CN109342613A - A method of for analyzing phenols endocrine disruptors in beverage - Google Patents
A method of for analyzing phenols endocrine disruptors in beverage Download PDFInfo
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Abstract
The invention belongs to technical field of food detection, and in particular to a method of for analyzing phenols endocrine disruptors in beverage.The present invention uses the magnetic covalent organic framework microballoon of nucleocapsid structure for solid phase extraction adsorbents, is based on magnetic solid phase extraction and liquid chromatography technology, establishes a kind of new method of trace phenols endocrine disruptors in sensitive analysis beverage.This method is to phenols endocrine disruptors minimum detection limit in beverage up to 0.08ng mL‑1, the range of linearity is 0.5-1000ng mL‑1, and the method for the present invention is reproducible.
Description
Technical field
The invention belongs to technical field of food detection, and in particular to one kind is for analyzing phenols endocrine disruptors in beverage
Method.
Background technique
Endocrine disruption chemical substance (EDCs) refers to a kind of xenobiotics, it will cause reproductive system, is immunized
System, the exception of animals and humans nervous system, and the disease incidence of certain tumours is caused to increase.It is special according to the structure of EDCs
Sign, can be divided into Polychlorinated biphenyls (PCBs), phthalate, phenols, heavy metal, organotin etc..Wherein, phenols incretion interferes
Object mainly includes 4- n-nonyl phenol (NP), 4- n-octyl phenol (OP) and bisphenols (BP), they are widely used as packaging material for food
Surfactant and plasticizer in production and synthesis.
Modern chromatographic techniques are since their detection limits are low, and speed is fast, high sensitivity, easy to operate, dry in phenols incretion
Object measurement aspect is disturbed to enjoy great popularity.In the analytic process of practical drink sample, directly adopt instrument analyze it is relatively difficult,
Therefore it is suitable to select, and quickly, simple sample-pretreating method is for the phenols endocrine disruptors in analysis beverage to closing weight
It wants.
Magnetic solid phases extract (MSPE) by the Sample Pretreatment Technique new as one kind, for being enriched with and measuring trace dirt
Contaminate object.In Magnetic solid phases extraction procedures, target analytes are directly located the absorption of the magnetic adsorbent in sample solution, then
Magnetic adsorbent can quick separating be without filtering or being centrifuged from suspension by using external magnet, ultimate analysis object quilt
Elution is for analyzing.The adsorbent of magnetic solid phase extraction is its core, decides selectivity, the sensitivity of corresponding analysis method
And application range.For magnetic solid phase microextraction, currently there is an urgent need to develop the absorption of length of cheap, highly selective and service life
Agent is for efficiently separating enrichment target contaminant.
Covalent organic framework (COFs) was a kind of porous crystalline polymer with covalent bonding structure unit, from 2005
Since reporting for the first time, many researchers give great concern to them.COF compared with MOF and other new materials, by
It is with good performance in its, such as adjustable aperture, the porosity in biggish aperture and rule, low crystalline density and good
Structural stability is widely used in being catalyzed, gas storage, photoelectron, chromatographic isolation, the fields such as chemical sensor.
Summary of the invention
The main purpose of the present invention is to provide a kind of methods for analyzing phenols endocrine disruptors in beverage.The present invention adopts
It is solid phase extraction adsorbents with the magnetic covalent organic framework microballoon of nucleocapsid structure, is based on magnetic solid phase extraction and liquid chromatogram skill
Art establishes a kind of new method of trace phenols endocrine disruptors in sensitive analysis beverage.
