CN113219101A - Detection and screening method for exogenous risk substances in wine and application of detection and screening method in detection - Google Patents
Detection and screening method for exogenous risk substances in wine and application of detection and screening method in detection Download PDFInfo
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- CN113219101A CN113219101A CN202110550185.3A CN202110550185A CN113219101A CN 113219101 A CN113219101 A CN 113219101A CN 202110550185 A CN202110550185 A CN 202110550185A CN 113219101 A CN113219101 A CN 113219101A
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- 238000012544 monitoring process Methods 0.000 description 1
- YTJSFYQNRXLOIC-UHFFFAOYSA-N octadecylsilane Chemical class CCCCCCCCCCCCCCCCCC[SiH3] YTJSFYQNRXLOIC-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000000447 pesticide residue Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 229930188195 rebaudioside Natural products 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000001040 synthetic pigment Substances 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/14—Preparation by elimination of some components
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/26—Conditioning of the fluid carrier; Flow patterns
- G01N30/28—Control of physical parameters of the fluid carrier
- G01N30/34—Control of physical parameters of the fluid carrier of fluid composition, e.g. gradient
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/86—Signal analysis
- G01N30/8624—Detection of slopes or peaks; baseline correction
- G01N30/8631—Peaks
Abstract
The application provides a method for detecting compounds in wine, which comprises ultra-high performance liquid chromatography-quadrupole electrostatic field orbital trap high-resolution mass spectrometry. The screening method for exogenous risk substances in the wine, which is established by the invention, is sensitive and accurate, and can be suitable for quality control of the wine.
Description
Technical Field
The invention relates to a substance detection method, in particular to a detection and screening method of exogenous risk substances in wine and application of the detection and screening method in detection.
Background
As a food, the safety of wine has been concerned more and more in recent years, the safety risk of wine exists in each production link, and the quality of raw materials, brewing water, fermentation process, filling and the like may bring potential safety risk to wine. Exogenous risk of wine refers to the risk caused by harmful substances introduced from the outside during the wine production process. These harmful risk substances are mainly derived from the brewing environment, the raw materials used, the production equipment, the packaging materials, etc. Mainly comprises food additives and illegal additives, pesticide residues, heavy metals and the like. Because the additive is allowed to be used in the food production and processing process, the additive can be used within a specified dosage range only according to the standard to avoid the occurrence of harmful effects, but because part of food providers have insufficient knowledge on food safety or are driven by economic benefits, a plurality of illegal addition events are derived to be used excessively, and the dangerous substances are more frequently generated in food and are the key point of daily food risk monitoring.
The detection of exogenous risk substance additives in wine currently comprises ion chromatography, capillary electrophoresis, high performance liquid chromatography-mass spectrometry and the like, wherein the detection sensitivity of the ion chromatography and the capillary electrophoresis is limited; the liquid chromatography method cannot provide the chemical structure information of the target compound, and is easy to generate false positive phenomenon due to matrix interference in the actual sample analysis. In recent years, some reports of detecting exogenous risk substances in wine by adopting a high performance liquid chromatography-mass spectrometry combined method are provided, such as the method for simultaneously detecting 16 sweetening agents, preservatives and pigments in wine by adopting high performance liquid chromatography-tandem mass spectrometry, such as the Wanglian; li Yongle and the like adopt a liquid chromatogram/linear ion trap-electrostatic field orbit trap high-resolution mass spectrometry method to rapidly screen synthetic pigments in the wine; chenghong and the like adopt ultra-fast liquid chromatography-tandem mass spectrometry to determine 9 preservatives and sweeteners in the wine. The methods have better stability and detection limit, but the methods are limited to single or several risk substances, have the problems of few analyzed varieties and low detection efficiency, do not establish an effective rapid screening method, and are difficult to meet the requirements of qualitative and quantitative rapid detection on the current food safety.
Disclosure of Invention
In order to overcome the deficiency of the prior art, the technical problem that this application solved is: provides a method for detecting and screening compounds in wine and application thereof in detection. In order to solve the above technical problem, the technical solution adopted in the present application is as follows.
In some embodiments, the present application provides a method for detecting a compound in wine, comprising ultra high performance liquid chromatography-quadrupole electrostatic field orbitrap high resolution mass spectrometry.
In some embodiments, the liquid chromatography uses a gradient elution with a mobile phase of: time 0 min: a mixed solution of 10 percent of methanol and 90 percent of 5-10 mmol/L ammonium acetate aqueous solution; time 1 minute: a mixed solution of 10 percent of methanol and 90 percent of 5-10 mmol/L ammonium acetate aqueous solution; time 5 minutes: a mixed solution of 70 percent of methanol and 30 percent of 5-10 mmol/L ammonium acetate aqueous solution; and time 11 minutes: a mixed solution of 85 percent of methanol and 15 percent of 5-10 mmol/L ammonium acetate aqueous solution. In some embodiments, the liquid chromatography column is a thermo hypersil GOLD aQ (150 × 2.1mm, 1.9 μm), a column temperature of 30-50 ℃, a flow rate: 300-.
In some embodiments, the mass spectrometry employs a heated HESI source, a simultaneous positive and negative ion scanning mode, capillary voltage + -3.2 kv, sheath gas flow rate 30-40 arb, auxiliary gas flow rate 15-30 arb, purge gas flow rate 0-5 arb, atomization temperature 220 ℃, ion transport tube temperature 350 ℃, and scanning mode being a first-stage full-scan auto-trigger secondary scanning mode; the scanning range is 80-1200 m/z, the primary mass spectrum resolution is 70000, and the secondary mass spectrum resolution is 17500.
