CN106404956B - High performance liquid chromatography-tandem mass internal standard method detects the method and its application of four kinds of organic acids in grape wine and/or fruit wine simultaneously - Google Patents
High performance liquid chromatography-tandem mass internal standard method detects the method and its application of four kinds of organic acids in grape wine and/or fruit wine simultaneously Download PDFInfo
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Abstract
The present invention discloses the method and application of organic acid in a kind of high performance liquid chromatography-tandem mass internal standard method detection grape wine and/or fruit wine, belongs to organic acid detection and application field.By High performance liquid chromatography mass spectrometry, optimize chromatography and Mass Spectrometer Method condition, direct injected after grape wine or fruit wine simple process measured, can quantitative detection go out the contents of the organic acids such as tartaric acid, malic acid, succinic acid, citric acid.The method detection limit of the detection organic acid is low; selectivity is good; pre-treatment is simple and quick; process free of losses; detection sensitivity is high; as a result accurate and reliable, it can be achieved that fast and accurately measured to 4 kinds of organic acids, blend littlefruit grape herb wine and fruit wine for quickly identification, the dining table safety of consumer and maintenance Ko-ji insects protected to develop in a healthy way and providing technical support.
Description
Technical field
The present invention relates to one kind to detect grape wine and/or fruit wine based on high performance liquid chromatography-tandem mass internal standard method simultaneously
In four kinds of organic acids method, belong to organic acid detection and applied technical field.
Background technique
With the rapid development of our country's economy with improvement of living standard, there is the grape wine of long history and cultural deposits
Increasingly liked by people with fruit wine, has gone on the daily dining table of common people.It passes through the tune to acid-base balance in human body
Section, is achieved the physiological activity of various enzymes, to promote being normally carried out for metabolism in vivo, is conducive to the body of drinking person
Body health.But there have illegal retailer to see currently on the market to be lucrative, utilizes the raw materials such as edible pigment, edible alcohol, sweetener
Blend production fake wine, such fake wine is luxurious high-end and atmospheric from the appearance and price is very high, can one bottle of cost be only a few members, and it is excessive
Intake edible pigment or sweetener will increase burden of liver and damage the health of consumer.Therefore, for protection consumer's
The sound development of dining table safety and maintenance grape wine and fruit wine market establishes a kind of quickly identification and blends littlefruit grape herb wine and fruit wine
Method has great importance.
Grape wine and the ingredient in fruit wine are considerably complicated, and wherein organic acid is important component, are to influence grape wine and fruit wine
Flavor and wine product quality an important factor for, and identify product quality one of important indicator.High quality grape wine and fruit
The kinds of organic acids and content of wine are mainly influenced by fermentation, there is up to tens kinds of organic acid ginsengs in entire fermentation process
With react, the highest four kinds of acid of content be tartaric acid (tartaric acid, 1.5~2.5g/L of content), malic acid (malic
Acid, 1.5~3.0g/L of content), succinic acid (succinic acid, 0.6~1.5g/L of content) and citric acid (citric
Acid, 0.10~0.15g/L of content).Fake producer is usually only added a large amount of to keep the flavor and mouthfeel of grape wine and fruit wine
Citric acid blent.Therefore, in national standard " grape wine " (GB 15037-2006), " wild grape wine " (GB/T
The maximum level of citric acid is defined in 27586-2011).Due in wine blend and without tartaric acid, malic acid and amber
These three substances of amber acid therefore being capable of auxiliary judgment wine blend or fruit wine to the detection of these three ingredients.
