMF).
The method that the solid-phase microextraction of the present invention detects perfluorochemical with Liquid Chromatography-tandem Mass, following condition is used: textile sample is cut into prescribed level during sample extraction, weigh a certain amount of being placed in polypropylene centrifuge tube, add aforementioned solid-phase micro-extraction coating and alkalescence synthetic perspiration, alkalescence synthetic perspiration is totally submerged sample, supersound process certain time in ultrasonic oscillator.
Aforementioned extraction conditions is preferably by target textile, it is cut into 5mm × 5mm size, weigh 2g sample to be placed in 50ml polypropylene centrifuge tube, add solid-phase micro-extraction coating and 40ml alkalescence synthetic perspiration to being totally submerged sample, 35 ± 2 DEG C of supersound process 60min in ultrasonic oscillator.
The solid-phase microextraction of the present invention and the method for Liquid Chromatography-tandem Mass detection perfluorochemical, farther include: the extract solution obtained utilizes liquid chromatography-tandem mass spectrometry instrument to carry out qualitative and quantitative analysis.
The present invention is with polyhydroxy material for solid-phase micro-extraction coating substrate, utilizing dimethyl stearyl [3-trimethoxy silicon propyl group] ammonium chloride and substrate generation Silanization reaction, preparation has high extraction rate, high stability, high selective novel solid phase micro extraction coating and uses it for the perfluorochemical detection of textile in situ；It is combined with liquid chromatography-tandem mass spectrometry instrument, it is provided that a kind of green test method measuring perfluorochemical simultaneously, poisonous and harmful, the use polluting the organic solvent of environment and the generation of waste liquid can be reduced, save extraction cost；Utilize the high selectivity of solid-phase microextraction simultaneously, the impurity in upper press proof product can be reduced in large quantities, extend the service life of chromatographic column, reduce maintenance cost.
Detailed description of the invention
It is desirable to provide a kind of method utilizing solid-phase micro-extraction coating and Liquid Chromatography-tandem Mass detection perfluorochemical.
Root according to the literature and consults Patents [European Patent NO.0522990A1], finds quaternary ammonium salt (R in water4N+) cation can be with perfluor acid compounds (CnFn+1COO-Or CnFn+1SO3-) anion generation ion pairing forms corresponding ionic bond (structural formula is shown in formula 1, as a example by PFOA), and can be desorbed under methanol solution.As long as so finding a kind of with quaternary ammonium salt (R4N+) material of cation as coating and is attached in substrate, it is possible to prepare novel solid-phase microextraction parts.The present inventor, through substantial amounts of test, screening, finds that silylating reagent dimethyl stearyl [3-trimethoxy silicon propyl group] ammonium chloride conventional on the market can meet above condition.This silylating reagent can form stable chemical combination key with band polyhydroxy material generation Silanization reaction, therefore has the features such as high stability, solvent resistant flushing and length in service life.It addition, with quaternary ammonium salt (R on this silylating reagent4N+) cation can form corresponding ionic bond with the anion generation ion pairing of PFCs, it is achieved to PFCs height selective extraction and high bioaccumulation efficiency.
Formula 1:PFOA anion matches with Quaternary ammonium cation
Based on above-mentioned discovery, the present inventor is with polyhydroxy material for solid-phase micro-extraction coating substrate, utilize dimethyl stearyl [3-trimethoxy silicon propyl group] ammonium chloride and substrate generation Silanization reaction, preparation has high extraction rate, high stability, high selective novel solid phase micro extraction coating in situ, and uses it for the perfluorochemical detection of textile.
Above-mentioned polyhydroxy material can be material commonly used in the art, such as timber, silicon dioxide, metal-oxide (titanium dioxide TI2O, zinc oxide ZnO, aluminium oxide Al2O3Deng) etc., it is not particularly limited.
When solid-phase micro-extraction coating synthesizes, it is impossible to introduce water, needing to use anhydrous solvent, the present invention uses DMF (DMF), and the available solvent of the present invention is not limited to this, any can realize all can using of function of the present invention.
