CN103743849A - Ion chromatography-high resolution mass spectrum hyphenation method for screening and authenticating multiple organic acids in dairy products synchronously and rapidly - Google Patents
Ion chromatography-high resolution mass spectrum hyphenation method for screening and authenticating multiple organic acids in dairy products synchronously and rapidly Download PDFInfo
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Abstract
The invention discloses an ion chromatography-high resolution mass spectrum hyphenation method for screening and authenticating multiple organic acids in dairy products synchronously and rapidly. The ion chromatography-high resolution mass spectrum hyphenation method comprises the following steps: extracting a to-be-tested sample by a potassium hydroxide solution, purifying the extracted liquid by a reverse phase filler pretreatment small column, separating by utilizing an Ion Pac AS19 chromatographic column, eluting KOH leacheate, detecting under a negative-ion mode by an Orbitrap high-resolution detector under a full scanning mode, comparing the detected data with the existing data, screening, and authenticating. The method lowers the sample pretreatment requirement, effectively saves sample pretreatment time, greatly shortens the reservation time of detected objects, and can exclude false positive; the collected data can be recalled repeatedly according to detection requirement.
Description
Technical field
The invention belongs to analytical chemistry field, be specifically related to a kind of rapid screening simultaneously and identify multiple organic acid chromatography of ions-high resolution mass spectrum method for combined use in dairy products.
Background technology
Organic acid in dairy products have suppress harmful bacteria breeding, differently flavoured effect is provided, in dairy products product extensively exist.Its main source is divided into produces interpolation and two kinds of approach of natural products: process of manufacture is often used malic acid, tartrate, citric acid, fumaric acid, phosphoric acid etc. as acidity regulator; Natural organic acids is mainly to produce free fatty acid as acetic acid, butyric acid by butter oil hydrolysis, the physiological metabolism of ox produces citric acid, orotic acid, uric acid, the kalabolism of bacterium and lactic acid bacteria produces lactic acid, acetic acid, pyruvic acid, propionic acid, formic acid, homotype lactic fermentation is lactic acid by most carbon source through pyruvic acid metabolic conversion, also can produce other organic acid and local flavor metabolic product.
Due to its relatively high security, except fumaric acid, in the national standard of China, these organic acids are used to not limitation regulation, maximum use amount is that " according to need of production " determined.But experimental study shows, eat for a long time or eat excessive organic acid and can produce infringement to human body equally, the acute toxicity tests that Qin Shuzhen etc. carry out in mouse shows: the toxicity of citric acid own is slight, but with heavy metal chelating after can cause liver cell diffuse necrosis, lobuli hepatis disappears.
For avoiding unrestricted, the immeasurable use organic acid of illegal retailer in food production, a lot of tissues and country have all made respective specified to organic acid usable range and limitation in the world: citric acid limitation 3000mg/kg in Codex Alimentary Commission (ACA) regulation fruit syrup, tartrate limitation 4000mg/kg, lactic acid limitation 2000mg/kg in infant's supplement, acetic acid limitation 5000mg/kg, fumaric acid limitation 700mg/kg in fresh pasta, noodles; European Union stipulates fumaric acid limitation 4000g/kg in drying powdery sweets potpourri, biscuit and rusk mesotartaric acid limitation 5000g/kg; China Taiwan stipulates especially separately must not use malic acid in baby food.
At present, in the detection technique in the fields such as food, environment, chemical industry, medical science, for negative ion, kation, water-soluble and polar micromolecules compound, often adopt ion chromatography technology.But ion chromatograph is longer detection time, is generally 40-60min, and only with retention time as qualitative, quantitative foundation, structural information cannot be provided, and the material identical for retention time cannot further carry out structural confirmation, thereby easily causes false positive results.
Mass-spectrometric technique can provide qualitative and quantitative detection more accurately in analytic process, relevant chromatography of ions mass spectrometric hyphenated technique has been reported in recent years, method rues etc. and to utilize capillary ion chromatography mass spectrometry analytical equipment to carry out the analysis of the water-soluble components such as organic acid, sugar, alcohol, but its Low Resolution Mass Spectra adopting only can be analyzed the set compound that standard items are provided, cannot to be difficult to obtain standard substance or without the unvested compound of laws and regulations requirement, carry out examination, be difficult to meet the testing requirement of various places, world today laws and regulations frequent updating; And Low Resolution Mass Spectra i.e. setup parameter before collection starts, cannot call multi-layer data repeatedly once gather.
