CN103558328B - Liquid chromatography tandem mass spectrometry measures the method for sesamol in essence and flavoring agent - Google Patents
Liquid chromatography tandem mass spectrometry measures the method for sesamol in essence and flavoring agent Download PDFInfo
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- CN103558328B CN103558328B CN201310601418.3A CN201310601418A CN103558328B CN 103558328 B CN103558328 B CN 103558328B CN 201310601418 A CN201310601418 A CN 201310601418A CN 103558328 B CN103558328 B CN 103558328B
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Abstract
The present invention relates to the detection method of sesamol in a kind of essence and flavoring agent, the method adopts liquid chromatography tandem mass spectrometry to measure, and adopts quantified by external standard method.This detection method has short, easy and simple to handle, highly sensitive, the advantage such as the recovery is high and reproducible detection time, the method chromatographic condition makes the chromatographic peak of sesamol be separated better with impurity chromatographic peak, and there is the good range of linearity, detection is limited to 0.002 μ g/mL, the recovery between 90.8% ~ 102.5%, relative standard deviation RSD<5% (n=6).
Description
Technical field
The invention belongs to technical field of chemical detection, relate to the assay method of sesamol, specifically a kind of method by sesamol in LC-ESI-MS/MS essence and flavoring agent.
Background technology
Current food-safety problem is subject to social concerns day by day.The adjuvant safety issue of cigarette additive, especially essence and flavoring agent also more and more receives publicity.
Sesamol, has another name called 3,4-methylenedioxyphenol, has very strong oxidation resistance, is the antioxidant being usually used in food, medicine and essence and flavoring agent field.But along with the progress of science and technology, the carcinogenic activity of sesamol is progressively cognitive, toxicology test finds, sesamol is toxic to animal glandular stomach, and glandular stomach can be caused to sting knurl or canceration.Within 2006, sesamol has been classified as food forbidding adjuvant by Japan.
At present, development process, ultraviolet spectrophotometry, thin-layered chromatography (TLC), gas chromatography mass spectrometry method (GC-MS) and high performance liquid chromatography (HPLC) etc. are mainly contained to the detection method of sesamol.But the problems such as it is loaded down with trivial details that these methods all exist pre-treatment step, and detection time is longer.Such as, longer problem detection time is there is by gas chromatography mass spectrometry method (GC-MS), the time detecting a sample wants more than 40 minutes, poor with high performance liquid chromatography (HPLC) sensitivity, detection limit (LOD) >=80ng/mL, and the sample size needed comparatively large (>=1g).
In recent years, along with the development of liquid chromatography tandem mass spectrometry (LC-MS/MS) technology, LC-MS/MS technology is widely used in compound analysis.Liquid chromatography tandem mass spectrometry (LC-MS/MS) analytical technology all has obvious advantage in sensitivity or in selectivity, and analysis time is shorter.In order in the industrial production, the safety indexes of a large amount of essence and flavoring agent sample is effectively monitored, be badly in need of a kind ofly quick, simple, sensitive, efficient liquid chromatography mass method to detect sesamol in essence and flavoring agent.
Summary of the invention
The object of the present invention is to provide the assay method of sesame phenol content in a kind of essence spice for cigarette, to realize quick, the Accurate Determining to sesame phenol content in essence spice for cigarette.
The object of the invention is to be achieved through the following technical solutions:
A detection method for sesamol in essence and flavoring agent, the method adopts liquid chromatography tandem mass spectrometry to measure, and adopts quantified by external standard method.
In a preferred embodiment, in the essence and flavoring agent described in invention, the detection method of sesamol comprises the following steps:
(1) preparation of standard solution; Take sesamol standard items, be mixed with the sesamol standard working solution with concentration gradient with methyl alcohol;
(2) preparation of sample solution: use methanol extraction sample, prepares sample solution after then filtering;
(3) liquid chromatography-tandem mass spectrometry analysis: utilize liquid chromatography-tandem mass spectrometry instrument to carry out detection to standard solution and sample solution respectively and analyze;
(4) calculating of sesame phenol content in essence spice for cigarette.
In a preferred embodiment, the detection method of sesamol in the essence and flavoring agent described in invention, wherein said essence and flavoring agent is essence spice for cigarette, and preferably, described essence and flavoring agent sample uses the sesamol in methanol extraction sample; Preferably, the methyl alcohol of extraction is concentration is 8 ~ 12%(v/v) methanol aqueous solution, more preferably, the methyl alcohol of extraction is concentration is 10%(v/v) methanol aqueous solution.
In a preferred embodiment, the detection method of sesamol in the essence and flavoring agent described in invention, the mode wherein extracted is ultrasonic extraction.