The solid-phase micro-extraction coating methanol prepared rinses coating surface, is then dried.
Textile sample being cut into prescribed level, weighs a certain amount of being placed in polypropylene centrifuge tube, add aforementioned solid-phase micro-extraction coating and alkalescence synthetic perspiration, alkalescence synthetic perspiration is totally submerged sample, supersound process certain time in ultrasonic oscillator.
The extract solution obtained utilizes liquid chromatography-tandem mass spectrometry instrument to carry out qualitative and quantitative analysis.
It is more fully described the present invention below in conjunction with following example.
Embodiment
Solid-phase micro-extraction coating synthesizes:
First the toothpick of tool lignin is made the size being applicable to solid-phase microextraction handle, is placed in reactor.Add 100ml toward reactor and be dried DMF (DMF), 5ml dimethyl stearyl [3-trimethoxy silicon propyl group] ammonium chloride, protect at nitrogen, under the conditions of 120 ± 5 DEG C, be stirred vigorously reaction 12h.After reaction, rinse coating surface with methanol, be then dried.
The extraction of perfluorochemical in textile:
Textile sample being cut into prescribed level, weighs a certain amount of being placed in polypropylene centrifuge tube, add aforementioned solid-phase micro-extraction coating and alkalescence synthetic perspiration, alkalescence synthetic perspiration is totally submerged sample, supersound process certain time in ultrasonic oscillator.
Sample size in extraction process, the extraction selection of solution, extraction temperature, solvent load and extraction time is the most following selects:
The optimization of solid-phase microextraction:
(1) sample size:
Use 0.508ug/m2PFOA and 0.504ug/m2The white cloth of PFOS, as sample, weighs 2g, extracts 1 hour as extraction solution with 40ml alkalescence synthetic perspiration at 35 DEG C.Relatively sample is cut into 50mm × 50mm, 20mm × 20mm, 10mm × 10mm, 5mm × 5mm and the impact of 1mm × 1mm size.
| Sample size | The PFOA response rate (%) | The PFOS response rate (%) |
| 50mm×50mm | 81.12 | 84.25 |
| 20mm×20mm | 86.48 | 87.53 |
| 10mm×10mm | 90.12 | 92.11 |
| 5mm×5mm | 95.32 | 95.78 |
| 1mm×1mm | 96.47 | 96.88 |
As seen from the above table, sample size can affect the response rate of perfluorochemical.Sample size is the least, and the response rate is the highest.When sample is cut into 1mm × 1mm size, recovery of extraction reaches the highest, but only than response rate height during 5mm × 5mm size a bit.In view of practical operation reason, it is believed that 5mm × 5mm sample size is most suitable.
(2) extraction solution selects:
Use 0.508ug/m2PFOA and 0.504ug/m2The white cloth of PFOS, as sample, weighs 2g, and sample is cut into 5mm × 5mm size, extracts 1 hour as extraction solution with 40ml solution at 35 DEG C.The aqueous solution selecting pH value to be 4.0,7.0 and 10.0, acid synthetic perspiration and alkalescence synthetic perspiration are as comparing.
| Solution | The PFOA response rate (%) | The PFOS response rate (%) |
| PH=4 aqueous solution | 0 | 0 |
| PH=7 aqueous solution | Almost without | Almost without |
| PH=10 aqueous solution | 98.66 | 98.83 |
| Acid synthetic perspiration | 0 | 0 |
| Alkalescence synthetic perspiration | 97.48 | 97.31 |
As seen from the above table, extraction solution alkaline perfluorochemical can obtain the preferable response rate.Alkalescence synthetic perspiration more can react the upper harm as brought to human body that wears clothes containing perfluorochemical.Therefore select alkalescence synthetic perspiration as extraction solution.
