CN107255690A - A kind of method of liquid chromatogram measuring malachite green - Google Patents
A kind of method of liquid chromatogram measuring malachite green Download PDFInfo
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- CN107255690A CN107255690A CN201710544860.5A CN201710544860A CN107255690A CN 107255690 A CN107255690 A CN 107255690A CN 201710544860 A CN201710544860 A CN 201710544860A CN 107255690 A CN107255690 A CN 107255690A
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- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
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- 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
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- G01N30/04—Preparation or injection of sample to be analysed
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Abstract
The invention discloses a kind of method of liquid chromatogram measuring malachite green, comprise the following steps：1) leucogentian violet standard working solution is prepared；2) sample pre-treatments；3) liquid collected by step 2 is subjected to high performance liquid chromatography measure.The method of the liquid chromatogram measuring malachite green is the improvement based on the pre-treating methods of national standard GB/T 20,361 2006, and cumbersome rotary evaporation step is instead of with the mode for merging extraction, and the entirety for reducing experiment takes.The recovery of standard addition of improved method complies fully with national standard 70 110% requirement between 74% 95%, available for the measure that malachite green is remained in actual aquatic products.
Description
Technical field
The present invention relates to biological residue detection technical field, more particularly to a kind of side of liquid chromatogram measuring malachite green
Method.
Background technology
Malachite green is not only a kind of poisonous and can be with carcinogenic triphenylmethane chemicals, and is that one kind can be killed
Parasite and the chemicals of sterilization.It can be with the saprolegniasis and protozoosis of rapid healing fish, while fish can effectively be controlled
The bacteriosises such as gyrodactyliasis, trichodinasis, branchiomycosis, doctylogyrosis, chilodoniasis, the ich of class.Due to market
On in addition to malachite green, can quickly control saprolegniasis without other chemicals, add malachite green it is cheap, operation letter
Single, consumption very little but effect is especially big, but remains incessant after repeated prohibition so being once widely used in aquaculture.
19 early 20th centurys in the end of the century, research finds that malachite green has the side effects such as high toxicity, high residue.Into aquatic products
Fat-soluble leucogentian violet can be metabolized in product, when malachite green enters human body, there can be potential carcinogenic, cause to human body
Abnormal, mutagenic effect.There is China all to forbid malachite green to use and food animal in the country such as America and Europe, must not in aquatic products
Detect malachite green vestigial.In 2002, malachite green was included into China《Food animal disables veterinary drug and its compound inventory》.
The method of current detection aquatic products Malachite Green and its metabolin leucogentian violet residual quantity mainly has：Light splitting
Photometry, thin-layered chromatography, high performance liquid chromatography tandem mass spectrum method, gas chromatography-mass spectrography etc..Although AAS is examined
Survey is more convenient quick but test limit is too high, and sensitivity is low and the degree of accuracy is poor.Thin-layered chromatography also have it is easy to detect efficiently
Advantage but it can not detect leucogentian violet.Although and high performance liquid chromatography tandem mass spectrum method, gas chromatography-mass spectrography are examined
The relatively low, sensitivity of survey limit is high and the degree of accuracy is also high, but operation is excessively cumbersome and cost is especially high, and practicality is too low.So
High performance liquid chromatography is to detect the prefered method of malachite green, because its advantage of lower cost, and with efficient, highly sensitive
The advantage of degree.High performance liquid chromatography is also set to standard detecting method in GB/T19857-2005.
The pre-treatment that stationary phases for HPLC determines aquatic products Malachite Green includes sampling, extraction, removal of impurities, extraction
Transfer, five big steps of elution.
