CN105158379B - A kind of method based on gel chromatography post detection PBDE Metabolism of hydroxyl content - Google Patents
A kind of method based on gel chromatography post detection PBDE Metabolism of hydroxyl content Download PDFInfo
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Abstract
The invention provides LC-MS detection PBDE and its gel chromatographic columnses of Metabolism of hydroxyl content, adopt and prepare with the following method：Gel and solvent are weighed, gel is mixed in solvent, shaken up swelling；A chromatographic column for dried and clean is taken, then to solvent is added in chromatographic column, the bubble between glass core filter plate lower section and piston is discharged, solvent is full of this segment space；Gel suspension is poured into chromatographic column, sea sand is added on gel layer, that is, the gel chromatographic columnses are obtained.The gel chromatography column preparation method is simple, can effectively overcome the matrix effect of complexity, the plurality of impurities in matrix containing organic pollution can be separated, so as to effectively remove plurality of impurities, it is to avoid the interference to follow-up organic contamination analyte detection.The present invention additionally provides the method based on above-mentioned gel chromatography post detection PBDE and its Metabolism of hydroxyl content simultaneously, and the method has the advantages that simple to operate, favorable reproducibility, sensitivity are high and the degree of accuracy is high.
Description
Technical field
The present invention relates to a kind of preparation method of the gel chromatographic columnses of LC-MS detection PBDE Metabolism of hydroxyl content,
And the detection method of the gel chromatography post detection PBDE Metabolism of hydroxyl content, belong to environment or food inspection technology neck
Domain.
Background technology
At present, the organic pollutant category in environment and food is more and more, such as PBDE and metabolin, and it is one
The organic brominated flame retardant of class halo (BFRs), due to good anti-flammability, it is in industrial circle by substantial amounts of use in various business
In industry product, such as electric equipment products and textile.The PBBs ether product of business mainly includes pentabromo-, eight bromines and ten bromines
Biphenyl Ether.Due to their physicochemical property and biological accumulation feature, such as environmental persistence and high hydrophobicity result in this kind of product
It is widely distributed in natural environment.Hydroxyl epoxide PBDE (OH-PBDEs) is a class similar with PBBs ether structure
Compound, its toxicity is much stronger than its parent compound (PBDES).It is not only able to cause the endocrinopathy of human body,
Indirectly health effect can also be caused to human body by destroying thyroid gland, or even people directly can also be caused by its neurotoxicity
Somatic nerves abnormal behavior.Matrix residing for PBDE Metabolism of hydroxyl content is generally sufficiently complex, and content is also little, often with μ g/
Kg is counted.At present, the detection method for determining PBDE metabolin comparative maturity is Liquid Chromatography-Mass Spectrometry, but its
The accuracy of result is largely limited by the impurity content of sample.If these impurity are without treatment, can be to follow-up organic
The testing result of pollutant produces larger interference, influences the result of detection.
The content of the invention
The present invention solves the deficiency in background technology, there is provided a kind of LC-MS detects PBDE hydroxy metabolite
The gel chromatographic columnses of thing, the gel chromatography column preparation method is simple, can effectively overcome the matrix effect of complexity, can be to containing organic
Plurality of impurities in pollutant matrix is separated, so as to effectively remove plurality of impurities, it is to avoid to follow-up organic pollution
The interference of detection.
