CN106018635B - The method and detection method of pre-treatment are carried out to tobacco or tobacco product - Google Patents
The method and detection method of pre-treatment are carried out to tobacco or tobacco product Download PDFInfo
- Publication number
- CN106018635B CN106018635B CN201610658005.2A CN201610658005A CN106018635B CN 106018635 B CN106018635 B CN 106018635B CN 201610658005 A CN201610658005 A CN 201610658005A CN 106018635 B CN106018635 B CN 106018635B
- Authority
- CN
- China
- Prior art keywords
- detection method
- dinitrophenylhydrazone
- tobacco
- solution
- tobacco product
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/067—Preparation by reaction, e.g. derivatising the sample
Abstract
The invention belongs to test and analyze field, the method for being related to a kind of pair of tobacco or tobacco product progress pre-treatment includes the following steps, (1) extracts tobacco sample or tobacco product sample with acetonitrile, obtains the first extract of carbonyl containing compound；(2) 2,4-dinitrophenylhydrazine and/or 2,4-dinitrophenylhydrazine solution is added into first extract and strong acid solution performs the derivatization, the extracting solution I of isolated carbonyl containing compound derivatization product.The invention further relates to method, kit and the purposes of carbonyls in detection tobacco or tobacco product.The present invention confirms for the first time contains carbonyls in tobacco and tobacco product, and the method for the present invention accurate quantitative analysis goes out carbonyl compound content in tobacco or tobacco product, and detection limit is low, high sensitivity, reproducible.
Description
Technical field
The invention belongs to test and analyze field, and in particular to the method for a kind of pair of tobacco or tobacco product progress pre-treatment,
The method for further relating to carbonyls in detection tobacco or tobacco product.
Background technique
Carbonyls is the important harmful components of one kind in the flue gas that drawing tobacco product generates, and is put into 44 kinds of flue gas
" the Huffman list " of harmful components.This kind of compound includes formaldehyde, acetaldehyde and methacrylaldehyde etc., and it is second that wherein content is maximum
Aldehyde.Low-Molecular-Weight Carbonyl Compounds have stronger ciliary toxicity, and strongest toxicity is low point of methacrylaldehyde, formaldehyde and acetaldehyde etc.
Son amount aldehyde compound, toxicity are gradually decreased as molecular weight increases.Carbonyls in flue gas mostlys come from cigarette
The pyrolytic of phenolic substances in straw-made articles, and the phenolic substances in tobacco product is formed by non enzymatic browning reacton
's.
Currently, the detection method of carbonyls includes: to trap main flume by glass fiber filter in main flume
Smoke Particulate carries out quantitative analysis with HPLC- UV detection device after extraction.Wherein, it extracts and to use
Solvent is usually the mixture of organic solvent and water.Moreover, it has been investigated that, the organic solvent ratio in solvent is excessively high, can lead
Causing the accuracy in detection of a part of carbonyls reduces, or even has some carbonyls that can not be detected.
So far, researcher not yet has found to contain carbonyls in tobacco or tobacco product, also have no to its into
The detection and analysis of row carbonyls.
Summary of the invention
The present inventor is through lot of experiments, it was confirmed that contains carbonyls in tobacco and/or tobacco product.The present invention
The method that people has also obtained a kind of pair of tobacco or tobacco product carries out pre-treatment, this method can be by the carbonyl in tobacco or tobacco product
Based compound extracts and is transformed into derivatization product.On this basis, the present inventor be also obtained a kind of detection tobacco or
The method of carbonyls in tobacco product, by detection carbonyls derivatization product come in tobacco or tobacco product
Carbonyls carries out quantitative detection.The accuracy of this method is high, and high sensitivity, detection limit is low, and repeatability is good.
The method that first aspect present invention is related to a kind of pair of tobacco or tobacco product carries out pre-treatment, includes the following steps:
(1) tobacco sample or tobacco product sample are extracted with acetonitrile, obtains the first extract of carbonyl containing compound；
(2) be added into first extract 2,4 dinitrophenyl hydrazine and/or 2,4 dinitrophenyl hydrazine solution and strong acid solution into
Row derivatization, the extracting solution I of isolated carbonyl containing compound derivatization product.
Further include following steps in one embodiment of first aspect present invention:
(3) weak base or weak caustic solution are added into extracting solution I, mixing obtains extracting solution II.
In one embodiment, the weak base is selected from one of pyridine and quinoline or a variety of, preferably pyridine.
In one embodiment, one in the acetonitrile solution of acetonitrile solution and quinoline of the weak caustic solution selected from pyridine
Kind is a variety of, preferably the acetonitrile solution of pyridine.
In one embodiment, the additive amount of the acetonitrile solution (in terms of pyridine) of pyridine or pyridine is 300-700 μ L/
(mL first extract), preferably 400-600 μ L/ (mL first extract), more preferably 500 μ L/ (mL first extract).
In one embodiment of first aspect present invention, including any one of the following A into O or multinomial:
A. the tobacco product is selected from one of flammable suction tobacco product and non-combustible suction tobacco product or a variety of；It is excellent
Selection of land, the tobacco product are flammable suction tobacco product, more preferably cigarette；
B. the carbonyls is in formaldehyde, acetaldehyde, acetone, propionic aldehyde, methacrylaldehyde, butyraldehyde, 2- butanone and crotonaldehyde
It is one or more；
C. in step (1), the solid-liquid ratio of the extraction is 1:(10-50) (g/mL), preferably 1:(10-30) (g/mL),
More preferably 1:20 (g/mL)；
D. in step (1), the extraction carries out under oscillating condition；
E. in step (1), extraction time be 10-60 minutes, preferably 20-50 minutes, more preferably 20 minutes, 30 minutes
Or 50 minutes；
F. in step (1), extraction temperature is room temperature, preferably 5 DEG C -40 DEG C, more preferably 10 DEG C -35 DEG C, further excellent
It is selected as 10 DEG C, 25 DEG C or 30 DEG C；
G. in step (2), 2,4-dinitrophenylhydrazine solution (in terms of 2,4-dinitrophenylhydrazine) or 2,4-dinitrophenylhydrazine
Additive amount be 0.2-5mg/ (mL first extract), preferably 1-3mg/ (mL first extract), more preferably 2mg/ (mL first extract)；
H. in step (2), the dosage of strong acid solution is 300-700 μ L/ (mL first extract), preferably 400-600 μ L/ (mL
First extract), more preferably 500 μ L/ (mL first extract)；
I. in step (2), 2,4-dinitrophenylhydrazine solution is the acetonitrile solution of 2,4-dinitrophenylhydrazine；Preferably, 2,4-
The concentration of 2,4-dinitrophenylhydrazine is 1-40mg/mL, more preferably 5-20mg/mL in the acetonitrile solution of dinitrophenylhydrazine, into one
Step is preferably 10mg/mL；
J. in step (2), strong acid solution is the acetonitrile solution of strong acid；Preferably, in the acetonitrile solution of strong acid strong acid it is dense
Degree is 0.05%-2% (W/W), more preferably 0.1%-1% (W/W), further preferably 0.2% (W/W)；
K. in step (2), strong acid solution is selected from one of perchloric acid solution and hydrofluoric acid solution or a variety of；
L. in step (2), the time of derivatization is 20-60 minutes, preferably 30-50 minutes, more preferably 40 minutes；
M. in step (2), the temperature of derivatization is room temperature, preferably 10 DEG C -35 DEG C；
N. in step (2), carbonyls derivatization product is selected from formaldehyde -2,4- dinitrophenylhydrazone, acetaldehyde -2,4- dinitro
Base phenylhydrazone, acetone -2,4- dinitrophenylhydrazone, propionic aldehyde -2,4- dinitrophenylhydrazone, methacrylaldehyde -2,4- dinitrophenylhydrazone, butyraldehyde -2,
4- dinitrophenylhydrazone, 2- butanone-2, one of 4- dinitrophenylhydrazone and crotonaldehyde -2,4- dinitrophenylhydrazone or a variety of；
