CN103254438A - Preparation method of triclosan carbon nano-tube molecule imprinted polymer and determination method of content of triclosan applied to daily chemical products - Google Patents
Preparation method of triclosan carbon nano-tube molecule imprinted polymer and determination method of content of triclosan applied to daily chemical products Download PDFInfo
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Abstract
The invention relates to a preparation method of a triclosan carbon nano-tube molecule imprinted polymer and a determination method of the content of triclosan applied to daily chemical products. The preparation method comprises the following steps of: firstly, synthesizing a template-functional monomer complex by taking triclosan (2,4,4'-trichloro-2'-hydroxydiphenyl ether) as a template molecule and 3-aminopropyl triethoxysilane as a functional monomer; and synthesizing a triclosan-imprinted carbon nano-tube polymer by using the complex and a silicon-coated carbon nano-tube through a gel-sol method. The triclosan-imprinted carbon nano-tube polymer has selective adsorption capability for triclosan molecules and is capable of directly and selectively extracting triclosan from a practical sample, and the content of triclosan in the practical sample is quantitatively analyzed by using a high performance liquid chromatography through an extracting solution obtained by eluting.
Description
Technical field
The present invention relates to the preparation method of triclosan carbon nanotube molecule imprinted polymer and be applied to the measuring method of triclosan content in the cosmetics of everyday use.
Background technology
(2,4,4'-, three chloro-2-dihydroxy diphenyl ethers are the broad-spectrum high efficacy antiseptic-germicides of present international popular triclosan) to triclosan, are widely used in the products such as all kinds of cosmeticses of everyday use, pharmaceutical preparation, foodstuff additive.Past, triclosan was extensively added in the middle of the various personal care articles, in shampoo, soap, toothpaste etc. and daily necessities footwear as antiseptic and antibiotic agent over more than 30 year.But triclosan can cause organism in water to poison or can produce many chlorine Dai dioxins materials behind photocatalytic degradation, caused great harm for people's health, the extensive application of triclosan has caused people's extensive concern to the pollution problem that river, lake etc. brings, and therefore the effective detection to triclosan is extremely important in the surrounding environment of human survival.
The triclosan residue analysis method mainly contains vapor-phase chromatography, gas/matter coupling method, high performance liquid chromatography and liquid chromatography-tandem mass spectrometry coupling method (LC-MS/MS) etc. at present.Owing to there is the problem of sample pre-treatments complexity and trace samplings enrichment difficulty, the rate of recovery during simultaneously for sample test is not high, the accuracy that influence is measured.The present invention adopts the method for surface molecule print, is carrier with bag silicon-carbon nanotube, has synthesized the molecular imprinting carbon nanotube polymer of triclosan by the process of gel-sol.This polymkeric substance has the absorption of kinetics faster, higher adsorptive capacity and higher selectivity to triclosan, uses the rate of recovery of its method to reach more than 90% by reality.This method cost is low, can be accurately and rapidly provide scientific basis and technical support for monitoring and the production quality control of the residual situation of triclosan in the actual sample.
