CN105319293A - Method for detecting trichlorfon chiral enantiomers in seawater - Google Patents
Method for detecting trichlorfon chiral enantiomers in seawater Download PDFInfo
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- CN105319293A CN105319293A CN201410380141.0A CN201410380141A CN105319293A CN 105319293 A CN105319293 A CN 105319293A CN 201410380141 A CN201410380141 A CN 201410380141A CN 105319293 A CN105319293 A CN 105319293A
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Abstract
The invention discloses a method for detecting trichlorfon chiral enantiomers in seawater. The method is characterized by comprising the following steps of picking and placing 90-110 mL of cultivation seawater into a beaker, adding 5-10 mg of trichlorfon standard substances, after the mixture is oscillated uniformly, adding 1-2 drops of a glacial acetic acid solution, passing 10-50 mL of the mixture through HLB solid-phase extraction columns, using 6-10 mL of ethy acetate for elution, blowing eluant with nitrogen to be dry approximately, conducting dissolution on mobile phases of residual liquid till the constant volume is 1 mL, adopting millipore filtration films for conducting filtration to obtain a solution A, and separating the trichlorfon enantiomer with normal hexane and isopropanol as the mobile phases, wherein the volume ratio of the normal hexane to the isopropanol is (85-95): (15-5); using a high performance liquid chromatography for detecting the solution A, selecting CHIRALCEL IC chiral columns, and controlling the column temperature to be 20-35 DEG C, the flow rate to be 0.7-1.0 mL/min and the wave length to be 207 nm. By means of the method, the resolution of the trichlorfon chiral enantiomer can be achieved successfully, thereby the residual amount of the trichlorfon chiral enantiomers in the seawater is detected, and the theoretical basis is provided for detection of chiral drug residuals in seawater.
Description
Technical field
The present invention relates to the detection method of metrifonate chiral enantiomer in a kind of seawater.
Background technology
Metrifonate [O, O-dimethyl-(2,2, the chloro-1-hydroxyethyl of 2-tri-) phosphonate ester] belong to chirality organophosphorus insecticide, to the cladocera of the fluke of fish inside and outside parasitism, nematode, spiny-headed worm and harm fry, fish-egg, oar angle class larva and kyllinga brevifolia etc., all there is good killing action.Metrifonate has an asymmetric carbon atom, a pair chiral enantiomer, and its enantiomer-specific structure formula is as shown in Fig. 1 .1-1.2.The afterproduct of metrifonate hydrolysis can combine with the cholinesterase of polypide, makes polypide neuromuscular function not normal, first excited, rear paralysis, until dead, Chang Zuowei antiparasitic agent is used for killing the Common Fish body parasites such as argulus to improve fishery production in sea-farming.The RD of metrifonate in sea-farming is 0.1 ~ 1mg/L, but in actual cultivation project, people usually use excessive metrifonate, thus causes occurring metrifonate medicament residue in breeding water body.Metrifonate also can produce toxic action (suppression cholinesterase activity) to nontarget organism, and the waste water residual with metrifonate enters river or marine, will endanger environment and human health directly or indirectly.
At present, many for the residue detection research of metrifonate in soil, environment, food, but still do not carry out analysis detection for metrifonate enantiomorph is residual, and in research in the past, usually do not distinguish the chiral enantiomer of sea-farming medication, so the data of the risk assessment institute foundation of aquatic products medicament residue are then not exclusively true.Therefore carry out the research of enantiomers of chiral drugs disassemble technique, the selectivity for metrifonate conventional in aquaculture remains behavior and carries out systematic study, greatly will advance chiral drug progress of research used for aquiculture and application.
Summary of the invention
Technical matters to be solved by this invention is to provide the detection method of metrifonate chiral enantiomer in a kind of seawater, adopt high performance liquid chromatography Chiral Stationary Phases to detect the residual quantity of metrifonate enantiomorph in seawater, successfully can realize the fractionation of metrifonate chiral enantiomer.