O. in step (1), before extraction, include the steps that carrying out tobacco sample or tobacco product sample broken.
The pre-treating method of the described in any item tobaccos of first aspect present invention or tobacco product is from tobacco or tobacco
The method of carbonyls is separated in product.
Second aspect of the present invention is related to a kind of method for detecting carbonyls in tobacco or tobacco product, including according to this
The step of described in any item pre-treating methods of invention first aspect obtain extracting solution I or extracting solution II；It further include with liquid phase color
The step of composing carbonyls derivatization product in tandem mass spectrometry measurement extracting solution I or extracting solution II.
It further include being incited somebody to action before liquid chromatography tandem mass spectrometry measurement in one embodiment of second aspect of the present invention
The step of extracting solution I or extracting solution II are filtered；Preferably, it is filtered using organic phase filter membrane；Preferably, organic phase is filtered
The aperture of film is 0.2-0.6 μm, more preferably 0.45 μm.
Described to be measured as quantitative detection in one embodiment of second aspect of the present invention, preferably inner mark method ration is examined
It surveys；It is highly preferred that internal standard compound is d3- 2,4 dinitrophenylhydrazone of formaldehyde.
In one embodiment of second aspect of the present invention, the operating condition of liquid chromatogram includes following a any into d
One or more:
A. chromatographic column is to wear peace Acclaim Explosive E2 liquid-phase chromatographic column；Preferably, the specification of chromatographic column is
250mm × 4.6mm, 5 μm,
B. the temperature of chromatographic column is 36 DEG C -50 DEG C, preferably 40 DEG C；
C. sample volume is 1-10 μ L, preferably 3-7 μ L, more preferably 5 μ L；
D. mobile phase is made of mobile phase A and Mobile phase B, and mobile phase A is acetonitrile, and Mobile phase B is water；
Preferably, the elution program of mobile phase are as follows: 0 minute, 60% (V/V) mobile phase A；26 minutes, 60% (V/V) flowing
Phase A；28 minutes, 70% (V/V) mobile phase A；43 minutes, 70% (V/V) mobile phase A；45 minutes, 60% (V/V) mobile phase A,
It remains to the 50th minute；Flow velocity is always 0.6mL/min.
In one embodiment of second aspect of the present invention, mass spectrographic operating condition or parameter include following 1) in 30)
Any one or multinomial:
1) ion source is electrospray ionisation source；
2) scanning mode is negative ion scan；
3) detection mode is multiple-reaction monitoring；
4) electron spray voltage is 3000-6000V, preferably 3500-5000V, more preferably 4500V；
5) ion source temperature is 400 DEG C -650 DEG C, preferably 450 DEG C -550 DEG C, more preferably 500 DEG C；
6) auxiliary gas Gas1 and/or Gas2 pressure be 40-70psi, preferably 50-60psi, more preferably 50psi or
60psi；
7) quota ion pair of formaldehyde -2,4- dinitrophenylhydrazone is 209.0/163.0；
8) qualitative ion pair of formaldehyde -2,4- dinitrophenylhydrazone is 209.0/151.0；
9) impact energy of formaldehyde -2,4- dinitrophenylhydrazone is -12V；
10) quota ion pair of acetaldehyde -2,4- dinitrophenylhydrazone is 223.0/163.0；
11) qualitative ion pair of acetaldehyde -2,4- dinitrophenylhydrazone is 223.0/181.0；
12) impact energy of acetaldehyde -2,4- dinitrophenylhydrazone is -16V；
13) quota ion pair of acetone -2,4- dinitrophenylhydrazone is 237.0/207.0；
14) qualitative ion pair of acetone -2,4- dinitrophenylhydrazone is 237.0/178.0；
15) impact energy of acetone -2,4- dinitrophenylhydrazone is -14V；
16) quota ion pair of propionic aldehyde -2,4- dinitrophenylhydrazone is 237.0/163.0；
17) qualitative ion pair of propionic aldehyde -2,4- dinitrophenylhydrazone is 237.0/152.0；
18) impact energy of propionic aldehyde -2,4- dinitrophenylhydrazone is -15V；
19) quota ion pair of methacrylaldehyde -2,4- dinitrophenylhydrazone is 235.0/158.0；
20) qualitative ion pair of methacrylaldehyde -2,4- dinitrophenylhydrazone is 235.0/163.0；
21) impact energy of methacrylaldehyde -2,4- dinitrophenylhydrazone is -16V；
22) quota ion pair of butyraldehyde -2,4- dinitrophenylhydrazone is 251.0/163.0；
23) qualitative ion pair of butyraldehyde -2,4- dinitrophenylhydrazone is 251.0/152.0；
24) impact energy of butyraldehyde -2,4- dinitrophenylhydrazone is -14V；
25) 2- butanone-2, the quota ion pair of 4- dinitrophenylhydrazone are 251.0/152.0；
26) 2- butanone-2, the qualitative ion pair of 4- dinitrophenylhydrazone are 251.0/163.0；
27) 2- butanone-2, the impact energy of 4- dinitrophenylhydrazone are -22V；
28) quota ion pair of crotonaldehyde -2,4- dinitrophenylhydrazone is 249.0/181.0；
29) qualitative ion pair of crotonaldehyde -2,4- dinitrophenylhydrazone is 249.0/172.0；
30) impact energy of crotonaldehyde -2,4- dinitrophenylhydrazone is -18V.
Third aspect present invention is related to a kind of kit, includes,
I. acetonitrile；
The acetonitrile solution of II.2,4- dinitrophenylhydrazine and/or 2,4 dinitrophenyl hydrazine；With
The acetonitrile solution of III, perchloric acid.
In one embodiment of third aspect present invention, the kit also includes that the acetonitrile of pyridine and/or pyridine is molten
Liquid.
