CN102507759B - Detection method of navy blue dye in textile - Google Patents
Detection method of navy blue dye in textile Download PDFInfo
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- CN102507759B CN102507759B CN201110313875.3A CN201110313875A CN102507759B CN 102507759 B CN102507759 B CN 102507759B CN 201110313875 A CN201110313875 A CN 201110313875A CN 102507759 B CN102507759 B CN 102507759B
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Abstract
The invention discloses a detection method of navy blue dye in textile, which comprises preparing a to-be-detected sample solution; preparing a standard solution; injecting gradient standard solutions into a liquid chromatography-tandem mass spectrometer, determining peak positions of the navy blue dye by a negative ion multiple reaction monitoring (MRM) mode, recording the peak area of a quantificational ion pair, and working out a standard curve equation with the concentration as x coordinate and the peak area as y coordinate; and determining the navy blue dye in a supernatant obtained from the first step and its peak area in the same way, and calculating according to the standard curve equation to obtain the content of the navy blue dye in the sample. The method can rapidly, accurately, qualitatively and quantitatively detect the navy blue dye in the textile.
Description
Technical field
The present invention relates to a kind of liquid chromatography-tandem mass spectrometry method for determining that in textile, navy blue dye detects that is applicable to.
Background technology
In recent years, European Union has implemented strict safeguard measure to textile, proposes more and more stricter ecology and requires and Social duty, and the rules that comprise forbidding dyestuff and other chemicals of issue have formed seeking unity of action of all members of European Union successively.European Union is one of principal market of China's textiles and other light industrial goods outlet, and for this reason, being necessary has a comprehensively understanding to the information of the relevant ecological textile rules of European Union and technical standard.The 2003/3/EC instruction of European Union's issue, 67/648/EC and 2001/C96E/18 decree have been reaffirmed, and forbid a kind of textile and leather and fur products of blue colorant, so-called navy blue dye is a kind of potpourri, call number 611-070-00-2, the category of genus azo dyes is the potpourri of two kinds of acid metal complex dyes, this potpourri comprises two components, and its molecular formula is respectively C
39H
23ClCrN
7O
12S2Na (CAS No.:118685-33-9) and C
46H
30CrN
10O
20S
23Na (without CAS No.).The trade name of this navy blue is navy blue 018112 (Navy Blue 018112) or dark blue 018112 (Navy 018112).Because it is a kind of potpourri, therefore there is no independent CAS No. or C.I. call number.Navy blue is a kind of new material, can't find in some handbook.It is reported, the mixing ratio of this potpourri is not yet announced.By general understanding, any ratio is all within the limited field of this instruction.The 2003/03/EC of the EU Committee instruction that on January 9th, 2003, issue was responsible for drafting by Germany of European Community's Official Journal, assert that navy blue (call number 611-070-00-2) has very high aquatic toxicity, and be difficult for degraded, can work the mischief to environment after entering environment with waste water.Be protection of the environment, this command request each member state converted this regulation to the rules of this country before 31 days Dec in 2003, and came into force from 30 days June in 2004.From 30 days June in 2004, each member state of the European Community will implement the 2003/03/EC of European Union instruction, this instruction regulation: forbid using navy blue dye on the textiles and leathers goods, and forbid selling the textiles and leathers goods that contain navy blue dye on market.
The mensuration of at present relevant textile forbidding azo dyes has following standard:
1, national standard
(1) GB/T 17592-2006 " mensuration of textile forbidding azo dyes ";
(2) GB/T 23344-2009 " mensuration of textile 4-aminoazabenzol ".
2, European Union's standard
(1) EN 14362-1:2003 " some is derived from the assay method part 1 of the aromatic amine of azo dyes textile: some azo dyes that need not to extract is measured ";
(2) EN 14362-2:2003 " some is derived from the assay method part 2 of the aromatic amine of azo dyes textile: the azo dyes that needs to extract from fiber is measured "
3, DIN
(1) DIN § 35LMBG82.02-2 " using the detection of some azo dyes on commodity analysis weaving commodity ";
(2) DIN § 35LMBG82.02-4 " commodity are analyzed the detection of using some azo dyes on dacron ".
