CN105510504B - Method for measuring imidazole, musk xylene and sesamol residue quantity in edible essence - Google Patents
Method for measuring imidazole, musk xylene and sesamol residue quantity in edible essence Download PDFInfo
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Abstract
The invention discloses a method for measuring the imidazole, musk xylene and sesamol residue quantity in edible essence and namely discloses a method for quantitatively analyzing the imidazole, musk xylene and sesamol residue quantity in edible essence. The method is a method for measuring the imidazole, musk xylene and sesamol residue quantity in edible essence based on a gas chromatography-tandem mass spectrometer. The method includes the steps of preparation of an internal standard solution, a standard work solution and a sample solution, gas chromatography-tandem mass spectrometer analysis, calculation of a measurement result, and the like. The method is easy and convenient to operate, sensitive in response and accurate in qualitative and quantitative analysis, and interference caused when sample matrixes are complex is effectively reduced.
Description
Technical field
The present invention relates to it is a kind of based on gas chromatogram-tandem mass spectrometer determine imidazoles in edible essence, musk xylene and
The method of sesamol residual quantity, belongs to food additive physical and chemical index detection technique field.
Background technology
Imidazoles (molecular structural formula is as follows), i.e. 1,3- ribavirins are a five-ring heterocycles armaticity organic compound,
Chemical formula is C3H4N2, molecular weight is 68.08, and No. CAS is 288-32-4, and it is also an alkaloid, white or light yellow solid
Body is crystallized, and soluble in water, ethanol, ether, chloroform, pyridine are slightly soluble in benzene, atomic to be dissolved in petroleum ether, with acidity, it may have alkali
Property.Imidazoles is plane five-membered cyclic compound, there is permanent dipole between its two nitrogen-atoms, and polarity is very strong, and dipole moment is
3.61D, and it is intermolecular there is hydrogen bond association, result in imidazoles and there is unusual high boiling point (256 DEG C).There is one in molecule
6 electron conjugated big π keys, therefore with typical armaticity.Remaining in pair of electrons, ring is provided with hydrogen with the nitrogen-atoms that σ keys are connected
Four atoms respectively provide an electronics bonding.Toxicology data shows that the material is poisonous, is 18.80mg/ to its mouse oral LD50
Kg, injection LD50 are 610mg/kg, and its toxicity and means of defence are similar to ethylenediamine.Additionally, the material may have danger to environment
Evil, should give to water body and pay special attention to.Comprehensive literature result, it is, in general, that imidazoles is not directly used as food additive,
It is introduced into probably as by-product greatly very much and uses.
Musk xylene (molecular structural formula is as follows), also known as 2,4,6- trinitro- -3, the 3- dimethyl -5- tert-butyl groups
Benzene, by meta-xylene with after isobutene. alkylation again nitration reaction and obtain, it is single compound, and different from Moschus day is belonged to
Right multicomponent mixture.Chemical formula is C12H15N3O6, molecular weight is 297.27, and No. CAS is 81-15-2, and yellow powder is presented
Shape or acicular crystal, have thicker musk odor, and fusing point is 112.5-114.5 DEG C, and boiling point is 200-202 DEG C, in 95% ethanol
Dissolubility be 7g/L (25 DEG C), be soluble in benzyl benzoate and diethyl phthalate, water insoluble, glycerol and the third two
Alcohol, there is dry sweet Moschus sample animal fragrance, and imposing manner is weaker but lasting is long.Musk xylene is used as high persistency, high biological accumulation
Property material, by EU chemicals management administration (ECHA) be classified as high attention rate material (Substances of Very High
Concern,SVHC).European Union's " health care and environmental science committee " carcinogenic, mutagenesis cause genotoxicity (CMR) expert work
Musk xylene is classified as the 3rd class material by group in the 29th meeting.International daily use chemicals fragrance association (IFRA) plans to be marked in IFRA
Advise that musk xylene is used not as daily use chemicals fragrance component in accurate 44th revised draft.International daily use chemicals spice institute (RIFM)
Also advise that musk xylene must not be used for lip product or dental care product.China's cosmetics health specification and European Union's cosmetics
Specify musk xylene for regulated substance in components of cosmetics (no in code (Council Direc2tive 76/768/EEC)
Dental care product must be used for), the limitation in essence, floral water and other products is respectively 1.0%, 0.4% and 0.03%.
