CN105929052B - The method of the method for building up and detection antioxidant and preservative in antioxidant and preservative high resolution mass spectrum data library - Google Patents
The method of the method for building up and detection antioxidant and preservative in antioxidant and preservative high resolution mass spectrum data library Download PDFInfo
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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Abstract
The present invention provides the methods of the method for building up and detection antioxidant and preservative in antioxidant and preservative high resolution mass spectrum data library, including：The single mark methanol solution for preparing antioxidant and preservative respectively establishes high resolution mass spectrum data library with being analyzed by mass spectrometry under anion full scan pattern under time of-flight mass spectrometer cation full scan pattern；Sample to be tested is extracted with alcoholic solution, is analyzed by mass spectrometry, according to the antioxidant and preservative in mass spectrometric data and high resolution mass spectrum data library detection sample to be tested.Compared with prior art, the present invention is detected antioxidant and preservative with target analysis strategy using high resolution mass spectrum, does not need complicated pre-treatment step, you can be carried out at the same time fast qualitative detection to a variety of antioxidants and preservative；Further not only accuracy height, high sensitivity, the unknown antioxidant and preservative that can also go out screening are combined with high resolution mass spectrum to qualitatively judge, expand research and application range using liquid chromatogram.
Description
Technical field
The invention belongs to technical field of chemical detection more particularly to antioxidant and preservative high resolution mass spectrum data libraries
The method of method for building up and detection antioxidant and preservative.
Background technology
2014 China Nian Ban national food safety standard GB 2760《The use of food additives》Compared with version in 2011,
Antioxidant list increases tea polyphenol-palmitate up to 27 kinds, and 4- phenylphenols, 2- phenyl benzene are eliminated in preservative list
Sodium phenolate, ethyl naphthol and sec-butylamine increase epsilon-polylysine and hydrochloride, lysozyme, and two editions amount to 30 kinds of preservatives.It faces
So many additive, how rapid screening multiple additives information, be always the hot spot of safety and supervision area.
Into enforcement tobacco consumption new variation, non-burning class tobacco product, such as smokeless tobacco system occur for Tobacco use control
The sale of product, novel tobacco product increases, and《The Framework Convention on Tobacco Control》Embodiment in, then suggest in tobacco
The use of additive is limited or is forbidden, but less to additive service condition research in smokeless tobacco at present.Above-mentioned China
Additive in national standard, such as preservative and antioxidant service condition, merit attention, develop fast and accurately screening
Method is the premise effectively supervised safely to additive.
There are many analysis and research about preservative and antioxidant, such as use comprehensive two dimensional gas chromatography/flight time mass spectrum
Preservative and antioxidant in method screening food, using Rtx-5 low-pole columns connect Rtx-17 polar column orthogonal separation components,
Determine 32 kinds of objects；Ultra performance liquid chromatography-tandem mass spectrometry measures the preservative and antioxidant in flavouring, solid phase
Multiple-reaction monitoring (MRM) is carried out after extracting and purifying pre-treatment, under electron spray quadrupole rod mass spectrum negative ion mode to analyze, quantitative determination
17 kinds of objects.GC × GC methods high resolution, peak capacity are big, but data processing is relatively complicated, are used for more than 100 kinds components
Complex matrices analysis has outstanding advantage, but for the slightly aobvious inconvenience of rapid screening；There are some superiorities for QqQ (MRM) sensitivity, but
It is not so good as high resolution mass spectrum in selectivity and analyte quantitative aspects.HPLC/TOF-MS targets analysis (Target analysis) exists
The numerous areas such as medicine, food, cosmetics are widely used.About the analysis of antioxidant in vegetable oil and preservative, method is adopted
With reverse phase C18 columns, 11 kinds of objects of quantitative analysis under negative ion mode, but for the influence of high resolution mass spectrum screening object
Factor is not inquired into further.
Also, first mass spectrometric database general at present is more, but the two level modal data library that can disclose acquisition is few, especially
It, can be to the result of analysis object if establishing corresponding second order ms database when being for certain particular analysis monitoring ranges
It is confirmed.Known target object target analysis in, can be searched in many chemical substance structure databases library obtain compound name,
The information such as molecular formula and structure, such as PUBCHEM, ChemSpider, ChEBI, but two level modal data information is only in MASSBANK
In have less content.
Invention content
In view of this, the technical problem to be solved in the present invention is to provide antioxidant and preservative high resolution mass spectrum data
The method of the method for building up in library and detection antioxidant and preservative, this method pre-treatment is simple, quick and precisely, high sensitivity.
The present invention provides a kind of methods of detection antioxidant and preservative, including：
S1 single mark methanol solution of antioxidant) is prepared；
Single mark methanol solution of the antioxidant is subjected to matter under time of-flight mass spectrometer cation full scan pattern
Spectrum analysis acquires the first level-one high resolution mass spectrum data and the first two level high resolution mass spectrum data of antioxidant；
Single mark methanol solution of the antioxidant is subjected to matter under time of-flight mass spectrometer anion full scan pattern
Spectrum analysis acquires the second level-one high resolution mass spectrum data and the second two level high resolution mass spectrum data of antioxidant；
Prepare single mark methanol solution of preservative；
Single mark methanol solution of the preservative is subjected to mass spectrum under time of-flight mass spectrometer cation full scan pattern
Analysis, acquires the first level-one high resolution mass spectrum data and the first two level high resolution mass spectrum data of preservative；
Single mark methanol solution of the preservative is subjected to mass spectrum under time of-flight mass spectrometer anion full scan pattern
Analysis acquires the second level-one high resolution mass spectrum data and the second two level high resolution mass spectrum data of preservative；
High resolution mass spectrum data library is established, the high resolution mass spectrum data library includes the first level-one high-resolution of antioxidant
Mass spectrometric data, the second level-one high resolution mass spectrum data of antioxidant, resists the first two level high resolution mass spectrum data of antioxidant
The one or two of second two level high resolution mass spectrum data of oxidant, the first level-one high resolution mass spectrum data of preservative, preservative
Second two level high resolution mass spectrum number of grade high resolution mass spectrum data, the second level-one high resolution mass spectrum data of preservative and preservative
According to；
S2 sample to be tested is extracted with alcoholic solution), obtains extracting solution；
The extracting solution is analyzed by mass spectrometry in time of-flight mass spectrometer cation full scan pattern, obtains extracting solution
First level-one high resolution mass spectrum data and the first two level high resolution mass spectrum data；
The extracting solution is analyzed by mass spectrometry under time of-flight mass spectrometer anion full scan pattern, obtains extracting solution
The second level-one high resolution mass spectrum data and the second two level high resolution mass spectrum data；
According to the first level-one high resolution mass spectrum data of extracting solution, the first two level high resolution mass spectrum data of extracting solution, carry
Take the second level-one high resolution mass spectrum data of liquid, the second two level high resolution mass spectrum data of extracting solution and step S1) in high score
Distinguish the antioxidant and preservative in mass spectrometry database detection sample to be tested.