These methods are testing methods of banned azo dyes in present general textile, almost can the forbidding azo dyes in all textiles be detected, but these methods all are not suitable for the detection of navy blue dye in textile.
The people such as the Deng Zhiguang of Inspection and Quarantine Technic Center, Guangdong Entry-Exit Inspection and Qu have applied for the patent of invention of " reversed-phase high-performance liquid chromatography detects the method for cyanine in textile " in 2008, publication number is CN101393179, and has delivered 2 pieces of relevant papers in " inspection and quarantine science " and " printing and dyeing ".The method adopts reversed-phased high performace liquid chromatographic, and the cyanine on cloth specimen is measured.With 70% methyl alcohol+30% potassium dihydrogen phosphate buffer solution as extract; With acetonitrile as the A mobile phase, with phosphate buffered saline as B mobile phase, gradient elution.The initial flow matched is 30: 70, and during termination, proportion of mobile phase is 30: 70, and be 40min detection time; Flow velocity is 1.0mL/min; Auto injection, sampling volume are 20 μ L; The detection wavelength is 254nm.Use Kromsil ODS-1C18,5 μ, 250mm * 4.6mm chromatographic column, column temperature is room temperature.In 0.006～0.04mg/mL and two scopes of 0.02～0.201mg/mL, cyanine concentration standard curve relation is good, and minimum detectability is 0.006mg/mL.Get 0.008mg/mL standard solution continuous sample introduction 5 times, precision degree (RSD) is 0.8932%.Get the extraction sample solution that 5 parts of equivalent (3mL) contain the cyanine cloth specimen, detect, obtaining average recovery rate is that 112.7%, RSD is 5.87%.
Although the method can be measured the cyanine dyestuff in textile, be difficult to navy blue dye is carried out qualitative conclusive evidence accurately, there is certain limitation in actual application.
It is inexorable trend that the ecology production of textile product, ecological consumption and ecology are processed, the developing ecology textile is related to the foreign exchange earning level of China's textile product, be related to the industry strategy of sustainable development, also will play considerable effect to China's textile industry of running business big and strong.China there is no the liquid chromatography-tandem mass spectrometry standard method that in textile, navy blue dye detects at present; in order to safeguard national basic security, ensure human health, to preserve the ecological environment; break through the TBT (Technical Barriers to Trade) of developed country; also in order to carry out cleaner production and enterprise self-technique development level, study and define that in textile product, the detection method of navy blue has important practical significance.
Summary of the invention
The technical problem to be solved in the present invention be to provide a kind of adopt the liquid chromatography-tandem mass spectrometry instrument quickly and accurately qualitative, quantitative measure the detection method of navy blue dye in textile.
In order to solve the problems of the technologies described above, the invention provides a kind of detection method that is applicable to navy blue dye in textile, comprise the following steps:
1), preparation testing sample solution:
A), add extraction agent in testing sample, first soaked 0.1～2 hour, be then in the ultrasound wave of 30～45kHz in frequency, be 40～70 ℃ of lower ultrasonic extraction 0～30min at bath temperature; Get respectively the rear sample residue of extract and extraction;
The solid-liquid ratio of described testing sample and extraction agent is: 1g/15～30mL;
B), with steps A) the sample residue washs with extraction agent after the extraction of gained, gets cleansing solution;
Described extraction agent and steps A) in the liquid ratio of testing sample be: 4～10mL/1g;
C), combining extraction liquid and cleansing solution, and be settled to the integer scale value with extraction agent; Must extract mixed liquor;
D), to get the said extracted mixed liquor centrifugal, the supernatant liquor of gained is placed in sample injection bottle and seals, purpose is to carry out qualitative and quantitative analysis for LC-MS/MS;
The above-mentioned centrifugal high speed centrifugation that is generally, for example 6000～10000 rev/mins;
2), preparation standard solution:
As solvent, the volumetric concentration of described acetonitrile in solvent is 10%～40% with the mixed liquor of acetonitrile and water;
Be C with above solvent with molecular formula
39H
23ClCrN
7O
12The navy blue dissolving of S2Na, being mixed with navy blue concentration is the gradient standard solution of 0.1～10 μ g/mL;
3), the gradient standard solution is injected liquid chromatography-tandem mass spectrometer, negative ion multiple-reaction monitoring (MRM) pattern is measured, and determines the peak position that of navy blue dye, record the right peak area of quota ion, take concentration as horizontal ordinate, peak area is ordinate, the production standard curvilinear equation;
4), get step 1) supernatant liquor of gained is by step 3) method measures navy blue and the peak area thereof in supernatant liquor, according to step 3) the typical curve equation of gained calculates, and obtains the navy blue content in testing sample.
