CN106323687A - Method for extracting aromatic amine, detection method, kit and application - Google Patents
Method for extracting aromatic amine, detection method, kit and application Download PDFInfo
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- CN106323687A CN106323687A CN201610629196.XA CN201610629196A CN106323687A CN 106323687 A CN106323687 A CN 106323687A CN 201610629196 A CN201610629196 A CN 201610629196A CN 106323687 A CN106323687 A CN 106323687A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/02—Devices for withdrawing samples
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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
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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
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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
- G01N2030/009—Extraction
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Abstract
The invention belongs to the field of detection analysis, and relates to a method for extracting aromatic amine. The method comprises the following steps that 1, a sample is extracted with a strong acid solution, separation is conducted, and an original extracting solution is obtained, wherein the sample is tobacco and/or a tobacco product; 2, the pH value of the original extracting solution is adjusted to be larger than 7, extraction is conducted with aliphatic ether, separation is conducted, and an extraction solution is obtained. The invention further relates to a method for detecting aromatic amine, a kit and application thereof. According to the method, quantitative analysis can be conducted on aromatic amine in the tobacco and/or the tobacco product rapidly and accurately, operation is easy and convenient, the sensitivity is high, and the reproducibility is good.
Description
Technical field
The invention belongs to detect analysis field, be specifically related to a kind of method extracting aromatic amine, further relate to detect aromatic amine
Method, test kit and application thereof.
Background technology
Aromatic amine compound has toxicity mostly, frequently as intermediate be present in synthetic dyestuffs, insecticide, rubber, plastics,
In the product such as binding agent and medicine.Wherein, the toxicity of some aromatic amine is very strong, and some is then potential carcinogen, such as 4-ammonia
Base biphenyl and 2-naphthylamines be exactly known to carcinogen.In the flue gas that drawing tobacco goods produce and in Nicotiana tabacum L. and tobacco product all
There is aromatic amine, but lower in the aromatic amine content relatively flue gas in Nicotiana tabacum L. and tobacco product.Therefore, Accurate Determining Nicotiana tabacum L. and Nicotiana tabacum L.
The safety evaluation of product is had the certain significance by the aromatic amine content in goods.
Up to now, the aromatic amine compound in the flue gas that drawing tobacco goods have been produced by research worker is examined
Surveying, detection method includes gas chromatography (GC), liquid chromatography (LC), high performance capillary electrophoresis and gas chromatography-mass spectrography
Method (GC/MS) etc..Wherein, gas chromatography, high performance liquid chromatography, easily by impurity interference effect, produce false positive issue；Gas
Though phase chromatograph-mass spectrometer coupling method can avoid the occurrence of false positive issue, but for the sample containing complicated ingredient, need to be in sample pre-treatments
In repeatedly extract, derivatization and cross column purification, operating process is complicated, the cycle is longer.
The Gas phase Smoke ratio produced with drawing tobacco goods, containing more composition in Nicotiana tabacum L. and tobacco product, background is more
Complexity, impurity interference when detection is analyzed is even more serious, and owing to the aromatic amine content in Nicotiana tabacum L. and tobacco product is lower, because of
This, be more not easy the content of Accurate Determining aromatic amine.The most also do not find the aromatic amine in Nicotiana tabacum L. or tobacco product be entered
The method of row Accurate Determining.
At present, a kind of method detecting aromatic amine of still needing, with the aromatic amine in accurate quantitative analysis Nicotiana tabacum L. or tobacco product.
Summary of the invention
The present inventor creatively obtains a kind of method extracting aromatic amine, compared to existing extracting method, the party
Method can extract the aromatic amine compound in Nicotiana tabacum L. and/or tobacco product to a greater degree, and extraction ratio is higher.Meanwhile, the present invention
People is also obtained a kind of method detecting aromatic amine, it is possible to carry out the aromatic amine compound in Nicotiana tabacum L. and/or tobacco product soon
Speed, quantitative analysis accurately, and detection limit is low, and sensitivity is higher, favorable reproducibility, operates the easiest.
First aspect present invention relates to a kind of method extracting aromatic amine, comprises the steps,
(1) sample is extracted with strong acid solution, isolated just extract；Described sample is Nicotiana tabacum L. and/or tobacco product；
(2) pH value of first extract is adjusted to more than 7, extract with aliphatic ether, isolated extract.
In one embodiment of first aspect present invention, also comprise the steps,
(3) remove the aliphatic ether in extract, be extracted thing, described extract be dissolved in methanol, obtain extracting solution.
In one embodiment, in step (3), make a return journey except aliphatic ether by extract is dried；Preferably, dry
Dry mode is that nitrogen dries up.
In one embodiment, in step (3), the volumetric usage of methanol is the 50%-200% of extract volume, excellent
Elect 80%-120% as, more preferably 100%.
In one embodiment, in step (3), before removing aliphatic ether, also include adding weak acid or weak in extract
Acid solution carries out the step mixed.
In one embodiment, described weak acid is acetic acid；Preferably, the purity of described acetic acid is 99%-100% (W/
W), more preferably 99.5% (W/W).
In one embodiment, described weak acid solution is aqueous acetic acid；Preferably, the concentration of described aqueous acetic acid
Less than 99% (W/W), more preferably 40%-70% (W/W), 50% (W/W), 60% (W/W) or 80% (W/W).
In one embodiment, the addition of described weak acid solution (in terms of weak acid) or weak acid as 0.1-0.8mL/ (mL
Extract), more preferably 0.3-0.7mL/ (mL extract), more preferably 0.5mL/ (mL extract).