(1) sample：Fish is removed the peel into squama, ridge muscle parts are taken.Sample does not take fish sirloin etc. to contain high-fat position, fatty meeting
Influence the effect of extracting and developing.(2) extract:Generally using acetonitrile as extractant, hydroboration can be typically added in extraction process
Malachite green is reduced into leucomalachite green by potassium solution, adds hydrochloric acid hydrogen amine aqueous solution to prevent the degraded of malachite green.(3) remove
It is miscellaneous：With acid or neutral alumina come the grease in adsorption sample.(4) extraction transfer：In GB/T20361-2006 diethylene glycol (DEG),
Vibrate, and continuously add hydroxylamine hydrochloride solution, p-methyl benzenesulfonic acid solution ammonium acetate buffer to enter in potassium borohydride addition supernatant
Row extracts centrifugation, merges supernatant and repeats once.Layer is removed after adding dichloromethane shaking, stratification toward supernatant
Organic phase, upper solution continuation dichloromethane and acetonitrile extract centrifugation, and organic phase rotary evaporation is merged after centrifugation near dry, is made
Malachite green is extracted in acetonitrile completely.(5) elute：PRS posts are arranged on solid-phase extraction device, upper end connection acidic oxidation
Aluminium post, is activated after pillar with acetonitrile, extract solution is crossed into post, removes acidic alumina column, PRS posts is dried up, with acetonitrile and ammonium acetate
Malachite green is eluted out by solution.Aquatic products Malachite Green High Performance Liquid Chromatography with Fluorescence Detection conditional is in national standard：
Chromatographic column：ODS-C18Post (250mm × 4.6mm), column temperature are 35 degree；Excitation wavelength：265nm, launch wavelength 360nm；Flow velocity is
1.3mL/min, sample size is 20 μ L；Liang Jian etc. experiment condition is：Flow velocity is 1.0mL/min, and sample size is 100 μ L, its inspection
Rising limit is 0.6 μ g/kg.Zhang Zongxiang etc. uses flow velocity for 1.0mL/min, and sample size is 10 μ L, its detection limit 0.75 μ g/kg.
The content of the invention
The technical problem to be solved in the present invention is：Although have that sensitivity is high, detection limit is low due to efficient liquid phase fluorescence method,
Not the features such as not needing expensive mass spectrum, but its pre-treatment step is cumbersome, multiple extraction merging, and to use the rotation wasted time and energy
Evaporation step, greatly reduces detection efficiency, so providing a kind of method of the liquid chromatogram measuring malachite green after optimization.
The present invention solve its technical problem solution be：A kind of method of liquid chromatogram measuring malachite green, including
Following steps：
1) leucogentian violet standard working solution is prepared；
2) sample pre-treatments；
3) liquid collected by step 2 is subjected to high performance liquid chromatography measure.
Due to method GB/T 20361-2006 stationary phases for HPLC, its pre-treatment step is cumbersome, and repeatedly extraction is closed
And, and the rotary evaporation step wasted time and energy is used, greatly reduce detection efficiency.So its pre-treatment is improved, to subtract
Change operating procedure, reduce the operating time, increase detection efficiency.
The step 2 is to optimize on the basis of GB/T19857-2005 and obtain, including：
2-1) extract 5g and smashed sample to pieces in centrifuge tube A, add the leucogentian violet mark that 500 μ L concentration are 50ng/mL
Quasi- working solution, stands 10 minutes, adds 3mL potassium borohydrides, 4mL acetonitriles, and vibration of ultrasonic wave 15 minutes, vibration is mixed 10 minutes,
Again plus 2mL dichloromethane, 2.5mL p-methyl benzenesulfonic acid, 1.5mL hydroxylamine hydrochlorides, 5mL ammonium acetates, vibration mixing 5 minutes；
Aluminum oxide 6.10g, 4.9 grams of sodium chloride 2-2) are added, vibration is mixed 5 minutes, and glass bar stirs；
2-3) the temperature of 5 DEG C of holding, 8000 leaves heart 5min for the first time, takes upper solution to centrifuge tube B；In centrifuge tube A
Middle addition 4mL dichloromethane, leaves the heart 5 minutes second 8000, takes upper solution to centrifuge tube B；Added again in centrifuge tube A
4mL dichloromethane, third time 8000 leaves the heart 5 minutes, takes upper solution to centrifuge tube B；10mL distillations are added in centrifuge tube B
Water, the heart is left 5 minutes with 8000, is then removed supernatant layer and is obtained extract solution；
Solid-phase extraction device 2-4) is terminated under PRS posts, upper end is connected with acidic alumina solid-phase extraction column, by extract solution with
PRS posts are crossed after the activation of 5mL acetonitriles；Extract solution crosses after post removal acidic alumina pillar, dries up PRS posts, by 1.5mL acetonitriles and
PRS posts are crossed after 1.5mL 0.1mol/L ammonium acetate solutions mixing；Collect all post liquid excessively to be determined.
Wherein, step 2-1) described in p-methyl benzenesulfonic acid concentration be 0.05mol/L；Described hydroxylamine hydrochloride solution be by
2.5g hydroxylamine hydrochlorides are dissolved in be made in 10mL water；Described ammonium acetate concentration is 0.125mol/L.