(3) extraction temperature:
Use 0.508ug/m2PFOA and 0.504ug/m2The white cloth of PFOS, as sample, weighs 2g, and sample is cut into 5mm × 5mm size, extracts 1 hour as extraction solution with 40ml alkalescence synthetic perspiration.Selecting temperature is that 25 DEG C, 30 DEG C, 35 DEG C and 40 DEG C of conducts are compared.
| Temperature | The PFOA response rate (%) | The PFOS response rate (%) |
| 25℃ | 89.59 | 90.34 |
| 30℃ | 93.15 | 94.37 |
| 35℃ | 95.68 | 96.31 |
| 40℃ | 96.13 | 96.76 |
As seen from the above table, extraction temperature is the highest, and the response rate of perfluorochemical is the highest.35 DEG C is the body temperature of human body, select 35 DEG C as extraction temperature, more can react the upper harm brought containing perfluorochemical that wears clothes to human body.
(4) solvent load:
Use 0.508ug/m2PFOA and 0.504ug/m2The white cloth of PFOS, as sample, weighs 2g, and sample is cut into 5mm × 5mm size, extracts 1 hour as extraction solution with alkalescence synthetic perspiration at 35 DEG C.Selecting solvent load is that 10ml, 20ml, 40ml and 60ml are as comparing.
| Solvent load | The PFOA response rate (%) | The PFOS response rate (%) |
| 10ml | 50.15 | 53.46 |
| 20ml | 90.47 | 90.13 |
| 40ml | 95.76 | 96.67 |
| 60ml | 96.15 | 96.83 |
As seen from the above table, solvent load is the most, and the response rate of perfluorochemical is the highest.Owing to difference is not too big between the response rate of 40ml and 60ml, in order to save resource, select 40ml as solvent load.
(5) extraction time:
Use 0.508ug/m2PFOA and 0.504ug/m2The white cloth of PFOS, as sample, weighs 2g, and sample is cut into 5mm × 5mm size, extracts as extraction solution with 40ml alkalescence synthetic perspiration at 35 DEG C.
| Time | The PFOA response rate (%) | The PFOS response rate (%) |
| 30min | 85.44 | 85.57 |
| 45min | 89.88 | 91.38 |
| 60min | 95.21 | 94.86 |
| 120min | 95.57 | 95.71 |
As seen from the above table, extraction time is the longest, and the response rate of perfluorochemical is the highest.But extraction time is at more than 60min, the response rate of perfluorochemical increases does not beats.In order to time-consuming, select 60min as extraction time.
Contrast through above-mentioned test data, optimum extraction conditions in extraction process is: by target textile, it is cut into 5mm × 5mm size, weigh 2g sample to be placed in 50ml polypropylene centrifuge tube, add solid-phase micro-extraction coating and 40ml alkalescence synthetic perspiration to being totally submerged sample, 35 ± 2 DEG C of supersound process 60min in ultrasonic oscillator.
The detection of PFOA and the PFOS response rate in extraction solution
Use the upper machine testing of liquid chromatography-tandem mass spectrometry instrument (Thermo Ultimate 3000-TSQ Quantiva) that aforesaid extraction solution is carried out qualitative and quantitative analysis, measure PFOA and the PFOS response rate.
Although described above is the embodiment of solid-phase microextraction-fluorimetric HPLC detection perfluorochemical; but; under the above-mentioned teaching of the present invention; those skilled in the art can carry out various improvement and deformation on the basis of above-described embodiment, and these improve or deformation is within the scope of the present invention.It will be understood by those skilled in the art that specific descriptions above are intended merely to explain the purpose of the present invention, be not intended to limit the present invention.Protection scope of the present invention is limited by claim and equivalent thereof.
Claims (7)
1. a solid-phase microextraction and the side of Liquid Chromatography-tandem Mass detection perfluorochemical
Method, it is characterised in that: include the preparation of solid-phase micro-extraction coating, described solid-phase micro-extraction coating with
Polyhydroxy material is solid-phase micro-extraction coating substrate, utilizes dimethyl stearyl [3-trimethoxy silicon
Propyl group] ammonium chloride obtains with substrate generation Silanization reaction.
Method the most according to claim 1, it is characterised in that: described polyhydroxy material is wood
Any one in material, silicon dioxide, metal-oxide.