Preferably, the step S1) be specially：
Prepare single mark methanol solution of antioxidant；
Single mark methanol solution of the antioxidant is subjected to liquid-phase chromatographic analysis, obtains the liquid chromatogram number of antioxidant
According to；
Single mark methanol solution of the antioxidant is subjected to matter under time of-flight mass spectrometer cation full scan pattern
Spectrum analysis acquires the first level-one high resolution mass spectrum data and the first two level high resolution mass spectrum data of antioxidant；
Single mark methanol solution of the antioxidant is subjected to matter under time of-flight mass spectrometer anion full scan pattern
Spectrum analysis acquires the second level-one high resolution mass spectrum data and the second two level high resolution mass spectrum data of antioxidant；
Prepare single mark methanol solution of preservative；
Single mark methanol solution of the preservative is subjected to liquid-phase chromatographic analysis, obtains the Liquid Chromatography data of preservative；
Single mark methanol solution of the preservative is subjected to mass spectrum under time of-flight mass spectrometer cation full scan pattern
Analysis, acquires the first level-one high resolution mass spectrum data and the first two level high resolution mass spectrum data of preservative；
Single mark methanol solution of the preservative is subjected to mass spectrum under time of-flight mass spectrometer anion full scan pattern
Analysis acquires the second level-one high resolution mass spectrum data and the second two level high resolution mass spectrum data of preservative；
High resolution mass spectrum data library is established, the mass spectrometry database includes the first level-one high resolution mass spectrum number of antioxidant
According to, the first two level high resolution mass spectrum data of antioxidant, the second level-one high resolution mass spectrum data of antioxidant, antioxidant
The second two level high resolution mass spectrum data, the first level-one high resolution mass spectrum data of preservative, preservative the first two level high score
Distinguish mass spectrometric data, the second two level high resolution mass spectrum data of the second level-one high resolution mass spectrum data of preservative and preservative.
Preferably, the step S2) be specially：
Sample to be tested is extracted with alcoholic solution, obtains extracting solution；
The extracting solution is first subjected to liquid-phase chromatographic analysis, obtains the Liquid Chromatography data of extracting solution；
By the extracting solution of liquid-phase chromatographic analysis mass spectrum point will be carried out in time of-flight mass spectrometer cation full scan pattern
Analysis obtains the first level-one high resolution mass spectrum data and the first two level high resolution mass spectrum data of extracting solution；
By the extracting solution of liquid-phase chromatographic analysis mass spectrum will be carried out under time of-flight mass spectrometer anion full scan pattern
Analysis obtains the second level-one high resolution mass spectrum data and the second two level high resolution mass spectrum data of extracting solution；
According to the Liquid Chromatography data of extracting solution, the first level-one high resolution mass spectrum data of extracting solution, extracting solution first
Second two level high resolution mass spectrum of two level high resolution mass spectrum data, the second level-one high resolution mass spectrum data of extracting solution, extracting solution
Data and step S1) in high resolution mass spectrum data library detection sample to be tested in antioxidant and preservative.
Preferably, the mobile phase A of the liquid-phase chromatographic analysis is formic acid water, and Mobile phase B is the mixed liquor of methanol and formic acid,
70% Mobile phase B isocratic elution.
Preferably, the Mass Spectrometry Conditions of the cation full scan pattern are：Electron spray ESI ion sources；Capillary voltage
3000~4000V；1~3Bar of atomization gas；Dry 150 DEG C~200 DEG C of temperature degree；2~10l/min of dry gas stream speed；Quality is swept
Retouch 50~1000amu of range m/z；Six grades of 150.0~300.0Vpp of bar radio-frequency voltage；Collision cell radio-frequency voltage 500.0~
800.0Vpp。
Preferably, the Mass Spectrometry Conditions of the anion full scan pattern are：Electron spray ESI ion sources；Capillary voltage
2500~3500V；1~3Bar of atomization gas；Dry 150 DEG C~200 DEG C of temperature degree；2~10l/min of dry gas stream speed；Quality is swept
Retouch 50~1000amu of range m/z；2.0~6.0eV of level four bars ion energy；Collision cell penetrates 5.0~10.0eV of energy；Collision cell
500.0~800.0Vpp of radio-frequency voltage；80.0~120.0 μ s of transmission time；3.0~7.0 μ s of prefocus frequency.
Preferably, the step S1) in level-one high resolution mass spectrum data and two level high resolution mass spectrum data accurate mass
Number error is less than or equal to 2mDa, and isotope peak shape deviation is less than or equal to 20.
Preferably, the antioxidant and preservative are thiabendazole, ethoxyquinoline, glycyrrhizic acid, p-Coumaric Acid, do not eat
It is sub- propyl propionate, natamycin, methyl hydroxybenzoate, ethylparaben, propylparaben, n Heptyl p hydroxybenzoate, right
Phenylphenol, benzyl p-hydroxybenzoate, 4-HBA butyl ester, 4-HBA isobutyl ester, 4- hexyl resorcins,
2,4-D acid, P-hydroxybenzoic acid n-octyl, ferulic acid, tert-butyl hydroquinone, 3,3- dithiodipropionic acid dilauryls ester,
Rosmarinic acid and ascorbic acid.
Preferably, the sample to be tested is smokeless tobacco.