Sesamol (molecular structural formula is as follows), also known as 3,4- methylenedioxyphenols, chemical formula is C7H6O3, molecule
Measure as 138.12, No. CAS is 533-31-3, and fusing point is 62-65 DEG C, and boiling point is 113-116 DEG C, is slightly soluble in water, and white is presented extremely
Light yellow crystals powder or granule, are soluble in ethanol, ether, and the synthetic technology of sesamol mainly has three：The first is from sesame
Extract in Oleum Sesami, it two is to carry out from pepper amine complete synthesis, and it three is semi-synthetic route from heliotropin.Semen Sesami
The cause tumor as shown by data of phenol：Rat oral TDLo is 874mg/kg/2Y-C, the RTECS standards of tumor-carcinogenic, gastrointestinal tract-swollen
Tumor；Its mouse oral TDLo is 1092mg/kg/2Y-C, the RTECS standards of tumor-carcinogenic, gastrointestinal tract-tumor；Rat oral TD is
1092mg/kg/2Y-C, the RTECS standards of tumor-carcinogenic, gastrointestinal tract-tumor；Its mouse oral TD be 1612mg/kg/2Y-C, tumor-
Carcinogenic RTECS standards, gastrointestinal tract-tumor.2006, Japanese MHLW was announced in the 42 kinds of food additive for disabling just
Including sesamol.
Edible essence is chemical combination material indispensable in daily life, production in light industry, and its safety is food totality
The very important one side of safety, and the source of foodsafety control, are at all raw materials for production, for that purpose it is necessary to right
The chemical combination material paid close attention in edible essence is monitored.Literature survey shows, existing to detect imidazoles, musk xylene and sesamol
Method mainly have gas chromatogram and liquid chromatograph.In view of imidazoles, musk xylene and sesamol are possible in edible essence
It is used, therefore explores a kind of method for fast and accurately detecting imidazoles, musk xylene and sesamol simultaneously, to edible perfume
The residual quantity of the series material control effectively in essence, and then ensures the safety in utilization of edible additive, just seems very
It is urgent and very necessary.
The content of the invention
It is contemplated that overcoming existing technological deficiency, there is provided one kind determines edible using gas chromatography tandem mass spectrometry instrument
The method of imidazoles, musk xylene and sesamol residual quantity in essence, trace in the method energy accurate quantification analysis edible essence
The residual quantity of imidazoles, musk xylene and sesamol, measurement result is accurate, sensitivity is high, and matrix interference is few.
Specifically, present invention employs technical scheme below：
A kind of method of imidazoles, musk xylene and sesamol residual quantity in measure edible essence, it is characterised in that described
Method is comprised the following steps：
(1) preparation of inner mark solution：The use of ethanol is solvent with phenylethyl propionate as internal standard substance, prepares inner mark solution；
(2) preparation of standard working solution：Standard substance with imidazoles, musk xylene and sesamol are used as object
Ethanol is solvent, and Jing stepwise dilutions are prepared into Standard Stock solutions, are then respectively adding a certain amount of inner mark solution, are prepared into mark
Quasi- working solution；
(3) preparation of sample solution：A certain amount of edible essence sample is weighed in centrifuge tube, a certain amount of water is added,
The inner mark solution of certain volume is accurately moved into again, is uniformly dispersed with eddy mixer；The ethanol of certain volume is added followed by, is surpassed
Sound is extracted, and adds a certain amount of anhydrous sodium sulfate, is stood after shaking up, be centrifuged in centrifuge, take the supernatant excessively organic
Phase filter membrane, obtains sample solution；
(4) gas chromatography tandem mass spectrometry instrument analysis：With gas chromatography tandem mass spectrometry instrument to standard working solution and sample
Solution is tested and analyzed；
(5) drafting of standard working curve and the calculating of sample result.