Detection about organic acid is there are many method, and in field of food, in addition to high performance liquid chromatography, there are also thin-layer chromatographys
The chromatograph joint used method of method, gas chromatography, makings, capillary electrophoresis and high performance liquid chromatography-tandem mass method (HPLC-MS/
MS) etc..Thin-layered chromatography accuracy is poor, can only qualitative or sxemiquantitative；Before gas chromatography and the chromatograph joint used method of makings
Processing needs the method by being esterified to derive organic acid, and step complexity is cumbersome；Capillary electrophoresis technique method sensitivity is low,
Reproducibility is poor.It is defined in " grape wine, fruit wine universaling analysis method " (GB/T15038-2006) and utilizes high-efficient liquid phase color
The method that spectral technology measures organic acid, but to carry out the activation of solid-phase extraction column, elution in the pretreatment process of this method and receive
Collect sample, it is very cumbersome, and the pigment in wine can also interfere the detection of organic acid, accuracy is low.The shortcomings that above analysis method,
Such as pretreatment process is cumbersome, accuracy and poor sensitivity and cannot be completely quantitative problem, limit these methods and detecting
Application in grape wine and fruit wine in organic acid.In addition, although HPLC-MS/MS method can be used for measuring organic acid in fruits and vegetables,
It is had not been reported using the method that HPLC-MS/MS method measures organic acid in grape wine and/or fruit wine.Therefore, establish it is a kind of simple,
Quickly, the method for accurately detecting organic acid in grape wine and/or fruit wine blends littlefruit grape herb wine and fruit wine with important for identification
Practical value.
Summary of the invention
The purpose of the present invention is to solve the above-mentioned problems, provides a kind of utilization high performance liquid chromatography tandem mass spectrum method
The method for measuring four kinds of organic acids in grape wine and/or fruit wine simultaneously.This method pre-treatment is simple, detection limit is low, selectivity is good,
Convenient, sensitivity and accuracy are high, can quickly detect 4 kinds of organic acids in grape wine and/or fruit wine, and littlefruit grape herb wine is blent in identification
Or fruit wine, there is safely important application value and practical significance to the dining table of protection consumer.
To achieve the goals above, the present invention adopts the following technical scheme:
The invention discloses high performance liquid chromatography-tandem mass (HPLC-MS/MS) internal standard method detection grape wine and/or
The application of organic acid in fruit wine.
A kind of high performance liquid chromatography-tandem mass (HPLC-MS/MS) internal standard method detects in grape wine and/or fruit wine simultaneously
The method of four kinds of organic acids, four kinds of organic acids are tartaric acid, malic acid, succinic acid, citric acid.
Preferably, the internal standard method uses toosendanin for internal standard compound, the study find that using toosendanin as internal standard, to four
Kind organic acid is noiseless.
Further, it the described method comprises the following steps:
(1) 4 kinds of organic acid standard solution are prepared and carry out high performance liquid chromatography tandem mass spectrum measurement；
(2) linear relationship and detection limit and quantitative limit of 4 kinds of organic acids are determined；
(3) grape wine and/or fruit wine sample are pre-processed and is measured；
(4) content of 4 kinds of organic acids is calculated according to sample detection data.
Preferably, step (1) or the chromatographic determination condition of (3) are as follows: selection Agilent Eclipse plus C18 (50 ×
4.6mm, 1.8 μm) chromatographic column, this chromatographic column good separating effect, each compound reached baseline separation, and since the column is shorter,
Compound outflow is very fast, and retention time is short, ideal；
Mobile phase: A phase is 0.15% aqueous formic acid, and B phase is acetonitrile, and the addition of formic acid has adjusted acid in A phase aqueous solution
Degree, is conducive to the separation of organic acid；Gradient elution program: gradient elution: 0~2.0min, A phase 100%；2.0-2.1min A phase
100% → 50%, B phase 0 → 50%；2.1-5.0min, A phase and B phase each 50%；5.0-5.1min, A phase 50% → 0；Finally put down
Weigh 4.9min；
Flow velocity: 0.6mL/min；Column temperature: 20 DEG C.
Tandem mass spectrum determination condition are as follows: ionization mode: electric spray ion source (ESI), acquisition mode: anion reacts prison more
(MRM) mode of survey, dry gas: high-purity N2, dry temperature degree: 200-350 DEG C, dry gas stream speed: 12L/min, atomizing pressure:
30psi, capillary voltage: 4000V.
Preferably, mass spectral analysis parameter is as follows under target components MRM mode:
Further, the step (1) is specifically includes the following steps: a series of at least six kinds of different qualities of accurate formulation are dense
Tartaric acid, malic acid, succinic acid, the citric acid standard working solution of degree, are added internal standard compound standard solution, and sample introduction measures to obtain
Standard spectrogram.
Further, step (2) specifically includes: the standard spectrogram that step (1) is obtained is respectively with 4 kinds of organic acids and internal standard
The peak area ratio of object carries out linear regression to the corresponding concentration proportion of the two, obtains linear relationship regression equation, related coefficient
And the range of linearity；Using the corresponding concentration of signal-to-noise ratio (S/N) >=3 as detection limit, (S/N) >=10 corresponding concentration is as quantitative limit.
