CN104198630A - Preparation method and application of amitraz molecular imprinting monolithic column - Google Patents
Preparation method and application of amitraz molecular imprinting monolithic column Download PDFInfo
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Abstract
The invention discloses a preparation method and application of an amitraz molecular imprinting monolithic column. The preparation method comprises the following steps: by taking amitraz as a template molecule, dissolving the template molecule into a mixed solution of acetonitrile and dodecyl alcohol, adding a functional monomer, pre-polymerizing at a low temperature, further adding a cross-linking agent and an initiator, introducing nitrogen, filling into a chromatographic column hollow tube of which the lower end is already sealed, sealing the upper end of the chromatographic column hollow tube, and initializing polymerization, thereby obtaining the molecular imprinting monolithic column. After the functional monomer, a pore-foaming agent and the template molecule which are not polymerized are washed off from the column by using a mixed solution of methanol and acetic acid, the molecular imprinting monolithic column which has a good adsorption effect and an enrichment effect on amitraz is obtained. Compared with a conventional body polymerization method, the preparation method has the characteristics that the preparation method is simple and convenient, the aftertreatment is simple, the recognition property is good, the cost is low, required instruments and reaction conditions are easy to achieve, and the like. The molecular imprinting monolithic column prepared by using the preparation method is capable of separating and detecting residual amitraz in foods.
Description
Technical field
The present invention relates to analytical chemistry field, specifically a kind of preparation method of Amitraz molecular engram integral column and the application aspect Amitraz retention analysis in food thereof.
Background technology
Amitraz is wide spectrum acaricide, moderate toxicity, the main activity that suppresses monoamine oxidase, have tag, food refusal and repellent action, also there are certain interior suction, fumigation action, all effective to the polypide of each stage of development of Tetranychidae, the mite class developing immunity to drugs for other acaricides is also effective, and can long-term control evil mite quantity go up after medication.Amitraz is widely used in preventing and treating the harmful mite on the crops such as fruit tree, vegetables, tealeaves, cotton, soybean and beet, if to becoming mite mite and mite ovum to have very strong action of contace poison and good penetration, also have certain interior suction, fumigation action.Homoptera pest is also had to good drug effect, also can be used for anti-eliminating aphis, the insect such as bollworm, red worm septempunctata simultaneously.Honeybee mite is also had to good prevention effect, also for the preventive and therapeutic effects of the external acarian of livestock and other evil mites, to vermins such as ox, sheep, pig, rabbits, as each stage polypide of mite, tick, lice etc. also has splendid killing effect.The drug effect of this medicine is long, once at home and abroad uses in a large number.But research is found Amitraz and metabolic product thereof human body is had to potential harm, can suppress to breathe, cause the problems such as nervous centralis decline and renal failure, and it can or cause poisoning by the transmission of food chain after skin absorbs.Therefore many countries forbid that Amitraz uses on honeybee acarid control in the world.But due to Amitraz low price, recent year beekeeper uses the trend of Amitraz control honeybee mite to increase year by year, causes Amitraz residual quantity severe overweight in honey, has influence on the honey export trade and the health of China.In order to control the residual quantity of Amitraz in food, must carry out separation and detection to the content of Amitraz in food, to guarantee food security.
The common methods that detects Amitraz has vapor-phase chromatography, liquid phase chromatography and gas chromatography-mass spectroscopy.Vapor-phase chromatography need to be carried out derivatization to Amitraz, and sample preparation process is more loaded down with trivial details; Gas chromatography-mass spectrography instrument and equipment is had relatively high expectations, expensive, and general laboratory is difficult to bear; And liquid phase chromatography pre-treatment is relatively simple, but need to buy specific chromatographic column, and price is relatively high, though and the chromatographic column of biological antibody can be identified target molecule specifically, the preparation process complexity of antibody, cost is high, manufacturing cycle is long, poor to the tolerance of environmental baseline.Therefore set up special and Amitraz analytical approach is imperative fast.
