CN105699580A - Method for measuring organic acid content based on precolumn derivatization LC-MS - Google Patents
Method for measuring organic acid content based on precolumn derivatization LC-MS Download PDFInfo
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- G—PHYSICS
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- 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
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- G—PHYSICS
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- 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
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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
- G01N2030/067—Preparation by reaction, e.g. derivatising the sample
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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
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
- G01N2030/8809—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample
- G01N2030/884—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample organic compounds
Abstract
The invention discloses a method for measuring organic acid content based on precolumn derivatization LC-MS, and belongs to the field of analytical chemistry.The method comprises the steps that 1, a sample to be tested, sodium carbonate and 2-bromoacetophenone are added to a solvent, a derivatization reaction is carried out for 20 h to 28 h at the temperature of 50 DEG C to 60 DEG C after even mixing, and the product is cooled for use; 2, the reaction product in the step 1 is taken for liquid chromatogram-mass spectrum analysis, and the content of organic acid in the sample to be detected is calculated by referring to a standard curve.A chemical modification technology is adopted for derivatization of the organic acid, the physicochemical characteristic of the organic acid is changed, the ionization efficiency can be improved in hygroplasm combined detection, matrix interference can be reduced, meanwhile, interference of inorganic salt and endogenous impurities is reduced, the signal strength ofanalyte is improved, and chromatographic separation and mass spectrometric detection are convenient; then a liquid chromatogram-mass spectrum combined technology is adopted for analyzing and detecting the derivatization product, qualitative and quantitative analysis on the organic acid can be achieved, and the advantages of being simple, efficient, high in detecting sensitivity, good in accuracy and the like are achieved.
Description
Technical field
The present invention relates to a kind of organic acid assay method, be specifically related to a kind of LC-MS based on column front derivation method measuring organic acid content, belong to analytical chemistry field。
Background technology
Organic acid is the class important substance affecting fruit-like flavour, its kind and content and the quality of fruit, local flavor are closely related, affect the Maturity of fruit, including tartaric acid, malic acid, citric acid, succinic acid etc., there is raising immunity of organisms, suppress cerebrum lipid peroxide to generate, the effect such as anticancer。Accurate analysis, measure organic acid kind and content in sample, kinds of organic acids research in root exudates and taste of fruit characteristic and quality evaluation are had great importance。
At present, organic acid assay method mainly include gas chromatography, high performance liquid chromatography, from chromatography and gas chromatography mass spectrometry, Liquid Chromatography/Mass Spectrometry, wherein gas chromatography needs first to be derived by organic acid as volatile substances when detection, complex operation and testing result accuracy are relatively low, though and high performance liquid chromatography is easy and simple to handle, result favorable reproducibility, but owing to organic acid polarity is relatively strong, retention time on a column is shorter, it is difficult to efficiently separate with impurity, it is impossible to ensure the sensitivity of detection。In addition in fruit, organic acid has similar chemical constitution more, and spectral quality is similar with pKa value, also seriously hinders and analyzes the carrying out measured。
Chemical derivatization technology is to be connected on target compound by chemical reaction by certain special groups, is converted into a kind of derivant with new physico-chemical property, then is analyzed derivant measuring, thus the method for indirect qualitative, quantitative target compound。In view of containing carboxylic group in organic acid, its derivatization can use for reference the analysis detection of perfluoro caprylic acid, sodium valproate, gamma-hydroxybutyric acid etc.。General, the derivatization reagent based on LC-MS should meet following 3 requirements: 1) requires not harsh to reaction condition, it is possible to fast quantification；2) generating a kind of derivant with after a certain component reaction in sample just for property, the separation of sample, detection be not by the interference of byproduct of reaction and excessive derivatization reagent；3) derivatization reagent is cheap and easy to get, versatility is good, can form metastable derivant with example reaction rapidly, effectively and specifically。
