CN110531011A - A kind of detection method of 2,4- diamino anisole sulfate - Google Patents
A kind of detection method of 2,4- diamino anisole sulfate Download PDFInfo
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- CN110531011A CN110531011A CN201910923138.1A CN201910923138A CN110531011A CN 110531011 A CN110531011 A CN 110531011A CN 201910923138 A CN201910923138 A CN 201910923138A CN 110531011 A CN110531011 A CN 110531011A
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- diamino anisole
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- 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
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- 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
Abstract
The invention discloses a kind of detection methods of 2,4- diamino anisole sulfate.The present invention uses Agilentporoshell 120SB-Aq liquid-phase chromatographic column, optimize parameters setting, 2 can be achieved under ultra-high pressure condition, 4- diamino anisole sulfate higher reservation degree and higher separative efficiency in the chromatography column, electric spray ion source mode is used again, and qualitative and quantitative analysis is carried out under cation and multiple-reaction monitoring pattern.The detection method pre-treatment of 2,4- diamino anisole sulfate of the invention is simple, easily operated, high sensitivity, and detection quickly, accurately, can meet to the requirement that 2,4- diamino anisole sulfate is detected in textile product.
Description
Technical field
The present invention relates to textile harmful substance detection fields, and in particular to one kind 2,4- diamino anisole sulfate
Detection method.
Background technique
2,4- diamino anisole sulfate, molecular formula C7H10N2O·H2SO4, be a kind of canescence to pansy or
Burgundy powder, is soluble in the organic solvents such as acetone, methanol, acetonitrile, ether, and essential information is shown in Table 1.
The essential information of 1 2,4- diamino anisole sulfate of table
As a kind of important intermediate, 2,4- diamino anisole sulfate are mainly used for organic pigment intermediate and dye
Send out the fields such as agent.Although it is with good chemical property, existing research is confirmed, may result in hereditary detect, very
It is extremely carcinogenic；And can it is toxic to aquatile and generate for a long time continue adverse effect, because it is with persistence, bioaccumulation and poison
The harm of property, has caused the highest attention of various circles of society, on January 2nd, 2019, OEKO-TEX issued the textile product of new edition
OEKO-TEX Standard 100, and 2,4- diamino anisole sulfate is formally included in its conventional detection project.
As it can be seen that establishing suitable method and being measured to the content of 2,4- diamino anisole sulfate in product is very
It is necessary to, however synthesis and application field are concentrated on for its research at present, about it, remaining detection is rare in the product
Report.Therefore, the quasi- physico-chemical property and feature according to 2,4- diamino anisole sulfate of the present invention, by pretreatment technology
Exploration, optimization with instrumental conditions, develop a kind of inspection for 2,4- diamino anisole sulphates content in product
Survey method provides technical support for the detection of the substance.
Summary of the invention
It is an object of the invention to provide a kind of 2,4- diamino anisole sulfuric acid in place of overcome the deficiencies in the prior art
The detection method of salt.
To achieve the above object, the technical solution adopted by the present invention is as follows:
The detection method of one kind 2,4- diamino anisole sulfate, comprising the following steps:
(1) textile sample is weighed, extraction agent is added, through ultrasonic extraction, centrifugation, supernatant liquid filtering is taken, obtains to test sample
Product liquid；
(2) standard working solution of gradient concentration is prepared for standard substance with 2,4- diamino anisole sulfate；
(3) it is worked by the standard of each concentration gradient in ultra performance liquid chromatography-mass spectrometer determination step (2) molten
Liquid obtains standard spectrogram, establishes standard working curve according to standard diagram；Under the same conditions by step (1) to test sample
Product liquid injection ultra performance liquid chromatography-mass spectrometer survey is measured, by comparison sample to be tested spectrogram and standard spectrogram
Retention time, in sample 2,4- diamino anisole sulfate carry out qualitative analysis；It is calculated by standard working curve molten
The concentration of 2,4- diamino anisole sulfate in liquid, is then calculated 2,4- diaminobenzene first in sample according to sample quality
The content of ether sulfate；
Wherein, chromatographic condition are as follows: chromatographic column selects Agilent poroshell 120SB-Aq, and sample volume is 1~5 μ L,
Column temperature is 40 DEG C；Mobile phase A is the ammonium acetate of 5~10mM, and Mobile phase B is methanol or acetonitrile, and Mobile phase B is protected in initial 1 minute
10~20% ratio is held, increase to 50~70% in 1~2min again and is kept for 1 minute, 100% is increased in 3~5min again and protects
0.5min is held, is subsequently reduced to 10~20%, and keep 1min；Flow velocity is 0.2~0.5mLmin-1；
Mass Spectrometry Conditions are as follows: Ionization mode is electron spray ion；Scanning mode is positive ion scan；Detection mode is mostly anti-
Answer monitoring pattern.