The present invention also provides a kind of antioxidant or the method for building up in preservative high resolution mass spectrum data library, including：
Prepare single mark methanol solution of antioxidant；
Single mark methanol solution of the antioxidant is subjected to matter under time of-flight mass spectrometer cation full scan pattern
Spectrum analysis acquires the first level-one high resolution mass spectrum data and the first two level high resolution mass spectrum data of antioxidant；
Single mark methanol solution of the antioxidant is subjected to matter under time of-flight mass spectrometer anion full scan pattern
Spectrum analysis acquires the second level-one high resolution mass spectrum data and the second two level high resolution mass spectrum data of antioxidant；
Prepare single mark methanol solution of preservative；
Single mark methanol solution of the preservative is subjected to mass spectrum under time of-flight mass spectrometer cation full scan pattern
Analysis, acquires the first level-one high resolution mass spectrum data and the first two level high resolution mass spectrum data of preservative；
Single mark methanol solution of the preservative is subjected to mass spectrum under time of-flight mass spectrometer anion full scan pattern
Analysis acquires the second level-one high resolution mass spectrum data and the two or two high-resolution grade mass spectrometric data of preservative；
High resolution mass spectrum data library is established, the high resolution mass spectrum data library includes the first level-one high-resolution of antioxidant
Mass spectrometric data, the second level-one high resolution mass spectrum data of antioxidant, resists the first two level high resolution mass spectrum data of antioxidant
The one or two of second two level high resolution mass spectrum data of oxidant, the first level-one high resolution mass spectrum data of preservative, preservative
Second two level high resolution mass spectrum number of grade high resolution mass spectrum data, the second level-one high resolution mass spectrum data of preservative and preservative
According to.
The present invention provides antioxidant and the method for building up and detection antioxidant in preservative high resolution mass spectrum data library
And the method for preservative, including：S1 single mark methanol solution of antioxidant) is prepared；Single mark methanol of the antioxidant is molten
Liquid is analyzed by mass spectrometry under time of-flight mass spectrometer cation full scan pattern, acquires the first level-one high-resolution of antioxidant
Mass spectrometric data and the first two level high resolution mass spectrum data；By single mark methanol solution of the antioxidant in time of-flight mass spectrometer
It is analyzed by mass spectrometry under anion full scan pattern, acquires the second level-one high resolution mass spectrum data and the second two level of antioxidant
High resolution mass spectrum data；Prepare single mark methanol solution of preservative；By single mark methanol solution of the preservative in the flight time
It is analyzed by mass spectrometry under mass spectrograph cation full scan pattern, acquires the first level-one high resolution mass spectrum data and first of preservative
Two level high resolution mass spectrum data；By single mark methanol solution of the preservative in time of-flight mass spectrometer anion full scan pattern
Under be analyzed by mass spectrometry, acquire the second level-one high resolution mass spectrum data of preservative and the second two level high resolution mass spectrum data；It builds
Vertical high resolution mass spectrum data library, the high resolution mass spectrum data library include antioxidant the first level-one high resolution mass spectrum data,
First two level high resolution mass spectrum data of antioxidant, the second level-one high resolution mass spectrum data of antioxidant, antioxidant
First two level high-resolution of the second two level high resolution mass spectrum data, the first level-one high resolution mass spectrum data of preservative, preservative
Second two level high resolution mass spectrum data of mass spectrometric data, the second level-one high resolution mass spectrum data of preservative and preservative；S2) will
Sample to be tested is extracted with alcoholic solution, obtains extracting solution；By the extracting solution in time of-flight mass spectrometer cation full scan pattern
It is analyzed by mass spectrometry, obtains the first level-one high resolution mass spectrum data and the first two level high resolution mass spectrum data of extracting solution；By institute
It states extracting solution to be analyzed by mass spectrometry under time of-flight mass spectrometer anion full scan pattern, the second level-one for obtaining extracting solution is high
Resolution mass spectra and the second two level high resolution mass spectrum data；According to the first level-one high resolution mass spectrum data of extracting solution, extraction
First two level high resolution mass spectrum data of liquid, the second level-one high resolution mass spectrum data of extracting solution, the second two level of extracting solution are high
Resolution mass spectra and step S1) in high resolution mass spectrum data library detection sample to be tested in antioxidant and preservative.With
The prior art is compared, and the present invention is detected antioxidant and preservative with target analysis strategy using high resolution mass spectrum,
Complicated pre-treatment step is not needed, you can fast qualitative detection is carried out at the same time to a variety of antioxidants and preservative；More into one
Not only accuracy is high, high sensitivity with detection method associated with high resolution mass spectrum using liquid chromatogram for step, can also go out to screening
Unknown antioxidant and preservative are qualitatively judged, and the range of research and application is expanded.
Description of the drawings
Fig. 1 is valve connecting mode schematic diagram when time of-flight mass spectrometer of the present invention uses direct mass spectrum sample introduction；
Fig. 2 is the level-one high resolution mass spectrum data library exemplary plot of Self-built Database in the embodiment of the present invention 1；
Fig. 3 is the two level high resolution mass spectrum data library exemplary plot of Self-built Database in the embodiment of the present invention 1；
Fig. 4 is to obtain the second order ms figure of unknown material under Auto MS/MS patterns in the embodiment of the present invention 2.
Specific implementation mode
Below in conjunction with the attached drawing of the embodiment of the present invention, technical solution in the embodiment of the present invention carries out clear, complete
Ground describes, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on this
Embodiment in invention, every other reality obtained by those of ordinary skill in the art without making creative efforts
Example is applied, shall fall within the protection scope of the present invention.
The present invention provides a kind of antioxidant and the method for building up in preservative high resolution mass spectrum data library, including：
Prepare single mark methanol solution of antioxidant；
Single mark methanol solution of the antioxidant is subjected to matter under time of-flight mass spectrometer cation full scan pattern
Spectrum analysis acquires the first level-one high resolution mass spectrum data and the first two level high resolution mass spectrum data of antioxidant；
Single mark methanol solution of the antioxidant is subjected to matter under time of-flight mass spectrometer anion full scan pattern
Spectrum analysis acquires the second level-one high resolution mass spectrum data and the second two level high resolution mass spectrum data of antioxidant；
Prepare single mark methanol solution of preservative；
Single mark methanol solution of the preservative is subjected to mass spectrum under time of-flight mass spectrometer cation full scan pattern
Analysis, acquires the first level-one high resolution mass spectrum data and the first two level high resolution mass spectrum data of preservative；
Single mark methanol solution of the preservative is subjected to mass spectrum under time of-flight mass spectrometer anion full scan pattern
Analysis acquires the second level-one high resolution mass spectrum data and the second two level high resolution mass spectrum data of preservative；
High resolution mass spectrum data library is established, the high resolution mass spectrum data library includes the first level-one high-resolution of antioxidant
Mass spectrometric data, the second level-one high resolution mass spectrum data of antioxidant, resists the first two level high resolution mass spectrum data of antioxidant
The one or two of second two level high resolution mass spectrum data of oxidant, the first level-one high resolution mass spectrum data of preservative, preservative
Second two level high resolution mass spectrum number of grade high resolution mass spectrum data, the second level-one high resolution mass spectrum data of preservative and preservative
According to.
