CN105319283A - Method for measuring content of terpyridine - Google Patents
Method for measuring content of terpyridine Download PDFInfo
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- CN105319283A CN105319283A CN201410341127.XA CN201410341127A CN105319283A CN 105319283 A CN105319283 A CN 105319283A CN 201410341127 A CN201410341127 A CN 201410341127A CN 105319283 A CN105319283 A CN 105319283A
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- 238000000034 method Methods 0.000 title claims abstract description 42
- JFJNVIPVOCESGZ-UHFFFAOYSA-N 2,3-dipyridin-2-ylpyridine Chemical compound N1=CC=CC=C1C1=CC=CN=C1C1=CC=CC=N1 JFJNVIPVOCESGZ-UHFFFAOYSA-N 0.000 title 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000000523 sample Substances 0.000 claims abstract description 52
- 239000012086 standard solution Substances 0.000 claims abstract description 33
- 239000012488 sample solution Substances 0.000 claims abstract description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 30
- 239000000243 solution Substances 0.000 claims abstract description 23
- 238000012360 testing method Methods 0.000 claims description 45
- 239000005630 Diquat Substances 0.000 claims description 28
- MXZACTZQSGYANA-UHFFFAOYSA-N chembl545463 Chemical compound Cl.C1=CC(OC)=CC=C1C(N=C1)=CN2C1=NC(C)=C2O MXZACTZQSGYANA-UHFFFAOYSA-N 0.000 claims description 28
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 16
- 238000004817 gas chromatography Methods 0.000 claims description 7
- FIKAKWIAUPDISJ-UHFFFAOYSA-L paraquat dichloride Chemical group [Cl-].[Cl-].C1=C[N+](C)=CC=C1C1=CC=[N+](C)C=C1 FIKAKWIAUPDISJ-UHFFFAOYSA-L 0.000 claims description 7
- 238000011084 recovery Methods 0.000 claims description 7
- 238000002137 ultrasound extraction Methods 0.000 claims description 3
- 238000001514 detection method Methods 0.000 abstract description 11
- 238000000605 extraction Methods 0.000 abstract description 5
- 239000011259 mixed solution Substances 0.000 abstract 1
- 238000005303 weighing Methods 0.000 abstract 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 30
- 150000002500 ions Chemical class 0.000 description 24
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 21
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 13
- 239000012224 working solution Substances 0.000 description 13
- 238000012546 transfer Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 239000003480 eluent Substances 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 7
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 7
- 238000010812 external standard method Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- ZXKXJHAOUFHNAS-FVGYRXGTSA-N (S)-fenfluramine hydrochloride Chemical compound [Cl-].CC[NH2+][C@@H](C)CC1=CC=CC(C(F)(F)F)=C1 ZXKXJHAOUFHNAS-FVGYRXGTSA-N 0.000 description 5
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical class OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 5
- 239000012482 calibration solution Substances 0.000 description 5
- 239000012159 carrier gas Substances 0.000 description 5
- 239000001307 helium Substances 0.000 description 5
- 229910052734 helium Inorganic materials 0.000 description 5
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 5
- 238000012544 monitoring process Methods 0.000 description 5
- 239000012452 mother liquor Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 4
- 238000001294 liquid chromatography-tandem mass spectrometry Methods 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000004009 herbicide Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 230000002363 herbicidal effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 244000269722 Thea sinensis Species 0.000 description 1
- HQGPAERHHSSKNE-UHFFFAOYSA-N acetonitrile;n-ethylethanamine;hydrate Chemical compound O.CC#N.CCNCC HQGPAERHHSSKNE-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- NDAUXUAQIAJITI-UHFFFAOYSA-N albuterol Chemical compound CC(C)(C)NCC(O)C1=CC=C(O)C(CO)=C1 NDAUXUAQIAJITI-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002420 orchard Substances 0.000 description 1
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- 229960002052 salbutamol Drugs 0.000 description 1
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- 239000003381 stabilizer Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000009333 weeding Methods 0.000 description 1
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- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention discloses a method for measuring the content of 2,2':6',2'-terpyridine. The method is a standard addition method. The method comprises the following steps: weighing a sample, adding sodium hydroxide and ethyl acetate, vibrating, performing supersonic extraction to obtain a solution of sample to be measured; then evenly mixing a series of 2,2':6',2'-terpyridine standard solutions with an equal volume ratio with the sample solution, then using a gas chromatography-mass spectrometer (GC-MS) to measure the responding values of the mixed solutions, taking concentration values as the horizontal coordinate and responding values as the vertical coordinate to draw a curve, and calculating the content of 2,2':6',2'-terpyridine in the sample. The provided method has the advantages that the pretreatment is simple and rapid, the detection cost is low, the detection limit is low, and the result is accurate.