To achieve the above object, the invention adopts the following technical scheme:
First aspect of the present invention provides a kind of magnetic covalent organic framework microballoon of nucleocapsid structure, the core-shell structure copolymer knot
The magnetic covalent organic framework microballoon of structure is prepared by following methods:
S1. by FeCl3·6H2O, Na3CO2·2H2O and sodium acetate are dissolved in ethylene glycol, and after mixing evenly, solution is turned
It moves in autoclave, is heated to 200 DEG C and continues 12 hours；After reaction, the magnetic Nano Fe that will obtain3O4Particle uses ethyl alcohol respectively
For several times with deionized water supersound washing, it is then dried in vacuo at 50 DEG C spare；
S2. magnetic Nano Fe step S1 being prepared3O4Particle, 1,3,5- tri- (4- aminophenyl) benzene and to benzene two
Formaldehyde is dissolved in dimethyl sulfoxide, is ultrasonically treated 5 minutes, and be slowly added to acetic acid, and after incubating 30 minutes, the brown for collecting generation is heavy
Starch, is then washed three times with anhydrous tetrahydro furan and anhydrous methanol, be dried in vacuo at room temperature to get.
The second aspect of the present invention provides the magnetic covalent organic framework microballoon of nucleocapsid structure described above in detection phenol
Application in class incretion interferent.
Preferably, the magnetic covalent organic framework microballoon of nucleocapsid structure described above phenols incretion in detection beverage
Application in chaff interferent.
Third aspect of the present invention provides a kind of method for analyzing phenols endocrine disruptors in beverage, use with
The magnetic covalent organic framework microballoon of the upper nucleocapsid structure is adsorbent, in conjunction with magnetic solid phase extraction and liquid chromatogram-fluorescence point
Analysis technology is tested and analyzed.
Preferably, the method for analyzing phenols endocrine disruptors in beverage, it is specific the following steps are included:
(1) sample pretreatment；
(2) magnetic solid phase extraction, the sample that is added that step (1) treated in vial, adjustment sample pH value is 2-12, addition
The magnetic covalent organic framework microsphere adsorbing agent of nucleocapsid structure described in claim 1 adjusts solution ion strength, ionic strength
For 0~20% NaCl, water-bath mechanical shaking extraction is separated from the water by adsorbent, and discards clear liquid；Eluent is added to separation
It in adsorbent out, repeats to elute after ultrasonic treatment, be consolidated after the solution of elution is mixed, is dry with eluent dissolution to get magnetic
Mutually extraction sample；
(3) the magnetic solid phase extraction sample that step (2) is prepared carries out liquid chromatogram-fluorescence detection.
Preferably, step (1) sample pretreatment, specifically: sample is centrifuged at 4-10 DEG C with 5000-10000rpm
To remove sediment, then by 0.22- μm of micro-pore-film filtration, supernatant is taken within 10-20 minutes.By finished tea beverage sample
It in the clean Brown Glass Brown glass bottles and jars only being stored in, is stored under the conditions of 4 DEG C, for subsequent magnetic solid phase extraction process.
Preferably, in step (2), eluent is any one in n-hexane, methylene chloride, acetone, methanol and ethyl alcohol；Institute
Stating eluent dosage is 2-12mL.
Preferably, extraction time is 10~60min, adsorbent amount 10-80mg in step (2).
Preferably, chromatographic column C8 column used in step (3): 150mm × 2.1mm, 5 μm；Column oven: 35 DEG C；Flow velocity: 1ml/
min；Sampling volume is 20 μ L.
Preferably, step (3) mobile phase are as follows: hplc grade water A and acetonitrile B；Using gradient elution: 0 minute, 40%B；24 points
Clock, 80%B；28 minutes, 80%B；28.2 minutes, 45%B and 30 minute, 45%B；Fluorescence detector is provided that excitation
Wavelength 220nm, launch wavelength 315nm.
The magnetic covalent organic framework microballoon that the present invention is prepared has biggish specific surface area and biggish pore volume, together
When in the aqueous solution and organic solvent of different pH value chemical property extremely stability.The core-that the present invention will be prepared for the first time
The magnetic covalent organic framework microballoon of shell structure is as solid phase extraction adsorbents for interfering phenols incretion in drink sample
The measurement of object.In solid phase extraction procedure, the present invention is to extract liquor type, dosage, sample solution ionic strength, sample pH,
The important factor in order condition such as adsorption time and adsorbent amount is optimized, and substantially increases to phenols in drink sample
The sensitivity of endocrine disruption analyte detection.