Summary of the invention
The preparation method of a kind of triclosan carbon nanotube molecule of the present invention imprinted polymer is with triclosan (2,4,4'-three chloro-2-dihydroxy diphenyl ethers, triclosan) being template molecule, is function monomer with the 3-aminopropyl triethoxysilane, the mixture of at first synthetic template-function monomer; This mixture synthesizes triclosan trace carbon nanotube polymer with bag silicon-carbon nanotube by the method for gel-sol; This polymkeric substance has selective adsorption capacity to the triclosan molecule, can be directly from actual sample selective extraction go out triclosan, the extracting solution that obtains behind wash-out goes out triclosan content in the actual sample with the high performance liquid chromatography quantitative analysis; The preparation method of described triclosan carbon nanotube molecule imprinted polymer comprises the steps:
(1) bag silicon-carbon nanotube CNTSiO
2Preparation
With carbon nanotube CNT, 3-aminopropyl triethoxysilane APTES, the cetyl trimethylammonium bromide CTAB of purifying, deionized water places reaction flask, obtains mixed liquor A through supersound process, under stirring; With tetraethoxysilane TEOS, deionized water, ethanol places reaction flask, through supersound process, obtains mixed liquid B under stirring; With A and B remix, supersound process stirs, and the pH of mixed value is transferred to 9.5; Centrifugation is cleaned solids with deionized water and ethanol, and the supernatant liquor after centrifugal is neutral, namely obtains CNTSiO
2Vacuum-drying;
(2) preparation of triclosan carbon nanotube molecule imprinted polymer CNTTCS-MIP
(2,4,4'-, three chloro-2-dihydroxy diphenyl ethers triclosan) are dissolved in the ethanol, stir to add 3-aminopropyl triethoxysilane APTES down, add tetraethoxysilane TEOS again, obtain triclosan-silane compound with triclosan; With the bag silicon-carbon nanotube CNTSiO that obtains in (1)
2Join in triclosan-silane compound solution, use acetic acid as catalyzer, stirring reaction; Products therefrom is with ethanol/hydrochloric acid soln wash-out, and is clean to the template wash-out; Be neutralized to neutrality with NaOH, with the deionized water washing, gained is triclosan carbon nanotube molecule imprinted polymer CNTTCS-MIP, vacuum-drying, for future use.
The supersound process condition is 35～40 ℃ of 20～30min down when preparing mixed liquor A and B in (1), and agitation condition is the top speed stirring 3～3.5h with magnetic stirring apparatus; Supersound process condition behind A and the B remix is 35～40 ℃ to be descended 1～2 hour; Agitation condition is the top speed stirring 10～20min with magnetic stirring apparatus; Product C NTSiO
280 ℃ of following vacuum-dryings.
Reaction conditions is under the room temperature 10～12 hours in (2); Product ethanol/6M hydrochloric acid wash-out, wherein ethanol/6M hydrochloric acid volume ratio is 1:1/v:v, and is clean to the template wash-out; NaOH with 0.1M is neutralized to neutrality again, washes with deionized water, and gained CNTTCS-MIP is 80 ℃ of vacuum-dryings.
Synthesizing of the non-imprinted polymer of carbon nanotube molecule is similar to the synthetic method of imprinted polymer, does not just add template molecule.
The reagent that the present invention is used and material:
Agents useful for same of the present invention unless otherwise indicated is analytical pure; Deionized water is through Aquapro Corporation, and AFZ-6000-U handles the deionized water that obtains;
Carbon nanotube (CNT, diameter: 60-100nm, length: 5-15 μ m);
Tetraethoxysilane (TEOS, 99.9%);
3-aminopropyl triethoxysilane (APTES, 99.9%);
Methyl alcohol (CH
3OH): chromatographically pure;
Cetyl trimethylammonium bromide (CTAB);
Ammoniacal liquor (NH
3H
2O);
Acetic acid (CH
3COOH);
Reference material: triclosan (TCS, C
12H
7Cl
3O
2, 99.9%); Para-chlorophenol (C
6H
5ClO, 99.9%); 2,4,6-trichlorophenol (C
6H
3Cl
3O, 99.9%);
Filter membrane: organic phase, 0.22 μ m
Testing tool:
High performance liquid chromatography: liquid chromatograph is furnished with UV-detector;
The TecnaiG2T2 transmission electron microscope;
The AVATAR360 Fourier infrared spectrum;
DN series nitrogen dries up instrument;
Pipettor: 0.50 μ L～10 μ L, 20 μ L～200 μ L and 100 μ L～1000 μ L.
Be used for the measuring method of environment actual sample triclosan content to be measured by the prepared triclosan carbon nanotube molecule imprinted polymer of the preparation method of aforesaid triclosan carbon nanotube molecule imprinted polymer, described environment actual sample to be measured can comprise the waste water that the daily used daily chemical products of river, lake water or people produces etc.