In some embodiments, the detection method further comprises diluting 5-20 times with ultrapure water. In some embodiments, the detection method further comprises centrifugation at 12000rpm/min at 4 ℃ to ambient temperature for 10 minutes. In some embodiments, the detection method further comprises 0.22 μm microfiltration.
In some embodiments, the present application provides a method of screening for a compound in wine, comprising: establishing standard data of at least one test compound; subjecting the sample to a detection method as described in some embodiments herein to obtain compound data; and performing matching analysis on the compound data and the standard data, and screening the test compound corresponding to the compound data.
In some embodiments, in the screening method, the compound data comprises: a compound liquid chromatography retention time for a plurality of compounds in the sample; compound molecular ions and/or characteristic fragment ion precise mass numbers of the plurality of compounds in the sample; a compound mass spectrum profile of the plurality of compounds in the sample; and a peak of a compound chromatographic response of the plurality of compounds in the sample. In some embodiments, in the screening method, the standard data comprises: standard liquid chromatography retention time of a standard solution of the test compound by the detection method of any one of claims 1 to 5; the number of standard molecular ions and/or characteristic fragment ions of the standard solution of the test compound, which are obtained by the detection method according to any one of claims 1 to 5, with a precise mass; and any one or more of standard mass spectrum spectra obtained by subjecting the standard solution of the test compound to the detection method according to any one of claims 1 to 5.
In some embodiments, the screening comprises screening the plurality of compounds for a retention time of the compound liquid chromatography within 3% of the retention time of the standard liquid chromatography and corresponding peaks of the compound chromatographic response greater than 1 x 104(ii) a The molecular ion and/or the characteristic fragment ion of the compound are in the exact mass number with the standard componentThe deviation of the accurate mass number of the daughter ions and/or the characteristic fragment ions is within 10ppm, and the corresponding chromatographic response peak value of the compound is more than 1 x 104(ii) a In the compound mass spectrogram, the abundance ratios of molecular ions, fragment ions and relative ions of the compound mass spectrogram and the standard mass spectrogram are matched; and/or the peak chromatographic response of the compound is greater than 1 x 104And (c) is as follows.
In some embodiments, the test compound is selected from one or more of the group consisting of acesulfame k, sodium saccharin, cyclamate, sucralose, aspartame, alitame, glycyrrhizin, neotame, rebaudioside D, stevioside, rebaudioside a, rebaudioside C, dulcoside a, rebaudioside B, rubusoside, lemon yellow, purplish red, amaranth, carmine, sunset yellow, acid red 2G, allura, brilliant blue, acid orange II, erythrosine, benzoic acid, and sorbic acid. In some embodiments, the standard solution is selected from the group consisting of 100 μ g/L aqueous acesulfame K, 100 μ g/L aqueous saccharin sodium, 100 μ g/L aqueous sodium cyclamate, 100 μ g/L aqueous sucralose, 100 μ g/L aqueous aspartame, 100 μ g/L aqueous alitame, 100 μ g/L aqueous glycyrrhizin, 100 μ g/L aqueous neotame, 100 μ g/L aqueous rebaudioside D, 100 μ g/L aqueous stevioside, 100 μ g/L aqueous rebaudioside A, 100 μ g/L aqueous rebaudioside C, 100 μ g/L aqueous dulcoside A, 100 μ g/L aqueous rebaudioside B, 100 μ g/L aqueous rebaudioside, 100 μ g/L aqueous lemon yellow, 100 μ g/L aqueous neotame, and combinations thereof, 100 μ G/L amaranth aqueous solution, 100 μ G/L carmine aqueous solution, 100 μ G/L sunset yellow aqueous solution, 100 μ G/L acid red 2G aqueous solution, 100 μ G/L allure red aqueous solution, 100 μ G/L brilliant blue aqueous solution, 100 μ G/L acid orange II aqueous solution, 100 μ G/L erythrosine aqueous solution, 5mg/L benzoic acid aqueous solution, and 5mg/L sorbic acid aqueous solution.
In some embodiments, the present application provides a method of detection as described in some embodiments of the present application or a method of screening as described in some embodiments of the present application for detecting one or more compounds selected from the group consisting of acesulfame k, saccharin sodium, cyclamate, sucralose, aspartame, alitame, glycyrrhizin, neotame, rebaudioside D, stevioside, rebaudioside a, rebaudioside C, dulcoside a, rebaudioside B, rubusoside, lemon yellow, new red, amaranth, carmine, sunset yellow, acid red 2G, allura red, brilliant blue, acid orange II, erythrosine, benzoic acid, and sorbic acid.
In some embodiments, the present application provides a use of a detection method as described in some embodiments of the present application or a screening method as described in some embodiments of the present application in detecting acesulfame k, saccharin sodium, cyclamate, sucralose, aspartame, alitame, glycyrrhizin, neotame, rebaudioside D, stevioside, rebaudioside a, rebaudioside C, dulcoside a, rebaudioside B, rubusoside, lemon yellow, new red, amaranth, carmine, sunset yellow, acid red 2G, allura, brilliant blue, acid orange II, erythrosine, benzoic acid, and sorbic acid.
The detection and screening method and its use in detection in some embodiments of the present application can bring about the following beneficial effects:
(1) the pretreatment is simple: only dilution, centrifugation and filtration are adopted.
(2) Safety and environmental protection: and an organic solvent is not used in the pretreatment process, so that the method is environment-friendly.
