CN106770722A - A kind of method of HBCD chiral isomer in detection animal muscle based on MSPD methods - Google Patents
A kind of method of HBCD chiral isomer in detection animal muscle based on MSPD methods Download PDFInfo
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Abstract
The invention discloses a kind of method of HBCD in detection animal muscle based on MSPD methods, the extraction conditions that MSPD extracts HBCD in animal muscle are optimized by response phase method；Then HBCD is detected using LC MS/MS methods.The 100ng/g of the range of linearity 0.5 of detection method, coefficient correlation is 0.056~0.18ng/g more than 0.98, LOD, LOQs is 0.187~0.602ng/g, the rate of recovery is 84.0%~117.3%, and precision RSD is 4.6%~12.5%, fully meets national standard《Good Laboratory controls specification food Physico-chemical tests》The requirement of (GB/T 27,404 2008).The method pre-treatment is simple and quick, and detection sensitivity is high, as a result accurately and reliably, environment-friendly, is a method with practical value, and the physical and mental health and social stability for ensuring food safety, protecting common people have important practical significance and social benefit.
Description
Technical field
The present invention relates to a kind of method of HBCD chiral isomer in detection animal muscle based on MSPD methods.
Background technology
HBCD (Hexabromocylcododecane, HBCD) is a kind of addition type bromide fire retardant, normal temperature
It is white solid under normal pressure, molecular formula is C12H18Br6, relative molecular mass 641.70,175-195 DEG C of molten point, octanol-water is matched somebody with somebody
Coefficient 5.62 (25 DEG C), smaller (20 DEG C) of solubility is 65.6ng/L in water, molten in the organic solvents such as acetonitrile, dichloromethane
Xie Du is larger.Because its bromine content is (up to 74.7%) higher, polystyrene is widely used in as a kind of excellent fire retardant
The fields such as foam, indoor decoration textile and electronic product, are the combustion inhibitor specials of plastic extrusion heated board.
Have scientific investigations showed that, HBCD shows toxicity, biological concentration and the difficult degradation of persistent pollutant in the environment
Etc. feature, the short-list for being put into Convention of Stockholm in 2009.The fat-soluble features of HBCD are made it easier in animal
Accumulated in body tissue, its accumulation phenomenon in edible animal muscle, adipose tissue is it has been reported that but currently without unification
Applicable standard detecting method.Therefore, in developmental research animal muscle the detection method of HBCD for ensuring food safety, protecting
The physical and mental health and social stability of common people have great importance.
HBCD commodity are main by three kinds of stereoisomers (α-, β-and γ-HBCD) composition, and are racemic compound,
All there is chiral isomer (i.e. enantiomter).Stereoisomer and its chiral isomer structure are as follows：
The higher boiling and gas chromatographic column of HBCD cannot separate the technology inferior position such as isomers causes gas chromatography not apply to
In the detection of HBCD.Existing document report, the chiral solvents such as cyclodextrin are added using Chiral liquid chromatography post or in the phase that circulates,
Can complete the separation of enantiomter using high performance liquid chromatography (HPLC), but method sample pre-treatments complexity sensitivity compared with
Difference, limits the application of its HBCD detection in animal muscle.The correlative study that in addition, there will be is most of only for the vertical of HBCD
Body isomers, i.e. α-HBCD, β-HBCD, γ-HBCD, in fact, every kind of stereoisomer is removable to be divided into two kinds of (+) and (-)
Absorption, metabolic process in chiral isomer, and organism have chiral selectivity, but on chiral resolution analysis method
Research report is less, therefore, the new detection method that HBCD chipal compounds are set up in exploitation has great significance.
The content of the invention
It is dynamic based on the detection of matrix solid phase dispersion (MSPD) method it is an object of the invention to provide one kind for above-mentioned prior art
The method of HBCD chiral isomer in thing muscle.The method can simply, fast and accurately in animal muscle
HBCD isomers is detected.