This measuring method comprises the steps:
1) preparation of triclosan standard reserving solution and triclosan standard operation solution:
The triclosan standard reserving solution: compound concentration is 50.0mgkg
-1, accurately take by weighing 2.500mg triclosan reference material (99.9%) accurately to 0.001mg, in the 50mL brown bottle, with mixing behind the dissolve with methanol, under 4 ℃ of conditions, preserve, be valid for three months;
Triclosan standard operation solution: during use the triclosan standard reserving solution is diluted with methyl alcohol, be mixed with 0.01,0.05,0.1,0.5 respectively, 1.0mgkg
-1Standard operation solution;
2) preparation of the standard reserving solution of triclosan, para-chlorophenol and 2,4,6-Trichlorophenol and standard operation solution thereof:
The standard reserving solution of triclosan, para-chlorophenol and 2,4,6-Trichlorophenol: the standard reserving solution compound concentration is 50.0mgkg
-1Accurately take by weighing the reference material (99.9%) of 2.500mg triclosan, para-chlorophenol and 2,4,6-Trichlorophenol respectively accurately to 0.001mg, place same 50mL brown bottle, with mixing behind the dissolve with methanol, under 4 ℃ of conditions, preserve, be valid for three months;
The preparation of the standard hybrid working solution of triclosan, para-chlorophenol and 2,4,6-Trichlorophenol:
Standard reserving solution with triclosan, para-chlorophenol and 2,4,6-Trichlorophenol during use dilutes with methyl alcohol, is mixed with 0.01,0.05,0.1,0.5 respectively, 1.0mgkg
-1Standard hybrid working solution;
3) preparation of sample: directly measure ambient water sample 50.0mL to be measured;
4) sample determination
(1) triclosan carbon nanotube molecule imprinted polymer selectivity experiment
Take by weighing triclosan carbon nanotube molecule imprinted polymer and each 5 parts of every part of 20mg of the non-imprinted polymer of carbon nanotube in method described in the claim 1 preparation, place 10 centrifuge tubes, add 10.0mL concentration respectively and be 1,5,10,20,30mgkg
-1Triclosan, para-chlorophenol, 2,4, the standard of 6-Trichlorophenol is mixed methanol solution, the 30min that vibrates under the room temperature with the centrifugal 5min of 4000r/min, collects supernatant liquid, cross 0.22 μ m filter membrane after, the 60 μ L that take a sample prepare to inject high performance liquid chromatography;
(2) sample pre-treatments: add a certain amount of triclosan standard operation solution in the ambient water sample, make that the concentration of triclosan is respectively 0.001,0.005,0.01mgkg
-1After crossing 0.22 μ m filter membrane, add 50mg triclosan trace carbon nanotube to adding in the target environmental water sample, this mixture is placed on the shaking table behind the concussion 30min, with the centrifugal 5min of 4000r/min, discard supernatant liquid.(9:1 v:v) in above-mentioned centrifuge tube, behind the concussion wash-out 12h, with the centrifugal 5min of 4000r/min, collects supernatant liquid, moves in another centrifuge tube behind the 0.22 μ m filter membrane excessively to add 20mL methyl alcohol/acetic acid.With nitrogen elutriant is blown near dried under room temperature, add the 1.0mL dissolve with methanol, the 60 μ L that take a sample prepare to inject high performance liquid chromatography;
Liquid phase chromatogram condition
A) chromatographic column: Shimadzu VP-ODS C18 post (150mm * 4.6mm, 5 μ m).
B) moving phase: methanol-water-acetic acid (70/20/10, v/v).
C) flow velocity: 1.0mLmin
-1
D) detector: UV-detector.
E) sample size: 20 μ L.
(3) high-performance liquid chromatogram determination: start, moving phase flushing chromatographic column is used in preheating, treats to begin the sample introduction test after the baseline stability.
Use sample (1), (2) sample introduction of preparing previously, each sample repeats 5 times, is averaged peak area and carries out quantitative analysis, the content (mgkg of each reference material in the test specimens
-1).
(4) qualitative analysis: utilize the retention time qualitative method.According to the retention time of triclosan reference material, determine the chromatographic peak of triclosan in the sample.
(5) quantitative analysis: adopt standard working curve to carry out quantitative analysis.
The response value of reference material to be measured all should be in the method linearity range in the sample.
The result calculates
(6) result calculates by formula (1):
A=aC+b……………………………………(1)
In the formula:
C---the content of triclosan in the sample, unit is every kilogram of (mgkg of milligram
-1);
The peak area of triclosan in the actual sample that A---instrument records;
A, b---the parameter in the typical curve.