The present invention is by ultra performance liquid chromatography tandem mass spectrometry to 2,4- diamino anisole sulfuric acid in textile product
Salt carries out qualitative and quantitative analysis；The present invention uses the liquid-phase chromatographic column of Agilent poroshell 120SB-Aq, and optimization is every
Target compound higher reservation degree and higher separation effect in the chromatography column can be achieved in parameter setting under ultra-high pressure condition
Rate, the ion pair for recycling tandem mass spectrum to generate carry out qualitative and quantitative analysis.Detection method pre-treatment of the invention is simple, easily
In operation, high sensitivity, detection is quickly, accurately.
Preferably, the chromatographic condition are as follows: chromatographic column selects Agilent poroshell 120SB-Aq, and sample volume is 5 μ
L, column temperature are 40 DEG C；Mobile phase A is the ammonium acetate of 5mM, and Mobile phase B is methanol, and Mobile phase B keeps 10% in initial 1 minute
Ratio increases to 50% in 1~2min again and is kept for 1 minute, increases to 100% in 3~5min again and keep 0.5min, be subsequently reduced to
10%, and keep 1min；Flow velocity is 0.3mLmin-1。
By preferred chromatographic condition, the peak shape symmetry of 2,4- diamino anisole sulfate is preferable, and response is also higher, point
From working well.
Preferably, the Mass Spectrometry Conditions are as follows: capillary voltage: 3300~3500V；Remove solvent temperature degree: 300~350
℃；Go solvent stream amount: 6~10L/h；Sheath temperature degree: 300~360 DEG C；Sheath throughput: 6~11L/min；Detection mode is more
Reaction monitoring mode.
It is highly preferred that the Mass Spectrometry Conditions are as follows: capillary voltage: 3500V；Remove solvent temperature degree: 350 DEG C；Remove solvent gas
Flow: 7L/h；Sheath temperature degree: 360 DEG C；Sheath throughput: 11L/min；Detection mode is multiple-reaction monitoring pattern.
Preferably, the extraction agent includes at least one of methanol, acetonitrile, acetone, preferably acetonitrile.Test discovery,
Using methylene chloride or water as extraction agent, the rate of recovery is below 80%, is not able to satisfy test request；And acetonitrile, acetone
Effect of extracting is preferable, and the rate of recovery can reach 85% or more.Wherein, when making extraction agent with acetonitrile, the matrix interference that is subject to compared with
Small, separating effect is optimal.
Preferably, in the step (2), extraction temperature is 60-80 DEG C, and ultrasonic time is not less than 60min, by preferred
Extraction temperature and ultrasonic time, effect of extracting efficiency are higher.
Preferably, in the step (2), the ratio of textile sample and extraction agent is 1g:10mL.
Compared with prior art, the invention has the benefit that
The present invention is by ultra performance liquid chromatography tandem mass spectrometry to 2,4- diamino anisole sulfuric acid in textile product
Salt carries out qualitative and quantitative analysis, and the optimal setting of parameter is analyzed by instrument, and 2,4- diamino anisole sulfate can be
Symmetrical chromatographic isolation peak is obtained in the 5.5min time.
The detection limit of detection method of the invention is low, and precision is good, and sample recovery of standard addition is high, meets in textile product
The test request of 2,4- diamino anisole sulfate.Related coefficient reaches 0.9996 in the concentration range of 1~20 μ g/L；Inspection
Rising limit and Quantitation Limit are all lower, respectively only 0.04 μ g/L and 0.14 μ g/L；RSD% < 2.5%；Sample average mark-on reclaims
Rate is 83.3%~96.2%.