Wherein, the preparation of step (1) inner mark solution includes：
(1a) internal standard storing solution：0.2g phenylethyl propionates are weighed, 0.0001g is accurate to, is dissolved with ethanol and is settled to
In 100mL volumetric flasks, shake up；
(1b) inner mark solution：0.1mL internal standard storing solutions are accurately pipetted, is settled in 100mL volumetric flasks with ethanol, shaken up.
In addition, the preparation of step (2) standard working solution includes：
(2a) primary standard storing solution：The each 0.1g of imidazoles, musk xylene and sesamol is weighed respectively, is accurate to
0.0001g, is dissolved and is settled in 100mL volumetric flasks with ethanol, is shaken up；
(2b) secondary standard storing solution：1mL primary standard storing solutions are accurately pipetted, in the volumetric flask of 100mL, ethanol is used
Dilute and be settled to scale；
(2c) standard working solution：The μ L of secondary standard storing solution 20,50 μ L, 100 μ L, 200 μ L, 500 μ are accurately pipetted respectively
In the volumetric flask of L and 1000 μ L to 10mL, then 100 μ L inner mark solutions are added respectively accurately, with ethanol dilution and be settled to scale,
Obtain series standard working solution.
Further, the preparation of step (3) sample solution includes：0.5g samples are weighed, 0.0001g is accurate to, 50mL is placed in
In centrifuge tube, 1mL water is added, accurately moves into 100 μ L inner mark solutions, be uniformly dispersed with eddy mixer, add 8mL ethanol,
Be placed in ultrasonic extraction 20min in supersonic generator, add 0.5g anhydrous sodium sulfates, 5min is stood after shaking up, after centrifugation
5min is centrifuged under 4000r/min rotating speeds in machine, the supernatant is taken and is crossed 0.45 μm of organic phase filter membrane, obtain sample feeding solution.
Preferably, the instrumental conditions of step (4) GC-MS/MS analyses are：Adopt specification for 30m × 0.25mm ×
0.25 μm of HP-INNOWAX capillary chromatographic columns；Carrier gas is helium, and constant current speed is 1.0mL/min；Input mode：Sample size
For 1 μ L, pulse Splitless injecting samples, sample introduction pulsating pressure is 25psi, and the time is 1min；Injector temperature is 250 DEG C；Transmission line
Temperature is 260 DEG C；It is 100 DEG C that heating schedule is initial temperature, and with the speed of 3 DEG C/min 240 DEG C are increased to, and keeps 5min；Matter
Analysis of spectrum condition is：Ionization mode be EI sources, positive ion mode；Ion source temperature：230℃；Quadrupole rod temperature：It is 150 DEG C；
Collision gas：Nitrogen, flow velocity 1.5mL/min, carrier gas helium flow velocity is 2.25mL/min；Multiple-reaction monitoring MRM patterns, detail parameters
It is listed in the table below:
The MRM parameter situations of object
In above method, step (5) Specification Curve of Increasing and result are calculated as follows：With object in standard working solution
Ratio with interior target concentration is abscissa, and object is carried out linear with the ratio of interior target peak area as vertical coordinate with chromatogram
Regression analyses, obtain standard working curve, by object in the sample solution measured under the same terms and interior target chromatographic peak face
Product ratio, substitutes into standard working curve, and according to following equation the content of object in edible essence sample is tried to achieve：
In formula：
W --- imidazoles, musk xylene and sesamol residual quantity in edible essence, unit is mg/kg；
The peak area of A --- imidazoles, musk xylene and sesamol；
As --- the peak area of internal standard substance phenylethyl propionate；
The intercept of b --- standard working curve；
Ms --- the quality of addition internal standard substance phenylethyl propionate, unit is μ g；
The slope of a --- standard working curve；
M --- the quality of edible essence sample, unit is to prop up.
