CN102393435A - Method for detecting content of trace amount MC in aquatic product - Google Patents
Method for detecting content of trace amount MC in aquatic product Download PDFInfo
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- CN102393435A CN102393435A CN2011103520150A CN201110352015A CN102393435A CN 102393435 A CN102393435 A CN 102393435A CN 2011103520150 A CN2011103520150 A CN 2011103520150A CN 201110352015 A CN201110352015 A CN 201110352015A CN 102393435 A CN102393435 A CN 102393435A
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Abstract
The invention relates to a method for detecting the content of trace amount MC (Microcystin) in an aquatic product, belongs to the analytical chemistry field, and in particular to the detection technical field of pollutants in aquatic products. In the method, enrichment purification technology and UPLC (Ultra Performance Liquid Chromatography) -Q (Quadrupole)-TOF (Time of Flight)-MS (Mass Spectrum) are cooperatively used and combined, so as to perform quantitative analysis to the MC and NOD (Nodularin) in the aquatic product. The processing steps comprise: ultrasonic extraction, solid phase extraction purification, and quick detection to MC-RR, MC-YR, MC-LR and NOD in the aquatic product by cooperatively using and combing the UPLC-Q-TOF-MS. The method established by the invention can quickly analyze the content of the MC in the aquatic product, and has high sensitivity, good specificity, easiness in operation, and high recovery ratio.
Description
Technical field
The present invention relates to the detection method of trace algae content of toxins in a kind of aquatic products, belong to the analytical chemistry field, more specifically relate to the detection technique field of pollutant in the aquatic products.The present invention combines the enriching and purifying technology with Ultra Performance Liquid Chromatography-quadrupole rod-flight time mass spectrum coupling, Microcystin in the aquatic products and joint ball algae toxin are carried out quantitative test.
Background technology
The most of water body in lake eutrophication aggravation of China in recent years causes the summer blue-green algae to breed in a large number, and " wawter bloom " phenomenon takes place.Blue-green algae decays and produces harmful cyanophycean toxin in the process, and wherein (microcystin, MC) (nodularin NOD) is two big types of hepatotoxin that the fresh water blue-green algae produces to Microcystin with joint ball algae toxin.MC has ring-type seven peptide structures; Stable in properties is a TPA, and is wherein common with MC-RR, MC-YR, MC-LR; The limit standard of MC-LR is 1 μ g/L in the world health organisation recommendations potable water, and recommendation crowd maximum can to tolerate daily intaking amount be every kilogram 0.04 μ g.NOD has the ring-type pentapeptide structure similar with MC, is direct carcinogen.It should be noted that the algae toxin not only threatens human health through potable water, and can in aquatic products such as animals and plants, assemble, threaten human health through food chain.
Owing to lack the effective measures that prevent that algal bloom from taking place at present, therefore to prevent and eliminate of the harm of algae toxin to people and animals, monitoring and control algae toxin limiting the quantity of in all kinds of aquatic products are efficient ways.The traditional detection means mainly contain biochemical analysis methods such as mouse peritoneal injection bioanalysis, ELISA, phosphoprotein phosphatase inhibition, but exist operation complicated, receive the complicated substrate disturbing effect big, and can not be used for shortcoming such as different types of Analysis and Identification.Liquid chromatography and mass spectrometry method have been applied to the detection of multiple algae toxin compound in water body and the biosome; And develop Ultra Performance Liquid Chromatography (Ultra Performance Liquid Chromatography in recent years; UPLC) method has characteristics such as analysis speed is fast, sample analysis flux height, sensitivity for analysis height, for the analysis of object in the complex biological body bigger advantage is arranged.Through combining mass spectrum to become the strong instrument of algae toxin qualitative, quantitative; Sample is converted into desolvated ion in mass spectrometer; Obtain valuable fragment through changing internal source voltage, particularly the characteristic fragmention comes the algae toxin in the detection of complex matrix, the algae toxin homolog of different molecular quality; Monitor those under certain retention time through Ultra Performance Liquid Chromatography-quadrupole rod-flight time mass spectrum coupling, the ionic strength of certain extra fine quality number reaches quantitative purpose.Therefore, set up highly sensitive, the recovery is high, trace MC-RR, MC-YR, MC-LR and NOD analytical approach in the aquatic products of favorable reproducibility, becomes the key of research.