To achieve the above object, the present invention uses following technical proposals：
The first aspect of the present invention, there is provided a kind of that the side that MSPD extracts HBCD in animal muscle is optimized by response phase method
Method, comprises the following steps：
(1) dispersant and eluant, eluent for being used using HBCD in MSPD methods extraction animal muscle are carried out as experimental factor
Single factor experiment；
(2) according to single factor experiment result, reversed material C18, dispersant florisil silica (Florisil) are chosen and is washed
De- agent acetonitrile (ACN) these three factors, set to factor level, are modeled using Box-Behnken Design, lead to
Applicability and reasonability that model is verified in variance analysis (ANOVA) are crossed, multiple regression equation Y=-2.24 × 10 are obtained6+2.90
×105A+1.06×106B+1.90×106C+2.24×105AB-7.33×105AC+1.50×105BC-2.66×105A2-
1.54×105B2-8.75×105C2；Wherein, Y：Peak area；A:C18 mass；B：ACN volumes；C:Florisil mass, it is determined that
The optimal conditions of model prediction.
The second aspect of the present invention, there is provided a kind of extracting method of HBCD in animal muscle, step is as follows：
By animal muscle sample freeze-drying to be extracted, dried animal muscle sample and Florisil are pressed into quality
Than being 1：(1.5-3) mixes, and is ground to well mixed；It is then transferred in polyethylene post of the bottom equipped with C18, using acetonitrile
Eluted, collected eluent；Eluent is blown to high pure nitrogen closely do, obtained final product.
Preferably, dried animal muscle sample and Florisil are 1 in mass ratio：2 mixing.
Preferably, dried animal muscle sample and the mass ratio that C18 is added are 1：(2-3)；More preferably 1：
2.4。
Preferably, the ratio of dried animal muscle sample and acetonitrile usage amount is：1g:(8-12)ml；Further preferably
For：1g:10ml.
The third aspect of the present invention, there is provided a kind of detection method of HBCD chiral isomers in animal muscle, step is as follows：
(1) HBCD is extracted by said extracted method, is dissolved with acetonitrile, prepare sample solution；
(2) sample solution is detected using LC-MS/MS.
In step (2), liquid phase chromatogram condition is：Chromatographic column EC 200/4NUCLEODEX β-PM posts, column temperature is 40 DEG C, stream
Dynamic phase：The acetonitrile/water solution of volume ratio 80/20, flow velocity：0.5mL/min.
In step (2), MS/MS conditions：Atmospheric pressure electrospray ionization source (ESI), negative ion mode collection, capillary voltage
4Kv, dry gas stream amount is that 3.0L/min temperature is 280 DEG C, and atomizing pressure 40psi, collision gas use high-purity nitrogen
(99.999%), capillary voltage 4Kv, collision voltage 90V.
Beneficial effects of the present invention：
(1) matrix solid phase dispersion (MSPD) is a kind of very effective extracting and purifying technology, particularly in complex matrices such as
In animal or plant tissue.The method greatly simplifies and shortens extraction process, greatly reduces solvent consumption and has non-
The normal good rate of recovery, with simple, cheap, sample scope it is wide, extract the easily operated, rate of recovery stabilization the features such as, thus obtain
Extensive use, and by many countries as standard method.In MSPD, the extracting and purifying species and proportioning of scattered adsorption agent,
Eluting solvent species and consumption are the keys for obtaining optimum efficiency.The present invention is inhaled by single factor experiment and response phase method to dispersion
The species of attached dose and eluting solvent, the proportioning of composite diffusion adsorbent, the consumption of eluting solvent are optimized.The response surface of foundation
Method model step is simple, easily realizes, the condition optimizing according to mathematical models is conducive to improve production efficiency and product product
Matter, reduce operating cost, meet Green Chemistry requirement.
(2) HBCD in animal muscle sample is extracted using the extraction conditions after present invention optimization, its recovery rate
Up to 80.7~98.2%.