Detailed description of the invention
Fig. 1 is influence of the different extraction agents to test result；
Fig. 2 is influence of the different extraction temperatures to test result；
Fig. 3 is influence of the different ultrasonic times to test result；
Fig. 4 is the MRM total ion chromatogram of 2,4- diamino anisole sulfate；
Fig. 5 is the daughter ion mass spectrum figure of 2,4- diamino anisole sulfate；
Fig. 6 is the standard working curve of 2,4- diamino anisole sulfate.
Specific embodiment
Purposes, technical schemes and advantages in order to better illustrate the present invention, below in conjunction with specific embodiment to the present invention
It further illustrates.It will be appreciated by those skilled in the art that described herein, specific examples are only used to explain the present invention, not
For limiting the present invention.
In embodiment, used experimental method is conventional method unless otherwise specified, material used, reagent etc.,
It is commercially available unless otherwise specified.
Embodiment is specific as follows using instrument and reagent:
Liquid chromatogram: Agilent 1290Infinity II, mass spectrum: 6460Agilent Triple Quad, U.S.'s peace
Jie Lun company；
Liquid-phase chromatographic column: Agilent poroshell 120SB-Aq (3.0*150mm, 2.7 μm), U.S.'s Agilent are public
Department；
Ultrasonic cleaner: 2300HT, Shanghai ANPEL Scientific Instrument Co., Ltd.；
Precise electronic assay balance: X205BDU type, sensibility reciprocal 0.01g, Mei Tele company, Switzerland；
Assay balance: AL204 type, sensibility reciprocal 0.1g, Mei Tele company, Switzerland；
Eddy mixer: XW-80A, Industrial Co., Ltd., upper Nereid section；
Table model high speed centrifuge: H1650, Changsha Xiang Yi centrifuge Instrument Ltd.；
2,4- diamino anisole sulfate standard substances: purity 98.5%, Tokyo chemical conversion industry Co., Ltd.；
Methanol, acetonitrile, acetone, methylene chloride (HPLC grades, U.S. Sigma)；
Ammonium acetate: chromatographically pure, Shanghai ANPEL Scientific Instrument Co., Ltd.；
Level-one water: Watson distilled water.
Embodiment 1
The detection method of one kind 2,4- diamino anisole sulfate, comprising the following steps:
(1) representative sample is taken, is shredded, size is not more than 2mm × 2mm, weighs 1.0g ± 0.1g sample, is put into 60mL
In reaction flask, add 10mL extraction agent, level-one water, methanol, acetonitrile, acetone and methylene chloride has been respectively adopted as extraction examination
Agent is put into ultrasonic cleaner after covering tightly and is extracted, room temperature is cooled to after taking-up, and extraction solution is taken to carry out centrifugal treating, uses
0.45 μm of membrane filtration sample is packed into sample introduction bottle, obtains analyte sample fluid；
(2) stock solution of 1000mg/L is diluted to the standard working solution of 1,2,5,10,20 μ g/L step by step with methanol；
(3) it is worked by the standard of each concentration gradient in ultra performance liquid chromatography-mass spectrometer determination step (2) molten
Liquid obtains standard spectrogram, establishes standard working curve according to standard diagram；Under the same conditions by step (1) to test sample
Product liquid injection ultra performance liquid chromatography-mass spectrometer survey is measured, by comparison sample to be tested spectrogram and standard spectrogram
Retention time, in sample 2,4- diamino anisole sulfate carry out qualitative analysis；It is calculated by standard working curve molten
The concentration of 2,4- diamino anisole sulfate in liquid, is then calculated 2,4- diaminobenzene first in sample according to sample quality
The content of ether sulfate；
Wherein, chromatographic condition: chromatographic column select Agilent poroshell 120SB-Aq, (3.0*150mm, 2.7 μm),
With 1.8 μm of guard columns (being Agilent company), sample volume is 1~5 μ L, and column temperature is 40 DEG C；Mobile phase A is 5~10mM's
Ammonium acetate, Mobile phase B are methanol, and Mobile phase B keeps 10~20% ratio in initial 1 minute, increase to 50 in 1~2min again~
70% and keep 1 minute, 100% is increased in 3~5min again and keeps 0.5min, is subsequently reduced to 10~20%, and keep 1min；
Flow velocity is 0.2~0.5mLmin-1；
Mass Spectrometry Conditions: in electric spray ion source positive ion mode (ESI+) under, first solution title compound is swept entirely
It retouches, obtains stable parent ion, select ion scan (SIM) model-based optimization fragmentation voltage (Fragmentor)；Carry out again son from
Son scanning chooses the high characteristic ion of response to as quantitative, qualitative ion pair, advanced optimizes collision energy
(Collision energy,CE).Mass Spectrometry Conditions after optimization are as follows: capillary voltage: 3300~3500V；Remove solvent temperature
Degree: 300~350 DEG C；Go solvent stream amount: 6~10L/h；Sheath temperature degree: 300~360 DEG C；Sheath throughput: 6~11L/min；
Multiple-reaction monitoring (MRM) mode.Parent ion, daughter ion, fragmentation voltage and collision energy are shown in Table 1.