In a preferred embodiment, the detection method of sesamol in the essence and flavoring agent described in invention, the preparation process of wherein said essence and flavoring agent sample is as follows: take appropriate essence and flavoring agent sample to be measured, add proper amount of methanol aqueous solution, ultrasonic extraction under room temperature, after filtration, obtains sample solution.Preferred filter type adopts filtering with microporous membrane, such as 0.22 μm of organic filter membrane or 0.45 μm of organic filter membrane.
In a specific embodiment, the preparation method of described essence and flavoring agent sample is specially: take about 0.1g sample, is placed in 25mL conical flask; Add 10% methanol aqueous solution 10mL, ultrasonic 30min under room temperature, by direct injected after 0.22 μm of organic membrane filtration.
In a preferred embodiment, the detection method of sesamol in the essence and flavoring agent described in invention, wherein chromatographiccondition is following one or more (i) in (v):
(i) adopt C18 chromatographic column,
Preferably, the specification of described chromatographic column is 50mm × 2.1mm i.d., 2.6 μm of particle diameters.
(ii) chromatogram column temperature is 28 ~ 32 DEG C, is preferably 30 DEG C,
(iii) sample size is 8 ~ 12 μ L, is preferably 10 μ L,
(iv) mobile phase: acetonitrile-ammonium acetate-acetic acid-aqueous solution,
Preferred mobile phase: A is acetonitrile, and B is 5mmoL/L ammonium acetate solution (containing 0.1% acetic acid), adopts isocratic elution program, volume ratio 50:50,
(v) flow velocity is 0.1 ~ 0.3ml/min, is preferably 0.2ml/min,
(vi) elution time is about 6min.
In a preferred embodiment, the detection method of sesamol in the essence and flavoring agent described in invention, wherein mass spectrophotometry condition is following one or more (i) in (iii):
(i) electricity consumption electrospray ionization trap tandem mass spectrum measures sesamol,
(ii) ion gun: electron spray ionisation source (ESI);
With Selective ion mode to qualitative, preferred ion pair is: daughter ion 109.0 (m/z), parent ion 139.1 (m/z).
In a specific embodiment, the detection method of sesamol in the essence and flavoring agent described in invention, wherein chromatographiccondition is: chromatographic column adopts Féraud door C
18liquid-phase chromatographic column, chromatogram column temperature is 30 DEG C, and sample size is 10 μ L, and flow velocity is 0.2ml/min; Mobile phase: A is acetonitrile, and B is 5mmoL/L ammonium acetate solution (containing 0.1% acetic acid), and adopt isocratic elution program, volume ratio 50:50, elution time is about 6min altogether.
In a preferred embodiment, the detection method of sesamol in the essence and flavoring agent described in invention, wherein mass spectrophotometry condition is: scan mode: positive ion scans; Detection mode: multiple-reaction monitoring (MRM); Electron spray voltage: 5000V; Ion source temperature: 350 DEG C; Assisted gas Gas1 pressure: 60psi; Assisted gas Gas2 pressure: 50psi; Remove a bunch voltage (DP): 40V; Impact energy (CE): 20V.
In a specific embodiment, the detection method of sesamol in the essence and flavoring agent described in invention, wherein said mass spectrophotometry condition is ion gun: electron spray ionisation source (ESI); Scan mode: positive ion scans; Detection mode: multiple-reaction monitoring (MRM); Electron spray voltage: 5000V; Ion source temperature: 350 DEG C; Assisted gas Gas1 pressure: 60psi; Assisted gas Gas2 pressure: 50psi; Remove a bunch voltage (DP): 40V; Impact energy (CE): 20V; Ion pair is chosen as: qualitative ion pair m/z139.1>109.0,139.1>81.1, quota ion is to m/z139.1>109.0.
In a preferred embodiment, the detection method of sesamol in essence and flavoring agent described in invention, wherein the preparation steps of the standard solution that external standard method is used is as follows: take 0.1g sesamol, be accurate to 0.0001g, be transferred in 1000mL volumetric flask after dissolving with methyl alcohol, and constant volume, be decided to be standard reserving solution; Pipette 0.01mL respectively, the standard reserving solution of 0.05mL, 0.1mL, 0.5mL, 1.0mL, in 100mL volumetric flask, uses extractant constant volume, then the concentration of sesamol is 0.01 μ g/mL, 0.05 μ g/mL, 0.1 μ g/mL, 0.5 μ g/mL, 1.0 μ g/mL.
In a preferred embodiment, the detection method of sesamol in essence and flavoring agent described in invention, wherein sesame phenol content computing method for: first with the chromatographic peak area of the object detected by standard solution, regretional analysis is carried out to its respective concentration, obtains typical curve; The chromatographic peak area of the object then detected by sample solution, substitutes into typical curve, namely obtains the sesamol concentration in sample, can calculate the content of sesamol in essence spice for cigarette thus.