(3) present invention is detected that detection process is simple, and all experimentss process only needs 15 to the chiral isomer of HBCD
Minute, consumption solvent is few；And the accuracy of detection method is good, the range of linearity 0.5-100ng/g of detection method, phase
Relation number is 0.056~0.18ng/g more than 0.98, LOD, and LOQs is 0.187~0.602ng/g, and relative recovery is 84.0%
~117.3%, precision RSD is 4.6%~12.5%, fully meets national standard《Good Laboratory control specification food reason
Change detection》The requirement of (GB/T 27404-2008).The method pre-treatment is simple and quick, and detection sensitivity is high, as a result accurately may be used
Lean on, it is environment-friendly, be a method with practical value, for ensure food safety, protect the physically and mentally healthy of common people and
Social stability has important practical significance and social benefit.
Brief description of the drawings
Fig. 1：Experiment of single factor optimizes dispersant；
Fig. 2：Single factor test Optimal Experimental eluent species；
Fig. 3 a- Fig. 3 c：HBCD peak area responses face figure, wherein, Fig. 3 a are the result that C18 consumptions and ACN are interacted, and Fig. 3 b are
Florisil consumptions and the result of ACN volumes interaction；3c is the result that Florisil consumptions and C18 consumptions are interacted；
Fig. 4：Sample2# sample chromatograms figure in embodiment 4.
Specific embodiment
The present invention is further illustrated in conjunction with the embodiments, it should explanation, and the description below is merely to explain this
Invention, is not defined to its content.
Reagent used, material and instrument are as follows in following embodiments：
Three kinds of isomer monomer standard items of HBCD (purity is all higher than 99%, 100 μ g/mL) are purchased from
AccuStandards companies (New Haven, USA).Three kinds of isomer monomers of HBCD of stable carbon isotope mark
(13C- α-,13C- β-,13C- γ-HBCD, purity more than 98%) purchased from Cambridge Isotope laboratories (Andover, MA,
USA), all of above standard specimen is diluted to 2 μ g/mL and is placed in -20 DEG C of refrigerators and preserves with Chromatographic Pure Methanol.Methyl alcohol, acetonitrile (ACN)
Tedia companies are purchased from acetone (chromatographic grade).N- propyl group ethylenediamine (PSA, 40-60 μm), C18 (50 μm) and florisil silica
(Florisil, 60-100 mesh) is purchased from Agela companies (Tianjin).Neutral alumina (Al2O3,100-200 mesh) and anhydrous sulphur
Sour magnesium (MgSO4) it is purchased from Sinopharm Chemical Reagent companies (Shanghai).
The type liquid chromatogram of Agilent 1200 with the triple quadrupole rods tandem mass spectrometry instrument of 6410 types (Palo Alto,
California,USA)。
What is do not illustrated is the conventional commercial product of this area.
Embodiment 1：Response phase method optimization MSPD extracts HBCD in animal muscle
1. sample preparation：
Choosing blank sample (chicken) carries out condition optimizing, and sample is purchased from the poultry supplier of one, Jinan supermarket, scene
Slaughter to ensure that chicken meat sample is fresh.Chicken meat grinder is rubbed to ensure homogeneity, and moisture removal is removed in freeze-drying.Use rope
Fat content is 13.6% (dry weight ratio does three groups of parallel tests) during family name's extraction method measures chicken.The result of blank assay shows,
HBCD is not detected in chicken meat sample.It is (dense that the HBCD standard reserving solutions prepared by addition methyl alcohol prepare mark-on sample
It is 10ng/g to spend), methyl alcohol is volatilized naturally under ventilation condition until sample recovery drying, the mark-on sample holding that will be prepared
- 20 DEG C of preservations in refrigerator.
2.MSPD experimental procedures：
1) post is filled：Chicken sample and dispersant are put in glass mortar and use pestle 2 minutes to well mixed, be transferred to
In polyethylene pillar of the bottom equipped with C18 (being dried up with nitrogen after being activated with appropriate methyl alcohol).It is compacted with a soft rod again
Filler is in case there is space in pillar.