The MRM of 1 2,4- diamino anisole sulfate of table analyzes parameter
Level-one water, methanol, acetonitrile, acetone and methylene chloride have been respectively adopted in the present embodiment as extraction agent, has compared
Their extraction efficiency.As a result as shown in Figure 1, the extraction efficiency of methylene chloride and water is below 80%, it is not able to satisfy test and wants
It asks；And the effect of extracting of acetonitrile and acetone is preferable, the rate of recovery can reach 85% or more.When making extraction agent with acetonitrile, by
Matrix interference it is smaller, separating effect is optimal.
Embodiment 2
The detection method of one kind 2,4- diamino anisole sulfate, comprising the following steps:
(1) representative sample is taken, is shredded, size is not more than 2mm × 2mm, weighs 1.0g ± 0.1g sample, is put into 60mL
In reaction flask, add 10mL acetonitrile, is put into ultrasonic cleaner after covering tightly and is extracted, 40~70 DEG C of extraction temperature, extraction time
For 45~120min, it is cooled to room temperature after taking-up, extraction solution is taken to carry out centrifugal treating, with 0.45 μm of membrane filtration sample, dress
Enter sample introduction bottle, obtains analyte sample fluid；
(2) stock solution of 1000mg/L is diluted to the standard working solution of 1,2,5,10,20 μ g/L step by step with methanol；
(3) it is worked by the standard of each concentration gradient in ultra performance liquid chromatography-mass spectrometer determination step (2) molten
Liquid obtains standard spectrogram, establishes standard working curve according to standard diagram；Under the same conditions by step (1) to test sample
Product liquid injection ultra performance liquid chromatography-mass spectrometer survey is measured, by comparison sample to be tested spectrogram and standard spectrogram
Retention time, in sample 2,4- diamino anisole sulfate carry out qualitative analysis；It is calculated by standard working curve molten
The concentration of 2,4- diamino anisole sulfate in liquid, is then calculated 2,4- diaminobenzene first in sample according to sample quality
The content of ether sulfate；
Wherein, chromatographic condition: chromatographic column select Agilent poroshell 120SB-Aq, (3.0*150mm, 2.7 μm),
With 1.8 μm of guard columns (being Agilent company), sample volume is 1~5 μ L, and column temperature is 40 DEG C；Mobile phase A is 5~10mM's
Ammonium acetate, Mobile phase B are methanol, and Mobile phase B keeps 10~20% ratio in initial 1 minute, increase to 50 in 1~2min again~
70% and keep 1 minute, 100% is increased in 3~5min again and keeps 0.5min, is subsequently reduced to 10~20%, and keep 1min；
Flow velocity is 0.2~0.5mLmin-1；
Mass Spectrometry Conditions: in electric spray ion source positive ion mode (ESI+) under, first solution title compound is swept entirely
It retouches, obtains stable parent ion, select ion scan (SIM) model-based optimization fragmentation voltage (Fragmentor)；Carry out again son from
Son scanning chooses the high characteristic ion of response to as quantitative, qualitative ion pair, advanced optimizes collision energy
(Collision energy,CE).Mass Spectrometry Conditions after optimization are as follows: capillary voltage: 3300~3500V；Remove solvent temperature
Degree: 300~350 DEG C；Go solvent stream amount: 6~10L/h；Sheath temperature degree: 300~360 DEG C；Sheath throughput: 6~11L/min；
Multiple-reaction monitoring (MRM) mode.Parent ion, daughter ion, fragmentation voltage and collision energy are shown in Table 1.
