CN109541088A - A kind of purification method of patulin, solid-phase extraction column and its application - Google Patents
A kind of purification method of patulin, solid-phase extraction column and its application Download PDFInfo
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Abstract
The present invention relates to a kind of purification method of patulin, solid-phase extraction column and its application.Sample to be clean is passed sequentially through the multi-walled carbon nanotube and neutral alumina of carboxylated by the present invention, or sample to be clean is passed sequentially through to the multi-walled carbon nanotube of neutral alumina and carboxylated；To realize the purification for biotoxins such as patulins.The present invention is suitable for the purification detection of various water fruits and vegetables and food samples, and impurity removal is thorough, method simple and effective.
Description
Technical field
The present invention relates to agricultural product security detection technique field, relate in particular to a kind of decontamination of biological toxin method,
Solid-phase extraction column and its application.
Background technique
Patulin (patulin, PAT), also known as clavacin are a kind of toxic polyketides.Mainly by blueness
Mould category (Penicillium), aspergillus (Aspergillus), paecilomyces (Paecilomyces) and the mould category of silk clothes
(Byssochlamys) some fungi in generates.PAT is a kind of worldwide fruits and vegetables pollutant, in a variety of fruits and vegetables and its
It is found in product, position PAT content highest of rotting especially in the fruit of fungal infection, up to 1000 μ g/kg or more；
Whole fruit average content is up to 21~746 μ g/kg.Due to the limitation of current processing technology, when the fruit for using morbidity rotten as
When raw material carry out the productions of products such as fruit juice, PAT is just as process of manufacture enters in processing finished product.In addition, processing
The delay of process or the temporary delay of semi-finished product in the process can all cause regrowing for toxin producing strains malicious with production, thus shape
Cause secondary pollution.There is the detection of PAT in the fruit products such as fruit juice, fruit wine at present.
PAT has acute toxicity, including the lung to animal, brain edema, liver, spleen, the damage of kidney and immune system
Toxic action；Also there is chronic toxicity, show the cytotoxicity to animal, genotoxicity, immunotoxicity and potential carcinogenic
Property；At present PAT by international cancer research institution (International Agency for Research on Cancer,
IARC) it is classified as the 3rd class carcinogen.PAT in human diet is mainly derived from by the apple and cider of mould contamination.Due to
PAT is difficult to completely remove in cider production process, and countries in the world and international organization have formulated the maximum of PAT in fruit and remained
Limitation.Countries in the world have further pushed the development of mycotoxin detection method to the mandatory provisions that mycotoxin is limited the quantity.Mesh
It is accurate that the detection method standard of preceding domestic and international mycotoxin mostly uses immune affinity column (IAC) to come in conjunction with HPLC or HPLC-MS/MS
It is quantitative, however, immunogenicity is poor since PAT is small molecule compound, still lack corresponding IAC product.The inspection of patulin
Survey belongs to trace analysis, and sample pre-treatments are most important, is directly related to the accuracy and reliability of result.Penicillium patulum at present
The detection method of element mainly includes thin-layered chromatography, high performance liquid chromatography, gas chromatography and hyphenated techniques chromatography etc..Sample
Extraction solvent is mainly the mixed liquor of ethyl acetate, acetonitrile or acetonitrile and water.The purifying of extracting solution mainly use natrium carbonicum calcinatum,
The purification methods such as C18 solid-phase extraction column, hydrophilic-lipophilic balance column, series connection PVPP-C18 column, Mycosep multiple function.Industry mark
Quasi- NY/T1650-2008 uses liquid chromatography for measuring patulin content.Mainly use MycosepTMThe more function of 228AflaPat
Energy column purifies sample, and the method is simple, quick, sensitive, accurate.But the multiple function is expensive and depends on import.
And C18 solid-phase extraction column, hydrophilic-lipophilic balance column, series connection PVPP-C18 column etc. all operate it is relative complex, by loading, elution and
The processes such as elution, it is time-consuming, it is also consumed by organic solvent, and also have limitation to sample, effect is but difficult to reach MycosepTM
The effect of 228AflaPat multiple function.
Currently, therefore still lacking a kind of method of cheap, easy to operate, quick enrichment purification patulin has
Necessity establishes efficient and reliable analysis method to monitor the generation and pollution condition of patulin in agricultural product.
Summary of the invention
It is poor to patulin detection clean-up effect in agricultural product present invention aims to solve existing Solid Phase Extraction column technology, it returns
The problem of yield is low, and reagent is complex, cannot carry out accurate detection to various water fruits and vegetables and food samples, into
And propose a kind of purification method of patulin, patulin is rapidly and efficiently detected with realizing.