In one embodiment of third aspect present invention, the kit also includes organic phase filter membrane and d3Formaldehyde -2,
4 dinitrophenylhydrazones.
In one embodiment of third aspect present invention, 2,4- dinitrobenzene in the acetonitrile solution of 2,4-dinitrophenylhydrazine
The concentration of hydrazine is 1-40mg/mL, preferably 5-20mg/mL, more preferably 10mg/mL.
In one embodiment of third aspect present invention, the concentration of perchloric acid is in the acetonitrile solution of perchloric acid
0.05%-2% (W/W), preferably 0.1%-1% (W/W), more preferably 0.2% (W/W).
Fourth aspect present invention is related to any kit of third aspect present invention at tobacco or the preceding place of tobacco product
Reason or the purposes in the carbonyls in detection tobacco or tobacco product；Preferably, the tobacco product is selected from flammable
One of suction tobacco product and non-combustible suction tobacco product are a variety of, more preferably flammable suction tobacco product, further
Preferably cigarette.
In one embodiment of fourth aspect present invention, the carbonyls be selected from formaldehyde, acetaldehyde, acetone, propionic aldehyde,
Any one or more in methacrylaldehyde, butyraldehyde, 2- butanone and crotonaldehyde.
In the present invention,
Unless otherwise instructed, " extraction " refers to using solvent appropriate and method, by soluble effective component from raw material
The process of leaching.
Unless otherwise instructed, " tobacco " refers to Solanaceae, Nicotiana (Nicotiana L.), annual or perennial herb,
Have a liking for class crop.This category is wild species mostly there are about more than 60 kinds.Main cultispecies have safflower tobacco and makhorka.The two
South America is originated in, is all spontaneous amphidiploid.Safflower tobacco is also known as Nicotiana tabacum, is worldwide commodity production cigarette
Kind.Multiple types are formed because of modulator approach and provenance, area, cultivation step difference again: flue-cured tobacco, burley tobaccos, Maryland, snow
Eggplant cigarette, fumigation, Turkish tobaccos, Dark sun-cured, Sun cured tobacco etc..There are many cultivars in each type again.Makhorka is with the former Soviet Union
With India cultivate it is more, there is a small amount of cultivation on the ground such as Xinjiang, China, Gansu.Henbane (N.alata Link and in this category
Otta) and powder blue smoke careless (N.glauca Graham) plantation is for ornamental.
Unless otherwise instructed, " tobacco product " refer to it is all or part of by tobacco leaf be raw material production, for aspirating, inhaling
It suckes, chew or the product of snuffing.The tobacco product includes but is not limited to cigarette and chewing tobacco.
Unless otherwise instructed, " flammable suction tobacco product " refers to that smog is lighted and sucked to needs, and smog can be directly sucked in,
Or the filtering through filter tip or water, the most commonly traditional cigarette of world-wide prevalence.
Unless otherwise instructed, " non-combustible suction tobacco product ", which refers to, does not need to burn, and reduces the tar etc. that burning generates
The needs that harmful components do not generate second-hand flue gas, and adapt to a certain extent and meet consumer to tobacco product, it is main to wrap
It includes smoke-free tobacco product, heat do not burn cigarette and electronic cigarette.The preparation process and combustion absorption type smoke of non-combustible suction tobacco product
Straw-made articles has marked difference.
Unless otherwise instructed, " carbonyls " refers to that the compound in molecule containing carbonyl is referred to as carbonyls.
Two representative class carbonyls are 1. aldehyde and ketone, 2. carboxylic acid and its derivative.
Unless otherwise instructed, " strong acid " refers to the acids that almost can all ionize in aqueous solution, has strong acidity anti-
It answers, such as hydrochloric acid HCl, sulfuric acid H2SO4, nitric acid HNO3, perchloric acid HCl4Deng.
Unless otherwise instructed, " weak base " refer in aqueous solution can only fraction ionization bases, have faintly alkaline reaction.
For example, ammonium hydroxide NH4OH, zinc hydroxide Zn (OH)2, aluminium hydroxide Al (OH)3。
Unless otherwise instructed, " internal standard method " refers to a kind of method that standard curve is drawn in instrument analysis.Its principle is: will
A certain amount of internal standard substance is added in the standard solution of various concentration level, and the signal for then finding out ingredient and internal standard compound to be measured is strong
The ratio between degree, as the longitudinal axis；The amount of ingredient to be measured or the ratio of ingredient to be measured and internal standard object amount are found out again, as horizontal axis, are drawn and are closed
It is curve.Under normal circumstances, the physics of internal standard substance used, chemical property are similar to ingredient to be measured, and can be with ingredient to be measured point
From.Internal standard method can eliminate measuring instrument, the variation of measuring condition, the influence of sample volume variation etc., so that it is accurate to improve analysis
Degree, is widely used in chromatography and spectrum analysis.
It is that the present invention obtains the utility model has the advantages that
1, present invention firstly discovers that containing carbonyls in tobacco, meanwhile, and find to contain in tobacco product for the first time
Carbonyls.
2, the carbonyls in tobacco or tobacco product can be extracted and be derived by pre-treating method of the invention
Change.
3, detection method of the invention, energy accurate quantitative analysis go out the carbonyls in tobacco or tobacco product, and detection limit is low,
High sensitivity, repeatability are good.
4, in detection method, use pure acetonitrile for extraction solvent, measurable carbonyl compound species are more, quasi-
Exactness is higher, and detection limit is lower, and sensitivity is higher.
5, in detection method, liquid chromatogram uses gradient elution, and the chromatographic peak of each carbonyls can be made to separate
Du Genggao.
Detailed description of the invention
In order to make the content of the present invention more clearly understood, it below according to specific embodiments of the present invention and combines
Attached drawing, the present invention is described in further detail, wherein
Fig. 1 is the flow chart that the present invention extracts carbonyls in tobacco or tobacco product；
Fig. 2 is the reaction equation of carbonyls of the present invention and 2,4 dinitrophenyl hydrazine derivative reaction；
Fig. 3 is the chromatogram of S3 grade standard working solution in the embodiment of the present invention 1；
Fig. 4 is the chromatogram of sample solution in the embodiment of the present invention 1；
Fig. 5 is the chromatogram of sample solution in comparative example 2 of the present invention.
Specific embodiment
Embodiment 1
1, material and reagent
The standard items (buying from lark prestige Science and Technology Ltd.) of (1) 8 kind of carbonyls -2,4- dinitrophenylhydrazone: first
Aldehyde -2,4- dinitrophenylhydrazone, acetaldehyde -2,4- dinitrophenylhydrazone, propionic aldehyde -2,4- dinitrophenylhydrazone, acetone -2,4- dinitrobenzene
Hydrazone, methacrylaldehyde -2,4- dinitrophenylhydrazone, butyraldehyde -2,4- dinitrophenylhydrazone, 2- butanone-2,4- dinitrophenylhydrazone and crotonaldehyde -2,
4- dinitrophenylhydrazone.