In one embodiment of first aspect present invention, including any one in following A to M or multinomial:
A., in step (1), described strong acid solution is strong acid aqueous solution；Preferably, described strong acid aqueous solution is selected from hydrochloric acid water
One or more in solution and aqueous solution of nitric acid；
B., in step (1), described strong acid solution is weak solution；
C., in step (1), the concentration of described strong acid solution is 1%-10% (W/W), preferably 2%-8% (W/W), more excellent
Elect 5% (W/W) as；
D., in step (1), the solid-liquid ratio of described extraction is 1:(20-100) (g/mL), preferably 1:(40-70) (g/mL),
More preferably 1:50 (g/mL)；
E. in step (1), extraction time is 10-150 minute, preferably 20-100 minute, more preferably 30 minutes；
F., in step (1), described extraction is carried out under ultrasound condition；
G., in step (2), the pH value of described just extract is adjusted to more than 8, preferably greater than 10, more preferably 13 with
On；
H., in step (2), adjust pH value by addition solid base or aqueous slkali in first extract, be preferably added to solid
Alkali；It is highly preferred that one or more that solid base is in sodium hydroxide and potassium hydroxide；
I., in step (2), before extraction, the step that the first extract having adjusted pH value is stood cooling is also included；Preferably, quiet
The time putting cooling is 5 minutes；
J. in step (2), described aliphatic ether is polarity aliphatic ether, and the most lower boiling polarity aliphatic ether more preferably boils
Point is for 40-70 DEG C, and further preferred boiling point is 50-60 DEG C；Preferably, described aliphatic ether is in ether and t-butyl methyl ether
One or more, more preferably t-butyl methyl ether；
K., in step (2), the consumption of described aliphatic ether is 5-40mL/ (g sample), preferably 10-30mL/ (g sample), more
It is preferably 20mL/ (g sample)；
L. in step (2), extraction time is 5-20 minute, preferably 10 minutes；
M., in step (1), described aromatic amine is selected from o-aminoazotoluene, 4-aminobphenyl, 2-amino-4-nitro first
The chloro-o-toluidine of benzene, benzidine, parachloroanilinum, 4-, 2-methoxyl group-5-monomethylaniline., 2-how amine, 4,4'-diaminourea hexichol
Methylmethane, 2,4 di amino toluene, 3,3'-dichloro-benzidine, 3,3'-dimethoxy benzidine, 3,3'-methyl-4,4'-diamino
Base diphenyl-methane, 4,4'-methylene-two-(2-chloroaniline), 4,4'-diaminodiphenyl ether, ortho-aminotoluene, 4-aminoazabenzol,
One or more in 2-aminoanisole, 2,4-dimethylaniline and 2,6-dimethylaniline.
Second aspect present invention relates to a kind of method detecting aromatic amine, including according to any one of first aspect present invention institute
The extracting method stated obtains extract and/or the step of extracting solution；Also include measuring extract with liquid chromatography tandem mass spectrometry
And/or the step of extracting solution.
In one embodiment of second aspect present invention, described in be determined as detection by quantitative, preferably inner mark method ration inspection
Survey；It is highly preferred that internal standard substance is d7-1-amino naphthalenes.
In one embodiment of second aspect present invention, it is any that the operating condition of liquid chromatograph includes in following a to d
One or multinomial:
A. chromatographic column is Féraud door Agilent ZORBAX SB-C3 liquid-phase chromatographic column；Preferably, the specification of chromatographic column is
150mm × 2.1mm i.d., 5 μm particle diameters；
B. the temperature of chromatographic column is 25-50 DEG C, preferably 30-50 DEG C, more preferably 40 DEG C；
C. sample size is 1-10 μ L, preferably 2-8 μ L, more preferably 3 μ L；
D. flowing is made up of mobile phase A and Mobile phase B, and mobile phase A is methanol, and Mobile phase B is 0.1% (V/V) acetic acid
Aqueous solution；Preferably, the elution program of flowing phase is as shown in the table,
In one embodiment of second aspect present invention, mass spectrographic operating condition or parameter include following 1) to 66) in
Any one or multinomial:
1) ion source is electron spray ionisation source；
2) scan mode is cation scanning；
3) detection mode is multiple-reaction monitoring；
4) electron spray voltage is 4000-7000V, preferably 5000-6000V, more preferably 5500V；
5) ion source temperature is 500-750 DEG C, preferably 550-700 DEG C, more preferably 650 DEG C；
6) auxiliary gas Gas1 and/or Gas2 pressure be 40-70psi, preferably 50-60psi, more preferably 50psi or
60psi；
7) quota ion of o-aminoazotoluene is to for 226.1/91.1；
8) the qualitative ion pair of o-aminoazotoluene is 226.1/121.1；
9) impact energy of o-aminoazotoluene is 20V；
10) quota ion of 4-aminobphenyl is to for 170.1/153.2；
11) the qualitative ion pair of 4-aminobphenyl is 170.1/152.1；
12) impact energy of 4-aminobphenyl is 20V；
13) quota ion of 2-amino-4-Methylnitrobenzene is to for 153.1/107.1；
14) the qualitative ion pair of 2-amino-4-Methylnitrobenzene is 153.1/89.9；
15) impact energy of 2-amino-4-Methylnitrobenzene is 25V；