High resolution mass spectrum has the function of mass resolution height and accurate molecular weight, therefore the requirement of sample pre-treatments is reduced, and has effectively saved time for sample pretreatment; And due to its high-resolution advantage, without carry out segmentation in chromatographic resolution, separate and component to be measured can be identified, the chromatographic resolution time shortens to 30min left and right by original 50-60min thus; The data that high resolution mass spectrum gathers under full scan pattern can be called repeatedly according to detection demand, still can carry out Screening analysis in the situation that not providing standard substance, make up thus the deficiency of traditional Low Resolution Mass Spectra method; Its data dependency scanning can, in examination, be carried out qualitative confirmation by fragmention.By the mode of connecting with liquid chromatography, at aspects such as food inspection, proteomics, started to apply gradually in recent years, but still belonged to blank at the detection field of the application of connecting with chromatography of ions.
Summary of the invention
The invention provides a kind of rapid screening simultaneously and identify multiple organic acid chromatography of ions-high resolution mass spectrum method for combined use in dairy products.
A kind of rapid screening is simultaneously identified multiple organic acid chromatography of ions-high resolution mass spectrum method for combined use in dairy products, comprises the following steps:
Testing sample is extracted with potassium hydroxide solution, the little column purification of reverse phase filler pre-treatment for extract, use IonPac AS19 chromatographic column to separate, KOH leacheate wash-out, under negative ion mode, use afterwards Orbitrap high resolution detection device full scan mode detection, according to the data that record, carry out examination and evaluation;
Preferably, chromatographic condition is:
Column temperature: 35 ℃;
Flow velocity: 0.25mL/min;
Mobile phase: 30mM KOH;
Mass spectrum condition is:
Electric spray ion source;
Spray voltage: 5.00kV
Mass charge ratio range: 50-300
Capillary voltage :-21.00V
Pipe lens voltage :-128.70V
Capillary temperature: 350 ℃;
Sheath gas (N2) flow velocity: 17L/min (being 30arb);
Assisted gas (N2) flow velocity: 8L/min (being 10arb);
Resolution R=60000.
Further, the mass concentration of potassium hydroxide solution is 1%.
Further, described reverse phase filler pre-treatment pillar is RP pre-treatment pillar.
RP pre-treatment pillar is Thermo RP pre-treatment pillar.Further, RP pre-treatment pillar activates with 10mL water, 10mL methyl alcohol, 10mL water before using successively, afterwards again by extract loading.In practical operation, discard after front 5mL liquid, collect filtered fluid, filtered fluid separates by chromatographic column.
Further, chromatographic column adopting IonPac AS19,250mm × 2.1mm, 2.5 μ m.
Further, in chromatographic condition, sample chamber temperature: 10 ℃; Sample size: 10 μ L; Analysis time: 30min.
KOH leacheate gradient elution is that the on-line automatic generation of automatic generator KOH leacheate carries out gradient elution.
Can adopt the informations such as the molecular formula of Xcalibar software to each compound in sample, retention time, one-level mass spectrum mass-to-charge ratio, natural isotopic distribution.
The instrument using is: ion chromatography system: Dionex ICS-2000; High resolution mass spectrum system: Thermo LTQ-Orbitrap XL.
Beneficial effect of the present invention is as follows:
1, the present invention has set up a kind of while rapid screening and has identified multiple organic acid chromatography of ions-high resolution mass spectrum method for combined use in dairy products, the novel analytical equipment of chromatography of ions-high resolution mass spectrum of application has the feature of high resolving power, high sensitivity, reduce the requirement to sample pre-treatments, effectively saved time for sample pretreatment.
2, the present invention separates and can, by component identification to be measured, shorten greatly the retention time of measuring measured object without carry out segmentation in chromatographic resolution, from original ion chromatograph 40-60min, shortens to 30min left and right.
3, the present invention can provide accurate molecular weight when retention time is provided, in conjunction with applied analysis, can utilize its structural information to get rid of false positive this bidirectional information, utilizes its retention time to differentiate isomers.
4, the data that the present invention gathers under full scan pattern can be called repeatedly according to detection demand, and i.e. setup parameter before making up thus traditional Low Resolution Mass Spectra collection and starting, once gather the deficiency that cannot repeatedly call multi-layer data.
5, the present invention can carry out the Screening analysis of unvested object in the situation that not providing standard substance, is the very effectively application of the testing requirement of reply various places, world today laws and regulations frequent updating.
