CN109839465A - The Solid Phase Extraction detection method of antibiotic in a kind of toffee - Google Patents
The Solid Phase Extraction detection method of antibiotic in a kind of toffee Download PDFInfo
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- CN109839465A CN109839465A CN201910066355.3A CN201910066355A CN109839465A CN 109839465 A CN109839465 A CN 109839465A CN 201910066355 A CN201910066355 A CN 201910066355A CN 109839465 A CN109839465 A CN 109839465A
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- toffee
- antibiotic
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Abstract
The present invention provides a kind of Solid Phase Extraction detection methods of antibiotic in toffee.Toffee ultrafiltration membrane is obtained into toffee sample solution first with acetonitrile-water mixed liquor；Then after magnetic nanocomposites material being added, supernatant will be collected after magnetic Nano material absorption washing using magnet after ultrasonic extraction；After being finally evaporated supernatant using nitrogen evaporator, methanol is added to dissolve sample, sample is analyzed using HPLC- UV detection device, measures the concentration of antibiotic.Compared to the preceding prescription method of traditional ultrafiltration membrane and fiber material, method extraction efficiency of the invention is high, high sensitivity, and the present invention and unused the step of being centrifuged, and operates more simple.
Description
Technical field
The invention belongs to a kind of Solid Phase Extraction detection sides of antibiotic in technical field of food detection more particularly to toffee
Method.
Background technique
Consumption gradually increases milk in people's daily life, safety problem also more and more attention has been paid to.In recent years,
Antibiotic is widely used in aquaculture as antimicrobial and growth accelerator, and abusing for antibiotic will cause antibiotic in milk
Residual can enter human body by food chain, bring health risk.Meanwhile excessive antibiotic can also induce generation antibiotic resistance
Gene accelerates the propagation of antibiotic resistance.Research shows that long-term consumption antibiotic can destroy saponins by human intestinal bacteria balance, reduction is exempted from
Epidemic disease power, in some instances it may even be possible to there is teratogenesis, mutagenesis, carcinogenic adverse effect, therefore detect the antibiotic in toffee there is important meaning
Justice.
Because toffee mesostroma is complicated and antibiotic content is low, it is therefore desirable to use suitable sample-pretreating method to drop
Low matrix interference is simultaneously enriched with antibiotic.Currently, the sample-pretreating method of Extraction of Antibiotics mainly includes in milk
Liquid-phase extraction and Solid Phase Extraction, and the consumption of liquid-phase extraction organic solvent is more, it is environmentally protective, it is difficult to remove matrix interference, and be enriched with
It is ineffective.Then extraction time is long for traditional Solid Phase Extraction.Therefore the Solid Phase Extraction of antibiotic in efficient, sensitive toffee is developed
Detection method has great importance to the safety for guaranteeing toffee.
Summary of the invention
In order to solve organic solvent consumption in toffee sample-pretreating method, greatly, extraction time is long and sensitivity is low is asked
Topic.The present invention provides a kind of Solid Phase Extraction detection methods of antibiotic in efficient, sensitive toffee.
In order to achieve the above-mentioned object of the invention, the invention provides the following technical scheme:
The Solid Phase Extraction detection method of antibiotic in a kind of toffee, it is characterised in that the following steps are included:
(1) 1.0 g toffees are weighed, the ultrafiltration membrane that 100-300 nm is crossed after 8 mL acetonitrile-water mixed solution stirring and dissolvings of addition obtains
Toffee sample solution；
(2) after 20-30 mg magnetic nanocomposites material being added into toffee sample solution, the ultrasound 5 under the conditions of 25-30 DEG C
After min, magnetic Nano material is adsorbed using magnet and outwells supernatant；
(3) magnetic Nano material is inhaled using magnet by after 2 min of magnetic Nano material using eluent supersound washing magnet
Attached collection supernatant；
(4) after supernatant being evaporated using nitrogen evaporator, after 50 μ L methanol of addition dissolve sample, utilize high performance liquid chromatography-
UV detector analyzes sample, measures the concentration of antibiotic.