Further, step (3) specifically: accurate to measure grape wine and/or the dilution of fruit wine sample, filtering, sample introduction measurement
Obtain sample spectrogram.
Further, the step (4) specifically: the sample spectrogram and standard spectrogram for obtaining step (3) compare, qualitative
It determines the type of organic acid, while substituting into the content that linear equation quantitatively calculates organic acid.
A kind of high performance liquid chromatography-tandem mass (HPLC-MS/MS) quickly in detection grape wine and/or fruit wine 4 kinds it is organic
The method of acid is in the application for identifying wine blend and fruit wine.
The invention has the benefit that the present invention utilizes high performance liquid chromatography-tandem mass (HPLC-MS/MS) side for the first time
Method detects grape wine and/or fruit wine and its 4 kinds of tartaric acid, malic acid, succinic acid, citric acid organic acids.By optimization chromatography and
Mass Spectrometer Method condition flows out 4 kinds of organic acids from chromatographic column fastly, and retention time is short, realizes 4 kinds of sour quick separatings, and obtain
The chromatographic peak arrived is symmetrical, improves the sensitivity and accuracy of detection；And this method is to 4 kinds of sour detection selections with higher
Property, detection limit and quantitative limit be far below 4 kinds of sour contents in grape wine or fruit wine, and the organic acid that can measure low concentration contains
Amount, have the advantages that detection limit it is low, being capable of qualitative, quantitative accurate detection.
Technology using 4 kinds of organic acids in the HPLC-MS/MS detection grape wine and/or fruit wine set up is qualitative and quantitative
Detect 4 kinds of organic acids in grape wine and/or fruit wine, it is possible to authenticate wine blend or fruit wine.Base is eliminated by the way that internal standard is added
The influence of mass effect, while 4 kinds of organic acids of detection can mutually assist identifying wine blend or fruit wine, make testing result more
Accurately, and since HPLC-MS/MS technology using " double ion to " carries out qualitative, quantitative, the interference of endogenous material is avoided
With occur false positive determine result a possibility that.This method pre-treatment is simple and quick, process free of losses, and detection sensitivity is high, knot
Fruit is accurate and reliable, realizes the Accurate Determining that 4 kinds of organic acids are completed in 6 minutes, for quickly identification blend littlefruit grape herb wine and fruit wine,
The dining table safety and maintenance Ko-ji insects for protecting consumer develop in a healthy way and provide technical support.
Detailed description of the invention
Fig. 1 is 4 kinds of organic acid typical case's MRM chromatograms；
Fig. 2 is that the mass spectrometry parameters of 4 kinds of organic acids optimize figure, and A- optimizes fragmentation voltage, B- optimizing drying temperature degree；
Fig. 3 is 4 kinds of organic acid regression curves, A- tartaric acid, B- malic acid, C- citric acid, D- succinic acid.
Specific embodiment
The invention will be further described with embodiment with reference to the accompanying drawing.
Instrument and reagent
Key instrument used in experiment has: (Agilent is public for Agilent-1200 type quick separating high performance liquid chromatography
Department), 6410 type triplex tandem level four bars mass spectrums (Agilent company).Acetonitrile (chromatographically pure, Tedia company), formic acid, DL- apple
Acid (purity is greater than 99%) is purchased from Chengdu Ke Long chemical reagent factory, and tartaric acid, succinic acid (purity is greater than 99.5%) are purchased from day
The big luxuriant chemical reagent factory in Jinshi City, monohydrate potassium (purity is greater than 99.8%) recover the limited public affairs of development in science and technology purchased from Tianjin
Department, toosendanin (internal standard IS, lot number 121464-201102) are purchased from National Institute for Food and Drugs Control.
Experimental method
The processing of sample
The accurate grape wine or fruit wine sample 0.1mL of measuring is diluted to scale, mistake with pure water in clean 100mL volumetric flask
0.45 μm of filter membrane, it is to be measured.If measurement result exceeds the range of linearity, diluted multiple can be determined further according to the height of organic acid content
Afterwards, to be measured.
