CN107688010B - A method of detection fluoroquinolones - Google Patents
A method of detection fluoroquinolones Download PDFInfo
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- CN107688010B CN107688010B CN201710504616.6A CN201710504616A CN107688010B CN 107688010 B CN107688010 B CN 107688010B CN 201710504616 A CN201710504616 A CN 201710504616A CN 107688010 B CN107688010 B CN 107688010B
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Abstract
The invention discloses carry out purified treatment to milk matrix by magnetic solid phase microextraction using magnetic Nano material as scavenging material based on magnetic Nano material-carbon quantum dot fluorescence sensitivity detection fluoroquinolones method；It uses using poly(4-styrene sulfonic acid-co-maleic acid) sodium salt as carbon source and sulphur source, hydro-thermal method synthesis has the sulfur doping fluorescent carbon quantum dot of fluorescence sensitivity effect to fluoroquinolones, the concentration of its fluorescence signal intensity enhanced and fluoroquinolones is in some linear, establishes the high performance liquid chromatography of detection fluoroquinolones accordingly；The magnetic Nano material of preparation has excellent dispersibility and preferable catharsis, eliminate the interference of complicated substrate, and sulfur doping fluorescent carbon quantum dot has different degrees of fluorescence sensitivity to act on fluoroquinolones, measures a variety of fluoroquinolones simultaneously using high performance liquid chromatography；The method of the present invention has the outstanding features such as high sensitivity, favorable reproducibility.
Description
Technical field
The present invention relates to chemical analysis detection technique fields, specially a kind of to be based on magnetic Nano material purification-carbon quantum
The method for selecting fluoroquinolones in fluorescence sensitivity combination high performance liquid chromatography detection milk.
Background technique
Fluoroquinolones (QNS) is a kind of artificial synthesized broad-spectrum sterilization antibacterials, because it is with antimicrobial spectrum
Extensively, the features such as antibacterial action is strong, bioavilability is high, toxic side effect is small and other antibacterials are without cross resistance, and facing
It is widely used on bed.Since such drug is eliminated slowly in animal body, if being excessively used or improper use will cause animal
Medicament residue in source property product；Bacterial drug resistance problem, Central nervous system and joint portion are easy to cause after human body intake
Cause adverse reaction in position.Therefore the residue problem of fluoroquinolones attracts wide attention and payes attention to.China and Japan,
Fluoroquinolones is all included in the veterinary drug list that limitation uses by the country such as European Union, works up corresponding maximum residue limit,
The maximum residue limit of fluoroquinolones is between 20-100 μ g/kg in milk.
The detection method of fluo quinolone drug residual mainly has microbiological analysis, spectrophotometry, fluorescence light at present
Degree method and liquid chromatogram it is ultraviolet/the methods of fluorescence/mass spectroscopic assays.There are cumbersome, time-consuming, consumings in above-mentioned detection method
The disadvantages of a large amount of volatile organic solvents, sensitivity is low, poor reproducibility.Carbon quantum dot is generally less than 10 nm as a kind of partial size
New carbon, because of its excellent optical property, adjustable excitation and transmitting behavior, higher fluorescent stability is lower
Toxicity and good biocompatibility, are widely used in each field.Fluorescence of the carbon quantum dot for fluoroquinolones increases
It is quick, relevant report was done before this research group, but due to detecting using molecular fluorescence, for a variety of fluoroquinolones
Serious interference is detected, is unable to complete.Meanwhile carbon quantum dot fluorescence sensitivity combination high performance liquid chromatography detection has no any report.
Summary of the invention
The purpose of the present invention is to provide a kind of bases for detecting sensitive, simple complicated substrate sample extraction good purification
In magnetic Nano material purification-carbon quantum dot fluorescence sensitivity combination high performance liquid chromatography detection fluoroquinolones method.
The present invention prepares water-soluble sulfur doping fluorescence carbon quantum using poly(4-styrene sulfonic acid-co-maleic acid) sodium salt
Point, fluorescence quantum yield may be up to 40% or more, and have different degrees of fluorescence sensitivity to act on fluoroquinolones.