(3) The method for rapidly screening the exogenous risk substances in the wine is established, the analysis time is short, the types of the target substances are multiple, the screening efficiency of the exogenous risk substances in the wine is improved, and powerful guarantee is provided for exogenous risk prevention and control in the wine.
Drawings
FIG. 1 is a graph of normalized recovery of a solvent standard solution in some examples of the present application.
Fig. 2 is an ion flow graph of a screened target compound extraction in some embodiments of the present application.
Fig. 3-29 are secondary mass spectra of a screened compound of interest in some embodiments of the present application.
FIG. 30 is a graph of the effect of analysis of target compounds on different chromatography columns in some examples of the present application. The left is ZORBAX SB-C18 column and the right is ACQUITY UPLC HSS T3 column.
FIG. 31 is a graph of the effect of different dilution factors on the analysis of a target in some embodiments of the present application.
FIG. 32 is an extracted ion flow graph of an actual sample and a standard target in some embodiments of the present application.
Fig. 33 and 34 are secondary mass spectra of an actual sample and a standard target in some embodiments of the present application.
Detailed Description
In some embodiments, a pretreatment method for detection of exogenous risk substances in wine is provided. In some embodiments, a method of detecting an exogenous risk substance in wine is provided. In some embodiments, a method for detecting exogenous risk substances in wine using ultra-high performance liquid chromatography-quadrupole electrostatic field orbitrap high resolution mass spectrometry is provided. In some embodiments, a method for rapid screening of exogenous risk substances in wine is provided.
In some embodiments, a rapid screening method for exogenous risk substances in wine is provided, and comprises ultra-high performance liquid chromatography-quadrupole electrostatic field orbital trap high-resolution mass spectrometry. In some embodiments, a method for rapidly screening exogenous risk substances in wine is provided, and the method comprises sampling, diluting, centrifuging, filtering and ultra-high performance liquid chromatography-quadrupole electrostatic field orbitrap high-resolution mass spectrometry.
In some embodiments, sampling comprises measuring a volume of wine. In some embodiments, sampling comprises measuring 100-. In some embodiments, the diluting comprises diluting 5-20 times, preferably 10 times, with ultrapure water. In some embodiments, centrifugation comprises centrifugation at 12000rpm/min for 10 minutes at 4 ℃ to ambient conditions, and preferably at 12000rpm/min for 10 minutes. In some embodiments, the filtering comprises filtering with a 0.22 μm microporous filtration membrane.
In some embodiments, the filtered liquid is subjected to ultra performance liquid chromatography-quadrupole electrostatic field orbitrap high resolution mass spectrometry. In some embodiments, the ultra high performance liquid chromatography conditions comprise one or more of: ThermoHypersil GOLD aQ (150X 2.1mm, 1.9 μm) column, column temperature 30-50 ℃, flow rate: 300-400 μ L/min, the sample amount is 1-10 μ L, the mobile phase is methanol-5 mmol/L ammonium acetate water solution, and gradient elution is carried out. In some embodiments, the conditions for gradient elution are as in table 1 of example 1. In some embodiments, the ultra performance liquid chromatography column temperature is 40 ℃, flow rate: 350 mu L/min, and the sample injection amount is 10 mu L.
In some embodiments, the mass spectrometry conditions comprise one or more of: adopting a heating HESI source, a positive and negative ion simultaneous mode, and source parameters: capillary voltage is +/-3.2 kv, sheath gas flow rate is 30-40 arb (1arb is approximately equal to 0.3L/min), auxiliary gas flow rate is 15-30 arb, purge gas flow rate is 0-5 arb, atomization temperature is 220 ℃, ion transmission tube temperature is 350 ℃, and scanning mode is first-stage Full-scan automatic trigger second-stage scanning mode (Full MS/dd-MS 2); the scanning range is 80-1200 m/z, the primary mass spectrum resolution is 70000, and the secondary mass spectrum resolution is 17500. In some embodiments, the mass spectrum has a sheath gas flow rate of 40arb, an assist gas flow rate of 15arb, and a purge gas flow rate of 0 arb. In some embodiments, 1arb ≈ 0.3L/min. In some embodiments, 1arb ═ 0.3L/min.
In some embodiments, there is provided the use of the above detection method for detecting exogenous risk substances in wine. In some embodiments, exogenous risk substances in the wine include, but are not limited to: sweeteners (15 types): acesulfame potassium, saccharin sodium, cyclamate, sucralose, aspartame, alitame, glycyrrhizin, neotame, rebaudioside D, stevioside, rebaudioside a, rebaudioside C, dulcoside a, rebaudioside B, rubusoside; artificial pigments (10 types): lemon yellow, new red, amaranth, carmine, sunset yellow, acid red 2G, allura red, brilliant blue, acid orange II, erythrosine; preservatives (2 types): benzoic acid, sorbic acid.
