CN101344509B - Mass spectrometry method for tobacco and its product amino acid - Google Patents
Mass spectrometry method for tobacco and its product amino acid Download PDFInfo
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- CN101344509B CN101344509B CN2008100276961A CN200810027696A CN101344509B CN 101344509 B CN101344509 B CN 101344509B CN 2008100276961 A CN2008100276961 A CN 2008100276961A CN 200810027696 A CN200810027696 A CN 200810027696A CN 101344509 B CN101344509 B CN 101344509B
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Abstract
The invention discloses a mass spectrometric analysis method of amino acid in tobaccos and tobacco products, extracting solution of a sample to be tested is chromatographically resolved, and the mass spectrometric analysis of the extracting solution which comprises the building of specification curves in two different concentration series and the analyzing detection of free amino acid in a positive ion mode in the tobaccos that uses an electrospray ion trap tandom mass spectrometry is implemented. The mass spectrometric analysis method of amino acid in the tobaccos and the tobacco products of the invention implements the proper setting of the mass spectrometric conditions, adopts the positive ion mode and a full scanning form, determines different subsections and proper scanning range, realizes the analyzing detection of twenty free amino acids in the tobaccos, has high analyzing efficiency and good sensitivity and selectivity, and can be successfully applied into the analyzing detection of amino acid in various tobacco samples.
Description
Technical field
The invention belongs to chemical analysis detection technique field, be specifically related to one and grow tobacco and the mass spectrometric analysis method of product amino acid.
Background technology
Amino acid is the important component part in the tobacco leaf, is and smoke perfume, cigarette quality and the closely-related tobacco component of brand identity, and amino acid participates in the brown reaction of non-enzyme in the tobacco leaf, i.e. Maillard reaction, and this reaction can produce multiple important aroma component.Therefore, the amino acid of measuring in the tobacco all has crucial meaning to formula development, explained hereafter and quality control.
Tobacco component is quite complicated, and carrying out amino acid analysis with LC, automatic amino acid analyser, chromatography of ions (IC) and Capillary Electrophoresis methods such as (CE) often needs sample carried out numerous and diverse pre-treatments such as Solid-Phase Extraction, with the minimizing interference.Pre-treatment meetings such as existing Solid-Phase Extraction cause the loss of some amino acid (or amino acid derivativges) to a certain extent, and some disturbs impurity also to be difficult to eliminate by pre-treatment.LC and IC isochromatic spectrum method are mainly discerned compound by retention time, therefore must spend the more time gropes chromatographic separation condition and accurately judges determinand, and chromatographic process all is difficult to solve the problem that compound flows out altogether, causes some testing compound and chaff interference not to distinguish.
In recent years, along with the development of electro-spray ionization (ESI) and tandem mass spectrum (MS/MS) technology, liquid chromatography and esi-msn coupling (LC-ESI-MS/MS) are widely used in the complex compound analysis.But have not yet to see the relevant report that liquid chromatography and esi-msn coupling technique are used in the tobacco sample amino acid analysis.
Liquid chromatography and esi-msn coupling, mass spectrophotometry tobacco amino acid, mass spectral condition appropriately be provided with to amino acid whose accurately and high-sensitivity detection very important, different segmentation (Segment) can be called independently tuning file, suitable sweep limit helps reducing background noise and impurity disturbs, and is related to the sensitivity of detection.
Do not see at present the report that tobacco amino acid mass spectrophotometry condition is carried out the optimization setting of system.
Summary of the invention
The purpose of this invention is to provide one grows tobacco and the mass spectrometric analysis method of product amino acid.
Purpose of the present invention is achieved by the following technical programs:
Provide one to grow tobacco and the mass spectrometric analysis method of product amino acid, the testing sample extract carries out mass spectrophotometry after chromatographic resolution, described mass spectrophotometry is a typical curve of making two kinds of variable concentrations series, use the electron spray ion trap tandem mass spectrometry under positive ion mode to tobacco in free amino acid carry out analyzing and testing.