Description
Technical field
The invention belongs to agriculture weeding technique field, be specifically related to a kind of detection 2,2 ': 6 ', 2 " methods of-terpyridyl content.
Background technology
Paraquat, diquat dibromide belong to bipyridyl herbicides, and various places are on probation on the industrial crops such as tea place, orchard, sugarcane field, rubber plantation in recent years, obtain good effect, and be one of herbicide of China's extensive application, Ye Shi China herbicide exports more kind.2,2 ': 6 ', 2 " impurity that-terpyridyl is paraquat, produce in diquat dibromide production run.Because it has strong carcinogenesis, current FAO strictly controls its content in paraquat, diquat dibromide.
Generally adopt the steps such as extraction, purification, mensuration to 2 in paraquat, diquat dibromide at present, 2 ': 6 ', 2 " content of-terpyridyl detects, and international analysis of agricultural drugs coordination board (CIPAC) standard adopts LC/MS/MS method to detect.But LC/MS/MS instrument is bought and all very high height of cost of use, even much special testing agency of domestic common agricultural chemicals producer does not possess this financial strength; Secondly, its detecting step also relates to the qualitative confirmation etc. of extraction, Solid-Phase Extraction column purification and isomeride, complex steps.Therefore, the prospect of LC/MS/MS detection method replicability is at home poor.
In paraquat, diquat dibromide, 2,2 ': 6 ', 2 " detection of-terpyridyl content does not also have standard in China.Have researchist to adopt ethyl acetate to extract, basic step is as follows: first with purity rubric material preparation typical curve; Take about 2g sample again, add potassium hydroxide, sodium chloride, 6mL ethyl acetate, vibration, ultrasonic extraction 10min, repeats 5 times; Last GC/MS sample introduction is analyzed, and adopts external standard method production standard opisometer to calculate 2,2 ': 6 ', the 2 " content of-terpyridyl.The subject matter that this technology exists is that extraction step is loaded down with trivial details, will repeatedly extract 5 times, and due to the impact of matrix effect when GC/MS is quantitative, can cause quantitatively inaccurate, testing result usually can be made significantly higher.
Summary of the invention
To the present invention is directed in prior art 2,2 ': 6 ', 2 " detection of-terpyridyl content costly, complex steps or the inaccurate technical matters of testing result, object is to provide a kind of detection 2,2 ': 6 ', 2 " method of the content of-terpyridyl newly.
In detection sample of the present invention, 2,2 ': 6 ', 2 " method of-terpyridyl content is standard addition method, comprises the steps:
Steps A) take sample, add NaOH and/or potassium hydroxide and ethyl acetate, vibration, ultrasonic extraction, obtains testing sample solution;
Step B) by 2,2 ': 6 ', 2 "-terpyridyl series standard solution mixes the mark-on mixed liquor obtaining series concentration respectively than with testing sample solution with equal-volume; then use gas chromatography tandem mass spectrometer (GC/MS) to measure the response of the mark-on mixed liquor of series concentration; with in series standard solution 2; 2 ': 6 '; 2 " the concentration of-terpyridyl is horizontal ordinate, take response as ordinate, make curve and to calculate in sample 2,2 ': 6 ', 2 " content of-terpyridyl.
Wherein, described sample is paraquat and/or diquat dibromide sample.
Steps A) in, every 1g sample, adds 1 ~ 2mL1mol/L NaOH and/or potassium hydroxide, adds the ethyl acetate of 2mL, then shake 1 ~ 2min after vibration, and ultrasonic 15 ~ 30min gets upper solution as testing sample solution.
Step B) in, by 2,2 ': 6 ', 2 "-terpyridyl series standard solution mixes with testing sample solution with the volume ratio of 1: 1 respectively.
The recovery of standard addition of described standard addition method is 70% ~ 120%.The minimum detectability of described standard addition method is 0.1mg/kg.
Described response is peak area.
The absolute difference of twice independent test result that the precision of standard addition method of the present invention obtains under repeated condition is not more than 10% of the arithmetic mean of these two measured values.The absolute difference of the twice independence test result obtained under repeatability condition is not more than 20% of the arithmetic mean of these two measured values.
In detection sample of the present invention, 2,2 ': 6 ', 2 " method of-terpyridyl content has the advantages such as simple and quick, accurate, cheap, detection limit is low.