It is that the present invention obtains the utility model has the advantages that
(1) present invention establishes a kind of new method of trace phenols endocrine disruptors in sensitive analysis beverage, this method
To phenols endocrine disruptors minimum detection limit in beverage up to 0.08ng mL-1, the range of linearity is 0.5-1000ng mL-1, and
And the method for the present invention is reproducible.
(2) adsorbent that the present invention is extracted using the magnetic covalent organic framework microballoon of nucleocapsid structure as Magnetic solid phases,
Sorbent preparation method of the present invention is simple, and selectivity is sensitive, may be reused 20 times or more and still keeps high extraction
Efficiency.
Detailed description of the invention
The Figure of description for constituting a part of the invention is used to provide further understanding of the present invention, and of the invention shows
Examples and descriptions thereof are used to explain the present invention for meaning property, does not constitute improper limitations of the present invention.
Fig. 1 (A) Fe3O4TEM image of the microballoon under 25000 times of amplification factors；(B) magnetic covalent organic framework microballoon
The TEM image that amplification factor is 25000 times；(C) TAPB, TPA, Fe3O4With the FT-IR spectrum of magnetic covalent organic framework microballoon；
(D) Fe in air3O4With the XRD spectrum of magnetic covalent organic framework microballoon；(E) magnetic covalent organic framework microballoon microballoon is in sky
In gas, in methyl alcohol, in 1molL-124 hours in HCl, in 1molL-124 hours and in water 24 hours in NaOH
FT-IR spectrum；(F)Fe3O4With the magnetization curve of magnetic covalent organic framework microballoon；(G)Fe3O4With magnetic covalent organic framework
The N of microballoon2Absorption-desorption thermoisopleth；(H)Fe3O4With the pore-size distribution of magnetic covalent organic framework microballoon.
Influence of Fig. 2 different experimental conditions to experiment effect: (A) extract liquor type, (B) extract liquor volume, (C) sample body
Product, (D) pH value, (E) extraction time, (F) ionic strength.
The chromatography-mass spectroscopy figure of Fig. 3 green tea beverage sample: mark-on 100ngmL-1(a), 50ngmL-1 (b), 5ngmL-1(c) and blank green tea beverage sample (d)；(1) BPA, (2) BPAF, (3) OP, (4) NP.
Specific embodiment
It is noted that described further below be all exemplary, it is intended to provide further instruction to the present invention.Unless another
It indicates, all technical and scientific terms used herein has usual with general technical staff of the technical field of the invention
The identical meanings of understanding.
It should be noted that term used herein above is merely to describe specific embodiment, and be not intended to restricted root
According to exemplary embodiments of the present invention.As used herein, unless the context clearly indicates otherwise, otherwise singular
Also it is intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet
Include " when, indicate existing characteristics, step, operation and/or their combination.
In order to enable those skilled in the art can clearly understand technical solution of the present invention, below with reference to tool
The embodiment of the body technical solution that the present invention will be described in detail.
Drug and reagent
Bisphenol-A (BPA) and bisphenol AF (BPAF) are purchased from Aladdin reagent Chemical Co., Ltd. (Chinese Shanghai).4- n-octyl
Phenol (OP) and 4- n-nonyl phenol (NP) are purchased from Supelco company (U.S., Pennsylvania, Bell Feng Te).Six hydrations three
Iron chloride (FeCl3·6H2O), Sodium citrate dehydrate (Na3Cit·2H2O), dimethyl sulfoxide (DMSO), tetrahydrofuran (THF),
Ethylene glycol, acetic acid, hplc grade water, ethyl alcohol, 4A type molecular sieve are bought from traditional Chinese medicines reagent Chemical Co., Ltd. (Shanghai City, China).1,
3,5- tri- (4- aminophenyl) benzene (TAPB) and terephthalaldehyde (TPA) are purchased from Shanghai Mike woods Measurement for Biochemistry Co., Ltd
(Chinese Shanghai).Methanol, acetone and acetonitrile from Tedia company (U.S., Ohio) by buying.Methylene chloride and n-hexane from
Concord Technology Co., Ltd. (Chinese Tianjin) purchase.The every other reagent and chemicals used in this experiment at least divides
Analyse pure rank.Contain 1mgmL respectively by being dissolved in prepare in 10mL volumetric flask by 4 kinds of phenols-1BPA, BPAF, OP and
The stock solution of NP.Series of standards solution is obtained by diluting stock solution step by step with methanol.All solution is using it
Preceding needs are kept in dark place under the conditions of 4 DEG C.
