CN1288439C - Method for detecting tobacco specific nitrosamine by liquid phase chromatography and series mass spectrometry - Google Patents
Method for detecting tobacco specific nitrosamine by liquid phase chromatography and series mass spectrometry Download PDFInfo
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- CN1288439C CN1288439C CN 200410078824 CN200410078824A CN1288439C CN 1288439 C CN1288439 C CN 1288439C CN 200410078824 CN200410078824 CN 200410078824 CN 200410078824 A CN200410078824 A CN 200410078824A CN 1288439 C CN1288439 C CN 1288439C
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Abstract
The present invention relates to a method for detecting specific nitrosamine in tobacco by using a liquid phase chromatography and a tandem mass spectrometry, which is used for detecting the content of specific nitrosamine in cigarette smoke. The smoke gas is trapped and is put on a filter sheet, internal standard substances are added, and the filter sheet is oscillated and extracted by citric acid-phosphate buffer solution; under the protection of N2, organic phase extracting solution is concentrated, and hydrochloric acid is added for acidification; after the phase is separated, alkali solution is added into water phase for neutralization, the water phase solution is transferred into a reversed phase chemical bond solid-phase extraction column, water solution of polarity organic solvent is used for leaching, polarity organic solvent is used for elution, eluant is concentrated, and the eluant is analyzed by an LC/MS/MS instrument; according to quantitative area ratio of the component peak and the internal standard substance peak, the LC condition is the C18 liquid phase chromatography column, and a mobile phase is composed of ammonium acetate water solution and ammonium acetate acetonitrile solution; the MS/MS condition is positive ion mode ionization. The present invention has the advantages of good repetitiveness, high recovery ratio, low detection limit and easy operation.
Description
Technical field
The present invention relates to a kind of method of the N-of detection nitrosamine, particularly relate to a kind of method that detects the peculiar N-nitrosamine of tobacco.
Background technology
The peculiar N-nitrosamine of tobacco is a compounds that only is present in tobacco and the goods thereof.Although they are normally stable under physiological condition, it just has strong carcinogenesis by metabolism activation in vivo.In order to reduce the peculiar N-nitrosamine of tobacco to smoker and the healthy possible injury of involuntary smoker, control and reduce their content in tobacco and goods thereof, become an important problem, the content of the peculiar N-nitrosamine of tobacco will become an important indicator weighing the tobacco product quality.Therefore, since the nineties in last century, all the detection method of tobacco-specific nitrosamine in the tobacco has been carried out corresponding research both at home and abroad.Yet because the composition of tobacco and cigarette smoke is very complicated, tobacco-specific nitrosamine content wherein is atomic, so the research difficulty of this respect is very big, still needs deeply.People such as Prokopczyk (" Improved methodology for the quantitative assessment oftobacco-specific N-nitrosamines in tobacco by supercritical fluid extraction ", J.Agric.Food Chem., 1995,43:916-922) reported a kind of detection method, earlier with N-nitrosamine in the silicagel column supercritical fluid extraction tobacco that adds 10% methyl alcohol, extract is crossed the silica gel column chromatography purifying, concentrate behind the component wash-out, use gas chromatography/thermal energy analyzer (GC/TEA) analyzing and testing at last.This method only adopts silicagel column, can make many acid interfering components and N-nitrosamine wash-out simultaneously, influences the purification effect and the recovery; Secondly, the TEA detecting device all has response to all nitroso compounds, is difficult to distinguish other nitroso compound of common elution; Moreover TEA detecting device dead volume is big, has limited the scanning times of GC, makes its method detectability higher.Song etc. (" Supercritical fluid extractionand gas chromatography/mass spectrometry for the analysis of tobacco-specificnitrosamines in cigarettes ", Anal.Chem., 1999,71:1303-1308) reported a kind of detection method, earlier with the supercritical fluid extraction pipe tobacco that adds 10% methyl alcohol dressing agent, with sodium hydroxide solution washing ethyl acetate is the extract of solvent, concentrate the back and be further purified sample with positive mode, use the GC/MS analyzing and testing at last with silica gel base solid-phase extraction column.This method has only adopted highly basic washing, silica gel Solid-Phase Extraction column extracting, can make stronger nitrogen-containing compound of alkalescence and component to be measured wash-out simultaneously, influences the pre-service purification effect and the recovery.
Summary of the invention
The present invention be intended to solve the peculiar N-nitrosamine of tobacco detect in not good, the problem such as the recovery is low of purification effect, a kind of method that improves the detection tobacco-specific nitrosamine of purification effect and the recovery and easy and simple to handle, instrument highly versatile is provided.