Accompanying drawing explanation
Fig. 1 is the canonical plotting of embodiment 1 Plays addition method;
Fig. 2 is the canonical plotting of the external standard method in comparing embodiment 2;
Embodiment
Embodiment 1 standard addition method detects 2,2 ': 6 ', the 2 " content of-terpyridyl in diquat dibromide sample
Step 1) 2,2 ': 6 ', the 2 " preparations of-terpyridyl series standard solution
"-terpyridyl, in 25mL volumetric flask, by acetone diluted to scale, is mixed with the standard solution that concentration is about 1000mg/L to take 2,2 ': 6 ' of 0.0250g (being accurate to 0.0001g), 2.With this solution for mother liquor, get with transfer pipet appropriate in 100mL volumetric flask, with acetone constant volume, be mixed with the standard working solution that concentration is 10mg/L.
The standard working solution of 0.05mL, 0.10mL, 0.50mL, 1.00mL, 2.00mL is drawn respectively in 10mL volumetric flask with transfer pipet, with acetone constant volume, concentration must be become to be respectively the series standard solution of 0.05mg/L, 0.10mg/L, 0.50mg/L, 1.00mg/L, 2.00mg/L.
Step 2) preparation of testing sample solution
Take 2.00g (being accurate to ± 0.01g) diquat dibromide sample, put into 25mL color-comparison tube, add the sodium hydroxide solution of 2mL1mol/L, 4.0mL ethyl acetate is added again after careful vibration (can not be stained with on bottle cap), firmly shake 1min, ultrasonic 15min, is cooled to room temperature, gets upper solution as testing sample solution.
Step 3) quantitatively
Get 2,2 ': 6 ', 2 "-terpyridyl series standard solution, mixes with testing sample solution with 1: 1 volume ratio respectively; will obtain the mark-on mixed liquor of series concentration, uses gas chromatography tandem mass spectrometer (GC/MS) to measure the response of the mark-on mixed liquor of series concentration.
The operating conditions of GC/MS is as follows:
Chromatographic column: DB-XLBms, 30m × 0.25mm, 0.25 μm of thickness capillary column;
Column temperature: 100 DEG C 20 DEG C/min270 DEG C (4min);
Injector temperature: 260 DEG C;
Ion source temperature: 200 DEG C;
Connect boundary's temperature: 260 DEG C;
Carrier gas: high-pure helium;
Column flow rate: 1.9mL/min;
Scan mode: SIM;
Sample size: 1.0 μ L;
Input mode: Splitless injecting samples, opens diverting valve and dottle pin blow down valve after 1.5min;
The removal of solvents time: 3.5min;
Ion pair: quota ion 233, qualitative ion 232,205;
Retention time: 2,2 ': 6 ', 2 "-terpyridyl is about 9.2min.
With in series standard solution 2,2 ': 6 ', 2, " concentration of-terpyridyl is horizontal ordinate, and corresponding peak area is ordinate, drawing standard curve, calculates linear equation.
Obtain linear equation Y=aX+b, calculate the value of the X as Y=0,2 in testing sample solution, 2 ': 6 ', 2 "-terpyridyl content c
0=-X
2,2 ': 6 ', the 2 " content of-terpyridyl in diquat dibromide sample
In formula:
C
02,2 ': 6 ', the 2 " content (mg/L) of-terpyridyl in-testing sample solution
V-constant volume, namely adds the volume (mL) of ethyl acetate
W
0-sample quality (g)
Following data are obtained through mensuration
Spiked levels and the corresponding peak area of table 1 standard addition method
As shown in Figure 1, the equation obtained is Y=1.0375 × 10 to the typical curve of standard addition method
6x+2.5415 × 10
5r=0.9995
Result: in diquat dibromide sample 2,2 ': 6 ', 2 " testing result of the content of-terpyridyl is 0.50mg/kg.
The recovery of standard addition of embodiment 2 standard addition method
Step 1) 2,2 ': 6 ', the 2 " preparations of-terpyridyl series standard solution
"-terpyridyl, in 25mL volumetric flask, by acetone diluted to scale, is mixed with the standard solution that concentration is about 1000mg/L to take 2,2 ': 6 ' of 0.0250g (being accurate to 0.0001g), 2.With this solution for mother liquor, get with transfer pipet appropriate in 100mL volumetric flask, with acetone constant volume, be mixed with the standard working solution that concentration is 10mg/L.
The standard working solution of 0.05mL, 0.10mL, 0.50mL, 1.00mL, 2.00mL, 4.00mL is drawn respectively in 10mL volumetric flask with transfer pipet, with acetone constant volume, concentration must be become to be respectively the series standard solution of 0.05mg/L, 0.10mg/L, 0.50mg/L, 1.00mg/L, 2.00mg/L, 4.00mg/L.
