CN103739846A - Preparation method for quantum dot fluorescent imprinted polymer - Google Patents

Preparation method for quantum dot fluorescent imprinted polymer Download PDF

Info

Publication number
CN103739846A
CN103739846A CN201310734312.0A CN201310734312A CN103739846A CN 103739846 A CN103739846 A CN 103739846A CN 201310734312 A CN201310734312 A CN 201310734312A CN 103739846 A CN103739846 A CN 103739846A
Authority
CN
China
Prior art keywords
quantum dot
imprinted polymer
preparation
cdte
cyhalothrin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201310734312.0A
Other languages
Chinese (zh)
Other versions
CN103739846B (en
Inventor
卫潇
孟敏佳
宋志龙
周志平
闫永胜
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangsu University
Original Assignee
Jiangsu University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jiangsu University filed Critical Jiangsu University
Priority to CN201310734312.0A priority Critical patent/CN103739846B/en
Publication of CN103739846A publication Critical patent/CN103739846A/en
Application granted granted Critical
Publication of CN103739846B publication Critical patent/CN103739846B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Landscapes

  • Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)

Abstract

The invention provides a preparation method for a quantum dot fluorescent imprinted polymer and belongs to the technical field of preparation of environment-friendly materials. The preparation method comprises the following steps: firstly, synthesizing a precursor sodium hydrogen telluride in a needle pipe; synthesizing a water-soluble CdTe quantum dot by using thiomalic acid as a protection agent; finally, synthesizing the quantum dot fluorescent imprinted polymer which takes cyhalothrin as a template molecule by using a reverse micro-emulsion method so as to optically detect the cyhalothrin. The prepared quantum dot fluorescent imprinted polymer has high optical stability and pH (Potential of Hydrogen) stability and has the capability of selectively identifying the cyhalothrin.