Molecular imprinting is a kind of polymkeric substance technology of preparing that can mate completely with template molecule on space and binding site, has structure effect precordainment, identification specificity and practicality widely.Molecularly imprinted polymer has stability and reproducible, stable performance, resistance to extreme environment ability is strong, preparation process is easy and the feature such as with low cost.Therefore, molecularly imprinted polymer is widely used in the filler of solid-phase extraction column and chromatographic column.Along with the development of molecular imprinting, the molecular engram integral column that molecular engram and chromatogram technology of preparing are melted into a whole becomes the focus of research gradually.Integral post is carried out the fixing phase of in-situ polymerization preparation in post by organic or inorganic polymerization, can greatly reduce separating property that filling heterogeneity produces and the difference of parameter.Molecular engram integral column is combined with liquid phase chromatography analytical method can be convenient, fast, carry out exactly the detection of low-residual in food, to improve the analyzing and testing level of residue in China's food, guarantee food security, the development of promotion economic trade also tool is of great significance.
Summary of the invention
The object of the invention is to overcome the deficiency of existing Amitraz detection technique, adopt situ aggregation method to prepare the molecularly imprinted polymer of Amitraz, and then prepare Amitraz is had to good recognition performance, can be used for the bionical identification of Amitraz and the Amitraz molecular engram integral column of selective adsorption in food, this molecular engram integral column has the advantages such as identity is single-minded, detection sensitivity is high, adsorbance is high, preparation process is simple, with low cost.
A preparation method for Amitraz molecular engram integral column, preparation process is:
(1) template molecule is dissolved in pore-foaming agent, adds function monomer, after ultrasonic processing 5min mixes, put into 4 DEG C of refrigerators and carry out prepolymerization 24h, obtain prepolymerization system;
Described template molecule is Amitraz, described pore-foaming agent is that volume ratio is 1: the mixed solvent of the acetonitrile of 2-5 and dodecanol composition, and described function monomer is the combination of any one or two kinds in methacrylic acid, trifluoromethyl acrylate, acrylamide, 4-vinylpridine and methacrylate; The mol ratio of described template molecule and function monomer is 1: 3-8, and the volumetric molar concentration of template molecule in pore-foaming agent is 30mmol/L-70mmol/L;
(2) in the prepolymerization system making to step 1), add crosslinking chemical and initiating agent, ultrasonic processing 5min, after fully mixing, pass into nitrogen 10min-30min, then, the mixed solution of gained is injected to the chromatographic column void column pipe of bottom sealing, and seal the other end of chromatographic column, for subsequent use;
Described crosslinking chemical is any one in trimethylol-propane trimethacrylate or ethylene glycol dimethacrylate, and the addition of crosslinking chemical adds 5 times of function monomer molar weight for step 1); Described initiating agent is benzoyl peroxide or DMA, and the 0.2-0.4 that addition adds function monomer molar weight for step 1) doubly;
(3) mixed solution step (2) being made is placed under 20 DEG C of-80 DEG C of temperature conditions and carries out initiated polymerization, and polymerization time is 12h-72h, obtains molecular engram integral column;
(4) molecular engram integral column of step (3) is connected with constant-flux pump, adopt cleansing solution to carry out wash-out to molecular engram integral column, timing during this time samples the eluent of new outflow, and with the content of Amitraz in high-efficient liquid phase chromatogram technique analysis eluent, until stop wash-out in eluent during without Amitraz, then sealing is preserved, and obtains Amitraz molecular engram integral column.
Initiation temperature in described step 3) is 30 DEG C-40 DEG C, and polymerization time is 20h-48h.
Eluent in described step 4) is methyl alcohol-acetic acid mixed solvent, and described methyl alcohol and the volume ratio of acetic acid are 9: 1,8: 2 or 7: 3.
Beneficial effect
1. molecular engram integral column provided by the present invention has good recognition performance to Amitraz, can be for bionical identification, selective adsorption and the detection of Amitraz in food, to meet the needs that in complex matrices, trace residue quality testing is surveyed.Its preparation process is simple, and good stability is highly sensitive, while being applicable to grass-roots unit's sample detection, uses.
2. the molecular engram integral column in the present invention has the following advantages compared with common chromatographic column:
1. the molecularly imprinted polymer that adopted, have preparation easy, quick, to features such as extreme environment tolerance are strong.
2. material requested is easy to get, and is conventional raw material and reagent, cheap being easy to get.
3. molecular engram integral column is with low cost, more cheap than other chromatographic column, synthetic polymer treatment is simple, without grinding and dress post, aftertreatment can not destroy the structure of polymkeric substance, and gained monolithic column stationary phase has macroporous structure can ensure that mass transfer rate is fast, post is pressed lower.