Description of drawings
Fig. 1 is sol-gel technology preparing triclosan molecular imprinting carbon nanotube polymer synoptic diagram.
Fig. 2 is carbon nanotube CNT, bag silicon-carbon nanotube CNTSiO
2, triclosan carbon nanotube molecule imprinted polymer CNTTCS-MIP transmission electron microscope picture.
Fig. 3 is that triclosan molecular imprinting carbon nanotube polymer is to the kinetics absorption figure of triclosan.
Fig. 4 is that triclosan molecular imprinting carbon nanotube polymer and non-imprinted polymer are to the isothermal adsorption figure of triclosan.
Fig. 5 triclosan molecular imprinting carbon nanotube polymer is to the adsorption-desorption figure of triclosan.
Fig. 6 triclosan molecular imprinting carbon nano-tube material is to the absorption that adds standard specimen and the analysis diagram of triclosan in the environmental water sample.Fig. 6 A is river, and Fig. 6 B is lake water.Curve a is for adding 0.05 μ g mL
-1After the mark-on water sample of the standard operation solution of triclosan, curve b were the absorption of triclosan molecular imprinting carbon nano-tube material, curve c was water sample, and curve d is the color atlas of the triclosan of ethanol/6MHCl desorption.
The triclosan color atlas that Fig. 7 embodiment 2 rivers are measured.Curve a is for adding 0.5 μ g mL
-1After the mark-on water sample of the standard operation solution of triclosan, curve b were the non-trace carbon nano-tube material absorption of triclosan molecule, the water sample color atlas of mensuration, curve c were the color atlas after the absorption of triclosan molecular imprinting carbon nano-tube material.
The triclosan color atlas that Fig. 8 embodiment 3 lake water are measured.Curve a is for adding 0.5 μ g mL
-1After the mark-on water sample of the standard operation solution of triclosan, curve b were the non-trace carbon nano-tube material absorption of triclosan molecule, the water sample color atlas of mensuration, curve c were the color atlas after the absorption of triclosan molecular imprinting carbon nano-tube material.
From Fig. 2 carbon nanotube CNT, bag silicon-carbon nanotube CNTSiO
2, the clear the present invention of finding out successfully prepares triclosan molecularly imprinted polymer thin layer in the triclosan carbon nanotube molecule imprinted polymer CNTTCS-MIP transmission electron microscope picture.From the kinetics absorption figure of Fig. 3 triclosan molecular imprinting carbon nanotube polymer to triclosan, Fig. 4 triclosan molecular imprinting carbon nanotube polymer and non-imprinted polymer are to the isothermal adsorption figure of triclosan, Fig. 5 triclosan molecular imprinting carbon nanotube polymer among the adsorption-desorption figure of triclosan as can be seen, triclosan molecular imprinting carbon nanotube polymer has kinetics absorption faster to triclosan, higher adsorptive capacity and higher selectivity show that to the desorption result of triclosan triclosan molecular imprinting carbon nanotube polymer has functions of use repeatedly by triclosan molecular imprinting carbon nanotube polymer.
Embodiment
1) bag silicon-carbon nanotube (CNTSiO
2) preparation
With the CNT of 250mg purifying, 0.5mL APTES, 100mg CTAB, the 48mL deionized water places the 100mL Erlenmeyer flask, ultrasonic 20min under 40 ℃, then, the top speed stirring 3h with magnetic stirring apparatus gets mixed liquor A.With 5mLTEOS, the 3mL deionized water, 50mL ethanol places the 100mL Erlenmeyer flask, ultrasonic 20min under 40 ℃, then, the top speed stirring 3h with magnetic stirring apparatus gets mixed liquid B.Mixed liquor A with after B mixes again, at 40 ℃ of ultrasonic 1h down, then, is stirred 10min with the top speed of magnetic stirring apparatus, last, with ammoniacal liquor the pH of mixed value is transferred to 9.5.After the gained mixed solution is centrifugal, clean repeatedly for several times with deionized water and ethanol, the supernatant liquor after centrifugal is neutral, namely obtains wrapping silicon-carbon nanotube CNTSiO
2With resulting CNTSiO
280 ℃ of following vacuum-dryings, for future use.