Method the most according to claim 2, it is characterised in that: described metal-oxide is two
Titanium oxide TI2O, zinc oxide ZnO or aluminium oxide Al2O3。
Method the most according to claim 1, it is characterised in that: in solid-phase micro-extraction coating system
Time standby, use DMF (DMF) as solvent.
Method the most according to claim 1, it is characterised in that: use as follows during sample extraction
Condition: textile sample is cut into prescribed level, weighs a certain amount of being placed in polypropylene centrifuge tube, adds
Entering aforementioned solid-phase micro-extraction coating and alkalescence synthetic perspiration, alkalescence synthetic perspiration is totally submerged sample,
Supersound process certain time in ultrasonic oscillator.
Method the most according to claim 5, it is characterised in that: described extraction conditions is: will
Target textile, is cut into 5mm × 5mm size, weigh 2g sample be placed in 50ml polypropylene from
In heart pipe, add solid-phase micro-extraction coating and 40ml alkalescence synthetic perspiration to being totally submerged sample,
35 ± 2 DEG C of supersound process 60min in ultrasonic oscillator.
7. according to the method described in claim 5 or 6, it is characterised in that: farther include:
To extract solution utilize liquid chromatography-tandem mass spectrometry instrument to carry out qualitative and quantitative analysis.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610506004.6A CN105974041A (en) | 2016-06-28 | 2016-06-28 | Method for detecting perfluorinated compounds by using solid phase microextraction with liquid phase chromatography-tandem mass spectrum |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610506004.6A CN105974041A (en) | 2016-06-28 | 2016-06-28 | Method for detecting perfluorinated compounds by using solid phase microextraction with liquid phase chromatography-tandem mass spectrum |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105974041A true CN105974041A (en) | 2016-09-28 |
Family
ID=56954090
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610506004.6A Pending CN105974041A (en) | 2016-06-28 | 2016-06-28 | Method for detecting perfluorinated compounds by using solid phase microextraction with liquid phase chromatography-tandem mass spectrum |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105974041A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107677748A (en) * | 2017-10-09 | 2018-02-09 | 贵州省疾病预防控制中心 | The rapid screening detection method of perfluorochemical in a kind of breast milk |
| CN108732270A (en) * | 2018-05-18 | 2018-11-02 | 苏州市纤维检验所 | The instrument detection method of smell substance in a kind of mulberry silk product |
| CN109799291A (en) * | 2018-12-27 | 2019-05-24 | 通标标准技术服务有限公司 | The method for measuring perfluorochemical in sample |
| CN110133154A (en) * | 2019-06-20 | 2019-08-16 | 中山大学 | The measuring method of perfluorochemical precursor substance in Atmospheric particulates sampling membrane |
| CN110702494A (en) * | 2019-09-17 | 2020-01-17 | 广东省测试分析研究所（中国广州分析测试中心） | Preparation method and application of triphenylmethane dye and high-selectivity solid-phase microextraction probe of metabolic product of triphenylmethane dye |
| CN110954609A (en) * | 2019-10-22 | 2020-04-03 | 浙江省检验检疫科学技术研究院 | Gas chromatography-mass spectrometry combined determination method for perfluoroalkyl compound in textile |
| CN111366659A (en) * | 2020-04-20 | 2020-07-03 | 山东东岳高分子材料有限公司 | Method for detecting trace PFOA (perfluorooctanoic acid) in powdery fluoropolymer product |
| CN111413432A (en) * | 2020-04-20 | 2020-07-14 | 山东东岳高分子材料有限公司 | Method for detecting trace PFOA (perfluorooctanoic acid) in fluorine-containing polymer emulsion product |
| CN112033786A (en) * | 2020-08-19 | 2020-12-04 | 深圳市环境科学研究院 | Solid-phase extraction method for perfluorinated compounds in environmental water |