When analysis for fluo quinolone drug residual in milk measures, by Fe3O4Magnetic nano-particle is used for magnetic as scavenging material
Solid phase microextraction has significant clean-up effect to milk Matrix effects are eliminated；In combination with water-soluble sulfur doping fluorescence carbon quantum
The point fluorescence sensitivity effect different degrees of to fluoroquinolones, realizes to fluoroquinolones a variety of in complicated substrate milk
It is measured while medicament residue high sensitivity；Compared to conventional method, with low cost, high sensitivity, good purification it is excellent
Gesture.
The present invention is based in magnetic Nano material purification-carbon quantum dot fluorescence sensitivity combination high performance liquid chromatography detection milk
The method of fluoroquinolones includes the following steps:
(1) drafting of standard working curve: using citrate-phosphate disodium hydrogen buffer configure 8 concentration 0.01~
Fluoroquinolones standard solution within the scope of 20 μ g/L is added water-soluble sulfur doping fluorescent carbon quantum dot solution, uses lemon
Acid-disodium hydrogen phosphate buffer is settled to 5mL, is vortexed after mixing standing, detection that sample introduction is analyzed under high-efficient liquid phase chromatogram condition,
It is mapped with chromatographic peak area to its respective concentration and carries out regression analysis to get standard working curve is arrived, thus obtain fluoquinolone
The equation of linear regression of class drug；
(2) sample preparation: take 30-35mL milk heating water bath in tool plug centrifuge tube slow under stirring to 40-45 DEG C
0.5-1.0mol/L HCl is added, adjusts pH to 4.7-5.0, after above-mentioned suspension is cooled to room temperature, turns in 5000r/min
Speed is lower to be centrifuged 10 min, takes supernatant, is kept in dark place in 4 DEG C of refrigerator measurements to be analyzed；
(3) sample measures: the magnetic Nano material of suitable preparation is added in the supernatant for taking a certain amount of step (2) to prepare
Material after vortex mixes well it, carries out Magneto separate by additional magnet, discards magnetic Nano material, take out supernatant 1-
The water-soluble sulfur doping fluorescent carbon quantum dot solution of preparation is added in 2mL, with citrate-phosphate disodium hydrogen buffer tune pH and determines
Hold to 5mL, is vortexed after mixing standing, after 0.45 μm of water phase membrane filtration, inspection that sample introduction is analyzed under high-efficient liquid phase chromatogram condition
It surveys, substitutes into step (1) equation of linear regression, calculate the content of fluoroquinolones in sample.
The preparation method of the water-soluble sulfur doping fluorescent carbon quantum dot includes: to weigh poly- (the 4- styrene of 3.0-5.0g
Sulfonic acid-copolymerization-maleic acid) sodium salt, be added in 100 mL ultrapure waters, ultrasonic 5-10min, make its mix well to be formed it is colourless
Prescribed liquid, and it is transferred to ptfe autoclave, after 220-250 DEG C of heating 5-8h, cooled to room temperature, first use aperture
For 0.22 μm of membrane filtration, after with the bag filter that molecular cut off is 3000-3500Da carry out 24 h of dialysis treatment, obtain water-soluble
Property sulfur doping fluorescent carbon quantum dot, and be kept in dark place at 4 DEG C, it is spare.
The preparation method of the magnetic Nano material includes: that the preparation method of magnetic Nano material is to weigh 2.05-
2.50g iron ammonium sulfate and 1.41-2.00g ferric trichloride, after 50 mL deionized water dissolvings, under nitrogen protection, heating water bath
To after 75-85 DEG C, the ammonium hydroxide of 5-7mL concentration of volume percent 28% is added, continues to be stirred to react 30 min, be cooled to room temperature, uses
Deionized water is washed 3 times, is separated outside plus under magnet effect to get magnetic Fe3O4。
The fluoroquinolones is lavo-ofloxacin, Norfloxacin, Lomefloxacin, a kind of or several in gatifloxacin
Kind.
