CN109350996A - A kind of graphite multi-walled carbon nano-tube solid-phase extraction column and its application - Google Patents
A kind of graphite multi-walled carbon nano-tube solid-phase extraction column and its application Download PDFInfo
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- CN109350996A CN109350996A CN201811536751.XA CN201811536751A CN109350996A CN 109350996 A CN109350996 A CN 109350996A CN 201811536751 A CN201811536751 A CN 201811536751A CN 109350996 A CN109350996 A CN 109350996A
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- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G01N2030/062—Preparation extracting sample from raw material
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Abstract
The invention discloses a kind of graphite multi-walled carbon nano-tube solid-phase extraction column and its application, the graphite multi-walled carbon nano-tube solid-phase extraction column includes Solid Phase Extraction column tube, sieve plate and packing material, and the packing material is graphite multi-walled carbon nano-tube.The preparation step of graphite multi-walled carbon nano-tube are as follows: multi-walled carbon nanotube is placed in concentrated hydrochloric acid after immersion, it takes out and is washed with deionized to neutrality, drying is placed in high temperature graphitization furnace, it is warming up to 2400 DEG C ~ 2800 DEG C in an argon atmosphere, after keeping 20 ~ 40min, it is cooled to room temperature, heating and cooling rate are controlled in 4 ~ 6 DEG C/min, obtain the graphite multi-walled carbon nano-tube.Graphite multi-walled carbon nano-tube solid-phase extraction column provided by the present invention is had excellent performance, and with C18Or graphitized carbon etc. is compared for the conventional solid extraction column of filler, and solid-phase extraction column adsorption capacity of the invention is bigger, and it is stronger to the suction-operated of the various kinds of substrates chaff interferent such as pigment, it can effectively promote the clean-up effect to sample.
Description
Technical field
The invention belongs to chemical analysis test fields, are related to the pre-processing device of food, medicine and environmental analysis detection, especially
It is related to a kind of graphite multi-walled carbon nano-tube solid-phase extraction column and its application.
Background technique
Solid phase extraction techniques are based on liquid-solid phase chromatographic theory and are adsorbed in sample pretreatment process using solid-phase selective
With the liquid chromatography principle of selective elution, the separation of object and matrix is realized, to reach the purification of object, enrichment
Purpose.The influence of sample mesostroma chaff interferent can be effectively removed in the analysis process by solid phase extraction techniques, guarantee target
The accuracy and sensitivity of analyte detection.The technology is widely applied to food, medicine and environmental testing.
Multi-walled carbon nanotube is nanoscale hollow tube made of the class graphite plane curling being made of carbon hexatomic ring, is had good
Good chemical stability and high specific surface area is a kind of excellent adsorbent material.Based on its property, in recent years with more
Wall carbon nano tube be filler Solid Phase Extraction in gradually start to be applied, but due to its degree of graphitization is low and structure exist compared with
More defects, exist centainly leads to detect that the rate of recovery is relatively low, unstable result and clean-up effect are undesirable etc. lacks in application process
Point.
Summary of the invention
For above-mentioned technical problem of the existing technology, the purpose of the present invention is to provide a kind of graphitization multi wall carbon to receive
Mitron solid-phase extraction column and its application, graphite multi-walled carbon nano-tube solid-phase extraction column of the invention is as novel sample pre-treatments
Equipment, the sample pre-treatments purification process applied to pesticide residue determination in all kinds of samples such as edible agricultural product.
A kind of graphite multi-walled carbon nano-tube solid-phase extraction column, it is characterised in that including Solid Phase Extraction column tube, sieve plate and
Packing material, the packing material are graphite multi-walled carbon nano-tube, the preparation step of graphite multi-walled carbon nano-tube are as follows:
1) purify: multi-walled carbon nanotube is placed in concentrated hydrochloric acid after immersion, and multi-walled carbon nanotube is taken out simultaneously from concentrated hydrochloric acid
It is washed with deionized to neutrality, it is dry；
2) be graphitized: the multi-walled carbon nanotube after dry obtained by step 1) is placed in high temperature graphitization furnace, in ar gas environment
In be warming up to 2400 DEG C~2800 DEG C, after keeping 20~40min, be cooled to room temperature, heating and cooling rate control 4~6 DEG C/
Min obtains the graphite multi-walled carbon nano-tube.