Wherein, the antioxidant and preservative are preferably thiabendazole, ethoxyquinoline, glycyrrhizic acid, p-Coumaric Acid, do not have
Propyl galate, natamycin, methyl hydroxybenzoate, ethylparaben, propylparaben, n Heptyl p hydroxybenzoate,
P-phenyl phenol, benzyl p-hydroxybenzoate, 4-HBA butyl ester, 4-HBA isobutyl ester, 4- hexylresorcinols two
Phenol, 2,4-D acid, P-hydroxybenzoic acid n-octyl, ferulic acid, tert-butyl hydroquinone, 3,3- dithiodipropionic acid dilauryls
Ester, Rosmarinic acid and ascorbic acid, English name and molecular formula are shown in Table 1.
The title and molecular formula of 1 antioxidant of table and preservative
The present invention preferably prepares single mark methanol solution of antioxidant in accordance with the following methods：7.5~10.0mg is weighed respectively
The standard items of antioxidant are configured to the singly mark solution of 0.3~0.4mg/ml in methanol constant volume to 25ml volumetric flasks；Divide again
The singly mark solution for not pipetting 25~35 μ l, it is molten with the single mark methanol in methanol constant volume to 10ml volumetric flasks, being configured to 1.0 μ g/ml
Liquid.
Single mark methanol solution of the antioxidant is subjected to matter under time of-flight mass spectrometer cation full scan pattern
Spectrum analysis acquires the first level-one high resolution mass spectrum data and the first two level high resolution mass spectrum data of antioxidant；
Single mark methanol solution of the antioxidant is subjected to matter under time of-flight mass spectrometer anion full scan pattern
Spectrum analysis acquires the second level-one high resolution mass spectrum data and the second two level high resolution mass spectrum data of antioxidant；
Antioxidant list mark methanol solution of the present invention uses direct mass spectrum sample introduction, and valve connecting mode is as shown in Figure 1, anti-at this time
Single mark methanol solution of oxidant and preservative goes to connection port5 from mass spectrum atomization chamber injection port, disconnects the HPLC connection of port3
It connects, single mark methanol solution is pumped from atomization chamber injection port by needle and is introduced；The flow velocity of the needle pump is preferably set to 100~200 μ l/
H, more preferably 150~200 μ l/h are further preferably 160~190 μ l/h, most preferably 180 μ l/h.
Wherein, the Mass Spectrometry Conditions of the time of-flight mass spectrometer cation full scan pattern are preferably：Electron spray ESI ions
Source；3000~4000V of capillary voltage；1~3Bar of atomization gas；Dry 150 DEG C~200 DEG C of temperature degree；Dry gas stream speed 2~
10l/min；50~1000amu of mass scan range m/z；Six grades of 150.0~300.0Vpp of bar radio-frequency voltage；Collision cell radio frequency
500.0~800.0Vpp of voltage；More preferably：Electron spray ESI ion sources；Capillary voltage 3500V；Atomization gas 1.5Bar；It is dry
180 DEG C of pathogenic dryness temperature；Dry gas stream speed 6.0l/min；50~1000amu of mass scan range m/z；Six grades of bar radio-frequency voltages
200.0Vpp；Collision cell radio-frequency voltage 600.0Vpp.
The Mass Spectrometry Conditions of the time of-flight mass spectrometer anion full scan pattern are preferably：Electron spray ESI ion sources；Hair
2500~3500V of tubule voltage；1~3Bar of atomization gas；Dry 150 DEG C~200 DEG C of temperature degree；2~10l/ of dry gas stream speed
min；50~1000amu of mass scan range m/z；2.0~6.0eV of level four bars ion energy；Collision cell penetrate energy 5.0~
10.0eV；500.0~800.0Vpp of collision cell radio-frequency voltage；80.0~120.0 μ s of transmission time；Prefocus frequency 3.0~7.0
μs.；More preferably：Electron spray ESI ion sources；Capillary voltage 3000V；Atomization gas 1.5Bar；Dry 180 DEG C of temperature degree；It is dry
Pathogenic dryness flow velocity 6.0l/min；50~1000amu of mass scan range m/z；Level four bars ion energy 4.0eV；Collision cell penetrates energy
7.0eV；Collision cell radio-frequency voltage 600.0Vpp；100.0 μ s of transmission time；5.0 μ s of prefocus frequency.
Influence for elimination solvent to mass spectrometric data, preferably under cation full scan pattern and anion full scan pattern
It is all made of sodium methoxide solution correction mass spectrograph.The concentration of the sodium methoxide is preferably 1~50mmol/L, more preferably 5~
30mmol/L is further preferably 10~20mmol/L, most preferably 10mmol/L.
The the first level-one high resolution mass spectrum data and the first two level high resolution mass spectrum data of antioxidant are acquired, preferably accurately
Mass number error is less than or equal to 2mDa, and isotope peak shape deviation is less than or equal to 20；Acquire the second level-one high-resolution of antioxidant
Mass spectrometric data and the second two level high resolution mass spectrum data, preferably accurate mass number error are less than or equal to 2mDa, and isotope peak shape is inclined
Difference is less than or equal to 20.
Prepare single mark methanol solution of preservative；The preparation side of single mark methanol solution of the preparation method and antioxidant
Method is identical, and details are not described herein.
Single mark methanol solution of the preservative is subjected to mass spectrum under time of-flight mass spectrometer cation full scan pattern
Analysis, acquires the first level-one high resolution mass spectrum data and the first two level high resolution mass spectrum data of preservative；By the preservative
Single mark methanol solution be analyzed by mass spectrometry under time of-flight mass spectrometer anion full scan pattern, acquire the second of preservative
Level-one high resolution mass spectrum data and the second two level high resolution mass spectrum data；The time of-flight mass spectrometer cation full scan pattern
Same as above with anion full scan pattern, details are not described herein.