Described mass spectrophotometry condition is a nitrogen pressure: 0.64MPa; Helium pressure: 0.38MPa; Polarity: positive ionization; Scanning form: full scan; Acquisition time: 40min; Activationary time: 30ms; Sweep gas: 0LTQ unit; Spray voltage: 5kV; Capillary temperature: 350 ℃; Sweep limit: standard; Sweep speed: standard; Segmentation.Described segmentation is to be divided into 4 sections, and wherein the sheath gas of the 3rd segmentation and auxiliary gas are respectively 38LTQ unit and 0LTQ unit, and the sheath gas and the auxiliary gas of all the other segmentations are respectively 46LTQ unit and 19LTQ unit.Other parameters are determined by hands-off tuning or according to the mass spectral default setting of LTQ.
The invention has the beneficial effects as follows the appropriate setting that the mass spectrophotometry condition is provided, segmentation and each amino acid whose sweep limit have been carried out optimizing setting, effectively guarantee accuracy and high sensitivity that amino acid is detected.
Description of drawings
The extraction ion flow graph of Fig. 1 20 seed amino acids and interior mark norvaline
Ile and Leu extract the ion flow graph before Fig. 2 mark-on
Ile and Leu extract the ion flow graph behind Fig. 3 mark-on
Val and Nva extract the ion flow graph before Fig. 4 mark-on
Val and Nva extract the ion flow graph behind Fig. 5 mark-on
The amino acid whose second order ms figure in Fig. 6～26
Embodiment
Further describe the present invention below in conjunction with the drawings and specific embodiments.
Present embodiment is in the amino acid analysis that carries out tobacco and goods thereof detects, the method that adopts liquid-phase chromatographic analysis-esi-msn to analyze, in the process of experiment, the mass spectrophotometry condition is optimized, cooperate appropriate setting simultaneously, obtained accurate and highly sensitive experimental result the liquid-phase chromatographic analysis condition.
1, instrument, material and reagent
The LC-MS LTQ of U.S. power ﹠ light company liquid chromatography-iontrap mass spectrometer is equipped with automatic sampler, quaternary gradient mass spectrum pump, LTQ ion trap mass spectrometry charged spray ionization source (ESI), Xcalibur 1.4 SR1 system controlling softwares; Italy Claind N2LCMS nitrogen gas generator; France Millipore Element A10 water purification machine; U.S. Cole-Parmer 8892 ultrasonic cleaning machines; Sartorious CP225D electronic balance (Max 220g, d=0.01mg (80g), 0.1mg (220g)); Whatman 0.2 μ m nylon pin type filter; The tobacco powder that sample grinding machine grinds.
Kilnitamin standard solution (Fluka company) contains 17 seed amino acids, and concentration respectively is 1mM; Internal standard compound L-norvaline (the beautiful pearl east wind in Shanghai Bioisystech Co., Ltd); Asparagine water (Shanghai uncle bio tech ltd difficult to understand); Tryptophane, proline and glutamine (Chemical Reagent Co., Ltd., Sinopharm Group); γ-An Jidingsuan (Sigma company); L-piperidines-2-carboxylic acid, nine fluorine valeric acids (NFPA) (Aldrich company); Methyl alcohol and acetonitrile (MERCK company); The pure concentrated hydrochloric acid of top grade; Milli-Q level water, by Milliore Element A10 preparation, if without special instruction, water is Milli-Q level water in the experiment.
2, experimental technique
2.1 the thermoelectric HyPURITY C of chromatographic condition
18Chromatographic column (200mm * 2.1mm, 5 μ m), Agilent Reliance protection column sleeve and Eclipse XDB-C8 guard column (12.5 * 2.1mm, 5 μ m).Input mode: loopful (5 μ L); Flow velocity: 200 μ L/min; Column oven: 25 ℃; Sample disc temperature: 15 ℃; Irrigation with syringe volume (flush volume): 1000 μ L; Wash needle body long-pending (wash volume): 800 μ L.Mobile phase A: 99% water-1% acetonitrile-0.1%NFPA; Mobile phase B: 10% water-90% acetonitrile-0.1%NFPA.Eluent gradient sees Table 1.