Detection method of the present invention is optimized the disposal route of sample and chromatographic condition, reaches following effect:
(1) detection time is short: adopting the present invention to measure the sesame phenol content cycle in essence spice for cigarette only needs about 6 minutes; More than 220 sample can be detected every day.
(2) the present invention has easy and simple to handle, highly sensitive, that the recovery is high and reproducible advantage: the chromatographic condition of the inventive method makes the chromatographic peak of sesamol be separated better with impurity chromatographic peak, and there is good linear dependence, detection is limited to 0.002 μ g/mL, average recovery rate is 90.8% ~ 102.5%, average relative standard deviation RSD<5% (n=6).
Accompanying drawing explanation
Fig. 1 is the process flow diagram of detection method of the present invention;
Fig. 2 is that in embodiment 1, concentration is the chromatogram of sesamol in the standard solution of 0.5 μ g/mL;
Fig. 3 is the chromatogram of sample solution in embodiment 1;
Fig. 4 is the mass spectrogram of sesamol;
Fig. 5 is the typical curve that embodiment 1 obtains.
Embodiment
Below in conjunction with embodiment, embodiment of the present invention are described in detail, but it will be understood to those of skill in the art that the following example only for illustration of the present invention, and should not be considered as limiting scope of the present invention.Unreceipted actual conditions person in embodiment, the condition of conveniently conditioned disjunction manufacturer suggestion is carried out.Agents useful for same or the unreceipted production firm person of instrument, being can by the conventional products of commercial acquisition.
Embodiment 1
The present embodiment detects sesame phenol content in essence spice for cigarette, and detection method is as described below, and the process flow diagram of described detection method as shown in Figure 1.
(1) take 0.1g sesamol (analyzing pure), be accurate to 0.0001g, be transferred in 1000mL volumetric flask after dissolving with methyl alcohol, and constant volume, be decided to be standard reserving solution; Pipette 0.01mL respectively, 0.05mL, 0.1mL, 0.5mL, the standard reserving solution of 1.0mL in 100mL volumetric flask, with 10%(v/v) methanol aqueous solution constant volume, then the concentration of sesamol is 0.01 μ g/mL, 0.05 μ g/mL, 0.1 μ g/mL, 0.5 μ g/mL, 1.0 μ g/mL.The 4 DEG C of preservations of mark liquid lucifuge, under being positioned over normal temperature, can use after reaching normal temperature when taking.Do weekly a graticule;
(2) preparation of sample solution: the essence spice for cigarette sample to be measured taking about 0.1g, is placed in 25mL conical flask; Accurately add 10% methanol aqueous solution 10mL, ultrasonic 30min under room temperature, after 0.22 μm of organic membrane filtration, obtain sample solution, to be analyzed in 4 DEG C of preservations;
(3) chromatographiccondition is for adopting Féraud door C
18liquid-phase chromatographic column, chromatogram column temperature is 30 DEG C, and sample size is 10 μ L, and flow velocity is 0.2ml/min; Mobile phase: A is acetonitrile, and B is 5mmoL/L ammonium acetate solution (containing 0.1% (v/v) acetic acid), adopts isocratic elution program, volume ratio 50:50.Elution time is 6min altogether.Concentration is that the stratographic analysis of the standard solution of 0.5 μ g/mL the results are shown in Figure 2; The stratographic analysis of sample solution the results are shown in Figure 3;
(4) mass spectrophotometry condition is ion gun: electron spray ionisation source (ESI); Scan mode: positive ion scans; Detection mode: multiple-reaction monitoring (MRM); Electron spray voltage: 5000V; Ion source temperature: 350 DEG C; Assisted gas Gas1 pressure: 60psi; Assisted gas Gas2 pressure: 50psi; Remove a bunch voltage (DP): 40V; Impact energy (CE): 20V.The mass spectrogram of sesamol is shown in Fig. 4.The principle order high according to fragment abundance, selectivity is high, determines that ion pair is chosen as: qualitative ion pair m/z139.1>109.0,139.1>81.1, quota ion is to m/z139.1>109.0.
(4) calculating of sesame phenol content in essence spice for cigarette: first with the chromatographic peak area of the object detected by standard solution, regretional analysis is carried out to its respective concentration, obtain typical curve (see figure 5); The data such as the regression equation corresponding with typical curve, related coefficient are as shown in table 1.
The typical curve of table 1 sesamol and detectability
Then the chromatographic peak area detecting object recorded by sample, substitutes into typical curve, namely obtains the sesamol concentration in sample, and calculate the content of sesamol in essence spice for cigarette thus, computing formula is as follows
m=（A×S）/n
In formula:
The content of sesamol in m-every gram essence spice for cigarette, unit is microgram every gram (μ g/g);
The concentration (μ g/mL) of sesamol in A-sample;
S-liquor capacity (mL);
The quality (g) of n-take sample.