16) quota ion of benzidine is to for 184.1/156；
17) the qualitative ion pair of benzidine is 184.1/166；
18) impact energy of benzidine is 40V；
19) quota ion of parachloroanilinum is to for 128/93.1；
20) the qualitative ion pair of parachloroanilinum is 128/111.2；
21) impact energy of parachloroanilinum is 20V；
22) quota ion of the chloro-o-toluidine of 4-is to for 142/107.2；
23) the qualitative ion pair of the chloro-o-toluidine of 4-is 142/125.2；
24) impact energy of the chloro-o-toluidine of 4-is 23V；
25) quota ion of 2-methoxyl group-5-monomethylaniline. is to for 138.1/123.2；
26) the qualitative ion pair of 2-methoxyl group-5-monomethylaniline. is 138.1/105.2；
27) impact energy of 2-methoxyl group-5-monomethylaniline. is 20V；
28) quota ion of 2-how amine is to for 144.1/127.1；
29) the qualitative ion pair of 2-how amine is 144.1/77.2；
30) impact energy of 2-how amine is 25V；
31) quota ion of 4,4 '-diaminodiphenyl-methane is to for 199.1/106.2；
32) the qualitative ion pair of 4,4 '-diaminodiphenyl-methane is 199.1/77.2；
33) impact energy of 4,4 '-diaminodiphenyl-methane is 30V；
34) quota ion of 2,4 di amino toluene is to for 123.1/108；
35) the qualitative ion pair of 2,4 di amino toluene is 123.1/106.1；
36) impact energy of 2,4 di amino toluene is 23V；
37) quota ion of 3,3 '-dichloro-benzidine is to for 253.1/217.1；
38) the qualitative ion pair of 3,3 '-dichloro-benzidine is 253.1/182.1；
39) impact energy of 3,3 '-dichloro-benzidine is 30V；
40) quota ion of 3,3 '-dimethoxy benzidine is to for 245.2/230.2；
41) the qualitative ion pair of 3,3 '-dimethoxy benzidine is 245.2/213.2；
42) impact energy of 3,3 '-dimethoxy benzidine is 25V；
43) 3,3 '-methyl-4,4 ' quota ion of-MDA is to for 227.2/120.2；
44) 3,3 '-methyl-4,4 ' the qualitative ion pair of-MDA is 227.2/178.2；
45) 3,3 '-methyl-4,4 ' impact energy of-MDA is 25V；
46) quota ion of 4,4 '-methylene-two-(2-chloroaniline) is to for 267.2/231.2；
47) the qualitative ion pair of 4,4 '-methylene-two-(2-chloroaniline) is 267.2/140.2；
48) impact energy of 4,4 '-methylene-two-(2-chloroaniline) is 30V；
49) quota ion of 4,4 '-diaminodiphenyl ether is to for 201.1/108.3；
50) the qualitative ion pair of 4,4 '-diaminodiphenyl ether is 201.1/184；
51) impact energy of 4,4 '-diaminodiphenyl ether is 23V；
52) quota ion of ortho-aminotoluene is to for 108.1/91.4；
53) the qualitative ion pair of ortho-aminotoluene is 108.1/93.2；
54) impact energy of ortho-aminotoluene is 23V；
55) quota ion of 4-aminoazabenzol is to for 198.2/77.2；
56) the qualitative ion pair of 4-aminoazabenzol is 198.2/51.2；
57) impact energy of 4-aminoazabenzol is 23V；
58) quota ion of 2-aminoanisole is to for 124.4/109.2；
59) the qualitative ion pair of 2-aminoanisole is 124.1/92.3；
60) impact energy of 2-aminoanisole is 23V；
61) quota ion of 2,4-dimethylaniline is to for 122.1/107.2；
62) the qualitative ion pair of 2,4-dimethylaniline is 122.1/105.2；
63) impact energy of 2,4-dimethylaniline is 23V；
64) quota ion of 2,6-dimethylaniline is to for 122.1/105.3；
65) the qualitative ion pair of 2,6-dimethylaniline is 122.1/107.2；
66) impact energy of 2,6-dimethylaniline is 23V.
Third aspect present invention relates to a kind of test kit, comprises,
I. aqueous hydrochloric acid solution；
II. sodium hydrate solid and/or sodium hydrate aqueous solution；With
III. ether and/or t-butyl methyl ether.
In one embodiment, described test kit also comprises acetic acid and methanol；Preferably, the purity of described acetic acid is
99%-100% (W/W), more preferably 99.5% (W/W).
In one embodiment, described test kit also comprises liquid-phase chromatographic column；Preferably, described liquid-phase chromatographic column is luxuriant and rich with fragrance
Sieve door Agilent ZORBAX SB-C3 liquid-phase chromatographic column.
In one embodiment, described test kit also comprises 0.1% (V/V) acetic acid aqueous solution.
In one embodiment, the concentration of described aqueous hydrochloric acid solution is 1-10% (W/W), preferably 5% (W/W).
Fourth aspect present invention relates to test kit described in any one of third aspect present invention and is extracting and/or in detection sample
Aromatic amine in purposes；Described sample is Nicotiana tabacum L. and/or tobacco product.
In one embodiment of fourth aspect present invention, described aromatic amine is selected from o-aminoazotoluene, 4-amino connection
How are benzene, 2-amino-4-Methylnitrobenzene, benzidine, parachloroanilinum, the chloro-o-toluidine of 4-, 2-methoxyl group-5-monomethylaniline., 2-
Amine, 4,4'-diaminodiphenyl-methane, 2,4 di amino toluene, 3,3'-dichloro-benzidine, 3,3'-dimethoxy benzidine,
3,3'-methyl-4,4'-MDA, 4,4'-methylene-two-(2-chloroaniline), 4,4'-diaminodiphenyl ether, neighbour
One or many in toluidines, 4-aminoazabenzol, 2-aminoanisole, 2,4-dimethylaniline and 2,6-dimethylaniline
Kind.
In the present invention,
If no special instructions, " strong acid " refers to the acids that the most almost can all ionize, and has strong acidity anti-
Should, such as hydrochloric acid HCl, sulphuric acid H2SO4, nitric acid HNO3, perchloric acid HCl4Deng.