| CN114887605A (en) * | 2022-04-24 | 2022-08-12 | 中国农业科学院油料作物研究所 | Perfluoro cotton solid phase extraction material and application thereof in enrichment and detection of organic fluoride |
| CN116735743A (en) * | 2023-06-07 | 2023-09-12 | 重庆大学 | Method for simultaneously detecting type and total amount of perfluorinated compounds in organic solid sample |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104134606A (en) * | 2014-07-30 | 2014-11-05 | 中山大学 | Microextraction probe electrospray ion source and manufacturing method and application of microextraction probe electrospray ion source |
-
2016
- 2016-06-28 CN CN201610506004.6A patent/CN105974041A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104134606A (en) * | 2014-07-30 | 2014-11-05 | 中山大学 | Microextraction probe electrospray ion source and manufacturing method and application of microextraction probe electrospray ion source |
Non-Patent Citations (3)
| Title |
|---|
| JIEWEI DENG ET AL: "Coupling Solid-Phase Microextraction with Ambient Mass Spectrometry Using Surface Coated Wooden-Tip Probe for Rapid Analysis of Ultra Trace Perfluorinated Compounds in Complex Samples", 《ANALYTICAL CHEMISTRY》 * |
| MICHAEL P. MAWN ET AL: "Determination of extractable perfluorooctanoic acid (PFOA) in water,sweat simulant, saliva simulant, and methanol from textile and carpet samples by LC/MS/MS", 《ANALYST》 * |
| 陈春燕: "新型固相微萃取涂层的制备及其在环境分析中的应用", 《中国博士学位论文全文数据库（工程科技Ⅰ辑）》 * |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107677748B (en) * | 2017-10-09 | 2020-07-31 | 贵州省疾病预防控制中心 | Rapid screening and detecting method for perfluorinated compounds in breast milk |
| CN107677748A (en) * | 2017-10-09 | 2018-02-09 | 贵州省疾病预防控制中心 | The rapid screening detection method of perfluorochemical in a kind of breast milk |
| CN108732270A (en) * | 2018-05-18 | 2018-11-02 | 苏州市纤维检验所 | The instrument detection method of smell substance in a kind of mulberry silk product |
| CN108732270B (en) * | 2018-05-18 | 2021-04-09 | 苏州市纤维检验院 | Instrument detection method for odor substances in mulberry silk cotton products |
| CN109799291A (en) * | 2018-12-27 | 2019-05-24 | 通标标准技术服务有限公司 | The method for measuring perfluorochemical in sample |
| CN109799291B (en) * | 2018-12-27 | 2021-06-01 | 通标标准技术服务有限公司 | Method for determining perfluorinated compounds in sample |
| CN110133154A (en) * | 2019-06-20 | 2019-08-16 | 中山大学 | The measuring method of perfluorochemical precursor substance in Atmospheric particulates sampling membrane |
| CN110702494A (en) * | 2019-09-17 | 2020-01-17 | 广东省测试分析研究所（中国广州分析测试中心） | Preparation method and application of triphenylmethane dye and high-selectivity solid-phase microextraction probe of metabolic product of triphenylmethane dye |
| CN110954609A (en) * | 2019-10-22 | 2020-04-03 | 浙江省检验检疫科学技术研究院 | Gas chromatography-mass spectrometry combined determination method for perfluoroalkyl compound in textile |
| CN111413432A (en) * | 2020-04-20 | 2020-07-14 | 山东东岳高分子材料有限公司 | Method for detecting trace PFOA (perfluorooctanoic acid) in fluorine-containing polymer emulsion product |
| CN111366659A (en) * | 2020-04-20 | 2020-07-03 | 山东东岳高分子材料有限公司 | Method for detecting trace PFOA (perfluorooctanoic acid) in powdery fluoropolymer product |
| CN111413432B (en) * | 2020-04-20 | 2023-01-13 | 山东东岳高分子材料有限公司 | Method for detecting trace PFOA (perfluorooctanoic acid) in fluorine-containing polymer emulsion product |
| CN112033786A (en) * | 2020-08-19 | 2020-12-04 | 深圳市环境科学研究院 | Solid-phase extraction method for perfluorinated compounds in environmental water |
| CN114887605A (en) * | 2022-04-24 | 2022-08-12 | 中国农业科学院油料作物研究所 | Perfluoro cotton solid phase extraction material and application thereof in enrichment and detection of organic fluoride |
