CN115856169A - Method for simultaneously detecting 34 carbonyl compounds in kiwi fruit wine - Google Patents

Method for simultaneously detecting 34 carbonyl compounds in kiwi fruit wine Download PDF

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CN115856169A
CN115856169A CN202211604660.1A CN202211604660A CN115856169A CN 115856169 A CN115856169 A CN 115856169A CN 202211604660 A CN202211604660 A CN 202211604660A CN 115856169 A CN115856169 A CN 115856169A
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carbonyl compounds
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CN115856169B (en
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闫岩
李岑
邱树毅
周剑丽
曾祥勇
李豆南
敖红艳
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Guizhou University
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Abstract

The invention discloses a method for simultaneously detecting 34 carbonyl compounds in kiwi fruit wine, and belongs to the technical field of wine detection. The method for simultaneously detecting 34 carbonyl compounds in the kiwi fruit wine comprises the steps of carrying out derivatization reaction on a derivatization reagent and the carbonyl compounds, and then simultaneously detecting 34 carbonyl compounds including volatile acids, non-volatile acids, volatile aldehydes and non-volatile aldehydes in the kiwi fruit wine by combining UPLC-MS/MS.

Description

Method for simultaneously detecting 34 carbonyl compounds in kiwi fruit wine
Technical Field
The invention relates to a method for simultaneously detecting 34 carbonyl compounds in kiwi fruit wine, and belongs to the technical field of wine detection.
Background
The carbonyl compounds in the kiwi fruit wine mainly comprise acid compounds, aldehyde compounds and ketone compounds, have important influence on the aroma and taste of the wine, and the detection of the carbonyl compounds has important significance for evaluating the flavor quality of the kiwi fruit wine and monitoring the quality of the kiwi fruit wine.
At present, volatile acid compounds, volatile aldehydes and volatile ketone compounds in fruit wine are mainly detected directly by gas chromatography, non-volatile acid compounds are mainly detected by liquid chromatography or gas chromatography after derivatization, if carbonyl compounds in the fruit wine need to be detected at one time, gas chromatography and liquid chromatography need to be adopted, or a mode of detecting the carbonyl compounds in the fruit wine after direct detection and derivatization by gas chromatography is adopted, the method is tedious and time-consuming, and the purpose of one-time detection cannot be achieved; and sensitivity and accuracy are low.
As the prior art, the "Chemometric analysis of Chinese red wine using the solid bar Sorptive extraction with GC-MS analysis" disclosed by Tang et al has a detection limit of acetic acid of 618.50. Mu.g/L, 2-methylpropionic acid of 80.49. Mu.g/L, butyric acid of 80.08. Mu.g/L and benzaldehyde of 0.80. Mu.g/L;
in the 'key aroma components and formation thereof for aging yellow wine' disclosed by Wangcheng, the detection limit of acetic acid in yellow wine is 10.23 mug/L, the detection limit of 2-methylpropanoic acid is 5.11 mug/L, the detection limit of butyric acid is 10.47 mug/L, the detection limit of vanillin is 5.11 mug/L, the detection limit of benzaldehyde is 45.89 mug/L, and the detection limit of 3-hydroxy-2-butanone is 171.51 mug/L by adopting GC-MS.
The detection limit of UPLC in detecting lactic acid and acetic acid in Chinese liquor of different flavor type by Wang Han discloses ultra performance liquid chromatography for determining lactic acid and acetic acid content is 1mg/L.
Du et al, in "chromatography of key antibodies in Langyatai Baijiu with Jianan flavour by sensory-direct analysis", disclose a limit of caproic acid detection of 1203. Mu.g/L, acetic acid detection of 6325. Mu.g/L, butyric acid detection of 8459. Mu.g/L, furfural detection of 891. Mu.g/L.
Therefore, it is urgently needed to develop a detection method with high sensitivity and low detection limit.
Disclosure of Invention
[ problem ] to
Volatile acids, volatile aldehydes, volatile ketone compounds and non-volatile acid compounds in the prior art wine can not realize the effect of one-time detection, and the detection sensitivity is low, so that the batch operation is difficult.
[ solution ]
Aiming at the technical problems, the invention provides a method for simultaneously detecting 34 carbonyl compounds in kiwi fruit wine, which comprises the steps of reacting a derivatization reagent 3-nitrophenylhydrazine hydrochloride with volatile acids, non-volatile acids, volatile aldehydes and non-volatile aldehyde compounds under the action of catalysts N- (3-dimethylaminopropyl) -N' -ethylcarbodiimide hydrochloride and pyridine to obtain a derivatization reaction product, performing Ultra performance liquid chromatography-tandem mass spectrometry (Ultra performance liquid chromatography-mass spectrometry.
The invention aims to provide a method for simultaneously detecting 34 carbonyl compounds in kiwi fruit wine, which comprises the following steps:
(1) Derivatization treatment of kiwi fruit wine
Taking a kiwi fruit wine sample, firstly adding isotope internal standard propionic acid-d 6 solution, acetophenone-d 3 solution and nonanal-d 18 solution, then adding a derivatization reagent and a catalyst, carrying out derivatization reaction, and after the reaction is finished, passing through a membrane to obtain a solution to be detected;
(2) Establishment of a Standard Curve
Mixing and dissolving 34 carbonyl compounds to prepare a series of standard solutions with concentration, and adding an isotope internal standard solution, a derivatization reagent and a catalyst into the standard solutions to carry out derivatization reaction; after the reaction is finished, determining by using UPLC-MS/MS, and constructing a quantitative relation model by taking the peak area ratio of each carbonyl compound and the corresponding isotope internal standard as a vertical coordinate and the concentration ratio of each carbonyl compound and the corresponding isotope internal standard as a horizontal coordinate;
wherein the 34 carbonyl compounds comprise acid compounds, aldehyde compounds and ketone compounds; the isotope internal standard substance corresponding to the acid compound is propionic acid-d 6; the isotope internal standard substance corresponding to the aldehyde compound is nonanal-d 18; the isotope internal standard substance corresponding to the ketone compound is acetophenone-d 3;
(3) Determination of 34 carbonyl Compounds
Detecting the liquid to be detected in the step (1) by using UPLC-MS/MS, and calculating the content of 34 carbonyl compounds in the kiwi fruit wine according to the peak area ratio of each compound in the detected liquid to be detected and the corresponding isotope internal standard substance and the quantitative relation model established in the step (2);
in one embodiment, the concentration of the propionic acid-d 6 solution, the acetophenone-d 3 solution and the nonanal-d 18 solution in the step (1) is 200 to 500 μ g/L.
In one embodiment, the derivatizing agent of step (1) is a 3-nitrophenylhydrazine hydrochloride solution.
In one embodiment, the concentration of the derivatizing agent of step (1) is 100 to 200mmol/L; the compound is prepared by dissolving 3-nitrophenylhydrazine hydrochloride in 50% acetonitrile water solution.
In one embodiment, the catalyst is N- (3-dimethylaminopropyl) -N' -ethylcarbodiimide hydrochloride and pyridine.
In one embodiment, the concentration of N- (3-dimethylaminopropyl) -N' -ethylcarbodiimide hydrochloride in the catalyst is 100-120 mmol/L, wherein the mass proportion of pyridine is 6%; the specific configuration of the catalyst was N- (3-dimethylaminopropyl) -N' -ethylcarbodiimide hydrochloride and pyridine dissolved in 50% aqueous acetonitrile.
In one embodiment, in the system of the derivatization reaction in step (1), 10 μ L of an internal standard solution with a concentration of 500 μ g/L, 20 μ L of a 3-nitrophenylhydrazine hydrochloride solution with a concentration of 200mmol/L, 20 μ L of an N- (3-dimethylaminopropyl) -N' -ethylcarbodiimide hydrochloride solution (containing 6% pyridine) with a concentration of 120mmol/L, and 910 μ L of acetonitrile water with a volume fraction of 50% to 1mL are added to 40 μ L of a kiwi fruit wine sample.
In one embodiment, the derivatization reaction in step (1) is carried out at a water bath temperature of 40-60 ℃ for 20-30 min.
In one embodiment, the 34 carbonyl compounds of step (2) include formic acid, acetic acid, benzoic acid, 2-methylpropionic acid, butyric acid, caproic acid, caprylic acid, capric acid, malic acid, DL-p-hydroxyphenyllactic acid, 2-hydroxy-4-methylpentanoic acid, 2-furoic acid, 2, 3-dihydroxypropionic acid, 2-hydroxy-3-methylbutyric acid, 3-hydroxypropionic acid, succinic acid, lactic acid, glycolic acid, vanillic acid, syringic acid, caffeic acid, tartaric acid, citric acid, 3, 4-dihydroxybenzoic acid, furfural, vanillin, benzaldehyde, 5-methylfurfural, hexanal, acetaldehyde, 2, 3-butanedione, 3-penten-2-one, 3-pentanone, 3-hydroxy-2-butanone.
In one embodiment, the mass spectrometric conditions for UPLC-MS/MS detection of step (2): the ion source is in an ESI negative ion mode, the ion source temperature is 110-120 ℃, the desolvation temperature is 500-550 ℃, the capillary tube voltage is 2-3 KV, the collision voltage is 13-30 eV, the taper hole voltage is 21-37V, the taper hole airflow is 50L/h, and the desolvation airflow is 800L/h.
In one embodiment, the cone hole voltage V, the collision voltage eV, the quantitative parent ion m/z and the quantitative child ion m/z are specifically set as follows: formic acid derivatives 21/13/180.0/137.1, acetic acid derivatives 25/19/194.0/137.1, benzoic acid derivatives 33/17/256.1/150.1, 2-methylpropionic acid derivatives 33/19/222.1/137.1, butyric acid derivatives 33/19/222.1/137.1, hexanoic acid derivatives 33/21/250.1/137.2, octanoic acid derivatives 35/23/278.2/137.1, decanoic acid derivatives 37/27/306.2/137.1,2, 3-dihydroxypropionic acid derivatives 27/19/240.0/136.9, glycolic acid derivatives 25/15/210.2/137.0, 3-hydroxypropionic acid derivatives 23/13/224.2/194.0, lactic acid derivative 27/15/224.0/151.8,3, 4-dihydroxybenzoic acid derivative 31/29/288.2/108.2, 2-hydroxy-3-methylbutyric acid derivative 31/17/252.2/151.9, tartaric acid derivative 29/21/419.6/208.2, 2-furoic acid derivative 25/17/246.0/149.8, vanillic acid derivative 33/19/302.1/177.9, syringic acid derivative 35/25/332.2/150.0, malic acid derivative 29/19/403.4/207.9, succinic acid derivative 31/17/387.2/234.2, caffeic acid derivative 31/23/314.2/176.0, 2-hydroxy-4-methylvaleric acid derivative 31/17/266.2/151.8, DL-p-hydroxy-phenyllactic acid derivative 31/17/300.0/151.8, citric acid derivatives 35/30/596.3/222.2, acetaldehyde derivatives 21/15/177.9/137.0, vanillin derivatives 29/21/286.1/148.0, furfural derivatives 25/17/230.0/137.0, 5-methylfuran aldehyde derivatives 25/15/244.0/184.0, benzaldehyde derivatives 33/17/240.0/137.0, hexanal derivatives 27/19/234.0/136.9, 3-hydroxy-2-butanone derivatives 23/15/221.8/137.0, 3-penten-2-one derivatives 23/19/218.0/137.0, 3-pentanone derivatives 23/15/220.0/151.0,2, 3-butanedione derivatives 33/21/355.2/137.0, propionic acid-d 6 derivatives (internal standard) 27/19/213.2/137.2, acetophenone-d 3 derivatives (internal standard) 29/17/154.0, nonanal derivatives (internal standard) 29/23/19/137.0/257.138.138.138, and nonanal derivatives (internal standard) 138.0.
In one embodiment, the chromatography conditions for the UPLC-MS/MS detection are: c18 column (100 mm. Times.2.1 mm,1.7 μm); the column temperature is 40 ℃; mobile phase A: water +5mmol/L ammonium acetate +0.1% formic acid; b: acetonitrile/water (95/5, v/v) +5mmol/L ammonium acetate +0.1% formic acid; the flow rate is 0.3mL/min; the sample volume is 10 mu L; gradient elution.
In one embodiment, the gradient elution is performed in a procedure of 0 to 1min, B18%, 1 to 11min, B45%, 11 to 15min, B65%, 15 to 17, B100%, 17 to 19.5min, B100%, 19.5 to 20min, B18%, 20 to 23min, B18%.
The second purpose of the invention is to provide the application of the method in wine detection.
[ advantageous effects ]
(1) The invention provides a method for detecting 34 carbonyl compounds including volatile acids, non-volatile acids, volatile aldehydes and non-volatile aldehydes in kiwi fruit wine conveniently, efficiently and at one time.
(2) The method comprises the steps of reacting 3-nitrophenylhydrazine hydrochloride with carbonyl compounds under the action of a catalyst N- (3-dimethylaminopropyl) -N' -ethylcarbodiimide hydrochloride solution and pyridine, and quantifying the content of the kiwi fruit wine in a liquid chromatography-mass spectrometry mode, wherein the sensitivity of the method is higher than that of the method for detecting the carbonyl compounds in wine compounds in Gas chromatography-mass spectrometry (GC-MS) and UPLC methods in the existing literature.
Drawings
FIG. 1 is a graph of mass spectrometry condition optimization data for a formic acid derivative of comparative example 1; the method comprises the following steps of (A) optimizing a taper hole voltage, (B) optimizing a collision voltage, and (C) optimizing formic acid derivative mass spectrum fragments;
FIG. 2 is a graph of peak areas of carbonyl compounds at different derivatization temperatures in comparative example 2; the (A) is acetic acid, (B) is lactic acid, and (C) is furfural; (D) 2, 3-butanedione;
FIG. 3 is a graph showing peak areas of carbonyl compounds at different derivatization times in comparative example 3; the (A) is acetic acid, (B) is lactic acid, and (C) is furfural; (D) 2, 3-butanedione;
FIG. 4 is a graph of peak areas of carbonyl compounds detected by different mobile phases in comparative example 4; acetic acid (A), lactic acid (B), furfural (C), 2, 3-butanedione (D);
FIG. 5 is a mass spectrum diagram of 34 carbonyl compound derivatives in liquid chromatography-mass spectrometry multiple reaction monitoring scan mode.
Detailed Description
The 34 carbonyl compounds involved in example 1 of the present invention are formic acid, acetic acid, benzoic acid, 2-methylpropanoic acid, butyric acid, caproic acid, caprylic acid, capric acid, malic acid, DL-p-hydroxyphenyllactic acid, 2-hydroxy-4-methylpentanoic acid, 2-furoic acid, 2, 3-dihydroxypropionic acid, 2-hydroxy-3-methylbutyric acid, 3-hydroxypropionic acid, succinic acid, lactic acid, glycolic acid, vanillic acid, syringic acid, caffeic acid, tartaric acid, citric acid, 3, 4-dihydroxybenzoic acid, furfural, vanillin, benzaldehyde, 5-methylfuran aldehyde, hexanal, acetaldehyde, 2, 3-butanedione, 3-penten-2-one, 3-pentanone, 3-hydroxy-2-butanone, respectively; wherein, formic acid, acetic acid, butyric acid, caproic acid, caprylic acid, capric acid, malic acid, 2-furoic acid, succinic acid, glycolic acid, furfural, benzaldehyde, 5-methylfuran aldehyde, hexanal, 2, 3-butanedione, 3-pentanone, 3-hydroxy-2-butanone and acetophenone-d 3 are purchased from Beijing Bailingwei science and technology Limited;
DL-p-hydroxyphenyllactic acid, lactic acid, vanillic acid, syringic acid, caffeic acid, tartaric acid, citric acid, vanillin, acetaldehyde, propionic acid-d 6, purchased from sigma aldrich trade ltd;
benzoic acid, 2-methylpropionic acid, 2-hydroxy-3-methylbutyric acid, 3, 4-dihydroxybenzoic acid, nonanal-d 18 were purchased from Chishiai (Shanghai) chemical industry development Co., ltd;
3-hydroxypropionic acid, 3-penten-2-one purchased from Shanghai Michelin Biotechnology, inc.;
2, 3-Dihydroxypropionic acid was purchased from Hai Xianghui pharmaceutical science and technology, inc.; 2-hydroxy-4-methylpentanoic acid was purchased from Alfa Angsa chemical company, inc., and all standards were more than 95% pure.
Example 1
A method for simultaneously detecting 34 carbonyl compounds in kiwi fruit wine specifically comprises the following steps:
(1) Derivatization treatment of kiwi fruit wine
Adding 10 μ L isotope internal standard solution (propionic acid-d 6, acetophenone-d 3 and nonanal-d 18, the concentration is 500 μ g/L, dissolved in 50 vol ethanol water solution) into 40 μ L kiwi fruit wine sample, respectively, adding 20 μ L3-nitrophenylhydrazine hydrochloride solution (dissolved in acetonitrile water solution with volume fraction of 50%) with concentration of 200mmol/L, adding 20 μ L N- (3-dimethylaminopropyl) -N' -ethylcarbodiimide hydrochloride solution (containing 6% pyridine, dissolved in acetonitrile water solution with volume fraction of 50%) with concentration of 120mmol/L, mixing by vortex oscillation, heating in water bath at 40 deg.C for 30min, recovering to room temperature after heating in water bath, adding 910 μ L acetonitrile water with volume fraction of 50% to 1mL, and filtering with organic filter membrane (0.22 μm) for standby.
(2) Establishment of a Standard Curve
34 carbonyl compounds are dissolved in ethanol water solution with the volume fraction of 10 percent and are configured into a plurality of concentrations (formic acid, acetic acid, succinic acid, furfural are 250, 500, 1000, 2000, 4000, 8000, 16000; benzoic acid, 2-methylpropionic acid, butyric acid, caproic acid, caprylic acid, capric acid, glycolic acid, 3-hydroxypropionic acid, 3, 4-dihydroxybenzoic acid, 2-hydroxy-3-methylbutyric acid, tartaric acid, 2-furoic acid, vanillic acid, syringic acid, caffeic acid, 2-hydroxy-4-methylpentanoic acid, DL-p-hydroxy-phenyllactic acid, vanillin, 5-methylfurfural, benzaldehyde, hexanal, 3-penten-2-one, 3-pentanone, 2, 3-butanedione are 5, 10, 20, 40, 80, 160, 320, 2, 3-dihydroxypropionic acid, acetaldehyde are 20, 40, 80, 160, 320, 640, 1280; 1250 parts, 2500 parts, 5000 parts, 10000 parts, 20000 parts, 40000 parts and 80000 parts of 3-hydroxy-2-butanone, 500 parts, 1000 parts, 2000 parts, 4000 parts, 8000 parts, 16000 parts and 32000 parts, wherein the concentration units are all mu g/L, then 40 mu L of each solution with each concentration is respectively placed in a 0.5mL centrifuge tube, 10 mu L of isotope internal standard solution (propionic acid-d 6 part, acetophenone-d 3 part and nonanal-d 18 part) is added, then 20 mu L of 3-nitrophenylhydrazine hydrochloride solution with the concentration of 200mmol/L (dissolved in acetonitrile aqueous solution with the volume fraction of 50%) is added, then 20 mu L of N- (3-dimethylaminopropyl) -N' -ethyl carbodiimide hydrochloride solution with the concentration of 120mmol/L (containing 6% pyridine is added, dissolving in 50% acetonitrile water solution), carrying out vortex oscillation and uniform mixing, heating for 30 minutes in water bath at 40 ℃, carrying out derivatization treatment, after the reaction is finished, adding 910 mu L of acetonitrile water with the volume fraction of 50% to 1mL, carrying out UPLC-MS/MS determination, taking the peak area ratio of the carbonyl compound and the corresponding isotope internal standard substance as the ordinate, taking the concentration ratio of the carbonyl compound and the corresponding isotope internal standard substance as the abscissa, and respectively constructing a quantitative relation model of each compound, wherein the results are shown in Table 2;
wherein the 34 carbonyl compounds comprise acid compounds, aldehyde compounds and ketone compounds; the isotope internal standard substance corresponding to the acid compound is propionic acid-d 6 solution; the isotope internal standard substance corresponding to the aldehyde compound is nonanal-d 18 solution; the isotope internal standard substance corresponding to the ketone compound is acetophenone-d 3 solution;
detecting by adopting a multi-reaction monitoring scanning mode; mass spectrum conditions: the ion source is in an ESI negative ion mode, the ion source temperature is 120 ℃, the desolvation temperature is 500 ℃, the capillary tube voltage is 2KV, the collision voltage and the taper hole voltage are set according to the data recorded in the table 1, the taper hole airflow is 50L/h, and the desolvation airflow is 800L/h; the mass spectrometry detection conditions of the specific 34 carbonyl compounds are shown in table 1;
chromatographic conditions are as follows: c18 column (100 mm. Times.2.1 mm,1.7 μm); the column temperature is 40 ℃; mobile phase A: water +5mmol/L ammonium acetate +0.1% formic acid; b: acetonitrile/water (95/5, v) +5mmol/L ammonium acetate +0.1% formic acid; the flow rate is 0.3mL/min; the sample volume is 10 mu L; gradient elution procedure is 0-1min, B18%, 1-11min, B45%, 11-15min, B65%, 15-17, B100%, 17-19.5min, B100%, 19.5-20min, B18%, 20-23min, B18%.
(3) Determination of 34 carbonyl Compounds
And (3) detecting the to-be-detected fruit wine liquid after derivatization in the step (1) by using UPLC-MS/MS to obtain peak area ratios of the 34 carbonyl compounds to the internal standard, and calculating the content of the 34 carbonyl compounds in the kiwi fruit wine according to the standard curve model established in the step (2).
TABLE 1 Mass spectrometric detection conditions for 34 carbonyl compounds in kiwi fruit wine
Figure BDA0003996992680000061
Figure BDA0003996992680000071
Determination of results
1. Standard Curve and precision measurement
The linear regression equation of the 34 carbonyl compounds is shown in table 2, the correlation coefficients are all larger than 0.99, the daytime precision is 1.9% -6.9%, and the intraday precision is 4.6% -9.2%, and the requirements of the national standard 'laboratory quality control standard food physicochemical detection' (GB/T27404-2008) on the calibration curve and precision are met.
TABLE 2 Mass spectrometric detection conditions for 34 carbonyl compounds in kiwi fruit wine
Figure BDA0003996992680000081
Figure BDA0003996992680000091
2. Determination of recovery
According to the linear range of the 34 carbonyl compounds measured in the example 1, the intermediate concentration of the 34 carbonyl compounds in the range of establishing a standard curve is selected and added to the kiwi fruits, and the content change of the 34 carbonyl compounds before and after the addition is measured according to the detection method in the example 1, and the recovery rate is calculated.
Recovery rate = (concentration after addition-concentration before addition)/addition concentration × 100%.
The results are shown in Table 2; the recovery rates of the 34 carbonyl compounds are all in the range of 85.4-117.1 percent, and meet the requirements of the national standard of food physicochemical detection of laboratory quality control Specification (GB/T27404-2008) on the recovery rate.
3. Actual sample measurement results
The results of the determination of 24 carbonyl compounds in kiwi fruit wine (12 vol%) were shown in Table 3, which all enabled accurate quantitative determination:
TABLE 3 detection results (average, mg/L. + -. RSD) of 34 carbonyl compounds in Kiwi fruit wine (12%
Serial number Compound (I) Content (wt.) Serial number Compound (I) Content (wt.)
1 Formic acid 6.02±2.56 18 Syringic acid 0.007±1.94
2 Acetic acid 12.92±3.29 19 Malic acid 4.56±3.10
3 Benzoic acid 0.009±1.37 20 Succinic acid 6.16±5.22
4 2-Methylpropanoic acid 0.011±3.09 21 Caffeic acid 0.13±3.10
5 Butyric acid 0.013±0.87 22 2-hydroxy-4-methylpentanoic acid 0.21±1.33
6 Hexanoic acid 0.26±3.47 23 DL-p-hydroxy-phenyllactic acid 0.28±0.97
7 Octanoic acid 0.22±0.95 24 Citric acid 71.67±2.88
8 Capric acid 0.006±1.06 25 Acetaldehyde 0.35±1.09
9 2, 3-dihydroxypropionic acid 0.93±0.99 26 Vanillin 0.25±1.48
10 Glycolic acid 0.031±1.60 27 Furfural 1.87±0.93
11 3-hydroxypropionic acid 0.11±0.88 28 5-methylfuran aldehyde 0.009±6.01
12 Lactic acid 22.11±2.50 29 Benzaldehyde 0.075±1.07
13 3, 4-Dihydroxybenzoic acid 0.006±1.62 30 Hexaldehyde 0.038±2.33
14 2-hydroxy-3-methylbutyric acid 0.14±2.50 31 3-hydroxy-2-butanone 23.37±1.15
15 Tartaric acid 0.012±1.11 32 3-penten-2-ones 0.11±4.31
16 2-furoic acid 0.008±2.08 33 3-pentanone 0.061±1.80
17 Vanillic acid 0.13±4.41 34 2, 3-butanedione 0.23±3.69
Comparative example 1 Mass Spectrometry Condition optimization
Performing derivatization treatment on each carbonyl compound with the concentration of 1000 mug/L, finally diluting to 2.5mL, placing in a liquid phase vial, and performing direct sample injection analysis through mass spectrometry, wherein a mobile phase A is water, a mobile phase B is acetonitrile, and the flow rate is 0.2mL/min; the method comprises the steps of setting the cone hole voltage of a mass spectrum to be 1-50V, setting the collision voltage to be 1-50 eV, carrying out system optimization on the cone hole voltage and the collision voltage of derivatives obtained from 34 carbonyl compounds, carrying out quantitative analysis on the obtained daughter ions with the highest abundance, and carrying out auxiliary qualitative analysis on the ions with the second highest abundance.
Taking the optimization of the mass spectrum conditions of formic acid as an example, as shown in fig. 1, the derivative obtained by derivatization of formic acid with 3-nitrophenylhydrazine hydrochloride has the highest response at a cone-hole voltage of 21V (fig. 1A), so that the cone-hole voltage is determined to be 21V, and when the collision voltage is 13eV, a characteristic fragment with the best response (fig. 1B) is obtained, at this time, the mass spectrum fragments of the formic acid derivative are as shown in fig. 1C, so that 137.1 with the highest abundance is selected for quantification, and 151.3 with the second highest abundance is selected for auxiliary qualitative determination.
Comparative example 2 derivatization temperature optimization
Performing derivatization reaction at different reaction temperatures of 30 ℃, 40 ℃, 50 ℃ and 60 ℃ respectively by using water and acetonitrile as mobile phases under the condition that the derivatization time is 20min and based on the mass spectrometry condition of the embodiment 1; and acetic acid (1000. Mu.g/L), lactic acid (800. Mu.g/L), furfural (800. Mu.g/L) and 2, 3-butanedione (600. Mu.g/L) in representative volatile acid, non-volatile acid, aldehyde and ketone compounds were taken for detection, respectively.
As shown in FIG. 2, lactic acid, furfural and 2, 3-butanedione all had the highest peak area at 40 ℃, formic acid had the highest peak area at 40 ℃ and had no significant difference from the peak area at 50 ℃, and thus the temperature for derivatization was determined to be 40 ℃.
Comparative example 3 derivatization time optimization
Under the condition that the derivatization temperature is 40 ℃, water and acetonitrile are used as mobile phases, based on the mass spectrometry condition of example 1, preparing derivatization products respectively for different derivatization times of 20min, 25min, 30min, 35min and 40 min; and representative volatile acids, non-volatile acids, acetic acid (1000. Mu.g/L), lactic acid (800. Mu.g/L), furfural (800. Mu.g/L) and 2, 3-butanedione (600. Mu.g/L) among the aldehyde and ketone compounds were taken, respectively.
As shown in FIG. 3, lactic acid, furfural and 2, 3-butanedione each had the highest or higher peak area at 30min, and thus the derivatization temperature was determined to be 30min.
Comparative example 4 optimization of Mobile phase conditions
Respectively taking acetic acid (800 mu g/L), lactic acid (400 mu g/L), furfural (400 mu g/L) and 2, 3-butanedione (400 mu g/L) in representative acid, aldehyde and ketone compounds; on the basis of example 1, the mobile phases were adjusted to be: (1) water A and acetonitrile B; (2) water A +0.1% formic acid, acetonitrile B +0.1% formic acid; (3) water A +0.5% formic acid, acetonitrile B +0.5% formic acid; (4) water A +1mmol/L ammonium acetate, acetonitrile B +1mmol/L ammonium acetate; (5) water A +5mmol/L ammonium acetate, acetonitrile/water B (95/5, v/v) +5mmol/L ammonium acetate; (6) water A +5mmol/L ammonium acetate +0.5% formic acid, acetonitrile/water B (95/5, v/v) +5mmol/L ammonium acetate +0.5% formic acid; (7) water A +5mmol/L ammonium acetate +0.1% formic acid, acetonitrile/water B (95/5, v/v) +5mmol/L ammonium acetate +0.1% formic acid; and respectively detecting.
The results are shown in fig. 4, from which it can be seen that the four compounds all have the highest response intensity under the condition that the mobile phase is (7), and therefore the mobile phase is selected as phase a: water +5mmol/L ammonium acetate +0.1% formic acid; phase B: acetonitrile/water (95/5, v/v) +5mmol/L ammonium acetate +0.1% formic acid.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (10)

1. A method for simultaneously detecting 34 carbonyl compounds in kiwi fruit wine is characterized by comprising the following steps:
(1) Derivatization treatment of kiwi fruit wine
Adding isotope internal standard propionic acid-d 6 solution, acetophenone-d 3 solution and nonanal-d 18 solution into a kiwi fruit wine sample, adding a derivatization reagent and a catalyst, carrying out derivatization reaction, and after the reaction is finished, passing through a membrane to obtain a liquid to be detected;
(2) Creation of a Standard Curve
Mixing and dissolving 34 carbonyl compounds to prepare a series of standard solutions with concentration, and adding an isotope internal standard solution, a derivatization reagent and a catalyst into the standard solutions to carry out derivatization reaction; after the reaction is finished, determining by using UPLC-MS/MS, and constructing a quantitative relation model by taking the peak area ratio of each carbonyl compound and the corresponding isotope internal standard as a vertical coordinate and the concentration ratio of each carbonyl compound and the corresponding isotope internal standard as a horizontal coordinate;
wherein the 34 carbonyl compounds comprise acid compounds, aldehyde compounds and ketone compounds; the isotope internal standard substance corresponding to the acid compound is propionic acid-d 6; the isotope internal standard substance corresponding to the aldehyde compound is nonanal-d 18; the isotope internal standard substance corresponding to the ketone compound is acetophenone-d 3;
(3) Determination of 34 carbonyl Compounds
And (2) detecting the liquid to be detected in the step (1) by using UPLC-MS/MS, and calculating the content of 34 carbonyl compounds in the kiwi fruit wine according to the peak area ratio of each compound in the detected liquid to be detected and the corresponding isotope internal standard substance and the quantitative relation model established in the step (2).
2. The method as claimed in claim 1, wherein the concentration of the propionic acid-d 6 solution, the acetophenone-d 3 solution and the nonanal-d 18 solution in step (1) is 200-500 μ g/L.
3. The method of claim 1, wherein the derivatizing reagent of step (1) is 3-nitrophenylhydrazine hydrochloride solution with a concentration of 100 to 200mmol/L.
4. The process of claim 1, wherein the catalyst of step (1) is N- (3-dimethylaminopropyl) -N' -ethylcarbodiimide hydrochloride and pyridine.
5. The method as claimed in claim 1, wherein the derivatization reaction in step (1) is carried out by adding 10 μ L of an internal standard solution with a concentration of 500 μ g/L, 20 μ L of a 3-nitrophenylhydrazine hydrochloride solution with a concentration of 200mmol/L, and 20 μ L of an N- (3-dimethylaminopropyl) -N' -ethylcarbodiimide hydrochloride solution with a concentration of 120mmol/L, wherein the solution contains 6% pyridine, and adding 910 μ L of acetonitrile water with a volume fraction of 50% to 1mL per 40 μ L of the kiwi fruit wine sample.
6. The method of claim 1, wherein the 34 carbonyl compounds of step (2) comprise formic acid, acetic acid, benzoic acid, 2-methylpropionic acid, butyric acid, caproic acid, caprylic acid, capric acid, malic acid, DL-p-hydroxyphenyllactic acid, 2-hydroxy-4-methylpentanoic acid, 2-furoic acid, 2, 3-dihydroxypropionic acid, 2-hydroxy-3-methylbutyric acid, 3-hydroxypropionic acid, succinic acid, lactic acid, glycolic acid, vanillic acid, syringic acid, caffeic acid, tartaric acid, citric acid, 3, 4-dihydroxybenzoic acid, furfural, vanillin, benzaldehyde, 5-methylfuran aldehyde, hexanal, acetaldehyde, 2, 3-butanedione, 3-penten-2-one, 3-pentanone, 3-hydroxy-2-butanone.
7. The method of claim 1, wherein the mass spectrometry conditions of the UPLC-MS/MS detection of step (2) are: the ion source is in an ESI negative ion mode, the temperature of the ion source is 110-120 ℃, the temperature of the desolvation is 500-550 ℃, the voltage of a capillary tube is 2-3 KV, the collision voltage is 13-30 eV, the voltage of a taper hole is 21-37V, the air flow of the taper hole is 50L/h, and the air flow of the desolvation is 800L/h.
8. The method according to claim 7, wherein the cone-hole voltage V, the collision voltage eV, the quantified parent ions m/z, and the quantified daughter ions m/z are specified as: formic acid derivatives 21/13/180.0/137.1, acetic acid derivatives 25/19/194.0/137.1, benzoic acid derivatives 33/17/256.1/150.1, 2-methylpropionic acid derivatives 33/19/222.1/137.1, butyric acid derivatives 33/19/222.1/137.1, hexanoic acid derivatives 33/21/250.1/137.2, octanoic acid derivatives 35/23/278.2/137.1, decanoic acid derivatives 37/27/306.2/137.1,2, 3-dihydroxypropionic acid derivatives 27/19/240.0/136.9, glycolic acid derivatives 25/15/210.2/137.0, 3-hydroxypropionic acid derivatives 23/13/224.2/194.0, lactic acid derivative 27/15/224.0/151.8,3, 4-dihydroxybenzoic acid derivative 31/29/288.2/108.2, 2-hydroxy-3-methylbutyric acid derivative 31/17/252.2/151.9, tartaric acid derivative 29/21/419.6/208.2, 2-furoic acid derivative 25/17/246.0/149.8, vanillic acid derivative 33/19/302.1/177.9, syringic acid derivative 35/25/332.2/150.0, malic acid derivative 29/19/403.4/207.9, succinic acid derivative 31/17/387.2/234.2, caffeic acid derivative 31/23/314.2/176.0, 2-hydroxy-4-methylvaleric acid derivative 31/17/266.2/151.8, DL-p-hydroxy-phenyllactic acid derivative 31/17/300.0/151.8, 35/30/596.3/222.2 of citric acid derivative, 21/15/177.9/137.0 of acetaldehyde derivative, 29/21/286.1/148.0 of vanillin derivative, 25/17/230.0/137.0 of furfural derivative, 25/15/244.0/184.0 of 5-methylfuran aldehyde derivative, 33/17/240.0/137.0 of benzaldehyde derivative, 27/19/234.0/136.9 of hexanal derivative, 23/15/221.8/137.0 of 3-hydroxy-2-butanone derivative, 23/19/218.0/137.0 of 3-penten-2-one derivative, 23/15/220.0/151.0 of 3-pentanone derivative, 33/21/355.2/137.0 of 2, 33/21/355.2/137.0 of 3-butanedione derivative, 27/19/213.2/137.2 of propionic acid-d 6 derivative, 29/17/257.0 of acetophenone-d 3 derivative, and 33/294.0 of nonanal derivative.
9. The method of claim 1, wherein the chromatography conditions of the UPLC-MS/MS detection are: c18 column (100 mm. Times.2.1 mm,1.7 μm); the column temperature is 40 ℃; mobile phase A: water +5mmol/L ammonium acetate +0.1% formic acid; b: acetonitrile/water (95/5, v/v) +5mmol/L ammonium acetate +0.1% formic acid; the flow rate is 0.3mL/min; the sample volume is 10 mu L; gradient elution procedure is 0-1min, B18%, 1-11min, B45%, 11-15min, B65%, 15-17, B100%, 17-19.5min, B100%, 19.5-20min, B18%, 20-23min, B18%.
10. Use of the method according to any one of claims 1 to 9 in liquor testing.
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