High resolution mass spectrum data library is established, the high resolution mass spectrum data library includes the first level-one high-resolution of antioxidant
Mass spectrometric data, the second level-one high resolution mass spectrum data of antioxidant, resists the first two level high resolution mass spectrum data of antioxidant
The one or two of second two level high resolution mass spectrum data of oxidant, the first level-one high resolution mass spectrum data of preservative, preservative
Second two level high resolution mass spectrum number of grade high resolution mass spectrum data, the second level-one high resolution mass spectrum data of preservative and preservative
According to.The present invention preferably imports the level-one high resolution mass spectrum data of antioxidant and preservative and two level high resolution mass spectrum data
Library Editor softwares establish antioxidant and preservative high resolution mass spectrum data library.
Heretofore described high resolution mass spectrum data library preferably includes the title of antioxidant and preservative, No. CAS, chemistry
Formula, chemical constitution, molecular weight, first mass spectrometric data, second order ms data, object impact energy, fragments characteristic ion it is accurate
Mass number and precision.
The antioxidant and preservative high resolution mass spectrum data library that the present invention establishes can provide antioxidant and preservative
The parameter of compound essential information, the parameter and second order ms data of first mass spectrometric data.
It is anti-oxidant using above-mentioned antioxidant and the detection of preservative high resolution mass spectrum data library that the present invention also provides a kind of
The method of agent and preservative, including：
S1 single mark methanol solution of antioxidant) is prepared；
Single mark methanol solution of the antioxidant is subjected to matter under time of-flight mass spectrometer cation full scan pattern
Spectrum analysis acquires the first level-one high resolution mass spectrum data and the first two level high resolution mass spectrum data of antioxidant；
Single mark methanol solution of the antioxidant is subjected to matter under time of-flight mass spectrometer anion full scan pattern
Spectrum analysis acquires the second level-one high resolution mass spectrum data and the second two level high resolution mass spectrum data of antioxidant；
Prepare single mark methanol solution of preservative；
Single mark methanol solution of the preservative is subjected to mass spectrum under time of-flight mass spectrometer cation full scan pattern
Analysis, acquires the first level-one high resolution mass spectrum data and the first two level high resolution mass spectrum data of preservative；
Single mark methanol solution of the preservative is subjected to mass spectrum under time of-flight mass spectrometer anion full scan pattern
Analysis acquires the second level-one high resolution mass spectrum data and the second two level high resolution mass spectrum data of preservative；
High resolution mass spectrum data library is established, the high resolution mass spectrum data library includes the first level-one high-resolution of antioxidant
Mass spectrometric data, the second level-one high resolution mass spectrum data of antioxidant, resists the first two level high resolution mass spectrum data of antioxidant
The one or two of second two level high resolution mass spectrum data of oxidant, the first level-one high resolution mass spectrum data of preservative, preservative
Second two level high resolution mass spectrum number of grade high resolution mass spectrum data, the second level-one high resolution mass spectrum data of preservative and preservative
According to；
S2 sample to be tested is extracted with alcoholic solution), obtains extracting solution；
The extracting solution is analyzed by mass spectrometry in time of-flight mass spectrometer cation full scan pattern, obtains extracting solution
First level-one high resolution mass spectrum data and the first two level high resolution mass spectrum data；
The extracting solution is analyzed by mass spectrometry under time of-flight mass spectrometer anion full scan pattern, obtains extracting solution
The second level-one high resolution mass spectrum data and the second two level high resolution mass spectrum data；
According to the first level-one high resolution mass spectrum data of extracting solution, the first two level high resolution mass spectrum data of extracting solution, carry
Take the second level-one high resolution mass spectrum data of liquid, the second two level high resolution mass spectrum data of extracting solution and step S1) in high score
Distinguish the antioxidant and preservative in mass spectrometry database detection sample to be tested.
Wherein, the step S1) in establish antioxidant and the method in preservative high resolution mass spectrum data library is same as above,
Details are not described herein.
In the present invention, in order to further increase the screening speed and efficiency of antioxidant and preservative, the S1) in it is excellent
Choosing further includes liquid-phase chromatographic analysis, first by antioxidant or single mark methanol solution progress liquid-phase chromatographic analysis of preservative, then into
Row mass spectral analysis, i.e. LC-MS, at this point, the step S1 is preferably specially：
Prepare single mark methanol solution of antioxidant；
Single mark methanol solution of the antioxidant is subjected to liquid-phase chromatographic analysis, obtains the liquid chromatogram number of antioxidant
According to；
Single mark methanol solution of the antioxidant is subjected to matter under time of-flight mass spectrometer cation full scan pattern
Spectrum analysis acquires the first level-one high resolution mass spectrum data and the first two level high resolution mass spectrum data of antioxidant；
Single mark methanol solution of the antioxidant is subjected to matter under time of-flight mass spectrometer anion full scan pattern
Spectrum analysis acquires the second level-one high resolution mass spectrum data and the second two level high resolution mass spectrum data of antioxidant；
Prepare single mark methanol solution of preservative；
Single mark methanol solution of the preservative is subjected to liquid-phase chromatographic analysis, obtains the Liquid Chromatography data of preservative；
Single mark methanol solution of the preservative is subjected to mass spectrum under time of-flight mass spectrometer cation full scan pattern
Analysis, acquires the first level-one high resolution mass spectrum data and the first two level high resolution mass spectrum data of preservative；
Single mark methanol solution of the preservative is subjected to mass spectrum under time of-flight mass spectrometer anion full scan pattern
Analysis acquires the second level-one high resolution mass spectrum data and the second two level high resolution mass spectrum data of preservative；
High resolution mass spectrum data library is established, the high resolution mass spectrum data library includes the first level-one high-resolution of antioxidant
Mass spectrometric data, the second level-one high resolution mass spectrum data of antioxidant, resists the first two level high resolution mass spectrum data of antioxidant
The one or two of second two level high resolution mass spectrum data of oxidant, the first level-one high resolution mass spectrum data of preservative, preservative
Second two level high resolution mass spectrum number of grade high resolution mass spectrum data, the second level-one high resolution mass spectrum data of preservative and preservative
According to.
Wherein, the type of the antioxidant and preservative is same as above, and details are not described herein, is more preferably in the detection
Antioxidant and preservative as shown in Table 2.