The present invention solves the problems of the technologies described above adopted technical scheme: the detection method of metrifonate chiral enantiomer in a kind of seawater, is characterized in that comprising the following steps:
1) breeding seawater 90 ~ 110mL is got in beaker, add metrifonate standard items 5mg ~ 10mg, add 1 ~ 2 20wt% glacial acetic acid solution after vibration mixing, get 10 ~ 50mL and cross HLB solid phase extraction column, then use 6 ~ 10mL eluent ethyl acetate, eluent is collected in volumetric flask;
2) by step 1) in eluent ethylacetate nitrogen blow near dry, the mobile phase of raffinate normal hexane+isopropyl alcohol dissolves and is dissolved to 1mL, and obtaining solution A after adopting 0.22 μm of miillpore filter to filter, it is that 85 ~ 95:15 ~ 5 are separated metrifonate enantiomorph as mobile phase with normal hexane and isopropyl alcohol volume ratio;
3) high performance liquid chromatograph is adopted to detect above-mentioned solution A; Select CHIRALCELIC chiral column during detection, the column temperature of chiral column is 20 DEG C ~ 35 DEG C, normal hexane and isopropyl alcohol volume ratio be 85 ~ 95:15 ~ 5 as mobile phase, flow velocity during detection is 0.7mL/min ~ 1.0mL/min, and wavelength is 207nm.
As improvement, step 2 and 3) mobile phase also containing ethanol, it is separated with the impurity in water sample metrifonate enantiomorph as mobile phase than for 90:8 ~ 9.5:2 ~ 0.5 with ethanol contend with normal hexane, isopropyl alcohol.
Improve again, described step 2 and 3) the volume ratio of normal hexane, isopropyl alcohol and ethanol be 90:8.5:1.5.
Preferably, described step 3) detection time flow velocity be 1.0mL/min.
Preferably, described step 3) column temperature be 25 DEG C.
Preferably, described step 3) the filler of CHIRALCELIC chiral column be 5 μm of Silica Surface coating celluloses-three [3,5-dichlorophenyl carbamate].
Finally, described step 1) HLB solid phase extraction column be through the activation of methyl alcohol+water.
Compared with prior art, the invention has the advantages that: adopt high performance liquid chromatography Chiral Stationary Phases to detect the residual quantity of metrifonate enantiomorph in seawater, successfully achieve the fractionation of metrifonate chiral enantiomer, thus can detect, in seawater, chiral drug residue detection provides theoretical foundation the residual quantity of metrifonate enantiomorph in seawater.Wherein, enantiomorph and in 0.5mg/L ~ 10mg/L concentration range with the linear relationship that its response is good, regression equation and related coefficient are respectively y=20.795x – 1.7766, R
2=0.9993 and y=19.730x+2.9066, R
2=0.9992, the sample average recovery is respectively 89.07% and 82.93%, and day to day precision is respectively 6.77% and 6.29%, and quantitative limit is respectively 0.05mg/L and 0.04mg/L.
Accompanying drawing explanation
Fig. 1 .1 ~ 1.2 are metrifonate enantiomer-specific structure formulas provided by the invention;
Fig. 2 is the chromatogram of metrifonate in the embodiment of the present invention.
Embodiment
Below in conjunction with accompanying drawing embodiment, the present invention is described in further detail.
A detection method for metrifonate chiral enantiomer in seawater, comprises the following steps:
(1) breeding seawater 100mL is got in beaker, add metrifonate standard items 5mg ~ 10mg, 1 ~ 2 20wt% glacial acetic acid (analyzing pure) solution is added after vibration mixing, get 10 ~ 50mL to cross HLB solid phase extraction column and (activate through 5mL methyl alcohol+5mL water, then use 6 ~ 10mL eluent ethyl acetate, eluent is collected in 10mL volumetric flask;
(2) the eluent ethylacetate nitrogen in step (1) is blown near dry, raffinate normal hexane: isopropyl alcohol: ethanol dissolves according to 90:8.5:1.5 (v:v:v) and is dissolved to 1mL, and obtains solution A after adopting 0.22 μm of miillpore filter to filter;
(3) high performance liquid chromatograph is adopted to detect above-mentioned solution A; Select CHIRALCELIC chiral column during detection, the filler of this chiral column is 5 μm of Silica Surface coating celluloses-three [3,5-dichlorophenyl carbamate]; Normal hexane: isopropyl alcohol: ethanol is according to 90:8.5:1.5 (v:v:v) as mobile phase, and the column temperature of described chiral column is 20 DEG C ~ 35 DEG C; Flow velocity during detection is 0.7mL/min ~ 1.0mL/min, and wavelength is 207nm.