Technical scheme of the present invention is achieved in that
A. main flume is captured on filter disc, adds internal standard substance solution, with citric acid-phosphate buffered solution and cyclohexane to the filter disc common extraction of vibrating;
B. at N
2Under the gas shiled, concentrate the organic phase extract,, after being separated, add the aqueous slkali neutralization toward aqueous phase toward wherein adding hcl acidifying;
C. aqueous phase solution is changed over to anti-phase chemical bonding solid-phase extraction column,, use the polar organic solvent elution, collect eluant with the aqueous solution drip washing that contains polar organic solvent;
D. concentrate eluant, analyze with the LC/MS/MS instrument.The LC condition: the C18 liquid-phase chromatographic column, 40～60 ℃ of column temperatures, sample size 10～20 μ l, mobile phase flow rate 0.2～1ml/min, moving phase is made up of ammonium acetate solution and ammonium acetate acetonitrile solution, adopts linear gradient moving phase wash-out.MS/MS condition: positive ion mode ionization, 500～600 ℃ of source temperatures, spray nozzle voltage 4000～5000V;
E. the area ratio according to component peaks and internal standard compound peak carries out quantitative test.
Filter disc is a cambridge filter in steps A; Internal standard compound is a trimethyl
13C
3Mark click coffee because of, be solvent with methyl alcohol, concentration is 50-500ng/ml, consumption 0.1-2ml; Citric acid-phosphate buffered solution pH4-5, citric acid concentration 45-60mmol/l, ascorbic acid concentrations 10-30mmol/l, the volume ratio of citric acid-phosphate buffered solution and cyclohexane is 1: 0.5-2.
Concentration of hydrochloric acid 0.1-0.5mol/l in step B, consumption 1-5ml; Aqueous slkali is a sodium hydrate aqueous solution, and concentration is 0.5-2mol/l, and dropping to pH is 5.5-7.5.
Anti-phase chemical bonding solid-phase extraction column is an Oasis HLB solid-phase extraction column in step C, uses 1-10ml methyl alcohol and 1-10ml distilled water balance before the use in succession; Polar organic solvent is a methyl alcohol, and its concentration of aqueous solution is 2-8%, eluent consumption 1-20ml, scrub solution consumption 1-20ml.
The LC condition is in step D: liquid-phase chromatographic column is a Pinnacle II C18 post; Ammonium acetate solution and ammonium acetate acetonitrile solution concentration are 3-8mmol/l; The moving phase linear gradient is changed to 70%～100% ammonium acetate solution+30%～0% ammonium acetate acetonitrile solution, balance 3～10min, ammonium acetate solution is reduced to 50%～10% by 70%～100% linearity in 1～8min then, the ammonium acetate acetonitrile solution increases to 50%～90% by 30%～0% linearity simultaneously, keep 1～8min, then ammonium acetate solution increases to 70%～100% by 50%～10% linearity in 1-8min, the ammonium acetate acetonitrile solution is reduced to 30%-0% by 50%～90% linearity simultaneously, keeps 1-20min.
Beneficial effect of the present invention is: owing to adopted water-soluble buffer solution and organic solvent vibration to extract altogether, effectively improved the purification effect and the recovery.Because vibration is extracted altogether and made tobacco-specific nitrosamine is entered water-soluble buffer solution from the filter disc extraction, and then back extraction can finish in a step to organic phase, forms the phenomenon of foam when having avoided stripping in the past, and foam forms and will cause and lose and error.Especially, the citric acid-phosphate buffered solution in extracting altogether can be eliminated the influence of the stronger nitrogen-containing compound of alkalescence.In addition, hcl acidifying, be separated and can eliminate the influence of some neutral interfering components, the Solid-Phase Extraction purifying can be eliminated some non-target compounds.The LC/MS/MS experiment condition that this method is set, can effectively separate N '-nitroso-nornicotine is NNN, 4-(N-nitroso-methylamino)-1-(3-pyridine radicals)-the 1-butanone is NNK, N-nitroso-anabasine is NAT, N-nitroso-anabasine is four kinds of components to be measured of NAB and internal standard compound, is specially adapted to the accurate quantification of tobacco-specific nitrosamine in the cigarette smoke.This method is easy and simple to handle, so because of not adopting chromatographic column to save time, instrument highly versatile for the GC/TEA method.