Preferably, the volume ratio of acetonitrile and water is 1:9-10 in acetonitrile-water mixed solution as described in step (1).
Preferably, ultrafiltration membrane preparation method as described in step (1) are as follows: 1.0 g polyether sulfones are dissolved in 5 mL N- methyl-
Cast-solution is obtained in 2-Pyrrolidone-ionic liquid mixed solution, on a glass and in air by cast-solution paving
After placing 3 min, then glass plate is impregnated into 2-3 h in aqueous solution, the polyether sulfone ultrafiltration that aperture is 100-300 nm is prepared
Film.
Preferably, ionic liquid described in ultrafiltration membrane preparation method is the ionic liquid of imidazoles type.
Preferably, magnetic nanocomposites material preparation method described in step (2) are as follows: by 5.0 g eutectic solvents
Carbonization obtains amino-containing carbon nano-quantum point under the conditions of 200-300 DEG C in nitrogen, by 200 mg carbon nano-quantum points, 300
Mg graphene oxide is scattered in the FeCl of 20 mL, 0.16 mol/L3With the FeCl of 0.08 mol/L2After mixed solution, in 45-60
Ammonium hydroxide is slowly added dropwise under the conditions of DEG C into solution, until after the reaction was continued 3h, magnet is utilized to adsorb magnetic material after system pH is 10
Material, and magnetic nanocomposites material is both obtained after being dried twice with ethyl alcohol, water washing respectively.
Preferably, eutectic solvent described in magnetic nanocomposites material preparation method is choline chloride-urea, sweet tea
Dish alkali-urea, the eutectic solvent containing amino such as choline chloride-glycine；The grain of the magnetic nanocomposites material
Diameter is 200-400 nm.
Preferably, eluent described in step (3) is the methanol-acetonitrile mixed liquor that volume ratio is 1:1-3, the elution
The volume of liquid is 1-1.5 mL.
The method of the present invention high sensitivity, compared with prior art, the solid phase of antibiotic in a kind of toffee of the present invention
Extraction detection method has the advantages that.The present invention uses the ultrafiltration membrane of Ionic Liquid Modified, so that ultrafiltration membrane can not only
A large amount of protein impurities in toffee sample solution are removed, while in turn avoiding impurity blocking ultrafiltration membrane；Using carbon Nano quantum
The more antibiotic of point/grapheme material realize efficient extraction；The step of is carried out by magnetic modification, is avoided using centrifugation for material.Before
Processing method is easy to operate and is without the use of large-scale instrument, and the sensitivity of method combined highly effective liquid chromatogram-UV detector
It is low, quantitative detection can be carried out with the other antibiotic of Donna gram-grade.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, but embodiment is not to the technology of the present invention side
The restriction of case, it is all based on present invention teach that made variation or equivalent replacement, is within the scope of protection of the invention.
Embodiment one
(1) 1.0 g toffees are weighed, cross 100-300 after 8 mL acetonitrile-waters (1:10 volume ratio) mixed solution stirring and dissolving is added
The poly (ether-sulfone) ultrafiltration membrane of the imidazole ion liquid modification of nm obtains toffee sample solution；
(2) after 20 mg magnetic nanocomposites materials are added into toffee sample solution, under the conditions of 30 DEG C after 5 min of ultrasound,
Magnetic Nano material is adsorbed using magnet and outwells supernatant；
(3) utilize the methanol-acetonitrile eluent supersound washing magnet of 1.5 mL 1:1 volume ratios by 2 min of magnetic Nano material
Afterwards, collect supernatant after magnetic Nano material being adsorbed using magnet；
(4) after supernatant being evaporated using nitrogen evaporator, after 50 μ L methanol of addition dissolve sample, utilize high performance liquid chromatography-
UV detector analyzes sample, measurement quinolones, sulfamido, tetracycline antibiotics concentration.