Beneficial effect：The detection method of the present invention is optimized to sample treatment and chromatograph mass spectrum analysis condition
Confirm.Compared with prior art, the present invention has following excellent results：
(1) the inventive method creative use gas chromatography tandem mass spectrometry instrument determines imidazoles, musk xylene in edible essence
With the other residual quantity of sesamol trace level, it is low to solve such material residual quantity level, and complex matrices divide object
The impact of the factors such as analysis serious interference.
(2) present invention is in sample pretreatment process, for edible essence sample source extensively, the feature that differs of complexity,
Dissolved using the dicyandiamide solution of few dosage water+multiple dose ethanol, it is right in conjunction with being mixed uniformly using eddy mixer
Object is extracted.Method is novel, and easy to be reliable, strong innovation compensate for the deficiency of current methods.
(3) the inventive method utilizes inner mark method ration, without accurate constant volume, and be able to can reduce by pre-treating method weight
The error that existing property and instrument precision problem are brought.
Description of the drawings
Fig. 1 is the flow chart of assay method of the present invention；
Fig. 2 is that the ion of imidazoles, musk xylene and sesamol and internal standard phenylethyl propionate in standard working solution is checked colors
Spectrogram；
Fig. 3 be in edible essence (mark-on) sample imidazoles, musk xylene and sesamol and internal standard phenylethyl propionate from
Son is to chromatogram.
Specific embodiment
A kind of method that the present invention discloses imidazoles, musk xylene and sesamol residual quantity in quantitative analysiss edible essence,
Comprise the following steps：
(1) preparation of inner mark solution：The use of ethanol is solvent with phenylethyl propionate as internal standard substance, prepares inner mark solution；
(2) preparation of standard working solution：Standard substance with materials such as imidazoles, musk xylene and sesamols are as target
Thing, is solvent using ethanol, and Jing stepwise dilutions are prepared into Standard Stock solutions, are then respectively adding a certain amount of inner mark solution,
It is prepared into standard working solution；
(3) preparation of sample solution：A certain amount of edible essence sample is weighed in centrifuge tube, a certain amount of water is added,
The inner mark solution of certain volume is accurately moved into again, is uniformly dispersed with eddy mixer；The ethanol of certain volume is added followed by, is surpassed
Sound is extracted, and adds a certain amount of anhydrous sodium sulfate, is stood after shaking up.In centrifuge be centrifuged, take the supernatant excessively organic
Phase filter membrane, obtains sample solution；
(4) gas chromatography tandem mass spectrometry instrument analysis：Standard is worked with gas chromatography tandem mass spectrometry instrument (GC-MS/MS)
Solution and sample solution are tested and analyzed；
(5) drafting of standard working curve and the calculating of sample result.
The preparation of described inner mark solution, specifically includes following steps：(1) internal standard storing solution：Weigh 0.2g (to be accurate to
0.0001g) phenylethyl propionate, is dissolved and is settled in 100mL volumetric flasks with ethanol, is shaken up.(2) inner mark solution：Accurately pipette
0.1mL internal standard storing solutions, are settled in 100mL volumetric flasks with ethanol, are shaken up.
The preparation of described standard working solution specifically includes following steps：(1) primary standard storing solution：Miaow is weighed respectively
The each 0.1g of azoles, musk xylene and sesamol, is accurate to 0.0001g, is dissolved and is settled in 100mL volumetric flasks with ethanol, shakes
It is even.(2) secondary standard storing solution：1mL primary standard storing solutions are accurately pipetted, in the volumetric flask of 100mL, with ethanol dilution simultaneously
It is settled to scale.(3) standard working solution：Accurately pipette respectively the μ L of secondary standard storing solution 20,50 μ L, 100 μ L, 200 μ L,
In the volumetric flask of 500 μ L and 1000 μ L to 10mL, then 100 μ L inner mark solutions are added respectively accurately, with ethanol dilution and be settled to
Scale, obtains series standard working solution.