If no special instructions, " extraction " refers to utilize suitable solvent and method, by solubility effective ingredient from raw material
The process leached.
As without the explanation of special ratio, " aromatic amine " refers to that in amino molecule, part or all of hydrogen atom is taken by phenyl or other aromatic radical
The derivant in generation.Such as aniline, diphenylamines, triphenylamine etc..Aromatic amine is the solid of high boiling liquid or low melting point, has spy
Different abnormal smells from the patient, toxicity is big, is typically insoluble in water.
If no special instructions, " aliphatic ether " refers to the compound that two univalent fat hydrocarbyls and an oxygen atom connect, logical
Formula is R-O-R ', such as dimethyl ether CH3-O-CH3, diethyl ether C2H5OC2H5Deng.
If no special instructions, " nitrogen dries up " refers to that the surface that nitrogen is blown into heating sample carries out sample concentration or dry
Dry, have save time, easy to operate, the feature such as be easily controlled.
If no special instructions, " weak acid " refer in aqueous can only the acids of fraction ionization, have weak acid anti-
Should.Such as carbonic acid H2CO3, hydrosulphuric acid H2S, boric acid H3BO3Deng.
If no special instructions, " Nicotiana tabacum L. " refers to Solanaceae, Nicotiana (Nicotiana L.), annual or perennial herb,
Hobby class crop.This genus there are about more than 60 and plants, and is wild species mostly.Main cultispecies has safflower tobacco and Folium Nicotianae rusticae.The two
All originate in South America, be all spontaneous amphidiploid.Safflower tobacco, also known as Nicotiana tabacum, is worldwide commodity production cigarette
Kind.Again because of modulator approach and kind source, area, cultivation step is different and forms polytype: flue-cured tobacco, burley tobaccos, Maryland, snow
Eggplant cigarette, fumigation, Turkish tobaccos, Dark sun-cured, Sun cured tobacco etc..Each type has again a lot of cultivar.Folium Nicotianae rusticae is with the former Soviet Union
Cultivating more with India, there is a small amount of cultivation on the ground such as Xinjiang, China, Gansu.Henbane (N.alata Link and in this genus
Otta) plant for viewing and admiring with powder blue smoke grass (N.glauca Graham).
If no special instructions, " tobacco product " refers to that all or part of is that raw material produces, for suction, suction by Nicotiana tabacum L.
Suck, chew or the goods of snuffing.Described tobacco product includes but not limited to Medicated cigarette and chewing tobacco.
If no special instructions, " internal standard method " refers to draw in Instrumental Analysis a kind of method of standard curve.Its principle is: will
A certain amount of internal standard material adds in the standard solution of variable concentrations level time, and the signal then obtaining composition to be measured and internal standard substance is strong
The ratio of degree, as the longitudinal axis；Obtain the ratio of the amount of composition to be measured or composition to be measured and internal standard substance amount again, as transverse axis, draw and close
It it is curve.Generally, the physics of internal standard material used, chemical property are similar to composition to be measured, and can divide with composition to be measured
From.Internal standard method can eliminate measuring instrument, the change of measuring condition, the impact of sample size change etc., thus improves analysis precision
Degree, is widely used in chromatography and spectrum analysis.
The beneficial effect that the present invention obtains:
1, the extracting method of the present invention can extract the aromatic amine chemical combination in Nicotiana tabacum L. and/or tobacco product to a greater degree
Thing, extraction ratio is higher.
2, the detection method of the present invention can detect the aromatic amine in Nicotiana tabacum L. and/or tobacco product the most quickly and accurately
Compounds content.
3, the detection method detection limit of the present invention is low, sensitivity is higher, favorable reproducibility, operation are the easiest.
4, in detection method, Féraud door Agilent ZORBAX SB-C3 liquid-phase chromatographic column is used, can be by 20 kinds
Aromatic amine separates well, there's almost no peak shape tailing problem.
Accompanying drawing explanation
In order to make present disclosure be more likely to be clearly understood, below according to the specific embodiment of the present invention and combine
Accompanying drawing, the present invention is further detailed explanation, wherein
Fig. 1 is the flow chart of extracting method of the present invention.
Fig. 2 is the chromatogram of S3 grade standard working solution in the embodiment of the present invention 1.
Fig. 3 is the chromatogram of sample solution in comparative example 3.
Detailed description of the invention
Embodiment 1
1, material and reagent
The mixed standard solution of (1) 20 kind of aromatic amine (buy from lark prestige Science and Technology Ltd.): 20 kinds of aromatic amines are respectively
For: o-aminoazotoluene, 4-aminobphenyl, 2-amino-4-Methylnitrobenzene, benzidine, parachloroanilinum, the chloro-o-methyl-benzene of 4-
Amine, 2-methoxyl group-5-monomethylaniline., 2-how amine, 4,4'-diaminodiphenyl-methanes, 2,4 di amino toluene, 3,3'-dichloros
Benzidine, 3,3'-dimethoxy benzidines, 3,3'-methyl-4,4'-MDA, 4,4'-methylene-two-(2-chlorine
Aniline), 4,4'-diaminodiphenyl ethers, ortho-aminotoluene, 4-aminoazabenzol, 2-aminoanisole, 2,4-dimethylanilines, 2,
6-dimethylaniline；Concentration is 300 μ g/mL.
(2) internal standard substance d7-1-amino naphthalenes (buy from lark prestige Science and Technology Ltd.).
(3) inner mark solution: weigh d7-1-amino naphthalenes 10mg, is placed in 100mL volumetric flask, with methanol dilution to scale, joins
Make the one-level internal standard stock solution that concentration is 100 μ g/mL.Take one-level internal standard stock solution 1mL, be placed in 100mL volumetric flask,
With methanol dilution to scale, it is configured to the inner mark solution that concentration is 1 μ g/mL.