The influence of the present embodiment extraction temperature and ultrasonic time to test result, is compared experiment respectively.Work as extraction
When temperature is between 25~80 DEG C, contrast test result can be found that and (is detailed in Fig. 2-3), and temperature is more than rate of recovery energy after 60 DEG C
Reach maximum.When ultrasonic time reaches after sixty minutes, maximum extraction efficiency can be reached substantially.In view of practical factor,
Slective extraction temperature 60 C in experiment, ultrasound 60 minutes are the condition extracted.
Embodiment 3
The detection method of one kind 2,4- diamino anisole sulfate, comprising the following steps:
(1) representative sample is taken, is shredded, size is not more than 2mm × 2mm, weighs 1.0g ± 0.1g sample, is put into 60mL
In reaction flask, add 10mL acetonitrile, be put into ultrasonic cleaner after covering tightly and extracted, 60 DEG C of extraction temperature, extraction time is
60min is cooled to room temperature after taking-up, and extraction solution is taken to carry out centrifugal treating, and with 0.45 μm of membrane filtration sample, it is small to be packed into sample introduction
Bottle, obtains analyte sample fluid；
(2) stock solution of 1000mg/L is diluted to the standard working solution of 1,2,5,10,20 μ g/L step by step with methanol；
(3) it is worked by the standard of each concentration gradient in ultra performance liquid chromatography-mass spectrometer determination step (2) molten
Liquid obtains standard spectrogram, establishes standard working curve according to standard diagram；Under the same conditions by step (1) to test sample
Product liquid injection ultra performance liquid chromatography-mass spectrometer survey is measured, by comparison sample to be tested spectrogram and standard spectrogram
Retention time, in sample 2,4- diamino anisole sulfate carry out qualitative analysis；It is calculated by standard working curve molten
The concentration of 2,4- diamino anisole sulfate in liquid, is then calculated 2,4- diaminobenzene first in sample according to sample quality
The content of ether sulfate；
Wherein, chromatographic condition: chromatographic column selects Agilent poroshell 120SB-Aq column, and sample volume is 1~5 μ L,
Column temperature is 40 DEG C；Mobile phase A is respectively water, ammonium acetate, and Mobile phase B is respectively methanol, acetonitrile, and Mobile phase B is protected in initial 1 minute
10~20% ratio is held, increase to 50~70% in 1~2min again and is kept for 1 minute, 100% is increased in 3~5min again and protects
0.5min is held, is subsequently reduced to 10~20%, and keep 1min；Flow velocity is 0.2~0.5mLmin-1；
Mass Spectrometry Conditions: in electric spray ion source positive ion mode (ESI+) under, first solution title compound is swept entirely
It retouches, obtains stable parent ion, select ion scan (SIM) model-based optimization fragmentation voltage (Fragmentor)；Carry out again son from
Son scanning chooses the high characteristic ion of response to as quantitative, qualitative ion pair, advanced optimizes collision energy
(Collision energy,CE).Mass Spectrometry Conditions after optimization are as follows: capillary voltage: 3300~3500V；Remove solvent temperature
Degree: 300~350 DEG C；Go solvent stream amount: 6~10L/h；Sheath temperature degree: 300~360 DEG C；Sheath throughput: 6~11L/min；
Multiple-reaction monitoring (MRM) mode.Parent ion, daughter ion, fragmentation voltage and collision energy are shown in Table 1.
Methanol, acetonitrile is respectively adopted as organic phase in the present embodiment, and water, ammonium acetate are as water phase, organic phase and water phase two
Two combinations carry out condition optimizing.The result shows that methanol, acetonitrile difference are little in organic phase, and when using ammonium acetate as water phase, 2,4-
The response of diamino anisole sulfate is significantly improved compared with water as water phase.Therefore, comprehensively consider, the present invention is with methanol
With ammonium acetate as mobile phase.