Summary of the invention
The objective of the invention is to the aquatic products sample matrices complicated; Algae toxin trace exists; Problems such as the pretreatment technology difficulty is big; Intend exploitation a kind of highly sensitive, the recovery is high, analytical technology fast and accurately, realizes the quantitative measurement to MC-RR, MC-YR, MC-LR and NOD in the aquatic products sample.
Technical scheme of the present invention is following
The detection method of trace algae content of toxins takes by weighing the quantity of sample soaked in solvent in a kind of aquatic products, adopts ultrasonic auxiliary extraction mode; The algae toxin is extracted in the solvent; Through centrifuging, behind the concentrating under reduced pressure, will extract solid-phase extraction column on the concentrate; The wash-out liquid nitrogen blows concentrated, directly is used for Ultra Performance Liquid Chromatography-quadrupole rod-flying time mass spectrum analysis behind the constant volume.Step is:
A. the extraction of sample: cryodesiccated aquatic products sample is pulverized evenly, added normal butyl alcohol-methanol-water (volume ratio 1 ︰ 4 ︰ 15, down together) extract 5-10mL ratio by 0.20 g dry powder; After soaking 10 min, ultrasonic power is 150-250W, ultrasonic 10 min; The centrifugal 10-15 min of 12000 r/min pipettes supernatant liquor, precipitates twice of extracting again (condition is the same); Merge supernatant, be evaporated to 5 mL below 40 ℃.
B. sample enrichment and purifying: appearance enrichment algae toxin on the concentrate that the 500mg C18 solid-phase extraction column that adopts activation obtains steps A, control flow velocity 1mL/min; Successively with pure water, each 3-5mL flushing solid-phase extraction column of 10% methanol aqueous solution, control flow velocity 2mL/min; Use algae toxin on the methanol solution wash-out post of 5-10 mL 0.05-0.1% trifluoroacetic acid at last, control flow velocity 2-3mL/min, eluent nitrogen under 30 ℃ of conditions blows concentrated, in-18 ℃ of freezing preservations.
C. the freezing article of before the stratographic analysis step B being preserved filter constant volume 1.00mL with methanol constant volume and with the organic filter of 0.22 μ m.
D, Ultra Performance Liquid Chromatography-quadrupole rod-flying time mass spectrum analysis:
Liquid phase chromatogram condition: Ultra Performance Liquid Chromatography post: Acquity UPLC BEH C18 post, 2.1 mm * 100 mm * 1.7 μ m, column temperature is 45 ℃; Moving phase is A: water; B: acetonitrile; A, B all contain volume fraction 0.10% formic acid, and flow velocity is 0.30 mL/min; The gradient elution program is 0-6.0 min: contain B:20%-35%, all the other components are A; 6.0-8.0 min: contain B:35%-100%, all the other components are A;
Mass spectrum condition: Q-TOF-MS condition: electric spray ion source: positive ion electrospray is from pattern ESI+; Ion source temperature: 100 ℃; Desolventizing temperature degree: 250 ℃; Capillary voltage: 3.5 kV; Awl desolventizing airshed: 500 L/h; Taper hole voltage: 30 V; Taper hole airshed: 50 L/h; Level Four bar scope m/z:100-1500; Collision energy: 6V; TOF ion flight mode adopts V model, selects the ion monitoring pattern, and target compound confirms that with retention time and characteristic ion the drawing standard curve carries out quantitative measurement with external standard method.
The activation sequence of the described C18 solid-phase extraction column of step B is: 5mL chromatographically pure methyl alcohol, 5mL ultrapure water, 3mL 5% methanol aqueous solution, flow velocity is 1mL/min.
Stratographic analysis retention time and quota ion that wherein said algae toxin is MC-RR, MC-YR, MC-LR and NOD are seen table 1.
The stratographic analysis retention time and the quota ion of four kinds of algae toxin of table 1
| Compound | Retention time (min) | Quota ion |
| MC-RR | 4.28 | 519.84 |
| MC-YR | 5.85 | 1045.66 |
| MC-LR | 6.17 | 995.67 |
| NOD | 5.20 | 825.54 |
Trace algae content of toxins in the aquatic products is measured in Ultra Performance Liquid Chromatography-quadrupole rod that the present invention sets up-time-of-flight mass spectrometry (TOFMS) coupling.Detecting of this method is limited to 5.0-10.0 μ g/kg; In the scope of concentration 0.02-5 mg/kg, peak area and sample concentration are the good linear relation.