The citrate-phosphate disodium hydrogen pH of buffer is 6.0-7.0.
The magnetic Nano material dosage is 5-25 mg.
The water solubility sulfur doping fluorescent carbon quantum dot dosage is 300 μ L.
The vortex, which mixes to stand, refers to that vortex mixes 0.5-3 min, is then allowed to stand 5-10min.
The high-efficient liquid phase chromatogram condition are as follows: stationary phase C18Chromatographic column (4.6 mm × 250 mm, 5.0 μm)；Mobile phase ladder
Degree elution: 0 min: -0.5% phosphoric acid solution of acetonitrile (15:85, v/v), 12 min: acetonitrile -0.5% phosphoric acid solution (35:65, v/
v)；Flow velocity: 1.0 mL/min；Sample volume: 20 μ L；Column temperature: 30 DEG C；Fluorescence detector: 290 nm of excitation wavelength, launch wavelength
490 nm。
The present invention has the advantages that
1. the present invention is prepared for a kind of water-soluble fluorescence sulfur doping carbon with high quantum production rate using one step hydro thermal method
The nitrogen-doped carbon quantum dot of quantum dot, preparation has different degrees of fluorescence sensitivity effect to fluoroquinolones;
2. the Fe of preparation3O4Milk matrix of the magnetic nano-particle for interference measurement has apparent clean-up effect, in conjunction with magnetic
Solid phase microextraction, with advantage at low cost, Magneto separate speed is fast, easy to operate;
3. for the first time using magnetic solid phase extraction-carbon quantum dot fluorescence sensitivity technology combination high performance liquid chromatography to milk sample
A variety of fluo quinolone drug residuals are carried out while being measured in product, and method is easy to operate, quick, and residual for fluoroquinolones
The application of measurement high performance liquid chromatography is stayed to provide new approach.
Detailed description of the invention
Fig. 1 is the high-efficient liquid phase chromatogram of embodiment 1, and wherein a is that the measurement chromatic graph of blank milk is composed；B is milk sample
The measurement chromatic graph spectrum of water-soluble sulfur doping fluorescent carbon quantum dot is added before mark-on (0.5 μ g/mL) is non-purified；
Fig. 2 is that water-soluble sulphur is added in the milk sample mark-on (0.5 μ g/mL) of embodiment 1 after magnetic Nano material purifies
The measurement high-efficient liquid phase chromatogram of doping fluorescent carbon quantum dot (c).
Specific embodiment
Explanation, but this hair are described in further detail to technical solution of the present invention below in conjunction with specific embodiments
Bright protection scope is not limited to that.
Embodiment 1: 3 kinds of lavo-ofloxacin in milk, Lomefloxacin, gatifloxacin fluo quinolone drug residual contents
Measurement, specific steps are as follows:
(1) preparation method of water-soluble sulfur doping fluorescent carbon quantum dot (S-CQDs): poly- (the 4- styrene sulphur of 3.0 g is weighed
Acid-copolymerization-maleic acid) sodium salt, it is added in 100 mL ultrapure waters, 5 min of ultrasound make it mix well to form colorless and transparent liquid
Body, and it is transferred to ptfe autoclave, it is first 0.22 μ with aperture after 220 DEG C of 5 h of heating, cooled to room temperature
M membrane filtration, after with the bag filter that molecular cut off is 3500Da carry out 24 h of dialysis treatment, obtain water-soluble sulfur doping fluorescence
Carbon quantum dot, and be kept in dark place spare in 4 DEG C of refrigerators；
(2) preparation method of magnetic Nano material: 2.05 g iron ammonium sulfates and 1.41 g ferric trichlorides are weighed, with 50
After mL deionized water dissolving, under nitrogen protection, the ammonia of 5 mL concentration of volume percent 28% is added to after 80 DEG C in heating water bath
Water continues to be stirred to react 30 min, be cooled to room temperature, and is washed with deionized 3 times, outside plus magnet effect under separation to get