As the improvement that is applicable to the detection method of navy blue dye in textile of the present invention:
The liquid phase chromatogram condition that liquid chromatography-tandem mass spectrometry detects use is: flow velocity: 0.2～0.8mL/min; Column temperature: 20～40 ℃; Sampling volume: 1～10 μ L; Mobile phase is comprised of water and acetonitrile; The gradient elution program is: initial during to 1.5min water account for 80～99% of mobile phase volume, during greater than 1.5min～4min, water accounts for 1～20% of mobile phase volume, during greater than 4min～6min, water accounts for 80～99% of mobile phase volume;
That is, mobile phase: A: water, B: acetonitrile, the gradient elution program is: initial during to 1.5min, A: B is 80～99%: 1～20%; 1.5min after～during 4min, A: B is 1～20%: 80～99%; After 4min～and 6min, A: B is 80～99%: 1～20%;
The mass spectrum condition that described liquid chromatography-tandem mass spectrometry detects use is: ion gun is electric spray ion source; Detection mode is negative ion multiple-reaction monitoring (MRM) pattern; Capillary voltage is 2～4kV; Ion source temperature is 80～120 ℃; Desolventizing temperature degree is 150～380 ℃; The desolventizing gas velocity is 200～600L/h; Taper hole blowback air flow velocity is 10～50L/h; Quota ion is to being 450.1＞442.6, and qualitative ion pair is 450.1＞389.1; The ion residence time is 0.1～0.5s; Taper hole voltage is 20～40V; Collision voltage 10～30V.
As the further improvement that is applicable to the detection method of navy blue dye in textile of the present invention: the chromatographic column that liquid chromatography-tandem mass spectrometry detects use is: ACQUITY
BEH C
18, 1.7 μ m, 2.1 * 50mm.
As the further improvement that is applicable to the detection method of navy blue dye in textile of the present invention: the preparation method of the extraction agent described step 1) is as follows:
First form mixed solution by acetonitrile, sodium dihydrogen phosphate and water, in described mixed solution: the weight content of acetonitrile is 50～80%, and the weight content of sodium dihydrogen phosphate is 0.01～0.75%, and surplus is water;
The pH value of regulating mixed solution with the sodium hydroxide solution of 0.1～5mol/L again is 5～8, gets extraction agent.
As the further improvement that is applicable to the detection method of navy blue dye in textile of the present invention: step C step 1)), every 1g testing sample is settled to the extraction mixed liquor of 20～60mL with extraction agent.
In step 1 of the present invention) the preparation method of extraction agent in: acetonitrile and sodium dihydrogen phosphate are to be analyzed purely, and water is deionized water or distilled water.
The present invention compared with prior art has following remarkable result:
(1) adopt accurately qualitative, quantitative characteristics of liquid chromatography-tandem mass spectrometry, directly measure, acquired results than liquid chromatography more accurately and reliably.
(2) molecular formula of navy blue dye is C
39H
23ClCrN
7O
12S2Na has multi-charge, therefore adopts double ion to determine mass-to-charge ratio m/z, and resulting chromatographic peak is more sharp-pointed, symmetrical, and sensitivity is also higher than single electric charge mass-to-charge ratio pattern.