(4) standard working solution: by the mixed standard solution 1mL of 20 kinds of aromatic amines, is placed in 100mL brown volumetric flask,
Dissolve and constant volume with methanol, obtain one-level hybrid standard storing solution (concentration of 20 kinds of aromatic amines is 3 μ g/mL).Take one-level mixing
Standard reserving solution 5mL, is placed in 100mL brown volumetric flask, dissolves and constant volume with methanol, obtains two grades of hybrid standard storing solutions (20
The concentration planting aromatic amine is 150ng/mL).Draw respectively accurately two grades of hybrid standard storing solution 0.2mL, 0.4mL, 1mL,
2mL, 4mL and 10mL are in 100mL brown volumetric flask, with methanol dilution to scale, obtain S1-S6 grade standard working solution, its
In, the concentration of 20 kinds of aromatic amines is respectively 0.3ng/mL, 0.6ng/mL, 1.5ng/mL, 3ng/mL, 6ng/mL and 15ng/mL.
2, extract
According to the flow process of Fig. 1, the aromatic amine in Nicotiana tabacum L. is extracted.
Accurately weigh 0.5g offal sample (Yunnan tobacco after pulverizing), be placed in 50mL ground triangular flask, accurately add
The inner mark solution of the 1 μ g/mL of 50 μ L and the aqueous hydrochloric acid solution of 25mL5% (W/W), extract 30 minutes under ultrasound condition, at the beginning of obtaining
Extract.With solid sodium hydroxide, the pH value of first extract is regulated to 13 afterwards, after standing cooling 5 minutes, add the 10mL tert-butyl group
Methyl ether oscillation extraction 10 minutes, stands 5 minutes.In 1mL supernatant liquid, add 2 to 3 acetic acid and mix, after nitrogen dries up,
In residue, add 1mL methanol dissolve, obtain sample solution.Wherein, the purity of acetic acid is 99.5% (W/W).
3, detection
With the high performance liquid chromatography tandem mass spectrum instrument Qtrap 5500 of company (AB SCIEX) respectively to S1-S6 grade standard work
Make solution and sample solution carries out detection and analyzes.Wherein, the chromatogram of S3 grade standard working solution is as shown in Figure 2.
Operation condition of chromatogram: chromatographic column uses Féraud door Agilent ZORBAX SB-C3 liquid-phase chromatographic column, and specification is
150mm × 2.1mm i.d., 5 μm particle diameters；Chromatogram column temperature is 40 DEG C；Sample size is 3 μ L；Flowing phase: mobile phase A is methanol,
Mobile phase B is the acetic acid aqueous solution of 0.1% (V/V)；The gradient elution program of flowing phase is shown in Table 1.
Table 1 flows the gradient elution program of phase
Mass spectrum operation condition: ion source: electron spray ionisation source (ESI)；Scan mode: cation scans；Detection mode: many
Reaction monitoring (MRM)；Electron spray voltage: 5500V；Ion source temperature: 650 DEG C；Auxiliary gas Gas1 pressure: 60psi；Auxiliary gas
Gas2 pressure: 50psi.
The quota ion of each aromatic amine compound is shown in Table 2 to, qualitative ion pair and collision energy (CE).
Table 2 the MS detection parameters
4, calculate
(1) according to the testing result of S1-S6 grade standard working solution in above-mentioned 3, with aromatic amine compound and internal standard substance
Peak area ratio carries out linear regression to concentration ratio, obtains the standard curve equation of 20 kinds of aromatic amine compounds, is shown in Table 3.Wherein, horizontal
The ratio of the concentration of coordinate representation aromatic amine compound and internal standard substance concentration, vertical coordinate represent the peak area of aromatic amine compound with
The ratio of internal standard substance peak area.Take the standard working solution of least concentration, carry out 10 parallel assays, calculate standard deviation, 3 times
Standard deviation is detection limit, and 10 times of standard deviations are quantitative limit, are listed in table 3.
Standard curve equation, detection limit and the quantitative limit of table 3 aromatic amine compound
As shown in Table 3, detection method is low to the detection limit of 20 kinds of aromatic amine compounds, highly sensitive.
(2) according to the testing result of sample solution, in conjunction with the standard curve equation of aromatic amine compound in table 3, calculate
Aromatic amine content in sample solution, the aromatic amine content being calculated further in offal sample.At high, medium and low three water
20 kinds of aromatic amines carry out on Ping recovery of standard addition mensuration respectively, and each mark-on sample parallel measures and averages for three times, and examines
Examining the repeatability of testing result, result is as shown in table 4.
Table 4 response rate and repeatability
As shown in Table 4, detection method to the recovery of standard addition of 20 kinds of aromatic amines all more than 90%, accuracy
Height, and the repeatability of testing result is good.
Comparative example 1
Accurately weigh 0.5g offal sample similarly to Example 1, be placed in 50mL ground triangular flask, accurately add 50 μ L
The inner mark solution of 1 μ g/mL and the aqueous hydrochloric acid solution of 25mL5% (W/W), extract 30 minutes under ultrasound condition, obtain just extract.
First extract is adsorbed through first step SPE post (Waters Oasis MCX), with 1%HCL and methanol-eluted fractions remove neutral and other
Polar impurity, then with containing 5%NH4The methanol-eluted fractions of OH.Second step SPE is with nonpolar/hydrophobicity reversed-phase column (Waters Oasis
HLB) absorption, after eluent is concentrated, carries out LC-MS/MS analysis, and LC-MS/MS operating condition is same as in Example 1.