2) elute：Drip washing is carried out to pillar with eluant, eluent, eluent is collected in centrifuge tube, and High Purity Nitrogen is used at 45 DEG C
Air-blowing finally, residue is redissolved with 100 μ lACN near dry, and taking 10 μ l carries out Instrumental Analysis.
3. single factor experiment：
MSPD experimental performances are heavily dependent on the extraction efficiency to object and the clean-up effect to impurity.Extract
Efficiency is depended on chooses appropriate extractant, and clean-up effect is mainly influenceed by dispersant.According to the spy of musculature
Property, generally remove unnecessary fat from reversed material C18.For dispersant and eluant, eluent, the present embodiment utilizes single factor test
Experiment compares selection.
(1) investigation of dispersant
According to HBCD it is fat-soluble high the characteristics of, pertinent literature and " similar to mix " principle, three kinds of dispersants are chosen in experiment
Compare, including Forisil, PSA and Al2O3(usage amount is 1g), the peak area result of HBCD is compared (see
Fig. 1).It can be seen that Forisil obtains peak area higher, rate of recovery highest than other two kinds of dispersants.Therefore, connecing
From Forisil as dispersant in the experiment got off.
(2) investigation of eluant, eluent
According to the literature, HBCD Extraction solvents often use n-hexane, dichloromethane, methyl alcohol, acetonitrile, acetic acid in biological sample
Ethyl ester etc..It is first nonpolar with n-hexane etc. before object is eluted for the analysis of polar compound in animal tissue
Solvent removal fat, and HBCD is easily soluble in n-hexane, therefore can not be eluted using n-hexane in MSPD.Therefore, final choice
Methyl alcohol (MA), acetonitrile (ACN), ethyl acetate and dichloromethane (DCM) are contrasted as eluting solvent.Experimental result finds second
Dissolved with many fat residuals after acetoacetic ester and dichloromethane eluent, be not useable for Instrumental Analysis, after being eluted with ACN and MA solution compared with
For limpid, the peak area result of HBCD is shown in Fig. 2.Although (+) β-HBCD obtain the rate of recovery higher when using MA, its
The rate of recovery of its isomers is relatively low, particularly (+) α-HBCD isomers, and the MA rate of recovery is only the 20% of ACN.Consider, ACN
It is the optimal selection of elution experiments.
4. response phase method optimization
The usage amount of C18, Florisil and acetonitrile is optimized and research, the method using Box-Behnken designs
Can be with the relatively simple optimization for realizing parameter by the response surface (RSM) of orthogonal design, RSM passes through variance analysis again
(ANOVA) verified, be typically based on Design-Expert software (version 8.0) softwares to complete.Optimization level
Other and experimental design is shown in Table 1.According to ANOVA results (being shown in Table 2), in regression curve confidential interval 95%, multivariate regression models
It is significant, regression coefficient is 0.965, shows that 96.5% variable is applied to this model, loses plan analysis non-significant and also illustrate mould
Type has applicable reasonability for Optimal Experimental parameter.Fig. 3 (a-c) is HBCD peak area responses face figure, respectively is C18 use
The result that amount, Florisil consumptions and ACN volume threes interact two-by-two.There it can be seen that extraction efficiency is with ACN volumes
Increase and increase, increase as the consumption of Florisil increases, finally drawn under conditions of 5mLACN and 1gFlorisil
Peak-peak.Then, rate of recovery reduction.Similarly in other two response surface figures, 1.2gC18 obtains efficiency higher.It is comprehensive
Result above is closed, the optimum condition of MSPD is：5mLACN, 1gFlorisil and 1.2gC18.