Beneficial effect of the present invention: the inventive method employing mixed solvent effectively extracts, ultrasonic auxiliary extraction is simple to operate, fast; Adopt SPE to carry out enrichment, the enrichment multiple is high and the removal of impurity is effective; Adopt Ultra Performance Liquid Chromatography-quadrupole rod-time-of-flight mass spectrometry (TOFMS) coupling to detect, detectability is low, has higher sensitivity and degree of accuracy.The present invention provides that a kind of detectability is low, favorable reproducibility, highly sensitive, the recovery better, the analytical approach that operation is simple, can the express-analysis aquatic products in trace MC-RR, MC-YR, MC-LR and NOD.
Description of drawings
Fig. 1 MCs and NOD select the ion TIC,
A:MCs and NOD standard solution 20 μ g/L; B: wild freshwater mussel sample refined solution.
The MCs of Fig. 2 mark-on carp appearance and the mass spectrogram of NOD.
Embodiment
Below in conjunction with embodiment technical scheme of the present invention is done further to describe:
Embodiment 1:
1, the extraction of sample
Cryodesiccated aquatic products carp sample is pulverized evenly, added normal butyl alcohol-methanol-water (volume ratio 1 ︰ 4 ︰ 15, down together) extract 6 mL ratios by 0.20 g dry powder; After soaking 10 min, ultrasonic power is 150W, ultrasonic 10 min; Centrifugal 10 min of 12000 r/min pipette supernatant liquor, precipitate twice of extracting again (condition is the same); Merge supernatant, be evaporated to 5 mL below 40 ℃.
2, sample enrichment and purifying
The activation sequence of C18 solid-phase extraction column is: 5mL chromatographically pure methyl alcohol, 5mL ultrapure water, 3mL 5% methanol aqueous solution, flow velocity is 1mL/min.The 500mg C18 solid-phase extraction column that adopts activation is to appearance enrichment algae toxin on the above-mentioned concentrate, control flow velocity 1mL/min; Successively with pure water, each 5mL flushing solid-phase extraction column of 10% methanol aqueous solution, control flow velocity 2mL/min; Use algae toxin on the methanol solution wash-out post of 6 mL, 0.05% trifluoroacetic acid at last, control flow velocity 2mL/min, eluent nitrogen under 30 ℃ of conditions blows concentrated, in-18 ℃ of freezing preservations.
3, the freezing article of before the stratographic analysis step B being preserved filter constant volume 1.00mL with methanol constant volume and with the organic filter of 0.22 μ m.
4, Ultra Performance Liquid Chromatography-quadrupole rod-time-of-flight mass spectrometry (TOFMS) analysis condition is:
Liquid phase chromatogram condition: Ultra Performance Liquid Chromatography post: Acquity UPLC BEH C18 post (2.1 mm * 100 mm * 1.7 μ m), column temperature is 45 ℃; Moving phase is A: water; B: acetonitrile; A, B all contain 0.10% (volume fraction) formic acid.Flow velocity is 0.3 mL/min; The gradient elution program is B:20%-35% (0-6.0 min); 35%-100% (6.0-8.0 min); All the other components are A.
Mass spectrum condition: Q-TOF-MS condition: electric spray ion source: positive ion electrospray is from pattern (ESI+); Ion source temperature: 100 ℃; Desolventizing temperature degree: 250 ℃; Capillary voltage: 3.5 kV; Awl desolventizing airshed: 500 L/h; Taper hole voltage: 30 V; Taper hole airshed: 50 L/h; Level Four bar scope m/z:100-1500; Collision energy: 6V; TOF ion flight mode adopts V model.Select the ion monitoring pattern, target compound is confirmed with retention time and characteristic ion.
4, the drafting of typical curve is carried out quantitative measurement with external standard method
The drafting of described external standard method typical curve: accurately take by weighing 4 kinds of algae toxin; Be dissolved in 30% acetonitrile solution, be configured to the standard solution of series concentration, adopt Ultra Performance Liquid Chromatography-quadrupole rod-flight time mass spectrum coupling to analyze; Concentration with the algae toxin is horizontal ordinate respectively; Peak area is that ordinate returns, and obtains 4 typical curves and related coefficient and sees table 2, is used for the working sample analyte.In blank sample, add the standard solution of variable concentrations, through pre-treatment, the interpolation concentration that obtains 3 times of signal to noise ratio (S/N ratio)s is detectability.