6, data dependency scanning of the present invention can realize the object of carrying out qualitative confirmation by fragmention in examination.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in further detail;
Fig. 1 is the full scan high resolution mass spectrum figure of sample in example 1;
Fig. 2 is the XIC(a of sulfuric acid) and high resolution mass spectrum evaluation diagram (b);
Fig. 3 is the XIC(a of phosphoric acid) and high resolution mass spectrum evaluation diagram (b);
Fig. 4 is the XIC(a of lactic acid) and high resolution mass spectrum evaluation diagram (b);
Fig. 5 is the sample full scan high resolution mass spectrum figure (a) of the multiple samples in example 2 and the XIC of tartrate (b), lactic acid (c), citric acid (d) and malic acid (e) figure;
Fig. 6 is the high resolution mass spectrum figure of example 2 mesotartaric acid;
Fig. 7 is the high resolution mass spectrum figure of lactic acid in example 2;
Fig. 8 is the high resolution mass spectrum figure of wine citric acid in example 2;
Fig. 9 is the high resolution mass spectrum figure of malic acid in example 2.
Embodiment
For understanding better the present invention, will further illustrate the solution of the present invention by specific embodiment below, protection scope of the present invention should comprise the full content of claim, but is not limited to this.
A kind of rapid screening is simultaneously identified multiple organic acid chromatography of ions-high resolution mass spectrum method for combined use in dairy products, comprises the following steps:
Sample extraction: dairy products 1mL to be measured extracts fully and mixes with 10mL1% potassium hydroxide solution, at 4 ℃, the centrifugal 10min of 12000r/min.Get supernatant, to be clean;
Pre-treatment column purification: Thermo RP pre-treatment pillar, before using, RP pre-treatment pillar is successively with 10mL water, 10mL methyl alcohol, the activation of 10mL water; Afterwards again by supernatant loading;
Collect: discard the front 5mL filtered fluid that RP post flows out, collect rear end clear liquid, to be measured;
Upper machine testing: sample is carried out to examination and evaluation by chromatography of ions-high resolution mass spectrum combined instrument;
Chromatographic condition is:
Ion chromatography system: Dionex ICS2000
Chromatographic column: Dionex IonPac AS19,250mm × 2.1mm, 2.5 μ m;
Column temperature: 35 ℃;
Sample chamber temperature: 10 ℃;
Sample size: 10 μ L;
Flow velocity: 0.25mL/min;
Mobile phase: 30mMKOH;
Analysis time: 30min.
Mass spectrum condition:
High resolution mass spectrum system: Thermo LTQ-Orbitrap XL
Electric spray ion source; Negative ion mode;
Spray voltage: 5.00kV
Mass charge ratio range: 50-300
Capillary voltage :-21.00V
Pipe lens voltage :-128.70V
Capillary temperature: 350 ℃;
Sheath gas (N2) flow velocity: 17L/min (being 30arb);
Assisted gas (N2) flow velocity: 8L/min (being 10arb);
Scan pattern: Orbitrap detecting device full scan (Full Scan) mode detection;
The resolution R=60000 of full scan.
The informations such as molecular formula, retention time, one-level mass spectrum mass-to-charge ratio and the natural isotopic distribution by the XIC manager of Xcalibar software to each compound in sample.Can be by several known certain sour samples that have being done to positive control by this method, data measured and this data are compared, and carry out examination and evaluation.Or, with these data and existing database resource, as Chinese Academy of Sciences's compound reference type database, in data compare.Through comparison, embodiment 1 obtains three kinds of organic acids: sulfuric acid, phosphoric acid, lactic acid.Experimental result as shown in Figure 1, Figure 2, Figure 3 and Figure 4.
Fig. 1 is the full scan high resolution mass spectrum figure of sample in example 1;
Fig. 2 is the XIC(a of sulfuric acid) and high resolution mass spectrum evaluation diagram (b);
Fig. 3 is the XIC(a of phosphoric acid) and high resolution mass spectrum evaluation diagram (b);
Fig. 4 is the XIC(a of lactic acid) and high resolution mass spectrum evaluation diagram (b).
28 commercial dairy products are used and carry out sample preparation, apparatus measures, data analysis with the method for embodiment 1, obtain 4 kinds of organic acids: the screening results of tartrate, lactic acid, citric acid and malic acid.Experimental result is as shown in Fig. 5～9.