The beneficial effects of the invention are as follows：The method of the liquid chromatogram measuring malachite green is to be based on national standard GB/T
The improvement of 20361-2006 pre-treating methods, instead of cumbersome rotary evaporation step with the mode for merging extraction, reduces reality
The entirety tested takes.The recovery of standard addition of improved method complies fully with the requirement of 70-110% in national standard between 74%-95%,
Available for the measure that malachite green is remained in actual aquatic products.
Brief description of the drawings
Technical scheme in order to illustrate the embodiments of the present invention more clearly, makes required in being described below to embodiment
Accompanying drawing is briefly described.Obviously, described accompanying drawing is a part of embodiment of the present invention, rather than is all implemented
Example, those skilled in the art on the premise of not paying creative work, can also obtain other designs according to these accompanying drawings
Scheme and accompanying drawing.
Fig. 1 is National Standard Method chromatogram；
Fig. 2 is improved method chromatogram of the present invention.
Embodiment
In the examples where no specific technique or condition is specified, according to the technology or condition described by document in the art
(write such as with reference to J. Pehanorm Brookers, what Huang Peitang etc. was translated《Molecular Cloning:A Laboratory guide》, the third edition, Science Press) or
Person is carried out according to product description.Agents useful for same or the unreceipted production firm person of instrument, being can be by the normal of acquisition purchased in market
Advise product.
Embodiment 1：The preparation of standard liquid
0.25mL 100 μ g/mL leucogentian violet standard sample liquid 1-1) are accurately drawn into 25mL brown volumetric flasks,
Interstitial fluid in acetonitrile constant volume, as 1 μ g/mL leucogentian violet standards is used, -18 DEG C of refrigerator is placed in and is kept in dark place.
1-2) the accurate 1.250mL that draws holds in 25mL browns respectively in interstitial fluid from 1 μ g/mL leucogentian violet standard
In measuring bottle, acetonitrile constant volume, as 50.0ng/mL leucogentian violet standard working solution are used.
Embodiment 2：National Standard Method sample pre-treatments
Grass carp is scaled peeling, takes the muscle parts of ridge, put into after being cut into small pieces mixer blend it is homogeneous.
Sample that 5.00g blended is weighed in the 50ng/mL procrypsis that 500 μ L in 50mL centrifuge tube, are added into sample
Malachite green standard working solution, stands 10min, is vibrated after sequentially adding 10mL acetonitriles, 5g acidic aluminas with vortex mixer
2min, is centrifuged with high speed freezing centrifuge and centrifuges 5min in 8000r/min in 5 DEG C, take supernatant to 125mL separatory funnels, then
2mL diethylene glycol (DEG)s, 3mL 0.2mol/L potassium borohydrides are added into separatory funnel, 2min is vibrated.
Continuously add 1.5mL 20% hydroxylamine hydrochloride solution, 2.5mL 0.05mol/L p-methyl benzenesulfonic acid solution, 5.0mL
0.125mol/L ammonium acetate buffer solutions in 50mL centrifuge tubes, add 10mL acetonitriles after vibration 2min, then vibrate after 2min
5min is centrifuged, upper liquid merges in 125mL separatory funnels, and repeat this operation once.
20mL dichloromethane, band plug acutely shaking 2min, then stratification, transfer lower floor solution are added into separatory funnel
In 250mL eggplant-shape bottle, then the addition 5mL acetonitriles in separatory funnel, 10mL dichloromethane, 2min is shaken, and will be all molten
Liquid is gone in 50mL centrifuge tube, and 8000r/min centrifuges 5min again, merges lower floor's solution in eggplant-shape bottle, and 45 degree of rotations are steamed
A surplus drop is sent to, with 2.5mL acetonitrile dissolved residues.
Embodiment 3：The sample pre-treatments of improved method
Grass carp is scaled peeling, takes the muscle parts of ridge, put into after being cut into small pieces mixer blend it is homogeneous.