4. molecular engram integral column has specific recognition capability to template molecule, and selectivity is strong, and detection sensitivity is high, and whole preparation process is simple, time saving and energy saving, is easy to popularize.
5. molecular engram integral column stability of the present invention is better, and various article used all have longer storage life.
Embodiment
Following examples can make the present invention of those skilled in the art complete understanding, but do not limit the present invention in any way.
A preparation method for Amitraz molecular engram integral column, comprises the following steps:
(1) template molecule is dissolved in pore-foaming agent, adds function monomer, after ultrasonic processing 5min mixes, put into 4 DEG C of refrigerators and carry out prepolymerization 24h, obtain prepolymerization system;
Described template molecule is Amitraz, described pore-foaming agent is that volume ratio is 1: the mixed solvent of the acetonitrile of 2-5 and dodecanol composition, and described function monomer is the combination of any one or two kinds in methacrylic acid, trifluoromethyl acrylate, acrylamide, 4-vinylpridine and methacrylate; The mol ratio of described template molecule and function monomer is 1: 3-8, and the volumetric molar concentration of template molecule in pore-foaming agent is 30mmol/L-70mmol/L;
(2) in the prepolymerization system making to step (1), add crosslinking chemical and initiating agent, ultrasonic processing 5min, after fully mixing, pass into nitrogen 10min-30min, then, the mixed solution of gained is injected to the chromatographic column void column pipe of bottom sealing, and seal the other end of chromatographic column, for subsequent use;
Described crosslinking chemical is any one in trimethylol-propane trimethacrylate or ethylene glycol dimethacrylate, and the addition of crosslinking chemical adds 5 times of function monomer molar weight for step (1); Described initiating agent is benzoyl peroxide or DMA, and the 0.2-0.4 that addition adds function monomer molar weight for step (1) doubly;
(3) mixed solution step (2) being made is placed under 20 DEG C of-80 DEG C of temperature conditions and carries out initiated polymerization, and polymerization time is 12h-72h, obtains molecular engram integral column;
(4) molecular engram integral column that adopts methyl alcohol and acetic acid mixed liquor to obtain step (3) carries out wash-out, timing during this time samples the eluent of new outflow, and analyze the content of Amitraz in eluent, until stop wash-out in eluent during without Amitraz, then sealing is preserved, and obtains Amitraz molecular engram integral column.
Initiation temperature in described step (3) is 30 DEG C-40 DEG C, and polymerization time is 20h-48h.
Eluent in described step 4) is the mixed solution of methyl alcohol and acetic acid composition, and in mixed solution, the percent by volume of methyl alcohol is 70%-90%.
The Amitraz molecular engram integral column of preparing according to said method, can be for the mensuration of Amitraz in sample extracting solution, its using method is, molecular engram integral column (50mm × 4.6mm) and the PEEK joint of high performance liquid chromatograph are connected, kind and the ratio of setting mobile phase are acetonitrile: water: the ammoniacal liquor that mass concentration is 0.28% (79: 20: 1, V/V/V), detect wavelength 289nm, sample size 20
μl, column temperature is room temperature, flow velocity 1mL/min.
embodiment 1
(1) preparation of Amitraz molecular engram integral column
Take template molecule (Amitraz) 0.3mmol and be dissolved in 6mL pore-foaming agent acetonitrile and dodecanol mixed solution (1: 2, V/V) in, add function monomer methacrylic acid 0.9mmol, place 24h in 4 DEG C of refrigerators, monomer and template molecule are fully acted on, complete pre-polymerization process, obtain prepolymerization system.Then add successively crosslinking chemical trimethylol-propane trimethacrylate 4.5mmol and initiating agent benzoyl peroxide and N, the each 0.18mmol of accelerine, after ultrasonic 5min, pass into nitrogen 30min, mixed solution is injected to the chromatographic column void column pipe of bottom sealing, the then other end of sealing column.Formed mixed solution is placed in to initiated polymerization 24h at 30 DEG C, after polymerization finishes, open the sealing at post two ends, cover sieve plate, screw the bolt at chromatographic column two ends, receive on constant-flux pump, with methyl alcohol-acetic acid mixed liquor (7: 3, V/V) integral post is rinsed, timing during this time samples the eluent of new outflow, and with the content of Amitraz in high-efficient liquid phase chromatogram technique analysis eluent, until stop wash-out in eluent during without Amitraz, then sealing is preserved, and obtains Amitraz molecular engram integral column.The preparation of blank molecular engram integral column is except not adding template molecule, and other operations are the same.