Result shows:
1) the chromatographic peak peak area of 20 kinds of aromatic amine compounds that comparative example 1 records is less than the measurement result of embodiment 1, example
As, the peak area of the 2-naphthylamines that comparative example 1 measures is 3746, and the peak area of the 2-naphthylamines that embodiment 1 measures is 6658, explanation
The extraction ratio of extracting method of the present invention is higher, and the sensitivity of detection method is higher.
2) in comparative example 1, the recovery of standard addition of 20 kinds of aromatic amines, all not less than 90%, illustrates that detection method is compared
Higher in the accuracy of comparative example 1 detection method.
Comparative example 2
Replacing the t-butyl methyl ether in embodiment 1 with ether, remaining is carried out with reference to embodiment 1.
Result shows, compared with the extract that t-butyl methyl ether of the present invention is obtained by extraction, uses ether extraction, the extraction obtained
Taking liquid more muddy, impurity content is more, and contaminative is bigger.
Comparative example 3
Use C18Liquid-phase chromatographic column replaces the liquid-phase chromatographic column of embodiment 1, and remaining carries out with reference to embodiment 1, obtains sample molten
The chromatogram of liquid is as shown in Figure 3.
From the figure 3, it may be seen that compared with the liquid-phase chromatographic column of the present invention, use C18During liquid-phase chromatographic column, 20 kinds of aromatic amines can not
Separate well, and peak shape hangover is serious.
Obviously, above-described embodiment is only for clearly demonstrating example, and not restriction to embodiment.Right
For those of ordinary skill in the field, can also make on the basis of the above description other multi-form change or
Variation.Here without also cannot all of embodiment be given exhaustive.And the obvious change thus extended out or
Change among still in the protection domain of the invention.
Claims (10)
1. the method extracting aromatic amine, comprises the steps,
(1) sample is extracted with strong acid solution, isolated just extract；Described sample is Nicotiana tabacum L. and/or tobacco product；
(2) pH value of first extract is adjusted to more than 7, extract with aliphatic ether, isolated extract.
Extracting method the most according to claim 1, it also comprises the steps,
(3) remove the aliphatic ether in extract, be extracted thing, described extract be dissolved in methanol, obtain extracting solution；
Preferably, in step (3), make a return journey except aliphatic ether by extract is dried；It is highly preferred that drying mode is nitrogen
Dry up；
Preferably, in step (3), the volumetric usage of methanol is the 50%-200% of extract volume, more preferably 80%-
120%, more preferably 100%；
Preferably, in step (3), before removing aliphatic ether, also include adding weak acid in extract or weak acid solution mixes
Step；
It is highly preferred that described weak acid is acetic acid；It is further preferred that the purity of described acetic acid is 99%-100% (W/W), more
It is preferably 99.5% (W/W)；
It is highly preferred that described weak acid solution is aqueous acetic acid；It is further preferred that the concentration of described aqueous acetic acid is less than
99% (W/W), more preferably 40%-70% (W/W), 50% (W/W), 60% (W/W) or 80% (W/W)；
It is highly preferred that the addition of described weak acid solution (in terms of weak acid) or weak acid is as 0.1-0.8mL/ (mL extract), enter one
Step is preferably 0.3-0.7mL/ (mL extract), more preferably 0.5mL/ (mL extract).
Extracting method the most according to claim 1 and 2, it is characterised in that any one in following A to M or multinomial:
A., in step (1), described strong acid solution is strong acid aqueous solution；Preferably, described strong acid aqueous solution is selected from aqueous hydrochloric acid solution
With one or more in aqueous solution of nitric acid；
B., in step (1), described strong acid solution is weak solution；
C. in step (1), the concentration of described strong acid solution is 1%-10% (W/W), preferably 2%-8% (W/W), more preferably
5% (W/W)；
D., in step (1), the solid-liquid ratio of described extraction is 1:(20-100) (g/mL), preferably 1:(40-70) (g/mL), more excellent
Elect 1:50 (g/mL) as；
E. in step (1), extraction time is 10-150 minute, preferably 20-100 minute, more preferably 30 minutes；
F., in step (1), described extraction is carried out under ultrasound condition；
G., in step (2), the pH value of described just extract is adjusted to more than 8, preferably greater than 10, more preferably more than 13；
H., in step (2), adjust pH value by addition solid base or aqueous slkali in first extract, be preferably added to solid base；More
Preferably, one or more in sodium hydroxide and potassium hydroxide of solid base；
I., in step (2), before extraction, the step that the first extract having adjusted pH value is stood cooling is also included；Preferably, stand cold
But time is 5 minutes；
J. in step (2), described aliphatic ether is polarity aliphatic ether, and the most lower boiling polarity aliphatic ether, more preferably boiling point are
40-70 DEG C, further preferred boiling point is 50-60 DEG C；Preferably, described aliphatic ether one in ether and t-butyl methyl ether
Or multiple, more preferably t-butyl methyl ether；
K., in step (2), the consumption of described aliphatic ether is 5-40mL/ (g sample), preferably 10-30mL/ (g sample), more preferably
For 20mL/ (g sample)；
L. in step (2), extraction time is 5-20 minute, preferably 10 minutes；
M., in step (1), described aromatic amine is selected from o-aminoazotoluene, 4-aminobphenyl, 2-amino-4-Methylnitrobenzene, connection
The chloro-o-toluidine of aniline, parachloroanilinum, 4-, 2-methoxyl group-5-monomethylaniline., 2-how amine, 4,4'-diamino-diphenyl first
Alkane, 2,4 di amino toluene, 3,3'-dichloro-benzidine, 3,3'-dimethoxy benzidine, 3,3'-methyl-4,4'-diaminourea two
Phenylmethane, 4,4'-methylene-two-(2-chloroaniline), 4,4'-diaminodiphenyl ether, ortho-aminotoluene, 4-aminoazabenzol, 2-ammonia
One or more in base methyl phenyl ethers anisole, 2,4-dimethylaniline and 2,6-dimethylaniline.