1 magnetic Nano Fe of embodiment3O4With the preparation of magnetic covalent organic framework microballoon
(1) magnetic Nano Fe3O4Preparation
By FeCl3·6H2O (8.1g), Na3CO2·2H2O (1.5g) and sodium acetate (12.0g) are dissolved in ethylene glycol
In (200mL), then it is vigorously stirred.Then, the homogeneous yellow solution of acquisition is transferred in autoclave, is then heated to 200
DEG C continue 12 hours.After reaction, the Fe that will obtain3O4Microballoon uses ethyl alcohol and deionized water supersound washing for several times respectively, then 50
It is dried in vacuo at DEG C spare.
(2) preparation of magnetic covalent organic framework microballoon
The synthesis process of the magnetic covalent organic framework microballoon of nucleocapsid structure is as follows: 250mL three neck round bottom is used, it will
Fe3O4(0.3g), 1,3,5- tri- (4- aminophenyl) benzene (0.212g) and terephthalaldehyde (0.12g) are dissolved in dimethyl sulfoxide
In (DMSO, 120mL).And it is ultrasonically treated 5 minutes.Then, acetic acid (35M, 4mL) is slowly added to the help of ultrasonic treatment,
Brown precipitate (Fe is formed in the process3O4@COF) (about 10 minutes).After incubating 30 minutes, collected with the help of magnet
The brown precipitate of generation, is then washed three times with anhydrous tetrahydro furan and anhydrous methanol.Finally, preceding by brown precipitate using
Object is dried in vacuo at room temperature.
The Fe prepared by tem observation3O4With the high-amplification-factor form of magnetic covalent organic framework microballoon (Figure 1A and
1B).Two images show naked Fe3O4The shape of core is close to spherical shape, average diameter 150-250nm.Typical core-shell structure copolymer knot
Structure has been formed, by Fe3O4Core and COFs shell composition, the thickness of COFs shell is about 25nm.
FT-IR infrared spectroscopy confirms the successful synthesis (Fig. 1 C) of magnetic covalent organic framework microballoon.585cm-1The allusion quotation at place
Type absorption band is attributed to Fe-O-Fe vibration, 3421,1640 and 1388cm-1The absorption band at place shows that there are carboxyls.Magnetism covalently has
Machine skeleton microballoon and bare Fe3O4Core and TAPB with TPA monomer are compared, and prepared magnetic covalent organic framework microballoon exists
1450-1600cm-1And 1610cm-1There is new characteristic peak in place, respectively corresponds benzene skeleton in COF material and C=N key
Vibration.In addition, X-ray diffraction analysis (XRD) (Fig. 1 D) is for measuring the Fe with and without COF shell3O4Crystal structure and
Phase purity.The XRD of the magnetic covalent organic framework microballoon of synthesis is consistent with previous report, shows that the material successfully closes
At.By Fe3O4XRD be compared with magnetic covalent organic framework microballoon, the XRD of magnetic covalent organic framework microballoon shows
There is wide diffraction maximum at about 2.7 ° and 19.5 °, this may be as caused by the low-crystallinity of COF shell.
Chemical stability of the magnetic covalent organic framework microballoon in the aqueous solution and organic solvent of different pH value is to absorption
Have a significant impact with elution process, and determines that new material if appropriate for making MSPE adsorbent, therefore has vital meaning.
As referring to figure 1E, in 1molL-1HCl and 1molL-1The FT-IR observed in the aqueous solution and organic solvent of NaOH is infrared
Spectrum does not have significant change.This show magnetic covalent organic framework microballoon be under varying experimental conditions it is stable, this obviously
It is due to the strong C=N covalent bond in polyimides connecting framework.Therefore, magnetic covalent organic framework microballoon can be used as one kind
Suitable magnetic solid phase extraction adsorbent.