Embodiment 4
The detection method of one kind 2,4- diamino anisole sulfate, comprising the following steps:
(1) representative sample is taken, is shredded, size is not more than 2mm × 2mm, weighs 1.0g ± 0.1g sample, is put into 60mL
In reaction flask, add 10mL acetonitrile, be put into ultrasonic cleaner after covering tightly and extracted, 60 DEG C of extraction temperature, extraction time is
60min is cooled to room temperature after taking-up, and extraction solution is taken to carry out centrifugal treating, and with 0.45 μm of membrane filtration sample, it is small to be packed into sample introduction
Bottle, obtains analyte sample fluid；
(2) stock solution of 1000mg/L is diluted to the standard working solution of 1,2,5,10,20 μ g/L step by step with methanol；
(3) it is worked by the standard of each concentration gradient in ultra performance liquid chromatography-mass spectrometer determination step (2) molten
Liquid obtains standard spectrogram, establishes standard working curve according to standard diagram；Under the same conditions by step (1) to test sample
Product liquid injection ultra performance liquid chromatography-mass spectrometer survey is measured, by comparison sample to be tested spectrogram and standard spectrogram
Retention time, in sample 2,4- diamino anisole sulfate carry out qualitative analysis；It is calculated by standard working curve molten
The concentration of 2,4- diamino anisole sulfate in liquid, is then calculated 2,4- diaminobenzene first in sample according to sample quality
The content of ether sulfate；
Wherein, chromatographic condition: chromatographic column select respectively common C18 column, Agilent poroshell 120PFP column,
Agilent poroshell 120SB-Aq column, sample volume are 1~5 μ L, and column temperature is 40 DEG C；Mobile phase A is the acetic acid of 5~10mM
Ammonium, Mobile phase B are methanol, and Mobile phase B keeps 10~20% ratio in initial 1 minute, increase to 50~70% again in 1~2min
And kept for 1 minute, 100% is increased in 3~5min again and keeps 0.5min, is subsequently reduced to 10~20%, and keep 1min；Flow velocity
For 0.2~0.5mLmin-1；
Mass Spectrometry Conditions: in electric spray ion source positive ion mode (ESI+) under, first solution title compound is swept entirely
It retouches, obtains stable parent ion, select ion scan (SIM) model-based optimization fragmentation voltage (Fragmentor)；Carry out again son from
Son scanning chooses the high characteristic ion of response to as quantitative, qualitative ion pair, advanced optimizes collision energy
(Collision energy,CE).Mass Spectrometry Conditions after optimization are as follows: capillary voltage: 3300~3500V；Remove solvent temperature
Degree: 300~350 DEG C；Go solvent stream amount: 6~10L/h；Sheath temperature degree: 300~360 DEG C；Sheath throughput: 6~11L/min；
Multiple-reaction monitoring (MRM) mode.Parent ion, daughter ion, fragmentation voltage and collision energy are shown in Table 1.
The present embodiment has chosen common C18 column, Agilent poroshell 120PFP column, Agilent respectively
Poroshell 120SB-Aq column is studied, and the difference of different classes of chromatographic column is compared.Using common C18 column to 2,4- diamino
Base anisole sulphate is separated, and finds that the substance does not retain on common C18 column after many experiments；Use Agilent
Poroshell 120PFP column separates target compound, and experimental result is similar to using the result of C18 column, target chemical combination
Object does not also retain on the pillar；Use the liquid phase color of Agilent poroshell 120SB-Aq (3.0*150mm, 2.7 μm)
Column is composed, 2,4- diamino anisole sulfate higher reservation degree and higher point in pillar can be achieved under ultra-high pressure condition
From efficiency.Fig. 4 is the MRM total ion chromatogram that concentration is 0.1mg/L target compound, Fig. 52,4- diamino anisole
The daughter ion mass spectrum figure of sulfate.As can be seen that 2,4- diamino anisole sulfate peak shape symmetry it is preferable, response also compared with
Height, good separation.