The title and molecular formula of 2 antioxidant of table and preservative
The liquid chromatogram is liquid chromatogram well known to those skilled in the art, has no special limitation, the present invention
In preferably high performance liquid chromatography or ultra performance liquid chromatography；The mobile phase A of the liquid-phase chromatographic analysis is formic acid water, mobile phase
B is the mixed liquor of methanol and formic acid, 70% Mobile phase B isocratic elution；Wherein, the pH value of the formic acid water is preferably 2~3,
More preferably 2.5~3, it is further preferably 2.7；The volume content of formic acid is preferably 0.1%~0.3% in the mixed liquor, more excellent
It is selected as 0.1%~0.2%, is further preferably 0.1%~0.15%, most preferably 0.1%；Color used in the liquid-phase chromatographic analysis
It is preferably Luna C8 liquid-phase chromatographic columns to compose column；The specification of the chromatographic column is preferably the μ ms of 4.6mm × 3 150mm；The chromatography
The temperature of column is preferably 30 DEG C~40 DEG C, and more preferably 32 DEG C~38 DEG C, be further preferably 34 DEG C~36 DEG C, most preferably 35 DEG C；
The sampling volume of the liquid chromatogram is preferably 3~10 μ l, more preferably 5~10 μ l, is further preferably 5~8 μ l, most preferably 5 μ
l。
The condition of the mass spectral analysis is same as above, and details are not described herein.
Sample to be tested is extracted with alcoholic solution, obtains extracting solution；The sample to be tested is well known to those skilled in the art
Sample to be tested has no special limitation, is preferably smokeless tobacco in the present invention；The alcoholic solution is preferably methanol and water
Mixed liquor；The volume ratio of the methanol and water is preferably (1~5)：1, more preferably (2~4)：1, most preferably 3:1；It is described to wait for
Sample and the ratio of alcoholic solution are preferably 0.1g：(1~3) ml, more preferably 0.1g：2ml；The step of extraction, is preferred
For：Sample to be tested is mixed with alcoholic solution and carries out ultrasound successively, is vortexed, centrifuges, filtration treatment, obtains extracting solution；The ultrasound
Time be preferably 5~15min, more preferably 8~12min is further preferably 10min；The time of the vortex is preferably 10~
20min, more preferably 13~18min are further preferably 15min；The speed of the centrifugation is preferably 5000~20000r/min, more
Preferably 8000~15000r/min is further preferably 10000~12000r/min, most preferably 10000r/min；The centrifugation
Time be preferably 5~20min, more preferably 8~15min is further preferably 10min；The filtering preferably uses 0.1~0.5 μ
M filter membranes are filtered, and are more preferably filtered using 0.2 μm of filter membrane.
According to the present invention, extracting solution is first preferably subjected to liquid-phase chromatographic analysis, obtains the Liquid Chromatography data of extracting solution；It will
It is analyzed by mass spectrometry, is extracted in time of-flight mass spectrometer cation full scan pattern by the extracting solution of liquid-phase chromatographic analysis
First level-one high resolution mass spectrum data of liquid and the first two level high resolution mass spectrum data；It will be by the extracting solution of liquid-phase chromatographic analysis
It is analyzed by mass spectrometry under time of-flight mass spectrometer anion full scan pattern, obtains the second level-one high resolution mass spectrum of extracting solution
Data and the second two level high resolution mass spectrum data；
Wherein, the condition of the liquid chromatogram and the mass spectrographic condition are same as above, and details are not described herein；In order to subtract
Few influence of the solute to chromatographic data, it is preferred to use sodium methoxide solution corrects mass spectrograph；The concentration of the sodium methoxide is preferably 1~
50mmol/L, more preferably 5~30mmol/L are further preferably 10~20mmol/L, most preferably 10mmol/L.
According to the Liquid Chromatography data of extracting solution, the first level-one high resolution mass spectrum data of extracting solution, extracting solution first
Second two level high resolution mass spectrum of two level high resolution mass spectrum data, the second level-one high resolution mass spectrum data of extracting solution, extracting solution
Data and step S1) in high resolution mass spectrum data library detection sample to be tested in antioxidant and preservative.
The present invention does not need complicated pre-treatment step, you can it is quickly fixed to be carried out at the same time to a variety of antioxidants and preservative
Property detection；Not only accuracy is high, high sensitivity for detection method provided by the invention simultaneously, can also be unknown anti-oxidant to what is detected
Agent and preservative are qualitatively judged, and the range of research and application is expanded；The method of the present invention is accurate using high resolution mass spectrum acquisition
The resolution ratio of mass number, antioxidant and preservative is up to 2~30,000.
In order to further illustrate the present invention, with reference to embodiments to antioxidant provided by the invention and preservative high score
The method for building up and the method for detection antioxidant and preservative for distinguishing mass spectrometry database are described in detail.
Reagent used in following embodiment is commercially available.
Embodiment 1
1.1 standard solution are prepared
Standard solution：7.5-10.0mg standard items are weighed respectively, in methanol constant volume to 25mL volumetric flasks, are configured to 0.3-
Single mark methanol solution of 0.4mg/mL；The single mark methanol solution for pipetting 25-35 μ L respectively, with methanol constant volume to 10mL volumetric flasks
In, it is configured to single mark methanol solution of about 1.0 μ g/mL, 4 DEG C of refrigerations are for use.
1.2 Mass Spectrometry Conditions
Electron spray ESI ion sources：Cation full scan pattern, capillary voltage：3500V；Atomization gas：1.5Bar；It is dry
Temperature degree：180℃；Dry gas stream speed：6.0l/min；Mass scan range：m/z 50-1000amu；Six grades of bar radio-frequency voltages：
200.0Vpp；Collision cell radio-frequency voltage：600.0Vpp.
Anion full scan pattern；Capillary voltage：3000V；Atomization gas：1.5Bar；Dry temperature degree：180℃；It is dry
Gas velocity：6.0l/min；Mass scan range：m/z 50-1000amu；Quadrupole rod ion energy：4.0eV；Collision cell energy：
7.0eV；Collision cell radio-frequency voltage：600.0Vpp；Transmission time：100.0μs；Prefocus frequency：5.0μs.
Using the sodium formate solution of 10mmol/L as mass number correcting fluid under negative ions pattern.
Valve connecting mode when 1.3 mass spectrographs use direct mass spectrum sample introduction as shown in Figure 1, standard correction liquid from mass spectrum atomization chamber
Injection port goes to connection port 5, disconnects the HPLC connections of port 3, and single mark methanol solution is passed through needle from atomization chamber injection port
It pumps (syringe pump) to introduce, needle flow rate pump is set as 180 μ L/h.