From table 1 and Fig. 4, the chromatographic condition adopted makes the chromatographic peak of sesamol be separated better with impurity chromatographic peak, and has good correlativity, and detectability is at 0.002 μ g/mL.The content of the sesamol of the present embodiment sample is 5.1 μ g/g.
Embodiment 2
The present embodiment detects the repeatability of the inventive method and recovery of standard addition, and detection method is as described below.
Adopt the recovery of Standard Addition Method for Determination method of the present invention.Take essence spice for cigarette sample to be measured (this sample is identical with essence and flavoring agent sample used in embodiment 1 step (2)) 0.1g, each three parts, add 0.001mL respectively wherein, 0.005mL, the sesamol standard reserving solution of preparation in 0.01mL embodiment 1 step (1), then mark-on sample solution is prepared according to the compound method in embodiment 1 step (2) " preparation of sample solution ", each sample measures 6 times respectively, the condition of chromatogram and mass spectrophotometry is with embodiment 1, according to the recovery of standard addition of sesamol in Analysis result calculation this method essence spice for cigarette, result is as shown in table 2,
In table 2 essence spice for cigarette sesamol the recovery and repeatability (n=6)
As can be seen from Table 2, in 3 mark-on levels, utilize the method to detect the recovery of sesamol in essence spice for cigarette between 90.8% ~ 102.5%, the relative standard deviation of sample tests is less than 5%, illustrates that the recovery of this law is higher, and repeatability better.
Claims (12)
1. the detection method of sesamol in essence and flavoring agent, the method adopts liquid chromatography tandem mass spectrometry to measure, and adopt quantified by external standard method, wherein chromatographiccondition is: chromatographic column adopts C
18chromatographic column, chromatographic column specification is 50mm × 2.1mm i.d., 2.6 μm of particle diameters, and chromatogram column temperature is 28 ~ 32 DEG C, and sample size is 8 ~ 12 μ L, and flow velocity is 0.2ml/min; Mobile phase: A is acetonitrile, and B is 5mmoL/L ammonium acetate solution, and containing 0.1% acetic acid in this ammonium acetate solution, adopt isocratic elution program, volume ratio 50 ︰ 50, elution time is about 6min altogether.
2. the detection method of claim 1, wherein said essence and flavoring agent is essence spice for cigarette.
3. the detection method of claim 1, uses the sesamol in the essence and flavoring agent described in methanol extraction.
4. the detection method of claim 3, the methyl alcohol wherein extracted is the methanol aqueous solution of concentration 8 ~ 12v/v%.
5. the detection method of claim 3, the methyl alcohol wherein extracted is the methanol aqueous solution of concentration 10v/v%.
6. the detection method of claim 3 or 4, the mode wherein extracted is ultrasonic extraction.
7. the detection method of claim 1, the preparation process of the sample solution of wherein said essence and flavoring agent is as follows: take appropriate essence and flavoring agent sample to be measured, add proper amount of methanol aqueous solution, ultrasonic extraction under room temperature, after filtration, obtain sample solution.
8. the detection method of claim 1, wherein chromatogram column temperature is 30 DEG C, and sample size is 10 μ L.
9. the detection method of claim 1, what wherein mass spectrophotometry condition was following (i) in (iii) is one or more:
I () electricity consumption electrospray ionization trap tandem mass spectrum measures sesamol,
(ii) ion gun: electron spray ionisation source (ESI);
(iii) with Selective ion mode to qualitative.
10. the detection method of claim 9, wherein Selective ion mode to for: qualitative ion pair m/z139.1>109.0,139.1>81.1, quota ion is to m/z 139.1>109.0.
The detection method of 11. claims 9 or 10, wherein mass spectrophotometry condition is: scan mode: positive ion scans; Detection mode: multiple-reaction monitoring (MRM); Electron spray voltage: 5000V; Ion source temperature: 350 DEG C; Assisted gas Gas1 pressure: 60psi; Assisted gas Gas2 pressure: 50psi; Remove a bunch voltage (DP): 40V; Impact energy (CE): 20V.
The detection method of 12. claims 1, wherein the preparation steps of the standard solution that external standard method is used is as follows: take 0.1g sesamol, be accurate to 0.0001g, is transferred in 1000mL volumetric flask after dissolving with methyl alcohol, and constant volume, be decided to be standard reserving solution; Pipette 0.01mL respectively, the standard reserving solution of 0.05mL, 0.1mL, 0.5mL, 1.0mL, in 100mL volumetric flask, uses extractant constant volume, then the concentration of sesamol is 0.01 μ g/mL, 0.05 μ g/mL, 0.1 μ g/mL, 0.5 μ g/mL, 1.0 μ g/mL.
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