CN112924580A - Method for determining desoxyquinocetone and 3-methyl quinoxaline-2-carboxylic acid in seawater - Google Patents
Method for determining desoxyquinocetone and 3-methyl quinoxaline-2-carboxylic acid in seawater Download PDFInfo
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- CN112924580A CN112924580A CN202110107492.4A CN202110107492A CN112924580A CN 112924580 A CN112924580 A CN 112924580A CN 202110107492 A CN202110107492 A CN 202110107492A CN 112924580 A CN112924580 A CN 112924580A
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- desoxyquinocetone
- carboxylic acid
- column
- methyl quinoxaline
- seawater
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- BJPNADFNSANIPF-UHFFFAOYSA-N 3-methylquinoxaline-2-carboxylic acid Chemical compound C1=CC=C2N=C(C(O)=O)C(C)=NC2=C1 BJPNADFNSANIPF-UHFFFAOYSA-N 0.000 title claims abstract description 88
- MWUVOSGDEVWDFA-VAWYXSNFSA-N (e)-1-(3-methylquinoxalin-2-yl)-3-phenylprop-2-en-1-one Chemical compound CC1=NC2=CC=CC=C2N=C1C(=O)\C=C\C1=CC=CC=C1 MWUVOSGDEVWDFA-VAWYXSNFSA-N 0.000 title claims abstract description 76
- 239000013535 sea water Substances 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 29
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 62
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 57
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 31
- 235000019253 formic acid Nutrition 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000001179 sorption measurement Methods 0.000 claims abstract description 25
- 238000001514 detection method Methods 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 150000002500 ions Chemical class 0.000 claims description 61
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 36
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000003480 eluent Substances 0.000 claims description 13
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 claims description 11
- 238000004811 liquid chromatography Methods 0.000 claims description 9
- PBCJIPOGFJYBJE-UHFFFAOYSA-N acetonitrile;hydrate Chemical group O.CC#N PBCJIPOGFJYBJE-UHFFFAOYSA-N 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000010828 elution Methods 0.000 claims description 5
- 238000001819 mass spectrum Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- 238000012546 transfer Methods 0.000 claims description 5
- 238000004949 mass spectrometry Methods 0.000 claims description 4
- 238000000861 blow drying Methods 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 238000003556 assay Methods 0.000 claims 2
- 230000035945 sensitivity Effects 0.000 abstract description 6
- 238000002386 leaching Methods 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- 239000003344 environmental pollutant Substances 0.000 abstract description 2
- 239000012535 impurity Substances 0.000 abstract description 2
- 231100000719 pollutant Toxicity 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 28
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 10
- 241001465754 Metazoa Species 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 8
- 238000011084 recovery Methods 0.000 description 8
- TURHTASYUMWZCC-UHFFFAOYSA-N Olaquindox [BAN:INN] Chemical compound C1=CC=C2N([O-])C(C)=C(C(=O)NCCO)[N+](=O)C2=C1 TURHTASYUMWZCC-UHFFFAOYSA-N 0.000 description 7
- 239000011550 stock solution Substances 0.000 description 7
- 244000144977 poultry Species 0.000 description 6
- IOKWXGMNRWVQHX-VAWYXSNFSA-N (e)-1-(3-methyl-4-oxido-1-oxoquinoxalin-1-ium-2-yl)-3-phenylprop-2-en-1-one Chemical compound O=[N+]1C2=CC=CC=C2N([O-])C(C)=C1C(=O)\C=C\C1=CC=CC=C1 IOKWXGMNRWVQHX-VAWYXSNFSA-N 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
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- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
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- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 2
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- 241000282412 Homo Species 0.000 description 1
- 241000282887 Suidae Species 0.000 description 1
- HZEIGZRZVJNUIX-UHFFFAOYSA-N acetic acid;ethyl formate Chemical compound CC(O)=O.CCOC=O HZEIGZRZVJNUIX-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
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- 244000052616 bacterial pathogen Species 0.000 description 1
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- 239000002184 metal Substances 0.000 description 1
- BPMVRAQIQQEBLN-OBPBNMOMSA-N methyl n-[(e)-(1-hydroxy-4-oxidoquinoxalin-4-ium-2-ylidene)methyl]iminocarbamate Chemical compound C1=CC=C2N(O)C(=C/N=NC(=O)OC)/C=[N+]([O-])C2=C1 BPMVRAQIQQEBLN-OBPBNMOMSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
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- 238000000746 purification Methods 0.000 description 1
- UPUZGXILYFKSGE-UHFFFAOYSA-N quinoxaline-2-carboxylic acid Chemical compound C1=CC=CC2=NC(C(=O)O)=CN=C21 UPUZGXILYFKSGE-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
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- 239000011782 vitamin Substances 0.000 description 1
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- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
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- 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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- G01N30/02—Column chromatography
- G01N30/26—Conditioning of the fluid carrier; Flow patterns
- G01N30/28—Control of physical parameters of the fluid carrier
- G01N30/30—Control of physical parameters of the fluid carrier of temperature
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Abstract
The invention provides a method for determining desoxyquinocetone and 3-methyl quinoxaline-2-carboxylic acid in seawater, belonging to the technical field of detection of pollutants in seawater. According to the invention, the MAX column is adopted to enrich and purify the desoxyquinocetone and the 3-methyl quinoxaline-2-carboxylic acid in the seawater, so that the determination of the low-concentration desoxyquinocetone and the 3-methyl quinoxaline-2-carboxylic acid in the seawater can be realized; according to the invention, the adsorption column is leached by water firstly, most of water-soluble impurities are removed, and then the ethyl acetate solution of formic acid is adopted to elute the adsorption column after water leaching, so that the content of other substances in the liquid to be detected can be reduced, the detection interference on the desoxyquinocetone and the 3-methyl quinoxaline-2-carboxylic acid is avoided, and the detection sensitivity is improved.
Description
Technical Field
The invention relates to the technical field of detection of pollutants in seawater, and particularly relates to a method for determining desoxyquinocetone and 3-methyl quinoxaline-2-carboxylic acid in seawater.
Background
Modern breeding industry tends to be scaled and intensified day by day, and the use of antibiotics, vitamins, hormones, metal trace elements and the like becomes an essential part for guaranteeing the development of the marine breeding industry. Unfortunately, however, the phenomenon of drug abuse in farming is ubiquitous, driven by the lack of scientific knowledge and economic interest. The direct consequence of veterinary drug abuse is that veterinary drug residues in animal food, which, after ingestion by humans, affect human health. The potential harm of veterinary drug residues in animal food to human beings is more and more attracting attention. Only a set of simple and efficient drug residue determination method is established, which is the basis for effectively controlling the occurrence of drug residues.
Quinocetone (Quinocetone) is a quinoxaline growth promoting regulator developed by Lanzhou animal husbandry and veterinary research institute of Chinese academy of agricultural sciences, and is a national new agricultural and veterinary drug officially approved in 8 months in 2003 by the Ministry of agriculture. The medicine has the characteristics of obvious antibacterial effect, safe use and rapid metabolism, and is suitable for preventing diseases and promoting growth of livestock, poultry and aquatic organisms, as well as young livestock and poultry. Because the feed conversion rate can be improved, the feed additive has an inhibiting effect on various intestinal pathogenic bacteria (particularly gram-negative bacteria), and can obviously reduce the diarrhea incidence of livestock and poultry. Compared with the quinoxaline medicines which are forbidden for the purpose of explanation such as carbadox, olaquindox and the like, the quinocetone has high drug effect, low toxicity and relatively safe use, and is used in the cultivation of poultry, livestock and aquatic animals.
Quinocetone belongs to novel quinoxaline medicaments, and has the dual effects of broad-spectrum antibiosis and growth promotion. Due to obvious toxic and side effects, the European union forbids the use of olaquindox in 1998, and China forbids the use of olaquindox in poultry and aquatic animals and can only be used for the antibacterial treatment of bred pigs. The olaquindox is metabolized rapidly in animals, and 3-methyl quinoxaline-2-carboxylic acid (MQCA) which is a metabolite thereof is slowly eliminated and has long residual time. Currently, MQCA is generally used as a target object for olaquindox residue analysis and monitoring in various countries. MQCA is used as a marking residue of olaquindox in European Union, America and China, and aquatic products are regulated not to be detected.
Novel quinoxaline medicaments such as quinocetone and the like retain the antibacterial and growth promoting effects of the medicaments, reduce the toxicity and are applied more in livestock and poultry and aquaculture at present. Many studies have shown that it is metabolized in the aquatic animal body to produce MQCA and deoxygenation metabolites. Currently, regarding the relevant standards for detecting the MQCA, the high performance liquid chromatography for determining the residual amounts of 3-methyl quinoxaline-2-carboxylic acid and quinoxaline-2-carboxylic acid in animal-derived food by the Ministry of agriculture 781 bulletin-3-2006 and the high performance liquid chromatography for determining the residual amount of olaquindox metabolite in aquatic products by the Ministry of agriculture 1077 bulletin-5-2008 are all used for determining the residual amount of the MQCA in a sample by the high performance liquid chromatography, but the detection sensitivity is low.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for determining desoxyquinocetone and 3-methyl quinoxaline-2-carboxylic acid in seawater, which can accurately determine the content of desoxyquinocetone and 3-methyl quinoxaline-2-carboxylic acid in seawater and has high sensitivity.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a method for determining desoxyquinocetone and 3-methyl quinoxaline-2-carboxylic acid in seawater, which comprises the following steps:
passing the seawater to be detected through an MAX column to obtain an adsorption column; after the adsorption column is washed by water, eluting the obtained washed adsorption column by adopting ethyl acetate solution of formic acid, and taking the obtained eluent as a liquid to be detected; the volume fraction of formic acid in the ethyl acetate solution of formic acid is 2%;
detecting the liquid to be detected by adopting a liquid chromatography-mass spectrometry method to obtain peak areas of the desoxyquinocetone and the 3-methyl quinoxaline-2-carboxylic acid in the water body to be detected;
obtaining the content of the desoxyquinocetone and the 3-methyl quinoxaline-2-carboxylic acid in the water body to be detected based on a desoxyquinocetone concentration-peak area standard curve and a 3-methyl quinoxaline-2-carboxylic acid concentration-peak area standard curve;
the parameters of the liquid chromatography-mass spectrometry comprise liquid chromatography parameters and mass spectrometry parameters;
the liquid chromatography parameters include:
a chromatographic column: c18 column, 2.1mm × 100mm, particle size 1.7 μm;
temperature of the column: 40 ℃;
mobile phase A: acetonitrile;
mobile phase B: 0.5% by volume aqueous formic acid solution;
flow rate: 0.25 mL/min;
sample introduction amount: 10 mu L of the solution;
the gradient elution procedure was:
0.00min：5％A+95％B；
0.25min：5％A+95％B；
7.75min：95％A+5％B；
8.50min：95％A+5％B；
8.51min：5％A+95％B；
10.00min：5％A+95％B；
the mass spectrum parameters include:
an ion source: an electrospray ion source;
the scanning mode is as follows: scanning positive ions;
ion source temperature: 110 ℃;
ion transfer tube temperature: 350 ℃;
taper hole blowback air flow rate: 50L/h;
auxiliary air flow rate: 3L/min;
spraying voltage: 2500V;
the measured parent ions, daughter ions and collision energy include:
3-methyl quinoxaline-2-carboxylic acid: parent ion m/z: 189; daughter ion m/z: 145, 143; collision energy 14ev, 17 ev;
desoxyquinocetone: parent ion m/z: 275; daughter ion m/z: 143, 247; the collision energy was 40eV, 33 eV.
Preferably, the flow speed of the seawater to be detected flowing through the MAX column is 10-20 drops/min.
Preferably, the ratio of the volume of the ethyl acetate solution of formic acid to the volume of the MAX column is 1: 1-1: 2.
preferably, before the eluent is detected, nitrogen blow-drying and constant volume are sequentially carried out on the eluent; the temperature for blowing the nitrogen is 45 ℃.
Preferably, the constant volume reagent is acetonitrile-water solution of formic acid with the volume concentration of 0.1%; the volume ratio of acetonitrile to water in the acetonitrile-water solution is 70: 30.
the invention provides a method for determining desoxyquinocetone and 3-methyl quinoxaline-2-carboxylic acid in seawater, which comprises the following steps: passing the seawater to be detected through an MAX column to obtain an adsorption column; leaching the adsorption column by using water; eluting the obtained adsorption column with ethyl acetate solution of formic acid to obtain eluent as to-be-detected solution; the volume fraction of formic acid in the ethyl acetate solution of formic acid is 2%; detecting the liquid to be detected by adopting a liquid chromatography-mass spectrometry method to obtain peak areas of the desoxyquinocetone and the 3-methyl quinoxaline-2-carboxylic acid in the water body to be detected; obtaining the content of the desoxyquinocetone and the 3-methyl quinoxaline-2-carboxylic acid in the water body to be detected based on a desoxyquinocetone concentration-peak area standard curve and a 3-methyl quinoxaline-2-carboxylic acid concentration-standard curve; the parameters of the liquid chromatography-mass spectrometry comprise liquid chromatography parameters and mass spectrometry parameters; the liquid chromatography parameters include: a chromatographic column: c18 column, 2.1mm × 100mm, particle size 1.7 μm; temperature of the column: 40 ℃; mobile phase A: acetonitrile; mobile phase B: 0.5% by volume aqueous formic acid solution; flow rate: 0.25 mL/min; sample introduction amount: 10 mu L of the solution; the gradient elution procedure was: 0.00 min: 5% A + 95% B; 0.25 min: 5% A + 95% B; 7.75 min: 95% A + 5% B; 8.50 min: 95% A + 5% B; 8.51 min: 5% A + 95% B; 10.00 min: 5% A + 95% B; the mass spectrum parameters include: an ion source: an electrospray ion source; the scanning mode is as follows: scanning positive ions; ion source temperature: 110 ℃; ion transfer tube temperature: 350 ℃; taper hole blowback air flow rate: 50L/h; auxiliary air flow rate: 3L/min; spraying voltage: 2500V; the measured parent ions, daughter ions and collision energy include: 3-methyl quinoxaline-2-carboxylic acid: parent ion m/z: 189, daughter ion m/z: 145, 143, collision energy 14ev, 17 ev; desoxyquinocetone: parent ion m/z: 275, daughter ion m/z: 143, 247, collision energy 40ev, 33 ev.
According to the invention, the MAX column is adopted to enrich and purify the desoxyquinocetone and the 3-methyl quinoxaline-2-carboxylic acid in the seawater, so that the determination of the low-concentration desoxyquinocetone and the 3-methyl quinoxaline-2-carboxylic acid in the seawater can be realized; according to the invention, the adsorption column is leached by water firstly, most of water-soluble impurities are removed, and then the ethyl acetate solution of formic acid is adopted to elute the adsorption column after water leaching, so that the content of other substances in the liquid to be detected can be reduced, the detection interference on the desoxyquinocetone and the 3-methyl quinoxaline-2-carboxylic acid is avoided, and the detection sensitivity is improved. The data of the examples show that: the detection limit of the determination method provided by the invention on the desoxyquinocetone and the 3-methyl quinoxaline-2-carboxylic acid is 5 ng/L; the limit of quantification of the desoxyquinocetone and the 3-methyl quinoxaline-2-carboxylic acid is 10 ng/L.
Drawings
FIG. 1 is a selected ion flow diagram of a standard mixed solution in which the concentrations of 3-methyl quinoxaline-2-carboxylic acid and desoxyquinocetone are both 10.0 ng/mL;
FIG. 2 is a blank seawater selective ion flow diagram;
FIG. 3 is a selected ion flow diagram spectrogram of blank seawater after respectively adding 3-methyl quinoxaline-2-carboxylic acid and desoxyquinocetone with the concentration of 200.0 ng/L.
Detailed Description
The invention provides a method for determining desoxyquinocetone and 3-methyl quinoxaline-2-carboxylic acid in seawater, which comprises the following steps:
passing the seawater to be detected through an MAX column to obtain an adsorption column; leaching the adsorption column by using water, eluting the obtained leached adsorption column by using ethyl acetate solution of formic acid, and taking the obtained eluent as a liquid to be detected; the volume fraction of formic acid in the ethyl acetate solution of formic acid is 2%;
detecting the liquid to be detected by adopting a liquid chromatography-mass spectrometry method to obtain peak areas of the desoxyquinocetone and the 3-methyl quinoxaline-2-carboxylic acid in the water body to be detected;
and obtaining the content of the desoxyquinocetone and the 3-methyl quinoxaline-2-carboxylic acid in the water body to be detected based on the desoxyquinocetone concentration-peak area standard curve and the 3-methyl quinoxaline-2-carboxylic acid concentration-standard curve.
The method comprises the steps of enabling seawater to be detected to pass through an MAX column to obtain an adsorption column; and eluting the adsorption column by using water, and taking the obtained eluent as a liquid to be detected. In the invention, the flow speed of the seawater to be detected flowing through the MAX column is preferably 10-20 drops/min. In the present invention, the column volume of the MAX column is preferably 3mL or 6 mL. The desoxyquinocetone and the 3-methyl quinoxaline-2-carboxylic acid in the seawater to be detected are enriched on the MAX column through adsorption.
After the adsorption column is obtained, the adsorption column is leached by water, and the obtained eluent is used as the liquid to be detected. In the present invention, the ratio of the volume of water to the volume of the MAX column is preferably 1: 2. in the invention, water is adopted to drip wash the adsorption column, so that water-soluble substances on the adsorption column can be eluted, the detection interference on the desoxyquinocetone and the 3-methyl quinoxaline-2-carboxylic acid is avoided, and the sensitivity is improved.
After leaching is finished, the obtained centrifuged adsorption column is eluted by ethyl acetate solution of formic acid, and the obtained eluent is used as a liquid to be detected. In the invention, the volume fraction of formic acid in the ethyl acetate solution of formic acid is 2%; the ratio of the volume of the ethyl acetate solution of formic acid to the volume of the MAX column is preferably 1: 1-1: 2. in the invention, before the eluent is detected, nitrogen blow-drying and constant volume are preferably carried out in sequence; the temperature for drying by nitrogen is preferably 45 ℃; the constant volume reagent is preferably an acetonitrile-water solution of formic acid with the volume concentration of 0.1%; the volume ratio of acetonitrile to water in the acetonitrile-water solution is preferably 70: 30.
in the invention, the ethyl acetate solution of formic acid with the volume fraction of 2% is adopted to elute the eluted adsorption column, so that the desoxyquinocetone and the 3-methyl quinoxaline-2-carboxylic acid can be eluted; by controlling the ratio of ethyl acetate solution of formic acid to the MAX column volume to 1: 1-1: 2, not only can the desoxyquinocetone and the 3-methyl quinoxaline-2-carboxylic acid be completely eluted, but also excessive interference substances can be prevented from being eluted, and the detection sensitivity is improved.
After the liquid to be detected is obtained, the liquid to be detected is detected by adopting a liquid chromatography-mass spectrometry method, so that the peak areas of the desoxyquinocetone and the 3-methyl quinoxaline-2-carboxylic acid in the water body to be detected are obtained.
In the invention, the parameters of the liquid chromatography-mass spectrometry comprise liquid chromatography parameters and mass spectrometry parameters;
the liquid chromatography parameters include:
a chromatographic column: c18 column, 2.1mm × 100mm, particle size 1.7 μm;
temperature of the column: 40 ℃;
mobile phase A: acetonitrile;
mobile phase B: 0.5% by volume aqueous formic acid solution;
flow rate: 0.25 mL/min;
sample introduction amount: 10 mu L of the solution;
the gradient elution procedure was:
0.00min：5％A+95％B；
0.25min：5％A+95％B；
7.75min：95％A+5％B；
8.50min：95％A+5％B；
8.51min：5％A+95％B；
10.00min：5％A+95％B；
the mass spectrum parameters include:
an ion source: an electrospray ion source;
the scanning mode is as follows: scanning positive ions;
ion source temperature: 110 ℃;
ion transfer tube temperature: 350 ℃;
taper hole blowback air flow rate: 50L/h;
auxiliary air flow rate: 3L/min;
spraying voltage: 2500V;
the measured parent ions, daughter ions and collision energy include:
3-methyl quinoxaline-2-carboxylic acid: parent ion m/z: 189, daughter ion m/z: 145, 143, collision energy 14ev, 17 ev;
desoxyquinocetone: parent ion m/z: 275, daughter ion m/z: 143, 247, collision energy 40ev, 33 ev.
After the peak areas of the desoxyquinocetone and the 3-methyl quinoxaline-2-carboxylic acid in the water body to be detected are obtained, the content of the desoxyquinocetone and the 3-methyl quinoxaline-2-carboxylic acid in the water body to be detected is obtained based on a desoxyquinocetone concentration-peak area standard curve and a 3-methyl quinoxaline-2-carboxylic acid concentration-standard curve.
The method for acquiring the standard curve of the concentration of the desoxyquinocetone-peak area and the standard curve of the concentration of the 3-methyl quinoxaline-2-carboxylic acid is not particularly limited, and can be realized by adopting a standard curve acquisition mode well known by the technical personnel in the field.
The following examples are provided to describe the method for measuring desoxyquinocetone and 3-methyl quinoxaline-2-carboxylic acid in seawater according to the present invention in detail, but they should not be construed as limiting the scope of the present invention.
The parameters of the LC-MS used in the following examples include:
the liquid chromatography parameters include:
a chromatographic column: c18 column, 2.1mm × 100mm, particle size 1.7 μm;
temperature of the column: 40 ℃;
mobile phase A: acetonitrile;
mobile phase B: 0.5% by volume aqueous formic acid solution;
flow rate: 0.25 mL/min;
sample introduction amount: 10 mu L of the solution;
the gradient elution procedure was:
0.00min：5％A+95％B；
0.25min：5％A+95％B；
7.75min：95％A+5％B；
8.50min：95％A+5％B；
8.51min：5％A+95％B；
10.00min：5％A+95％B；
the mass spectrum parameters include:
an ion source: an electrospray ion source;
the scanning mode is as follows: scanning positive ions;
ion source temperature: 110 ℃;
ion transfer tube temperature: 350 ℃;
taper hole blowback air flow rate: 50L/h;
auxiliary air flow rate: 3L/min;
spraying voltage: 2500V;
the measured parent ions, daughter ions and collision energy include:
3-methyl quinoxaline-2-carboxylic acid: parent ion m/z: 189; daughter ion m/z: 145, 143; collision energy 14ev, 17 ev;
desoxyquinocetone: parent ion m/z: 275; daughter ion m/z: 143, 247; the collision energy was 40eV, 33 eV.
Example 1
Acquisition of a standard curve:
dissolving the desoxyquinocetone in acetonitrile to prepare a desoxyquinocetone stock solution with the concentration of 100 mug/mL;
dissolving 3-methyl quinoxaline-2-carboxylic acid in acetonitrile to prepare a 3-methyl quinoxaline-2-carboxylic acid stock solution with the concentration of 100 mu g/mL;
putting 1.0mL of the desoxyquinocetone stock solution and 1.0mL of the 3-methyl quinoxaline-2-carboxylic acid stock solution into a 100mL volumetric flask, and performing constant volume on acetonitrile to obtain 1.0 mu g/mL of mixed standard stock solution of the desoxyquinocetone and the 3-methyl quinoxaline-2-carboxylic acid;
respectively diluting the mixed standard stock solutions of the desoxyquinocetone and the 3-methyl quinoxaline-2-carboxylic acid with the concentrations of 1.0 mu g/mL and 10, 50, 100 and 200 mu L by 100, 50, 20, 10 and 5 times to obtain serial standard mixed solutions of the desoxyquinocetone and the 3-methyl quinoxaline-2-carboxylic acid with the concentrations of 10ng/mL, 20ng/mL, 50ng/mL, 100ng/mL and 200 ng/mL;
detecting the obtained series of standard mixed liquids by adopting the liquid chromatography-mass spectrometry to obtain peak areas of the desoxyquinocetone and the 3-methyl quinoxaline-2-carboxylic acid;
and establishing a standard curve of the concentration-peak area of the desoxyquinocetone and a standard curve of the concentration-peak area of the 3-methyl quinoxaline-2-carboxylic acid based on the concentrations and corresponding peak areas of the desoxyquinocetone and the 3-methyl quinoxaline-2-carboxylic acid.
Specifically, the standard curve of the concentration-peak area of the desoxyquinocetone is as follows: 3058 x +2057.98, coefficient of correlation R20.995; wherein x represents the concentration of the desoxyquinocetone, and y represents the peak area of the desoxyquinocetone.
The standard curve of the concentration-peak area of the 3-methyl quinoxaline-2-carboxylic acid is as follows: 2109 x +1403.52, correlation coefficient R20.996; wherein x represents the concentration of 3-methyl quinoxaline-2-carboxylic acid, and y represents the peak area of 3-methyl quinoxaline-2-carboxylic acid.
Example 2
Detection limit and quantification limit
Determining the detection limit of the upper machine concentration according to the 3-time signal-to-noise ratio of the desoxyquinocetone and the 3-methyl quinoxaline-2-carboxylic acid, and converting the detection limit into the detection limit concentration of the desoxyquinocetone and the 3-methyl quinoxaline-2-carboxylic acid in the seawater. The results were: the detection limit of the desoxyquinocetone is 5ng/L, and the detection limit of the 3-methyl quinoxaline-2-carboxylic acid is 5 ng/L.
Determining the quantitative limit of the upper machine concentration according to the 10-time signal-to-noise ratio of the desoxyquinocetone and the 3-methyl quinoxaline-2-carboxylic acid, and converting into the quantitative limit concentration of the desoxyquinocetone and the 3-methyl quinoxaline-2-carboxylic acid in the seawater. The results were: the quantitative limit of the desoxyquinocetone is 10 ng/L; the limit of quantification of 3-methyl quinoxaline-2-carboxylic acid is 10 ng/L.
Example 3
Recovery and precision of the process
The standard solution was added to the blank seawater sample to prepare 3 sets of standard addition samples of different concentrations, each concentration sample was measured in parallel for 6, and the method recovery and precision were calculated, with the results shown in tables 1 and 2.
TABLE 13 recovery and precision test results for methyl quinoxaline-2-carboxylic acid
As can be seen from table 1: when the addition amount of the 3-methyl quinoxaline-2-carboxylic acid is 10.0-200.0 ng/L, the recovery rate of the 3-methyl quinoxaline-2-carboxylic acid is 72.3-91.8%; the relative standard deviation in each batch is less than 8%, and the relative deviation between batches is less than 6%.
TABLE 2 Dedioxyquinocetone recovery and precision test results
As can be seen from table 2: the recovery rate of the desoxyquinocetone is 70.2-90.1%; the relative standard deviation in each batch is less than 10%, and the relative deviation between batches is less than 8%.
Fig. 1 is a selected ion flow diagram of a standard mixed solution in which the concentrations of 3-methyl quinoxaline-2-carboxylic acid and desoxyquinocetone are both 10.0ng/mL, wherein: a is a spectrogram of 3-methyl quinoxaline-2-carboxylic acid 189 more than 143, b is a spectrogram of 3-methyl quinoxaline-2-carboxylic acid 189 more than 145, c is a spectrogram of desoxyquinocetone 275 more than 143, and d is a spectrogram of desoxyquinocetone 275 more than 247;
FIG. 2 is a blank seawater selective ion flow diagram, wherein, a is a spectrogram of 3-methyl quinoxaline-2-carboxylic acid 189 > 143, b is a spectrogram of 3-methyl quinoxaline-2-carboxylic acid 189 > 145, c is a spectrogram of desoxyquinocetone 275 > 143, and d is a spectrogram of desoxyquinocetone 275 > 247;
FIG. 3 is a selected ion flow chart of blank seawater after adding 3-methyl quinoxaline-2-carboxylic acid and desoxyquinocetone with the concentration of 200.0ng/L respectively, wherein, a is a chart of 3-methyl quinoxaline-2-carboxylic acid 189 being more than 143, b is a chart of 3-methyl quinoxaline-2-carboxylic acid 189 being more than 145, c is a chart of desoxyquinocetone 275 being more than 143, and d is a chart of desoxyquinocetone 275 being more than 247;
as can be seen from figures 1, 2 and 3, the 3-methyl quinoxaline-2-carboxylic acid and the desoxyquinocetone have sharp peak shapes and high signal-to-noise ratio, and can meet the requirement of accurate quantification.
Example 4
Adopting an MAX solid phase extraction column (a mixed anion exchange column with the column volume of 6mL), an MCX solid phase extraction column (a mixed cation exchange column with the column volume of 6mL) and an HLB solid phase extraction column, diluting a standard stock solution with seawater to obtain desoxyquinocetone with the concentration of 100 mug/L and an MQCA standard solution, and eluting and collecting the desoxyquinocetone and the MQCA standard solution by using the MAX solid phase extraction column (the mixed anion exchange column with the column volume of 6mL), the MCX solid phase extraction column and the HLB solid phase extraction column with 3mL of aqueous solution and 10mL of ethyl formate acetate with the volume concentration of 2% after activation; blowing to dry with nitrogen at 40 ℃, adding 1mL acetonitrile-water solution (wherein the volume ratio of acetonitrile to water is 70: 30) containing formic acid with the volume concentration of 0.1% into the mixture, fixing the volume, and measuring the volume on a machine.
The recovery rates of the MCX solid phase extraction column and the HLB solid phase extraction column to the two target compounds are lower than 40 percent.
The MAX solid phase extraction column meets the requirements on the purification effect and recovery rate of all components.
In the standard, ethyl formate and ethyl acetate with the volume concentration of 2% are used as eluent of the MAX solid-phase extraction column, and the volume of the eluent is studied, so that 6mL of ethyl formate and ethyl acetate with the volume concentration of 2% can completely elute the target compound.
Example 5
And (3) taking 10 actual water samples of three aquaculture farms in Shandong to determine results. After being treated according to the method, the 3-methyl quinoxaline-2-carboxylic acid is detected on the machine, and the calculated results show that three water samples respectively have 13.1ng/L, 15.8ng/L and 20.2 ng/L.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (5)
1. A method for measuring desoxyquinocetone and 3-methyl quinoxaline-2-carboxylic acid in seawater is characterized by comprising the following steps:
passing the seawater to be detected through an MAX column to obtain an adsorption column; after the adsorption column is washed by water, eluting the obtained washed adsorption column by adopting ethyl acetate solution of formic acid, and taking the obtained eluent as a liquid to be detected; the volume fraction of formic acid in the ethyl acetate solution of formic acid is 2%;
detecting the liquid to be detected by adopting a liquid chromatography-mass spectrometry method to obtain peak areas of the desoxyquinocetone and the 3-methyl quinoxaline-2-carboxylic acid in the water body to be detected;
obtaining the content of the desoxyquinocetone and the 3-methyl quinoxaline-2-carboxylic acid in the water body to be detected based on a desoxyquinocetone concentration-peak area standard curve and a 3-methyl quinoxaline-2-carboxylic acid concentration-peak area standard curve;
the parameters of the liquid chromatography-mass spectrometry comprise liquid chromatography parameters and mass spectrometry parameters;
the liquid chromatography parameters include:
a chromatographic column: c18 column, 2.1mm × 100mm, particle size 1.7 μm;
temperature of the column: 40 ℃;
mobile phase A: acetonitrile;
mobile phase B: 0.5% by volume aqueous formic acid solution;
flow rate: 0.25 mL/min;
sample introduction amount: 10 mu L of the solution;
the gradient elution procedure was:
0.00min：5％A+95％B；
0.25min：5％A+95％B；
7.75min：95％A+5％B；
8.50min：95％A+5％B；
8.51min：5％A+95％B；
10.00min：5％A+95％B；
the mass spectrum parameters include:
an ion source: an electrospray ion source;
the scanning mode is as follows: scanning positive ions;
ion source temperature: 110 ℃;
ion transfer tube temperature: 350 ℃;
taper hole blowback air flow rate: 50L/h;
auxiliary air flow rate: 3L/min;
spraying voltage: 2500V;
the measured parent ions, daughter ions and collision energy include:
3-methyl quinoxaline-2-carboxylic acid: parent ion m/z: 189; daughter ion m/z: 145, 143; collision energy 14ev, 17 ev;
desoxyquinocetone: parent ion m/z: 275; daughter ion m/z: 143, 247; the collision energy was 40eV, 33 eV.
2. The method according to claim 1, wherein the flow rate of the seawater to be measured passing through the MAX column is 10-20 drops/min.
3. The assay of claim 1, wherein the ratio of the volume of the ethyl acetate solution of formic acid to the volume of the MAX column is 1: 1-1: 2.
4. the assay method according to claim 1, wherein the eluent is sequentially subjected to nitrogen blow-drying and constant volume before detection; the temperature for blowing the nitrogen is 45 ℃.
5. The method according to claim 4, wherein the constant volume reagent is acetonitrile-water solution of formic acid with volume concentration of 0.1%; the volume ratio of acetonitrile to water in the acetonitrile-water solution is 70: 30.
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