(2) internal standard compound d3- formaldehyde -2,4- dinitrophenylhydrazone is bought from lark prestige Science and Technology Ltd..
(3) internal standard stock solution: it is 50ng/mL's that internal standard compound d3- formaldehyde -2,4- dinitrophenylhydrazone, which is configured to concentration with acetonitrile,
Internal standard stock solution.
(4) standard working solution: weighing 8 kinds of carbonyls -2,4- dinitrophenylhydrazone standard items and internal standard compound, and second is added
Nitrile dissolution, is configured to the 5 grade standard working solutions with concentration gradient.Each carbonyls -2,4- in 5 grade standard working solutions
The concentration of dinitrophenylhydrazone is as shown in table 1, and internal standard compound concentration is 50ng/mL.
The concentration (ng/mL) of each carbonyls -2,4- dinitrophenylhydrazone in 15 grade standard working solution of table
| Serial number | Substance | S1 | S2 | S3 | S4 | S5 |
| 1 | Formaldehyde -2,4- dinitrophenylhydrazone | 10.01 | 30.03 | 50.05 | 100.10 | 300.30 |
| 2 | Acetaldehyde -2,4- dinitrophenylhydrazone | 7.43 | 22.30 | 37.16 | 74.33 | 222.98 |
| 3 | Acetone -2,4- dinitrophenylhydrazone | 10.48 | 31.44 | 52.40 | 104.80 | 314.41 |
| 4 | Propionic aldehyde -2,4- dinitrophenylhydrazone | 9.80 | 29.40 | 49.00 | 97.99 | 293.97 |
| 5 | Methacrylaldehyde -2,4- dinitrophenylhydrazone | 4.86 | 14.59 | 24.32 | 48.63 | 145.90 |
| 6 | Butyraldehyde -2,4- dinitrophenylhydrazone | 9.50 | 28.50 | 47.50 | 94.99 | 284.97 |
| 7 | 2- butanone-2,4- dinitrophenylhydrazone | 8.42 | 25.26 | 42.11 | 84.21 | 252.63 |
| 8 | Crotonaldehyde -2,4- dinitrophenylhydrazone | 9.46 | 28.39 | 47.32 | 94.64 | 283.93 |
In terms of carbonyls, the material concentration in 5 grade standard working solutions is as shown in table 2.Internal standard compound concentration is still
50ng/mL.It, can appropriate extension standards working solution coverage area if sample concentration exceeds standard working solution coverage area.
Material concentration (ng/mL) in 2 standard working solution of table in terms of carbonyls
| Serial number | Substance | S1 | S2 | S3 | S4 | S5 |
| 1 | Formaldehyde | 1.43 | 4.29 | 7.15 | 14.30 | 42.90 |
| 2 | Acetaldehyde | 1.46 | 4.38 | 7.30 | 14.60 | 43.80 |
| 3 | Acetone | 2.55 | 7.66 | 12.77 | 25.54 | 76.62 |
| 4 | Propionic aldehyde | 2.39 | 7.16 | 11.94 | 23.88 | 71.64 |
| 5 | Methacrylaldehyde | 1.15 | 3.46 | 5.77 | 11.54 | 34.62 |
| 6 | Butyraldehyde | 2.71 | 8.14 | 13.57 | 27.14 | 81.42 |
| 7 | 2- butanone | 2.41 | 7.22 | 12.03 | 24.06 | 72.18 |
| 8 | Crotonaldehyde | 2.65 | 7.95 | 13.25 | 26.50 | 79.50 |
2, it extracts
The carbonyls in tobacco is extracted according to the process of Fig. 1.
Tobacco leaf 1 (Yunnan tobacco) is milled to offal, 1g offal sample is accurately weighed, is placed in 50mL centrifuge tube, accurately
The oscillation extraction of 20mL acetonitrile is added, extraction temperature is 25 DEG C, and extraction time is 30 minutes；Take extraction after first extract 1mL in
In 10mL volumetric flask, the acetonitrile solution and 500 μ L concentration that the 2,4-dinitrophenylhydrazine of 200 μ L10mg/mL is added are 0.2% (W/
W the acetonitrile solution of perchloric acid) mixes, is placed at room temperature for 40 minutes and performs the derivatization reaction (reaction equation is as shown in Figure 2).
Later, 500 μ L pyridines and 20 μ L internal standard stock solutions are added, with acetonitrile constant volume to 10mL, crosses 0.45 μm of organic phase filter membrane, obtains sample
Product solution.
3, it detects
With high performance liquid chromatography tandem mass spectrum instrument (ABSCIEX company Qtrap 5500) respectively to 5 grade standard working solutions
It is tested and analyzed with sample solution.The chromatogram of S3 grade standard working solution is as shown in Figure 3.The chromatogram of sample solution is as schemed
Shown in 4.
Operation condition of chromatogram: chromatographic column, which uses, wears peace Acclaim Explosive E2 liquid-phase chromatographic column, specification 250mm
× 4.6mm, 5 μm,Chromatogram column temperature is 40 DEG C；Sample volume is 5 μ L；Mobile phase: mobile phase A is acetonitrile, Mobile phase B
For water；The gradient elution program of mobile phase: 0 minute, 60% (V/V) mobile phase A；26 minutes, 60% (V/V) mobile phase A；28 points
Clock, 70% (V/V) mobile phase A；43 minutes, 70% (V/V) mobile phase A；45 minutes, 60% (V/V) mobile phase A；Remain to
50 minutes；Flow velocity is always 0.6mL/min.
Mass spectrum operation condition: ion source: electrospray ionisation source (ESI)；Scanning mode: anion scanning；Detection mode: more
Reaction monitoring (MRM)；Electron spray voltage: 4500V；Ion source temperature: 500 DEG C；Assist gas Gas1 pressure: 60psi；Assist gas
Gas2 pressure: 50psi.
Quota ion pair, qualitative ion pair and the collision energy (CE) of each carbonyls -2,4- dinitrophenylhydrazone are shown in Table
3。
3 carbonyls -2,4- dinitrophenylhydrazone mass spectrometry parameters of table
4, it calculates
(1) according to the testing result of 5 grade standard working solutions in above 3., with carbonyls -2,4- dinitrophenylhydrazone
Linear regression is carried out to the concentration ratio of carbonyls -2,4- dinitrophenylhydrazone and internal standard compound with the peak area ratio of internal standard compound, is obtained
To calibration curve equation, it is shown in Table 4.Wherein, the concentration of carbonyls -2,4- dinitrophenylhydrazone is with the carbonyls in table 2
Densimeter.
In calibration curve equation, abscissa indicates that carbonyls -2,4- dinitrophenylhydrazone concentration is (dense with carbonyls
Degree meter) and internal standard compound concentration proportion, ordinate expression carbonyls -2,4- dinitrophenylhydrazone peak area and internal standard compound peak area
Ratio.Taking minimum concentration standard working solution, 10 parallel determinations calculate standard deviation, and 3 times of standard deviations are detection limit, and 10
Times standard deviation is quantitative limit, is listed in table 4.