Table 1 eluent gradient
Time moving phase moving phase
Time Eluent Eluent
(min) A(％) B(％)
0.0 100 0
8.0 100 0
8.1 90 10
25.0 90 10
25.1 75 25
32.0 80 20
32.5 100 0
40.0 100 0
2.2 mass spectrum condition nitrogen pressure: 0.64MPa; Helium pressure: 0.38MPa; Polarity: positive ionization; Scanning form: full scan; Acquisition time: 40min; Activationary time: 30ms; Sweep gas: 0LTQ unit; Spray voltage: 5kV; Capillary temperature: 350 ℃; Sweep limit: standard; Sweep speed: standard; Settings such as segmentation, split time, separation width, normalization collision energy see Table 2, and wherein the sheath gas of the 3rd segmentation and auxiliary gas are respectively 38LTQ unit and 0LTQ unit, and the sheath gas and the auxiliary gas of all the other segmentations are respectively 46LTQ unit and 19LTQ unit.Other parameters are determined by hands-off tuning or according to the mass spectral default setting of LTQ.
Condition setting such as table 2 segmentation, split time, separation width, normalization collision energy
2.3 standard curve making adopts inner mark method ration.Mark norvaline concentration was the amino-acid mixed and standard solution I (aspartic acid (Asp) of 1.7 μ M in preparation contained, serine (Ser), glutamine (Gln), threonine (Thr), glutamic acid (Glu), cystine (Cys), γ-An Jidingsuan (Gaba), nipecotic acid (Pip), valine (Val), dl-methionine (Met), histidine (His), tyrosine (Tyr), lysine (Lys), isoleucine (Ile), arginine (Arg), leucine (Leu), the concentration of phenylalanine (Phe) and tryptophane (Try) is the 0.03M HCl solution of 50 μ M); Mark norvaline concentration was the amino-acid mixed and standard solution II (concentration of proline (Pro) and asparagine (Asn) is respectively the 0.03M HCl solution of 500 μ M) of 1.7 μ M in preparation contained.With containing norvaline concentration is that the 0.03M HCl of 1.7 μ M is made into series concentration to standard solution I and standard solution II, the production standard curve.
2.4 sample preparation takes by weighing 0.1～0.2g offal and places conical flask, add 20mL and contain the 0.03MHCl solution that norvaline concentration is 1.7 μ M, ultrasonic concussion 15min sways conical flask and makes the solution concentration distributed uniform for a moment, direct injected behind 0.2 μ m membrane filtration.
3, experimental result
3.1 determining of chromatographic condition
3.1.1 amino acid is to the requirement of temperature
When temperature was higher, amino-acid mixed mark reacted easily, and some amino acid content is reduced.Therefore, all amino acid standard solution should in time be kept at below 2 ℃ when not using, and when analytic sample sample disc are set in 15 ℃ of lower temperature.Amino acid may change in post when higher for fear of column temperature, and column oven is set in 25 ℃.Another benefit that suitably reduces column temperature is obviously to increase isomers leucine (Leu) and the degree of separation of isoleucine (Ile) on chromatographic column, sees accompanying drawing 1.But it is low that column temperature should not be set, in order to avoid the post pressure is excessive, also makes Phe and Try go out the peak simultaneously and postpone, and increases analysis time.
3.1.2 chromatographic column and moving phase
At C
18Tested multiple moving phase on the analytical column, the result shows Thermo HyPURITYC
18Cooperate 99% water-1% acetonitrile-0.1%NFPA and 10% water-90% acetonitrile-0.1%NFPA to make moving phase and can obtain good chromatographic peak profile and suitable chromatographic run time, and can make isomers Leu and Ile reach baseline separation, see accompanying drawing 1.NFPA is as moving phase modifier.In addition, NFPA also helps and strengthens electrospray ionization mass spectrum to amino acid whose positive ionization detection signal.
The easy wash-out NFPA of acetonitrile, too much NFPA increases background interference easily, influences detection sensitivity, and therefore, the usage ratio of Mobile phase B is difficult for too high, and experiment below 25%, can reach the effect that good separation detects to the proportional control of Mobile phase B.Be noted that NFPA can constantly gather and slowly change the character of stationary phase in chromatographic column, amino acid whose appearance time is changed.In order to guarantee good retention time reappearance, carry out qualitative and quantitative analysis more easily, behind sample introduction 100 pins,, strip the NFPA that gathers with 100% acetonitrile flushing chromatographic column 30min more, use sample introduction after the moving phase balance chromatographic column again.
3.1.3 the selection of internal standard compound
Norvaline is not stored in the tobacco amino acid, and is stable and can separate fully on chromatogram with its isomers valine under this experiment condition, and price is lower, is more satisfactory internal standard compound.