The research of the invention finds that the filling out as step purification solid-phase extraction column using the nano material with bigger serface
Material is filled, it is preferable for the purification of patulin etc. mycotoxin, with MycosepTMThe clean-up effect of 228 solid-phase extraction columns is close
Seemingly or more preferably.Wherein, the multi-walled carbon nanotube of carboxylated has good absorption property to impurity, and it is miscellaneous can significantly to remove interference
Matter；Neutral alumina can effectively remove the polar impurity in fruits and vegetables.Therefore, above two filler compounding can effectively remove in sample
Impurity, sample after processing is very clean, and liquid phase detects noiseless peak, and matrix effect almost all is gone when liquid quality detection
It removes；Sensitivity does not have significant change after continuous sample introduction, and triple mass spectrometric ion sources of level four bars still keep clean.Based on above-mentioned
The present invention is specifically proposed for research.
Specifically, the present invention provides a kind of purification method of biotoxin, including sample to be clean is passed sequentially through into carboxylic
The multi-walled carbon nanotube and neutral alumina of base, or sample to be clean is passed sequentially through into the more of neutral alumina and carboxylated
Wall carbon nano tube；To realize the purification for biotoxin.
The study found that sample to be clean purified by the multi-walled carbon nanotube and neutral alumina of carboxylated it is successive
Sequence does not have significant difference for clean-up effect, and two kinds of purification methods can meet testing requirements.
Further, the functionalized multi-wall carbonnanotubes internal diameter is 3~5nm, and outer diameter is 8~15nm；Length is preferred
50 μm or so.
Further, the neutral alumina (as positive chromatograph packing material), partial size are 40~60 μm, preferably average grain diameter
It is 50 μm.
The functionalized multi-wall carbonnanotubes, neutral alumina are commercially available to be bought.
Leakage method can be used when specific purification, i.e., be directly added into sample to be clean (such as extracting solution containing patulin)
Using the functionalized multi-wall carbonnanotubes as filler solid-phase extraction column (or using the neutral alumina as filler solid phase extract
Take column)；Efflux after collecting column, adding using the neutral alumina is the solid-phase extraction column of filler (or with described
Functionalized multi-wall carbonnanotubes are the solid-phase extraction column of filler)；Efflux after collecting column can be obtained purified to net
Change sample.Related impurities are retained by solid-phase extraction column.
More easy purification method is prepared first with the functionalized multi-wall carbonnanotubes and the neutral alumina
For the solid-phase extraction column of filler, sample to be clean is directly added into the solid-phase extraction column, the efflux after collecting column can obtain
Obtain purified sample to be clean.When being purified using this solid-phase extraction column, in solid-phase extraction column filler with it is to be clean
The volume ratio of sample solution is preferred for 1:2-1:20.
In addition to patulin, purification method of the present invention is also particularly suitable vomitoxin (DON), zearalenone
(ZEN), other neutral or acidic toxins purifications such as aflatoxin.
Conventional method in that art preparation can be used in the sample to be clean.
Measuring samples include the fruits and vegetables such as apple, hawthorn, pears.
Further, purified sample can be analyzed using liquid chromatogram or Liquid Chromatography-Tandem Mass Spectrometry instrument, is led to
It crosses multiple-reaction monitoring (MRM) mode and carries out accurate quantitative analysis.
Further, it is based on the studies above, the present invention also provides a kind of solid-phase extraction columns, for realizing for patulin
The rapidly and efficiently purification of equal biotoxins.
Specifically, a kind of solid-phase extraction column comprising the functionalized multi-wall carbonnanotubes filler and the neutral oxygen
Change Al filler.
Further, in the solid-phase extraction column functionalized multi-wall carbonnanotubes filler and neutral alumina Al filler volume
Than for 1:5-1:20.
Further, the solid-phase extraction column further include positioned at functionalized multi-wall carbonnanotubes filler and neutral alumina it
Between sieve plate；The sieve plate is mainly used for separating functionalized multi-wall carbonnanotubes filler and neutral alumina Al filler.
Further, the solid-phase extraction column further includes upper sieve plate and/or lower sieve plate.
Hole diameter of sieve (perforated) plate of the present invention is 10~30 μm, and preferably its aperture is 22 μm.
The sieve plate can be polyethylene or polytetrafluoroethylene (PTFE) material, it is commercially available to buy.