2) preparation of triclosan molecular imprinting carbon nanotube polymer (CNTTCS-MIP)
The 1g triclosan is dissolved in the 20mL ethanol, adds 2mL APTES again, behind this mixture stirring 20min, add 4mL TEOS again, stir 20min, obtain triclosan-silane compound.With 1g CNTSiO
2Join in triclosan-silane compound solution, add the acetic acid of 1mL1M again as catalyzer.Under the room temperature, stir 10h.Products therefrom is with ethanol/6M hydrochloric acid (1:1/v:v) wash-out, and is clean to the template wash-out.NaOH with 0.1M is neutralized to neutrality, uses the deionized water wash clean.Gained CNTTCS-MIP is 80 ℃ of vacuum-dryings, for future use.
3) preparation of A, triclosan standard reserving solution and triclosan standard operation solution:
The triclosan standard reserving solution: compound concentration is 50.0mgkg
-1, accurately take by weighing 2.500mg triclosan reference material (99.9%) accurately to 0.001mg, in the 50mL brown bottle, with mixing behind the dissolve with methanol, under 4 ℃ of conditions, preserve, be valid for three months;
Triclosan standard operation solution: during use the triclosan standard reserving solution is diluted with methyl alcohol, be mixed with 0.01,0.05,0.1,0.5 respectively, 1.0mgkg
-1Standard operation solution;
The standard reserving solution of B, triclosan, para-chlorophenol and 2,4,6-Trichlorophenol and the preparation of standard operation solution thereof:
The standard reserving solution of triclosan, para-chlorophenol and 2,4,6-Trichlorophenol: the standard reserving solution compound concentration is 50.0mgkg
-1Accurately take by weighing the reference material (99.9%) of 2.500mg triclosan, para-chlorophenol and 2,4,6-Trichlorophenol respectively accurately to 0.001mg, place same 50mL brown bottle, with mixing behind the dissolve with methanol, under 4 ℃ of conditions, preserve, be valid for three months;
The preparation of the standard hybrid working solution of triclosan, para-chlorophenol and 2,4,6-Trichlorophenol:
Standard reserving solution with triclosan, para-chlorophenol and 2,4,6-Trichlorophenol during use dilutes with methyl alcohol, is mixed with 0.01,0.05,0.1,0.5 respectively, 1.0mgkg
-1Standard hybrid working solution;
C, the experiment of triclosan carbon nanotube molecule imprinted polymer selectivity
Take by weighing triclosan carbon nanotube molecule imprinted polymer and each 5 parts of every part of 20mg of the non-imprinted polymer of carbon nanotube in method described in the claim 1 preparation, place 10 centrifuge tubes, add 10.0mL concentration respectively and be 1,5,10,20,30mgkg
-1Triclosan, para-chlorophenol, 2,4, the standard of 6-Trichlorophenol is mixed liquid, the 30min that vibrates under the room temperature with the centrifugal 5min of 4000r/min, collects supernatant liquid, cross 0.22 μ m filter membrane after, the 60 μ L that take a sample inject high performance liquid chromatography;
D, add a certain amount of triclosan standard operation solution in the ambient water sample, make that the concentration of triclosan is respectively 0.001,0.005,0.01mgkg
-1After crossing 0.22 μ m filter membrane, add 50mg triclosan trace carbon nanotube to adding in the target environmental water sample, this mixture is placed on the shaking table behind the concussion 30min, with the centrifugal 5min of 4000r/min, discard supernatant liquid.(9:1 v:v) in above-mentioned centrifuge tube, behind the concussion wash-out 12h, with the centrifugal 5min of 4000r/min, collects supernatant liquid, moves in another centrifuge tube behind the 0.22 μ m filter membrane excessively to add 20mL methyl alcohol/acetic acid.With nitrogen elutriant is blown near dried under room temperature, add the 1.0mL dissolve with methanol, the 60 μ L that take a sample inject high performance liquid chromatography;
4) high-performance liquid chromatogram determination: start, moving phase flushing chromatographic column is used in preheating, treats to begin the sample introduction test after the baseline stability;
Be used in (C) and (D) in prepared sample sample introduction, each sample repeats 5 times, is averaged peak area and carries out quantitative analysis, the content (mgkg of each reference material in the test specimens
-1);
(4) qualitative analysis: utilize the retention time qualitative method.According to the retention time of triclosan reference material, determine the chromatographic peak of triclosan in the sample;
(5) quantitative analysis: adopt standard working curve to carry out quantitative analysis;
The response value of reference material to be measured all should be in the method linearity range in the sample;