The typical curve equation of four kinds of algae toxin of table 2, related coefficient
| Component to be measured | The typical curve equation | Related coefficient (r) | LDL/(ng/g) |
| MC-RR | Y=52.23X+1.806 | 0.9997 | 6.0 |
| MC-YR | Y=9.312X-0.067 | 0.9995 | 12.0 |
| MC-LR | Y= 28.04X-0.107 | 1.000 | 12.0 |
| NOD | Y=76.15X-0.388 | 1.000 | 5.0 |
5, the mensuration of the sample and the recovery
Gather aquatic products carp sample to be measured; After 1 pair of sample effectively extracts set by step; 2 carry out enrichment and purifying set by step; 3 carry out Ultra Performance Liquid Chromatography-quadrupole rod-flight time mass spectrum coupling and detect set by step again, and with the above-mentioned typical curve that obtains relatively, finally obtain the content of Microcystin MC-RR in the carp sample, MC-YR, MC-LR and joint ball algae toxin through converting.
After adopting identical carp sample to carry out freeze drying; Adopt to soak and add the target mode adds Microcystin MC-RR, MC-YR, MC-LR and joint ball algae toxin NOD successively by the addition of 0.5 ng/g standard solution; Carry out pre-service and measure the content of four kinds of algae toxin, and carry out the recovery according to following formula and calculate.
R=（
C-
C 0）/0.5×100%
R-the recovery, %
CThe algae content of toxins of-interpolation standard solution aquatic products sample, ng/g;
C 0-do not add the algae content of toxins of standard solution aquatic products sample, ng/g;
The mensuration of the recovery is all carried out 6 parallel experiments for blank sample and mark-on.The recovery of this method and precision, as shown in table 3.
The recovery of table 3 this method and precision
| Component to be measured | Carp sample value ρ/(ng/g) | The recovery/% | RSD /% |
| MC-RR | N.D. | 86 | 6.4 |
| MC-YR | N.D. | 76 | 6.7 |
| MC-LR | N.D. | 89 | 2.0 |
| NOD | N.D. | 87 | 4.5 |
Embodiment 2:
1, the extraction of sample
Cryodesiccated aquatic products freshwater mussel sample is pulverized evenly, added normal butyl alcohol-methanol-water (volume ratio 1 ︰ 4 ︰ 15, down together) extract 10mL ratio by 0.20 g dry powder; After soaking 10 min, ultrasonic power is 200W, ultrasonic 10 min; Centrifugal 15 min of 12000 r/min pipette supernatant liquor, precipitate twice of extracting again (condition is the same); Merge supernatant, be evaporated to 5 mL below 40 ℃.
2, sample enrichment and purifying
The activation sequence of C18 solid-phase extraction column is: 5mL chromatographically pure methyl alcohol, 5mL ultrapure water, 3mL 5% methanol aqueous solution, flow velocity is 1mL/min.The 500mg C18 solid-phase extraction column that adopts activation is to appearance enrichment algae toxin on the above-mentioned concentrate, control flow velocity 1mL/min; Respectively with pure water, each 5mL flushing solid-phase extraction column of 10% methanol aqueous solution, control flow velocity 2mL/min; Use algae toxin on the methanol solution wash-out post of 8 mL, 0.1% trifluoroacetic acid at last, control flow velocity 3mL/min, eluent nitrogen under 30 ℃ of conditions blows concentrated, in-18 ℃ of freezing preservations.
3. filter constant volume 1.00mL with methanol constant volume and with the organic filter of 0.22 μ m before the stratographic analysis.
Ultra Performance Liquid Chromatography-quadrupole rod-time-of-flight mass spectrometry (TOFMS) analysis condition is:
Liquid phase chromatogram condition: Ultra Performance Liquid Chromatography post: Acquity UPLC BEH C18 post (2.1 mm * 100 mm * 1.7 μ m), column temperature is 45 ℃; Moving phase is A: water; B: acetonitrile; A, B all contain 0.10% (volume fraction) formic acid.Flow velocity is 0.3 mL/min; The gradient elution program is B:20%-35% (0-6.0 min); 35%-100% (6.0-8.0 min).
Mass spectrum condition: Q-TOF-MS condition: electric spray ion source: positive ion electrospray is from pattern (ESI+); Ion source temperature: 100 ℃; Desolventizing temperature degree: 250 ℃; Capillary voltage: 3.5 kV; Awl desolventizing airshed: 500 L/h; Taper hole voltage: 30 V; Taper hole airshed: 50 L/h; Level Four bar scope m/z:100-1500; Collision energy: 6V; TOF ion flight mode adopts V model.Select the ion monitoring pattern, target compound is confirmed with retention time and characteristic ion.