Step 2) preparation of testing sample solution
Take 15 parts, 2.00g (being accurate to ± 0.01g) diquat dibromide sample, put into 25mL color-comparison tube, accurately add the standard working solution that 0.02mL, 0.20mL, 0.40mL concentration is 10mg/L respectively, each interpolation volume repeats 5 times, obtain diquat dibromide and add sample, add the sodium hydroxide solution of 2mL1mol/L, 4.0mL ethyl acetate is added again after careful vibration (can not be stained with on bottle cap), firmly shake 1min, ultrasonic 15min, be cooled to room temperature, get upper solution as testing sample solution.
Step 3) quantitatively
Get 2,2 ': 6 ', 2 "-terpyridyl series standard solution, mixes with each part testing sample solution with 1: 1 volume ratio respectively; obtain the mark-on mixed liquor of series concentration, uses gas chromatography tandem mass spectrometer (GC/MS) to measure the response of the mark-on mixed liquor of series concentration.
The operating conditions of GC/MS is as follows:
Chromatographic column: DB-XLBms, 30m × 0.25mm, 0.25 μm of thickness capillary column;
Column temperature: 100 DEG C 20 DEG C/min270 DEG C (4min);
Injector temperature: 260 DEG C;
Ion source temperature: 200 DEG C;
Connect boundary's temperature: 260 DEG C;
Carrier gas: high-pure helium;
Column flow rate: 1.9mL/min;
Scan mode: SIM;
Sample size: 1.0 μ L;
Input mode: Splitless injecting samples, opens diverting valve and dottle pin blow down valve after 1.5min;
The removal of solvents time: 3.5min;
Ion pair: quota ion 233, qualitative ion 232,205;
Retention time: 2,2 ': 6 ', 2 "-terpyridyl is about 9.2min.
With in series standard solution 2,2 ': 6 ', 2, " concentration of-terpyridyl is horizontal ordinate, and corresponding peak area is ordinate, drawing standard curve, calculates linear equation.
Obtain linear equation Y
i=a
ix
i+ b
i, calculate and work as Y
ix when=0
ivalue, in i-th part of testing sample solution 2,2 ': 6 ', 2 "-terpyridyl content c
i=-X
i
I-th part of diquat dibromide adds 2,2 ': 6 ', the 2 " content of-terpyridyl in sample
In formula:
I represents the 1st part, the 2nd part ... the 15th increment product
C
i2,2 ': 6 ', the 2 " content (mg/L) of-terpyridyl in-the i-th part of testing sample solution
V-constant volume, namely adds the volume (mL) of ethyl acetate
W
i-the i-th increment quality (g)
Recovery of standard addition
In formula:
P
ithe recovery of standard addition of-the i-th part of diquat dibromide sample
Q
i-the i-th part of diquat dibromide adds 2,2 ': 6 ', 2 "-terpyridyl content (mg/kg) in sample
Q
02,2 ': 6 ', the 2 " content (mg/kg) of-terpyridyl in the diquat dibromide sample that-embodiment 1 records
A-step 2) in 2,2 ': 6 ', 2 "-terpyridyl add scalar, the concentration of the standard working solution of interpolation and the product (μ g) of volume
Table 2 recovery of standard addition
The recovery scope allowed is 70% ~ 120%
The precision of embodiment 3 standard addition method
Step 1) 2,2 ': 6 ', the 2 " preparations of-terpyridyl series standard solution
"-terpyridyl, in 25mL volumetric flask, by acetone diluted to scale, is mixed with the standard solution that concentration is about 1000mg/L to take 2,2 ': 6 ' of 0.0250g (being accurate to 0.0001g), 2.With this solution for mother liquor, get with transfer pipet appropriate in 100mL volumetric flask, with acetone constant volume, be mixed with the standard working solution that concentration is 10mg/L.
The standard working solution of 0.05mL, 0.10mL, 0.50mL, 1.00mL, 2.00mL, 4.00mL is drawn respectively in 10mL volumetric flask with transfer pipet, with acetone constant volume, concentration must be become to be respectively the series standard solution of 0.05mg/L, 0.10mg/L, 0.50mg/L, 1.00mg/L, 2.00mg/L.