(3) assay method disclosed by the invention is better in 0.1～1.0 μ g/mL linear relationship, and linearly dependent coefficient is 0.999712; In 2～10 μ g/mL scopes, linearly dependent coefficient r is 0.998829.The method minimum detectability is 0.08mg/kg, and the reversed-phase high-performance liquid chromatography of announcing far below the people such as Deng Zhiguang of Inspection and Quarantine Technic Center, Guangdong Entry-Exit Inspection and Qu detects the minimum detectability 6mg/kg of the method for cyanine in textile.
(4) adopt the mixed solution of acetonitrile, sodium dihydrogen phosphate and water as the extraction agent of navy blue dye, the acetonitrile proportion is larger, makes that in textile samples, navy blue dye can access extraction comparatively thoroughly.
(5) proportion is the ultrasound wave of 30～45kHz, is 40～70 ℃ of lower ultrasonic extraction 0～30min at bath temperature, simple and convenient extraction, easy operating.
(6) liquid chromatography is used C
18Chromatographic column, adopt water commonly used and acetonitrile as mobile phase, gradient elution, can be in 6 minutes, that molecular weight is larger, navy blue dye with 2 negative charges effectively separates with other compositions on chromatographic column, and to obtain retention time be 2.37min, and the chromatographic peak that peak shape is sharp-pointed, symmetrical, resolution is higher is convenient to mass spectrophotometry.
Sample extraction method of the present invention is ultrasonic extraction, adopt Liquid Chromatography-Tandem Mass Spectrometry that extract is measured, liquid phase chromatogram condition adopts water and acetonitrile commonly used, adopt the gradient elution mode in 6 minutes, object effectively to be separated with other compositions, far below 40 minutes of people's methods such as Deng Zhiguang.And utilize the doubly charged characteristics of this material, adopt double charge to determine mass-to-charge ratio m/z, can carry out simultaneously qualitative, quantitative conclusive evidence accurately to the navy blue dye in textile, the detection lower bound is 0.08mg/kg, well below the detection lower bound of patent CN101393179 method, advanced very obvious with novelty.
Description of drawings
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in further detail.
Fig. 1 is the standard substance liquid chromatography-tandem mass spectrometry total ions chromatogram of navy blue dye.
Fig. 2 is the many reactive ion monitorings of the liquid chromatography-tandem mass spectrometry of navy blue dye mass spectrogram.
In figure:
Upper figure is quota ion to being many reactive ions monitoring mass spectrograms of 450.1＞442.6;
Figure below is that qualitative ion pair is many reactive ion monitoring mass spectrograms of 450.1＞389.1.
Fig. 3 is the linear equation of navy blue dye.
Embodiment
Below in conjunction with embodiment and Comparative Examples, the present invention is set forth, yet protection scope of the present invention is not only to be confined to following examples.The person of an ordinary skill in the technical field all can realize result of the present invention according to content disclosed by the invention.
1 reagent and material
Except as otherwise herein provided, it is pure that agents useful for same is analysis, and the chromatogram water meets the one-level water of GB/T 6682-2008 regulation.
1.1 acetonitrile chromatographically pure
1.2 potassium dihydrogen phosphate
1.3 NaOH
1.4 navy blue dye (C
39H
23ClCrN
7O
12S2Na) standard items (purity is 93%).
2 instrument and equipments
2.1 liquid chromatography-tandem mass spectrometry instrument: be furnished with electric spray ion source (ESI).
2.2 balance: be accurate to 0.001g and 0.0001g.
2.3 ultrasonic extraction instrument: power: 400W.
2.4 hydro-extractor: 4000r/min.
2.550mL, 500mL, 1000mL volumetric flask.