4, the drafting of typical curve is carried out quantitative measurement with external standard method
The drafting of described external standard method typical curve: accurately take by weighing 4 kinds of algae toxin; Be dissolved in 30% acetonitrile solution, be configured to the standard solution of series concentration, adopt Ultra Performance Liquid Chromatography-quadrupole rod-flight time mass spectrum coupling to analyze; Concentration with the algae toxin is horizontal ordinate respectively; Peak area is that ordinate returns, and obtains 4 typical curves and related coefficient and sees table 2, is used for the working sample analyte.In blank sample, add the standard solution of variable concentrations, through pre-treatment, the interpolation concentration that obtains 3 times of signal to noise ratio (S/N ratio)s is detectability.
5, the mensuration of the sample and the recovery
Gather aquatic products freshwater mussel sample to be measured; After 1 pair of sample effectively extracts set by step; 2 carry out enrichment and purifying set by step; 3 carry out Ultra Performance Liquid Chromatography-quadrupole rod-flight time mass spectrum coupling and detect set by step again, and with the above-mentioned typical curve that obtains relatively, finally obtain through converting Microcystin-RR in the freshwater mussel sample ,-YR ,-content of LR and joint ball algae toxin.
Adopt same freshwater mussel sample to carry out freeze drying; Adopt to soak and add the addition adding standard solution of target mode by 5.0 ng/g; Carry out pre-service and measure Microcystin-RR ,-YR ,-content of LR and joint ball algae toxin, and carry out the recovery according to following formula and calculate.
R=（
C-
C 0）/5.0×100%
R-the recovery, %
CThe algae content of toxins of-interpolation standard solution aquatic products sample, ng/g;
C 0-do not add the algae content of toxins of standard solution aquatic products sample, ng/g;
The mensuration of the recovery is all carried out 6 parallel experiments for blank sample and mark-on.The recovery of this method and precision, as shown in table 4.
The recovery of table 4 this method and precision
| Component to be measured | Freshwater mussel sample value ρ/(ng/g) | The recovery/% | RSD /% |
| MC-RR | 1.09 | 89 | 5.2 |
| MC-YR | N.D. | 81 | 7.1 |
| MC-LR | 0.84 | 94 | 4.0 |
| NOD | N.D. | 91 | 3.3 |
The foregoing description only supplies the usefulness of explanation invention, rather than to qualification of the present invention, any scheme after the simple change of the present invention is all belonged to protection scope of the present invention.
Claims (3)
1. the detection method of trace algae content of toxins in the aquatic products is characterized in that:
Take by weighing the quantity of sample soaked in solvent; Adopt ultrasonic auxiliary extraction mode, the algae toxin is extracted in the solvent, through centrifuging; Behind the concentrating under reduced pressure; The algae toxin is extracted solid-phase extraction column on the concentrate, and the wash-out liquid nitrogen blows concentrated, directly is used for Ultra Performance Liquid Chromatography-quadrupole rod-flying time mass spectrum analysis behind the constant volume; This method may further comprise the steps successively:
(1), the extraction of sample: cryodesiccated aquatic products sample is pulverized evenly, is added normal butyl alcohol-methanol-water volume ratio 1 ︰ 4 ︰ 15 extract 5-10mL ratios in 0.20 g dry powder, soak 10 min after; Ultrasonic power is 150-250W, ultrasonic 10 min, the centrifugal 10-15 min of 12000 r/min; Pipette supernatant liquor; Deposition merges supernatant with the extracting twice again of the same condition, is evaporated to 5 mL below 40 ℃;
(2), sample enrichment and purifying: appearance enrichment algae toxin on the concentrate that the 500mg C18 solid-phase extraction column that adopts activation obtains step (1), control flow velocity 1mL/min; Successively with pure water, each 3-5mL flushing solid-phase extraction column of 10% methanol aqueous solution, control flow velocity 2mL/min; Use algae toxin on the methanol solution wash-out post of 5-10 mL 0.05%-0.1% trifluoroacetic acid at last, control flow velocity 2-3mL/min, eluent nitrogen under 30 ℃ of conditions blows concentrated, in-18 ℃ of freezing preservations;