4 calibration curve equation of table, detection limit and quantitative limit
| Object | Equation of linear regression | r | Detection limit (μ g/g) | Quantitative limit (μ g/g) |
| Formaldehyde | Y=0.16x+0.012 | 0.9994 | 0.14 | 0.5 |
| Acetaldehyde | Y=0.18x-0.039 | 0.9998 | 0.14 | 0.5 |
| Acetone | Y=0.23x-0.042 | 0.9995 | 0.26 | 0.9 |
| Propionic aldehyde | Y=0.27x+0.033 | 0.9994 | 0.30 | 1.0 |
| Methacrylaldehyde | Y=0.25x-0.07 | 0.9997 | 0.15 | 0.5 |
| Butyraldehyde | Y=0.29x-0.016 | 0.9996 | 0.30 | 1.0 |
| 2- butanone | Y=0.19x-0.026 | 0.9998 | 0.25 | 0.9 |
| Crotonaldehyde | Y=0.24x-0.061 | 0.9997 | 0.26 | 0.9 |
(2) according to the peak area testing result of carbonyls -2,4- dinitrophenylhydrazone in sample solution and internal standard compound, knot
The calibration curve equation for closing table 4, is calculated the concentration of carbonyls in sample solution, tobacco leaf is calculated further according to following formula
The content of middle carbonyls, the results are shown in Table 5.
Wherein,
Carbonyl compound content in y-tobacco leaf, μ g/g；
Carbonyl compound concentration in c-sample solution, μ g/mL；
V-sample solution volume, mL；
M-tobacco leaf weight, g.
Embodiment 2
Referring to the method for embodiment 1, detect that tobacco leaf 2, tobacco leaf 3, tobacco leaf 4, each carbonyls contains in tobacco leaf 5 respectively
Amount, the results are shown in Table 5.
The content (μ g/g) of carbonyls in the different tobacco leaves of table 5
| Formaldehyde | Acetaldehyde | Acetone | Propionic aldehyde | Methacrylaldehyde | Butyraldehyde | 2- butanone | Crotonaldehyde | |
| Tobacco leaf 1 | 2.33 | 1.46 | 2.26 | 1.03 | LOQ | LOQ | LOQ | LOQ |
| Tobacco leaf 2 | 2.46 | 1.72 | 1.93 | LOQ | LOQ | LOQ | LOQ | LOQ |
| Tobacco leaf 3 | 2.98 | 2.06 | 2.85 | 1.24 | LOQ | LOQ | LOQ | LOQ |
| Tobacco leaf 4 | 3.04 | 2.13 | 2.97 | LOQ | LOQ | LOQ | LOQ | LOQ |
| Tobacco leaf 5 | 1.96 | 1.43 | 2.31 | LOQ | LOQ | LOQ | LOQ | LOQ |
Note: LOQ expression is not detected.
As shown in Table 5, the method for the present invention is lower to the detection limit of carbonyls, and sensitivity is higher.
Embodiment 3
On that basis of example 1, by 8 kinds of carbonyls respectively with high, medium and low three horizontal mark-ons, each mark-on sample
Product parallel determination is averaged three times, is measured the rate of recovery and repeatability (RSD), be the results are shown in Table 6.
The rate of recovery and repeatability of 6 method of table
As shown in Table 6, for the method for the present invention to the recovery of standard addition of 8 kinds of carbonyls all 92% or more, detection is accurate
Degree is high, and repeatability is good.
Comparative example 1
Pure acetonitrile is replaced to extract tobacco leaf 1 by the mixed solvent of 1:1 and 2:1 with the volume ratio of acetonitrile and water respectively,
Remaining operation is carried out referring to embodiment 1.
The content for determining each carbonyls in tobacco leaf 1 is as shown in table 7.
Table 7
Note: LOQ expression is not detected.
By the testing result comparison of tobacco leaf 1 in table 7 and table 5 it is found that compared with being extracted with the mixed solvent of acetonitrile and water, this
The accuracy that inventive method detects when being extracted with pure acetonitrile is higher, and measurable carbonyl compound species are more, and detection limit is lower,
Sensitivity is higher.
Comparative example 2
Isocratic elution is carried out as mobile phase using 60% (V/V) acetonitrile+40% (V/V) water, remaining operation is referring to implementation
Example 1 carries out, and the chromatogram for obtaining sample solution is as shown in Figure 5.
Comparison diagram 4-5 is it is found that compared with making mobile phase isocratic elution with 60% (V/V) acetonitrile+40% (V/V) water, this hair
The gradient elution that bright method uses can well separate the chromatographic peak of each carbonyls.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (64)
1. a kind of method of carbonyls in detection tobacco or tobacco product, including locate before being carried out to tobacco or tobacco product
The step of reason, extracting solution I of acquisition carbonyl containing compound derivatization product；It further include being mentioned with liquid chromatography tandem mass spectrometry measurement
The step of taking carbonyls derivatization product in liquid I；
Wherein, pre-treatment is carried out to tobacco or tobacco product by following step:
(1) tobacco sample or tobacco product sample are extracted with acetonitrile, obtains the first extract of carbonyl containing compound；
(2) 2,4 dinitrophenyl hydrazine and/or 2,4 dinitrophenyl hydrazine solution is added into first extract and strong acid solution spreads out
Biochemistry, the extracting solution I of isolated carbonyl containing compound derivatization product；
Also, the tobacco product be it is all or part of by tobacco leaf be raw material production, for aspirating, sucking, chew or snuffing
Product；The carbonyls in formaldehyde, acetaldehyde, acetone, propionic aldehyde, methacrylaldehyde, butyraldehyde, 2- butanone and crotonaldehyde one
Kind is a variety of.
2. a kind of method of carbonyls in detection tobacco or tobacco product, including locate before being carried out to tobacco or tobacco product
The step of reason, extracting solution II of acquisition carbonyl containing compound derivatization product；It further include being measured with liquid chromatography tandem mass spectrometry
In extracting solution II the step of carbonyls derivatization product；
Wherein, pre-treatment is carried out to tobacco or tobacco product by following step:
(1) tobacco sample or tobacco product sample are extracted with acetonitrile, obtains the first extract of carbonyl containing compound；
(2) 2,4 dinitrophenyl hydrazine and/or 2,4 dinitrophenyl hydrazine solution is added into first extract and strong acid solution spreads out
Biochemistry, the extracting solution I of isolated carbonyl containing compound derivatization product；
(3) weak base or weak caustic solution are added into extracting solution I, mixing obtains extracting solution II；
Also, the tobacco product be it is all or part of by tobacco leaf be raw material production, for aspirating, sucking, chew or snuffing
Product；The carbonyls in formaldehyde, acetaldehyde, acetone, propionic aldehyde, methacrylaldehyde, butyraldehyde, 2- butanone and crotonaldehyde one
Kind is a variety of.