Realize technical scheme that above-mentioned purpose of the present invention used for：
A kind of LC-MS detects the gel chromatographic columnses of PBDE metabolin, and the gel chromatographic columnses are using such as lower section
It is prepared by method：(1) Aquapak A-440 and solvent, are weighed, wherein every 1 gram of polystyrene correspondence measures 5~8 milliliters of solvents, it is described
Solvent be the mixed solution of hexamethylene and ethyl acetate, Aquapak A-440 is mixed in solvent, shake up, then carry out molten
Swollen, swelling time is more than 24 hours, after swelling equilibrium, pours out supernatant and suspended particulate impurity, standby；
(2) chromatographic column and a silica gel hose of dried and clean, are taken, silica gel hose is connected under chromatographic column
End exit, then accounts for the solvent of column volume 20~30% to addition in chromatographic column, stands, until the glass core in chromatographic column
Bubble-free is overflowed in filter plate, then opens piston, extrudes silica gel hose, the gas between discharge glass core filter plate lower section and piston
Bubble, makes solvent full of this segment space, is then shut off piston；
(3) Aquapak A-440 and solvent after, will be swelling be poured into beaker, are sufficiently stirred for until Aquapak A-440 is equal
Even suspension in a solvent, is obtained gel suspension, and then gel suspension is poured into chromatographic column by the top of chromatographic column,
Make gel suspension natural subsidence, when the gel suspension of column bottom is deposited to 1/5 column volume, open chromatographic column lower end
Piston, and flow velocity to 2~3mL/min is adjusted, then proceed to pour at gel suspension to column volume 5/6, and keep gel to begin
Immersion eventually in a solvent, after after the complete Equalsettlement of gel, adds the sea sand of 1/12 column volume on gel layer, paves, i.e.,
The gel chromatographic columnses are obtained.
The volume ratio of solvent cyclohexane and ethyl acetate described in step (1) is 1:1.
The draw ratio of the chromatographic column described in step (2) is 8~10:1.
The present invention additionally provides the method based on above-mentioned gel chromatography post detection PBDE Metabolism of hydroxyl content simultaneously, should
Method has the advantages that simple to operate, favorable reproducibility, sensitivity are high and the degree of accuracy is high.The method is comprised the following steps：(1), will treat
Test sample product are with diatomite according to 1:8~10 volume ratio mixing, then with hexamethylene and ethyl acetate according to 1:1 volume ratio mixing
Solution afterwards is eluted, and collects and concentrate testing sample eluent, and concentrate A is obtained；
(2), internal standard carbon 13 is added to mark-the OH-BDE-17 of internal standard 4 ', 3 '-OH-BDE-28,2 '-OH- in concentrate A
BDE-28、4′-OH-BDE-49、6-OH-BDE-47、2′-OH-BDE-68、6-OH-BDE-85、5′-OH-BDE-99、4′-OH-
The mixed standard solution of BDE-101,3 '-OH-BDE-154 and 4-OH-BDE-187, concentration is 100ng/mL；Above material is added
Enter in concentrate and be well mixed, then concentrate is injected in chromatographic column, until the liquid level of concentrate is concordant with sea sand face；
(3), eluted using the hexamethylene and ethyl acetate of 1.2~1.4 times of column volumes, elution flow rate be 1.00~
1.50mL/min, discards the eluent of preceding 50~60% column volume, collects the eluent of remainder in evaporative flask, subsequently passes through
Rotary evaporation blows with nitrogen and is concentrated into 0.9~1.1mL, and concentrate B is obtained, for LC-MS detections；
(4), concentrate B is injected in LC-MS, using C18 liquid-phase chromatographic columns, mobile phase uses the acetonitrile of solvent I and solvent
II water is constituted, and gradient conditions compare I for solvent:II by 50~60:40~50 to 70~80:20~30, at first 18~22 points
Clock, flow velocity is 0.35~0.40mL min-1；Before operation, column equilibration 4~6 minutes, column temperature is set to 38~42 DEG C, post sample introduction
Volume is 8~12 μ L, and mass detector uses negative electrospray ion gun ESI, multiple-reaction monitoring pattern；Gas curtain gas, atomization
Gas, collision gas are nitrogen；Flow velocity is 4~6L/min, and temperature is 340~360 DEG C, and protection air-flow speed is 10~12L/min, temperature
Spend is 380~420 DEG C；Capillary and spray nozzle voltage are respectively 3300~3600V and 450~550V；Nebulizer pressure and electronics
Multiplier electrode is respectively set to 45~55psi and 750~850V；The residence time that each multiple-reaction monitoring is changed into 18~
22ms；
(5), using Isotope internal standard dilution standard measure, i.e., with testing concentration as abscissa, determinand peak area and phase
The isotopic peak area ratio answered is ordinate, obtains working curve, so that 4 '-OH-BDE-17 in testing sample in calculating,
3′-OH-BDE-28、2′-OH-BDE-28、4′-OH-BDE-49、6-OH-BDE-47、2′-OH-BDE-68、6-OH-BDE-85、
The content of 5 '-OH-BDE-99,4 '-OH-BDE-101,3 '-OH-BDE-154 and 4-OH-BDE-187.