Magnetic Fe3O4Nano material；
(3) following concentration the drafting of standard working curve: is configured using 7.0 citrate-phosphate disodium hydrogen buffer of pH
Lavo-ofloxacin, Lomefloxacin, three kinds of fluoroquinolones of gatifloxacin standard mixed liquor: 0.01,0.05,0.1,
0.5,1,5,10,20 μ g/mL, is added the water-soluble nitrogen doping fluorescent carbon quantum dot of 300 μ L steps (1) preparation, and uses lemon
Acid-disodium hydrogen phosphate buffer is settled to 5 mL, is vortexed and mixes 1min standing 10min, after 0.45 μm of water phase membrane filtration,
Detection that sample introduction is analyzed under the best liquid phase chromatogram condition of optimization return to the mapping of its respective concentration and divide with chromatographic peak area
Analysis is shown in Table 1 to get the equation of linear regression to standard working curve, wherein high-efficient liquid phase chromatogram condition are as follows: stationary phase C18Chromatography
Column (4.6 mm × 250 mm, 5.0 μm)；Eluent gradient elution: 0 min: -0.5% phosphoric acid solution of acetonitrile (15:85, v/v),
12 min: -0.5% phosphoric acid solution of acetonitrile (35:65, v/v)；Flow velocity: 1.0 mL/min；Sample volume: 20 μ L；Column temperature: 30 DEG C；
Fluorescence detector: 290 nm of excitation wavelength, 490 nm of launch wavelength；
The equation of linear regression and parameters of each quinolone drugs of table 1
(4) it sample preparation: takes 30 mL milk to have heating water bath in plug centrifuge tube in 50 mL and is stirred lower slow to 40 DEG C
It is slow that 0.5 mol/L HCl is added, pH to 4.7-5.0 is adjusted, after above-mentioned suspension is cooled to room temperature, in 5000r/min revolving speed
10 min of lower centrifugation, take supernatant, are kept in dark place in 4 DEG C of refrigerator measurements to be analyzed；
(5) sample measures: the magnetic Nano material of 25 mg steps (2) preparation is added in the supernatant for taking step (4) to prepare
Material, 3 min of vortex mixed carry out Magneto separate by additional magnet, discard magnetic Nano material, take out supernatant 1mL, be added
The water-soluble sulfur doping fluorescent carbon quantum dot solution of 300 μ L steps (1) preparation, with citrate-phosphate disodium hydrogen buffer tune pH
To 7.0, and be settled to 5mL, be vortexed and mix after 1min stands 10min, through 0.45 μm of water phase membrane filtration optimization best liquid
Detection (same to step (3) condition) that sample introduction is analyzed under phase chromatographic condition, substitutes into step (3) regression equation, levofloxacin is calculated
The content of star is 0.127 μ g/mL, and the content of Lomefloxacin is 0.023 μ g/mL, and the content of gatifloxacin is 0.010 μ g/
mL。
Fig. 1 is the high-efficient liquid phase chromatogram of embodiment 1, and wherein a is that the measurement chromatic graph of blank milk is composed；B is milk sample
The measurement chromatic graph spectrum of water-soluble sulfur doping fluorescent carbon quantum dot is added before mark-on (0.5 μ g/mL) is non-purified；Fig. 2 c is milk sample
The measurement chromatic graph spectrum of water-soluble sulfur doping fluorescent carbon quantum dot is added in mark-on (0.5 μ g/mL) after magnetic Nano material purifies；
From Fig. 1,2 results: the present embodiment preparation is to water-soluble sulfur doping fluorescent carbon quantum dot to fluoroquinolones medicine
Object has stronger fluorescence sensitivity effect, and the measurement result through magnetic Nano material purification front and back compares it is found that this method is eliminated
Complicated substrate interference, and have more significant raising to the effect of enhanced sensitivity of determinand.The method of the present invention is easy to operation, cost
It is cheap, it is environmentally protective, complicated substrate interference can be eliminated, and high-sensitivity analysis detection and more advantage.