In some embodiments, this includes establishing an accurate mass database of test compounds. In some embodiments, the method comprises establishing a mass spectral library of the test compound. In some embodiments, the accurate mass database includes compound name, molecular formula, chromatographic retention time, and accurate mass number information for molecular and characteristic fragment ions. In some embodiments, the mass spectral library comprises secondary mass spectra generated by applying different collision energies to the test compound. In some embodiments, the accurate mass database establishment method comprises preparing standard solutions of the test compound at a concentration of sweetener, pigment 100. mu.g/L, preservative 5mg/L, respectively. In some embodiments, the accurate mass database establishment method comprises direct sample injection by using a peristaltic pump equipped with the ultra-high performance liquid chromatography-quadrupole electrostatic field orbitrap high-resolution mass spectrometry instrument. In some embodiments, the accurate mass database building method includes performing analytical detection in positive and negative ion modes, respectively. In some embodiments, the accurate mass database building method comprises determining the molecular ion accurate mass number of the corresponding test compound. In some embodiments, the accurate mass database building method includes applying collision energy to each test compound to obtain fragment ions for each compound. In some embodiments, the accurate mass database building method comprises optimizing electrospray voltage, ion source temperature, sheath gas flow, mass spectrometry key parameters. In some embodiments, the accurate quality database establishment method comprises preparing a mixed standard solution of the compounds to be tested with the concentrations of the sweetener, the pigment of 100 mug/L and the preservative of 5mg/L, and optimizing the separation conditions of the ultra-high performance liquid chromatography to obtain the chromatographic retention time of each compound. In some embodiments, the accurate mass database building method comprises separately inputting the name, molecular formula, molecular ion accurate mass number, fragment ion accurate mass number, chromatographic retention time for each compound. In some embodiments, the mass spectrum library establishment method comprises preparing standard solutions of the test compound at a concentration of sweetener, pigment 100. mu.g/L, and preservative 5mg/L, respectively. In some embodiments, the mass spectrum library establishment method comprises direct sample injection analysis by using a peristaltic pump equipped with the ultra-high performance liquid chromatography-quadrupole electrostatic field orbitrap high-resolution mass spectrometry instrument. In some embodiments, the mass spectral library creation method comprises setting a series of different collision energies, fragmenting the target compound to obtain a secondary mass spectrum for each compound. In some embodiments, the mass spectral library building method comprises inputting and storing all secondary mass spectral spectra. In some embodiments, the mass spectral library establishment method can result in a mass spectral library of all compounds to be tested.
In some embodiments, an experimental data alignment analysis is included. In some embodiments, the comparative analysis of the test data comprises the comparative analysis of the results of the test data from the sample testing against an established database of accurate mass numbers and mass spectra of the test compounds. In some embodiments, the comparative analysis of experimental data comprises a positive sample only if the exact mass numbers, chromatographic retention times, and secondary mass spectra of the molecular ion and the two characteristic fragment ions all match in the exact mass database. In some embodiments, the experimental data comparison analysis comprises setting a mass number extraction window and a retention time window, and performing comparison analysis on the collected sample data according to the set parameters. In some embodiments, the comparison analysis of experimental data includes performing the extraction of the exact mass number of molecular ions in the database according to set parameters, such as mass number extraction window, chromatographic peak response. In some embodiments, the comparative analysis of experimental data comprises the mass number of the molecular ion of the target compound in the database if present in the data collected from the full scan of the sample, and the peak response of the chromatogram is not less than 1 × 104Then, the comparison of the accurate mass number of the molecular ions is successful. In some embodiments, the comparative analysis of experimental data comprises the mass number of the molecular ion of the target compound in the database if present in the data collected from the full scan of the sample, and the peak response of the chromatogram is not less than 1 × 105Then, the comparison of the accurate mass number of the molecular ions is successful. In some embodiments, the experimental data alignment analysis comprises setting the chromatographic retention time bias to 0.5%. In some embodiments, the comparative analysis of experimental data comprises considering a retention time match as successful if the chromatographic retention time of the molecular ions falls within 0.5% of the corresponding retention time deviation in the database. In some embodiments, the experimental data alignment analysis comprises setting the chromatographic retention time bias to 2%. In some embodiments, the comparative analysis of experimental data includes if chromatographic retention of molecular ions is presentIf the time difference is within 2% of the corresponding retention time deviation in the database, the retention time matching is considered to be successful. In some embodiments, the experimental data alignment analysis comprises setting the chromatographic retention time bias to 3%. In some embodiments, the comparative analysis of experimental data comprises considering a retention time match as successful if the chromatographic retention time of the molecular ions falls within 3% of the corresponding retention time deviation in the database. In some embodiments, the experimental data alignment analysis includes alignment of the characteristic fragment ions in the database with the fragment ions obtained from the experimental result collection. In some embodiments, the comparative analysis of experimental data comprises a successful match if the experimental value does not deviate by more than 5ppm from the exact mass number of fragment ions in the database. In some embodiments, the comparative analysis of experimental data comprises a successful match if the experimental value does not deviate by more than 10ppm from the exact mass number of fragment ions in the database. In some embodiments, the comparative analysis of experimental data comprises comparing secondary mass spectra obtained from the experimental acquisition to a library of mass spectra. In some embodiments, the comparison analysis of experimental data includes comparison of molecular ions, fragment ions, and relative ion abundance ratios, and if all matches, the match is deemed successful.
To further clarify the technical solutions and effects adopted by the present application to achieve the intended purpose, the following detailed description is given of specific embodiments, structures, features and effects according to the present application with reference to the accompanying drawings and preferred embodiments.
The 10 pigments, 2 preservatives in the following examples 1 to 7 were purchased from the national center for standards substance; 15 sweeteners were purchased from Sigma, usa; ammonium acetate was purchased from Sigma, usa; methanol, available from TEDIA corporation, usa.
Ultra high performance liquid chromatography-quadrupole electrostatic field orbitrap high resolution mass spectrometer (Thermo Fisher Scientific), analytical balance (METTLER TOLEDO XP205), pure water instrument (icompu RM-220), centrifuge (HettichMikro 220R, germany).
A chromatographic column: ZORBAX SB-C18 (100X 2.1mm, 1.8 μm) by Agilent; thermo's Hypersil GOLD aQ (150X 2.1mm, 1.9 μm); ACQUITY UPLC HSS T3 (100X 2.1mm, 1.8 μm) from Waters.