Embodiment 5
The detection method of one kind 2,4- diamino anisole sulfate, comprising the following steps:
(1) representative sample is taken, is shredded, size is not more than 2mm × 2mm, weighs 1.0g ± 0.1g sample, is put into 60mL
In reaction flask, add 10mL acetonitrile, be put into ultrasonic cleaner after covering tightly and extracted, 60 DEG C of extraction temperature, extraction time is
60min is cooled to room temperature after taking-up, and extraction solution is taken to carry out centrifugal treating, and with 0.45 μm of membrane filtration sample, it is small to be packed into sample introduction
Bottle, obtains analyte sample fluid；
(2) stock solution of 1000mg/L is diluted to the standard working solution of 1,2,5,10,20 μ g/L step by step with methanol；
(3) it is worked by the standard of each concentration gradient in ultra performance liquid chromatography-mass spectrometer determination step (2) molten
Liquid obtains standard spectrogram, establishes standard working curve according to standard diagram, as shown in Figure 6；2,4- diamino anisole sulfate
Linear equation and related coefficient it is as shown in table 2；
The linear equation and related coefficient of 2 2,4- diamino anisole sulfate of table
Under the same conditions by step (1) analyte sample fluid injection ultra performance liquid chromatography-mass spectrometer survey into
Row measurement, by the retention time in comparison sample to be tested spectrogram and standard spectrogram, to 2,4- diamino anisole sulphur in sample
Hydrochlorate carries out qualitative analysis；The concentration of 2,4- diamino anisole sulfate in solution is calculated by standard working curve, then
The content of 2,4- diamino anisole sulfate in sample is calculated according to sample quality；
Wherein, chromatographic condition: chromatographic column select Agilent poroshell 120SB-Aq, (3.0*150mm, 2.7 μm),
With 1.8 μm of guard columns (being Agilent company), sample volume is 5 μ L, and column temperature is 40 DEG C；Mobile phase A is the ammonium acetate of 5mM,
Mobile phase B is methanol, and Mobile phase B keeps 1% ratio in initial 1 minute, increases to 50% in 1~2min again and is kept for 1 minute,
100% is increased in 3~5min again and keeps 0.5min, is subsequently reduced to 10%, and keep 1min；Flow velocity is 0.3mLmin-1；
Mass Spectrometry Conditions: in electric spray ion source positive ion mode (ESI+) under, first solution title compound is swept entirely
It retouches, obtains stable parent ion, select ion scan (SIM) model-based optimization fragmentation voltage (Fragmentor)；Carry out again son from
Son scanning chooses the high characteristic ion of response to as quantitative, qualitative ion pair, advanced optimizes collision energy
(Collision energy,CE).Mass Spectrometry Conditions after optimization are as follows: capillary voltage: 3500V；Remove solvent temperature degree: 350
℃；Go solvent stream amount: 7L/h；Sheath temperature degree: 360 DEG C；Sheath throughput: 11L/min；Multiple-reaction monitoring (MRM) mode.Mother from
Son, daughter ion, fragmentation voltage and collision energy are shown in Table 1.
Method detection limit
Under the analytical test strip part of the present embodiment, instrument analysis is carried out to the standard sample of various concentration, using 3 times and
10 times of signal-to-noise ratio (S/N) detect 2, the 4- diamino anisole sulfate detection limit (LOD) and quantitative limit (LOQ) that determine
It limits (LOD) and quantitative limit (LOQ) is respectively 0.04 μ g/L and 0.14 μ g/L, blank test result is respectively less than method detection limit, fills
Divide the test request for meeting 2,4- diamino anisole sulfate in textile.
Precision Experiment
Blank sample is taken, is shredded, size is not more than 2mm × 2mm, adds the storage of 1,5,20 3 level concentrations of μ g/L respectively
Standby liquid carries out mark-on reclaims measurement, and each mark-on horizontal parallel is tested 6 times, the results are shown in Table 3.As can be seen from Table 3, add at 3 kinds
Under mark is horizontal, 2, the 4- diamino anisole sulfate recovery of standard addition that be averaged is 83.3%~96.2%, shows the test method
Accuracy is high；Relative standard deviation is not more than 2.5%, shows that the analysis method precision is high, therefore this method can satisfy survey
Examination requires.
The rate of recovery and precision of 3 2,4- diamino anisole sulfate of table
In conclusion the present invention uses the liquid-phase chromatographic column of Agilent poroshell 120SB-Aq, it is each by optimizing
Target compound higher reservation degree and higher separation effect in the chromatography column can be achieved in item parameter setting under ultra-high pressure condition
Rate, the ion pair for recycling tandem mass spectrum to generate carry out qualitative and quantitative analysis, and pre-treatment is simple, easily operated, high sensitivity,
Detection quickly, accurately, can meet to the requirement that 2,4- diamino anisole sulfate is detected in textile product.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention rather than protects to the present invention
The limitation of range is protected, although the invention is described in detail with reference to the preferred embodiments, those skilled in the art should
Understand, it can be with modification or equivalent replacement of the technical solution of the present invention are made, without departing from the essence of technical solution of the present invention
And range.