Embodiment 2: 3 kinds of lavo-ofloxacin in milk, Lomefloxacin, gatifloxacin fluo quinolone drug residual contents
Measurement, specific steps are as follows:
(1) preparation method of water-soluble sulfur doping fluorescent carbon quantum dot (S-CQDs): poly- (the 4- styrene sulphur of 4.0 g is weighed
Acid-copolymerization-maleic acid) sodium salt, it is added in 100 mL ultrapure waters, ultrasonic 8min makes it mix well to form colorless and transparent liquid
Body, and it is transferred to ptfe autoclave, it is first 0.22 μm with aperture after 250 DEG C of heating 6h, cooled to room temperature
Membrane filtration, after with the bag filter that molecular cut off is 3200Da carry out 24 h of dialysis treatment, obtain water-soluble sulfur doping fluorescence
Carbon quantum dot, and be kept in dark place spare in 4 DEG C of refrigerators；
(2) preparation method of magnetic Nano material: 2.20 g iron ammonium sulfates and 1.61 g ferric trichlorides are weighed, with 50
After mL deionized water dissolving, under nitrogen protection, the ammonia of 6mL concentration of volume percent 28% is added to after 75 DEG C in heating water bath
Water continues to be stirred to react 30 min, be cooled to room temperature, and is washed with deionized 3 times, outside plus magnet effect under separation to get
Magnetic Fe3O4Nano material；
(3) drafting of standard working curve: with 1 step of embodiment (3)；
(4) 35mL milk heating water bath in tool plug centrifuge tube is taken to be slowly added to 1.0mol/L under stirring to 45 DEG C
HCl adjusts pH to 4.7-5.0 and is centrifuged 10 min under 5000r/min revolving speed after above-mentioned suspension is cooled to room temperature, takes
Supernatant is kept in dark place in 4 DEG C of refrigerator measurements to be analyzed；
(5) sample measures: 10 mg step (2) magnetic Nano materials are added in the supernatant for taking step (4) to prepare, and are vortexed
0.5 min is mixed, Magneto separate is carried out by additional magnet, discards magnetic Nano material, takes out supernatant 2mL, 300 μ L are added
The water-soluble sulfur doping fluorescent carbon quantum dot solution of step (1) preparation, with citrate-phosphate disodium hydrogen buffer tune pH to 6.0,
And it is settled to 5mL, it is vortexed after mixing 2min standing 5min, through 0.45 μm of water phase membrane filtration, in the best liquid chromatogram of optimization
Under the conditions of sample introduction is analyzed detection (condition is with embodiment 1), substitute into step (3) regression equation, containing for lavo-ofloxacin is calculated
Amount is 0.067 μ g/mL, and the content of Lomefloxacin is 0.013 μ g/mL.
Embodiment 3: the survey of lavo-ofloxacin, 3 kinds of Lomefloxacin, gatifloxacin quinolones medicament relict contents in milk
It is fixed, specific steps are as follows:
(1) preparation method of water-soluble sulfur doping fluorescent carbon quantum dot (S-CQDs): poly- (the 4- styrene sulphur of 5.0 g is weighed
Acid-copolymerization-maleic acid) sodium salt, it is added in 100 mL ultrapure waters, ultrasonic 10min makes it mix well to form colorless and transparent liquid
Body, and it is transferred to ptfe autoclave, it is first 0.22 μm with aperture after 230 DEG C of heating 7h, cooled to room temperature
Membrane filtration, after with the bag filter that molecular cut off is 3000Da carry out 24 h of dialysis treatment, obtain water-soluble sulfur doping fluorescence
Carbon quantum dot, and be kept in dark place spare in 4 DEG C of refrigerators；
(2) preparation method of magnetic Nano material: 2.45 g iron ammonium sulfates and 2.00 g ferric trichlorides are weighed, with 50
After mL deionized water dissolving, under nitrogen protection, the ammonia of 7mL concentration of volume percent 28% is added to after 88 DEG C in heating water bath
Water continues to be stirred to react 30 min, be cooled to room temperature, and is washed with deionized 3 times, outside plus magnet effect under separation to get