The orthogonal experiment response surface optimization design matrix of table 1
Table 2 variance analysis (ANOVA) result summary sheet
Embodiment 2：The extraction of HBCD in self-control animal muscle standard sample
1. test specimen：
Using the chicken without HBCD as blank sample, the HBCD standard reserving solutions that addition methyl alcohol is prepared are prepared into mark-on
Sample (concentration is 10ng/g), makes methyl alcohol volatilize naturally until sample recovers drying under ventilation condition.
2. the HBCD in mark-on sample is extracted according to the preferred extraction conditions of embodiment 1, specific extracting method is such as
Under：
1) post is filled：0.5g mark-on chicken samples and 1g florisil silicas (Florisil) are put in glass mortar and are ground with pestle
Mill is transferred in bottom equipped with 1.2gC18's (being dried up with nitrogen after being activated with appropriate methyl alcohol) for 2 minutes to well mixed
In 10ml polyethylene pillars.Filler is compacted in case occurring space in pillar with a soft rod again.
2) elute：Drip washing is carried out to pillar with 5mlACN, eluent is collected in centrifuge tube, and High Purity Nitrogen is used at 45 DEG C
Air-blowing finally, residue is redissolved with 100 μ lACN near dry, and taking 10 μ l carries out Instrumental Analysis.
After testing, the HBCD in animal muscle sample is extracted using the extraction conditions after present invention optimization, 6 kinds
The average recoveries of HBCD isomers are 87.4%.
The mass ratio that mark-on chicken meat sample and Florisil are added is 1：It is adjusted in the range of (1.5-3), by mark-on
Chicken meat sample is with acetonitrile usage amount in 1g:It is adjusted in the range of (8-12) ml, after testing, the recovery rate model of multiple mark-on samples
Enclose is 80.7~97.5%.
Comparative example 1：The extraction of HBCD in self-control animal muscle standard sample
The preparation method of test specimen is with embodiment 2；
HBCD in test specimen is extracted, extracting method is as follows：
1) post is filled：0.5g mark-on chicken sample is crushed, is transferred to and (is lived with appropriate methyl alcohol equipped with 1.2gC18 in bottom
Dried up with nitrogen after change) 10ml polyethylene pillars in.Filler is compacted in case occurring space in pillar with a soft rod again.
2) elute：With 5ml n-hexanes-dichloromethane (1：1, V/V) drip washing is carried out to pillar, eluent is collected in centrifuge tube
In, and it is blown to high pure nitrogen at 45 DEG C near dry, and finally, residue is redissolved with 100 μ lACN, taking 10 μ l carries out Instrumental Analysis.
After testing, the HBCD in animal muscle sample is extracted using the extraction conditions after present invention optimization, it is carried
It is 42.5% to take rate.
Comparative example 2：The extraction of HBCD in self-control animal muscle standard sample
The preparation method of test specimen is with embodiment 2；
HBCD in test specimen is extracted, extracting method is as follows：
1) post is filled：0.5g mark-on chicken samples and 2g florisil silicas (Florisil) are put in glass mortar and are ground with pestle
Mill is transferred in bottom equipped with 0.5gC18's (being dried up with nitrogen after being activated with appropriate methyl alcohol) for 2 minutes to well mixed
In 10ml polyethylene pillars.Filler is compacted in case occurring space in pillar with a soft rod again.
2) elute：Carry out drip washing to pillar with 10mlACN, collect eluent in centrifuge tube, and with high-purity at 45 DEG C
Nitrogen is blown to closely do, and finally, residue is redissolved with 100 μ lACN, and taking 10 μ l carries out Instrumental Analysis.
After testing, the HBCD in animal muscle sample is extracted using the extraction conditions after present invention optimization, it is carried
It is 69.4% to take rate.
Comparative example 3：The extraction of HBCD in self-control animal muscle standard sample
The preparation method of test specimen is with embodiment 2；
HBCD in test specimen is extracted, extracting method is as follows：
1) post is filled：0.5g mark-on chicken samples and 0.5g florisil silicas (Florisil) are put in glass mortar and use pestle
Grinding is transferred in bottom equipped with 1.5gC18's (being dried up with nitrogen after being activated with appropriate methyl alcohol) for 2 minutes to well mixed
In 10ml polyethylene pillars.Filler is compacted in case occurring space in pillar with a soft rod again.