3. detection method according to claim 2, wherein in step (3), the weak base in pyridine and quinoline one
Kind is a variety of.
4. detection method according to claim 2, wherein in step (3), the weak base is pyridine.
5. detection method according to claim 2, wherein in step (3), the acetonitrile that the weak caustic solution is selected from pyridine is molten
One of acetonitrile solution of liquid and quinoline is a variety of.
6. detection method according to claim 2, wherein in step (3), the weak caustic solution is that the acetonitrile of pyridine is molten
Liquid.
7. the detection method according to claim 4 or 6, wherein in step (3), be equivalent in every milliliter of first extract with pyrrole
The additive amount of the acetonitrile solution of the pyridine of pyridine meter is 300-700 μ L, or is equivalent to the additive amount of pyridine in every milliliter of first extract
For 300-700 μ L.
8. the detection method according to claim 4 or 6, wherein in step (3), be equivalent in every milliliter of first extract with pyrrole
The additive amount of the acetonitrile solution of the pyridine of pyridine meter is 400-600 μ L, or is equivalent to the additive amount of pyridine in every milliliter of first extract
For 400-600 μ L.
9. the detection method according to claim 4 or 6, wherein in step (3), be equivalent in every milliliter of first extract with pyrrole
The additive amount of the acetonitrile solution of the pyridine of pyridine meter is 500 μ L, or being equivalent to the additive amount of pyridine in every milliliter of first extract is 500
μL。
10. detection method according to claim 1 or 2, it is characterised in that following any one or multinomial of the A into N:
A. the tobacco product is selected from one of flammable suction tobacco product and non-combustible suction tobacco product or a variety of；
B. in step (1), the solid-liquid ratio of the extraction is 1:(10-50) (g/mL)；
C. in step (1), the extraction carries out under oscillating condition；
D. in step (1), extraction time is 10-60 minutes；
E. in step (1), extraction temperature is room temperature；
F. in step (2), the additive amount of the 2,4-dinitrophenylhydrazine solution in every milliliter of first extract in terms of 2,4-dinitrophenylhydrazine
Additive amount for 2,4-dinitrophenylhydrazine in 0.2-5mg or every milliliter of first extract is 0.2-5mg；
G. in step (2), the dosage of strong acid solution is 300-700 μ L in every milliliter of first extract；
H. in step (2), 2,4-dinitrophenylhydrazine solution is the acetonitrile solution of 2,4-dinitrophenylhydrazine；
I. in step (2), strong acid solution is the acetonitrile solution of strong acid；
J. in step (2), strong acid solution is selected from one of perchloric acid solution and hydrofluoric acid solution or a variety of；
K. in step (2), the time of derivatization is 20-60 minutes；
L. in step (2), the temperature of derivatization is room temperature；
M. in step (2), carbonyls derivatization product is selected from formaldehyde -2,4- dinitrophenylhydrazone, acetaldehyde -2,4- dinitrobenzene
Hydrazone, acetone -2,4- dinitrophenylhydrazone, propionic aldehyde -2,4- dinitrophenylhydrazone, methacrylaldehyde -2,4- dinitrophenylhydrazone, butyraldehyde -2,4- two
Nitro phenylhydrazone, 2- butanone-2, one of 4- dinitrophenylhydrazone and crotonaldehyde -2,4- dinitrophenylhydrazone or a variety of；
N. in step (1), before extraction, further include the steps that crushing tobacco sample or tobacco product sample.
11. detection method according to claim 10, in A, the tobacco product is flammable suction tobacco product.
12. detection method according to claim 10, in A, the tobacco product is cigarette.
13. detection method according to claim 10, in B, in step (1), the solid-liquid ratio of the extraction is 1:
(10-30)(g/mL)。
14. detection method according to claim 10, in B, in step (1), the solid-liquid ratio of the extraction is 1:20
(g/mL)。
15. detection method according to claim 10, in D, in step (1), extraction time is 20-50 minutes.
16. detection method according to claim 10, in D, in step (1), extraction time is 20 minutes, 30 minutes
Or 50 minutes.
17. detection method according to claim 10, in E, in step (1), extraction temperature is 5-40 DEG C.
18. detection method according to claim 10, in E, in step (1), extraction temperature is 10-35 DEG C.
19. detection method according to claim 10, in E, in step (1), extraction temperature is 10 DEG C, 25 DEG C or 30
℃。
20. detection method according to claim 10, in F, in step (2), with 2,4- bis- in every milliliter of first extract
The additive amount of the 2,4-dinitrophenylhydrazine solution of nitrophenyl hydrazine meter is 2,4- dinitrobenzene in 1-3mg or every milliliter of first extract
The additive amount of hydrazine is 1-3mg.
21. detection method according to claim 10, in F, in step (2), with 2,4- bis- in every milliliter of first extract
The additive amount of the 2,4-dinitrophenylhydrazine solution of nitrophenyl hydrazine meter is 2,4-dinitrophenylhydrazine in 2mg or every milliliter of first extract
Additive amount be 2mg.
22. detection method according to claim 10, in G, in step (2), strong acid solution in every milliliter of first extract
Dosage be 400-600 μ L.
23. detection method according to claim 10, in G, in step (2), strong acid solution in every milliliter of first extract
Dosage be 500 μ L.
24. detection method according to claim 10, in H, in step (2), the acetonitrile of 2,4-dinitrophenylhydrazine is molten
The concentration of 2,4 dinitrophenyl hydrazine is 1-40mg/mL in liquid.
25. detection method according to claim 10, in H, in step (2), the acetonitrile of 2,4-dinitrophenylhydrazine is molten
The concentration of 2,4 dinitrophenyl hydrazine is 5-20mg/mL in liquid.
26. detection method according to claim 10, in H, in step (2), the acetonitrile of 2,4-dinitrophenylhydrazine is molten
The concentration of 2,4 dinitrophenyl hydrazine is 10mg/mL in liquid.
27. detection method according to claim 10, in I item, in step (2), strong acid in the acetonitrile solution of strong acid
Concentration is 0.05%-2% (W/W).
28. detection method according to claim 10, in I item, in step (2), strong acid in the acetonitrile solution of strong acid
Concentration is 0.1%-1% (W/W).
29. detection method according to claim 10, in I item, in step (2), strong acid in the acetonitrile solution of strong acid
Concentration is 0.2% (W/W).
30. detection method according to claim 10, in K, the time of derivatization is 30-50 minutes.
31. detection method according to claim 10, in K, the time of derivatization is 40 minutes.
32. detection method according to claim 10, in L, the temperature of derivatization is 10 DEG C -35 DEG C.
33. detection method according to claim 1 or 2 further includes inciting somebody to action before liquid chromatography tandem mass spectrometry measurement
The step of extracting solution I or extracting solution II are filtered.