4. the method detecting aromatic amine, obtains extraction including according to the extracting method according to any one of claims 1 to 3
Liquid and/or the step of extracting solution；Also include measuring extract and/or the step of extracting solution with liquid chromatography tandem mass spectrometry.
Detection method the most according to claim 4, wherein, described in be determined as detection by quantitative, preferably inner mark method ration inspection
Survey；It is highly preferred that internal standard substance is d7-1-amino naphthalenes.
6. during according to the detection method described in claim 4 or 5, wherein, the operating condition of liquid chromatograph includes following a to d
Any one or multinomial:
A. chromatographic column is Féraud door Agilent ZORBAX SB-C3 liquid-phase chromatographic column；Preferably, the specification of chromatographic column is 150mm
× 2.1mm i.d., 5 μm particle diameters；
B. the temperature of chromatographic column is 25-50 DEG C, preferably 30-50 DEG C, more preferably 40 DEG C；
C. sample size is 1-10 μ L, preferably 2-8 μ L, more preferably 3 μ L；
D. flowing is made up of mobile phase A and Mobile phase B, and mobile phase A is methanol, and Mobile phase B is that 0.1% (V/V) acetic acid is water-soluble
Liquid；Preferably, the elution program of flowing phase is as shown in the table,
7. according to the detection method described in claim 4 or 5, wherein, mass spectrographic operating condition or parameter include following 1) to 66)
In any one or multinomial:
1) ion source is electron spray ionisation source；
2) scan mode is cation scanning；
3) detection mode is multiple-reaction monitoring；
4) electron spray voltage is 4000-7000V, preferably 5000-6000V, more preferably 5500V；
5) ion source temperature is 500-750 DEG C, preferably 550-700 DEG C, more preferably 650 DEG C；
6) auxiliary gas Gas1 and/or Gas2 pressure be 40-70psi, preferably 50-60psi, more preferably 50psi or
60psi；
7) quota ion of o-aminoazotoluene is to for 226.1/91.1；
8) the qualitative ion pair of o-aminoazotoluene is 226.1/121.1；
9) impact energy of o-aminoazotoluene is 20V；
10) quota ion of 4-aminobphenyl is to for 170.1/153.2；
11) the qualitative ion pair of 4-aminobphenyl is 170.1/152.1；
12) impact energy of 4-aminobphenyl is 20V；
13) quota ion of 2-amino-4-Methylnitrobenzene is to for 153.1/107.1；
14) the qualitative ion pair of 2-amino-4-Methylnitrobenzene is 153.1/89.9；
15) impact energy of 2-amino-4-Methylnitrobenzene is 25V；
16) quota ion of benzidine is to for 184.1/156；
17) the qualitative ion pair of benzidine is 184.1/166；
18) impact energy of benzidine is 40V；
19) quota ion of parachloroanilinum is to for 128/93.1；
20) the qualitative ion pair of parachloroanilinum is 128/111.2；
21) impact energy of parachloroanilinum is 20V；
22) quota ion of the chloro-o-toluidine of 4-is to for 142/107.2；
23) the qualitative ion pair of the chloro-o-toluidine of 4-is 142/125.2；
24) impact energy of the chloro-o-toluidine of 4-is 23V；
25) quota ion of 2-methoxyl group-5-monomethylaniline. is to for 138.1/123.2；
26) the qualitative ion pair of 2-methoxyl group-5-monomethylaniline. is 138.1/105.2；
27) impact energy of 2-methoxyl group-5-monomethylaniline. is 20V；
28) quota ion of 2-how amine is to for 144.1/127.1；
29) the qualitative ion pair of 2-how amine is 144.1/77.2；
30) impact energy of 2-how amine is 25V；
31) quota ion of 4,4 '-diaminodiphenyl-methane is to for 199.1/106.2；
32) the qualitative ion pair of 4,4 '-diaminodiphenyl-methane is 199.1/77.2；
33) impact energy of 4,4 '-diaminodiphenyl-methane is 30V；
34) quota ion of 2,4 di amino toluene is to for 123.1/108；
35) the qualitative ion pair of 2,4 di amino toluene is 123.1/106.1；
36) impact energy of 2,4 di amino toluene is 23V；
37) quota ion of 3,3 '-dichloro-benzidine is to for 253.1/217.1；
38) the qualitative ion pair of 3,3 '-dichloro-benzidine is 253.1/182.1；
39) impact energy of 3,3 '-dichloro-benzidine is 30V；
40) quota ion of 3,3 '-dimethoxy benzidine is to for 245.2/230.2；
41) the qualitative ion pair of 3,3 '-dimethoxy benzidine is 245.2/213.2；
42) impact energy of 3,3 '-dimethoxy benzidine is 25V；
43) 3,3 '-methyl-4,4 ' quota ion of-MDA is to for 227.2/120.2；
44) 3,3 '-methyl-4,4 ' the qualitative ion pair of-MDA is 227.2/178.2；
45) 3,3 '-methyl-4,4 ' impact energy of-MDA is 25V；
46) quota ion of 4,4 '-methylene-two-(2-chloroaniline) is to for 267.2/231.2；
47) the qualitative ion pair of 4,4 '-methylene-two-(2-chloroaniline) is 267.2/140.2；
48) impact energy of 4,4 '-methylene-two-(2-chloroaniline) is 30V；
49) quota ion of 4,4 '-diaminodiphenyl ether is to for 201.1/108.3；
50) the qualitative ion pair of 4,4 '-diaminodiphenyl ether is 201.1/184；
51) impact energy of 4,4 '-diaminodiphenyl ether is 23V；
52) quota ion of ortho-aminotoluene is to for 108.1/91.4；
53) the qualitative ion pair of ortho-aminotoluene is 108.1/93.2；
54) impact energy of ortho-aminotoluene is 23V；
55) quota ion of 4-aminoazabenzol is to for 198.2/77.2；
56) the qualitative ion pair of 4-aminoazabenzol is 198.2/51.2；
57) impact energy of 4-aminoazabenzol is 23V；
58) quota ion of 2-aminoanisole is to for 124.4/109.2；
59) the qualitative ion pair of 2-aminoanisole is 124.1/92.3；
60) impact energy of 2-aminoanisole is 23V；
61) quota ion of 2,4-dimethylaniline is to for 122.1/107.2；
62) the qualitative ion pair of 2,4-dimethylaniline is 122.1/105.2；
63) impact energy of 2,4-dimethylaniline is 23V；
64) quota ion of 2,6-dimethylaniline is to for 122.1/105.3；
65) the qualitative ion pair of 2,6-dimethylaniline is 122.1/107.2；
66) impact energy of 2,6-dimethylaniline is 23V.