1.4 correct mass spectrograph with the sodium formate solution of 10mmol/L, acquire level-one, the two level matter of antioxidant and preservative
Modal data makes accurate mass number error≤2mDa, isotope peak shape deviation≤20.
1.5 open the self-built new databases of Library Editor softwares, import collected antioxidant and preservative
Level-one, second order ms data.Level-one, the two level high resolution mass spectrum data example of Self-built Database are as shown in Figure 2 and Figure 3.
Embodiment 2
2.1 standard solution are prepared
Standard reserving solution：7.5~10.0mg standard items are weighed respectively, in methanol constant volume to 25mL volumetric flasks, are configured to
Single mark methanol solution of 0.3-0.4mg/mL；The single mark methanol solution for pipetting 25-35 μ L respectively, with methanol constant volume to 10mL capacity
In bottle, it is configured to single mark methanol solution of about 1.0 μ g/mL, 4 DEG C of refrigerations are for use.
Single mark working solution：Single mark of 1.0 μ g/mL is diluted 1 times (about mono- marks of 500ppb) respectively；Mixed mark work is molten
Liquid：Single mark methanol solution of 15-20 μ L 0.3-0.4mg/mL is pipetted respectively, until in 10mL volumetric flasks, (about with methanol constant volume
The mixed marks of 500ppb).4 DEG C of refrigerations are for use.
2.2 chromatographic condition
High-efficient liquid phase chromatogram condition：Luna C8 liquid-phase chromatographic columns (μ ms of 4.6mm × 3 150mm, Phenomenex companies).
Mobile phase A is formic acid water (pH 2.7), and Mobile phase B is methanol (0.1% formic acid)；Sampling volume is 5 μ L；Column temperature is
35℃；Flow velocity is 400 μ L/min；70%B isocratic elutions.
2.3 Mass Spectrometry Conditions
Electron spray ESI ion sources：Cation full scan pattern, capillary voltage：3500V；Atomization gas：1.5Bar；It is dry
Temperature degree：180℃；Dry gas stream speed：6.0l/min；Mass scan range：m/z 50-1000amu；Six grades of bar radio-frequency voltages：
200.0Vpp；Collision cell radio-frequency voltage：600.0Vpp.
Anion full scan pattern；Capillary voltage：3000V；Atomization gas：1.5Bar；Dry temperature degree：180℃；It is dry
Gas velocity：6.0l/min；Mass scan range：m/z 50-1000amu；Quadrupole rod ion energy：4.0eV；Collision cell energy：
7.0eV；Collision cell radio-frequency voltage：600.0Vpp；Transmission time：100.0μs；Prefocus frequency：5.0μs.
Using the sodium formate solution of 10mmol/L as mass number correcting fluid under negative ions pattern.
2.4 sample treatment
Five parts of 0.1g (being accurate to 0.01g) smokeless tobacco samples are weighed in centrifuge tube, 2mL methanol is added:Aqueous solution (body
Product ratio 3:1), ultrasonic 10min, vortex 15min, 10000r/min centrifugation 10min, takes supernatant to cross 0.2 μm of filter membrane, is extracted
Liquid.
Every part takes 200 μ L mixing to be used as tobacco extraction liquid matrix, and mixed mark, a concentration of 250ppb is added.
2.5 establish high resolution mass spectrum screening database
Chromatography and level-one, second order ms data are obtained with single mark methanol solution, data prediction is using Bruker companies
Data Analysis softwares obtain object accurate mass number and retention time, and Smart Formula manually identify color
Spectral peak establishes database using Target Analysis softwares, and database includes mainly the sub- matter lotus of object quasi-molecular ion peak
Than, projects such as retention time, molecular formula, object English name.
2.6 data processing
Data prediction obtains object accurate mass number and reservation using the Data Analysis softwares of Bruker companies
Time, Smart Formula manually identify chromatographic peak, using self-built high resolution mass spectrum screening database qualitatively screening mesh
Compound is marked, mass number error range is ± 5.0mDa, isotope peak shape deviation decision content≤20.
The result of multiple target objects rapid screening known to 2.7
For the known substance of Target Analysis screenings hit, this experiment is 18 under negative ion mode, positive ion mode
The screening results of kind of object are as shown in table 2, mass number error≤5.0mDa, isotope peak shape deviation is respectively less than 20, retains
Time drift≤0.15min.And the Ion response for the compound that score value is 2 is relatively low.
Influence factor about Target Analysis：Under identical chromatographic conditions, the retention time of the compound is drifted about very
It is small；Analyze the object screening that smokeless tobacco extraction solution adds mixed mark solution and mixed mark methanol solution, screening score value phase
Together, illustrate that matrix has little effect screening results；Under HPLC and UPLC analysis conditions, the resolution ratio of object and sensitive
Degree has differences, and under the conditions of HPLC, object separating degree is high, and under the conditions of UPLC, response increase be conducive to content it is low from
Sub- screening, the advantage of high resolution mass spectrum make that in two kinds of chromatographic conditions preferable screening results can be obtained；And mass number is accurate
Property be influence screening results key factor, before experiment, need to time of-flight mass spectrometer carry out mass number correction, testing
In, each sample introduction is corrected using sodium formate, and mass number error requirements have been met, and improves screening hit rate.
3 antioxidant of table and preservative target analysis result (* is isomer)
The unknown material that 2.8 pairs of screenings go out carries out qualitative
For the unknown material that Target Analysis screenings are arrived, its molecular formula can be predicted, carry out second order ms figure confirmation,
To identify unknown material.Such as in tobacco substrate assay, under negative ion mode, setting mass number error≤5.0mDa, mSigma values
Less than 50, unknown material ion m/z=191.0544 is retrieved, predicts that the unknown material molecular formula is shown in Table 4.
The molecular formula for the unknown material quasi-molecular ion that table 4 is predicted
Molecular formula C is retrieved in PUBCHEM Chemicals Databases7H12O6, retrieval result is chinic acid, and chinic acid is antioxygen
Agent and antisepsis antistaling agent can be used as fragrance-enhancing tobacco agent.
C8H8N4O2Retrieval result be 4-methyl-6-nitro-1,4-dihydro-1,2,4-benzotriazine；
Other do not retrieve compound name.
The second order ms figure of the unknown material is obtained under Auto MS/MS patterns as shown in figure 4, the mass spectrometric data measured can be
It is retrieved in existing mass spectrometry database (such as Mass Bank), 5 is shown in Table with the mass number difference of D- (-)-Quinic acid, it should
Database has the ESI-QqTOF-MS data of a compound more than 800, document to claim its data source non-standard unified analysis condition.