Further, the invention also includes the preparation methods of above-mentioned solid phase extraction column, comprising: in solid-phase extraction column ontology
One layer of sieve plate is added in bottom, and functionalized multi-wall carbonnanotubes filler is added on this sieve plate or neutral alumina is filled out
Material, adds another layer of sieve plate thereon, and neutral alumina Al filler or functionalized multi-wall carbonnanotubes filler are added on this sieve plate,
One layer of sieve plate is added thereon, is compressed to get solid-phase extraction column.
The present invention also provides application of the above-mentioned solid phase extraction column in terms of the biotoxins purification such as patulin.
The utility model has the advantages that
(1) solid-phase extraction column provided by the invention, is suitable for various water fruits and vegetables and food samples, and sample acetonitrile/water mentions
After taking, column, purification can be directly crossed.Compared with general solid phase extraction method, the method is more simple and efficient, saves at sample
The time of reason and cost, the consumption for reducing organic solvent, make that the pre-treatment of Mycotoxin identification is more convenient, efficient, standard.
(2) the present invention is based on the solid-phase extraction column preparation step of a step cleaning principle is simple, specific apparatus is not depended on, it is conventional
It can be prepared in laboratory；Experiment flow is very fast, can carry out pre-treatment to sample in batches, every batch of can handle 30 simultaneously, entirely
Column process is crossed no more than 1 hour；
(3) functionalized multi-wall carbonnanotubes and neutral alumina Al filler can be commercialized to obtain, if with single branch solid phase extraction
The loading for taking column is functionalized multi-wall carbonnanotubes 20mg, and neutral alumina Al filler is 400mg, Na Danzhi solid-phase extraction column
Price is no more than 10 yuan, and compared with existing commercialization solid phase column, while guaranteeing clean-up effect, cost is greatly saved；
(4) solid-phase extraction column provided by the invention, it is net as a step using the nano material with bigger serface for the first time
The packing material for changing solid-phase extraction column, for the purification to mycotoxin.The multi-walled carbon nanotube of carboxylated has very impurity
Good absorption property, can significantly remove interference impurity；Neutral alumina can effectively remove the polar impurity in fruits and vegetables.Therefore,
Two kinds of filler compoundings can effectively remove the impurity in sample, and sample after processing is very clean, and liquid phase detects noiseless peak, liquid
Matrix effect almost all removes when quality detection；Sensitivity does not have significant change, triple level four bars mass spectrographs after continuous sample introduction
Ion source still keep clean.
Detailed description of the invention
Fig. 1 is solid-phase extraction column structural schematic diagram of the present invention, wherein 1 is column tube (solid-phase extraction column ontology), 2 be sieve plate, 3
It is sieve plate for functionalized multi-wall carbonnanotubes filler, 4,5 be neutral alumina Al filler (positive chromatograph packing material), and 6 be sieve plate.
Fig. 2 is 6 scavenging solution HPLC testing result figure of embodiment；A is solvent mark, b MycosepTM228 solid-phase extraction columns
Clean-up effect, c are the clean-up effect of 1 solid-phase extraction column of embodiment.
Specific embodiment
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..
Following hole diameter of sieve (perforated) plate is 10-30 μm, and average pore size is 22 μm, and material is polyethylene or polytetrafluoroethylene (PTFE)；Following carboxylic
Base multi-walled carbon nano-tube filler internal diameter is 3~5nm, and outer diameter is 8~15nm, and length is 50 μm；Following neutral alumina is (i.e. just
To chromatograph packing material) partial size be 40~60 μm, average grain diameter be 50 μm.
Following sieve plate, functionalized multi-wall carbonnanotubes filler, neutral alumina are purchased from the limited public affairs of Beijing Ci Weite science and technology
Department.
(ontology) internal diameter of column tube used in solid-phase extraction column is 12.7mm, and volume 6mL, material is polypropylene or glass.
1 solid-phase extraction column of embodiment and its preparation
Solid-phase extraction column, structure are as shown in Figure 1, comprising: wherein column tube (solid-phase extraction column ontology) 1, sieve plate 2, carboxyl
Multi-walled carbon nano-tube filler 3, sieve plate 4, neutral alumina Al filler (positive chromatograph packing material) 5, sieve plate 6.Wherein, the carboxylic accommodated
Base multi-wall carbon tube filler and neutral alumina packing volume are respectively 0.2mL, 2mL.