A kind of graphite multi-walled carbon nano-tube solid-phase extraction column, it is characterised in that in step 1), multi-wall carbon nano-tube
It is 4~8h, preferably 6h that pipe, which is placed in time for impregnating in concentrated hydrochloric acid,.
A kind of graphite multi-walled carbon nano-tube solid-phase extraction column, it is characterised in that in step 1), dry temperature
It is 80~100 DEG C, the dry time is 8~12h.
The application that the graphite multi-walled carbon nano-tube solid-phase extraction column is measured in fruits and vegetables or Pesticide Residues in Tea.
The application that the graphite multi-walled carbon nano-tube solid-phase extraction column is measured in fruits and vegetables or Pesticide Residues in Tea,
It is characterized in that fruits and vegetables or Tea Samples are placed in centrifuge tube by crushing, acetonitrile is added and carries out homogenate extraction with homogenizer,
Then sodium chloride is added and carries out layering of saltouing, by the graphite multi-walled carbon nano-tube solid-phase extraction column after taking supernatant to be concentrated
Isolation of purified is carried out, the pesticide in fruits and vegetables or tealeaves is enriched in eluent, finally detects to the pesticide in eluent.
The application that the graphite multi-walled carbon nano-tube solid-phase extraction column is measured in fruits and vegetables or Pesticide Residues in Tea,
The eluant, eluent that isolation of purified uses is characterized in that as the mixed liquor of acetonitrile and toluene composition, the volume ratio of the acetonitrile and toluene is
2~4:1, preferably 3:1.
The application that the graphite multi-walled carbon nano-tube solid-phase extraction column is measured in fruits and vegetables or Pesticide Residues in Tea,
Be characterized in that the step of detecting to the pesticide in eluent are as follows: eluent be concentrated into it is close dry after, redissolved with organic solvent, so
It is detected afterwards by GC-MS/MS.
The application that the graphite multi-walled carbon nano-tube solid-phase extraction column is measured in fruits and vegetables or Pesticide Residues in Tea,
It is characterized in that the organic solvent is n-hexane.
Compared with the existing technology, the beneficial effect that the present invention obtains is:
(1) graphite multi-walled carbon nano-tube solid-phase extraction column provided by the present invention is had excellent performance, and by being prepared
Graphite multi-walled carbon nano-tube have purity is high, character rule, physical imperfection is few, all has to strong acid, highly basic, high temperature fabulous
Stability, large specific surface area, absorption property are good.With with C18Or graphitized carbon etc. is compared for the conventional solid extraction column of filler,
Solid-phase extraction column adsorption capacity of the invention is bigger, and the compounds such as usual pigment have plane macromolecular structure, due to structure
Similitude, such compound are easy to be interacted with graphite multi-walled carbon nano-tube and effectively adsorbed by of the invention.Phase
Than in pigment molecular, pesticide molecule compound and the effect of graphite multi-walled carbon nano-tube are relatively weak, furthermore in Solid Phase Extraction
By using the eluent containing toluene in column elution process, the pesticide for being graphitized multi-walled carbon nanotube absorption can effectively be washed
It takes off, to eliminate interference of the matrix such as pigment to detection pesticide, is effectively promoted (of the invention to the clean-up effect of sample
Graphite multi-walled carbon nano-tube only generates absorption to impurity chaff interferents such as pigments in sample, and to most of organic phosphorus, organic
Chlorine and pyrethroid pesticide do not generate suction-operated substantially, therefore can reach ideal separating effect, and embodying should
The applicable popularity of solid-phase extraction column.With using multi-walled carbon nanotube as the solid-phase extraction column of filler compared with, solid phase extraction of the invention
Column adsorption effect is taken to stablize, it is ensured that the rate of recovery and stability of testing result promote the veracity and precision of testing result.