Embodiment 1, a kind of detection method that is applicable to navy blue dye in textile comprise the following steps:
1), preparation testing sample solution:
1., acetonitrile, sodium dihydrogen phosphate are mixed according to the weight ratio of 70: 0.247: 29.753 with water; Then with 2mol/L NaOH, the pH value of solution is adjusted to 7.5; Get extraction agent.
2., get the 5.0g testing sample, it is shredded to 0.5cm * 0.5cm mixing.
Take above-mentioned sample 1g (being accurate to 0.001g), be placed in 50mL tool plug graduated cylinder, add the 20mL extraction agent, sample is soaked 2 hours (under room temperature); Then being in the ultrasound wave of 40kHz in frequency, is 60 ℃ of lower ultrasonic extraction 30min at bath temperature; After being cooled to room temperature, inclining extract to the volumetric flask of 50mL.
3., with step 2. after the extraction of gained the sample residue with extraction agent (the same) washing of 5mL, get cleansing solution;
4., cleansing solution is added to step 2. in the volumetric flask that extract is housed of gained, i.e. combining extraction liquid and cleansing solution, and be settled to 50mL with extraction agent (the same), thus obtain extracting mixed liquor.
5., the extraction mixed liquor of getting above-mentioned 5mL (8000 rev/mins) centrifugal 5min at a high speed, get the supernatant liquor of 5mL; Get supernatant liquor 1mL and be placed in sample injection bottle and seal, carry out qualitative and quantitative analysis for LC-MS/MS.
2), preparation standard solution:
As solvent, the volumetric concentration of acetonitrile in solvent is 10% with the mixed liquor of acetonitrile and water;
Accurately getting molecular formula is C
39H
23ClCrN
7O
12The navy blue dye 0.0500g (being accurate to 0.0001g) of S2Na is in the volumetric flask of 50mL, be settled to scale with above solvent (being that acetonitrile is molten with mixing of water), liquid is mixed with the stock solution that concentration is 100 μ g/mL, get respectively successively again in the volumetric flask of stock solution 50 μ L, 150 μ L, 250 μ L, 350 μ L and L to 5 50mL of 500 μ of 100 μ g/mL, with the molten scale that is settled to of above acetonitrile and mixing of water, thereby be mixed with the gradient standard solution that navy blue concentration is respectively 0.1,0.3,0.5,0.7,1.0 these 5 concentration of μ g/mL.
3), above-mentioned gradient standard solution is injected liquid chromatography-tandem mass spectrometer, negative ion multiple-reaction monitoring (MRM) pattern is measured, and determines the peak position that of navy blue dye, record the right peak area of quota ion, take concentration as horizontal ordinate, peak area is ordinate, the production standard curvilinear equation.Specific as follows:
Chromatographic condition is:
Chromatographic column: ACQUITY
BEH C
18, 1.7 μ m, 2.1 * 50mm, or suitable person;
Flow velocity: 0.3mL/min;
Column temperature: 40 ℃;
Sampling volume: 3 μ L;
Mobile phase is comprised of water (claim not only mobile phase A) and acetonitrile (but also claiming Mobile phase B); The gradient elution program sees Table 1:
The gradient elution program list of table 1 Liquid Chromatography-Tandem Mass Spectrometry
| Time (min) | Flow velocity (mL/min) | Water (%) | Acetonitrile (%) |
| 0 | 0.3 | 99 | 1 |
| 0～1.5 | 0.3 | 99 | 1 |
| Greater than 1.5～4 | 0.3 | 1 | 99 |
| Greater than 4～6 | 0.3 | 99 | 1 |
The mass spectrum condition is:
Ion gun: electric spray ion source;
B) detection mode: negative ion multiple-reaction monitoring (MRM) pattern;
C) capillary voltage: 3KV (negative ion);
D) ion source temperature: 120 ℃;
E) desolventizing temperature degree: 380 ℃;
F) desolventizing gas velocity: 600L/h;
G) taper hole blowback air flow velocity: 50L/h;
H) other mass spectrum conditions are referring to table 2.
Table 2 navy blue dye mass spectrum condition table
Annotate:
*The expression quota ion.