Embodiment two
(1) 1.0 g toffees are weighed, cross 100-300 nm after 8 mL acetonitrile-waters (1:9 volume ratio) mixed solution stirring and dissolving is added
Imidazole ion liquid modification poly (ether-sulfone) ultrafiltration membrane obtain toffee sample solution；
(2) after 20 mg magnetic nanocomposites materials are added into toffee sample solution, under the conditions of 25 DEG C after 5 min of ultrasound,
Magnetic Nano material is adsorbed using magnet and outwells supernatant；
(3) utilize the methanol-acetonitrile eluent supersound washing magnet of 1.5 mL 1:2 volume ratios by 2 min of magnetic Nano material
Afterwards, collect supernatant after magnetic Nano material being adsorbed using magnet；
(4) after supernatant being evaporated using nitrogen evaporator, after 50 μ L methanol of addition dissolve sample, utilize high performance liquid chromatography-
UV detector analyzes sample, measurement quinolones, sulfamido, tetracycline antibiotics concentration.
Comparative example 1
(1) 1.0 g toffees are weighed, cross 100-300 nm after 8 mL acetonitrile-waters (1:9 volume ratio) mixed solution stirring and dissolving is added
The poly (ether-sulfone) ultrafiltration membrane of commercialization obtain toffee sample solution；
(2) after the active carbon of 20 mg commercialization is added into toffee sample solution, under the conditions of 25 DEG C after 5 min of ultrasound, 8000
Supernatant is outwelled after being centrifuged 5min under the conditions of rpm；
(3) after using 2 min of methanol-acetonitrile eluent supersound washing active carbon of 1.5 mL 1:2 volume ratios, 000 rpm condition
Supernatant is collected after lower centrifugation 5min；
(4) after supernatant being evaporated using nitrogen evaporator, after 50 μ L methanol of addition dissolve sample, utilize high performance liquid chromatography-
UV detector analyzes sample, measurement quinolones, sulfamido, tetracycline antibiotics concentration.
Comparative example 2
(1) 1.0 g toffees are weighed, cross 100-300 nm after 8 mL acetonitrile-waters (1:9 volume ratio) mixed solution stirring and dissolving is added
The poly (ether-sulfone) ultrafiltration membrane of commercialization obtain toffee sample solution；
(2) after the aluminum oxide of 20 mg commercialization is added into toffee sample solution, under the conditions of 25 DEG C after 5 min of ultrasound,
Supernatant is outwelled after being centrifuged 5min under the conditions of 8000 rpm；
(3) after using 2 min of methanol-acetonitrile eluent supersound washing aluminum oxide of 1.5 mL 1:2 volume ratios, 8000
Supernatant is collected after being centrifuged 5min under the conditions of rpm；
(4) after supernatant being evaporated using nitrogen evaporator, after 50 μ L methanol of addition dissolve sample, utilize high performance liquid chromatography-
UV detector analyzes sample, measurement quinolones, sulfamido, tetracycline antibiotics concentration.
Method Performance
(1) quantitative limit is used as using 3 times of instrument signal/noise ratio as detection limit and 10 times of signal-to-noise ratio, detection embodiment 1,2 and right
The sensitivity of ratio 1,2 methods；
(2) with the extraction efficiency of following formula calculation method, the effect of extracting of embodiment 1,2 and comparative example 1,2 methods is detected.
V in formula, c respectively indicate the volume of sample and the antibiotic concentration of analysis after methanol dissolves sample, and m is indicated in sample
The quality of the antibiotic of certain analysis.
The sensitivity and extraction yield of method in embodiment 1,2 and comparative example 1,2
As can be seen from the table, compared to the ultrafiltration membrane and sorption extraction material with commercialization, the ultrafiltration membrane that the present invention uses with
And after sorption extraction material is to sample pre-treatments, the sensitivity of method is higher and effect of extracting is more preferable, before having preferably application
Scape.