The preparation of described sample solution specifically includes procedure below：Weigh 0.5g (being accurate to 0.0001g) in 50mL from
In heart pipe, 1mL water is added, accurately move into 100 μ L inner mark solutions, be uniformly dispersed with eddy mixer, add 8mL ethanol, put
The ultrasonic extraction 20min in supersonic generator, adds 0.5g anhydrous sodium sulfates, and 5min is stood after shaking up.After centrifuge
It is interior that 5min is centrifuged under 4000r/min rotating speeds, take the supernatant and cross 0.45 μm of organic phase filter membrane, obtain sample feeding solution.
Described GC-MS/MS is analyzed, and its instrumental conditions is：Using HP-INNOWAX (30m × 0.25mm × 0.25 μ
M) capillary chromatographic column；Carrier gas is helium, and constant current speed is 1.0mL/min；Input mode：Sample size be 1 μ L, pulse regardless of
Stream sample introduction, sample introduction pulsating pressure is 25psi, and the time is 1min；Injector temperature is 250 DEG C；Transmission line temperature is 260 DEG C；Rise
It is 100 DEG C that warm program is initial temperature, and with the speed of 3 DEG C/min 240 DEG C are increased to, and keeps 5min.Its mass spectral analyses condition is：
Ionization mode be EI sources, positive ion mode；Ion source temperature：230℃；Quadrupole rod temperature：It is 150 DEG C；Collision gas：Nitrogen,
Flow velocity 1.5mL/min, carrier gas (helium) flow velocity is 2.25mL/min；Multiple-reaction monitoring (MRM) pattern, detail parameters are listed in down
Table.
The MRM parameter situations of object
Described Specification Curve of Increasing and result is calculated as follows：With object in standard working solution and interior target concentration it
Than for abscissa, object carries out linear regression analyses with the ratio of interior target peak area as vertical coordinate with chromatogram, is marked
Quasi- working curve.By object in the sample solution measured under the same terms and interior target chromatographic peak area ratio, standard work is substituted into
Make curve, the content of object in edible essence sample is tried to achieve according to following equation：
In formula：
W --- imidazoles, musk xylene and sesamol residual quantity in edible essence, unit is milligrams per kilogram (mg/kg)；
The peak area of A --- imidazoles, musk xylene and sesamol；
As --- the peak area of internal standard substance phenylethyl propionate；
The intercept of b --- standard working curve；
Ms --- the quality of addition internal standard substance phenylethyl propionate, unit is microgram (μ g)；
The slope of a --- standard working curve；
M --- the quality of edible essence sample, unit is to prop up.
Below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1
The present embodiment is as follows to the detection method of trace imidazoles, musk xylene and sesamol residual quantity in edible essence
(flow chart of the detection method is as shown in Figure 1)：
(1) preparation of inner mark solution
1. internal standard storing solution：0.2060g phenylethyl propionates are accurately weighed, in the volumetric flask of 100mL, is dissolved simultaneously with ethanol
It is settled to scale.2. inner mark solution：0.1mL internal standard storing solutions are accurately pipetted, in the volumetric flask of 100mL, with ethanol dilution simultaneously
It is settled to scale.Wherein the concentration of phenylethyl propionate is 2.06 μ g/mL.