3.1.4 the discriminating of amino acid isomer
Leucine (Leu) and isoleucine (Ile), valine (Val) and norvaline (Nva) be isomers each other, and second order ms is similar, can't singly be identified with mass spectrum, therefore needs to distinguish in conjunction with chromatographic resolution.Experiment adds a certain amount of Ile and Val respectively by the mark-on method, and peak sequence is judged.After adding Ile or Val standard, the chromatographic peak height that flows out previously obviously increases, and peak area obviously increases, and can judge that Ile and Val flow out earlier than Leu and Nva respectively, sees that accompanying drawing 2～accompanying drawing 5 extracts the ion flow graph.
3.2 determining of mass spectrum condition
On the basis that the optimization of above-mentioned chromatographic condition is provided with, the present invention appropriately is provided with the mass spectrophotometry condition again, obtain to amino acid whose accurately and high-sensitivity detection.
Experiment has contrasted secondary full scan (Full MS2) and has selected two kinds of scan patterns of ion monitoring (SIM).The secondary full scan can reduce background interference effectively, obtains higher sensitivity, and selectivity is better than SIM, and it is preferable to detect effect, so experimental selection secondary full scan carries out quantitative test.In the second order ms of 21 seed amino acids, see accompanying drawing 6～26, except that Arg and Cys, the main fragment ion of all the other amino acid is decarboxylation, dehydroxylation or deamination base peak, i.e. [M-HCOOH+H]
+, [M-H
2O+H]
+Or [M-N
2H+H]
+The accurate choice relation of quota ion is to the quantitative feature selecting of mass spectrum.Quota ion is preferentially chosen the bigger feature daughter ion of relative abundance, to obtain sensitivity preferably.For Glu, the characteristic of factor ion m/z130 is not strong, has Interference Peaks overlapping, therefore selects relative abundance time strong decarboxylation base peak m/z102.
Different segmentation (Segment) can be called independently tuning file, helps improving the sensitivity of detection.The retention time of experimental basis chromatographic peak divides 4 segmentations at interval.Suitable sweep limit helps reducing background noise and impurity disturbs, and improves the sensitivity and the accuracy that detect, and experiment has been carried out optimization setting to each amino acid whose sweep limit, is shown in Table 2.
3.3 determining of pre-treatment condition
3.3.1 different influences of extracting solution to chromatographic peak profile
The present invention extracts the amino acid in the tobacco with the acid solution of variable concentrations, comprises formic acid, acetate and hydrochloric acid solution.Experiment finds that 1mM acetate extracts solution and makes amino acid whose chromatographic peak bifurcated cracking such as Val, Nva, His, Ile and Leu, and along with the raising of concentration, and the phenomenon of chromatographic peak bifurcated cracking is more for obviously.Formic acid extracts solution also similar phenomenon.HCl extracts solution then can be at C
18Obtain peak shape preferably on the post.
3.3.2 the different extraction effects that extract solution
Experiment has contrasted several extraction effect of extraction solution commonly used, i.e. 70% methanol solution, 80% ethanolic solution and 0.1M HCl.Take by weighing the tobacco sample of equivalent,, come the extraction effect of three kinds of solution of comparison by contrast amino acid chromatographic peak area.By table 3 as seen, the amino acid content of 80% alcohol extract is minimum, and several amino acids content such as the Val of 70% methanol extraction, His, Tyr, Lys, Phe and Try all are starkly lower than uses 0.1M HCl to extract.Relatively comprehensive, the extraction effect of the hydrochloric acid solution of 0.1M is better.
The different extraction effect contrasts of extracting solution of table 3
3.3.3 the extraction effect of the HCl solution of variable concentrations
Take by weighing equivalent offal sample, contrast variable concentrations HCl extracts the extraction effect (table 4) of solution.0.1M HCl is relatively poor to the extraction effect of Ser, Glu, Lys and Arg, the extraction effect to Lys and Arg of 0.05MHCl is all bad.0.03M HCl obviously increases the extraction effect of Lys.Relatively comprehensive, select for use 0.03MHCl as extracting solution.
The extraction effect contrast of the HCl solution of table 4 variable concentrations
3.3.4 the extraction time
Take by weighing the 0.1g offal, add the 20mL extraction solution, under ultrasonic concussion, extract 15min, 30min, 45min and 60min respectively, cross the laggard LC-MS of 0.2 μ m filter membrane and analyze.Each sample advances two pins, and peak area is averaged.Experiment finds that the extraction time of 15min can reach extraction effect.Because sample weighting amount is less, the extraction solvent amount substantially exceeds sample weighting amount, and amino acid can be dissolved in hydrochloric acid solution faster, therefore can reach dissolution equilibrium faster.