The patent of invention of publication No. CN103698450A discloses a kind of organic acid method in gas chromatography-mass spectrum detection cell, including: in born of the same parents' intracellular metabolite matter sample, add amino acid derived dose, centrifuging and taking supernatant after constant temperature standing, supernatant is carried out gas chromatography-mass spectrometry analysis, wherein amino acid derived dose is the trifluoroacetyl amine aqueous solution of trim,ethylchlorosilane, gas chromatographic column adopts HP-5MS or DB-5MS capillary column, detector temperature 250 DEG C, staged maintains 3min after being warming up to 300 DEG C, mass spectral analysis adopts EI ion source, detector is level Four bar, ionization energy 70eV, ion source surface temperature 280 DEG C。The method can measure in born of the same parents such as multiple organic acid such as succinic acid, malic acid, citric acids, and chromatography is respond well, but testing result accuracy and sensitivity need raising。
Summary of the invention
It is an object of the invention to provide a kind of LC-MS based on column front derivation method measuring organic acid content, the method is easy and simple to handle, and testing result accuracy is good, highly sensitive, less costly。
In order to realize object above, the technical solution adopted in the present invention is:
Based on the LC-MS of the column front derivation method measuring organic acid content, comprise the following steps:
1) testing sample, sodium carbonate and 2-bromoacetophenone are added in solvent, after mixing at 50～60 DEG C derivative reaction 20～28h, cool down standby；
2) take step 1) in product carry out LC-MS analysis, reference standard curve calculates organic acid content in testing sample。
Common binary or tribasic organic acid in described organic acid such as fruit, such as malic acid, citric acid etc.。
Step 1) in sodium carbonate can react generation sodium citrate with organic acid (such as malic acid, citric acid etc.), compare organic acid, its sodium salt is more easy to and reacts generation derivative products with 2-bromoacetophenone。
Step 1) in 2-bromoacetophenone be chemical derivatization reagent, two kinds of products can be generated with organic acid reaction, a kind of it is and the product 1 of a carboxyl generation esterification in organic acid, another kind is and the product 2 of two carboxyl generation esterifications, owing to product 1 is difficult to efficiently separate with impurity in liquid-phase chromatographic analysis, elite product 2 of selecting makes qualitative and quantitative analysis。Experiments verify that, testing result will not be produced harmful effect by the excessive interpolation of 2-bromoacetophenone。
Step 1) in solvent can adopt anhydrous acetonitrile, ethyl acetate, oxolane etc.。Preferably without water-acetonitrile, character is more stable。Experiments verify that, testing result more or less all will not be produced harmful effect by anhydrous acetonitrile addition。
Step 1) in for promoting testing sample (when making standard curve, take organic acid standard substance to be measured), sodium carbonate disperses in anhydrous acetonitrile, dissolves completely, can first by testing sample (when making standard curve, take organic acid standard substance to be measured), sodium carbonate be dissolved in a small amount of water, then at anhydrous acetonitrile mix。
Step 2) in the chromatographic condition of LC-MS analysis be: chromatographic column: Agilent EclipsePlusC18, specification: 2.1 × 150mm, 3.5 μm；Mobile phase: 0.1% acetic acid aqueous solution: methanol (v/v)=2:3, analysis time: 0～12min, flow velocity: 0.2mL/min；Sample size: 5 μ L。
Step 2) in the Mass Spectrometry Conditions of LC-MS analysis be: ion source: electron spray ionisation source (ESI) positive ion mode；Capillary voltage: 4500V；Dry temperature: 220 DEG C；Dry gas stream speed: 4L/min；Atomization gas air pressure: 199.9KPa。Liquid phase adopts Agilent 1260 type chromatograph of liquid, and mass spectrum adopts Brooker amaZonSL ion trap mass spectrometer。
Step 2) manufacture method of standard curve is: takes organic acid standard substance to be measured and is configured to the standard solution of series concentration, standard solution adds sodium carbonate and 2-bromoacetophenone, and at 50～60 DEG C derivative reaction 20～28h, react complete, take product and carry out LC-MS analysis, with the peak area corresponding to product, its concentration is done regression analysis, obtain the relation curve of material concentration and peak area。
Beneficial effects of the present invention:
Organic acid is performed the derivatization process by chemical modification technology by the present invention, change its physicochemical characteristics, Ionization Efficiency can be improved in LC-MS detects, reduce matrix interference, reduce the interference of inorganic salt and endogenous impurity simultaneously, improve the signal intensity of analyte, it is simple to chromatographic isolation and Mass Spectrometer Method, recycling LC-MS-MS analysis detection derivatization product, can realize organic acid qualitative and quantitative analysis。Relative to existing organic acid detection technique, the method has advantages such as simple, efficient, adopts conventional chromatogram post can realize efficiently separating of object and impurity, and mass spectral analysis is respond well, and detection sensitivity is high, and accuracy is good。
In the present invention, chemical derivatization reagent 2-bromoacetophenone has the advantages such as big, the derivative efficiency of molar absorption coefficient is high, cheap and easy to get。It addition, adopt electron spray ionisation source positive ion mode can significantly improve the sensitivity (comparing LC-MS negative ion mode) of detection during mass spectral analysis, it is adaptable to low content organic acid analysis detects。
Accompanying drawing explanation
Fig. 1 is the liquid matter figure of citric acid derivatization product in embodiment 1；
Fig. 2 is the mass spectrum of citric acid derivatization product 1；
Fig. 3 is the mass spectrum of citric acid derivatization product 2；
Fig. 4 is the standard curve of the corresponding citric acid concentration of citric acid derivatization product 2；
Fig. 5 is the liquid matter figure of malic acid derivatization product in embodiment 2；
Fig. 6 is the mass spectrum of malic acid derivatization product 1 '；
Fig. 7 is the mass spectrum of malic acid derivatization product 2 '；
Fig. 8 is the standard curve of the corresponding malic acid concentration of malic acid derivatization product 2 '。
Detailed description of the invention
The present invention is only described in further detail by following embodiment, but does not constitute any limitation of the invention。
Embodiment 1
LC-MS based on column front derivation measures the method for citric acid content in Fructus Citri Limoniae juice, comprises the following steps:
1) preparation of derivatization reagent, sodium carbonate liquor and citric acid standard solution
Accurately weighing the 2-bromoacetophenone of 19.9mg in dry reagent vials, add 10mL anhydrous acetonitrile and be configured to the stock solution A of concentration 0.01mol/L, sealing is placed in refrigerator and stores for future use；
Accurately weighing the sodium carbonate of 5.3mg in dry reagent vials, add 0.5mL water dissolution sodium carbonate, add 9.5mL anhydrous acetonitrile and be configured to the stock solution B of concentration 0.005mol/L, sealing is placed in refrigerator and stores for future use；
Accurately weighing the citric acid of 6.4mg in dry reagent vials, add 1.5mL water dissolution citric acid, add 8.5mL anhydrous acetonitrile and be configured to the stock solution C of concentration 0.003mol/L, sealing is placed in refrigerator and stores for future use；Take 5 dry centrifuge tubes, measure the anhydrous acetonitrile of 1000 μ L respectively, it is separately added into the stock solution C of 1000 μ L, 333 μ L, 143 μ L, 85 μ L, 67 μ L more successively, is configured to the serial citric acid standard solution that concentration is 320 μ g/mL, 160 μ g/mL, 80 μ g/mL, 50 μ g/mL, 40 μ g/mL；
2) standard curve is made
Derivative reaction: measure the citric acid standard solution of 500 μ L series concentration respectively in the flask of 50mL, according to mol ratio citric acid: sodium carbonate: 2-bromoacetophenone=1:1:1 adds stock solution A and stock solution B, mix homogeneously, reacts 24h in 55 DEG C of oil baths when, react complete, cooling；
LC-MS detects: taking citric acid derivatization product and carry out High Performance Liquid Chromatography/Mass Spectrometry analysis, liquid matter figure is shown in Fig. 1；The testing conditions of high performance liquid chromatography is: chromatographic column: Agilent EclipsePlusC18, specification: 2.1 × 150mm, 3.5 μm；Mobile phase: 0.1% (percentage by volume) acetic acid aqueous solution: methanol (v/v)=2:3, analysis time: 0～12min, flow velocity: 0.2mL/min；Sample size: 5 μ L；Mass spectrographic testing conditions is: ion source: electron spray ionisation source (ESI) positive ion mode；Capillary voltage: 4500V；Dry temperature: 220 DEG C；Dry gas stream speed: 4L/min；Atomization gas air pressure: 199.9KPa；Liquid phase adopts Agilent 1260 type chromatograph of liquid, and mass spectrum adopts Brooker amaZonSL ion trap mass spectrometer；