HPLC condition
Chromatographic column: (50mm × 4.6mm, 1.8 μm, U.S. Agilent is public for Agilent Eclipse plus C18 chromatographic column
Department).Mobile phase: A phase is 0.15% aqueous formic acid, and B phase is acetonitrile.Gradient elution: 0~2.0min, A phase 100%；2.0-
2.1min, A phase 100% → 50%, B phase 0 → 50%；2.1-5.0min, A phase and B phase each 50%；5.0-5.1min, A phase 50%
→0；Finally balance 4.9min.Flow velocity: 0.6mL/min.Column temperature: 20 DEG C, sample volume: 10 μ L.
MS/MS condition
Ion source: electric spray ion source (ESI), using anion multiple-reaction monitoring (MRM) mode, dry gas: high-purity N2,
Dry temperature degree: 350 DEG C, dry gas stream speed: 12L/min, atomizing pressure: 30psi, capillary voltage: 4000V.Other mass spectrums
Parameter is shown in Table 1.
Mass spectrometry parameters condition under 1 target components MRM mode of table
Chromatographic condition optimization
When detecting the organic acid in grape wine using HPLC-MS/MS, it is most important that select optimal chromatographic isolation item
Part.It include the type of chromatographic column, the pH value of mobile phase, flow velocity and column temperature etc. in these conditions.In determining chromatography column
Under part, the pH value of mobile phase, flow velocity imitate column and the separation of chromatographic peak is affected, the too low then disengaging time of flow velocity is too long,
Column effect is poor；Column temperature also significantly affects column effect, and column temperature increases the viscosity that can reduce mobile phase and improves mass-transfer efficiency, but too high
Chromatographic column filler can be destroyed again, thus the selection of chromatographic condition be it is considerably complicated, to integrate numerous consideration factors.
It has carried out selection to chromatographic column first to investigate, hit and miss experiment Thermo Scientific BDS Hypersil
C18 chromatographic column (100 × 4.6mm, 3 μm, 1# column), Thermo Scientific HILIC XDB-C18 chromatographic column (100 ×
4.6mm, 3 μm, 2# column), 3 sections of chromatographies such as Agilent Eclipse plus C18 chromatographic column (50 × 4.6mm, 1.8 μm, 3# column)
Column.Through overtesting discovery when using 1# column and 2# column, there is bifurcated peak in malic acid and tartaric acid, and citric acid chromatographic peak drags
Tail.The 3# column under identical chromatographic conditions, good separating effect, each compound have reached baseline separation, and since the column is shorter, chemical combination
Logistics is very fast out, and retention time is short, ideal.
Secondly, the pH value of mobile phase, flow velocity and gradient are optimized.By detected object it is acid compared with
By force, soluble easily in water, according to " similar to mix " principle, a certain amount of formic acid adjusting acidity is added in mobile phase and is conducive to organic acid
Separation, but mobile phase acidity Tai Gaoyi loss chromatographic column and the detection for being unfavorable for mass spectrum anion, as a result, it has been found that, in acetonitrile-
When 0.15% aqueous formic acid system is as mobile phase, chromatographic peak profile is symmetrical.And use mass spectrum ESI condition, the flow velocity of mobile phase
It is usually no more than 0.6mL/min, otherwise since the limitation gasified with spray condition can greatly reduce sensitivity.100%
When 0.15% aqueous formic acid, tartaric acid and malic acid appearance are very fast, and retention time is respectively 1.01min and 1.38min, and lemon
Lemon acid and succinic acid retain relatively by force in the chromatography column, and appearance is slower, therefore under the premise of not influencing separating degree, improves second rapidly
Nitrile ratio flows out citric acid quickly with succinic acid to 50%.
Finally, chromatogram column temperature is optimized.It is arranged 20-60 DEG C of column temperature (60 DEG C of chromatographic column highest tolerable temperature),
As a result, it has been found that as the temperature rises, all Compound Retention times shorten, but peak area does not have a significant change, and separating degree
It is deteriorated, therefore following experiment uses 20 DEG C of column temperature.Typical chromatogram is shown in Fig. 1.
MS/MS condition optimizing
It is higher that Mass Spectrometer Method condition can be such that sample parent ion acquisition maximum transmitted efficiency and daughter ion has in mass spectrum
Response intensity, directly affects detection sensitivity and accuracy, mainly includes to dry temperature degree, fragmentation voltage and collision energy
Deng optimization.