(2) preparation method of solid phase extraction column stuffing graphite multi-walled carbon nano-tube is simply controllable in the present invention, can operate
Property it is strong, be easy to produce in batches and use, graphitization multi wall carbon of the present invention after 2400~2800 DEG C of high-temperature process receives
Mitron, can be observed the carbonization structure for having more regular by high resolution transmission electron microscope, it is more untreated or
It is less than under the conditions of 2400 DEG C of high-temperature process, the graphite linings of carbon nanotube show higher continuity and systematicness, multi wall
Carbon nanotube both ends are blocked, and the defect of carbon nanotube is effectively reduced.Furthermore it is miscellaneous to can remove thermally labile for high-temperature process
Matter obtains the carbon nanotube of extreme high purity.In the graphite multi-walled carbon nano-tube preparation process of invention, multi-walled carbon nanotube passes through
Concentrated hydrochloric acid, which impregnates, removes impurity metal ion and other soluble impurities etc., has in the subsequent graphitizing process of multi-walled carbon nanotube
There is higher purity；
(3) graphitization solid-phase extraction column is at low cost, and applicable sample scope is wide, the accuracy of experimental result and the equal energy of precision
Reach higher level, application value is high.
Specific embodiment
The present invention is further explained in the light of specific embodiments, but the scope of protection of the present invention is not limited thereto.
Embodiment 1:
A kind of graphite multi-walled carbon nano-tube solid-phase extraction column, including (Solid Phase Extraction column tube is high-purity to Solid Phase Extraction column tube
Spend polypropylene material), sieve plate (sieve plate is high purity polyethylene material, and number of screen decks is 2) and packing material, the filling
Material is graphite multi-walled carbon nano-tube.
The preparation step of graphite multi-walled carbon nano-tube are as follows:
1) purify: multi-walled carbon nanotube is placed in concentrated hydrochloric acid (concentration is about 30%) after immersion 6h, by multi-walled carbon nanotube
It takes out and is washed with deionized to neutrality from concentrated hydrochloric acid, 10h is then dried at 100 DEG C；
2) multi-walled carbon nanotube after dry obtained by step 1) is placed in high temperature graphitization furnace, in an argon atmosphere with 5 DEG C/
Min is warming up to 2800 DEG C, after keeping 30min, is cooled to room temperature with the rate of temperature fall of 5 DEG C/min, it is more to obtain the graphitization
Wall carbon nano tube.The outer diameter of graphite multi-walled carbon nano-tube is 8-15nm, and length is 10-50 μm.
The graphite multi-walled carbon nano-tube solid-phase extraction column of the present embodiment the preparation method comprises the following steps: the volume of Solid Phase Extraction column tube
For 6mL, a sieve plate is placed in the bottom of Solid Phase Extraction column tube, graphite multi-walled carbon nano-tube 300mg filling obtained above
In the inside of Solid Phase Extraction column tube, Solid Phase Extraction column tube side wall is touched, keeps filler distribution uniform, another sieve plate is placed in solid phase
The top of column tube is extracted, filler is compressed, makes to load height at 1.0cm (± 0.1cm), that is, prepares and complete the graphitization multi wall
Carbon nanotube solid-phase extraction column.
Embodiment 2:
Weigh eight parts of samples to be tested, every part for 20g through the uniform tomato sample of crushing, stirring in centrifuge tube, will wherein
Six parts of 100 μ L of acetone soln (concentration of every kind of pesticide is 1 μ g/mL) for being separately added into 131 kinds of pestsides synthesis standard items, in addition
Two parts are separately added into 100 μ L acetone as control, mix after standing 1 hour, are separately added into 40.0mL acetonitrile, are existed with homogenizer
1min is extracted in 15000r/min homogenate, and 5g sodium chloride is added, and after acutely shaking 1min, is centrifuged 5min in 3000r/min, is taken supernatant
Liquid 20.0mL is concentrated into about 2mL, obtains sample to be clean.