(2) sign of molecular engram integral column
Adopt high performance liquid chromatography to characterize the trace effect of molecular engram integral column, the chromatographic condition of measuring Amitraz is: molecular engram integral column (50mm × 4.6mm), and mobile phase is acetonitrile: water: 0.28% ammoniacal liquor (79: 20: 1, V/V/V), detect wavelength 289nm, sample size 20
μl, column temperature is room temperature, flow velocity 1mL/min.Measure the dead time with acetone.
According to the result of chromatographic determination, the capacity factor measure of calculation template molecular engram integral column and blank molecular engram integral column, and calculate the trace factor of molecular engram integral column.Capacity factor measure
k=(
t r-
t 0)/
t 0(in formula
t rfor the retention time of component,
t 0for the dead time of acetone mensuration), trace factor IF=
k mIP/
k nIP(in formula
k mIP,
k nIPbe respectively the capacity factor measure of trace post and blank post, as shown in table 1.
the capacity factor measure of table 1 molecular engram integral column and the trace factor
| Medicine name | k MIP | k NIP | IF |
| Amitraz | 3.02 | 1.03 | 2.93 |
The foundation of Amitraz typical curve: precision takes Amitraz, making its concentration with acetonitrile constant volume is 10
μg/L, 20
μg/L, 50
μg/L, 100
μg/L, 200
μg/L, 500
μg/L and 1000
μg/L.6 repetitions of each concentration, repeat 6 days, do typical curve, and typical curve equation is: Y=95.08X+0.24, in formula, Y is peak area, X be Amitraz in solution concentration (
μg/L), correlation coefficient r is 0.99995.
(3) detection of molecular engram integral column to actual sample
Respectively by 1000
μg/L Amitraz standard solution adds in honey and pig liver tissue, makes Amitraz concentration in sample reach respectively 10
μg/kg, 50
μg/kg and 100
μg/kg, sample after extracting and purifying, the concentration of Amitraz in working sample, each concentration repeats 6 times, calculates its recovery.
The extraction of Amitraz in honey: take sample (honey fully mixes) 5g(and be accurate to 0.01g) put into 50mL tool plug centrifuge tube, add 5.0mL sodium hydroxide solution (0.1mol/L) whirlpool and mix 1min, add again 10mL normal hexane and 5mL isopropyl alcohol, whirlpool mixes 1min, in the centrifugal 5min of 3000r/min, supernatant is transferred in another centrifuge tube.In 35 DEG C of-40 DEG C of water-baths, rotary evaporation is concentrated into dryly, with 0.5mL acetonitrile dissolved residue, is transferred to 1.5mL centrifuge tube; Add 0.5mL water dissolved residue, merge and be transferred to 1.5mL centrifuge tube, in the centrifugal 5min of 10000 r/min, solution is crossed 0.45 μ m filter membrane, for the mensuration of sample Amitraz.
The extraction of Amitraz in pig liver: pig liver takes test portion 5g(and is accurate to 0.01g after shredding and mixing) in tool plug centrifuge tube, add alkaline aqueous solution (water intaking 1000mL, with the sodium hydroxide solution tune pH to 9.0 of 1 mol/L) 10mL, whirlpool mixes, the centrifugal 10min of 4200r/min, gets supernatant in another centrifuge tube, and residue adds alkaline aqueous solution 10mL, repeat to extract once, merge twice supernatant.In 70 DEG C of thermostatic drying chambers, leave standstill 50min, cooling, add normal hexane 10mL, whirlpool mixes, leave standstill 5min, the centrifugal 10min of 4200r/min, gets upper strata normal hexane in round-bottomed flask, and subnatant adds normal hexane 5mL re-extract once, merge normal hexane layer liquid twice, turn and be evaporated to dryly in 45 DEG C, dissolve residue with normal hexane 2.0mL, then cross 0.45
μm filter membrane, for the mensuration of sample Amitraz.