(6) result calculates by formula (1):
A=aC+b……………………………………(1)
In the formula:
C---the content of triclosan in the sample, unit is every kilogram of (mgkg of milligram
-1);
The peak area of triclosan in the actual sample that A---instrument records;
A, b---the parameter in the typical curve; (a is 985.2; B is 4.3)
Use the triclosan carbon nanotube and in river, carry out the test of the triclosan rate of recovery.(0.1,0.3,0.5ug/L) adding 100mg triclosan carbon nanotube extracts in the river after at the 100mL mark-on.After this mixture placed on the shaking table concussion 30min, with the centrifugal 5min of 4000r/min, discard supernatant liquid.(9:1 v:v) in above-mentioned centrifuge tube, behind the concussion wash-out 12h, with the centrifugal 5min of 4000r/min, collects supernatant liquid, moves in another centrifuge tube behind the 0.22 μ m filter membrane excessively to add 40mL methyl alcohol/acetic acid.With nitrogen elutriant is blown near dried under room temperature, add the 1.0mL dissolve with methanol, the 60 μ L that take a sample inject high performance liquid chromatography and measure.
Measurement result sees Table 1.
Use the triclosan carbon nanotube and in lake water, carry out the test of the triclosan rate of recovery.(0.1,0.3,0.5ug/L) adding 100mg triclosan carbon nanotube extracts in the lake water after at the 100mL mark-on.After this mixture placed on the shaking table concussion 30min, with the centrifugal 5min of 4000r/min, discard supernatant liquid.(9:1 v:v) in above-mentioned centrifuge tube, behind the concussion wash-out 12h, with the centrifugal 5min of 4000r/min, collects supernatant liquid, moves in another centrifuge tube behind the 0.22 μ m filter membrane excessively to add 40mL methyl alcohol/acetic acid.With nitrogen elutriant is blown near dried under room temperature, add the 1.0mL dissolve with methanol, the 60 μ L that take a sample inject high performance liquid chromatography and measure.
Measurement result sees Table 2.
Table 1
(RSD is relative standard deviation)
Table 2
Claims (4)
1. the preparation method of a triclosan carbon nanotube molecule imprinted polymer is characterized in that, with triclosan (2,4,4'-, three chloro-2-dihydroxy diphenyl ethers triclosan) are template molecule, be function monomer with the 3-aminopropyl triethoxysilane, the mixture of at first synthetic template-function monomer; This mixture synthesizes triclosan trace carbon nanotube polymer with bag silicon-carbon nanotube by the method for gel-sol; This polymkeric substance has selective adsorption capacity to the triclosan molecule, can be directly from actual sample selective extraction go out triclosan, the extracting solution that obtains behind wash-out goes out triclosan content in the actual sample with the high performance liquid chromatography quantitative analysis; The preparation method of described triclosan carbon nanotube molecule imprinted polymer comprises the steps:
(1) bag silicon-carbon nanotube CNTSiO
2Preparation
With carbon nanotube CNT, 3-aminopropyl triethoxysilane APTES, the cetyl trimethylammonium bromide CTAB of purifying, deionized water places reaction flask, obtains mixed liquor A through supersound process, under stirring; With tetraethoxysilane TEOS, deionized water, ethanol places reaction flask, through supersound process, obtains mixed liquid B under stirring; With A and B remix, supersound process stirs, and the pH of mixed value is transferred to 9.5; Centrifugation is cleaned solids with deionized water and ethanol, and the supernatant liquor after centrifugal is neutral, namely obtains CNTSiO
2Vacuum-drying;
(2) preparation of triclosan carbon nanotube molecule imprinted polymer CNTTCS-MIP
(2,4,4'-, three chloro-2-dihydroxy diphenyl ethers triclosan) are dissolved in the ethanol, stir to add 3-aminopropyl triethoxysilane APTES down, add tetraethoxysilane TEOS again, obtain triclosan-silane compound with triclosan; With the bag silicon-carbon nanotube CNTSiO that obtains in (1)
2Join in triclosan-silane compound solution, use acetic acid as catalyzer, stirring reaction; Products therefrom is with ethanol/hydrochloric acid soln wash-out, and is clean to the template wash-out; Be neutralized to neutrality with NaOH, with the deionized water washing, gained is triclosan carbon nanotube molecule imprinted polymer CNTTCS-MIP, vacuum-drying;
(3) preparation of the non-imprinted polymer of carbon nanotube molecule
The preparation method of the non-imprinted polymer of carbon nanotube molecule and the synthetic method of imprinted polymer be not except adding the template molecule, and step is identical.