Example 1 determination of exogenous Risk substances in wine by chromatography column (ThermoHypersil GOLD aQ)
The experimental method comprises the following steps:
[ PREPARATION OF STANDARD SOLUTION ]
Respectively and accurately weighing 0.1000g of 27 standard substances in a 100mL brown volumetric flask, dissolving the 27 standard substances with ultrapure water, diluting to 100mL, preparing a 1000mg/L standard stock solution, and storing the stock solution in a refrigerator at 4 ℃.
[ pretreatment of sample ]
Adding 100 μ L of wine sample into 2mL PV centrifuge tube, adding 900 μ L of ultrapure water, mixing, centrifuging at 4 deg.C for 10min at 12000rpm/min, collecting supernatant, and filtering with 0.22 μm microporous membrane.
[ Instrument analysis ]
And performing ultra-high performance liquid chromatography-quadrupole electrostatic field orbit trap high-resolution mass spectrometry detection.
The conditions of the ultra-high performance liquid chromatography are as follows: thermo's Hypersil GOLD aQ (150X 2.1mm, 1.9 μm) column, detection temperature 40 deg.C, sample size 10 μ L; the flow rate was 350. mu.L/min, the analysis time was 15min, and the composition ratio of the mobile phase in the gradient elution is shown in Table 1.
TABLE 1 composition ratio of mobile phase in gradient elution
The mass spectrum conditions are as follows: adopting a heating HESI source, a positive and negative ion simultaneous mode, and source parameters: capillary voltage 3.2kv, sheath gas flow rate 40arb (1arb is approximately equal to 0.3L/min), auxiliary gas flow rate 15arb, purge gas flow rate 0arb, atomization temperature 220 ℃, ion transport tube temperature 350 ℃; and (2) adopting a primary Full-scan automatic triggering secondary scanning mode (Full MS/dd-MS2), wherein the mass-to-charge ratio range of primary mass spectrum scanning is 80-1150 m/z, the resolution is 70000, and the Maximum IT: 200ms, AGC target: 1e6(ii) a The mass-to-charge ratio range of the secondary mass spectrum scanning is as follows: the resolution of 50-1150 m/z is 17500, Maximum IT: 200ms, AGC target: 5e4。
Establishment of accurate mass database and mass spectrum library of compound to be tested
Establishing an accurate quality database: respectively preparing standard solutions of the compounds to be detected with the concentrations of sweetener (100 mug/L), pigment (100 mug/L) and preservative (5mg/L), directly injecting samples by using a peristaltic pump equipped with an ultra-high performance liquid chromatography-quadrupole electrostatic field orbital trap high-resolution mass spectrometer, and respectively carrying out analysis and detection in a positive ion mode and a negative ion mode to determine the accurate mass number of the molecular ions of the corresponding compounds to be detected; collision energy is applied to each test compound to obtain fragment ions of each compound.
The actual molecular ion mass number, fragment ion, and collision energy of the test compound are shown in Table 2.
TABLE 2 exact molecular ion mass number and fragment ion, collision energy of the test compound
Note: "-" indicates that the crash energy employed is normalized crash energy: 30. 50, 70eV
Preparing a mixed standard solution of the compounds to be detected with the concentration of the sweetening agent, the pigment of 100 mu g/L and the preservative of 5mg/L, and optimizing the separation condition of the ultra-high performance liquid chromatography to obtain the chromatographic retention time of each compound.
Establishing an accurate quality database: respectively inputting the name, molecular formula, molecular ion accurate mass number, fragment ion accurate mass number and chromatogram retention time of each compound, and also inputting the response threshold of the compound to be detected, and when the signal response of the compound to be detected exceeds the threshold, further performing secondary mass spectrometry on the corresponding molecular ions.
Matrix effect
The grape wine is rich in organic acid, saccharide, pigment and other components, and thus has complicated matrix. When the sample is subjected to spray ionization, the non-volatile components in the matrix and the substances to be detected compete in the ionization process of the droplet surface, and the ionization efficiency at the electrospray interface is influenced. These non-volatile matrix components attract the droplets together, prevent them from breaking down into smaller droplets, enhance (ion enhance) or hinder (ion inhibit) the efficiency of analyte ion formation, and there is a matrix effect. Eliminating matrix effect and selecting proper sample pretreatment method; selecting appropriate chromatographic separation conditions; calibration with a matrix standard solution, etc. After the pretreatment method and the instrument conditions are optimized, the matrix effect still exists in the solvent standard preparation, as shown in figure 1, the matrix enhancement effect (the recovery rate is 120-173%) exists in the low-concentration standard addition recovery of most natural sweeteners, the low-concentration standard addition of artificial pigment lemon yellow and the standard addition recovery rate of preservatives (benzoic acid and sorbic acid) are lower than 20%, and the matrix inhibition effect exists. The invention adopts the matrix standard solution for correction, and can well eliminate the matrix effect.