2) elute：Drip washing is carried out to pillar with 2mlACN, eluent is collected in centrifuge tube, and High Purity Nitrogen is used at 45 DEG C
Air-blowing finally, residue is redissolved with 100 μ lACN near dry, and taking 10 μ l carries out Instrumental Analysis.
After testing, the HBCD in animal muscle sample is extracted using the extraction conditions after present invention optimization, it is carried
It is 70.5% to take rate.
Embodiment 3：The Method validation of the detection method of HBCD in animal muscle sample
Testing conditions are as follows to be detected to the HBCD in animal muscle sample using LC-MS/MS methods：
Liquid phase chromatogram condition：Chromatographic column：EC 200/4NUCLEODEX β-PM posts (200mm × 4.6mm, 5 μm), column temperature
It is 40 DEG C.Mobile phase：Acetonitrile/water solution (80/20, V/V)；Flow velocity：0.5mL/min；Sampling volume：10μL.
MS/MS conditions：Atmospheric pressure electrospray ionization source (ESI), negative ion mode collection, capillary voltage 4Kv dries gas
Flow is that 3.0L/min temperature is 280 DEG C, and atomizing pressure 40psi, collision gas use high-purity nitrogen (99.999%), capillary
Tube voltage 4Kv, collision voltage 90V.Internal standard compound parent ion and the daughter ion difference of HBCD isomers and its isotope marks
It is 640.7 → (80.9,78.9) and 652.8 → (80.9,78.9).
Under above-mentioned optimum condition, to the linear of detection method, recovery of standard addition, detection limit, quantitative limit and precision etc.
The experimental study that methodology index is carried out, and by national standard《Good Laboratory controls specification food Physico-chemical tests》(GB/
T27404-2008) evaluated, final result is shown in Table 3.Coefficient correlation in range of linearity 0.5-100ng/g is arrived 0.996
It is linear good between 0.999, meet the requirement of " calibration curve coefficient correlation is not less than 0.98 " in GB.In terms of 3 times of signal to noise ratios
Calculate, minimum detectability (LOD), with 10 times of signal-to-noise ratio computations, show that quantitative limit (LOQs) exists between 0.056~0.18ng/g
Between 0.187~0.602ng/g.Eight groups of parallel tests calculate the recovery of standard addition of three levels (5,20 and 100ng/g)
And precision, as a result show the average recovery rate of object between 84.0%~117.3%, relative standard deviation (RSD) value
Between 4.6%~12.5%, the requirement of " rate of recovery 60~120%, the coefficient of variation is less than 15% " in GB is fully met.
The MSPD-LC-MS/MS methods of table 3 detect HBCD methodologies parameter (ng/g)
It should be noted that：The existing analysis detection to HBCD stereoisomers, being not directed to chiral HBCD is carried out
Analysis, the test limit and quantitative limit of the analysis method of its report may be than relatively low.But, detection method of the invention is simultaneously right
The chiral isomer of tri- kinds of isomers of HBCD is detected that the difficulty of detection is significantly higher than and carries out HBCD stereoisomers merely
Detection, the methodology parameter of both detection methods does not have comparativity.And using determining that detection method of the invention is reached
Amount limit, precision and recovery of standard addition result have been substantially better than Standard, achieve unexpected effect.
Embodiment 4：The detection of actual sample
In order to verify the validity of detection method of the invention, choose wide from the main grown place-Shandong Province of brominated flame-retardant
Two cocks (Sample1#~2#), the two parts of porks (Sample3#~4#) that Rao Shi buys are tied for experimental subjects is detected
Fruit is shown in Table 4 (in terms of dry weights), and Sample2# sample chromatogram figures are shown in Fig. 4.Detected in chicken Sample1# and Sample2# sample
(±) α-HBCD and (±) γ-HBCD, without discovery (±) β-HBCD, and do not detect HBCD in two portions of porks, illustrate
The existing animal sources contaminated threat of agricultural product of HBCD production districts.