2-1) extract 5g and smashed sample to pieces in centrifuge tube A, add the leucogentian violet mark that 500 μ L concentration are 50ng/mL
Quasi- working solution, stands 10 minutes, adds 3mL potassium borohydrides, 4mL acetonitriles, and vibration of ultrasonic wave 15 minutes, vibration is mixed 10 minutes,
Again plus 2mL dichloromethane, 2.5mL p-methyl benzenesulfonic acid, 1.5mL hydroxylamine hydrochlorides, 5mL ammonium acetates, vibration mixing 5 minutes；
Aluminum oxide 6.10g, 4.9 grams of sodium chloride 2-2) are added, vibration is mixed 5 minutes, and glass bar stirs；
2-3) the temperature of 5 DEG C of holding, 8000 leaves heart 5min for the first time, takes upper solution to centrifuge tube B；In centrifuge tube A
Middle addition 4mL dichloromethane, leaves the heart 5 minutes second 8000, takes upper solution to centrifuge tube B；Added again in centrifuge tube A
4mL dichloromethane, third time 8000 leaves the heart 5 minutes, takes upper solution to centrifuge tube B；10mL distillations are added in centrifuge tube B
Water, the heart is left 5 minutes with 8000, is then removed supernatant layer and is obtained extract solution；
Solid-phase extraction device 2-4) is terminated under PRS posts, upper end is connected with acidic alumina solid-phase extraction column, by extract solution with
PRS posts are crossed after the activation of 5mL acetonitriles；Extract solution crosses after post removal acidic alumina pillar, dries up PRS posts, by 1.5mL acetonitriles and
PRS posts are crossed after 1.5mL 0.1mol/L ammonium acetate solutions mixing；Collect all post liquid excessively to be determined.
Ammonium acetate buffer solution (0.125mol/L)：Weigh 9.64g anhydrous acetic acid ammoniums to be dissolved in 1000mL distilled water, 4
DEG C preserve.
Ammonium acetate buffer solution (0.1mol/L)：7.71g anhydrous acetic acid ammoniums are weighed to be dissolved in 1000mL distilled water.
Solution of potassium borohydride (0.2mol/L)：Weigh 0.54g potassium borohydride fishes to be dissolved in 50mL distilled water, now with existing
With.
20% hydroxylamine hydrochloride solution：12.5g hydroxylamine hydrochlorides are weighed to be dissolved in 50mL distilled water.
P-methyl benzenesulfonic acid solution (0.05mol/L)：0.95g p-methyl benzenesulfonic acid is weighed to be dissolved in 100mL distilled water.
Embodiment 4：High performance liquid chromatography is determined
3-1) chromatographic condition
Chromatographic column：Short column：XB-C18Post, internal diameter 4.6*150mm, 5 μm of granularity；Long column：Athena C18- WP, internal diameter 4.6*
250mm, 5 μm of granularity；
Mobile phase：Acetonitrile+0.125mol/L ammonium acetate buffer solutions=80+20 (volume fraction)；
Flow velocity：1.3mL/min, sample size：20μL；
Column temperature：35 DEG C, excitation wavelength：265nm, launch wavelength：360nm.
3-2) chromatographic determination
According to chromatographic condition, respectively to leucogentian violet standard working solution, National Standard Method sample and improved method sample extraction
Liquid carries out chromatography, record retention time and peak area, and qualitative according to the retention time of standard working solution, external standard is legal
Amount.Fig. 1 is obtained for National Standard Method chromatogram, Fig. 2 is improved method chromatogram.
Measurement result is as follows：
Grass carp sample determines malachite green content National Standard Method and improved method contrast table
The recovery of standard addition that National Standard Method is understood according to upper table and Fig. 1 and Fig. 2 is 92%, and relative standard deviation is
3.67%；And improved method recovery of standard addition is 95%, relative standard deviation is 2.03%.Require to reclaim in GB/T20361-2006
Rate is 70%~110%, and both of the above all meets and relative standard deviation is smaller.Wherein improved method detection has subtracted rotary evaporation
This cumbersome operation so that spend the time less, detection, which is got up, more to be facilitated, and cost is lower.
The better embodiment to the present invention is illustrated above, but the invention is not limited to the implementation
Example, those skilled in the art can also make a variety of equivalent modifications or replace on the premise of without prejudice to spirit of the invention
Change, these equivalent modifications or replacement are all contained in the application claim limited range.