Utilize instrument workstation automatic integration, obtain quota ion to 450.1＞442.6 peak area, result is specific as follows:
0.1 the peak area of the standard solution of μ g/mL is 312.3;
0.3 the peak area of the standard solution of μ g/mL is 1143.7;
0.5 the peak area of the standard solution of μ g/mL is 2007.0;
0.7 the peak area of the standard solution of μ g/mL is 2962.9;
1.0 the peak area of the standard solution of μ g/mL is 4137.2;
Therefore, get the described linear equation y=4297.5x-122.1 of Fig. 3, linearly dependent coefficient r is 0.999712.
4), get step 1) supernatant liquor of gained is by step 3) navy blue dye measured in testing sample solution of method (namely substitutes the gradient standard solution of 3 μ L with the supernatant liquor of 3 μ L, all the other are equal to), utilize the typical curve (linear equation) of setting up, get the navy blue content of supernatant liquor; Extension rate (being the conversion relation between sample 1g and supernatant liquor) per sample again; Obtain the navy blue content in testing sample.
5), qualitative analysis
Corresponding step 4), under same test conditions, in sample, determinand has identical retention time with the standard substance that detects simultaneously, and in the standard solution spectrogram that the relative abundance of the qualitative ion of sample and concentration approach, the relative abundance of corresponding qualitative ion compares, if deviation is no more than the scope of table 3 regulation, can be judged to be and has corresponding determinand in sample.
The maximum allowable offset of relative abundance of ions during the qualitative conclusive evidence of table 3
| Relative abundance of ions, % | ＞50 | ＞20～50 | ＞10～20 | ≤10 |
| The maximum deviation that allows, % | ±20 | ±25 | ±30 | ±50 |
6), quantitative test
Corresponding step 4), this method adopts external standard method quantitative, according to measured matter content situation in sample liquid, the selected close standard operation solution of concentration, standard operation solution and sample liquid equal-volume ginseng is injected sample measure, standard operation solution and treat that the response of navy blue dye in sample measuring liquid all should be in the range of linearity of instrument.
Annotate 1: if the detection response of sample liquid exceeds the range of linearity that instrument detects, can suitably dilute rear mensuration.
Annotate 2: under above-mentioned chromatographic condition, the liquid chromatography-tandem mass spectrometry total ion current figure of navy blue dye and many reactive ions monitoring (MRM) mass spectrogram are referring to Fig. 2.
7), detect lower bound
When sample introduction concentration was 0.1 μ g/mL, S/N was 185.Determine concentration limit with 3 times of signal to noise ratio (S/N ratio)s (S/N=3), therefore, this method is 0.08mg/kg to the mensuration lower bound of navy blue dye in textile.
Experiment 1, recovery experiment and Precision Experiment
With the cloth of embodiment 1 with the known navy blue dye C that do not contain in advance
39H
23ClCrN
7O
12The basic cloth of S2Na (CAS No.:118685-33-9) adds C
39H
23ClCrN
7O
12The S2Na standard solution, the sample of having tested the heterogeneities such as cotton, terylene and silk has carried out the interpolation recovery test, make its concentration in sample be respectively 5mg/kg, 10mg/kg and 50mg/kg (should be respectively 0.1 μ g/mL, 0.2 μ g/mL and 1 μ g/mL corresponding to the concentration in analytical solution), every group is repeated 6 times, the sample that obtains adds recovery sample peak area and sees Table 4, and corresponding sample concentration sees Table 5.
Add sample peak area result (n=6) corresponding to recovery test in table 4, cotton, terylene and silk sample
Add sample concentration (n=6) corresponding to recovery test in table 5, cotton, terylene and silk sample
Embodiment 2, a kind of detection method that is applicable to navy blue dye in textile, its difference from Example 1 are following (all the other are equal to embodiment):
1), get the 5.0g testing sample, it is shredded to 0.5cm * 0.5cm mixing.