(2) preparation of standard working solution
1. primary standard storing solution：Primary standard storing solution：It is each that imidazoles, musk xylene and sesamol are weighed respectively
0.1000g, 0.1020g and 0.1019g, are dissolved and are settled in 100mL volumetric flasks with ethanol, are shaken up.2. secondary standard deposit
Liquid：1mL primary standard storing solutions are accurately pipetted, in the volumetric flask of 100mL, with ethanol dilution and scale is settled to.3. standard
Working solution：The μ L of secondary standard storing solution 20,50 μ L, 100 μ L, 200 μ L, 500 μ L and 1000 μ L to 10mL are accurately pipetted respectively
Volumetric flask in, then add 100 μ L inner mark solutions respectively accurately, with ethanol dilution and be settled to scale, obtain series standard work
Solution.The concentration range of wherein imidazoles be 0.02~1.00 μ g/mL, musk xylene concentration range be 0.0204~1.02 μ
The concentration range of g/mL and sesamol is 0.0202~1.019 μ g/mL, and wherein the concentration of internal standard phenylethyl propionate is 0.0206 μ
g/mL。
(3) preparation of sample solution
Edible essence with market pin weighs 0.5132g samples in 50mL centrifuge tubes to analyze object, adds
1mL water, accurately moves into 100 μ L inner mark solutions, is uniformly dispersed with eddy mixer, adds 8mL ethanol, is placed in ultrasound wave generation
Ultrasonic extraction 20min in device, adds 0.5g anhydrous sodium sulfates, and 5min is stood after shaking up.In centrifuge in 4000r/min
5min is centrifuged under rotating speed, the supernatant is taken and is crossed 0.45 μm of organic phase filter membrane, obtain sample feeding solution.
(4) gas chromatography tandem mass spectrometry analysis
Taking the standard working solution and sample solution to be measured of 6 variable concentrations respectively carries out gas chromatography tandem mass spectrometry analysis
(in the standard working solution, typical mark-on sample solution the chromatogram of object and internal standard substance as shown in Figure 2 to 3).
Its instrumental conditions is：Using HP-INNOWAX (30m × 0.25mm × 0.25 μm) capillary chromatographic column；Carrier gas
For helium, constant current speed is 1.0mL/min；Input mode：Sample size is 1 μ L, pulse Splitless injecting samples, and sample introduction pulsating pressure is
25psi, the time is 1min；Injector temperature is 250 DEG C；Transmission line temperature is 260 DEG C；It is 100 that heating schedule is initial temperature
DEG C, 240 DEG C are increased to the speed of 3 DEG C/min, keep 5min.Its mass spectral analyses condition is：Ionization mode be EI sources, cation
Pattern；Ion source temperature：230℃；Quadrupole rod temperature：It is 150 DEG C；Collision gas：Nitrogen, flow velocity 1.5mL/min, carrier gas (helium
Gas) flow velocity be 2.25mL/min；Multiple-reaction monitoring (MRM) pattern, detail parameters are listed in the table below.
The MRM parameter situations of object
(5) Specification Curve of Increasing and result are calculated
First, the ratio with object in standard working solution and interior target concentration is as abscissa, with object in chromatogram
Ratio with interior target peak area is vertical coordinate, carries out linear regression analyses, obtains standard working curve.Take the standard of least concentration
Working solution, does 9 Parallel testing analyses, calculates its standard deviation, and with the corresponding concentration of 3 times of standard deviation, conversion draws
The detection limit of method.The data such as regression equation, correlation coefficient, the detection limit corresponding with standard working curve see the table below.
The working curve and detection limit of analysis method
By object in the sample solution measured under the same terms and interior target chromatographic peak area ratio, standard work is substituted into bent
Line, according to following equation the content of object in edible essence sample is tried to achieve.
In formula：
W --- imidazoles, musk xylene and sesamol residual quantity in edible essence, unit is milligrams per kilogram (mg/kg)；
The peak area of A --- imidazoles, musk xylene and sesamol；
As --- the peak area of internal standard substance phenylethyl propionate；
The intercept of b --- standard working curve；
Ms --- the quality of addition internal standard substance phenylethyl propionate, unit is microgram (μ g)；
The slope of a --- standard working curve；
M --- the quality of edible essence sample, unit is to prop up.
8 kinds of main Pyrazine fragrance matter testing results see the table below in edible essence sample main flume in the present embodiment：
| Material title | Content (mg/kg) |
| Imidazoles | ND |
| Musk xylene | ND |
| Sesamol | ND |
Remarks：ND represents that result is less than detection limit not detect.