Magnetic Fe3O4Nano material；
(3) drafting of standard working curve: with 1 step of embodiment (3)；
(4) 32mL milk heating water bath in tool plug centrifuge tube is taken to be slowly added to 0.8mol/L under stirring to 42 DEG C
HCl adjusts pH to 4.7-5.0 and is centrifuged 10 min under 5000r/min revolving speed after above-mentioned suspension is cooled to room temperature, takes
Supernatant is kept in dark place in 4 DEG C of refrigerator measurements to be analyzed；
(5) sample measures: the magnetic Nano material of 15 mg steps (2) preparation is added in the supernatant for taking step (2) to prepare
Material, 1 min of vortex mixed carry out Magneto separate by additional magnet, discard magnetic Nano material, take out supernatant 1mL, be added
The water-soluble sulfur doping fluorescent carbon quantum dot solution of 300 μ L steps (1) preparation, with citrate-phosphate disodium hydrogen buffer tune pH
To 6.0 and be settled to 5mL, be vortexed mix 3 min stand 8 min after, through 0.45 μm of water phase membrane filtration optimization best liquid
Detection that sample introduction is analyzed under phase chromatographic condition, substitutes into step (3) regression equation, and the content that lavo-ofloxacin is calculated is 0.085
μ g/mL, the content of gatifloxacin are 0.029 μ g/mL.
Embodiment 4: the survey of lavo-ofloxacin, 3 kinds of Lomefloxacin, gatifloxacin quinolones medicament relict contents in milk
It is fixed, specific steps are as follows:
(1) preparation method of water-soluble sulfur doping fluorescent carbon quantum dot (S-CQDs): poly- (the 4- styrene sulphur of 3.5 g is weighed
Acid-copolymerization-maleic acid) sodium salt, it is added in 100 mL ultrapure waters, ultrasonic 6min makes it mix well to form colorless and transparent liquid
Body, and it is transferred to ptfe autoclave, it is first 0.22 μm with aperture after 220 DEG C of heating 7h, cooled to room temperature
Membrane filtration, after with the bag filter that molecular cut off is 3400Da carry out 24 h of dialysis treatment, obtain water-soluble sulfur doping fluorescence
Carbon quantum dot, and be kept in dark place spare in 4 DEG C of refrigerators；
(2) preparation method of magnetic Nano material: 2.25 g iron ammonium sulfates and 1.90 g ferric trichlorides are weighed, with 50
After mL deionized water dissolving, under nitrogen protection, the ammonia of 5mL concentration of volume percent 28% is added to after 80 DEG C in heating water bath
Water continues to be stirred to react 30 min, be cooled to room temperature, and is washed with deionized 3 times, outside plus magnet effect under separation to get
Magnetic Fe3O4Nano material；
(3) drafting of standard working curve: with 1 step of embodiment (3)；
(4) 33mL milk heating water bath in tool plug centrifuge tube is taken to be slowly added to 0.6mol/L under stirring to 44 DEG C
HCl adjusts pH to 4.7-5.0 and is centrifuged 10 min under 5000r/min revolving speed after above-mentioned suspension is cooled to room temperature, takes
Supernatant is kept in dark place in 4 DEG C of refrigerator measurements to be analyzed；
(5) sample measures: the magnetic Nano material of 6mg step (2) preparation is added in the supernatant for taking step (2) to prepare,
2 min of vortex mixed carries out Magneto separate by additional magnet, discards magnetic Nano material, take out supernatant 2mL, 300 μ are added
The water-soluble sulfur doping fluorescent carbon quantum dot solution of L step (1) preparation, extremely with citrate-phosphate disodium hydrogen buffer tune pH
7.0, and be settled to 5mL, be vortexed and mix after 0.5 min stands 6min, through 0.45 μm of water phase membrane filtration optimization best liquid
Detection that sample introduction is analyzed under phase chromatographic condition, substitutes into step (3) regression equation, and the content that lavo-ofloxacin is calculated is 0.135
μ g/mL, the content of Lomefloxacin are 0.024 μ g/mL, and the content of gatifloxacin is 0.016 μ g/mL.