Step 2) preparation of testing sample solution
Take 5 parts, 2.00g (being accurate to ± 0.01g) diquat dibromide sample, put into 25mL color-comparison tube, add the sodium hydroxide solution of 2mL1mol/L, 4.0mL ethyl acetate is added again after careful vibration (can not be stained with on bottle cap), firmly shake 1min, ultrasonic 15min, is cooled to room temperature, gets upper solution as testing sample solution.
Step 3) quantitatively
Get 2,2 ': 6 ', 2 "-terpyridyl series standard solution, mixes with each part testing sample solution with 1: 1 volume ratio respectively; obtain the mark-on mixed liquor of series concentration, uses gas chromatography tandem mass spectrometer (GC/MS) to measure the response of the mark-on mixed liquor of series concentration.
The operating conditions of GC/MS is as follows:
Chromatographic column: DB-XLBms, 30m × 0.25mm, 0.25 μm of thickness capillary column;
Column temperature: 100 DEG C 20 DEG C/min270 DEG C (4min);
Injector temperature: 260 DEG C;
Ion source temperature: 200 DEG C;
Connect boundary's temperature: 260 DEG C;
Carrier gas: high-pure helium;
Column flow rate: 1.9mL/min;
Scan mode: SIM;
Sample size: 1.0 μ L;
Input mode: Splitless injecting samples, opens diverting valve and dottle pin blow down valve after 1.5min;
The removal of solvents time: 3.5min;
Ion pair: quota ion 233, qualitative ion 232,205;
Retention time: 2,2 ': 6 ', 2 "-terpyridyl is about 9.2min.
With in series standard solution 2,2 ': 6 ', 2, " concentration of-terpyridyl is horizontal ordinate, and corresponding peak area is ordinate, drawing standard curve, calculates linear equation.
Obtain linear equation Y
j=a
jx
j+ b
j, calculate and work as Y
jx when=0
jvalue, in jth part testing sample solution 2,2 ': 6 ', 2 "-terpyridyl content c
j=-X
j
2,2 ': 6 ', the 2 " content of-terpyridyl in jth part diquat dibromide sample
In formula:
J represents the 1st part, the 2nd part ... the 5th increment product
C
j2,2 ': 6 ', the 2 " content (mg/L) of-terpyridyl in-jth part testing sample solution
V-constant volume, namely adds the volume (mL) of ethyl acetate
W
j-jth increment quality (g)
Table 3 precision
The absolute difference of the twice independent test result obtained under repeated condition is not more than 10% of the arithmetic mean of these two measured values.
The minimum detectability of embodiment 4 standard addition method
Step 1) 2,2 ': 6 ', the 2 " preparations of-terpyridyl series standard solution
"-terpyridyl, in 25mL volumetric flask, by acetone diluted to scale, is mixed with the standard solution that concentration is about 1000mg/L to take 2,2 ': 6 ' of 0.0250g (being accurate to 0.0001g), 2.With this solution for mother liquor, get with transfer pipet appropriate in 100mL volumetric flask, with acetone constant volume, be mixed with the standard working solution that concentration is 10mg/L.
With transfer pipet draw respectively 0.05mL, 0.10mL, 0.50mL, 1.00mL, 2.00mL, standard working solution in 10mL volumetric flask, with acetone constant volume, concentration must be become to be respectively the series standard solution of 0.05mg/L, 0.1mg/L, 0.5mg/L, 1.0mg/L, 2.0mg/L.
Step 2) preparation of testing sample solution
Take 2.00g (being accurate to ± 0.01g) diquat dibromide sample, put into 25mL color-comparison tube, add the sodium hydroxide solution of 2mL1mol/L, 4.0mL ethyl acetate is added again after careful vibration (can not be stained with on bottle cap), firmly shake 1min, ultrasonic 15min, is cooled to room temperature, gets upper solution as testing sample solution.
Step 3) quantitatively
Get 2,2 ': 6 ', 2 "-terpyridyl series standard solution, mixes with testing sample solution with 1: 1 volume ratio respectively; will obtain the mark-on mixed liquor of series concentration, uses gas chromatography tandem mass spectrometer (GC/MS) to measure the response of the mark-on mixed liquor of series concentration.
The operating conditions of GC/MS is as follows:
Chromatographic column: DB-XLBms, 30m × 0.25mm, 0.25 μm of thickness capillary column;
Column temperature: 100 DEG C 20 DEG C/min270 DEG C (4min);
Injector temperature: 260 DEG C;
Ion source temperature: 200 DEG C;
Connect boundary's temperature: 260 DEG C;
Carrier gas: high-pure helium;
Column flow rate: 1.9mL/min;
Scan mode: SIM;
Sample size: 1.0 μ L;
Input mode: Splitless injecting samples, opens diverting valve and dottle pin blow down valve after 1.5min;
The removal of solvents time: 3.5min;
Ion pair: quota ion 233, qualitative ion 232,205;
Retention time: 2,2 ': 6 ', 2 "-terpyridyl is about 9.2min.