Embodiment
Embodiment one
Add 1.0ml 300ng/ml trimethyl toward the diameter 92mm cambridge filter that has captured 20 9mg 555 board cigarette smokes earlier
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3Mark click coffee is because of methanol solution, adds pH 4.3 citric acids-phosphate buffered solution and each 30ml of cyclohexane that contains 53mmol/l citric acid and 20mmol/l ascorbic acid again, to the filter disc common extraction of vibrating.After separation obtains the organic phase extract, N
2Be concentrated into about 1ml under the protection, again toward wherein adding 1ml 0.1mol/l hcl acidifying, the back that is separated drips the 1mol/l sodium hydroxide solution to pH 7.0 toward aqueous phase.Quantitatively change the gained aqueous phase solution over to distill isorrheic U.S. Waters company in succession with 3ml methyl alcohol and 3ml Oasis HLB solid-phase extraction column, use 3ml 5% methanol aqueous solution drip washing then, with the elution of 5ml methyl alcohol.Eluant is concentrated into 1ml, analyzes for LC/MS/MS.The LC condition is: the Pinnacle II C18 liquid-phase chromatographic column of U.S. Restek company, 60 ℃ of column temperatures, sample size 10 μ l, mobile phase flow rate 0.25ml/min, moving phase is made up of 5mmol/l ammonium acetate solution and ammonium acetate acetonitrile solution, the moving phase linear gradient is changed to 95% ammonium acetate solution+5% ammonium acetate acetonitrile solution, balance 6min, ammonium acetate solution is reduced to 20% by 95% linearity in 6min then, the ammonium acetate acetonitrile solution increases to 80% by 5% linearity simultaneously, keeps 4min, and then ammonium acetate solution increases to 95% by 20% linearity in 2min, the ammonium acetate acetonitrile solution is reduced to 5% by 80% linearity simultaneously, keeps 10min.Under this experiment condition, four kinds of key component NNN of tobacco-specific nitrosamine, NNK, NAT and NAB can with trimethyl
13C
3Mark click coffee detects by MS/MS because of effectively separating again, quantitatively various component concentrations to be measured.The MS/MS condition is: positive ion mode ionization, 600 ℃ of source temperatures, spray nozzle voltage 5000V.The component to be measured and the trimethyl that obtain according to integraph
13C
3Mark click coffee because of peak area ratio carry out quantitative test.By extracting the ion flow map analysis as can be known, signal to noise ratio (S/N ratio) is higher, noiseless substantially peak, and the sample purifying is good, and peak shape is symmetry sharply.
Embodiment two
With methyl alcohol is solvent, presses table 1 concentration range configuration series and mixes standard specimen solution, wherein trimethyl
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3Mark click coffee is because of being 300ng/ml; Under above-mentioned experiment condition, carry out the LC/MS/MS analyzing and testing then, with component peaks on the chromatogram and trimethyl
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3Mark click coffee is response signal because of the area ratio at peak, according to 6 kinds of 3 horizontal survey results that mix standard specimen solution, set up the typical curve of NNN, NNK, NAT and four kinds of components of NAB, the linearly dependent coefficient of each typical curve is followed successively by 0.9992,0.9980,0.9990 and 0.9992, shows the remarkable linear dependence of response signal and concentration of component; By 3 times of definite method detection limits of 5 horizontal survey result standards of least concentration mixing standard specimen solution deviation, experimental result sees Table 2, shows that the method detection limit is low, the method sensitivity.
Table 1 series is mixed standard specimen solution key component concentration
| The standard specimen numbering | 1 | 2 | 3 | 4 | 5 | 6 |
| NNN/ng/ml NNK/ng/ml NAT/ng/ml NAB/ng/ml | 2.75 2.75 2.50 2.50 | 27.5 27.5 25.0 25.0 | 110 110 100 100 | 275 275 250 250 | 550 550 500 500 | 2750 2750 2500 1000 |
The detection limit of table 2 LC/MS/MS method
| NNN | NNK | NAT | NAB | |
| Detection limit/ng/ml | 0.17 | 0.24 | 0.05 | 0.19 |
The blended type cigarette of getting the same trade mark is by said sample pre-service and LC/MS/MS analyzing and testing, repeat 5 replicate determinations, calculate the relative standard deviation RSD% that measures, experimental result sees Table 3, for the trace components analysis in the complicated substrate, such presentation of results method repeated fairly good.