Take above-mentioned sample 1g (being accurate to 0.001g), be placed in 50mL tool plug graduated cylinder, add the 15mL extraction agent, sample is soaked 1.5 hours (under room temperature); Then being in the ultrasound wave of 40kHz in frequency, is 60 ℃ of lower ultrasonic extraction 20min at bath temperature; After being cooled to room temperature, inclining extract to the volumetric flask of 50mL.
2), with step 1) the sample residue with extraction agent (the same) washing of 5mL, gets cleansing solution after the extraction of gained;
3), cleansing solution is added to step 2) in the volumetric flask that extract is housed of gained, i.e. combining extraction liquid and cleansing solution, and be settled to 25mL with extraction agent (the same), thus obtain extracting mixed liquor.
4), the extraction mixed liquor of getting above-mentioned 5mL (8000 rev/mins) centrifugal 5min at a high speed, get the supernatant liquor of 5mL; Get supernatant liquor 1mL and be placed in sample injection bottle and seal, carry out qualitative and quantitative analysis for LC-MS/MS.
5), preparation standard solution:
As solvent, the volumetric concentration of acetonitrile in solvent is 10% with the mixed liquor of acetonitrile and water;
Accurately getting molecular formula is C
39H
23ClCrN
7O
12The navy blue dye 0.0500g (being accurate to 0.0001g) of S2Na is in the volumetric flask of 50mL, be settled to scale with above solvent, liquid is mixed with the stock solution that concentration is 100 μ g/mL, get respectively successively again in the volumetric flask of stock solution 200 μ L, 300 μ L, 500 μ L, 700 μ L and L to 5 10mL of 1000 μ of 100 μ g/mL, with the molten scale that is settled to of above acetonitrile and mixing of water, be mixed with the gradient standard solution that navy blue concentration is respectively 2,3,5,7 and 10 these 5 concentration of μ g/mL.
6), typical curve: (with embodiment 1) sample introduction under selected chromatogram and mass spectrum condition, above working concentration is respectively 5 standard operation solution such as 2,3,5,7 and 10 μ g/mL and repeats at least sample introduction 3 times, obtain the mean value of peak area, to sample introduction concentration and detecting device peak area drawing standard working curve, peak area is directly proportional to mass concentration, utilize instrument workstation automatic integration, obtain quota ion to 450.1＞442.6 peak area, result is specific as follows:
The peak area of the standard solution of 2 μ g/mL is 4956.3;
The peak area of the standard solution of 3 μ g/mL is 55384.2;
The peak area of the standard solution of 5 μ g/mL is 160945.9;
The peak area of the standard solution of 7 μ g/mL is 252228.8;
The peak area of the standard solution of 10 μ g/mL is 437730.6;
Therefore, obtain linear equation y=52685.1x-102251, linearly dependent coefficient r is 0.998829.
Experiment 2, recovery experiment and Precision Experiment
With the cloth of embodiment 2 with the known navy blue dye C that do not contain in advance
39H
23ClCrN
7O
12The basic cloth of S2Na (CAS No.:118685-33-9) adds C
39H
23ClCrN
7O
12The S2Na standard solution, the sample of having tested the heterogeneities such as cotton, terylene and silk has carried out the interpolation recovery test, makes the concentration of navy blue dye in sample be respectively 100mg/kg.Add C
39H
23ClCrN
7O
12The sample of S2Na is measured as stated above, and every group is repeated 6 times; Corresponding concentration and peak area see Table 6.
Add recovery test result (n=6) in table 6, cotton, terylene and silk sample
At last, it is also to be noted that, what more than enumerate is only several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be arranged.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.