Firstly, analyzing respectively 4 kinds of organic acids in scanning-mode it, respective molecular ion peak (parent ion) is determined；
Secondly, under the mode of selection ion detection (SIM), input sample mother ion mass-to-charge ratio optimizes fragmentation voltage
(Fragmentor, 0V~140V) guarantees the maximum transmitted efficiency of parent ion, i.e., more to reaches collision cell, specific experiment as far as possible
As a result see Fig. 2A；Again, under daughter ion scan pattern, the mass-to-charge ratio and different collision energies (0V~40V) of parent ion are inputted,
Influence of the different collision energies to parent ion and daughter ion peak intensity is investigated, collision energy when daughter ion maximum intensity is optimized,
Best daughter ion mass-to-charge ratio is determined simultaneously；Finally, dry 200 DEG C -350 DEG C of gas temperature range is arranged, investigated most under MRM mode
Drying temperature degree when good sensitivity, concrete outcome are shown in Fig. 2 B.By testing above, best fragmentation voltage, collision energy are determined
Parameter is as shown in table 1.The Mass Spectrometry Conditions of internal standard toosendanin are with reference to " Chinese Pharmacopoeia one " (version in 2015) " Fructus meliae toosendan " kind
Regulation under " assay " item.
1.3 linear relationships and detection limit
Take appropriate tartaric acid, malic acid, succinic acid, citric acid standard solution accurate formulation 0.25,0.5,1.0,2.0,
5.0, a series of standard working solution of different quality concentration of 10.0 μ g/mL, toosendanin standard solution, which is added, makes its concentration be
2.0 μ g/mL, by above-mentioned condition difference sample introduction measurement, with the quota ion peak area internal scalar quantity quasi-molecular ions face of 4 kinds of organic acids
Product ratio is ordinate (Y), and using 4 kinds of organic acid concentrations, as abscissa (X) progress linear regression, (linear graph is shown in internal standard concentration ratio
Fig. 3 A-D), obtain regression equation, related coefficient and the range of linearity；Using the corresponding concentration of signal-to-noise ratio (S/N) >=3 as detection limit,
(S/N) >=10 corresponding concentration is as quantitative limit, obtains tartaric acid, malic acid, succinic acid, the detection limit of citric acid and quantitative
Limit, the results are shown in Table 2.As can be seen from the results, within the scope of 0.25-10 μ g/mL, the regression coefficient of 4 kinds of organic acids is all larger than
0.99, linear good, detection limit and quantitative limit are far below the content in grape wine and fruit wine, therefore, can pass through diluted sample
It is measured after product.
Linear equation, the range of linearity, related coefficient, quantitative limit and the detection limit of 2 four kinds of organic acids of table
Embodiment 2
The identification of wine blend or fruit wine: utilize established detection method to 10 grape wine commercially
And 1 Howthorn Wine sample, by being analyzed after handling the step of embodiment 2, measurement result is shown in Table 3.There it can be seen that
4 kinds of organic acids of 1-3# sample have detection, and content range is 0.104~1.88g/L, and wherein citric acid content corresponds with correspondence
Maximum level in the national standard " grape wine " (GB 15037-2006) of execution, " wild grape wine " (GB/T 27586-2011)
It is required that (dry, half-dried, sweet tea half mould is not more than 1.0g/L, and sweet tea type is not more than 2.0g/L).Citric acid content model in other 7 samples
It encloses and tartaric acid, malic acid, amber is not detected more than 2.5~7 times of limitation of corresponding mark execution standard for 5.06~9.07g/L
Acid, illustrating product not is to be suspected by fruit fermenting and producing to blend fake wine.In order to which whether the method for verifying foundation is accurate, again
It has detected 2 quality index such as total reducing sugar, sugar-free extract of 4~11# sample and 1 pigment that may illegally add is carmine, knot
Fruit shows that total reducing sugar, sugar-free extract index do not meet standard requirements yet, and detected famille rose, further confirms that this 7 samples are
Fake wine.These results suggest that the method for 4 kinds of organic acids of quick measurement that the present invention establishes is suitable for identifying wine blend and fruit
Wine.