The anhydrous sulphur of about 1cm high is added in the graphite multi-walled carbon nano-tube solid-phase extraction column that embodiment 1 obtains respectively
The top of the packing material in graphite multi-walled carbon nano-tube solid-phase extraction column is arranged in sour sodium, anhydrous sodium sulfate.Column chromatography point
Before purification, the acetonitrile-methylbenzene solution (V of 4mL is first usedAcetonitrile: VToluene=3:1) prewashing column, when liquid level reaches at the top of sodium sulphate, by
Sample to be clean obtained above is transferred in graphite multi-walled carbon nano-tube solid-phase extraction column that (sample i.e. to be clean is placed on sulfuric acid
At the top of sodium), then 2mL acetonitrile-methylbenzene solution (V is used every timeAcetonitrile: VToluene=3:1) the sample liquid bottle for containing sample to be clean is washed three times,
And cleaning solution is transferred in graphite multi-walled carbon nano-tube solid-phase extraction column.Then about 25mL acetonitrile-methylbenzene solution (V is usedAcetonitrile:
VToluene=3:1) graphite water multi-walled carbon nano-tube solid-phase extraction column, all effluxes are collected in rotary evaporation bottle, and 40
Spin concentration after being redissolved with n-hexane, is settled to 2.0mL, carries out GC-MS/MS after crossing 0.45 μm of filter membrane to close dry in DEG C water-bath
Analysis, testing result are as shown in table 1.Testing result, which is shown, is not detected 131 kinds of pesticides in two parts of control samples, remaining six parts of mark-on
In sample (spiked levels of every kind of pesticide are 5 μ g/kg) 131 kinds of pesticide recovery of standard addition of detection 80.4%-105% it
Between, relative standard deviation is not more than 9.4%, illustrates to isolate and purify through graphite multi-walled carbon nano-tube solid-phase extraction column of the invention
Afterwards, influence of a variety of matrix such as pigment and fatty acid to detection in tomato sample is eliminated, is improved residual in tomato sample
Stay the accuracy of Pesticides Testing.
The more similar solid-phase extraction column of graphite multi-walled carbon nano-tube solid-phase extraction column of the invention has cost lower, only
It is good to change effect, while the Solid Phase Extraction testing result meets the residual testing requirements of European Union's SANTE/11813/2017 agriculture.
131 kinds of pesticides are averaged recovery of standard addition (%) and precision (n=6) in 1. tomato sample of table
Solid-phase extraction column must meet simultaneously, and matrix interference object can be adsorbed effectively, and object can be eluted effectively.Cause
This loading for investigating graphitized carbon nano pipe in the solid-phase extraction column that graphite multi-walled carbon nano-tube is packing material respectively exists
100, to the pre-treatment effect of sample when 200,300,400,500mg.20g tomato sample is remained using the above method
When Pesticides Testing, when graphite multi-walled carbon nano-tube loading is 300mg, clean-up effect is preferable, and the rate of recovery and precision are equal
It meets the requirements, in order to save raw material, the graphite multi-walled carbon nano-tube loadings are finally 300mg ± 10mg.
Embodiment 3:
Eight parts of samples to be tested are weighed, every part is 2g through crushing the commercially available Longjing tea sample mixed in centrifuge tube, will wherein
Six parts of 100 μ L of acetone soln (concentration of every kind of pesticide is 1 μ g/mL) for being separately added into 131 kinds of pestsides synthesis standard items, two parts
100 μ L acetone are separately added into as control, mixes and stands 1 hour.It is separately added into 15mL acetonitrile, with homogenizer in 15000r/min
1min is extracted in homogenate, is centrifuged 5min in 3000r/min, is taken supernatant in rotary evaporation bottle.Sample residue uses 15mL again respectively
Acetonitrile repeats to extract once, and combined extract after centrifugation is concentrated into about 2mL, obtains sample to be clean.