Claims (4)
1. a kind of method of liquid chromatogram measuring malachite green, it is characterised in that comprise the following steps：
1) leucogentian violet standard working solution is prepared；
2) sample pre-treatments, it includes step：
2-1) extract 5g and smashed sample to pieces in centrifuge tube A, add the leucogentian violet standard work that 500 μ L concentration are 50ng/mL
Make liquid, stand 10 minutes, add 3mL potassium borohydrides, 4mL acetonitriles, vibration of ultrasonic wave 15 minutes, vibration mixing 10 minutes, then add
2mL dichloromethane, 2.5mL p-methyl benzenesulfonic acid, 1.5mL hydroxylamine hydrochlorides, 5mL ammonium acetates, vibration are mixed 5 minutes；
Aluminum oxide 6.10g, 4.9 grams of sodium chloride 2-2) are added, vibration is mixed 5 minutes, and glass bar stirs；
2-3) the temperature of 5 DEG C of holding, 8000 leaves heart 5min for the first time, takes upper solution to centrifuge tube B；Add in centrifuge tube A
Enter 4mL dichloromethane, leave the heart 5 minutes second 8000, take upper solution to centrifuge tube B；Again 4mL is added in centrifuge tube A
Dichloromethane, third time 8000 leaves the heart 5 minutes, takes upper solution to centrifuge tube B；10mL distilled water is added in centrifuge tube B,
The heart is left with 8,000 5 minutes, is then removed supernatant layer and is obtained extract solution；
Solid-phase extraction device 2-4) is terminated under PRS posts, upper end is connected with acidic alumina solid-phase extraction column, by extract solution with 5mL
PRS posts are crossed after acetonitrile activation；Extract solution crosses removal acidic alumina pillar after post, PRS posts is dried up, by 1.5mL acetonitriles and 1.5mL
0.1mol/L ammonium acetate solutions mixing after cross PRS posts；Collect all post liquid excessively to be determined；
3) collected post liquid of crossing is subjected to high performance liquid chromatography measure.
2. the method for liquid chromatogram measuring malachite green according to claim 1, it is characterised in that step 2-1) described in
P-methyl benzenesulfonic acid concentration is 0.05mol/L.
3. the method for liquid chromatogram measuring malachite green according to claim 1, it is characterised in that step 2-1) described in
Hydroxylamine hydrochloride solution is to be dissolved in being made in 10mL water by 2.5g hydroxylamine hydrochlorides.
4. the method for liquid chromatogram measuring malachite green according to claim 1, it is characterised in that step 2-1) described in
Ammonium acetate concentration is 0.125mol/L.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108152493A (en) * | 2017-12-19 | 2018-06-12 | 广州安诺科技股份有限公司 | The method for detecting aquatic products Malachite Green |
| CN108776188A (en) * | 2018-04-26 | 2018-11-09 | 许昌学院 | A kind of pre-treating method of aquatic products Malachite Green residue detection |
| CN109633045A (en) * | 2018-12-20 | 2019-04-16 | 广州广电计量检测股份有限公司 | A kind of method that Liquid Chromatography-Tandem Mass Spectrometry measures 6 kinds of pigment residue amounts in aquatic products simultaneously |
| CN109655549A (en) * | 2019-01-24 | 2019-04-19 | 梧州市食品药品检验所 | A kind of method of quick detection fish Malachite Green |
| CN110208441A (en) * | 2019-01-17 | 2019-09-06 | 广西科技大学 | The rapidly extracting and detection method of concealed malachite green in fresh-water fishes |
| CN110221062A (en) * | 2019-07-01 | 2019-09-10 | 郑州中道生物技术有限公司 | A kind of aquatic products Malachite Green rapid detection method |
| CN110501450A (en) * | 2019-09-25 | 2019-11-26 | 厦门鉴科检测技术有限公司 | The detection method of brilliant green in soil |
-
2017
- 2017-07-06 CN CN201710544860.5A patent/CN107255690A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108152493A (en) * | 2017-12-19 | 2018-06-12 | 广州安诺科技股份有限公司 | The method for detecting aquatic products Malachite Green |
| CN108776188A (en) * | 2018-04-26 | 2018-11-09 | 许昌学院 | A kind of pre-treating method of aquatic products Malachite Green residue detection |
| CN109633045A (en) * | 2018-12-20 | 2019-04-16 | 广州广电计量检测股份有限公司 | A kind of method that Liquid Chromatography-Tandem Mass Spectrometry measures 6 kinds of pigment residue amounts in aquatic products simultaneously |
| CN110208441A (en) * | 2019-01-17 | 2019-09-06 | 广西科技大学 | The rapidly extracting and detection method of concealed malachite green in fresh-water fishes |
| CN109655549A (en) * | 2019-01-24 | 2019-04-19 | 梧州市食品药品检验所 | A kind of method of quick detection fish Malachite Green |
| CN110221062A (en) * | 2019-07-01 | 2019-09-10 | 郑州中道生物技术有限公司 | A kind of aquatic products Malachite Green rapid detection method |
| CN110501450A (en) * | 2019-09-25 | 2019-11-26 | 厦门鉴科检测技术有限公司 | The detection method of brilliant green in soil |
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Application publication date: 20171017 |