Fe3O4It is shown in figure 1f with the magnetic hysteresis loop of magnetic covalent organic framework microballoon.Two kinds of sample performance excess of export are suitable
Magnetism, the saturation magnetization value of magnetic covalent organic framework microballoon are 62.5emug-1Although with naked Fe3O4
(81.5emu·g-1) compared to being declined slightly.Magnetic covalent organic framework microballoon has very high saturation magnetization and outside
Magnetic sensitivity.As shown in the illustration of Fig. 1 F, it can be well dispersed in water, form brown suspension.Suspension is non-
Often uniformly, it does not precipitate overnight.However, magnetic covalent organic framework microballoon can be by means of external magnet uniformly dividing from them
Very quick aggregation (about 1 minute) is realized in granular media, thus muddy solution becomes to clarify.
By N2The Brunauer-Emmett-Teller of the magnetic covalent organic framework microballoon of adsorption isotherm line computation compares table
Area is 166.5m2·g-1, pore volume 0.26cm3·g-1.They are significantly larger than naked Fe3O4Microballoon, value are respectively
10.7m2·g-1And 0.11m3·g-1(Fig. 1 G and Fig. 1 H).The biggish specific surface area of magnetic covalent organic framework microballoon
(166.5m2·g-1) and biggish pore volume (0.26m3·g-1) make it than individual Fe3O4Microballoon is more suitable for magnetic solid phase extraction
Take adsorbent.
A kind of method for analyzing phenols endocrine disruptors in beverage of embodiment 2
It the described method comprises the following steps:
(1) sample pretreatment
Sample is centrifuged 10 minutes with 10000rpm at 4 DEG C to remove sediment, then passes through 0.22- μm of microporous barrier mistake
Filter, takes supernatant.In the clean Brown Glass Brown glass bottles and jars only that finished tea beverage sample is stored in, it is stored under the conditions of 4 DEG C, is used for
Subsequent magnetic solid phase extraction process.
(2) magnetic solid phase extraction
25mL sample solution is added in vial, sample pH 6,40mg magnetism is then added in the solution covalently to be had
Machine skeleton microballoon.Mixture is shaken 30 minutes in water bath chader with 300 revs/min at room temperature.Then, by means of position
Magnet outside vial is separated from the water by adsorbent, and supernatant is discarded completely.Next, 3ml methanol is added
Into isolated magnetic solid phase extraction adsorbent, and pass through the 3 minutes elution analysis objects that are ultrasonically treated 3 minutes and are vortexed.It repeats again
The analytic function.The solution of elution is mixed and at 30 DEG C nitrogen drying it is dry.Finally, dissolving residue using 250 μ L methanol.With
The magnetic covalent organic framework microballoon crossed is preceding in the next use to use methanol supersound washing three times.
(3) liquid chromatogram-fluorescence detection
Use the Shimadzu LC-20A high performance liquid chromatography (day equipped with RF-20A fluorescence detector (FLD) (Japan, Shimadzu)
This, Shimadzu) it is analyzed.Chromatographic column C8 column (150mm × 2.1mm, 5 μm)；Column oven: 35 DEG C；Flow velocity: 1ml/min；Sample introduction body
Product is 20 μ L；Mobile phase: (A) hplc grade water and (B) acetonitrile.Gradient elution are as follows: (1) 0 minute, 40%B；(2) 24 minutes, 80%
B；(3) 28 minutes, 80%B；(4) 28.2 minutes, 45%B and (5) 30 minutes, 45%B.Being provided that for fluorescence detector is sharp
Send out wavelength 220nm, launch wavelength 315nm.
Test example
(1) magnetic solid phase extraction condition optimizing
In order to evaluate extracting power of the magnetic covalent organic framework microballoon as magnetic solid phase extraction coating, four kinds of phenols are selected
Incretion interferent BPA, BPAF, OP, NP are investigated as target contaminant, using liquid chromatogram-fluorescence detector into
Row detection.During the experiment, by the rate of recovery come evaluation test effect.