Claims (8)
1. a kind of based on magnetic Nano material-carbon quantum dot fluorescence sensitivity detection fluoroquinolones method, feature exists
In: specific step is as follows:
(1) 8 concentration the drafting of standard working curve: are configured in 0.01~20 μ using citrate-phosphate disodium hydrogen buffer
Water-soluble sulfur doping fluorescent carbon quantum dot solution is added, with citric acid-in fluoroquinolones standard solution within the scope of g/L
Disodium hydrogen phosphate buffer is settled to 5mL, is vortexed after mixing standing, detection that sample introduction is analyzed under high-efficient liquid phase chromatogram condition, with
Chromatographic peak area, which maps to its respective concentration, carries out regression analysis to get standard working curve is arrived, and thus obtains fluoroquinolones
The equation of linear regression of drug；
(2) sample preparation: 30-35mL milk heating water bath in tool plug centrifuge tube is taken to be slowly added under stirring to 40-45 DEG C
0.5-1.0mol/L HCl adjusts pH to 4.7-5.0, obtains suspension, after above-mentioned suspension is cooled to room temperature, in
It is centrifuged 10 min under 5000r/min revolving speed, takes supernatant, is kept in dark place in 4 DEG C of refrigerator measurements to be analyzed；
(3) sample measures: magnetic Nano material is added in the supernatant of step (2) preparation, after vortex mixes well it, leads to
It crosses additional magnet and carries out Magneto separate, discard magnetic Nano material, take out supernatant 1-2mL, water-soluble sulfur doping fluorescent carbon is added
Quantum dot solution with citrate-phosphate disodium hydrogen buffer tune pH and is settled to 5mL, is vortexed after mixing standing, through 0.45 μm of water
After phase membrane filtration, detection that sample introduction is analyzed under high-efficient liquid phase chromatogram condition substitutes into step (1) equation of linear regression, calculates
The content of fluoroquinolones in sample；
The preparation method of the water solubility sulfur doping fluorescent carbon quantum dot is to weigh poly- (the 4- styrenesulfonic acid-co-of 3.0-5.0g
Maleic acid) sodium salt, it is added in 100 mL ultrapure waters, ultrasonic 5-10min makes it mix well to form colourless transparent liquid, and
It is transferred to ptfe autoclave, is first 0.22 μm with aperture after 220-250 DEG C of heating 5-8h, cooled to room temperature
Membrane filtration, after with the bag filter that molecular cut off is 3000-3500Da carry out 24 h of dialysis treatment, obtain water-soluble sulfur doping
Fluorescent carbon quantum dot, and be kept in dark place at 4 DEG C, it is spare.
2. according to claim 1 detect fluoroquinolones based on magnetic Nano material-carbon quantum dot fluorescence sensitivity
Method, it is characterised in that: the preparation method of magnetic Nano material be weigh 2.05-2.50g iron ammonium sulfate and 1.41-
2.00g ferric trichloride, after 50 mL deionized water dissolvings, under nitrogen protection, 5-7mL is added to after 75-85 DEG C in heating water bath
The ammonium hydroxide of concentration of volume percent 28% continues to be stirred to react 30 min, be cooled to room temperature, and is washed with deionized 3 times, outside
Add the lower separation of magnet effect to get magnetic Fe3O4。
3. according to claim 1 detect fluoroquinolones based on magnetic Nano material-carbon quantum dot fluorescence sensitivity
Method, it is characterised in that: fluoroquinolones is lavo-ofloxacin, Norfloxacin, Lomefloxacin, a kind of in gatifloxacin
Or it is several.
4. according to claim 1 detect fluoroquinolones based on magnetic Nano material-carbon quantum dot fluorescence sensitivity
Method, it is characterised in that: citrate-phosphate disodium hydrogen pH of buffer be 6.0-7.0.