In the present embodiment, the mobile phase that normal hexane and isopropyl alcohol volume ratio are 95:5,90:10 and 85:15 is used to carry out chiral resolution to metrifonate respectively in step (2 and 3), split result is as shown in table 1, can find out, along with the increase of isopropanol ratios in mobile phase, mobile phase polarity strengthens, and therefore degree of separation reduces, use the best of mobile phase to consist of normal hexane and isopropyl alcohol volume fraction be respectively 90 and 10, under this proportion of mobile phase condition, Chiral Separation is respond well.
Table 1
During owing to detecting, flow velocity difference splits effect possibility difference, the present embodiment select volume fraction be respectively 90 and 10 normal hexane and isopropyl alcohol as under the prerequisite of mobile phase, have detected the fractionation situation between enantiomorph when flow velocity is 0.7mL/min, 0.8mL/min, 0.9mL/min, 1.0mL/min respectively, split result is as shown in table 2, is separated required time the shortest when flow velocity is 1mL/min.Therefore flow velocity when the present embodiment detects is preferably 1mL/min.
Table 2
Keep other chromatographic condition constant, the present embodiment has also investigated the impact of column temperature on metrifonate enantiomorph chiral separation.Table 3 is the split result of metrifonate under different column temperature, can find out, along with column temperature raises, degree of separation has downtrending, but metrifonate enantiomorph all can reach baseline separation under following temperature, because the too high meeting of column temperature makes the lost of life of chromatographic column, therefore, the present embodiment preferably close to 25 DEG C of room temperature as optimum column temperature.
Table 3
When carrying out sample determination, because in right metrifonate chromatographic peak and water sample, the chromatographic peak of impurity can not realize baseline separation, therefore in mobile phase, add a certain proportion of ethanol, make it realize baseline separation, result is as shown in table 4.When normal hexane: isopropyl alcohol: during proportion of ethanol 90:8.5:1.5, right metrifonate can be separated with water sample, also can ensure that experiment completes in the short period of time simultaneously.
Table 4
Get breeding seawater 90 ~ 110mL in beaker, add metrifonate standard items 5mg ~ 10mg, 1 ~ 2 20wt% glacial acetic acid solution is added after vibration mixing, get 10 ~ 50mL, cross HLB pillar afterwards, ethyl acetate 8mL wash-out, wash-out liquid nitrogen blows crosses machine testing on 0.22 μm of organic filter membrane to being settled to 1mL with mobile phase after near dry.Metrifonate concentration within the scope of 0.5mg/L ~ 10mg/L with the linear relationship that its response is good, represent concentration with X, Y represents left metrifonate peak area.Regression equation and related coefficient are y=20.795x – 1.7766, R
2=0.9993.Right metrifonate concentration within the scope of 0.5mg/L ~ 10mg/L with the linear relationship that its response is good, represent concentration with Y, X represents right metrifonate peak area.Regression equation and related coefficient are and related coefficient is y=19.730x+2.9066, R
2=0.9992.In seawater blank sample, add the metrifonate standard solution of these 3 concentration of 0.7mg/L, 2mg/L and 8mg/L, carry out recovery experiment by this law.Each interpolation concentration operation repetitive 3 times, calculate the recovery and precision, the sample average recovery of S-(+)-trichlorfon and R-(-)-trichlorfon is respectively 89.07% and 82.93%, day to day precision is respectively 6.77% and 6.29%, and quantitative limit is respectively 0.05mg/L and 0.04mg/L.