Six kinds of factors for influencing experimentation are optimized using single factor test optimization, including eluent type, extraction
Take time, adsorbent amount, pH, ionic strength and effluent volume (Fig. 2).In test, eluent type includes: methanol, second
Nitrile, acetone, methylene chloride and n-hexane, effluent volume range are 2-12mL, and ionic strength is adjusted using NaCl,
The NaCl that ionic strength range is 0~20%, extraction time range are 10~60min, and pH range is 2~12, adsorbent amount
For 10-80mg.The optimum test condition of final choice is selected as: eluent, 6mL methanol (3mL × 2)；Sample pH, 6；Magnetism is altogether
Valence organic backbone microballoon dosage, 40 milligrams；Extraction time, 30 minutes；NaCl, 0%.
MSPE method after optimization is in 0.05-1000ngmL-1Concentration range in show good linear relationship (R
≥0.995).Detection limit (LOD) range for being 3 based on signal-to-noise ratio (S/N) is 0.08 to 0.21ngmL-1.It is counted by S/N=10
Quantitative limit (LOQ) range of calculation is 0.39 to 0.85ngmL-1.For four kinds of phenols endocrine disruptors, in a few days deviation (n=
5) and in the daytime deviation (n=5) is respectively 0.39-4.99% and 1.57-5.21%.In addition, magnetic covalent organic framework microballoon can
It is lost with reuse 20 times or more without significant extraction efficiency.Shown in table 1 specific as follows.
1 Methodological Analysis performance of table
(2) actual sample is analyzed
For the applicability for verifying institute's method for building up, four kinds of different plastics package tea beverage are analyzed in optimal conditions.
In this test, four kinds of different plastics package tea beverage from four different manufacturers are used as actual sample.These four
Tea beverage is as follows: the icy bleak tea of Unified China Pty Ltd (TaiWan, China) production, Chef Kang's Pty Ltd (China
Tianjin) production jasmine tea, Dary food group (Fujian China Quanzhou) production green plum green tea, NongFuShanQuan Co., Ltd
The honey peach oolong tea of (Zhejiang Province, China Hangzhou) production.These four tea beverage are bought from local supermarket's (Jinan China).
It is respectively 5,50 and 100ngmL by the way that concentration is added-1The standard solution of phenols endocrine disruptors study
The rate of recovery.As shown in table 2, phenols endocrine disruptors are not detected in four kinds of plastics package tea beverage, the rate of recovery exists
Between 81.3% and 118.0% (RSD 0.1-8.3%).These results indicate that different beverage bases is to this novel MSPE
Method has little effect.The typical chromatogram of plastics package green tea beverage sample is as shown in Figure 3.These results indicate that this
Novel MSPE method can be used for measuring four kinds of phenols endocrine disruptors of trace level in practical drink sample.
The analysis result of 2 actual sample of table
aIt is not detected
bRate of recovery average value ± standard deviation
The present invention has synthesized the magnetic covalent organic framework of nucleocapsid structure at room temperature, and combines liquid chromatogram-fluorescence inspection
Device is surveyed, the magnetic solid phase microextraction-liquid chromatogram-fluorescence analysis for establishing polarity phenols endocrine disruptors in analysis beverage is newly square
Method.Low (the minimum reachable 0.08ng mL of new method detection limit-1), wide (the 0.5-1000ng mL of the range of linearity-1), reproducible (day
It is interior, 0.39%-4.99%, in the daytime, 1.57%-5.21%), and phenols incretion in practical drink sample can be successfully applied to
The analysis of chaff interferent.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of magnetic covalent organic framework microballoon of nucleocapsid structure, which is characterized in that the magnetism of the nucleocapsid structure is covalently
Organic backbone microballoon is prepared by following methods:
S1. by FeCl3·6H2O, Na3CO2·2H2O and sodium acetate are dissolved in ethylene glycol, and after mixing evenly, solution is transferred to
In autoclave, it is heated to 200 DEG C and continues 12 hours；After reaction, the magnetic Nano Fe that will obtain3O4Particle with ethyl alcohol and is gone respectively
Ionized water supersound washing for several times, is then dried in vacuo at 50 DEG C spare；
S2. magnetic Nano Fe step S1 being prepared3O4Particle, 1,3,5- tri- (4- aminophenyl) benzene and terephthalaldehyde
It is dissolved in dimethyl sulfoxide, is ultrasonically treated 5 minutes, and be slowly added to acetic acid, after incubating 30 minutes, collects the brown precipitate of generation
Object, is then washed three times with anhydrous tetrahydro furan and anhydrous methanol, be dried in vacuo at room temperature to get.