It is a kind of very effective processing method that gel is separated, when the mixture of different molecular size in matrix flows through gel
During chromatographic column, the network structure that the molecule bigger than gel mesh can not enter in microgel particle, and by exclusion Gel particulate outside,
As hole of the solvent between microgel particle flows downward and flows out outside post at first；The molecule smaller than mesh can be different degrees of
Freely come in and go out the inside and outside of microgel particle network structure, and the holdup time in the chromatography column is more long, so due to different size of point
The distance that is passed through of son is different and separated, macromolecular substances are first eluted out, such as protein, and small-molecule substance is by rear wash-out
Out, such as PBDE and metabolin.Therefore, sample is right by that after gel chromatography separation purification, can remove most of impurity
The accuracy for determining PBDE Metabolism of hydroxyl content has facilitation.Then sample solution is concentrated, is surveyed for LC-MS
It is fixed.
First have to expect preferable separating effect, gel must carry out swelling treatment, it is swelling after, gel volume is carried out
Expansion, among solvent penetration to gel, the network structure of microgel particle can be just fully extended, and such macromolecular substances could be arranged
Resistance, small-molecule substance can freely come in and go out, so as to reach good isolation of purified effect.
Secondly dress post must be wanted uniformly, smooth, it is impossible to have bubble.Bubble is typically derived from the sky below glass core filter plate
Among gap, by the way of silica gel hose exhaust bubble, solvent can be made full of dead between glass core filter plate lower section and piston
Volume, so as to suppress the generation of bubble.During post is filled, the homogeneity of gel is also extremely important, and what gel was filled i.e. can not mistake
Pine can not tension, if dress it is too loose, in chromatography process, gel layer height can decline, the tension of dress, then elute resistance too
Greatly, analysis time is extended.And dress column method of the invention is used, the tightness of gel is just right.
The present invention has used sea sand in the top layer of chromatographic column, and sea sand main component is silica, stable in properties, not with it
He reacts at compound, and sea sand can flatten gel in the filling process, and then in loading and elution process, due to
Sea sand cushioning effect, gel will not be kicked up because of impulsive force.
Present invention agents useful for same in purification process is environmentally friendly reagent, and hexamethylene and ethyl acetate are compared with dichloromethane
Small toxicity, the pollution to environment is also small.The present invention can avoid the stronger dichloromethane solvent of operating personnel's contact toxicity, and it is right to reduce
The harmfulness of human body and environment.
The present invention is also optimized to liquid chromatography mass condition, and mobile phase is adjusted by changing the proportioning of mobile phase
The power of polarity, makes testing compound obtain good separating effect.Secondly mass detector uses multiple-reaction monitoring pattern
(MRM) detection limit of testing compound can be significantly improved, while the pattern has high selectivity so that analysis test result is more
For accurate.Gas curtain gas, the optimization of the flow velocity and temperature of atomization gas, collision gas and protection gas can guarantee that sample has good ion
Change efficiency and less ambient interferences.
The present invention from analysis method, selected Isotope internal standard dilution method to quantify, this method quantitatively on
More accurate science, can exclude due to the error that the interference (ion suppression etc) of sample mesostroma causes, while in sample
Internal standard compound is added before product purification can also investigate the damaed cordition in whole experiment process to target compound.