Assemble method first inserts a piece of sieve plate 6 in Xiang Zhuguan 1, and 2mL neutral alumina Al filler 5 is added) it is further filled with second piece
Sieve plate 4 is added 0.2mL carboxylated multi-wall carbon tube filler 3, is further filled with third block sieve plate 2, compresses.
2 solid-phase extraction column of embodiment and its preparation
Solid-phase extraction column, structure is as shown in Figure 1, the difference with embodiment 1 is only that carboxylated multi-wall carbon tube filler
Volume is 0.5mL.
3 solid-phase extraction column of embodiment and its preparation
Solid-phase extraction column, the difference with embodiment 1 are only that: exchanging functionalized multi-wall carbonnanotubes filler 3 and neutral oxygen
Change the position of Al filler (positive chromatograph packing material) 5.
4 solid-phase extraction column of embodiment and its preparation
Solid-phase extraction column, the difference with embodiment 2 are only that: exchanging functionalized multi-wall carbonnanotubes filler 3 and neutral oxygen
Change the position of Al filler (positive chromatograph packing material) 5.
The leakage method of 5 mycotoxin of embodiment
(1) accurately weighing 5.0g (being accurate to 0.01g) homogeneous, good apple, hawthorn and pears sample is placed in centrifuge tube with cover
In, it is added 25mL Acidifying acetonitrile solution (ethane nitrile content 80% contains 1% formic acid), after vortex oscillation 2min, the vibration of 150r/min room temperature
It swings and extracts 30min.Then 2g sodium chloride is added to saltout, 5min is centrifuged at 10000 × g, it is to be clean to collect supernatant.
(2) take 4mL supernatant, respectively nature by 1 solid-phase extraction column of embodiment, 2 solid-phase extraction column of embodiment and
MycosepTM228 solid-phase extraction columns, the supernatant after collecting column, nitrogen blows close dry at 60 DEG C.
(3) residue is dissolved with acetonitrile solution (10/90, v/v), after crossing 0.22 μm of filter membrane, filtered fluid (i.e. scavenging solution)
To which sample introduction is analyzed.
Embodiment 6 carries out HPLC detection and analysis to the sample (i.e. scavenging solution) of embodiment 5
1, it is as follows to test and analyze condition:
The condition of liquid phase separation are as follows: chromatographic column is Agilent Zorbax T3 column, column length 150mm, internal diameter 4.6mm, partial size
3.5μm；Eluent gradient is elution requirement: 0min~13min is 5% acetonitrile and 95% water, and 13min~15min is 100% second
Nitrile, 15min~20min are 5% acetonitrile and 95% water.Flow velocity is 0.8mL/min；Chromatographic column column temperature is 40 DEG C；Sample volume is 100
μL；Ultraviolet detection wavelength is 276nm.
2, the repeatability and the coefficient of variation of solid phase extraction column for patulin:
Blank sample 5.0g after measured is weighed, the standard solution of three horizontal above-mentioned patulins is added, mixes well,
And stand 2h at room temperature, carry out pre-treatment according to the method for embodiment 5 and measure content, each processing method is measured in parallel 6
Part.Testing result is shown in Table 1-2 (TIANZHU XINGNAO Capsul and the coefficient of variation of opening up green toxin) and Fig. 2.The result shows that embodiment 1,2 is solid
Mutually sample is cleaner after extraction column purification.
The rate of recovery and precision of the scavenging solution patulin of 1 embodiment of table, 1 solid-phase extraction column preparation
2 Mycosep of tableTMThe rate of recovery and precision of the scavenging solution patulin of 228 solid-phase extraction columns preparation
Embodiment 7 carries out HPLC-MS/MS detection and analysis to the sample (i.e. scavenging solution) of embodiment 5
1, it is as follows to test and analyze condition:
(1) condition of liquid phase separation are as follows: chromatographic column be Waters UPLC CORTECS C18 column (100mm × 2.1mm,
1.6 μm) or with its kin reverse-phase chromatographic column, mobile phase is (A) 1mM ammonium acetate aqueous solution and (B) methanol.Flow velocity is
0.3mL/min carries out gradient elution, and condition of gradient elution is as shown in table 3 below:
3 eluent gradient elution program (volume) of table
(2) Mass Spectrometry Conditions: ion source module: negative ions mode (ESI+And ESI-)；Spray voltage: 2.5kv (ESI+)
With -0.8kv (ESI-)；Gasification temperature: 500 DEG C；Dry gas stream speed: 12mL/min；Sampling volume is 5 μ L；13 kinds of mycotoxins
Mass spectrometry parameters be shown in Table 4.