Embodiment 2
The present embodiment is as follows to the precision of the present invention and the detection method of recovery of standard addition：
Essence sample used adds appropriate standard solution to it and obtains test sample to analyze object with embodiment 1
Product.Then, withinday precision experiment has been carried out respectively, and withinday precision experiment is same sample parallel assay under identical conditions
6 times (same batch processed), calculates respectively the relative standard deviation (RSD) of 6 parallel determinations, and measurement result see the table below.
Result shows in table, the in a few days repeated RSD of this experimental technique<10%, for the quantitative analyses of trace materialss, show
Method has good precision.
With test specimen used by replica test to analyze object, processed according to above-mentioned sample-pretreating method, plus
Enter the standard specimen of the suitable content of its burst size, carry out substrate mark-on test, as a result see the table below.As can be seen from the table, sample
Between 84.50%~118.88%, illustration method has preferable accuracy to recovery of standard addition.
| Material title | RSD (%) |
| Imidazoles | 89.65 |
| Musk xylene | 94.37 |
| Sesamol | 104.24 |
What the standard solution used in the present embodiment was only illustrated by taking one of concentration as an example, other concentration value institutes
The standard solution Jing gas chromatography tandem mass spectrometries instrument of preparation analyzes obtained standard curve and regression equation and above-described embodiment
Identical, here is not being enumerated.Illustrated embodiment is intended merely to be better understood from the inventive method, not with any restriction
The method of effect, i.e. said method or the above-mentioned situation of equivalent is all contained in the protection domain of technical scheme.
Embodiments of the present invention are described in detail above in conjunction with accompanying drawing, but the invention is not restricted to above-mentioned enforcement
Mode, in the ken that art those of ordinary skill possesses, can be with without departing from present inventive concept
Under the premise of make a variety of changes.
Claims (5)
1. it is a kind of determine edible essence in imidazoles, musk xylene and sesamol residual quantity method, it is characterised in that the side
Method is comprised the following steps：
(1) preparation of inner mark solution：The use of ethanol is solvent with phenylethyl propionate as internal standard substance, prepares inner mark solution；
(2) preparation of standard working solution：Standard substance with imidazoles, musk xylene and sesamol as object, using ethanol
For solvent, Jing stepwise dilutions are prepared into Standard Stock solutions, are then respectively adding a certain amount of inner mark solution, are prepared into standard work
Make solution；
(3) preparation of sample solution：A certain amount of edible essence sample is weighed in centrifuge tube, a certain amount of water is added, then it is accurate
The inner mark solution of certain volume is really moved into, is uniformly dispersed with eddy mixer；It is added followed by the ethanol of certain volume, ultrasound extraction
Take, add a certain amount of anhydrous sodium sulfate, stand after shaking up, be centrifuged in centrifuge, take the supernatant and cross organic faciess filter
Film, obtains sample solution；
(4) gas chromatography tandem mass spectrometry instrument analysis：With gas chromatography tandem mass spectrometry instrument to standard working solution and sample solution
Tested and analyzed；
(5) drafting of standard working curve and the calculating of sample result,
Wherein, the instrumental conditions of step (4) GC-MS/MS analyses are：Specification is adopted for 30m × 0.25mm × 0.25 μm
HP-INNOWAX capillary chromatographic columns；Carrier gas is helium, and constant current speed is 1.0mL/min；Input mode：Sample size be 1 μ L, arteries and veins
Splitless injecting samples are rushed, sample introduction pulsating pressure is 25psi, and the time is 1min；Injector temperature is 250 DEG C；Transmission line temperature is 260
℃；It is 100 DEG C that heating schedule is initial temperature, and with the speed of 3 DEG C/min 240 DEG C are increased to, and keeps 5min；Mass spectral analyses condition
For：Ionization mode be EI sources, positive ion mode；Ion source temperature：230℃；Quadrupole rod temperature：It is 150 DEG C；Collision gas：Nitrogen
Gas, flow velocity 1.5mL/min, carrier gas helium flow velocity is 2.25mL/min；Multiple-reaction monitoring MRM patterns, detail parameters are listed in the table below:
The MRM parameter situations of object
2. it is according to claim 1 determine edible essence in imidazoles, musk xylene and sesamol residual quantity method, its
It is characterised by, the preparation of step (1) inner mark solution includes：
(1a) internal standard storing solution：0.2g phenylethyl propionates are weighed, 0.0001g is accurate to, 100mL appearances are dissolved and be settled to ethanol
In measuring bottle, shake up；
(1b) inner mark solution：0.1mL internal standard storing solutions are accurately pipetted, is settled in 100mL volumetric flasks with ethanol, shaken up.