Compared with prior art, its advantage and advantage are the present invention：
The gelling performance prepared in the present invention is superior, and the padding of gel describes careful specific in the method, pin
It is strong to property, so as to strengthen operability.Therefore, the gel purification chromatographic column that prepared by the method can overcome the matrix of complexity to imitate
Should, the plurality of impurities in the matrix of Metabolism of hydroxyl content containing polybrominated biphenyl can be removed, eliminate to follow-up PBDE hydroxyl generation
Thank to the interference of analyte detection generation；Follow-up detection method also gives the most suitable parameter of instrument, makes the result of analysis more accurate
It is reliable.Importantly, solidifying purification chromatographic column prepared by the method is simple to operate, the results showed, detect many using the method
The organic pollutions such as bromo biphenyl class compound have the advantages that sensitivity is high, the degree of accuracy is high, favorable reproducibility and the rate of recovery are high.
Specific embodiment
Detailed specific description is done to the present invention with reference to specific embodiment, but protection scope of the present invention not office
It is limited to following examples.
Gel chromatographic columnses and its inspection of PBDE Metabolism of hydroxyl content are detected for the LC-MS that the inspection present invention is provided
The feasibility and superiority of survey method, present inventor specially add PBDE Metabolism of hydroxyl content in dairy products
Mixed standard solution and inner mark solution, the preparation of the gel purification chromatographic column that the dairy products of mark-on solution are provided using the present invention
Separated with fill method, the instrument parameter provided according to the present invention is detected.Determine through gel purification chromatogram post separation
The content of the PBDE hydroxyl of dairy products afterwards its metabolin, according to the result concentration and known organic concentration of detection
Difference, to the method prepare gel purification chromatographic column separation and instrument detection feasibility and superiority be estimated.
Embodiment 1
100g Aquapak A-440s are taken, the hexamethylene of 500mL is immersed in：Ethyl acetate (1:1) in, shake up, then carry out
Swelling, swelling time is one day, after swelling equilibrium, pours out supernatant and suspended particulate impurity, standby.Take a clean color
Spectrum post (ID：2.5cm×L:20cm), the hexamethylene of about 5cm is added：Ethyl acetate (1:1), stand, until the glass in chromatographic column
Bubble-free is overflowed in glass core filter plate, then opens piston, extrudes silica gel hose, discharge glass core filter plate lower section and piston it
Between bubble, make solvent full of this segment space, be then shut off piston.Aquapak A-440 and solvent after will be swelling pour into burning
In cup, it is sufficiently stirred for until the uniform suspension of Aquapak A-440 in a solvent, is obtained gel suspension, then by gel suspension
Liquid is poured slowly into chromatographic column by the top of chromatographic column, makes gel suspension natural subsidence, when the gel of column bottom hangs
Supernatant liquid is deposited during to 1/5 column volume, opens chromatographic column lower end piston, and adjusts flow velocity to 2~3mL/min, then proceedes to pour into
Gel suspension keeps gel to soak all the time in a solvent at 17cm, after after the complete Equalsettlement of gel, gel layer it
Upper addition sea sand 1.6cm high, paves, that is, the gel chromatographic columnses are obtained.
2g milk powder treated in advance is weighed, is mixed with the diatomite of 16g, with the hexamethylene of 150mL：Ethyl acetate (1:
1) wash-out extraction is carried out, extract is collected, 1mL is concentrated into, concentrate A is obtained.Internal standard carbon 13 is added to mark in concentrate A interior
4 '-OH-BDE-17 of mark, 3 '-OH-BDE-28,2 '-OH-BDE-28,4 '-OH-BDE-49,6-OH-BDE-47,2 '-OH-BDE-
68th, the mixing mark of 6-OH-BDE-85,5 '-OH-BDE-99,4 '-OH-BDE-101,3 '-OH-BDE-154 and 4-OH-BDE-187
Quasi- solution, concentration is 100ng/mL；Above material is added in concentrate and is well mixed, then concentrate chromatographic column is injected into
It is interior, until the liquid level of concentrate is concordant with sea sand face.