With in series standard solution 2,2 ': 6 ', 2 " concentration of-terpyridyl is horizontal ordinate; corresponding peak area is ordinate, drawing standard curve, calculates linear equation; and series concentration typical curve 2,2 ': 6 ', the 2 " signal to noise ratio (S/N ratio) at-terpyridyl peak read on instrument workstation.
Under these conditions, concentration is 2 of 0.05mg/L, 2 ': 6 ', 2 "-terpyridyl standard solution signal to noise ratio (S/N ratio) is 10, then using this point as minimum point; "-terpyridyl minimum detectable activity is 0.05ng, in diquat dibromide sample 2 to calculate 2; 2 ': 6 ', 2,2 ': 6 ', 2 "-terpyridyl minimal detectable concentration is 0.1mg/kg.
Conclusion: adopt method of the present invention to measure diquat dibromide sample to have simply, facilitate, degree of accuracy and the advantage such as precision is good, and minimum detectability meets the requirements.
Comparing embodiment 1 adopts CIPAC method to detect 2,2 ': 6 ', the 2 " content of-terpyridyl in diquat dibromide sample
A: the preparation of calibration solution: take 2 of 12.5 ± 0.5mg (being accurate to 0.1mg), 2 ': 6 ', 2 "-terpyridyl 2 parts; put into 25mL volumetric flask; dilution in acetonitrile is stand-by to scale, accurately pipettes this solution 1mL to 10mL volumetric flask and the "-terpyridyl standard reserving solution that by dilution in acetonitrile to scale, obtains 2; 2 ': 6 ', 2.Accurately pipetting the above-mentioned storing solution of 0.5mL respectively and be also diluted to scale with acetonitrile-water-diethylamine solution to 50mL volumetric flask, is calibration solution.
B: sample preparation: get 2.0g diquat dibromide sample, puts into the vial with cover of 14mL, adds the sodium hydroxide solution of 0.1mL diethylamine, 2.0mL1mol/L, accurately add 10mL ethyl acetate, fill in lid, turn upside down for several times to guarantee to mix completely, leave standstill 5min.This vial is put into the plastic test tube of the with a lid of a solvent resistant corrosion and sealing, with the centrifugal 2min of 2500rpm, supernatant is for subsequent use.
C: get MCX solid-phase extraction column (60mg/3mL) two, respectively successively with 3mL acetonitrile, 2mL water, 3mL saturated nacl aqueous solution, 3mL water, the activation of 3mL acetonitrile.Get 5mL supernatant for subsequent use, be added on a solid-phase extraction column at twice, coutroi velocity makes it drip off in about 15s, collects eluent in the glass test tube of clean dried, add 2mL eluent ethyl acetate, coutroi velocity makes it drip off in about 10s, drains, and collects eluent in same glass test tube, add 750 μ L trifluoroacetic acids, then this solution is added in second solid-phase extraction column, naturally drip, discard efflux; In glass test tube, add 2mL eluent A (ethyl acetate volume/trifluoroacetic acid volume=20/1), proceed in second solid-phase extraction column, naturally drip, discard efflux; In solid-phase extraction column, add 2mL eluent B (acetonitrile volume/water volume/trifluoroacetic acid=70/30/1), coutroi velocity makes it drip off in about 10s, drains, discards efflux; Finally, with 2mL eluent C (acetonitrile volume/water volume/diethylamine=70/30/5) wash-out solid-phase extraction column, drain, collect efflux, to be measured.
D: detect with LC/MS/MS, basic operation condition is as follows.
Chromatographic column: AgilentC8 (150mm × 3mmi.d. particle diameter 3 μm)
Mobile phase A: add 2mL diethylamine in 1L water
Mobile phase B: add 2mL diethylamine in 1L acetonitrile
Table 3 eluent gradient
Flow velocity: 0.5mL/min
Column temperature: 40 DEG C
Sample size: 20 μ L
Monitoring mode: Salbutamol Selected Ion Monitoring (MRM)
Detect ion pair: 234/78,234/130,234/155,234/207
Retention time: 2,2 ': 6 ', 2 "-terpyridyl retention time is about 3.6min
E: terpyridyl isomeride is qualitative
Be calculated as follows calibration solution in 2,2 ': 6 ', 2 "-terpyridyl MRM response factor:
Wherein:
H
s234/78=calibration effects of ion is to the response peak area of 234/78MRM monitoring channel
H
s234/155=calibration effects of ion is to the response peak area of 234/115MRM monitoring channel
H
s234/207=calibration effects of ion is to the response peak area of 234/207MRM monitoring channel
H
s234/130=calibration effects of ion is to the response peak area of 234/130MRM monitoring channel
R
mRM=MRM response factor
R is calculated to each peak in sample
mRMif, the R at some peaks
mRMwith calibration solution R
mRMaverage value within ± 50%, then thinks 2,2 ': 6 ', the 2 " isomeride of-terpyridyl.