Claims (3)
1. be applicable to the detection method of navy blue dye in textile, it is characterized in that comprising the following steps:
1), preparation testing sample solution:
A), add extraction agent in testing sample, first soaked 0.1～2 hour, be then in the ultrasound wave of 30～45kHz in frequency, be 40～70 ℃ of lower ultrasonic extraction 0～30min at bath temperature; Get respectively the rear sample residue of extract and extraction;
The solid-liquid ratio of described testing sample and extraction agent is: 1g/15 ~ 30mL;
B), with steps A) the sample residue washs with extraction agent after the extraction of gained, gets cleansing solution;
Described extraction agent and steps A) in the liquid ratio of testing sample be: 4 ~ 10mL/ 1g;
C), combining extraction liquid and cleansing solution, and be settled to the integer scale value with extraction agent; Must extract mixed liquor;
D), to get the said extracted mixed liquor centrifugal, the supernatant liquor of gained is placed in sample injection bottle and seals, purpose is to carry out qualitative and quantitative analysis for LC-MS/MS;
2), preparation standard solution:
As solvent, the volumetric concentration of described acetonitrile in solvent is 10% ~ 40% with the mixed liquor of acetonitrile and water;
Be C with above solvent with molecular formula
39H
23ClCrN
7O
12The navy blue dissolving of S2Na, being mixed with navy blue concentration is the gradient standard solution of 0.1 ~ 10 μ g/mL;
3), the gradient standard solution is injected liquid chromatography-tandem mass spectrometer, negative ion multiple-reaction monitoring (MRM) pattern is measured, and determines the peak position that of navy blue dye, record the right peak area of quota ion, take concentration as horizontal ordinate, peak area is ordinate, the production standard curvilinear equation;
The liquid phase chromatogram condition that described liquid chromatography-tandem mass spectrometry detects use is: flow velocity: 0.2～0.8mL/min; Column temperature: 20～40 ℃; Sampling volume: 1～10 μ L; Mobile phase is comprised of water and acetonitrile; The gradient elution program is: initial during to 1.5min water account for 80～99% of mobile phase volume, during 1.5min～4min, water accounts for 1～20% of mobile phase volume, during 4min ~ 6min, water accounts for 80～99% of mobile phase volume;
The mass spectrum condition that described liquid chromatography-tandem mass spectrometry detects use is: ion gun is electric spray ion source; Detection mode is negative ion multiple-reaction monitoring (MRM) pattern; Capillary voltage is 2～4kV; Ion source temperature is 80～120 ℃; Desolventizing temperature degree is 150～380 ℃; The desolventizing gas velocity is 200～600L/h; Taper hole blowback air flow velocity is 10～50L/h; Quota ion is to being 450.1/442.6, and qualitative ion pair is 450.1/389.1; The ion residence time is 0.1～0.5s; Taper hole voltage is 20～40V; Collision voltage 10～30V;
The chromatographic column that described liquid chromatography-tandem mass spectrometry detects use is: ACQUITY UPLC BEH C
18, 1.7 μ m, 2.1 * 50mm;
4), the supernatant liquor of getting the step 1) gained measures navy blue and peak area thereof in supernatant liquor by the step 3) method, calculates according to the typical curve equation of step 3) gained, obtains the navy blue content in testing sample.
2. the detection method that is applicable to navy blue dye in textile according to claim 1 is characterized in that:
The preparation method of the extraction agent in described step 1) is as follows:
First form mixed solution by acetonitrile, sodium dihydrogen phosphate and water, in described mixed solution: the weight content of acetonitrile is 50 ~ 80%, and the weight content of sodium dihydrogen phosphate is 0.01 ~ 0.75%, and surplus is water;
Using the pH value of the sodium hydroxide solution adjusting mixed solution of 0.1 ~ 5mol/L is 5～8 again, gets extraction agent.
3. the detection method that is applicable to navy blue dye in textile according to claim 1 and 2, it is characterized in that: the step C of described step 1)), every 1g testing sample is settled to the extraction mixed liquor of 20 ~ 60 mL with extraction agent.
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| 反相HPLC快速测定"蓝色素";邓志光 等;《印染》;20081231(第17期);35-39 * |
| 反相高效液相色谱"蓝色素"快速检测方法研究;邓志光 等;《检验检疫科学》;20081231;第18卷(第5期);6-9 * |
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