Eluted with 120mL solvents, discarded preceding 60mL eluents, elution flow rate is 1.00mL/min.60mL after collection
Eluent, eluent is evaporated to 1.0mL, and concentrate B is obtained, for LC-MS detections.
Concentrate B is injected in LC-MS, concentrate B is injected in LC-MS, using C18 liquid-phase chromatographic columns, mobile phase is adopted
Constituted with acetonitrile (solvent I) and water (solvent II), gradient conditions compare I for solvent:II by 50:50 to 70:30 at first 18 points
Clock, flow velocity is 0.35mL min-1.Before operation, column equilibration 4 minutes.Column temperature is set to 38 DEG C, and post sampling volume is 8 μ L.Mass spectrum
Detector uses negative electrospray ion gun ESI, multiple-reaction monitoring pattern (MRM).Gas curtain gas, atomization gas, collision gas are nitrogen
Gas.Flowing rate is 4L/min, and temperature is 340 DEG C, and protection air-flow speed is optimized for 10L/min, and temperature is 380 DEG C.Capillary and
Spray nozzle voltage is respectively 3300V and 450V.Nebulizer pressure and electron multiplier voltage are respectively set to 45psi and 750V.Each
The residence time that multiple-reaction monitoring is changed is 18ms.
Sample is quantified with Isotope internal standard dilution method, and is calculated the rate of recovery, measured 4 '-OH-BDE-17,3 '-OH-
BDE-28、2′-OH-BDE-28、4′-OH-BDE-49、6-OH-BDE-47、2′-OH-BDE-68、6-OH-BDE-85、5′-OH-
The rate of recovery of BDE-99,4 '-OH-BDE-101,3 '-OH-BDE-154 and 4-OH-BDE-187 is 85%~108%.
The result of the above-mentioned rate of recovery is met in european union directive (European Union document 2002/657/EC)
Related request.That is the rate of recovery need to be in the range of 70%~110% during 1 μ g/kg ＜ P 10 μ g/kg of ＜, and P refers to the concentration of determinand.
Embodiment 2
100g Aquapak A-440s are taken, the hexamethylene of 800mL is immersed in：Ethyl acetate (1:1) in, shake up, then carry out
Swelling, swelling time is one day, after swelling equilibrium, pours out supernatant and suspended particulate impurity, standby.Take a clean color
Spectrum post (ID：3cm×L:30cm), the hexamethylene of about 7.5cm is added：Ethyl acetate (1:1), stand, until the glass in chromatographic column
Bubble-free is overflowed in glass core filter plate, then opens piston, extrudes silica gel hose, discharge glass core filter plate lower section and piston it
Between bubble, make solvent full of this segment space, be then shut off piston.Aquapak A-440 and solvent after will be swelling pour into burning
In cup, it is sufficiently stirred for until the uniform suspension of Aquapak A-440 in a solvent, is obtained gel suspension, then by gel suspension
Liquid is poured slowly into chromatographic column by the top of chromatographic column, makes gel suspension natural subsidence, when the gel of column bottom hangs
Supernatant liquid is deposited during to 1/5 column volume, opens chromatographic column lower end piston, and adjusts flow velocity to 2~3mL/min, then proceedes to pour into
Gel suspension is highly located to 25cm, and keeps gel to soak all the time in a solvent, after after the complete Equalsettlement of gel, in gel
2.5cm sea sands high are added on layer, is paved, that is, the gel chromatographic columnses are obtained.