As shown in Figure 1, this method successfully can realize the fractionation of metrifonate chiral enantiomer, and the degree of separation of two metrifonate enantiomorphs is 7.29.
Claims (7)
1. the detection method of metrifonate chiral enantiomer in seawater, is characterized in that comprising the following steps:
1) breeding seawater 90 ~ 110mL is got in beaker, add metrifonate standard items 5mg ~ 10mg, add 1 ~ 2 20wt% glacial acetic acid solution after vibration mixing, get 10 ~ 50mL and cross HLB solid phase extraction column, then use 6 ~ 10mL eluent ethyl acetate, eluent is collected in volumetric flask;
2) by step 1) in eluent ethylacetate nitrogen blow near dry, the mixed liquor of raffinate normal hexane+isopropyl alcohol dissolves as mobile phase and is dissolved to 1mL, and obtaining solution A after adopting 0.22 μm of miillpore filter to filter, it is that 85 ~ 95:15 ~ 5 are separated metrifonate enantiomorph as mobile phase with normal hexane and isopropyl alcohol volume ratio;
3) high performance liquid chromatograph is adopted to detect above-mentioned solution A; Select CHIRALCELIC chiral column during detection, the column temperature of chiral column is 20 DEG C ~ 35 DEG C, normal hexane and isopropyl alcohol volume ratio be 85 ~ 95:15 ~ 5 as mobile phase, flow velocity during detection is 0.7mL/min ~ 1.0mL/min, and wavelength is 207nm.
2. detection method according to claim 1, it is characterized in that: described step 2 and 3) mobile phase also containing ethanol, it is separated with the impurity in water sample metrifonate enantiomorph as mobile phase than for 90:8 ~ 9.5:2 ~ 0.5 with ethanol contend with normal hexane, isopropyl alcohol.
3. detection method according to claim 2, is characterized in that: described step 2 and 3) the volume ratio of normal hexane, isopropyl alcohol and ethanol be 90:8.5:1.5.
4. detection method according to claim 1, is characterized in that: described step 3) detection time flow velocity be 1.0mL/min.
5. detection method according to claim 1, is characterized in that: described step 3) column temperature be 25 DEG C.
6. detection method according to claim 1, is characterized in that: described step 3) the filler of CHIRALCELIC chiral column be 5 μm of Silica Surface coating celluloses-three [3,5-dichlorophenyl carbamate].
7. detection method according to claim 1, is characterized in that: described step 1) HLB solid phase extraction column be through the activation of methyl alcohol+water.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU1709824C (en) * | 1989-12-22 | 1995-10-20 | Государственный научно-исследовательский институт "Химаналит" | Method of preparing indicator paper for organophosphorus pesticide assay |
| US20070148719A1 (en) * | 2005-12-23 | 2007-06-28 | Industrial Technology Research Institute | Bioassay element and its producing method |
| CN102507820A (en) * | 2011-10-18 | 2012-06-20 | 山东农业大学 | Method for detecting trichlorfon and monocrotophos |
| CN102628844A (en) * | 2012-04-09 | 2012-08-08 | 湖南省食品药品检验研究院 | Content determining method for trichlorfon in dried fish |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU1709824C (en) * | 1989-12-22 | 1995-10-20 | Государственный научно-исследовательский институт "Химаналит" | Method of preparing indicator paper for organophosphorus pesticide assay |
| US20070148719A1 (en) * | 2005-12-23 | 2007-06-28 | Industrial Technology Research Institute | Bioassay element and its producing method |
| CN102507820A (en) * | 2011-10-18 | 2012-06-20 | 山东农业大学 | Method for detecting trichlorfon and monocrotophos |
| CN102628844A (en) * | 2012-04-09 | 2012-08-08 | 湖南省食品药品检验研究院 | Content determining method for trichlorfon in dried fish |
Non-Patent Citations (6)
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Application publication date: 20160210 |