2. the preparation method of triclosan carbon nanotube molecule imprinted polymer according to claim 1, it is characterized in that, the supersound process condition is 35～40 ℃ of 20～30min down when preparing mixed liquor A and B (1), and agitation condition is the top speed stirring 3～3.5h with magnetic stirring apparatus; Supersound process condition behind A and the B remix is 35～40 ℃ descends 1～2h; Agitation condition is the top speed stirring 10～20min with magnetic stirring apparatus; Product C NTSiO
280 ℃ of following vacuum-dryings.
3. the preparation method of triclosan carbon nanotube molecule imprinted polymer according to claim 1 is characterized in that, reaction conditions is 10～12h under the room temperature in (2); Product ethanol/6M hydrochloric acid wash-out, wherein ethanol/6M hydrochloric acid volume ratio is 1:1/v:v, and is clean to the template wash-out; NaOH with 0.1M is neutralized to neutrality again, washes with deionized water, and gained CNTTCS-MIP is 80 ℃ of vacuum-dryings.
4. the prepared triclosan carbon nanotube molecule imprinted polymer of the preparation method of the described triclosan carbon nanotube molecule of one of claim 1～3 imprinted polymer is used for the measuring method of environment actual sample triclosan content to be measured, it is characterized in that, comprise the steps:
1) preparation of triclosan standard reserving solution and triclosan standard operation solution:
The triclosan standard reserving solution: compound concentration is 50.0mgkg
-1, accurately take by weighing 2.500mg triclosan reference material (99.9%) accurately to 0.001mg, in the 50mL brown bottle, with mixing behind the dissolve with methanol, under 4 ℃ of conditions, preserve, be valid for three months;
Triclosan standard operation solution: during use the triclosan standard reserving solution is diluted with methyl alcohol, be mixed with 0.01,0.05,0.1,0.5 respectively, 1.0mgkg
-1Standard operation solution;
2) preparation of the standard reserving solution of triclosan, para-chlorophenol and 2,4,6-Trichlorophenol and standard operation solution thereof:
The standard reserving solution of triclosan, para-chlorophenol and 2,4,6-Trichlorophenol: the standard reserving solution compound concentration is 50.0mgkg
-1Accurately take by weighing the reference material (99.9%) of 2.500mg triclosan, para-chlorophenol and 2,4,6-Trichlorophenol respectively accurately to 0.001mg, place same 50mL brown bottle, with mixing behind the dissolve with methanol, under 4 ℃ of conditions, preserve, be valid for three months;
The preparation of the standard hybrid working solution of triclosan, para-chlorophenol and 2,4,6-Trichlorophenol:
Standard reserving solution with triclosan, para-chlorophenol and 2,4,6-Trichlorophenol during use dilutes with methyl alcohol, is mixed with 0.01,0.05,0.1,0.5 respectively, 1.0mgkg
-1Standard hybrid working solution;
3) preparation of sample: directly measure ambient water sample 50.0mL to be measured;
4) sample determination
(1) triclosan carbon nanotube molecule imprinted polymer selectivity experiment
Take by weighing triclosan carbon nanotube molecule imprinted polymer and each 5 parts of every part of 20mg of the non-imprinted polymer of carbon nanotube in method described in the claim 1 preparation, place 10 centrifuge tubes, add 10.0mL concentration respectively and be 1,5,10,20,30mgkg
-1Triclosan, para-chlorophenol, 2,4, the standard of 6-Trichlorophenol is mixed methanol solution, the 30min that vibrates under the room temperature with the centrifugal 5min of the speed of 4000r/min, collects supernatant liquid, cross 0.22 μ m filter membrane after, the 60 μ L that take a sample prepare to inject high performance liquid chromatography;