F: result calculates
By step c confirm 2,2 ': 6 ', 2 "-terpyridyl isomeride, all isomeride peak areas are added and, according to calibration solution correction factor calculation sample in terpyridyl content
Table 5 standard addition method of the present invention and CIPAC method are in same sample, 2,2 ': 6 ', 2 " testing result of-terpyridyl content compares
Result: the sample method adopting this law to measure is easy, step is simple, saves time, consistent with International Standards Method result.
Comparing embodiment 2 external standard method detects 2,2 ': 6 ', 2 " content of-terpyridyl and the impacts of matrix effect in diquat dibromide sample
Step 1) 2,2 ': 6 ', the 2 " preparations of-terpyridyl series standard solution
"-terpyridyl, in 25mL volumetric flask, by acetone diluted to scale, is mixed with the standard solution that concentration is about 1000mg/L to take 2,2 ': 6 ' of 0.0250g (being accurate to 0.0001g), 2.With this solution for mother liquor, get with transfer pipet appropriate in 100mL volumetric flask, with acetone constant volume, be mixed with the standard working solution that concentration is 10mg/L.
The standard working solution of 0.05mL, 0.10mL, 0.50mL, 1.00mL, 2.00mL, 4.00mL is drawn respectively in 10mL volumetric flask with transfer pipet, with acetone constant volume, concentration must be become to be respectively the series standard solution of 0.05mg/L, 0.10mg/L, 0.50mg/L, 1.00mg/L, 2.00mg/L.
Step 2) preparation of testing sample solution
Take 2.00g (being accurate to ± 0.01g) diquat dibromide sample, put into 25mL color-comparison tube, add potassium hydroxide solution and the 2gNacl of 2mL1mol/L, 6.0mL ethyl acetate is added again after careful vibration (can not be stained with on bottle cap), firmly shake 1min, ultrasound wave extracts 10min, leaves standstill 30min, repeat extraction 5 times, get upper solution as testing sample solution.
Step 3) quantitatively
After instrument stabilizer, according to following test condition, gas chromatography tandem mass spectrometer (GC/MS) is used to measure the response of series standard solution and sample solution.
The operating conditions of GC/MS is as follows:
Chromatographic column: DB-XLBms, 30m × 0.25mm, 0.25 μm of thickness capillary column;
Column temperature: 100 DEG C 20 DEG C/min270 DEG C (4min);
Injector temperature: 260 DEG C;
Ion source temperature: 200 DEG C;
Connect boundary's temperature: 260 DEG C;
Carrier gas: high-pure helium;
Column flow rate: 1.9mL/min;
Scan mode: SIM;
Sample size: 1.0 μ L;
Input mode: Splitless injecting samples, opens diverting valve and dottle pin blow down valve after 1.5min;
The removal of solvents time: 3.5min;
Ion pair: quota ion 233, qualitative ion 232,205;
Retention time: 2,2 ': 6 ', 2 "-terpyridyl is about 9.2min.
With in series standard solution 2,2 ': 6 ', 2, " concentration of-terpyridyl is horizontal ordinate, and corresponding peak area is ordinate, drawing standard curve, calculates linear equation, and calculates 2,2 ': 6 ', 2 " the content c of-terpyridyl in testing sample solution according to this.
2,2 ': 6 ', the 2 " content of-terpyridyl in diquat dibromide sample
In formula:
2,2 ': 6 ', the 2 " content (mg/L) of-terpyridyl in c-testing sample solution
V-constant volume, namely adds the volume (mL) of ethyl acetate
W-sample quality (g)
Concentration and the corresponding peak area of the standard working solution of table 6 external standard method
As shown in Figure 2, the equation obtained is Y=5.3097 × 10 to the typical curve of external standard method
5x+4.9430 × 10
4r=0.9990
" content of-terpyridyl, testing result is 1.2mg/kg to conclusion: adopt 2,2 ': 6 ', 2 in quantified by external standard method diquat dibromide sample, and its result is apparently higher than the testing result using International Standards Method to obtain.