The repeatability of tobacco-specific nitrosamine assay in the table 3 blended type cigarette flue gas
| Experiment numbers | 1 | 2 | 3 | 4 | 5 | RSD％ |
| NNN/ng/ props up NNK/ng/ and props up NAT/ng/ and prop up NAB/ng/ and prop up | 122.84 46.03 162.73 18.47 | 134.08 45.23 154.12 17.25 | 128.56 43.96 159.46 18.70 | 116.48 44.86 167.64 16.86 | 120.15 40.57 172.95 16.87 | 5.60 4.81 4.63 5.05 |
Captured in the cambridge filter of cigarette smoke mixing the adding of standard specimen solution, experimentize according to said sample pre-service and LC/MS/MS analyzing detecting method then, according to actual addition and measured result, calculate the recovery of various components, experimental result sees Table 4, and the recovery that shows four kinds of components is all more than 90%.
The mensuration of the table 4 method recovery
| NNN | NNK | NAT | NAB | |
| Addition/ng actual measured amount/ng the recovery/% | 200 186.52 93.26 | 200 190.24 95.12 | 200 180.33 90.17 | 100 91.09 91.09 |
Claims (5)
1, a kind of method with detecting tobacco specific nitrosamine by liquid phase chromatography and series mass spectrometry is characterized in that the step of the method is as follows:
A, main flume is captured on filter disc, adds internal standard substance solution, with citric acid-phosphate buffered solution and cyclohexane to the filter disc common extraction of vibrating;
B, at N
2Under the gas shiled, concentrate the organic phase extract,, after being separated, add the aqueous slkali neutralization toward aqueous phase toward wherein adding hcl acidifying;
C, change aqueous phase solution over to anti-phase chemical bonding solid-phase extraction column,, use the polar organic solvent elution, the collection eluant with the aqueous solution drip washing that contains polar organic solvent;
D, concentrated eluant are analyzed LC condition: C18 liquid-phase chromatographic column with the LC/MS/MS instrument, 40～60 ℃ of column temperatures, sample size 10～20 μ l, mobile phase flow rate 0.2～1ml/min, moving phase is made up of ammonium acetate solution and ammonium acetate acetonitrile solution, adopts linear gradient moving phase wash-out; MS/MS condition: positive ion mode ionization, 500～600 ℃ of source temperatures, spray nozzle voltage 4000～5000V;
E, carry out quantitative test according to the area ratio at component peaks and internal standard compound peak.
2, detection tobacco-specific nitrosamine method according to claim 1 is characterized in that filter disc is a cambridge filter in steps A; Internal standard compound is a trimethyl
13C
3Mark click coffee because of, be solvent with methyl alcohol, concentration is 50-500ng/ml, consumption 0.1-2ml; Citric acid-phosphate buffered solution pH4-5, citric acid concentration 45-60mmol/l, ascorbic acid concentrations 10-30mmol/l, the volume ratio of citric acid-phosphate buffered solution and cyclohexane is 1: 0.5-2.
3, detection tobacco-specific nitrosamine method according to claim 1 is characterized in that concentration of hydrochloric acid 0.1-0.5mol/l in step B, consumption 1-5ml; Aqueous slkali is a sodium hydrate aqueous solution, and concentration is 0.5-2mol/l, and dropping to pH is 5.5-7.5.
4, detection tobacco-specific nitrosamine method according to claim 1 is characterized in that anti-phase chemical bonding solid-phase extraction column is an Oasis HLB solid-phase extraction column in step C, uses 1-10ml methyl alcohol and 1-10ml distilled water balance before the use in succession; Polar organic solvent is a methyl alcohol, and its concentration of aqueous solution is 2-8%, eluent consumption 1-20ml, scrub solution consumption 1-20ml.
5, detection tobacco-specific nitrosamine method according to claim 1 is characterized in that the LC condition is in step D: liquid-phase chromatographic column is a Pinnacle II C18 post; Ammonium acetate solution and ammonium acetate acetonitrile solution concentration are 3-8mmol/l; The moving phase linear gradient is changed to 70%～100% ammonium acetate solution+30%～0% ammonium acetate acetonitrile solution, balance 3～10min, ammonium acetate solution is reduced to 50%～10% by 70%～100% linearity in 1～8min then, the ammonium acetate acetonitrile solution increases to 50%～90% by 30%～0% linearity simultaneously, keep 1～8min, then ammonium acetate solution increases to 70%～100% by 50%～10% linearity in 1-8min, the ammonium acetate acetonitrile solution is reduced to 30%-0% by 50%～90% linearity simultaneously, keeps 1-20min.
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