For the ordinary skill in the art, specific embodiment is only exemplarily described the present invention,
Obviously the present invention specific implementation is not subject to the restrictions described above, as long as use the inventive concept and technical scheme of the present invention into
The improvement of capable various unsubstantialities, or not improved the conception and technical scheme of the invention are directly applied to other occasions
, it is within the scope of the present invention.
Claims (7)
1. the Solid Phase Extraction detection method of antibiotic in a kind of toffee, it is characterised in that the following steps are included:
(1) 1.0 g toffees are weighed, the ultrafiltration membrane that 100-300 nm is crossed after 8 mL acetonitrile-water mixed solution stirring and dissolvings of addition obtains
Toffee sample solution；
(2) after 20-30 mg magnetic nanocomposites material being added into toffee sample solution, the ultrasound 5 under the conditions of 25-30 DEG C
After min, magnetic Nano material is adsorbed using magnet and outwells supernatant；
(3) magnetic Nano material is inhaled using magnet by after 2 min of magnetic Nano material using eluent supersound washing magnet
Attached collection supernatant；
(4) after supernatant being evaporated using nitrogen evaporator, after 50 μ L methanol of addition dissolve sample, utilize high performance liquid chromatography-
UV detector analyzes sample, measures the concentration of antibiotic.
2. the Solid Phase Extraction detection method of antibiotic in a kind of toffee according to claim 1, it is characterised in that step (1)
Described in acetonitrile-water mixed solution in the volume ratio of acetonitrile and water be 1:9-10.
3. the Solid Phase Extraction detection method of antibiotic in a kind of toffee according to claim 1, it is characterised in that step
(1) ultrafiltration membrane preparation method described in are as follows: 1.0 g polyether sulfones are dissolved in 5 mL n-methyl-2-pyrrolidone-ionic liquid
Mixed solution in obtain cast-solution, after cast-solution paving is placed 3 min on a glass and in air, then by glass
Plate impregnates 2-3 h in aqueous solution and the poly (ether-sulfone) ultrafiltration membrane that aperture is 100-300 nm is prepared.
4. ultrafiltration membrane preparation method according to claim 2, it is characterised in that the ionic liquid is imidazoles type
Ionic liquid.
5. the Solid Phase Extraction detection method of antibiotic in a kind of toffee according to claim 1, it is characterised in that step
(2) the magnetic nanocomposites material preparation method described in are as follows: by 5.0 g eutectic solvent 200-300 DEG C of items in nitrogen
Carbonization obtains amino-containing carbon nano-quantum point under part, disperses 200 mg carbon nano-quantum points, 300 mg graphene oxides in
The FeCl of 20 mL, 0.16 mol/L3With the FeCl of 0.08 mol/L2After mixed solution, delay under the conditions of 45-60 DEG C into solution
It is slow that ammonium hydroxide is added dropwise, until after system pH is 10, after the reaction was continued 3h, magnetic material is adsorbed using magnet, and use ethyl alcohol, water respectively
Magnetic nanocomposites material is both obtained after washing twice drying.
6. magnetic nanocomposites material preparation method according to claim 5, it is characterised in that the eutectic is molten
Agent is choline chloride-urea, glycine betaine-urea, the eutectic solvent containing amino such as choline chloride-glycine；The magnetic
Property nano complexes material partial size be 200-400 nm.