5. according to claim 1 detect fluoroquinolones based on magnetic Nano material-carbon quantum dot fluorescence sensitivity
Method, it is characterised in that: magnetic Nano material dosage be 5-25 mg.
6. according to claim 1 detect fluoroquinolones based on magnetic Nano material-carbon quantum dot fluorescence sensitivity
Method, it is characterised in that: water-soluble sulfur doping fluorescent carbon quantum dot dosage be 300 μ L.
7. according to claim 1 detect fluoroquinolones based on magnetic Nano material-carbon quantum dot fluorescence sensitivity
Method, it is characterised in that: be vortexed mix stand refers to vortex mix 0.5-3 min, be then allowed to stand 5-10min.
8. according to claim 1 detect fluoroquinolones based on magnetic Nano material-carbon quantum dot fluorescence sensitivity
Method, which is characterized in that high-efficient liquid phase chromatogram condition are as follows: stationary phase C18Chromatographic column, eluent gradient elution, 0 min: second
- 0.5% phosphoric acid solution of nitrile, wherein -0.5% phosphoric acid solution of acetonitrile be the phosphoric acid solution of acetonitrile and mass concentration 0.5% by volume
15:85 is mixed to prepare；12 min: -0.5% phosphoric acid solution of acetonitrile, wherein -0.5% phosphoric acid solution of acetonitrile is acetonitrile and mass concentration
35:65 is mixed to prepare 0.5% phosphoric acid solution by volume；1.0 mL/min of flow velocity；Sample volume is 20 μ L；Column temperature: 30 DEG C；
Fluorescence detector: 290 nm of excitation wavelength, 490 nm of launch wavelength.
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| CN113075313B (en) * | 2021-03-22 | 2022-09-30 | 武汉海关技术中心 | Method for measuring quinolone drugs in environmental water and fish |
| CN114099350B (en) * | 2021-11-05 | 2024-07-02 | 青岛大学 | Carbon quantum dot-magnetic nanoparticle compound, preparation method and application thereof |
| CN114460052B (en) * | 2022-01-11 | 2023-06-20 | 武汉理工大学 | Method for directly detecting concentration of sodium pyruvate based on fluorescent carbon quantum dots |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102081078A (en) * | 2011-02-24 | 2011-06-01 | 北京吉天仪器有限公司 | Method for measuring residual quantities of four fluoroquinolone medicaments in animal food |
| CN104749262A (en) * | 2013-12-27 | 2015-07-01 | 中国科学院沈阳应用生态研究所 | Method of rapidly determining fluoroquinolone type medicines in faeces of livestock and poultry |
| CN105670632A (en) * | 2015-12-31 | 2016-06-15 | 长江大学 | Magnetic fluorescent bifunctional quantum dot, and preparation method and application thereof |
| CN106753352A (en) * | 2016-11-15 | 2017-05-31 | 山西大学 | A kind of fluorescent carbon quantum dot of N doping and its preparation method and application |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102081078A (en) * | 2011-02-24 | 2011-06-01 | 北京吉天仪器有限公司 | Method for measuring residual quantities of four fluoroquinolone medicaments in animal food |
| CN104749262A (en) * | 2013-12-27 | 2015-07-01 | 中国科学院沈阳应用生态研究所 | Method of rapidly determining fluoroquinolone type medicines in faeces of livestock and poultry |
| CN105670632A (en) * | 2015-12-31 | 2016-06-15 | 长江大学 | Magnetic fluorescent bifunctional quantum dot, and preparation method and application thereof |
| CN106753352A (en) * | 2016-11-15 | 2017-05-31 | 山西大学 | A kind of fluorescent carbon quantum dot of N doping and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| Shan Sun等.Toward High-Efficient Red Emissive Carbon Dots: Facile Preparation,Unique Properties, and Applications as Multifunctional Theranostic Agents.《Chemistry of Materials》.2016,全文. * |
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