In sample, the recovery of Amitraz is as shown in table 2.
the recovery of table 2 molecular engram integral column in different substrates
| Medicament categories | Mark-on concentration ( μg/kg） | The honey recovery (%) | The recovery in pig liver (%) |
| Amitraz | 10 | 94.3±1.7 | 80.2±4.3 |
| ? | 50 | 95.4±2.4 | 95.5±2.2 |
| ? | 100 | 103.2±1.3 | 86.8±3.7 |
embodiment 2
(1) preparation of Amitraz molecular engram integral column and sign
Basic process is with embodiment 1, pore-foaming agent is 5mL acetonitrile and dodecanol (1: 3, V/V) mixed solution, the prepolymerization time is 48h, function monomer trifluoromethyl acrylate 2.4mmol, crosslinking chemical trimethylol-propane trimethacrylate 12mmol, initiating agent benzoyl peroxide and N, the each 0.24mmol of accelerine, polymerization temperature is 35 DEG C, time is 20h, template molecule eluent is methyl alcohol-acetic acid mixed liquor (8: 2, V/V), the capacity factor measure of gained integral post and the trace factor are in table 3, gained typical curve equation is: Y=94.23X+0.35, correlation coefficient r is 0.99996.
the capacity factor measure of table 3 molecular engram integral column and the trace factor
| ? | k MIP | k NIP | IF |
| Amitraz | 2.37 | 0.95 | 2.49 |
(2) detection of molecular engram integral column to actual sample
Molecular engram integral column is connected in liquid chromatograph, adopts high performance liquid chromatography to measure (each sample replicate determination 3 times) to the Amitraz in sample, chromatographic condition is with embodiment 1, and calculates its recovery, the results are shown in Table 4.
the recovery of table 4 molecular engram integral column in different substrates
| Medicine name | Mark-on concentration ( μg/kg） | The recovery in honeybee (%) | The recovery in pig liver (%) |
| Amitraz | 10 | 90.2±4.2 | 83.4±3.3 |
| ? | 50 | 95.5±3.9 | 85.2±4.5 |
| ? | 100 | 97.8±2.4 | 87.6±2.6 |
embodiment 3
(1) preparation of Amitraz molecular engram integral column and sign
Basic process is with embodiment 1, pore-foaming agent is 8mL acetonitrile and dodecanol (1: 5, V/V) mixed solution, the prepolymerization time is 24h, function monomer is 4-vinylpridine 1.5mmol, crosslinking chemical is trimethylol-propane trimethacrylate 7.5mmol, initiating agent is benzoyl peroxide and N, the potpourri of accelerine, wherein, benzoyl peroxide 0.3 mmol, N, accelerine 0.15mmol, polymerization temperature is 40 DEG C, time is 36h, template molecule eluent is methyl alcohol-acetic acid mixed liquor (9: 1, V/V), it is as shown in the table 5 for the capacity factor measure of gained integral post and the trace factor, gained typical curve equation is: Y=96.41X+0.29, correlation coefficient r is 0.99994.
the column capacity of table 5 molecular engram integral column and the trace factor
| Medicine name | k MIP | k NIP | The trace factor |
| Amitraz | 3.22 | 1.21 | 2.7 |
(2) detection of molecular engram integral column to actual sample
Adopt high performance liquid chromatography to carry out measuring (each sample replicate determination 3 times) to the Amitraz in eluent, chromatographic condition, with embodiment 1, calculates its recovery, the results are shown in Table 6.