7. the Solid Phase Extraction detection method of antibiotic in a kind of toffee according to claim 1, it is characterised in that step
(3) eluent described in is the methanol-acetonitrile mixed liquor that volume ratio is 1:1-3, and the volume of the eluent is 1-1.5 mL.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022193861A1 (en) * | 2021-03-15 | 2022-09-22 | 深圳市易瑞生物技术股份有限公司 | Solvent substitution-based magnetic solid-phase extraction method |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103105446A (en) * | 2011-11-15 | 2013-05-15 | 南昌大学 | Method for enriching beta-lactam penicillins antibiotics in liquid milk |
| CN104045076A (en) * | 2014-01-17 | 2014-09-17 | 中国科学院上海微***与信息技术研究所 | Graphene oxide quantum dot preparation method |
| CN105327626A (en) * | 2015-11-19 | 2016-02-17 | 福州顺升科技有限公司 | Composite nanofiltration membrane and preparation method thereof |
| US20170137704A1 (en) * | 2013-08-19 | 2017-05-18 | Baker Hughes Incorporated | Apparatus and Methods for Stimulating Reservoirs Using Fluids Containing Nano/Micro Heat Transfer Elements |
| CN108318609A (en) * | 2018-03-24 | 2018-07-24 | 厦门市诚安毅科技有限公司 | A kind of pesticide residue detection method of supermolecule solvent joint QuEChERS |
| US20180238917A1 (en) * | 2013-02-18 | 2018-08-23 | Sphere Medical Limited | Analyte extraction apparatus and method |
| CN108896676A (en) * | 2018-07-12 | 2018-11-27 | 吉林化工学院 | A kind of magnetic Nano microsphere and its method to five kinds of trace fluoroquinolone antibiotics extractions and analysis in water body |
-
2019
- 2019-01-24 CN CN201910066355.3A patent/CN109839465A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103105446A (en) * | 2011-11-15 | 2013-05-15 | 南昌大学 | Method for enriching beta-lactam penicillins antibiotics in liquid milk |
| US20180238917A1 (en) * | 2013-02-18 | 2018-08-23 | Sphere Medical Limited | Analyte extraction apparatus and method |
| US20170137704A1 (en) * | 2013-08-19 | 2017-05-18 | Baker Hughes Incorporated | Apparatus and Methods for Stimulating Reservoirs Using Fluids Containing Nano/Micro Heat Transfer Elements |
| CN104045076A (en) * | 2014-01-17 | 2014-09-17 | 中国科学院上海微***与信息技术研究所 | Graphene oxide quantum dot preparation method |
| CN105327626A (en) * | 2015-11-19 | 2016-02-17 | 福州顺升科技有限公司 | Composite nanofiltration membrane and preparation method thereof |
| CN108318609A (en) * | 2018-03-24 | 2018-07-24 | 厦门市诚安毅科技有限公司 | A kind of pesticide residue detection method of supermolecule solvent joint QuEChERS |
| CN108896676A (en) * | 2018-07-12 | 2018-11-27 | 吉林化工学院 | A kind of magnetic Nano microsphere and its method to five kinds of trace fluoroquinolone antibiotics extractions and analysis in water body |
Non-Patent Citations (6)
| Title |
|---|
| CALHAN, SELDA DOGAN 等: "One-pot synthesis of hydrophilic and hydrophobic fluorescent carbon dots using deep eutectic solvents as designer reaction media", 《JOURNAL OF MATERIALS SCIENCE》 * |
| JIANG, BIN 等: "Enhanced separation performance of PES ultrafiltration membranes by imidazole-based deep eutectic solvents as novel functional additives", 《JOURNAL OF MEMBRANE SCIENCE》 * |
| 彭泽泽 等: "石墨烯-碳量子点复合材料的电化学性能研究", 《武汉科技大学学报》 * |
| 李亚珍: "功能石墨烯-新型固相萃取技术在抗生素残留分析中的应用研究", 《中国优秀硕士学位论文全文数据库》 * |
| 李龙飞: "磁性固相萃取在牛乳抗生素残留检测中的应用", 《乳业科学与技术》 * |
| 魏宗彧等: "磁性复合材料在分离分析中的应用研究进展", 《分析试验室》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022193861A1 (en) * | 2021-03-15 | 2022-09-22 | 深圳市易瑞生物技术股份有限公司 | Solvent substitution-based magnetic solid-phase extraction method |
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Application publication date: 20190604 |