8. a test kit, comprises,
I. aqueous hydrochloric acid solution；
II. sodium hydrate solid and/or sodium hydrate aqueous solution；With
III. ether and/or t-butyl methyl ether；
Preferably, described test kit also comprises acetic acid and methanol；It is highly preferred that the purity of described acetic acid is 99%-100% (W/
W), more preferably 99.5% (W/W)；
Preferably, described test kit also comprises liquid-phase chromatographic column；It is highly preferred that described liquid-phase chromatographic column is Féraud door Agilent
ZORBAX SB-C3 liquid-phase chromatographic column；
Preferably, described test kit also comprises 0.1% (V/V) acetic acid aqueous solution；
Preferably, the concentration of described aqueous hydrochloric acid solution is 1-10% (W/W), more preferably 5% (W/W).
9. test kit described in claim 8 is extracting and/or is detecting the purposes in the aromatic amine in sample；Described sample is Nicotiana tabacum L.
And/or tobacco product.
Purposes the most according to claim 9, wherein, described aromatic amine selected from o-aminoazotoluene, 4-aminobphenyl,
2-amino-4-Methylnitrobenzene, benzidine, parachloroanilinum, the chloro-o-toluidine of 4-, 2-methoxyl group-5-monomethylaniline., 2-how amine,
4,4'-diaminodiphenyl-methane, 2,4 di amino toluene, 3,3'-dichloro-benzidine, 3,3'-dimethoxy benzidine, 3,
3'-methyl-4,4'-MDA, 4,4'-methylene-two-(2-chloroaniline), 4,4'-diaminodiphenyl ether, adjacent first
One or more in aniline, 4-aminoazabenzol, 2-aminoanisole, 2,4-dimethylaniline and 2,6-dimethylaniline.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109580808A (en) * | 2018-11-27 | 2019-04-05 | 上海烟草集团有限责任公司 | A kind of method that QuEChERS-LC-MS/MS measures 10 kinds of aromatic amines in cigarette smoke simultaneously |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102608232A (en) * | 2012-03-17 | 2012-07-25 | 中国烟草总公司郑州烟草研究院 | Method for detecting 10 types of aromatic amines compounds in cigarette mainstream smoke by liquid chromatography-tandem mass spectrometry |
| CN102608233A (en) * | 2012-03-17 | 2012-07-25 | 中国烟草总公司郑州烟草研究院 | Method for detecting four main types of aromatic amines in cigarette filters by liquid chromatography-tandem mass spectrometry |
| CN103760288A (en) * | 2014-01-28 | 2014-04-30 | 国家烟草质量监督检验中心 | Test method of banned azo-dye in cigarette paper |
| CN105181876A (en) * | 2015-10-21 | 2015-12-23 | 国家烟草质量监督检验中心 | Method of measuring residual amount of 4-aminoazobenzene in paper for cigarettes |
| CN105548430A (en) * | 2015-12-10 | 2016-05-04 | 苏州国环环境检测有限公司 | Method for detecting aniline in soil |
-
2016
- 2016-08-04 CN CN201610629196.XA patent/CN106323687A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102608232A (en) * | 2012-03-17 | 2012-07-25 | 中国烟草总公司郑州烟草研究院 | Method for detecting 10 types of aromatic amines compounds in cigarette mainstream smoke by liquid chromatography-tandem mass spectrometry |
| CN102608233A (en) * | 2012-03-17 | 2012-07-25 | 中国烟草总公司郑州烟草研究院 | Method for detecting four main types of aromatic amines in cigarette filters by liquid chromatography-tandem mass spectrometry |
| CN103760288A (en) * | 2014-01-28 | 2014-04-30 | 国家烟草质量监督检验中心 | Test method of banned azo-dye in cigarette paper |
| CN105181876A (en) * | 2015-10-21 | 2015-12-23 | 国家烟草质量监督检验中心 | Method of measuring residual amount of 4-aminoazobenzene in paper for cigarettes |
| CN105548430A (en) * | 2015-12-10 | 2016-05-04 | 苏州国环环境检测有限公司 | Method for detecting aniline in soil |
Non-Patent Citations (1)
| Title |
|---|
| 张廷贵 等: "液相色谱串联质谱法测定烟用纸张中的芳香胺", 《中国造纸》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109580808A (en) * | 2018-11-27 | 2019-04-05 | 上海烟草集团有限责任公司 | A kind of method that QuEChERS-LC-MS/MS measures 10 kinds of aromatic amines in cigarette smoke simultaneously |
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