Claims (7)
1. one kind 2, the detection method of 4- diamino anisole sulfate, which comprises the following steps:
(1) textile sample is weighed, extraction agent is added, through ultrasonic extraction, centrifugation, supernatant liquid filtering is taken, obtains analyte sample fluid；
(2) standard working solution of gradient concentration is prepared for standard substance with 2,4- diamino anisole sulfate；
(3) pass through the standard working solution of each concentration gradient in ultra performance liquid chromatography-mass spectrometer determination step (2),
Standard spectrogram is obtained, standard working curve is established according to standard diagram；Under the same conditions by the analyte sample fluid in step (1)
Injection ultra performance liquid chromatography-mass spectrometer survey is measured, and passes through the guarantor in comparison sample to be tested spectrogram and standard spectrogram
The time is stayed, qualitative analysis is carried out to 2,4- diamino anisole sulfate in sample；It is calculated in solution by standard working curve
Then 2,4- diamino anisole sulphur in sample is calculated according to sample quality in the concentration of 2,4- diamino anisole sulfate
The content of hydrochlorate；
Wherein, chromatographic condition are as follows: chromatographic column selects 120 SB-Aq of Agilent poroshell, and sample volume is 1~5 μ L, column temperature
It is 40 DEG C；Mobile phase A is the ammonium acetate of 5~10mM, and Mobile phase B is methanol or acetonitrile, and Mobile phase B keeps 10 in initial 1 minute
~20% ratio increases to 50~70% in 1~2min again and is kept for 1 minute, increases to 100% in 3~5min again and keep
0.5min is subsequently reduced to 10~20%, and keeps 1min；Flow velocity is 0.2~0.5mLmin-1；
Mass Spectrometry Conditions are as follows: Ionization mode is electron spray ion；Scanning mode is positive ion scan；Detection mode is more reaction prisons
Survey mode.
2. the detection method of 2,4- diamino anisole sulfate shown according to claim 1, which is characterized in that the chromatography
Condition are as follows: chromatographic column selects 120 SB-Aq of Agilent poroshell, and sample volume is 5 μ L, and column temperature is 40 DEG C；Mobile phase A is
The ammonium acetate of 5mM, Mobile phase B are methanol, and Mobile phase B keeps 10% ratio in initial 1 minute, are increased to again in 1~2min
50% and keep 1 minute, 100% is increased in 3~5min again and keeps 0.5min, is subsequently reduced to 10%, and keep 1min；Flow velocity
For 0.3mLmin-1。
3. the detection method of 2,4- diamino anisole sulfate shown according to claim 1, which is characterized in that the mass spectrum
Condition is as follows: capillary voltage: 3300~3500V；Remove solvent temperature degree: 300~350 DEG C；Go solvent stream amount: 6~10L/
h；Sheath temperature degree: 300~360 DEG C；Sheath throughput: 6~11L/min；Detection mode is multiple-reaction monitoring pattern.
4. the detection method of 2,4- diamino anisole sulfate according to shown in claim 3, which is characterized in that the mass spectrum
Condition is as follows: capillary voltage: 3500V；Remove solvent temperature degree: 350 DEG C；Go solvent stream amount: 7L/h；Sheath temperature degree: 360
℃；Sheath throughput: 11L/min；Detection mode is multiple-reaction monitoring pattern.
5. the detection method of 2,4- diamino anisole sulfate according to claim 1, which is characterized in that the extraction
Reagent includes at least one of methanol, acetonitrile, acetone, preferably acetonitrile.
6. the detection method of 2,4- diamino anisole sulfate according to claim 1 or 5, which is characterized in that described
In step (1), extraction temperature is 60-80 DEG C, and ultrasonic time is not less than 60min.
7. the detection method of 2,4- diamino anisole sulfate according to claim 6, which is characterized in that the step
(1) in, the ratio of textile sample and extraction agent is 1g:10mL.
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