| CN114887605B (en) * | 2022-04-24 | 2023-10-03 | 中国农业科学院油料作物研究所 | Perfluoro cotton solid phase extraction material and application thereof in enrichment and detection of organic fluoride |
| CN116735743A (en) * | 2023-06-07 | 2023-09-12 | 重庆大学 | Method for simultaneously detecting type and total amount of perfluorinated compounds in organic solid sample |
| CN116735743B (en) * | 2023-06-07 | 2024-03-22 | 重庆大学 | Method for simultaneously detecting type and total amount of perfluorinated compounds in organic solid sample |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105974041A (en) | Method for detecting perfluorinated compounds by using solid phase microextraction with liquid phase chromatography-tandem mass spectrum | |
| CN103913528B (en) | Quantitative detection method for pyrethriods pesticides in fresh tea | |
| CN104991017B (en) | Liquid chromatogram-tandem mass spectrometry method for determining isothiazolinone bactericides contained in water-based adhesive | |
| CN103926348A (en) | Analytical method of simultaneously measuring residues of organophosphorus pesticide and pyrethriods pesticide in fresh leaves | |
| CN102288691A (en) | Method for assaying short-chain chlorinated paraffin wax in plastics, rubbers and textile materials | |
| CN107179362A (en) | Method for detecting pesticide residue of fruit and vegetable carbendazim | |
| CN104931597A (en) | Method capable of simultaneously detecting varieties of pesticide residues in aquatic product | |
| CN103995074B (en) | Method for detecting residual quantity of organochlorine pesticides in raw milk | |
| CN103913538B (en) | The quantitative detecting method of organophosphorus insecticide in a kind of tea fresh leaves | |
| Liang et al. | Determination of trace chlorophenols endocrine disrupting chemicals in water sample using [Bmim] BF4-NaH2PO4 aqueous two-phase extraction system coupled with high performance liquid chromatography | |
| CN110174470A (en) | The high-flux detection method of marine biotoxins in a kind of aquatic products | |
| CN104535548B (en) | Method for rapidly detecting sulfonamide antibacterial medicines in milk by using in-tube solid-phase micro-extraction technology | |
| CN108760920A (en) | A method of cyazofamid and its metabolite residue amount are measured based on HPLC-MSMS methods | |
| CN106645486B (en) | A kind of method of liquid chromatogram high resolution mass spectrum measurement soil glyphosate residual quantity | |
| CN102866226B (en) | Method for using pyrazosulfuron-ethyl molecularly imprinted polymer for analyzing sulfonylurea herbicide and application thereof | |
| CN101158671A (en) | Triclosan fast analysis method in surroundings water sample | |
| CN104849385B (en) | Gas chromatographic mass spectrometry determination method for chlorobenzene compounds | |
| CN105891344A (en) | Technology for rapidly detecting and confirming multiple ultraviolet light absorbers in cosmetics | |
| CN104849383A (en) | Method for determining nitroimidazole drug in bee pollen powder through combination of rapid solvent extraction-gel chromatography purification-LC/MS/MS | |
| CN106404507A (en) | Leaf vegetable gibberellins residue detection sample pretreatment method and detection method | |
| CN109374777A (en) | A kind of detection method of pesticide residues in vegetables medicine auxiliary agent | |
| CN104483433B (en) | A kind of measure the method for bis-phenol-S in daily necessities | |
| CN101458240A (en) | Thin-layer chromatography developing agent for detecting melamine residual and analytical method | |
| CN108828102B (en) | Method for determining content of pineapple ester and jasmal in essence and flavor | |
| CN103776931A (en) | Measuring method of ethylamine in workplace air |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160928 |
|
| RJ01 | Rejection of invention patent application after publication |