2. the magnetic covalent organic framework microballoon of nucleocapsid structure described in claim 1 is in detection phenols endocrine disruptors
Using.
3. application according to claim 2, which is characterized in that the answering in phenols endocrine disruptors in detection beverage
With.
4. a kind of method for analyzing phenols endocrine disruptors in beverage, which is characterized in that using described in claim 1
The magnetic covalent organic framework microballoon of nucleocapsid structure is adsorbent, in conjunction with magnetic solid phase extraction and liquid chromatogram-fluorescence analysis
It is tested and analyzed.
5. according to the method described in claim 4, it is characterized in that, it is specific the following steps are included:
(1) sample pretreatment；
(2) magnetic solid phase extraction, the sample that is added that step (1) treated in vial, adjustment sample pH value is 2-12, addition right
It is required that the magnetic covalent organic framework microsphere adsorbing agent of 1 nucleocapsid structure, solution ion strength is adjusted, ionic strength is 0~
20% NaCl, water-bath mechanical shaking extraction is separated from the water by adsorbent, and discards clear liquid；Eluent is added to and is isolated
It in adsorbent, repeats to elute after ultrasonic treatment, be dissolved after the solution of elution is mixed, is dry with eluent to get magnetic solid phase extraction
Take sample；
(3) the magnetic solid phase extraction sample that step (2) is prepared carries out liquid chromatogram-fluorescence detection.
6. according to the method described in claim 5, it is characterized in that, step (1) sample pretreatment, specifically: by sample in 4-
It, then by 0.22- μm of micro-pore-film filtration, was taken with 5000-10000rpm centrifugation 10-20 minutes with removing sediment at 10 DEG C
Clear liquid.In the clean Brown Glass Brown glass bottles and jars only that finished tea beverage sample is stored in, it is stored under the conditions of 4 DEG C, for subsequent
Magnetic solid phase extraction process.
7. according to the method described in claim 5, it is characterized in that, eluent is n-hexane, methylene chloride, third in step (2)
Any one in ketone, methanol and ethyl alcohol；The eluent dosage is 2-12mL.
8. according to the method described in claim 5, it is characterized in that, extraction time is 10~60min, adsorbent in step (2)
Dosage is 10-80mg.
9. according to the method described in claim 5, it is characterized in that, chromatographic column C8 column used in step (3): 150mm × 2.1mm, 5
μm；Column oven: 35 DEG C；Flow velocity: 1ml/min；Sampling volume is 20 μ L.