Optimization of chromatographic conditions
The ammonium acetate is added into a mobile phase system, so that the retention of a target compound on a chromatographic column is facilitated, the ionization degree is improved, and the signal response is enhanced. The invention compares the influence of acetonitrile-5 mmol/L ammonium acetate solution, methanol-5 mmol/L ammonium acetate solution and methanol-10 mmol/L ammonium acetate solution mobile phase systems on the resolution, peak shape and the like of a target compound. The results show that the preservative has uneven baseline and poor peak shape in the acetonitrile-ammonium acetate aqueous solution mobile phase system. The 27 target compounds can be well separated and well responded in a methanol-ammonium acetate aqueous solution mobile phase system, and the isomeride stevioside and rebaudioside B are separated from the baseline through the optimization of a gradient elution program. The methanol-5 mmol/L ammonium acetate aqueous solution and the methanol-10 mmol/L ammonium acetate aqueous solution mobile phase system have no obvious difference in response to a target object, and the methanol-5 mmol/L ammonium acetate aqueous solution is selected as the optimal mobile phase in consideration of environmental protection and cost problems. The extracted ion flow diagram of the target compound is shown in fig. 2.
Mass spectrometry condition optimization
Scanning the standard solution of 27 compounds in a positive ion mode and a negative ion mode respectively, and finding that except aspartame, the abundance intensity of molecular ion peaks of other target compounds in the negative ion mode is higher than that in the positive ion mode; aspartame has the strongest abundance of its molecular ions in positive ion mode. AnSaimi, saccharin sodium, sodium cyclamate and 9 pigments containing Na+Or K+In the absence of all Na+Or K+Then, none or part of the sites react with H+Combined to finally form [ M-nNa + mH](n-m)-or [ M-nNa + mH](n-m)-ions. Aspartame contains-NH2Group, susceptible to form [ M + H ] in positive ion mode]+Ions. The preservatives benzoic acid, sorbic acid and the remaining 11 sweeteners contain-OH and, in the negative ion mode, lose H+Form [ M-H ]]-Ions. The invention selects a mode of simultaneously scanning positive and negative ions, and obtains information such as ionization modes, accurate mass numbers and the like of 27 target compounds after optimizing conditions. The method adopts a full MS/dd-MS2 mode of Q active high-resolution mass spectrum to analyze 27 target compounds, and in the actual scanning process, when molecular ions in a target list are found by primary full scanning and the signal intensity exceeds a preset value, a data-dependent sub-ion scanning mode is triggered, so that secondary ion full-scanning mass spectrum information corresponding to the accurate mass number of the molecular ions is obtained and is shown in figures 3 to 29, and qualitative confirmation is realized.
Linear range and detection limit
Under the optimized condition, a series of mixed standard solutions of 27 compounds are prepared, and a standard curve is drawn by taking a peak area (y) as a vertical coordinate and taking a mass concentration (x) as a horizontal coordinate. The detection Limit (LOD) is determined according to a 3-fold signal-to-noise ratio determination method, and the limit of quantification (LOQ) is determined according to a 10-fold signal-to-noise ratio determination method, and the results are shown in Table 3. As can be seen from table 3, the 27 target compounds have good linear relationship within the respective mass concentration ranges, and the relevant dilutions are all > 0.991; the quantitative limit of the method is between 0.2 and 263.7 mu g/L.
Linear ranges, regression equations, correlation coefficients and quantitative limits for the 327 exogenous risk substances in Table
Recovery and precision
27 kinds of exogenous risk substances are added into a blank wine sample, and the added standard mass concentration of the sweetener and the artificial pigment is 3 levels of 100.0, 200.0 and 500.0 mu g/L respectively. As the limit of the preservative benzoic acid in the wine is 0.2g/kg, and the quantitative limit is different from the sweetener and artificial pigment in order of magnitude, the standardized mass concentration of the preservative is 3 levels of 10mg/L, 20mg/L and 50 mg/L. Pretreatment was performed as described above, followed by instrumental analysis, 3 replicates per addition level, resulting in process recovery and precision, with the results shown in table 4. The average recovery rate of exogenous risk substances in 27 kinds of wine at 3 addition levels is 76.0-115.5%, and the Relative Standard Deviation (RSD) is 0.4-12.0%, which shows that the precision and the accuracy are better.
TABLE 4 sample recovery test results with additional labeling
EXAMPLE 2 Effect of selection of different chromatography columns on the effectiveness of the analysis
The 27 target compounds range from medium polarity to polarity, and the present invention compares the effects of ZORBAX SB-C18 (2.1X 100mm, 1.8 μm), ACQUITY UPLC HSS T3 (2.1X 100mm, 1.8 μm), Hypersil GOLD aQ (150X 2.1mm, 1.9 μm)3 columns on the degree of separation, response, peak shape, etc. of the target compounds.
The column was as follows, and the rest of the experimental procedure was the same as in example 1.
A chromatographic column 1: ZORBAX SB-C18 (2.1X 100mm, 1.8 μm)
And (3) chromatographic column 2: ACQUITY UPLC HSS T3 (2.1X 100mm, 1.8 μm)
A chromatographic column 3: hypersil GOLD aQ (150X 2.1mm, 1.9 μm)
As a result, the natural sweetener concentration is higher than 100 mug/L, and the peak of the natural sweetener concentration on an ACQUITY UPLC HSS T3 chromatographic column is forked; when ZORBAX SB-C18 was used, the preservative had poor polarity and retention, and the artificial pigments lemon yellow and carmine had split peaks, as shown in FIG. 30. The 27 exogenous risk substances completely achieve baseline separation on the Hypersil GOLD aQ chromatographic column, and the peak shapes are symmetrical and sharp. The Hypersil GOLD aQ chromatographic column is a polar modified octadecylsilane chemically bonded silica chromatographic column, and a polar embedding and end-capping technology is adopted, so that higher retention and separation degree can be provided for polar compounds, and a symmetrical peak shape can be obtained.
Example 3 Effect of different dilution factors on assay Effect
The effect of different dilution factors on the analytical effect was analyzed, the dilution factors are as follows, and the rest of the experimental procedures are the same as in example 1.