The mass spectrometry parameters of 4 mycotoxin of table
2, the repeatability and the coefficient of variation of mycotoxin solid-phase extraction column:
Blank sample 5.0g after measured is weighed, above-mentioned 13 kinds of mycotoxin mixed standard solutions of 10LOQ are added, it is sufficiently mixed
It is even, and stand 2h at room temperature, carry out pre-treatment according to the method for embodiment 5 and measure content, each processing method is surveyed in parallel
It is 6 parts fixed.The TIANZHU XINGNAO Capsul and the coefficient of variation of all mycotoxins are shown in Table 5.
The rate of recovery and precision of 5 13 kinds of mycotoxins of table
Note: the "-" rate of recovery is lower than 10%
As can be seen from Table 5, solid-phase extraction column of the present invention not only has preferable clean-up effect to patulin, while can
Realize aflatoxin, 13 kinds of mycotoxins such as fusarium toxin purify simultaneously, and the rate of recovery is able to satisfy EC regulations requirement, warp
Purified sample is cleaner.MycosepTM228 decontaminating columns are mainly for aflatoxin, as can be seen from Table 5,4 kinds of Huangs
The rate of recovery of aspertoxin is all higher, but compared with solid-phase extraction column of the invention, the higher vomitoxin of recall rate in corn
(DON) and the rate of recovery of zearalenone (ZEN) is lower than 70%, is not able to satisfy EC regulations requirement.Due to DON, ZEN, T-
2, aflatoxin has the mycotoxin of related limit standard laws and regulations requirement to patulin for China, uses solid phase of the invention
Extraction column can realize that finite quantity normaltoxin pollutes accurate quantitative in sample, and clean-up effect is preferable.
Although above having used general explanation, specific embodiment and test, the present invention is made to retouch in detail
It states, but on the basis of the present invention, it can be made some modifications or improvements, this is apparent to those skilled in the art
's.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to claimed
Range.
Claims (10)
1. a kind of purification method of biotoxin, which is characterized in that the multi wall including sample to be clean to be passed sequentially through to carboxylated
Carbon nanotube and neutral alumina, or sample to be clean is passed sequentially through to the multi-wall carbon nano-tube of neutral alumina and carboxylated
Pipe；To realize the purification for biotoxin.
2. purification method according to claim 1, which is characterized in that the functionalized multi-wall carbonnanotubes internal diameter be 3~
5nm, outer diameter are 8~15nm；And/or the neutral alumina, partial size are 40~60 μm.
3. purification method according to claim 2, which is characterized in that the functionalized multi-wall carbonnanotubes length is 50 μm
Left and right；And/or the neutral alumina average grain diameter is 50 μm.
4. purification method according to claim 1-3, which is characterized in that prepared first with the carboxylated multi wall
Carbon nanotube and the neutral alumina are the solid-phase extraction column of filler, and sample to be clean is directly added into the solid-phase extraction column,
Efflux after collecting column can be obtained purified sample to be clean.
5. purification method according to claim 4, which is characterized in that filler and sample solution to be clean in solid-phase extraction column
Volume ratio be 1:2-1:20.
6. a kind of solid-phase extraction column, which is characterized in that including functionalized multi-wall carbonnanotubes filler and neutral alumina Al filler.
7. solid-phase extraction column according to claim 6, which is characterized in that the functionalized multi-wall carbonnanotubes internal diameter is 3
~5nm, outer diameter are 8~15nm；And/or the neutral alumina, partial size are 40~60 μm.
8. solid-phase extraction column according to claim 7, which is characterized in that the functionalized multi-wall carbonnanotubes length is 50
μm or so；And/or the neutral alumina average grain diameter is 50 μm；And/or carboxylated multi wall carbon in the solid-phase extraction column
Nanotube filler and the volume ratio of neutral alumina Al filler are 1:5-1:20.
9. application of any one of the claim 6-8 solid-phase extraction column in terms of biotoxin purification.
10. purification method according to claim 1-5 or application as claimed in claim 9, which is characterized in that institute
Stating biotoxin includes patulin, vomitoxin, zearalenone, aflatoxin.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111109591A (en) * | 2019-10-25 | 2020-05-08 | 新疆红旗坡农业发展集团有限公司 | Intestinal microecology high-efficiency reconstruction type apple enzyme and processing technology |
| CN111304036A (en) * | 2019-10-25 | 2020-06-19 | 新疆红旗坡农业发展集团有限公司 | Appetizing and summer-heat relieving type sugar-core apple raw wine and efficient deep processing technology |
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