3g milk powder treated in advance is weighed, is mixed with the diatomite of 30g, with the hexamethylene of 250mL：Ethyl acetate (1:
1) wash-out extraction is carried out, extract is collected, 1mL is concentrated into, concentrate A is obtained.Internal standard carbon 13 is added to mark in concentrate A interior
4 '-OH-BDE-17 of mark, 3 '-OH-BDE-28,2 '-OH-BDE-28,4 '-OH-BDE-49,6-OH-BDE-47,2 '-OH-BDE-
68th, the mixing mark of 6-OH-BDE-85,5 '-OH-BDE-99,4 '-OH-BDE-101,3 '-OH-BDE-154 and 4-OH-BDE-187
Quasi- solution, concentration is 100ng/mL；Above material is added in concentrate and is well mixed, then concentrate chromatographic column is injected into
It is interior, until the liquid level of concentrate is concordant with sea sand face.
Eluted with 250mL solvents, discarded preceding 150mL eluents, elution flow rate is 1.5mL/min.100mL after collection
Eluent, eluent is evaporated to 1.0mL, and concentrate B is obtained, for LC-MS detections.
Concentrate B is injected in LC-MS, using C18 liquid-phase chromatographic columns, mobile phase uses acetonitrile (solvent I) and water (solvent
II) constitute, gradient conditions compare I for solvent:II by 60:40 to 80:20 at first 22 minutes, and flow velocity is 0.40mL min-1.
Before operation, column equilibration 6 minutes.Column temperature is set to 42 DEG C, and post sampling volume is 12 μ L.Mass detector uses negative electrospray
Ion gun ESI, multiple-reaction monitoring pattern (MRM).Gas curtain gas, atomization gas, collision gas are nitrogen.Flowing rate is 6L/min, temperature
It is 360 DEG C to spend, and protection air-flow speed is optimized for 12L/min, and temperature is 420 DEG C.Capillary and spray nozzle voltage be respectively 3600V and
550V.Nebulizer pressure and electron multiplier voltage are respectively set to 55psi and 850V.During the stop of each multiple-reaction monitoring conversion
Between be 22ms.
Sample is quantified with Isotope internal standard dilution method, and is calculated the rate of recovery, measured 4 '-OH-BDE-17,3 '-OH-
BDE-28、2′-OH-BDE-28、4′-OH-BDE-49、6-OH-BDE-47、2′-OH-BDE-68、6-OH-BDE-85、5′-OH-
The rate of recovery of BDE-99,4 '-OH-BDE-101,3 '-OH-BDE-154 and 4-OH-BDE-187 is 85%~108%.
The result of the above-mentioned rate of recovery is met in european union directive (European Union document 2002/657/EC)
Related request.That is the rate of recovery need to be in the range of 70%~110% during 1 μ g/kg ＜ P 10 μ g/kg of ＜, and P refers to the concentration of determinand.
Claims (1)
1. a kind of method based on gel chromatography post detection PBDE Metabolism of hydroxyl content, the gel chromatographic columnses are using such as
Gel chromatographic columnses prepared by lower section method：(1) Aquapak A-440 and solvent, are weighed, wherein every 1 gram of polystyrene correspondence measures 5
~8 milliliters of solvents, described solvent is hexamethylene and the mixed solution of ethyl acetate, and Aquapak A-440 is mixed in into solvent
In, shake up, then carry out it is swelling, swelling time be more than 24 hours, after swelling equilibrium, pour out supernatant and suspended particulate be miscellaneous
Matter, it is standby；
(2) chromatographic column and a silica gel hose of dried and clean, are taken, silica gel hose is connected under chromatographic column and is brought out
At mouthful, the solvent of column volume 20~30% is then accounted for addition in chromatographic column, stood, until the glass core filter plate in chromatographic column
Middle bubble-free is overflowed, and then opens piston, extrudes silica gel hose, discharges the bubble between glass core filter plate lower section and piston,
Make solvent full of this segment space, be then shut off piston；