The measurement (unit: g/L) of 4 kinds of organic acids in 3 actual sample of table
Note: N.D.- is not detected
Above-mentioned, although the foregoing specific embodiments of the present invention is described with reference to the accompanying drawings, not protects model to the present invention
The limitation enclosed, those skilled in the art should understand that, based on the technical solutions of the present invention, those skilled in the art are not
Need to make the creative labor the various modifications or changes that can be made still within protection scope of the present invention.
Claims (5)
1. one kind detects grape wine or fruit wine mesotartaric acid, malic acid, amber by high performance liquid chromatography-tandem mass internal standard method
4 kinds of acid, citric acid organic acids identify the method for wine blend or fruit wine, which comprises the following steps:
(1) 4 kinds of organic acid standard solution are prepared and carry out high performance liquid chromatography tandem mass spectrum detection；
(2) linear relationship and detection limit and quantitative limit of 4 kinds of organic acids are determined；
(3) grape wine or fruit wine sample are pre-processed and is measured；
(4) content of 4 kinds of organic acids is calculated according to sample detection data；
The internal standard method uses toosendanin for internal standard compound；
It is characterized in that step (1) or the chromatographic determination condition of (3) are as follows: chromatographic column: Agilent Eclipse plus C18,50
× 4.6mm, 1.8 μm；
Mobile phase A is the water containing 0.15% formic acid, and Mobile phase B is acetonitrile；Gradient elution program: gradient elution: 0 ~ 2.0min, A phase
100%；2.0-2.1min, A phase 100% → 50%, B phase 0 → 50%；2.1-5.0min, A phase and B phase each 50%；5.0-5.1min, A
Phase 50% → 0；Finally balance 4.9min；
Flow velocity 0.6mL/min；Column temperature: 20 DEG C；
Mass spectroscopy condition are as follows: ionization mode: electric spray ion source,
Acquisition mode: anion multiple-reaction monitoring pattern,
Dry gas: high-purity N2, dry temperature degree: 200-350 DEG C,
Atomizing pressure: 30 psi, capillary voltage: 4000 V.
2. detecting winestone in grape wine or fruit wine by high performance liquid chromatography-tandem mass internal standard method as described in claim 1
4 kinds of acid, malic acid, succinic acid, citric acid organic acids identify the method for wine blend or fruit wine, characterized in that the step
Suddenly (1) specifically includes the following steps: a series of at least six kinds of different quality concentration of accurate formulation tartaric acid, malic acid, amber
Acid, citric acid standard working solution, are added internal standard compound standard solution, and sample introduction measures to obtain standard spectrogram.
3. detecting winestone in grape wine or fruit wine by high performance liquid chromatography-tandem mass internal standard method as described in claim 1
4 kinds of acid, malic acid, succinic acid, citric acid organic acids identify the method for wine blend or fruit wine, characterized in that step (2)
Specifically include: the standard spectrogram that step (1) is obtained is corresponding to the two to the peak area ratio of internal standard compound with 4 kinds of organic acids respectively
Concentration proportion carry out linear regression, obtain linear relationship regression equation, related coefficient and the range of linearity；With signal-to-noise ratio >=3 pair
The concentration answered is detection limit, and the corresponding concentration in signal-to-noise ratio >=10 is as quantitative limit.
4. detecting winestone in grape wine or fruit wine by high performance liquid chromatography-tandem mass internal standard method as described in claim 1
4 kinds of acid, malic acid, succinic acid, citric acid organic acids identify the method for wine blend or fruit wine, characterized in that step (3)
Specifically: it is accurate to measure grape wine or the dilution of fruit wine sample, it filters, sample introduction measures to obtain sample spectrogram.
5. detecting winestone in grape wine or fruit wine by high performance liquid chromatography-tandem mass internal standard method as described in claim 1
4 kinds of acid, malic acid, succinic acid, citric acid organic acids identify the method for wine blend or fruit wine, characterized in that the step
Suddenly (4) specifically: the sample spectrogram and standard spectrogram for obtaining step (3) compare, and the type of qualitative determining organic acid is contemporary
Enter the content that linear equation quantitatively calculates organic acid.
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| CN116879441A (en) * | 2023-07-13 | 2023-10-13 | 合肥工业大学 | Detection method for organic acid in food based on liquid chromatography-mass spectrometry |
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