Dilution factor 1: diluting with ultrapure water by 5 times
Dilution factor 2: diluting with ultrapure water by 10 times
Dilution factor 3: diluting with ultrapure water 20 times
The effect of 3 different dilution times on the analysis effect of the target object was examined in this experiment, as shown in fig. 31. The dilution times are too small, the content of interferents in the wine is high, and certain interference exists on the target substances, so that the recovery rate is higher or lower; the target substance is diluted with a large dilution factor, the peak shape is poor, and the recovery rate is not ideal. When the dilution multiple is 10, the recovery rate of the 27 exogenous risk substances is between 71.3 and 101.4 percent. The dilution factor of 10 was chosen as the optimal dilution factor.
EXAMPLE 4 Effect of different centrifugation temperatures on the Effect of analysis
The effect of different centrifugation temperatures on the analytical results was analyzed, the centrifugation temperatures were as follows, and the rest of the experimental procedures were the same as in example 1.
Centrifugation temperature 1: normal temperature (about 20 degree)
Centrifugation temperature 2: 10 deg.C
Centrifugation temperature 3: 4 deg.C
The experiment investigates the influence of different centrifugal temperatures on the analysis effect of the target object. The wine contains lipid, saccharide, etc., and some target compounds have poor peak shape and trailing peak when centrifuged at normal temperature and 10 deg.C. Under the condition of low temperature, lipid and carbohydrate substances are crystallized, and solid-liquid separation is carried out during centrifugation, so that the influence of the low-temperature crystallized substances such as the lipid and the carbohydrate in the wine on the analysis peak shape of the target substance is eliminated.
Example 5 optimization of mass spectrometry conditions: effect of atomization temperature on analytical Effect
The invention analyzes the influence of different atomization temperatures on the analysis effect, the atomization temperatures are as follows, and the rest experimental steps are the same as example 1.
Atomization temperature 1: 200 deg.C
Atomization temperature 2: 220 deg.C
Atomization temperature 3: 240 ℃ C
The appropriate atomization temperature can enable the target compound to have better sensitivity and response value, the too high atomization temperature can cause the analyte to be decomposed and not to be detected, the too low atomization effect is poor, the sensitivity of the target compound is low, and the like. The experiment investigates the influence of different atomization temperatures on the analysis effect of the target object under the mass spectrum condition. The results show that: at the atomizing temperature of 200 ℃, the response of compounds such as benzoic acid, sorbic acid and the like is low, because the atomizing temperature is low, the atomizing effect is poor, and the response of target compounds is low; when the atomization temperature is 240 ℃, the response of benzoic acid and sorbic acid is low. The optimum atomization temperature is 220 ℃.
EXAMPLE 6 detection of exogenous Risk substances in actual samples
27 exogenous risk substances were detected in 10 commercial wines using the method of example 1. The results are shown in Table 5, wherein the wine sample No. 7 contains acesulfame potassium in an amount of 65.3. mu.g/L.
TABLE 5 results of screening for exogenous risk substances in wine samples
Remarking: ND: below the detection limit
Example 7 comparative analysis of exogenous Risk substances in actual samples
The results of the actual sample experimental data in example 6 were compared with the established accurate mass database and mass spectrum library of the target compound, and the comparison results are shown in table 6. The extracted ion flow graph and secondary mass spectrum of the actual sample and the standard target are shown in fig. 32 to 34. The result shows that the retention time deviation is 1.2 percent, the mass deviation of molecular ions and fragment ions is 0-0.3 ppm, the abundance ratio of the secondary mass spectrum is completely matched, and the fact that the actual sample contains the substance can be confirmed by comparing and analyzing the precise mass database and the mass spectrum library of the acesulfame potassium and the compound to be detected in the actual sample.
TABLE 6 results of comparison analysis of actual samples with databases and spectral libraries
The above embodiments are only preferred embodiments of the present application, and the protection scope of the present application is not limited thereto, and any insubstantial changes and substitutions made by those skilled in the art based on the present application are intended to be covered by the present application.
Claims (10)
1. A method for detecting compounds in wine is characterized by comprising ultra-high performance liquid chromatography-quadrupole electrostatic field orbital trap high-resolution mass spectrometry.
2. The detection method of claim 1, wherein the liquid chromatography is performed
Using gradient elution, the mobile phase of the gradient elution is:
time 0 min: a mixed solution of 10 percent of methanol and 90 percent of 5-10 mmol/L ammonium acetate aqueous solution;
time 1 minute: a mixed solution of 10 percent of methanol and 90 percent of 5-10 mmol/L ammonium acetate aqueous solution;
time 5 minutes: a mixed solution of 70 percent of methanol and 30 percent of 5-10 mmol/L ammonium acetate aqueous solution; and
time 11 minutes: a mixed solution of 85 percent of methanol and 15 percent of 5-10 mmol/L ammonium acetate aqueous solution;
and/or
The column was ThermoHypersil GOLD aQ (150X 2.1mm, 1.9 μm), the column temperature was 30-50 ℃, the flow rate: 300-.
3. The detection method of claim 1, wherein the mass spectrometry is performed
Adopting a heating HESI source and a positive and negative ion simultaneous scanning mode, wherein the capillary voltage is +/-3.2 kv, the sheath gas flow rate is 30-40 arb, the auxiliary gas flow rate is 15-30 arb, the purging gas flow rate is 0-5 arb, the atomization temperature is 220 ℃, the ion transmission tube temperature is 350 ℃, and the scanning mode is a first-stage full-scanning automatic triggering second-stage scanning mode; the scanning range is 80-1200 m/z, the primary mass spectrum resolution is 70000, and the secondary mass spectrum resolution is 17500.