(2) sample pre-treatments: add a certain amount of triclosan standard operation solution in the ambient water sample, make that the concentration of triclosan is respectively 0.001,0.005,0.01mgkg
-1Behind 0.22 μ m filter membrane, add 50mg triclosan carbon nanotube molecule imprinted polymer to adding in the target environmental water sample, this mixture is placed on the shaking table behind the concussion 30min, with the centrifugal 5min of 4000r/min, discard supernatant liquid.Adding 20mL concentration is 9:1, and v:v methyl alcohol/acetic acid behind the concussion wash-out 12h, with the centrifugal 5min of the speed of 4000r/min, is collected supernatant liquid in above-mentioned centrifuge tube, move in another centrifuge tube behind the 0.22 μ m filter membrane excessively.With nitrogen elutriant is blown near dried under room temperature, add the 1.0mL dissolve with methanol, the 60 μ L that take a sample prepare to inject high performance liquid chromatography;
(3) high-performance liquid chromatogram determination: start, moving phase flushing chromatographic column is used in preheating, treats to begin the sample introduction test after the baseline stability;
Be used in sample sample introduction prepared in (1) and (2), each sample repeats 5 times, is averaged peak area and carries out quantitative analysis, the content (mgkg of each reference material in the test specimens
-1);
(4) qualitative analysis: utilize the retention time qualitative method.According to the retention time of triclosan reference material, determine the chromatographic peak of triclosan in the sample;
(5) quantitative analysis: adopt standard working curve to carry out quantitative analysis;
The response value of reference material to be measured all should be in the method linearity range in the sample;
(6) result calculates by formula (1):
A=aC+b……………………………………(1)
In the formula:
C---the content of triclosan in the sample, unit is every kilogram of (mgkg of milligram
-1);
The peak area of triclosan in the actual sample that A---instrument records;
A, b---the parameter in the typical curve;
Described liquid chromatography test condition is:
A) chromatographic column: Shimadzu VP-ODS C18 post (150mm * 4.6mm, 5 μ m);
B) moving phase: methanol-water-acetic acid (70/20/10, v/v);
C) flow velocity: 1.0mLmin
-1
D) detector: UV-detector;
E) sample size: 20 μ L.
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| CN103926281A (en) * | 2014-05-06 | 2014-07-16 | 济南大学 | Preparation method of triclosan (TCS) molecular imprinting sensor with gold and carbon nanotube modified electrode |
| CN108318595A (en) * | 2018-01-15 | 2018-07-24 | 北京建筑大学 | A kind of assay method of adsorption equilibrium costant in colloidal solution |
| CN113209948A (en) * | 2021-05-19 | 2021-08-06 | 齐鲁工业大学 | Preparation method and application of multi-template molecularly imprinted composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103926281A (en) * | 2014-05-06 | 2014-07-16 | 济南大学 | Preparation method of triclosan (TCS) molecular imprinting sensor with gold and carbon nanotube modified electrode |
| CN103926281B (en) * | 2014-05-06 | 2016-03-02 | 济南大学 | The preparation method of gold carbon nano tube modified electrode triclosan molecular engram sensor |
| CN108318595A (en) * | 2018-01-15 | 2018-07-24 | 北京建筑大学 | A kind of assay method of adsorption equilibrium costant in colloidal solution |
| CN108318595B (en) * | 2018-01-15 | 2020-11-06 | 北京建筑大学 | Method for measuring adsorption equilibrium constant in colloidal solution |
| CN113209948A (en) * | 2021-05-19 | 2021-08-06 | 齐鲁工业大学 | Preparation method and application of multi-template molecularly imprinted composite material |
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