3. it is according to claim 1 determine edible essence in imidazoles, musk xylene and sesamol residual quantity method, its
It is characterised by, the preparation of step (2) standard working solution includes：
(2a) primary standard storing solution：The each 0.1g of imidazoles, musk xylene and sesamol is weighed respectively, 0.0001g is accurate to, and is used
Ethanol dissolves and is settled in 100mL volumetric flasks, shakes up；
(2b) secondary standard storing solution：1mL primary standard storing solutions are accurately pipetted, in the volumetric flask of 100mL, ethanol dilution is used
And it is settled to scale；
(2c) standard working solution：Accurately pipette respectively the μ L of secondary standard storing solution 20,50 μ L, 100 μ L, 200 μ L, 500 μ L and
In the volumetric flask of 1000 μ L to 10mL, then 100 μ L inner mark solutions are added respectively accurately, with ethanol dilution and be settled to scale, obtain
Series standard working solution.
4. it is according to claim 1 determine edible essence in imidazoles, musk xylene and sesamol residual quantity method, its
It is characterised by, the preparation of step (3) sample solution includes：0.5g samples are weighed, 0.0001g is accurate to, 50mL centrifuge tubes are placed in
In, 1mL water is added, 100 μ L inner mark solutions are accurately moved into, it is uniformly dispersed with eddy mixer, 8mL ethanol is added, it is placed in super
Ultrasonic extraction 20min in sonic generator, add 0.5g anhydrous sodium sulfates, 5min is stood after shaking up, in centrifuge
5min is centrifuged under 4000r/min rotating speeds, the supernatant is taken and is crossed 0.45 μm of organic phase filter membrane, obtain sample feeding solution.
5. it is according to claim 1 determine edible essence in imidazoles, musk xylene and sesamol residual quantity method, its
It is characterised by, step (5) Specification Curve of Increasing and result are calculated as follows：With object in standard working solution and interior target concentration
Ratio be abscissa, object carries out linear regression analyses with the ratio of interior target peak area as vertical coordinate with chromatogram, obtains
Standard working curve, by object in the sample solution measured under the same terms and interior target chromatographic peak area ratio, substitutes into standard
Working curve, according to following equation the content of object in edible essence sample is tried to achieve：
In formula：
W --- imidazoles, musk xylene and sesamol residual quantity in edible essence, unit is mg/kg；
The peak area of A --- imidazoles, musk xylene and sesamol；
As --- the peak area of internal standard substance phenylethyl propionate；
The intercept of b --- standard working curve；
Ms --- the quality of addition internal standard substance phenylethyl propionate, unit is μ g；
The slope of a --- standard working curve；
M --- the quality of edible essence sample, unit is to prop up.
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| CN111220761A (en) * | 2020-03-11 | 2020-06-02 | 宁夏倬昱新材料科技有限公司 | High performance liquid chromatography analysis method for determining imidazole content in alkaline reaction solution |
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| CN101441204A (en) * | 2008-12-30 | 2009-05-27 | 谱尼测试科技（北京）有限公司 | Method for measuring musk xylene content in electric and consumer goods materials |
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