34. detection method according to claim 33, wherein be filtered using organic phase filter membrane.
35. detection method according to claim 34, wherein the aperture of organic phase filter membrane is 0.2-0.6 μm.
36. detection method according to claim 34, wherein the aperture of organic phase filter membrane is 0.45 μm.
37. detection method according to claim 1 or 2, wherein described to be measured as quantitative detection.
38. the detection method according to claim 37, wherein described to be measured as inner mark method ration detection.
39. the detection method according to claim 38, wherein internal standard compound is d3- formaldehyde -2,4 dinitrophenylhydrazone.
40. detection method according to claim 1 or 2, wherein the operating condition of liquid chromatogram includes following a into d
Any one is multinomial:
A. chromatographic column is to wear peace Acclaim Explosive E2 liquid-phase chromatographic column；
B. the temperature of chromatographic column is 36 DEG C -50 DEG C；
C. sample volume is 1-10 μ L；
D. mobile phase is made of mobile phase A and Mobile phase B, and mobile phase A is acetonitrile, and Mobile phase B is water.
41. detection method according to claim 40, in a, the specification of chromatographic column is 250mm × 4.6mm, 5 μm,
42. detection method according to claim 40, in b, the temperature of chromatographic column is 40 DEG C.
43. detection method according to claim 40, in c, sample volume is 3-7 μ L.
44. detection method according to claim 40, in c, sample volume is 5 μ L.
45. detection method according to claim 40, in d, the elution program of mobile phase are as follows: 0 minute, 60% (V/
V) mobile phase A；26 minutes, 60% (V/V) mobile phase A；28 minutes, 70% (V/V) mobile phase A；43 minutes, 70% (V/V) stream
Dynamic phase A；45 minutes, 60% (V/V) mobile phase A remained to the 50th minute；Flow velocity is always 0.6mL/min.
46. detection method according to claim 1 or 2, wherein mass spectrographic operating condition or parameter include it is following 1) extremely
30) any one or multinomial in:
1) ion source is electrospray ionisation source；
2) scanning mode is negative ion scan；
3) detection mode is multiple-reaction monitoring；
4) electron spray voltage is 3000-6000V；
5) ion source temperature is 400 DEG C -650 DEG C；
6) auxiliary gas Gas1 and/or Gas2 pressure is 40-70psi；
7) quota ion pair of formaldehyde -2,4- dinitrophenylhydrazone is 209.0/163.0；
8) qualitative ion pair of formaldehyde -2,4- dinitrophenylhydrazone is 209.0/151.0；
9) impact energy of formaldehyde -2,4- dinitrophenylhydrazone is -12V；
10) quota ion pair of acetaldehyde -2,4- dinitrophenylhydrazone is 223.0/163.0；
11) qualitative ion pair of acetaldehyde -2,4- dinitrophenylhydrazone is 223.0/181.0；
12) impact energy of acetaldehyde -2,4- dinitrophenylhydrazone is -16V；
13) quota ion pair of acetone -2,4- dinitrophenylhydrazone is 237.0/207.0；
14) qualitative ion pair of acetone -2,4- dinitrophenylhydrazone is 237.0/178.0；
15) impact energy of acetone -2,4- dinitrophenylhydrazone is -14V；
16) quota ion pair of propionic aldehyde -2,4- dinitrophenylhydrazone is 237.0/163.0；
17) qualitative ion pair of propionic aldehyde -2,4- dinitrophenylhydrazone is 237.0/152.0；
18) impact energy of propionic aldehyde -2,4- dinitrophenylhydrazone is -15V；
19) quota ion pair of methacrylaldehyde -2,4- dinitrophenylhydrazone is 235.0/158.0；
20) qualitative ion pair of methacrylaldehyde -2,4- dinitrophenylhydrazone is 235.0/163.0；
21) impact energy of methacrylaldehyde -2,4- dinitrophenylhydrazone is -16V；
22) quota ion pair of butyraldehyde -2,4- dinitrophenylhydrazone is 251.0/163.0；
23) qualitative ion pair of butyraldehyde -2,4- dinitrophenylhydrazone is 251.0/152.0；
24) impact energy of butyraldehyde -2,4- dinitrophenylhydrazone is -14V；
25) 2- butanone-2, the quota ion pair of 4- dinitrophenylhydrazone are 251.0/152.0；
26) 2- butanone-2, the qualitative ion pair of 4- dinitrophenylhydrazone are 251.0/163.0；
27) 2- butanone-2, the impact energy of 4- dinitrophenylhydrazone are -22V；
28) quota ion pair of crotonaldehyde -2,4- dinitrophenylhydrazone is 249.0/181.0；
29) qualitative ion pair of crotonaldehyde -2,4- dinitrophenylhydrazone is 249.0/172.0；
30) impact energy of crotonaldehyde -2,4- dinitrophenylhydrazone is -18V.
47. detection method according to claim 46, the 4) in item, and electron spray voltage is 3500-5000V.
48. detection method according to claim 46, the 4) in item, and electron spray voltage is 4500V.
49. detection method according to claim 46, the 5) in item, and ion source temperature is 450 DEG C -550 DEG C.
50. detection method according to claim 46, the 5) in item, and ion source temperature is 500 DEG C.
51. detection method according to claim 46, the 6) in item, and auxiliary gas Gas1 and/or Gas2 pressure is 50-
60psi。
52. detection method according to claim 46, the 6) in item, auxiliary gas Gas1 and/or Gas2 pressure be 50psi or
60psi。
53. purposes of the following kit in the carbonyls in detection tobacco or tobacco product；
Wherein, the kit includes:
I. acetonitrile；
The acetonitrile solution of II.2,4- dinitrophenylhydrazine and/or 2,4 dinitrophenyl hydrazine；With
The acetonitrile solution of III, perchloric acid；
Also, the tobacco product be it is all or part of by tobacco leaf be raw material production, for aspirating, sucking, chew or snuffing
Product；The carbonyls in formaldehyde, acetaldehyde, acetone, propionic aldehyde, methacrylaldehyde, butyraldehyde, 2- butanone and crotonaldehyde one
Kind is a variety of.
54. purposes according to claim 53, wherein the kit also includes the acetonitrile solution of pyridine and/or pyridine.
55. purposes according to claim 53, wherein the kit also includes organic phase filter membrane and d3Formaldehyde -2,4 two
Nitro phenylhydrazone.
56. purposes according to claim 53, wherein in the kit, in the acetonitrile solution of 2,4-dinitrophenylhydrazine
The concentration of 2,4 dinitrophenyl hydrazine is 1-40mg/mL.
57. purposes according to claim 53, wherein in the kit, in the acetonitrile solution of 2,4-dinitrophenylhydrazine
The concentration of 2,4 dinitrophenyl hydrazine is 5-20mg/mL.