4. The detection method of claim 1, further comprising:
diluting with ultrapure water by 5-20 times;
centrifuging at 12000rpm/min at 4-normal temperature for 10 min; and
filtering with 0.22 μm microporous membrane
Any one or more of.
5. A method for screening compounds in wine, comprising:
establishing standard data of at least one test compound;
subjecting the sample to the detection method of any one of claims 1 to 4 to obtain compound data; and
and performing matching analysis on the compound data and the standard data, and screening the test compound corresponding to the compound data.
6. The screening method of claim 5,
the compound data include:
a compound liquid chromatography retention time for a plurality of compounds in the sample;
compound molecular ions and/or characteristic fragment ion precise mass numbers of the plurality of compounds in the sample;
a compound mass spectrum profile of the plurality of compounds in the sample; and
a peak in a compound chromatographic response of the plurality of compounds in the sample
Any one or more of;
and/or
The standard data includes:
standard liquid chromatography retention time obtained by subjecting a standard solution of the test compound to the detection method according to any one of claims 1 to 4;
the number of standard molecular ions and/or characteristic fragment ions of the standard solution of the test compound, which are obtained by the detection method according to any one of claims 1 to 4, with a precise mass; and
standard mass spectrum obtained by carrying out detection method according to any one of claims 1 to 4 on standard solution of the test compound
Any one or more of.
7. The screening method of claim 6, wherein the screening comprises
Screening the plurality of compounds
The retention time of the compound liquid chromatogram is within 3% of the retention time of the standard liquid chromatogram, and the corresponding chromatographic response peak value of the compound is more than 1 x 104(ii) a And/or
In the accurate mass number of the compound molecular ions and/or the characteristic fragment ions, the deviation of the accurate mass number of the compound molecular ions and/or the characteristic fragment ions from the accurate mass number of the standard molecular ions and/or the characteristic fragment ions is within 10ppm, and the corresponding chromatographic response peak value of the compound is more than 1 x 104(ii) a And/or
In the compound mass spectrogram, the abundance ratios of molecular ions, fragment ions and relative ions of the compound mass spectrogram and the standard mass spectrogram are matched; and/or
The chromatographic response peak value of the compound is more than 1 x 104In (1).
8. The screening method of claim 6,
the test compound is selected from one or more of the group consisting of acesulfame potassium, saccharin sodium, sodium cyclamate, sucralose, aspartame, alitame, glycyrrhizin, neotame, rebaudioside D, stevioside, rebaudioside A, rebaudioside C, dulcoside A, rebaudioside B, rubusoside, lemon yellow, purplish red, amaranth, carmine, sunset yellow, acid red 2G, allura red, brilliant blue, acid orange II, erythrosine, benzoic acid and sorbic acid, and/or
The standard solution is selected from the group consisting of 100 μ g/L aqueous acesulfame K solution, 100 μ g/L aqueous saccharin sodium solution, 100 μ g/L aqueous sodium cyclamate solution, 100 μ g/L aqueous sucralose solution, 100 μ g/L aqueous aspartame solution, 100 μ g/L aqueous alitame solution, 100 μ g/L aqueous glycyrrhizin solution, 100 μ g/L aqueous neotame solution, 100 μ g/L aqueous rebaudioside D solution, 100 μ g/L aqueous stevioside solution, 100 μ g/L aqueous rebaudioside A solution, 100 μ g/L aqueous rebaudioside C solution, 100 μ g/L aqueous dulcoside A solution, 100 μ g/L aqueous rebaudioside B solution, 100 μ g/L aqueous rubusoside solution, 100 μ g/L aqueous lemon yellow solution, 100 μ g/L aqueous neotame solution, 100 μ g/L aqueous rebaudioside A solution, and mixtures thereof, 100 μ G/L amaranth aqueous solution, 100 μ G/L carmine aqueous solution, 100 μ G/L sunset yellow aqueous solution, 100 μ G/L acid red 2G aqueous solution, 100 μ G/L allure red aqueous solution, 100 μ G/L brilliant blue aqueous solution, 100 μ G/L acid orange II aqueous solution, 100 μ G/L erythrosine aqueous solution, 5mg/L benzoic acid aqueous solution, and 5mg/L sorbic acid aqueous solution.
9. Use of the assay of any one of claims 1 to 4 or the screening method of any one of claims 5 to 8 for the detection of one or more compounds selected from the group consisting of acesulfame potassium, saccharin sodium, cyclamate, sucralose, aspartame, alitame, glycyrrhizin, neotame, rebaudioside D, stevioside, rebaudioside a, rebaudioside C, dulcoside a, rebaudioside B, rubusoside, lemon yellow, purplish red, amaranth, carmine, sunset yellow, acid red 2G, allura red, brilliant blue, acid orange II, erythrosine, benzoic acid, and sorbic acid.
10. Use of the detection method of any one of claims 1 to 4 or the screening method of any one of claims 5 to 8 in the detection of acesulfame k, sodium saccharin, cyclamate, sucralose, aspartame, alitame, glycyrrhizin, neotame, rebaudioside D, stevioside, rebaudioside a, rebaudioside C, dulcoside a, rebaudioside B, rubusoside, lemon yellow, purplish red, amaranth, carmine, sunset yellow, acid red 2G, allura red, brilliant blue, acid orange II, erythrosine, benzoic acid, and sorbic acid.
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