3.4 method validation
20 kinds of amino acid whose content in tobacco to be measured differ greatly, and what have is lower than detectability, and as Cys, the then content that has is up to more than 0.2%, as Pro.In order to measure 20 seed amino acids simultaneously, the typical curve of two kinds of variable concentrations series has been set up in experiment, i.e. the typical curve that the higher Pro of content and Asn are set up a kind of concentration series is set up the typical curve of another kind of concentration series to other amino acid.Like this, a sample single injected sampling just can draw all amino acid whose test datas, reaches to save time the purpose of raising the efficiency.
The detection limit of method is determined with S/N=3 by the amino acid standard model of practical measurement series low concentration.The method detection limit is good, between 0.01～0.05 μ M (S/N=3), and related coefficient (r
2) all greater than 0.9977, precision is between 0.78～4.93RSD%.The recovery of method is determined in experiment by standard addition method.Accurately take by weighing offal 204.09mg, extract, replicate determination 5 times, the foundation of averaging and calculating as the recovery with the 20mL extract.Take by weighing three parts of offals then, be respectively 191.60mg, 209.80mg and 159.33mg, the sample treatment according to 2.4, mark-on makes mark-on concentration be respectively 1 μ M, 10 μ M and 20 μ M respectively.Wherein, content is lower than the amino acid of 1 μ M, only carries out 1 μ M mark-on and reclaim experiment, content is lower than the amino acid of 1.5 μ M, carry out the experiment of 1 μ M and 10 μ M mark-ons,, carry out the experiment of 10 μ M and 20 μ M mark-ons for content higher Asn and Pro.Between 81～108%, the recovery of Ile and Arg is lower substantially for the amino acid recovery, is respectively 75% and 53%.The detection limit of 20 seed amino acids, quantitative limit, the range of linearity, related coefficient, precision and the recovery see Table 5.
The detection limit (LOD) of table 5 20 seed amino acids, the range of linearity, related coefficient (r
2), precision
Claims (1)
1. one grow tobacco and the mass spectrometric analysis method of product amino acid, the testing sample extract carries out mass spectrophotometry after chromatographic resolution, it is characterized in that described mass spectrophotometry is a typical curve of making two kinds of variable concentrations series, use the electron spray ion trap tandem mass spectrometry under positive ion mode to tobacco in free amino acid carry out analyzing and testing; Described mass spectrophotometry condition is a nitrogen pressure: 0.64MPa; Helium pressure: 0.38MPa; Polarity: positive ionization; Scanning form: full scan; Acquisition time: 40min; Activationary time: 30ms; Sweep gas: 0LTQ unit; Spray voltage: 5kV; Capillary temperature: 350 ℃; Sweep limit: standard; Sweep speed: standard; Segmentation; Described segmentation is to be divided into 4 sections, and wherein the sheath gas of the 3rd segmentation and auxiliary gas are respectively 38LTQ unit and 0LTQ unit, and the sheath gas and the auxiliary gas of all the other segmentations are respectively 46LTQ unit and 19LTQ unit.
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| CN1532544A (en) * | 2003-03-20 | 2004-09-29 | 华中科技大学同济医学院附属同济医院 | Method for detecting organic acid/amino acid metabolic product by filter paper shect gas chromatography-mass spectrum analysis |
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| CN1532544A (en) * | 2003-03-20 | 2004-09-29 | 华中科技大学同济医学院附属同济医院 | Method for detecting organic acid/amino acid metabolic product by filter paper shect gas chromatography-mass spectrum analysis |
Non-Patent Citations (2)
| Title |
|---|
| Bernhardt Mayer-Helm et al.Method development for the determination of selected pesticides on tobacco by high-performace liquid chromatography-electrospray ionisation-tandem mass spectrometry.《Talanta》.2007,1184-1190. * |
| Hui-Ling lee et al.Liquid chromatography/tandem mass spectrometric method for the simultaneous determination of tobacco-specific nitrosamine NNK and its five metabolites.《Talanta》.2007,76-80. * |
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