Data process: from total ion current figure, extraction and the mass spectrum of the derivatization product 1 ([M+1]+quasi-molecular ion peak m/z=310.98) of a carboxyl generation esterification are (see Fig. 2, [M+Na]+quasi-molecular ions m/z=333.04 in figure), and with the mass spectrum of the derivatization product 2 ([M+1]+quasi-molecular ion peak m/z=429.08) of two carboxyl generation esterifications (see Fig. 3, [M+Na]+quasi-molecular ions m/z=451.09 in figure), owing to product 1 is difficult to efficiently separate with impurity in liquid-phase chromatographic analysis, elite product 2 of selecting makes qualitative and quantitative analysis；With citric acid concentration for abscissa X, it is vertical coordinate Y with the peak area corresponding to the derivatization product 2 of two carboxyl generation esterifications, with quantified by external standard method (see Fig. 4), within the scope of citric acid concentration 13.33～106.6 μ g/mL, obtain standard curve 1:Y=2837180X+42515600, r=0.9966；
3) mensuration of citric acid content in Fructus Citri Limoniae juice
Derivative reaction: take 500 μ L Fructus Citri Limoniae juice in the flask of 50mL, adds 500 μ L stock solution A and 500 μ L stock solution B, mix homogeneously, reacts 24h, react complete in 55 DEG C of oil baths when, cooling；
LC-MS detects: takes product and carries out High Performance Liquid Chromatography/Mass Spectrometry analysis；High performance liquid chromatography and mass spectrographic testing conditions are ibid；
Data process: the mass spectrum of the derivatization product 2 of extraction and two carboxyl generation esterifications from total ion current figure, by detecting the peak area corresponding to product 2, obtained the content of citric acid in detection sample by standard curve, then calculate that to obtain the content of citric acid in Fructus Citri Limoniae juice be 19.4 μ g/mL。
Embodiment 2
LC-MS based on column front derivation measures the method for malic acid content in Sucus Mali pumilae, comprises the following steps:
1) preparation of derivatization reagent, sodium carbonate liquor and malic acid standard solution
Accurately weighing the 2-bromoacetophenone of 19.9mg in dry reagent vials, add 10mL anhydrous acetonitrile and be configured to the stock solution A of concentration 0.01mol/L, sealing is placed in refrigerator and stores for future use；
Accurately weighing the sodium carbonate of 5.3mg in dry reagent vials, add 0.5mL water dissolution sodium carbonate, add 9.5mL anhydrous acetonitrile and be configured to the stock solution B of concentration 0.005mol/L, sealing is placed in refrigerator and stores for future use；
Accurately weighing the malic acid of 6.7mg in dry reagent vials, add 1mL water dissolution malic acid, add 9mL anhydrous acetonitrile and be configured to the stock solution C of concentration 0.005mol/L, sealing is placed in refrigerator and stores for future use；Take 5 dry centrifuge tubes, measure the anhydrous acetonitrile of 1000 μ L respectively, it is separately added into 333 μ L, 143 μ L, 67 μ L more successively, 32 μ L, the stock solution C of 21 μ L, is configured to the Series Apples acid standard solution that concentration is 167.5 μ g/ml, 83.8 μ g/ml, 42.1 μ g/ml, 20.8 μ g/ml, 13.8 μ g/ml。
2) standard curve is made
Derivative reaction: measure the malic acid standard solution of 500 μ L series concentration respectively in the flask of 50mL, according to mol ratio malic acid: sodium carbonate: 2-bromoacetophenone=1:1:1 adds stock solution A and stock solution B, mix homogeneously, reacts 24h in 55 DEG C of oil baths when, react complete, cooling；
LC-MS detects: taking malic acid derivatization product and carry out High Performance Liquid Chromatography/Mass Spectrometry analysis, liquid matter figure is shown in Fig. 5；The testing conditions of high performance liquid chromatography is: chromatographic column: Agilent EclipsePlusC18, specification: 2.1 × 150mm, 3.5 μm；Mobile phase: 0.1% acetic acid aqueous solution: methanol (v/v)=2:3, analysis time: 0～12min, flow velocity: 0.2mL/min；Sample size: 5 μ L；Mass spectrographic testing conditions is: ion source: electron spray ionisation source (ESI) positive ion mode；Capillary voltage: 4500V；Dry temperature: 220 DEG C；Dry gas stream speed: 4L/min；Atomization gas air pressure: 199.9KPa；
Data process: from total ion current figure, extraction and the mass spectrum of the derivatization product 1 ' ([M+1]+quasi-molecular ion peak m/z=252.94) of a carboxyl generation esterification are (see Fig. 6, [M+Na]+quasi-molecular ions m/z=274.94 in figure), and with the mass spectrum of the derivatization product 2 ' ([M+1]+quasi-molecular ion peak m/z=371.04) of two carboxyl generation esterifications (see Fig. 7, [M+Na]+quasi-molecular ions m/z=393.08 in figure), owing to product 1 is difficult to efficiently separate with impurity in liquid-phase chromatographic analysis, elite product 2 ' of selecting makes qualitative and quantitative analysis；With malic acid concentration for abscissa X, it is vertical coordinate Y with the peak area corresponding to the derivatization product 2 ' of two carboxyl generation esterifications, with quantified by external standard method (see Fig. 8), within the scope of malic acid concentration 4.65～55.83 μ g/mL, obtain standard curve 2:Y=8971190X+115583000, r=0.9754；