(3), the freezing article of before the stratographic analysis step (2) being preserved filter constant volume 1.00mL with methanol constant volume and with the organic filter of 0.22 μ m;
(4), Ultra Performance Liquid Chromatography-quadrupole rod-flying time mass spectrum analysis:
Liquid phase chromatogram condition: Ultra Performance Liquid Chromatography post: Acquity UPLC BEH C18 post, 2.1 mm * 100 mm * 1.7 μ m, column temperature is 45 ℃; Moving phase is A: water; B: acetonitrile; A, B all contain volume fraction 0.10% formic acid, and flow velocity is 0.30 mL/min; The gradient elution program is 0-6.0 min: contain B:20%-35%, all the other components are A; 6.0-8.0 min: contain B:35%-100%, all the other components are A;
Mass spectrum condition: Q-TOF-MS condition: electric spray ion source: positive ion electrospray is from pattern ESI+; Ion source temperature: 100 ℃; Desolventizing temperature degree: 250 ℃; Capillary voltage: 3.5 kV; Awl desolventizing airshed: 500 L/h; Taper hole voltage: 30 V; Taper hole airshed: 50 L/h; Level Four bar scope m/z:100-1500; Collision energy: 6V; TOF ion flight mode adopts V model, selects the ion monitoring pattern, and target compound confirms that with retention time and characteristic ion the drawing standard curve carries out quantitative measurement with external standard method.
2. the detection method of trace algae content of toxins in the aquatic products according to claim 1; It is characterized in that: the activation sequence of the described C18 solid-phase extraction column of step B is: 5mL chromatographically pure methyl alcohol, 5mL ultrapure water, 3mL 5% methanol aqueous solution, flow velocity is 1mL/min.
3. the detection method of trace algae content of toxins in the aquatic products according to claim 1 is characterized in that: wherein said algae toxin is Microcystin MC-RR, MC-YR, MC-LR and joint ball algae toxin NOD.
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| CN103543219A (en) * | 2013-09-17 | 2014-01-29 | 北京市水产科学研究所 | Method for extracting cyanobacteria toxin from urban eutrophic cyanobacterial bloom water |
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| CN106546456A (en) * | 2015-09-22 | 2017-03-29 | 广州禾信分析仪器有限公司 | Method for detecting microcystin in aquatic product |
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| CN113092609A (en) * | 2021-03-31 | 2021-07-09 | 中国海洋大学 | Preparation method of Gymnodimine toxin standard substance |
| CN117538459A (en) * | 2024-01-09 | 2024-02-09 | 北京林业大学 | Method for measuring 7 algae toxins in environmental sample by liquid chromatography-mass spectrometry |
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Cited By (10)
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| CN103076420A (en) * | 2012-12-31 | 2013-05-01 | 江苏省环境监测中心 | Method for detecting multicomponent microcystins through ultra-high performance liquid chromatography/triple quadrupole tandem mass spectrometry |
| CN103543219A (en) * | 2013-09-17 | 2014-01-29 | 北京市水产科学研究所 | Method for extracting cyanobacteria toxin from urban eutrophic cyanobacterial bloom water |
| CN104977383A (en) * | 2015-06-18 | 2015-10-14 | 中山鼎晟生物科技有限公司 | Method for rapidly and quantitatively detecting microcystins in spirulina food |
| CN106546456A (en) * | 2015-09-22 | 2017-03-29 | 广州禾信分析仪器有限公司 | Method for detecting microcystin in aquatic product |
| CN106546456B (en) * | 2015-09-22 | 2019-11-19 | 广州禾信分析仪器有限公司 | The detection method of Microcystin in aquatic products |
| CN108949765A (en) * | 2018-06-22 | 2018-12-07 | 中国人民解放军第二军医大学 | With the aptamers and its application of nodularins-R specific binding |
| CN108949765B (en) * | 2018-06-22 | 2021-12-24 | 中国人民解放军第二军医大学 | Aptamer specifically combined with nodulotoxin-R and application thereof |
| CN113092609A (en) * | 2021-03-31 | 2021-07-09 | 中国海洋大学 | Preparation method of Gymnodimine toxin standard substance |
| CN113092609B (en) * | 2021-03-31 | 2022-03-29 | 中国海洋大学 | Preparation method of Gymnodimine toxin standard substance |
| CN117538459A (en) * | 2024-01-09 | 2024-02-09 | 北京林业大学 | Method for measuring 7 algae toxins in environmental sample by liquid chromatography-mass spectrometry |
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