(3) Aquapak A-440 and solvent after, will be swelling be poured into beaker, are sufficiently stirred for until Aquapak A-440 is uniform
Suspend in a solvent, gel suspension is obtained, then gel suspension is poured into chromatographic column by the top of chromatographic column, make to coagulate
Colloidal suspension liquid natural subsidence, when the gel suspension of column bottom is deposited to 1/5 column volume, opens chromatographic column lower end and lives
Plug, and flow velocity to 2~3mL/min is adjusted, then proceed to pour at gel suspension to column volume 5/6, and keep gel all the time
Immersion in a solvent, after after the complete Equalsettlement of gel, adds the sea sand of 1/12 column volume on gel layer, paves, that is, make
Obtain the gel chromatographic columnses；
It is characterized in that：The method of the detection PBDE Metabolism of hydroxyl content is comprised the following steps：(1), by testing sample
With diatomite according to 1:8~10 volume ratio mixing, then with hexamethylene and ethyl acetate according to 1:1 volume ratio is mixed molten
Liquid is eluted, and collects and concentrate testing sample eluent, and concentrate A is obtained；
(2), internal standard carbon 13 is added to mark-the OH-BDE-17 of internal standard 4 ', 3 '-OH-BDE-28,2 '-OH-BDE- in concentrate A
28、4′-OH-BDE-49、6-OH-BDE-47、2′-OH-BDE-68、6-OH-BDE-85、5′-OH-BDE-99、4′-OH-BDE-
101st, the mixed standard solution of 3 '-OH-BDE-154 and 4-OH-BDE-187, concentration is 100ng/mL；Above material is added dense
In contracting liquid and it is well mixed, then concentrate is injected in chromatographic column, until the liquid level of concentrate is concordant with sea sand face；
(3), eluted using the hexamethylene and ethyl acetate of 1.2~1.4 times of column volumes, elution flow rate be 1.00~
1.50mL/min, discards the eluent of preceding 50~60% column volume, collects the eluent of remainder in evaporative flask, subsequently passes through
Rotary evaporation blows with nitrogen and is concentrated into 0.9~1.1mL, and concentrate B is obtained, for LC-MS detections；
(4), concentrate B is injected in LC-MS, using C18 liquid-phase chromatographic columns, mobile phase uses the acetonitrile of solvent I and the water of solvent II
Composition, gradient conditions compare I for solvent:II by 50~60:40~50 to 70~80:20~30, at first 18~22 minutes, stream
Speed is 0.35~0.40mL min-1；Before operation, column equilibration 4~6 minutes, column temperature is set to 38~42 DEG C, and post sampling volume is
8~12 μ L, mass detector uses negative electrospray ion gun ESI, multiple-reaction monitoring pattern；Gas curtain gas, atomization gas, collision
Gas is nitrogen；Flow velocity is 4~6L/min, and temperature is 340~360 DEG C, and protection air-flow speed is 10~12L/min, and temperature is 380
~420 DEG C；Capillary and spray nozzle voltage are respectively 3300~3600V and 450~550V；Nebulizer pressure and electron multiplier voltage
It is respectively set to 45~55psi and 750~850V；The residence time that each multiple-reaction monitoring is changed is 18~22ms；
(5), using Isotope internal standard dilution standard measure, i.e., with testing concentration as abscissa, determinand peak area with it is corresponding
Isotopic peak area ratio is ordinate, working curve is obtained, so as to calculate 4 '-OH-BDE-17 in testing sample, 3 '-OH-
BDE-28、2′-OH-BDE-28、4′-OH-BDE-49、6-OH-BDE-47、2′-OH-BDE-68、6-OH-BDE-85、5′-OH-
The content of BDE-99,4 '-OH-BDE-101,3 '-OH-BDE-154 and 4-OH-BDE-187.
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| 聚苯乙烯凝胶色谱柱分离头孢呋辛钠聚合物杂质;倪静文等;《分析测试学报》;20110131;第30卷(第1期);1-5 * |
| 适用于凝胶渗透色谱的多孔硅微球的研制;吉林化工研究院物化室;《分析化学》;19761231;第4卷(第5期);363-371 * |
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