3) mensuration of malic acid content in Sucus Mali pumilae
Derivative reaction: take 500 μ L Sucus Mali pumilae in the flask of 50mL, adds 500 μ L stock solution A and 500 μ L stock solution B, mix homogeneously, reacts 24h, react complete in 55 DEG C of oil baths when, cooling；
LC-MS detects: takes product and carries out High Performance Liquid Chromatography/Mass Spectrometry analysis；High performance liquid chromatography and mass spectrographic testing conditions are ibid；
Data process: the mass spectrum of the derivatization product 2 ' of extraction and two carboxyl generation esterifications from total ion current figure, by detecting the peak area corresponding to product 2 ', obtained the content of malic acid in detection sample by standard curve, then calculate that to obtain the content of malic acid in Sucus Mali pumilae be 15.3 μ g/mL。
Embodiment 3
LC-MS based on column front derivation measures the method for citric acid, malic acid content in blended fruit juice, comprises the following steps:
1) preparation of derivatization reagent, sodium carbonate liquor, citric acid and malic acid standard solution is with embodiment 1,2；
2) citric acid, malic acid standard curve making also with embodiment 1,2；
3) mensuration of citric acid, malic acid content in blended fruit juice
Derivative reaction: take 500 μ L blended fruit juices in the flask of 50mL, adds 500 μ L stock solution A and 500 μ L stock solution B, mix homogeneously, reacts 24h, react complete in 55 DEG C of oil baths when, cooling；
LC-MS detects: takes product and carries out High Performance Liquid Chromatography/Mass Spectrometry analysis；High performance liquid chromatography and mass spectrographic testing conditions are ibid；
Data process: extract the mass spectrum of the derivatization product 2 with two carboxyl generation esterifications and derivatization product 2 ' from total ion current figure, by detecting the peak area corresponding to product 2, product 2 ', obtained the content of citric acid, malic acid in detection sample by standard curve 1,2, then calculate the content respectively 12.5 μ g/mL and 13.6 μ g/mL obtaining citric acid in blended fruit juice, malic acid。
Claims (6)
1. based on the LC-MS of the column front derivation method measuring organic acid content, it is characterised in that: comprise the following steps:
1) testing sample, sodium carbonate and 2-bromoacetophenone are added in solvent, after mixing at 50～60 DEG C derivative reaction 20～28h, cool down standby；
2) take step 1) in product carry out LC-MS analysis, reference standard curve calculates organic acid content in testing sample。
2. method according to claim 1, it is characterised in that: described organic acid is the binary in fruit or tribasic organic acid。
3. method according to claim 1, it is characterised in that: step 1) in solvent be anhydrous acetonitrile, ethyl acetate or oxolane。
4. method according to claim 1, it is characterised in that: step 2) in the chromatographic condition of LC-MS analysis be: chromatographic column: Agilent EclipsePlusC18, specification: 2.1 × 150mm, 3.5 μm；Mobile phase: with volume basis, 0.1% acetic acid aqueous solution: methanol=2:3, analysis time: 0～12min, flow velocity: 0.2mL/min；Sample size: 5 μ L。
5. method according to claim 1, it is characterised in that: step 2) in the Mass Spectrometry Conditions of LC-MS analysis be: ion source: electron spray ionisation source positive ion mode；Capillary voltage: 4500V；Dry temperature: 220 DEG C；Dry gas stream speed: 4L/min；Atomization gas air pressure: 199.9KPa。
6. method according to claim 1, it is characterized in that: step 2) manufacture method of standard curve is: takes organic acid standard substance to be measured and is configured to the standard solution of series concentration, standard solution adds sodium carbonate and 2-bromoacetophenone, and at 50～60 DEG C derivative reaction 20～28h, react complete, take product and carry out LC-MS analysis, with the peak area corresponding to product, its concentration is done regression analysis, obtain the relation curve of material concentration and peak area。
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| CN110573478B (en) * | 2017-04-20 | 2023-02-28 | 梅塔博隆股份有限公司 | Mass spectrometry method for detecting and quantifying organic acid metabolites |
| JP7285218B2 (en) | 2017-04-20 | 2023-06-01 | メタボロン，インコーポレイテッド | Mass spectrometry to detect and quantify organic acid metabolites |
| CN112955239A (en) * | 2018-07-27 | 2021-06-11 | 沃特世科技公司 | Liquid chromatography/mass spectrometry method for polar molecule analysis |
| CN112955239B (en) * | 2018-07-27 | 2022-11-29 | 沃特世科技公司 | Liquid chromatography/mass spectrometry method for polar molecule analysis |
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