10. according to the method described in claim 5, it is characterized in that, step (3) mobile phase are as follows: hplc grade water A and acetonitrile B；It adopts
With gradient elution: 0 minute, 40%B；24 minutes, 80%B；28 minutes, 80%B；28.2 minutes, 45%B and 30 minute, 45%
B；Fluorescence detector is provided that excitation wavelength 220nm, launch wavelength 315nm.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101337695A (en) * | 2008-08-07 | 2009-01-07 | 上海交通大学 | Method for preparing nanometer ferroferric oxide microballoons with particle diameter adjustable by microwave |
| CN101728046A (en) * | 2009-11-23 | 2010-06-09 | 中国科学院宁波材料技术与工程研究所 | Method for preparing mono-disperse magnetic controllable Fe3O4-SiO2 nuclear shell ball cluster |
| CN102633307A (en) * | 2012-04-19 | 2012-08-15 | 上海交通大学 | Method for hydrothermally preparing mono-dispersed hollow magnetic nanometer particles |
| CN103318974A (en) * | 2013-07-04 | 2013-09-25 | 南通宝聚颜料有限公司 | Preparation method of ferroferric oxide magnetic carrier |
| CN105384146A (en) * | 2015-12-09 | 2016-03-09 | 唐山建华科技发展有限责任公司 | Graphene-loaded nanometer Fe<3>O<4>/ZnO composite and preparation method thereof |
| CN105597713A (en) * | 2016-03-11 | 2016-05-25 | 山东省分析测试中心 | Magnetic solid-phase extraction material and preparation method and application thereof |
| CN105664861A (en) * | 2016-04-20 | 2016-06-15 | 福州大学 | Magnetic covalent organic framework nanocomposite material and preparation method and application |
| CN105879842A (en) * | 2016-06-22 | 2016-08-24 | 郑州大学 | Magnetic PAFs solid-phase extracting agent and preparation method and application thereof |
| CN107860834A (en) * | 2017-10-23 | 2018-03-30 | 山东省分析测试中心 | A kind of method that trace perfluorinated compound is analyzed using magnetic organic framework material |
-
2018
- 2018-09-18 CN CN201811087301.7A patent/CN109342613B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101337695A (en) * | 2008-08-07 | 2009-01-07 | 上海交通大学 | Method for preparing nanometer ferroferric oxide microballoons with particle diameter adjustable by microwave |
| CN101728046A (en) * | 2009-11-23 | 2010-06-09 | 中国科学院宁波材料技术与工程研究所 | Method for preparing mono-disperse magnetic controllable Fe3O4-SiO2 nuclear shell ball cluster |
| CN102633307A (en) * | 2012-04-19 | 2012-08-15 | 上海交通大学 | Method for hydrothermally preparing mono-dispersed hollow magnetic nanometer particles |
| CN103318974A (en) * | 2013-07-04 | 2013-09-25 | 南通宝聚颜料有限公司 | Preparation method of ferroferric oxide magnetic carrier |
| CN105384146A (en) * | 2015-12-09 | 2016-03-09 | 唐山建华科技发展有限责任公司 | Graphene-loaded nanometer Fe<3>O<4>/ZnO composite and preparation method thereof |
| CN105597713A (en) * | 2016-03-11 | 2016-05-25 | 山东省分析测试中心 | Magnetic solid-phase extraction material and preparation method and application thereof |
| CN105664861A (en) * | 2016-04-20 | 2016-06-15 | 福州大学 | Magnetic covalent organic framework nanocomposite material and preparation method and application |
| CN105879842A (en) * | 2016-06-22 | 2016-08-24 | 郑州大学 | Magnetic PAFs solid-phase extracting agent and preparation method and application thereof |
| CN107860834A (en) * | 2017-10-23 | 2018-03-30 | 山东省分析测试中心 | A kind of method that trace perfluorinated compound is analyzed using magnetic organic framework material |
Non-Patent Citations (4)
| Title |
|---|
| GUO LIN ET AL.: "Room-temperature synthesis of core-shell structured magnetic covalent organic frameworks for efficient enrichment of peptides and simultaneous exclusion of proteins", 《CHEMCOMM》 * |
| LEI CHEN ET AL.: "Preparation of core-shell structured magnetic covalent organic framework nanocomposites for magnetic solid-phase extraction of bisphenols from human serum sample", 《TALANTA》 * |
| NING LI ET AL.: "Magnetic covalent organic frameworks based on magnetic solid phase extraction for determination of six steroidal and phenolic endocrine disrupting chemicals in food samples", 《MICROCHEMICAL JOURNAL》 * |
| 杨健 等: "辛醇辅助磁固相萃取-HPLC检测环境水中酚类物质", 《云南大学学报（自然科学版）》 * |
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|---|---|---|---|---|
| CN109912807A (en) * | 2019-02-18 | 2019-06-21 | 山东省分析测试中心 | A kind of preparation method and applications of covalent organic frame material |
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