The analysis result (dry weight, ng/g) of the HBCD isomers of table 4 and its enantiomer in actual chicken meat sample
The above, the only present invention preferably specific embodiment, but protection scope of the present invention is not limited thereto,
It is any to be familiar with those skilled in the art in the technical scope that the present invention is disclosed, technology according to the present invention scheme and its invention
Design is subject to equivalent or change, should all be included within the scope of the present invention.
Claims (9)
1. it is a kind of that the method that MSPD extracts HBCD in animal muscle is optimized by response phase method, it is characterised in that including following step
Suddenly：
(1) dispersant and eluant, eluent for being used using HBCD in MSPD methods extraction animal muscle carry out Dan Yin as experimental factor
Element experiment；
(2) according to single factor experiment result, choose reversed material C18, dispersant Florisil and eluant, eluent CAN these three because
Element, sets to factor level, is modeled using Box-Behnken Design, is verified by variance analysis (ANOVA)
The applicability and reasonability of model, obtain multiple regression equation Y=-2.24 × 106+2.90×105A+1.06×106B+1.90
×106C+2.24×105AB-7.33×105AC+1.50×105BC-2.66×105A2-1.54×105B2-8.75×105C2；
Wherein, Y：Peak area；A:C18 mass；B：ACN volumes；C:Florisil mass, determines the optimal conditions of model prediction.
2. in a kind of animal muscle HBCD extracting method, it is characterised in that step is as follows：
By animal muscle sample freeze-drying to be extracted, it is in mass ratio by dried animal muscle sample and Florisil
1：(1.5-3) mixes, and is ground to well mixed；It is then transferred in polyethylene post of the bottom equipped with C18, is carried out using acetonitrile
Wash-out, collects eluent；Eluent is blown to high pure nitrogen closely do, obtained final product.
3. extracting method as claimed in claim 2, it is characterised in that dried animal muscle sample and Florisil press matter
Amount is than being 1：2 mixing.
4. extracting method as claimed in claim 2, it is characterised in that the matter that dried animal muscle sample is added with C18
Amount is than being 1：(2-3).
5. extracting method as claimed in claim 4, it is characterised in that the matter that dried animal muscle sample is added with C18
Amount is than being 1：2.4.
6. the method for claim 1, it is characterised in that the ratio of dried animal muscle sample and acetonitrile addition
For：1g:(8-12)ml；Preferably 1g:10ml.
7. in a kind of animal muscle HBCD chiral isomers detection method, it is characterised in that step is as follows：
(1) extracting method as described in claim 2 extracts HBCD, is dissolved with acetonitrile, prepares sample solution；
(2) sample solution is detected using LC-MS/MS.
8. detection method as claimed in claim 7, it is characterised in that in step (2), liquid phase chromatogram condition is：Chromatographic column EC
200/4NUCLEODEX β-PM posts, column temperature is 40 DEG C, mobile phase：The acetonitrile/water solution of volume ratio 80/20, flow velocity：0.5mL/
min。
9. detection method as claimed in claim 7, it is characterised in that in step (2), MS/MS conditions：Atmospheric pressure electrospray electricity
From source, negative ion mode collection, capillary voltage 4Kv, dry gas stream amount is that 3.0L/min temperature is 280 DEG C, atomizing pressure
40psi, collision gas use high-purity nitrogen, capillary voltage 4Kv, collision voltage 90V.
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| CN109541057A (en) * | 2018-11-16 | 2019-03-29 | 环境保护部华南环境科学研究所 | A kind of aquatic products tetrabromobisphenol A and hexabromocyclododecane associated detecting method |
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