Difference between 5 unknown material experiment value of table and the second order ms data of database retrieval
Claims (2)
1. a kind of method of detection antioxidant and preservative, which is characterized in that including：
S1 single mark methanol solution of antioxidant) is prepared；
Single mark methanol solution of the antioxidant is subjected to liquid-phase chromatographic analysis, obtains the Liquid Chromatography data of antioxidant；
Single mark methanol solution of the antioxidant is subjected to mass spectrum point under time of-flight mass spectrometer cation full scan pattern
Analysis, acquires the first level-one high resolution mass spectrum data and the first two level high resolution mass spectrum data of antioxidant；
Single mark methanol solution of the antioxidant is subjected to mass spectrum point under time of-flight mass spectrometer anion full scan pattern
Analysis acquires the second level-one high resolution mass spectrum data and the second two level high resolution mass spectrum data of antioxidant；
Prepare single mark methanol solution of preservative；
Single mark methanol solution of the preservative is subjected to liquid-phase chromatographic analysis, obtains the Liquid Chromatography data of preservative；
Single mark methanol solution of the preservative is analyzed by mass spectrometry under time of-flight mass spectrometer cation full scan pattern,
Acquire the first level-one high resolution mass spectrum data and the first two level high resolution mass spectrum data of preservative；
Single mark methanol solution of the preservative is analyzed by mass spectrometry under time of-flight mass spectrometer anion full scan pattern,
Acquire the second level-one high resolution mass spectrum data and the second two level high resolution mass spectrum data of preservative；
High resolution mass spectrum data library is established, the high resolution mass spectrum data library includes the first level-one high resolution mass spectrum of antioxidant
It is data, the first two level high resolution mass spectrum data of antioxidant, the second level-one high resolution mass spectrum data of antioxidant, anti-oxidant
Second two level high resolution mass spectrum data of agent, the first level-one high resolution mass spectrum data of preservative, the first two level of preservative are high
Second two level high resolution mass spectrum data of resolution mass spectra, the second level-one high resolution mass spectrum data of preservative and preservative；
S2 sample to be tested is extracted with alcoholic solution), obtains extracting solution；The sample to be tested is smokeless tobacco；
The extracting solution is first subjected to liquid-phase chromatographic analysis, obtains the Liquid Chromatography data of extracting solution；
It will be analyzed by mass spectrometry, obtain in time of-flight mass spectrometer cation full scan pattern by the extracting solution of liquid-phase chromatographic analysis
To the first level-one high resolution mass spectrum data and the first two level high resolution mass spectrum data of extracting solution；
It will be analyzed by mass spectrometry under time of-flight mass spectrometer anion full scan pattern by the extracting solution of liquid-phase chromatographic analysis,
Obtain the second level-one high resolution mass spectrum data and the second two level high resolution mass spectrum data of extracting solution；
According to the Liquid Chromatography data of extracting solution, the first level-one high resolution mass spectrum data of extracting solution, the first two level of extracting solution
High resolution mass spectrum data, the second level-one high resolution mass spectrum data of extracting solution, the second two level high resolution mass spectrum data of extracting solution
With step S1) in high resolution mass spectrum data library detection sample to be tested in antioxidant and preservative；
The mobile phase A of the liquid-phase chromatographic analysis is formic acid water, and Mobile phase B is the mixed liquor of methanol and formic acid, 70% flowing
Phase B isocratic elutions；
The Mass Spectrometry Conditions of the time of-flight mass spectrometer cation full scan pattern are：Electron spray ESI ion sources；Capillary voltage
3000~4000V；1~3Bar of atomization gas；Dry 150 DEG C~200 DEG C of temperature degree；2~10l/min of dry gas stream speed；Quality is swept
Retouch 50~1000amu of range m/z；Six grades of 150.0~300.0Vpp of bar radio-frequency voltage；Collision cell radio-frequency voltage 500.0~
800.0Vpp；
The Mass Spectrometry Conditions of the time of-flight mass spectrometer anion full scan pattern are：Electron spray ESI ion sources；Capillary voltage
2500~3500V；1~3Bar of atomization gas；Dry 150 DEG C~200 DEG C of temperature degree；2~10l/min of dry gas stream speed；Quality is swept
Retouch 50~1000amu of range m/z；2.0~6.0eV of level four bars ion energy；Collision cell penetrates 5.0~10.0eV of energy；Collision cell
500.0~800.0Vpp of radio-frequency voltage；80.0~120.0 μ s of transmission time；3.0~7.0 μ s of prefocus frequency；
The antioxidant and preservative are thiabendazole, ethoxyquinoline, glycyrrhizic acid, p-Coumaric Acid, propylgallate, receive
It is his mycin, methyl hydroxybenzoate, ethylparaben, propylparaben, n Heptyl p hydroxybenzoate, p-phenyl phenol, right
Hydroxy benzoic acid benzyl ester, 4-HBA butyl ester, 4-HBA isobutyl ester, 4- hexyl resorcins, 2,4-D are sour, right
Hydroxybenzoic acid n-octyl, ferulic acid, tert-butyl hydroquinone, 3,3- dithiodipropionic acid dilauryls ester, Rosmarinic acid with
Ascorbic acid.
2. according to the method described in claim 1, the it is characterized in that, step S1) in level-one high resolution mass spectrum data and two
The accurate mass number error of grade high resolution mass spectrum data is less than or equal to 2mDa, and isotope peak shape deviation is less than or equal to 20.
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| CN106770803A (en) * | 2017-02-27 | 2017-05-31 | 江苏江大源生态生物科技股份有限公司 | Polyphenols HPLC/Q TOF MS detection methods in a kind of propolis |
| CN108037195A (en) * | 2017-11-20 | 2018-05-15 | 广西壮族自治区食品药品检验所 | The screening method and system of chemical composition are added in a kind of rice flour |
| CN108426953A (en) * | 2018-03-02 | 2018-08-21 | 内蒙古蒙牛乳业（集团）股份有限公司 | The method for detecting natamycin content in dairy produce |
| CN108828110B (en) * | 2018-09-11 | 2021-09-21 | 广东出入境检验检疫局检验检疫技术中心 | Method for determining residual quantity of benzimidazole drugs in chicken fat |
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