the recovery of table 6 molecular engram integral column in different substrates
| Medicine name | Mark-on concentration ( μg/kg） | The recovery in honey (%) | The recovery in pig liver (%) |
| Amitraz | 10 | 90.8±2.1 | 87.2±2.7 |
| Amitraz | 50 | 94.3±2.5 | 89.4±2.3 |
| Amitraz | 100 | 93.1±1.3 | 90.1±1.8 |
Claims (4)
1. the preparation method of Amitraz molecular engram integral column, is characterized in that, preparation process is:
(1) acetonitrile and dodecanol are hybridly prepared into mixed solvent by the ratio that is, 1:2-5 according to volume ratio, then Amitraz is dissolved wherein, add afterwards function monomer, after ultrasonic processing 5min mixes, put into 4 DEG C of refrigerator prepolymerization 24h, obtain prepolymerization system;
Described function monomer is the combination of any one or two kinds in methacrylic acid, trifluoromethyl acrylate, acrylamide, 4-vinylpridine and methacrylate; The mol ratio of described Amitraz and function monomer is 1:3-8, and the volumetric molar concentration of Amitraz in mixed solvent is 30mmol/L-70mmol/L;
(2) in the prepolymerization system making to step (1), add crosslinking chemical and initiating agent, ultrasonic processing 5min, after fully mixing, pass into nitrogen 10min-30min, then the mixed solution of gained is injected to the chromatographic column void column pipe of bottom sealing, and seal the other end of chromatographic column, for subsequent use;
Described crosslinking chemical is any one in trimethylol-propane trimethacrylate or ethylene glycol dimethacrylate, and the addition of crosslinking chemical adds 5 times of function monomer molar weight for step (1); Described initiating agent is benzoyl peroxide or DMA, and the 0.2-0.4 that addition adds function monomer molar weight for step (1) doubly;
(3) chromatographic column step (2) being filled is placed under 20 DEG C of-80 DEG C of temperature conditions carries out initiated polymerization, and polymerization time is 12h-72h, obtains molecular engram integral column;
(4) molecular engram integral column that adopts cleansing solution to obtain step (3) carries out wash-out, timing during this time samples the eluent of new outflow, and with the content of Amitraz in high-efficient liquid phase chromatogram technique analysis eluent, until stop wash-out in eluent during without Amitraz, then sealing is preserved, and obtains Amitraz molecular engram integral column.
2. the preparation method of Amitraz molecular engram integral column according to claim 1, is characterized in that: the initiation temperature in described step (3) is 30 DEG C-40 DEG C, and polymerization time is 20h-48h.
3. the preparation method of Amitraz molecular engram integral column according to claim 1, is characterized in that: the eluent in described step 4) is the mixed solution of methyl alcohol and acetic acid composition, and in mixed solution, the percent by volume of methyl alcohol is 70%-90%.
4. the application of the Amitraz molecular engram integral column that according to claim 1 prepared by method in the retention analysis of food Amitraz detects.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106093268A (en) * | 2016-08-26 | 2016-11-09 | 佛山市南海东方澳龙制药有限公司 | A kind of detection method of Amitraz content |
| CN112881565A (en) * | 2021-03-05 | 2021-06-01 | 山东新华制药股份有限公司 | HPLC detection method of triphenyldiamidine related substances |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002018466A1 (en) * | 2000-08-30 | 2002-03-07 | Mip Technologies Ab | Method and device for recognition of a target molecule by means of molecularly imprinted polymers |
| WO2002068958A1 (en) * | 2001-02-26 | 2002-09-06 | Klaus Mosbach | Molecularly imprinted scintillation polymers |
| CN1583804A (en) * | 2004-06-10 | 2005-02-23 | 中国农业大学 | Use and preparation of molecular track polymer of sulfonyl urea herbicide |
| CN103884802A (en) * | 2012-12-19 | 2014-06-25 | 中国科学院大连化学物理研究所 | Amnesic shellfish toxin molecularly imprinted monolithic column and application thereof |
-
2014
- 2014-08-28 CN CN201410428364.XA patent/CN104198630B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002018466A1 (en) * | 2000-08-30 | 2002-03-07 | Mip Technologies Ab | Method and device for recognition of a target molecule by means of molecularly imprinted polymers |
| WO2002068958A1 (en) * | 2001-02-26 | 2002-09-06 | Klaus Mosbach | Molecularly imprinted scintillation polymers |
| CN1583804A (en) * | 2004-06-10 | 2005-02-23 | 中国农业大学 | Use and preparation of molecular track polymer of sulfonyl urea herbicide |
| CN103884802A (en) * | 2012-12-19 | 2014-06-25 | 中国科学院大连化学物理研究所 | Amnesic shellfish toxin molecularly imprinted monolithic column and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| JUN MATSUI ET AL: "A Molecularly Imprinted Nicotine-Selective Polymer", 《ANALYTICAL LETTERS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106093268A (en) * | 2016-08-26 | 2016-11-09 | 佛山市南海东方澳龙制药有限公司 | A kind of detection method of Amitraz content |
| CN112881565A (en) * | 2021-03-05 | 2021-06-01 | 山东新华制药股份有限公司 | HPLC detection method of triphenyldiamidine related substances |
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| CN104198630B (en) | 2015-09-30 |
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