The anhydrous sodium sulfate of about 1cm high, anhydrous slufuric acid is added in graphite multi-walled carbon nano-tube solid-phase extraction column respectively
The top of the packing material in graphite multi-walled carbon nano-tube solid-phase extraction column is arranged in sodium.Before column chromatography for separation purification, first use
Acetonitrile-methylbenzene solution (the V of 5mLAcetonitrile: VToluene=3:1) prewashing column, when liquid level reach sodium sulphate at the top of when, by it is obtained above to
Purification sample is transferred on graphite multi-walled carbon nano-tube solid-phase extraction column (sample i.e. to be clean is placed at the top of sodium sulphate), then often
It is secondary to use 2mL acetonitrile-methylbenzene solution (VAcetonitrile: VToluene=3:1) washing contains the rotary evaporation bottle of sample to be clean three times, and will wash
Liquid is transferred in amino multi-wall carbon nanotube solid-phase extraction column.Then about 25mL acetonitrile-methylbenzene solution (V is usedAcetonitrile: VToluene=3:
1) amino multi-wall carbon nanotube solid-phase extraction column is washed, collects all effluxes in rotary evaporation bottle, and in 40 DEG C of water-baths
Middle spin concentration is done to close, after being redissolved with n-hexane, is settled to 2.0mL, carries out GC-MS/MS analysis, inspection after crossing 0.45 μm of filter membrane
The results are shown in Table 2 for survey.Testing result shows that 131 kinds of pesticides are not detected in two parts of control samples, remaining six parts of mark-on sample
131 kinds of pesticide recovery of standard addition are detected in (spiked levels of every kind of pesticide are 50 μ g/kg) between 80.2%-109.5%,
Relative standard deviation is no more than 9.9%.Experimental result is shown in Table 2.
131 kinds of pesticides are averaged recovery of standard addition (%) and precision (n=6) in 2. Tea Samples of table
Content described in this specification is only to enumerate to inventive concept way of realization, and protection scope of the present invention is not answered
When the concrete form for being seen as limited by embodiment and being stated.
Claims (7)
1. a kind of graphite multi-walled carbon nano-tube solid-phase extraction column, it is characterised in that including Solid Phase Extraction column tube, sieve plate and fill out
Material is filled, the packing material is graphite multi-walled carbon nano-tube, the preparation step of graphite multi-walled carbon nano-tube are as follows:
1) purify: multi-walled carbon nanotube is placed in concentrated hydrochloric acid after immersion, and multi-walled carbon nanotube is taken out and spent from concentrated hydrochloric acid
Ion water washing is dry to neutrality；
2) be graphitized: the multi-walled carbon nanotube after dry obtained by step 1) is placed in high temperature graphitization furnace, is risen in an argon atmosphere
Temperature is cooled to room temperature after keeping 20 ~ 40min to 2400 DEG C -2800 DEG C, in 4 ~ 8 DEG C/min, i.e., heating and rate of temperature fall control
The graphite multi-walled carbon nano-tube is made.
2. a kind of graphite multi-walled carbon nano-tube solid-phase extraction column as described in claim 1, it is characterised in that more in step 1)
It is 4 ~ 8h, preferably 6h that wall carbon nano tube, which is placed in time for impregnating in concentrated hydrochloric acid,.
3. a kind of graphite multi-walled carbon nano-tube solid-phase extraction column as described in claim 1, it is characterised in that high in step 2
Temperature in warm graphitizing furnace is warming up to 2600 ~ 2800 DEG C.
4. the graphite multi-walled carbon nano-tube solid-phase extraction column as described in claim 1 ~ 3 any one is in fruits and vegetables or Pesticides in Tea
The application of medicine residues detecton.
5. application as claimed in claim 4, it is characterised in that fruits and vegetables or Tea Samples are placed in centrifuge tube by crushing, are added
Enter acetonitrile and carry out homogenate extraction with homogenizer, sodium chloride is then added and carries out layering of saltouing, passes through institute after taking supernatant to be concentrated
It states graphite multi-walled carbon nano-tube solid-phase extraction column and carries out isolation of purified, the pesticide in fruits and vegetables or tealeaves is enriched in eluent,
Finally the pesticide in eluent is detected.
6. application as claimed in claim 5, it is characterised in that the eluant, eluent that isolation of purified uses is acetonitrile and toluene composition
The volume ratio of mixed liquor, the acetonitrile and toluene be 2 ~ 4:1, preferably 3: 1.
7. application as claimed in claim 5, it is characterised in that the step of being detected to the pesticide in eluent are as follows: eluent
After being concentrated into close do, is redissolved with organic solvent, then detected by GC-MS/MS.
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Cited By (1)
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| CN114674950A (en) * | 2022-03-18 | 2022-06-28 | 衢州市疾病预防控制中心 | Method for quantitatively determining anesthetic |
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