Claims (7)
1. one kind to be detected in sample 2,2 ': 6 ', 2 " method of-terpyridyl content, the method is standard addition method, comprises the steps:
Steps A) take sample, add NaOH and/or potassium hydroxide and ethyl acetate, vibration, ultrasonic extraction, obtains testing sample solution;
Step B) by 2,2 ': 6 ', 2 "-terpyridyl series standard solution mixes the mark-on mixed liquor obtaining series concentration respectively than with testing sample solution with equal-volume, then measures the response of the mark-on mixed liquor of series concentration with gas chromatography tandem mass spectrometer, with in series standard solution 2; 2 ': 6 '; 2 " the concentration of-terpyridyl is horizontal ordinate, take response as ordinate, makes curve and to calculate in sample 2,2 ': 6 ', 2 " content of-terpyridyl.
2. the method for claim 1, is characterized in that: described sample is paraquat and/or diquat dibromide sample.
3. the method for claim 1, is characterized in that: steps A) in, every 1g sample, add 1 ~ 2mL1mol/L NaOH and/or potassium hydroxide, add the ethyl acetate of 2mL after vibration, then shake 1 ~ 2min, ultrasonic 15 ~ 30min, gets upper solution as testing sample solution.
4. the method for claim 1, is characterized in that: step B) in, by 2,2 ': 6 ', 2 "-terpyridyl series standard solution mixes with testing sample solution with the volume ratio of 1: 1 respectively.
5. the method for claim 1, is characterized in that: the recovery of standard addition of described standard addition method is 70% ~ 120%.
6. the method for claim 1, is characterized in that: the minimum detectability of described standard addition method is 0.1mg/kg.
7. the method for claim 1, is characterized in that: described response is peak area.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105259285A (en) * | 2015-10-15 | 2016-01-20 | 陕西出入境检验检疫局检验检疫技术中心 | Rapid detection method of pyridine pesticides in plant extract |
| CN109085277A (en) * | 2018-07-20 | 2018-12-25 | 重庆天地药业有限责任公司 | The detection method of residual solvent pyridine in a kind of cefminox sodium |
| CN111323528A (en) * | 2020-04-11 | 2020-06-23 | 上海阿拉丁生化科技股份有限公司 | Analysis and detection method for content of bathophenanthroline |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6372730B1 (en) * | 1999-08-04 | 2002-04-16 | The Procter & Gamble Company | 2-decarboxy-2-phosphinico Prostaglandin F analogs |
| WO2010091264A2 (en) * | 2009-02-06 | 2010-08-12 | Perkinelmer Health Sciences, Inc. | Simultaneous detection of estrogen and non estrogen steroids |
| CN102353742A (en) * | 2011-09-29 | 2012-02-15 | 贵州中烟工业有限责任公司 | Method for selectively measuring 7 benzene series in white latex for cigarette through static headspace-gas chromatograph mass spectrum |
-
2014
- 2014-07-17 CN CN201410341127.XA patent/CN105319283A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6372730B1 (en) * | 1999-08-04 | 2002-04-16 | The Procter & Gamble Company | 2-decarboxy-2-phosphinico Prostaglandin F analogs |
| WO2010091264A2 (en) * | 2009-02-06 | 2010-08-12 | Perkinelmer Health Sciences, Inc. | Simultaneous detection of estrogen and non estrogen steroids |
| CN102353742A (en) * | 2011-09-29 | 2012-02-15 | 贵州中烟工业有限责任公司 | Method for selectively measuring 7 benzene series in white latex for cigarette through static headspace-gas chromatograph mass spectrum |
Non-Patent Citations (1)
| Title |
|---|
| 王鸣华等: "敌草快中三联吡啶的气-质联用定量分析研究", 《南京农业大学学报》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105259285A (en) * | 2015-10-15 | 2016-01-20 | 陕西出入境检验检疫局检验检疫技术中心 | Rapid detection method of pyridine pesticides in plant extract |
| CN105259285B (en) * | 2015-10-15 | 2017-07-25 | 陕西出入境检验检疫局检验检疫技术中心 | The quick determination method of pyridine farm chemical in one Plant Extracts |
| CN109085277A (en) * | 2018-07-20 | 2018-12-25 | 重庆天地药业有限责任公司 | The detection method of residual solvent pyridine in a kind of cefminox sodium |
| CN111323528A (en) * | 2020-04-11 | 2020-06-23 | 上海阿拉丁生化科技股份有限公司 | Analysis and detection method for content of bathophenanthroline |
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