58. purposes according to claim 53, wherein in the kit, in the acetonitrile solution of 2,4-dinitrophenylhydrazine
The concentration of 2,4 dinitrophenyl hydrazine is 10mg/mL.
59. purposes according to claim 53, wherein in the kit, perchloric acid in the acetonitrile solution of perchloric acid
Concentration is 0.05%-2% (W/W).
60. purposes according to claim 53, wherein in the kit, perchloric acid in the acetonitrile solution of perchloric acid
Concentration is 0.1%-1% (W/W).
61. purposes according to claim 53, wherein in the kit, perchloric acid in the acetonitrile solution of perchloric acid
Concentration is 0.2% (W/W).
62. purposes according to claim 53, wherein the tobacco product is selected from flammable suction tobacco product and non-burns and sucks
One of formula tobacco product is a variety of.
63. purposes according to claim 53, wherein the tobacco product is flammable suction tobacco product.
64. purposes according to claim 53, wherein the tobacco product is cigarette.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610658005.2A CN106018635B (en) | 2016-08-12 | 2016-08-12 | The method and detection method of pre-treatment are carried out to tobacco or tobacco product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610658005.2A CN106018635B (en) | 2016-08-12 | 2016-08-12 | The method and detection method of pre-treatment are carried out to tobacco or tobacco product |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106018635A CN106018635A (en) | 2016-10-12 |
| CN106018635B true CN106018635B (en) | 2019-05-10 |
Family
ID=57135133
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610658005.2A Active CN106018635B (en) | 2016-08-12 | 2016-08-12 | The method and detection method of pre-treatment are carried out to tobacco or tobacco product |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106018635B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106872603B (en) * | 2017-03-02 | 2019-11-08 | 国家烟草质量监督检验中心 | The high-performance liquid chromatogram determination method of formaldehyde and acetaldehyde in a kind of quick-fried pearl of cigarette filter |
| CN107966518B (en) * | 2017-12-07 | 2020-08-11 | 中国烟草总公司郑州烟草研究院 | Treatment method of smokeless tobacco product and determination method of small molecular aldehyde in smokeless tobacco product |
| CN109142566A (en) * | 2018-07-30 | 2019-01-04 | 苏州中汽检测技术服务有限公司 | The separation method and measuring method of automotive upholstery volatile matter methacrylaldehyde and acetone |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101701941A (en) * | 2009-11-05 | 2010-05-05 | 中国烟草总公司郑州烟草研究院 | Method fro determining content of volatile carbonyl compound in main stream smoke of cigarette |
| CN105021733A (en) * | 2015-07-19 | 2015-11-04 | 国家烟草质量监督检验中心 | Method for determination of cigarette cut tobacco main carbonyl compounds by UPLC-IE method |
-
2016
- 2016-08-12 CN CN201610658005.2A patent/CN106018635B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101701941A (en) * | 2009-11-05 | 2010-05-05 | 中国烟草总公司郑州烟草研究院 | Method fro determining content of volatile carbonyl compound in main stream smoke of cigarette |
| CN105021733A (en) * | 2015-07-19 | 2015-11-04 | 国家烟草质量监督检验中心 | Method for determination of cigarette cut tobacco main carbonyl compounds by UPLC-IE method |
Non-Patent Citations (3)
| Title |
|---|
| LC-ESI-MS/MS法检测卷烟滤嘴中8种挥发性羰基化合物;余晶晶等;《烟草科技》;20131231(第9期);摘要，第1.2.2、2.3节，表2 |
| 直接衍生／高效液相色谱法分析水基胶中羰基化合物;万小红等;《分析测试学报》;20111231;第30卷(第12期);1412-1418 |
| 高效液相色谱法测定电子烟烟液中8种挥发性羰基化合物;陈刚等;《安徽农业科学》;20141231;第42卷(第31期);11072-11074，11082 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106018635A (en) | 2016-10-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Kim et al. | Determination of tobacco-specific nitrosamines in replacement liquids of electronic cigarettes by liquid chromatography–tandem mass spectrometry | |
| Chen et al. | Mainstream smoke chemical analyses for 2R4F Kentucky reference cigarette | |
| CN103163270B (en) | Method for detecting eight volatile carbonyl compounds in cigarette filter tip through liquid chromatography-tandem mass spectrometry | |
| CN103257196B (en) | Method for detecting alkaloids and nitrosamines in tobaccos simultaneously | |
| CN107764917B (en) | Method for determining key volatile components in cigarette blasting beads | |
| Pang et al. | Carbonyl compounds in gas and particle phases of mainstream cigarette smoke | |
| CN104237431B (en) | The assay method of TSNAs in a kind of electronic cigarette smog | |
| CN106018635B (en) | The method and detection method of pre-treatment are carried out to tobacco or tobacco product | |
| CN102353741A (en) | Method for measuring contents of four kinds of tobacco-specific nitrosamines in cigarette mainstream smoke | |
| CN105954402B (en) | Gas-chromatography-flame ion/tandem mass spectrum detection method of alkaloid in a kind of cigarette mainstream flue gas | |
| CN107271584B (en) | Method for trapping carbonyl compounds and tobacco-specific nitrosamines in cigarette mainstream smoke, extraction method and determination method | |
| CN104142374A (en) | Method for measuring content of carbonyl compound in electronic tobacco juice by adopting direct derivation/high performance liquid chromatography | |
| Cho et al. | Use of a gas-tight syringe sampling method for the determination of tobacco-specific nitrosamines in E-cigarette aerosols by liquid chromatography-tandem mass spectrometry | |
| CN110907565B (en) | Method for measuring carbonyl-containing aroma components in smoke of cigarette heated without combustion | |
| Lee et al. | Analytical methods for determination of carbonyl compounds and nicotine in electronic no-smoking aid refill solutions | |
| CN106442753B (en) | A kind of method of TSNAs content in measurement cigarette mainstream flue gas | |
| Jiang et al. | Simultaneous determination of multiple components in cigarettes by mechanochemical extraction and direct analysis in real time mass spectrometry in minutes | |
| CN106174696A (en) | Prepare the method for Fructus Momordicae charantiae extract, Fructus Momordicae charantiae extract and application thereof | |
| CN106093235B (en) | It is a kind of for measuring the extract liquor and its application method of moisture and nicotine content in cigarette mainstream flue gas | |
| Li et al. | Simultaneous ultrafast determination of six alkaloids in mainstream cigarette smoke by DART-MS/MS | |
| CN104155403B (en) | A kind of method measuring hymexazol pesticide residues content | |
| Halim et al. | Alkaloids produced by Cestrum nocturnum and Cestrum diurnum | |
| CN104897836B (en) | The method of quinic acid, test kit and application thereof in detection sample | |
| CN104101677B (en) | Liquid chromatography tandem mass spectrometry measures the method for Geraniol in essence and flavoring agent | |
| CN104849391B (en) | A kind of extract the method for chinic acid, kit and application thereof in sample |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |