CN106442839A - Measuring method for N4-desoxymequindox, 3-methyl-2-acetyl-quinoxaline and MQCA in seawater - Google Patents
Measuring method for N4-desoxymequindox, 3-methyl-2-acetyl-quinoxaline and MQCA in seawater Download PDFInfo
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- CN106442839A CN106442839A CN201610988652.XA CN201610988652A CN106442839A CN 106442839 A CN106442839 A CN 106442839A CN 201610988652 A CN201610988652 A CN 201610988652A CN 106442839 A CN106442839 A CN 106442839A
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- Prior art keywords
- mequindox
- mqca
- measuring method
- pure
- formic acid
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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 18
- 239000013535 sea water Substances 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title claims abstract description 10
- XXKIXPWTFVBBJF-UHFFFAOYSA-N 1-(3-methylquinoxalin-2-yl)ethanone Chemical compound C1=CC=C2N=C(C)C(C(=O)C)=NC2=C1 XXKIXPWTFVBBJF-UHFFFAOYSA-N 0.000 title abstract 3
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 4
- CUJMCPPBTUATEJ-UHFFFAOYSA-N 1-(3-methyl-4-oxido-1-oxoquinoxalin-1-ium-2-yl)ethanone Chemical compound C1=CC=C2[N+](=O)C(C(=O)C)=C(C)N([O-])C2=C1 CUJMCPPBTUATEJ-UHFFFAOYSA-N 0.000 claims description 33
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 241000790917 Dioxys <bee> Species 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 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 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 8
- 235000019253 formic acid Nutrition 0.000 claims description 8
- PBCSDDOCZANXMI-UHFFFAOYSA-N 3-methylquinoline-2-carboxylic acid Chemical compound C1=CC=C2N=C(C(O)=O)C(C)=CC2=C1 PBCSDDOCZANXMI-UHFFFAOYSA-N 0.000 claims description 6
- 238000002414 normal-phase solid-phase extraction Methods 0.000 claims description 6
- 238000003556 assay Methods 0.000 claims description 5
- 238000004949 mass spectrometry Methods 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000003643 water by type Substances 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- BSYNRYMUTXBXSQ-UHFFFAOYSA-N Aspirin Chemical compound CC(=O)OC1=CC=CC=C1C(O)=O BSYNRYMUTXBXSQ-UHFFFAOYSA-N 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- -1 USA) Substances 0.000 claims description 2
- 238000010811 Ultra-Performance Liquid Chromatography-Tandem Mass Spectrometry Methods 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000004807 desolvation Methods 0.000 claims description 2
- HQVFCQRVQFYGRJ-UHFFFAOYSA-N formic acid;hydrate Chemical compound O.OC=O HQVFCQRVQFYGRJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- 238000005457 optimization Methods 0.000 claims description 2
- 230000002572 peristaltic effect Effects 0.000 claims description 2
- 239000012071 phase Substances 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 239000012086 standard solution Substances 0.000 claims description 2
- 239000011550 stock solution Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000004704 ultra performance liquid chromatography Methods 0.000 claims description 2
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 2
- 239000012498 ultrapure water Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003640 drug residue Substances 0.000 abstract description 7
- 238000009395 breeding Methods 0.000 abstract description 4
- 230000001488 breeding effect Effects 0.000 abstract description 4
- 230000003115 biocidal effect Effects 0.000 abstract description 3
- 230000006378 damage Effects 0.000 abstract description 2
- 238000011161 development Methods 0.000 abstract description 2
- 238000001819 mass spectrum Methods 0.000 abstract 1
- 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 8
- 229950010210 olaquindox Drugs 0.000 description 7
- 241001465754 Metazoa Species 0.000 description 6
- 239000003550 marker Substances 0.000 description 4
- 239000002207 metabolite Substances 0.000 description 4
- 231100000419 toxicity Toxicity 0.000 description 4
- 230000001988 toxicity Effects 0.000 description 4
- 239000003814 drug Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 241000287828 Gallus gallus Species 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000009364 mariculture Methods 0.000 description 2
- 150000003248 quinolines Chemical class 0.000 description 2
- 239000000273 veterinary drug Substances 0.000 description 2
- 208000031404 Chromosome Aberrations Diseases 0.000 description 1
- 230000005778 DNA damage Effects 0.000 description 1
- 231100000277 DNA damage Toxicity 0.000 description 1
- 206010013654 Drug abuse Diseases 0.000 description 1
- 206010064571 Gene mutation Diseases 0.000 description 1
- 206010019851 Hepatotoxicity Diseases 0.000 description 1
- 231100000703 Maximum Residue Limit Toxicity 0.000 description 1
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 210000004100 adrenal gland Anatomy 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 229940111121 antirheumatic drug quinolines Drugs 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 231100000005 chromosome aberration Toxicity 0.000 description 1
- 231100000313 clinical toxicology Toxicity 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000006806 disease prevention Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000029142 excretion Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000009313 farming Methods 0.000 description 1
- 230000007686 hepatotoxicity Effects 0.000 description 1
- 231100000304 hepatotoxicity Toxicity 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000003834 intracellular effect Effects 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 210000001853 liver microsome Anatomy 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 210000003205 muscle Anatomy 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 244000144977 poultry Species 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 208000011117 substance-related disease Diseases 0.000 description 1
- 238000011287 therapeutic dose Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000820 toxicity test Toxicity 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 229910052722 tritium Inorganic materials 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
- G01N2030/8809—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample
- G01N2030/884—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample organic compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
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- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention discloses a measuring method for N4-desoxymequindox, 3-methyl-2-acetyl-quinoxaline and MQCA (3-methylquinoxaline-2-carboxylic acid) in seawater. The organism drug residue index is indirectly reflected with the measuring method. The measuring method includes the steps of instrument and reagent selecting and mixing, sample extracting and purifying and specific chromatographic condition and mass spectrum selecting. Compared with the prior art, the organism drug residue index is indirectly reflected with the measuring method for the N4-desoxymequindox content, the 3-methyl-2-acetyl-quinoxaline content and the MQCA (3-methylquinoxaline-2-carboxylic acid) content in seawater, the measuring method has the advantages of being high in speed, low in cost and free of damage to bred marine products, rapid and accurate data supporting is provided for the antibiotic abuse condition in current breeding industries, and healthy development of the breeding industries is facilitated.
Description
Technical field
The present invention relates to taking off an oxygen Mequindox in mariculture technology field, specifically a kind of sea water, taking off dioxy acetyl
First quinoline and MQCA（3- methylquinoline -2- carboxylic acid）Assay method.
Background technology
Modern farming increasingly tends to scale, intensive, using antibiotic, vitamin, hormone, metal trace element
Deng more becoming guarantee mariculture industry and develop a requisite ring.Unfortunately, due to shortage and the warp of scientific knowledge
Ji the ordering about of interests, the phenomenon generally existing of Drug abuse in cultivation.In China, situation is particularly acute.Abuse the direct of veterinary drug
Consequence is the residual for causing veterinary drug in animal food, after intake human body, affects the health of the mankind.Beast in animal food
Medicine remains the attention that the potential hazard to people more and more causes people.Only set up a set of simple and effective drug residue to determine
Method, is the basis for efficiently controlling drug residue generation.
Olaquindox（Olaquindox）Also known as olaquindox, Olaquindox, it is early 1970s by West Germany's Baeyer pharmaceutical factory
The feed additive of synthesis is developed, because which has broad-spectrum antimicrobial effect and growth promoting function, is widely used in livestock and poultry cultivation, antibacterial
Treatment and the control and prevention of disease of aquatic animal.But a large amount of biological toxicity tests show：Excessive olaquindox can be residual in animal body
Stay, with obvious cumulative toxicity, the toxic and side effects such as the effect of carcinogenic, aberration inducing and DNA damage.In view of human health is caused
Harm, olaquindox is classified as disabling medicine by EU Committee EC2788/98 resolution, also specifies quinoline in domestic NY5070-2002 criterion
Ethanol disables fisheries drug.But olaquindox itself is unstable, in animal body can short time intracellular metabolite become ten multi-products, wherein 3-
Methylquinoline -2- carboxylic acid（MQCA）It is one of major metabolite, which is relatively stable in vivo, is Codex Alimentary Commission
One of residual marker of identification, therefore generally using olaquindox metabolite MQCA as residual marker.China's agricultural in 2003
Portion defines the maximum residue limit of MQCA in muscle and liver organization and is respectively 4 μ g/kg and 50 μ g/kg.
Mequindox（Mequindox, MEQ）Also known as LIJUNJING, belong to quinolines, be the tool that China voluntarily develops
There is a class novel chiral synthon of independent intellectual property right.Due to broad spectrum antibiotic activity, being widely used on China's veterinary clinic.But
It is that production practices show, Mequindox toxicity is bigger than normal, dosage is higher than that 3～5 times of therapeutic dose or long-time can be drawn when continuously using
Play poisoning even dead.Clinical toxicology research also points out which cause gene mutation, chromosomal aberration, with hepatotoxicity,
Adrenal gland's toxicity and two generation breeding toxicity.
To Mequindox, metabolite in hepatomicrosome has carried out relative quantification to the Liu Zhaoying of Hua Zhong Agriculture University, it is believed that N
4- take off an oxygen Mequindox be main metabolites of the Mequindox in pig, chicken and rat liver microsomes it
One.The Yin Fujun of Hua Zhong Agriculture University then carried out tritium mark Mequindox in rat, chicken and pig body absorption distribution, excretion and
Metabolism is studied, and final determination takes off dioxy Mequindox（3- methyl -2- acetyl group-quinoxaline）For Mequindox at these three
Residual marker in animal body.
Mesh first three residual marker is both needed to the methods different by three kinds and is determined respectively, there is no by a sample
Carry out the precedent that three kinds of residual markers are once determined.The elder generation of organism drug residue is more no embodied by breeding seawater indirectly
Example.
Content of the invention
The purpose of the present invention be open a kind of by determine in sea water take off an oxygen Mequindox, take off dioxy Mequindox and
MQCA（3- methylquinoline -2- carboxylic acid）So as to embody indirectly the assay method of organism drug residue index, including instrument with
The selection of reagent and allotment, sample extraction and purification, specific chromatographic condition and Mass Spectrometry Conditions.
Compared with prior art, the present invention can by determine sea water in take off an oxygen Mequindox, take off dioxy Mequindox and
MQCA（3- methylquinoline -2- carboxylic acid）Content so as to embody indirectly organism drug residue index, with speed is fast, cost
Low feature to cultivating marine product fanout free region, and then the situation of current cultivation industry abuse of antibiotics is provided fast and accurately
Data are supported, may advantageously facilitate the sound development of cultivation industry.
Specific embodiment：
The assay method of an oxygen Mequindox, de- dioxy Mequindox and MQCA is taken off in a kind of sea water, it is characterised in that：
A) instrument and reagent：
Ultra Performance Liquid Chromatography-tandem mass spectrometer (Quattro Premier XE, Waters, USA), ultra-pure water instrument
(Milli-Q Gradient, Millipore, France), high speed centrifuge (TGL-10C, Town in Shanghai booth scientific instrument
Factory), ultrasonic cleaner (KQ-600E, Kunshan Ultrasonic Instruments Co., Ltd.), Nitrogen evaporator (N-EVAPTM112,
Organomation Associates, USA), Full-automatic solid phase extraction instrument (ASPEC XL4+, GILSON, France)；Methanol
(chromatographically pure), acetonitrile (chromatographically pure), formic acid (top pure grade), hydrochloric acid（Top pure grade）, ethyl acetate（Chromatographically pure）, formic acid（Top grade
Pure）, sodium acetate（Top pure grade）, solid phase extraction column (MAX 60mg 3mL, Waters, USA)；Mequindox metabolite：MQCA
（German Dr.）Purity>98%, an oxygen Mequindox and de- dioxy Mequindox is taken off by Wuhan Green's Baeyer biotechnology company
Synthesis, purity>90%；Mixed standard solution：Appropriate Mequindox metabolite standard substance are weighed, is dissolved with acetonitrile, be made into 100
Mg/L Standard Stock solutions；
B) pre-treating method
500mL seawater sample is measured, solid phase extraction column is activated with 3mL methanol and 3mL water in advance, and seawater sample is added, and is used
3mL aqueous solution drip washing, ethyl acetate eluting of the 6mL containing 2% formic acid is collected；At 40 DEG C, nitrogen is dried up, and adds 1mL to contain 0.1% formic acid
Acetonitrile-aqueous solution（70:30, v/v）1mL constant volume, Ultra Performance Liquid Chromatography tandem mass spectrometry is determined；An oxygen acetyl is wherein taken off
First quinoline, de- dioxy Mequindox and MQCA（3- methylquinoline -2- carboxylic acid）Quantitative limit be：10ng/L；
C) chromatographic condition：
Chromatographic column：ACQUITYTMUPLC BEHC18(1.7μm, 2.1mm i.d.×100mm)；Chromatogram column temperature：40℃；Stream
Dynamic phase：Acetonitrile (A) and contain 0.5% formic acid water (B)；Flow velocity：0.25mL/min；Sample size：10μL；Column temperature：40℃；Three kinds of second
Acyl first quinoline metabolite liquid phase gradient elution program is as follows：
D) Mass Spectrometry Conditions：
Compound concentration is 1 μ g/mL, tri- kinds of Mequindox metabolite and tunes automatically liquid, using peristaltic pump input mode (10 μ L/
Min), tune automatically, the Mass Spectrometry Conditions of optimization are as follows：Ionization mode：Cation (ESI+)；Ionization voltage：2.50 kV；
Taper hole voltage：30 V；Ion source temperature：110℃；Taper hole blowback gas velocity：50 L/h；Desolvation temperature：350℃；Precipitation
Agent gas velocity：700 L/h；Argon flow velocity：0.11 mL/min；Other specification is as follows, and * represents quota ion：
.
Claims (1)
1. the assay method of an oxygen Mequindox, de- dioxy Mequindox and MQCA is taken off in sea water, it is characterised in that：
A) instrument and reagent：
Ultra Performance Liquid Chromatography-tandem mass spectrometer (Quattro Premier XE, Waters, USA), ultra-pure water instrument
(Milli-Q Gradient, Millipore, France), high speed centrifuge (TGL-10C, Town in Shanghai booth scientific instrument
Factory), ultrasonic cleaner (KQ-600E, Kunshan Ultrasonic Instruments Co., Ltd.), Nitrogen evaporator (N-EVAPTM112,
Organomation Associates, USA), Full-automatic solid phase extraction instrument (ASPEC XL4+, GILSON, France)；Methanol
(chromatographically pure), acetonitrile (chromatographically pure), formic acid (top pure grade), hydrochloric acid（Top pure grade）, ethyl acetate（Chromatographically pure）, formic acid（Top grade
Pure）, sodium acetate（Top pure grade）, solid phase extraction column (MAX 60mg 3mL, Waters, USA)；Mequindox metabolite：MQCA
（German Dr.）Purity>98%, an oxygen Mequindox and de- dioxy Mequindox is taken off by Wuhan Green's Baeyer biotechnology company
Synthesis, purity>90%；Mixed standard solution：Appropriate Mequindox metabolite standard substance are weighed, is dissolved with acetonitrile, be made into 100
Mg/L Standard Stock solutions；
B) pre-treating method
500mL seawater sample is measured, solid phase extraction column is activated with 3mL methanol and 3mL water in advance, and seawater sample is added, and is used
3mL aqueous solution drip washing, ethyl acetate eluting of the 6mL containing 2% formic acid is collected；At 40 DEG C, nitrogen is dried up, and adds 1mL to contain 0.1% formic acid
Acetonitrile-aqueous solution（70:30, v/v）1mL constant volume, Ultra Performance Liquid Chromatography tandem mass spectrometry is determined；An oxygen acetyl is wherein taken off
First quinoline, de- dioxy Mequindox and MQCA（3- methylquinoline -2- carboxylic acid）Quantitative limit be：10ng/L；
C) chromatographic condition：
Chromatographic column：ACQUITYTM UPLC BEHC18 (1.7μm, 2.1mm i.d.×100mm)；Chromatogram column temperature：40℃；
Mobile phase：Acetonitrile (A) and contain 0.5% formic acid water (B)；Flow velocity：0.25mL/min；Sample size：10μL；Column temperature：40℃；Three kinds
Mequindox metabolite liquid phase gradient elution program is as follows：
D) Mass Spectrometry Conditions：
Compound concentration is 1 μ g/mL, tri- kinds of Mequindox metabolite and tunes automatically liquid, using peristaltic pump input mode (10 μ L/
Min), tune automatically, the Mass Spectrometry Conditions of optimization are as follows：Ionization mode：Cation (ESI+)；Ionization voltage：2.50 kV；
Taper hole voltage：30 V；Ion source temperature：110℃；Taper hole blowback gas velocity：50 L/h；Desolvation temperature：350℃；Precipitation
Agent gas velocity：700 L/h；Argon flow velocity：0.11 mL/min；Other specification is as follows, and * represents quota ion：
.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108845150A (en) * | 2018-04-09 | 2018-11-20 | 山东省海洋资源与环境研究院 | The match of detection quinoline is more in a kind of fresh water and seawater, more, the method for 2- quinoxaline carboxylic acid of deoxidation quinoline match |
| CN112924580A (en) * | 2021-01-27 | 2021-06-08 | 山东省海洋资源与环境研究院(山东省海洋环境监测中心、山东省水产品质量检验中心) | Method for determining desoxyquinocetone and 3-methyl quinoxaline-2-carboxylic acid in seawater |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102070540A (en) * | 2010-12-31 | 2011-05-25 | 广州自远生物科技有限公司 | 1-oxygen-2-(1-ethoxy)-3-methyl-quinoxaline, and preparation method and application thereof |
| CN102070539A (en) * | 2010-12-31 | 2011-05-25 | 广州自远生物科技有限公司 | 1-oxo-2-methyl-3-(1-ethoxyl)-quinoxaline and preparation method and application thereof |
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2016
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108845150A (en) * | 2018-04-09 | 2018-11-20 | 山东省海洋资源与环境研究院 | The match of detection quinoline is more in a kind of fresh water and seawater, more, the method for 2- quinoxaline carboxylic acid of deoxidation quinoline match |
| CN108845150B (en) * | 2018-04-09 | 2021-02-05 | 山东省海洋资源与环境研究院 | Method for detecting cyadox, deoxycyadox, 2-quinoxaline carboxylic acid in fresh water and seawater |
| CN112924580A (en) * | 2021-01-27 | 2021-06-08 | 山东省海洋资源与环境研究院(山东省海洋环境监测中心、山东省水产品质量检验中心) | Method for determining desoxyquinocetone and 3-methyl quinoxaline-2-carboxylic acid in seawater |
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| CN106442839B (en) | 2017-12-12 |
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