Fig. 5 is the sample full scan high resolution mass spectrum figure (a) of the multiple samples in example 2 and the XIC of tartrate (b), lactic acid (c), citric acid (d) and malic acid (e) figure;
Fig. 6 is the high resolution mass spectrum figure of example 2 mesotartaric acid;
Fig. 7 is the high resolution mass spectrum figure of lactic acid in example 2;
Fig. 8 is the high resolution mass spectrum figure of wine citric acid in example 2;
Fig. 9 is the high resolution mass spectrum figure of malic acid in example 2.
Obviously; the above embodiment of the present invention is only for example of the present invention is clearly described; and be not the restriction to embodiments of the present invention; for those of ordinary skill in the field; can also make other changes in different forms on the basis of the above description; here cannot give all embodiments exhaustively, everyly belong to apparent variation or the still row in protection scope of the present invention of variation that technical scheme of the present invention extends out.
Claims (6)
1. rapid screening is identified multiple organic acid chromatography of ions-high resolution mass spectrum method for combined use in dairy products simultaneously, it is characterized in that, comprises the following steps:
Testing sample is extracted with potassium hydroxide solution, the little column purification of reverse phase filler pre-treatment for extract, use IonPac AS19 chromatographic column to separate, KOH leacheate wash-out, under negative ion mode, use afterwards Orbitrap high resolution detection device full scan mode detection, according to the data that record, carry out examination and evaluation;
Preferably, chromatographic condition is:
Column temperature: 35 ℃;
Flow velocity: 0.25mL/min;
Mobile phase: 30mM KOH;
Mass spectrum condition is:
Electric spray ion source;
Spray voltage: 5.00kV;
Mass charge ratio range: 50-300;
Capillary voltage :-21.00V;
Pipe lens voltage :-128.70V;
Capillary temperature: 350 ℃;
Sheath gas velocity: 17L/min;
Assisted gas flow velocity: 8L/min;
Resolution R=60000.
2. chromatography of ions-high resolution mass spectrum method for combined use as claimed in claim 1, is characterized in that, the mass concentration of described potassium hydroxide solution is 1%.
3. chromatography of ions-high resolution mass spectrum method for combined use as claimed in claim 1, is characterized in that, described reverse phase filler pre-treatment pillar is RP pre-treatment pillar.
4. chromatography of ions-high resolution mass spectrum method for combined use as claimed in claim 1, is characterized in that, described RP pre-treatment pillar activates with 10mL water, 10mL methyl alcohol, 10mL water before using successively, afterwards again by extract loading.
5. chromatography of ions-high resolution mass spectrum method for combined use as claimed in claim 1, is characterized in that, described IonPac AS19 chromatographic column is 50mm × 2.1mm, 2.5 μ m.
6. chromatography of ions-high resolution mass spectrum method for combined use as claimed in claim 1, is characterized in that, in chromatographic condition, and sample chamber temperature: 10 ℃; Sample size: 10 μ L; Analysis time: 30min.
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| CN105203649A (en) * | 2014-06-20 | 2015-12-30 | 北大方正集团有限公司 | Method for detecting L-(+)-tartaric acid in moxifloxacin hydrochloride |
| CN105784908A (en) * | 2016-04-13 | 2016-07-20 | 广东中烟工业有限责任公司 | Ion chromatography detection method for six negative ions in cigarette paper |
| CN107064404A (en) * | 2017-01-13 | 2017-08-18 | 伊犁师范学院 | The method of ion-chromatographic determination hawthorn mesotartaric acid, oxalic acid and citric acid content |
| CN114755341A (en) * | 2022-04-24 | 2022-07-15 | 中国科学院微生物研究所 | Ion chromatography and mass spectrometry combined method for detecting lactic acid and short-chain fatty acid |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105203649A (en) * | 2014-06-20 | 2015-12-30 | 北大方正集团有限公司 | Method for detecting L-(+)-tartaric acid in moxifloxacin hydrochloride |
| CN105203649B (en) * | 2014-06-20 | 2017-07-04 | 北大方正集团有限公司 | The detection method of L (+) tartaric acid in moxifloxacin hydrochloride |
| CN105784908A (en) * | 2016-04-13 | 2016-07-20 | 广东中烟工业有限责任公司 | Ion chromatography detection method for six negative ions in cigarette paper |
| CN107064404A (en) * | 2017-01-13 | 2017-08-18 | 伊犁师范学院 | The method of ion-chromatographic determination hawthorn mesotartaric acid, oxalic acid and citric acid content |
| CN114755341A (en) * | 2022-04-24 | 2022-07-15 | 中国科学院微生物研究所 | Ion chromatography and mass spectrometry combined method for detecting lactic acid and short-chain fatty acid |
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