Description

A kind of preparation method of quantum dot fluorescence imprinted polymer
Technical field
The present invention relates to a kind of preparation method of quantum dot fluorescence imprinted polymer, belong to environment functional material preparing technical field.
Background technology
The pyrethroid insecticideses such as Deltamethrin, Fenvalerate, lambda-cyhalothrin, owing to having the features such as pesticidal residual quantity high, in vegetables and fruit is lower, are widely used in China.The residual analyzing and testing of pyrethrins insecticide is mainly used chromatography, as liquid phase chromatography, vapor-phase chromatography and Liquid Chromatography/Mass Spectrometry.Chromatography has the high rate of recovery, good circulation ratio and lower detection limit, but needs loaded down with trivial details sample pretreatment process.The method of conventional sample pre-treatments has solvent extraction technology, supercritical extraction technique, microwave-assisted extraction technique, membrane separation technique and solid phase extraction techniques etc.Although these methods respectively have distinct advantages, also respectively there is its limitation.As solvent extraction technology in a large number with an organic solvent, easily produce secondary pollution; Although supercritical extraction has, easily realize separated with target compound, the free of contamination advantage of solvent, complicated operation, cost are high; There is the blockage problem of film in membrane separation technique; The conventional sorbent material selectivity of solid phase extraction techniques is poor.Therefore, residual for complicated component in environment, chrysanthemum ester pollutant that character phase Sihe content is on the low side, set up and improve quick, sensitive and optionally analysing and detecting method be the task of top priority of carrying out the residual monitoring of chrysanthemum ester pollutant.
Along with analyzing improving constantly of requiring, particularly pharmaceutical analysis, environmental analysis, food analysis and product detect the growing of demand, and sensor, as important detection means, more and more receives people's concern.Organic have good molecular recognition function with biological sensitive materials, molecularly imprinted polymer material wherein can be for the target compound customization of " cutting the garment according to the figure ", the single-minded identification of realization to target molecule, can compare favourably with natural biological recognition system (enzyme-to-substrate), there is preparation simple, good stability, life-span is long, easily preserve, the feature such as cheap, in Solid-Phase Extraction, chiral separation, simulation biological antibody, catalysis and and synthetic aspect be widely used, to solve environment, biology waits simple and direct that in complex system, specific target molecules highly selective is identified, reliable means.
Molecular imprinting is that preparation has the process of single-minded recognition capability polymkeric substance to a certain specific molecular, and the polymkeric substance of preparation is called molecularly imprinted polymer.The general formation supramolecular complex that first template molecule and selected function monomer interacted of the preparation process of molecularly imprinted polymer, under linking agent effect, form polymkeric substance again, finally by certain means, remove after template molecule, in the molecularly imprinted polymer of acquisition, just left binding site template molecule to specific recognition.In recent years, the structure of molecularly imprinted polymer effect precordainment, specific recognition and extensive practicality have attracted more and more many scientific workers' interest and favor.
Quantum dot is as optical material, because it has excellent photoelectric properties, larger specific surface area and quantum size effect is in these years used widely in research fields such as biological chemistry, molecular biology, genomics, proteomics, bio-molecular interactions.In these researchs, quantum dot fluorescence probe and imaging in vivo thereof are one of emphasis of research at present.Quantum dot is compared with traditional organic fluorescence element, there is good photostabilization, compared with large Stokes shift and a series of features such as fluorescence spectrum is narrow and symmetrical, and there is fluorescent characteristic, be expected to develop into the novel light-emitting biomarker material with development prospect of a class.
Through the literature search of prior art is found, " the Selective Recognition of 2 that Pan Jianming etc. deliver for 2011 on < < The Journal of Physical Chemistry C > > (physical chemistry C), 4, 6-TriehloroPhenol by Molecularly Imprinted Polymers Based on Magnetic Halloysite Composites " (the surface imprinted selectivity identification 2 of halloysite nanotubes magnetic composite, 4, 6-Trichlorophenol), this article has successfully been prepared magnetic molecularly imprinted matrix material for selective separation 2, 4, 6-Trichlorophenol, there is good selectivity." measuring the Study of New Method of niacin norfloxacin based on CdTe quantum dot " that Wei Hong etc. 2011 deliver on < < chemistry journal > >, this article has successfully utilized detection that the fluorescence property of CdTe quantum dot is simple, quick, sensitive niacin norfloxacin.Yet the former testing process workload is larger, speed is slow, and sensitivity is lower; Latter lacks certain universality and selectivity.Therefore, high-sensitive fluoroscopic examination is combined with molecular imprinting, utilize fluorescent signal to make up the defect that molecularly imprinted polymer lacks signal conduction, prepare molecular imprinting fluorescent optical sensor, meet anti-interference, the high selection of sensory device, high-sensitive demand, become the study hotspot in the fields such as current sensing, separation.The preparation of molecular imprinting fluorescent optical sensor is further expanded range of application and the using method of MIPs in analyzing and testing, and the selectivity of MIPs also makes the sensitivity of compound fluorescent probe and selectivity be significantly improved simultaneously.Utilizing molecular imprinting fluorescent optical sensor to carry out the research that thereby optical analysis reaches fast, convenience detects residual quantity necessitates.
Summary of the invention
First sodium borohydride, tellurium powder and water generate presoma NaHTe solution in syringe under oxygen-free environment.Then the CdCl that has mercaptosuccinic acid (MSA) to exist that the pH that presoma is injected into letting nitrogen in and deoxidizing is 10.5-11.5 22.5H 2in the O aqueous solution, at nitrogen protection 100-110 oback flow reaction under C condition, according to the difference of return time, has obtained the quantum dot of different size.Finally utilize reverse microemulsion method to synthesize and take lambda-cyhalothrin as template molecule, (3-aminopropyl)-Trimethoxy silane (APTS) is function monomer, the fluorescence molecule imprinted polymer that tetraethoxy (TEOS) is linking agent, and for optical detection lambda-cyhalothrin.The fluorescence molecule imprinted polymer of preparation has good optics and pH stability, and has the ability of selectivity identification lambda-cyhalothrin.
The technical solution used in the present invention is :
A preparation method for quantum dot fluorescence imprinted polymer, according to following steps:
(1) sodium borohydride (NaBH4) and tellurium powder are joined in syringe, and then add redistilled water that solid is dissolved completely; Syringe is positioned in the container of a filled with water, keeps reaction to spend the night, final white liquid is required presoma NaHTe solution.
(2), under the condition of letting nitrogen in and deoxidizing, the presoma NaHTe solution that step (1) is obtained is injected into the CdCl that mercaptosuccinic acid (MSA) exists 22.5H 2in the O aqueous solution, mixing solutions is under nitrogen protection condition 100 oc-110 oCback flow reaction, according to the difference of return time, obtains the quantum dot (20 minutes to 6 hours time, obtains wavelength 526nm to the quantum dot of 650nm) of different size.
(3) in there-necked flask, add hexanaphthene, Triton-100 and n-hexyl alcohol, then add the aqueous solution of the CdTe quantum dot of preparation in step (2), continue to stir 15-30 min, then add TEOS and ammoniacal liquor, stir 1.5-2.0 hour.
(4) APTS and lambda-cyhalothrin (LC) are dissolved in cyclohexane solution completely, after fully mixing, gained mixing solutions are joined in the mixing solutions of step (3) to sealing and stir and spend the night; After reaction finishes, add acetone soln breakdown of emulsion, be finally precipitated polymkeric substance (CdTe@SiO 2@LC); With eluent by primary template molecule lambda-cyhalothrin from CdTe@SiO 2in@LC, elute wash-out three times; Remove after template molecule, obtain quantum dot fluorescence imprinted polymer CdTe@SiO 2@MIPs.
Wherein, the mol ratio of the sodium borohydride described in step (1) and tellurium powder is 2-4:1.
Wherein, the CdCl that has mercaptosuccinic acid (MSA) to exist described in step (2) 22.5H 2the pH of the O aqueous solution is 10.5-11.5; Wherein, CdCl 22.5H 2the mol ratio of O, MSA and NaHTe is 0.4-1:1-1.5:0.2, and wherein the molar weight of NaHTe draws according to the molar weight of tellurium powder in step (1); Described back flow reaction temperature is 100 oc-110 oC.
Wherein, the volume ratio of hexanaphthene, Triton-100 and the n-hexyl alcohol described in step (3) is 15:3.2-3.6:3.2-3.6; The aqueous solution of the described CdTe quantum dot adding and hexanaphthene volume ratio are 0.6-0.8:15; The volume ratio of described TEOS, ammoniacal liquor and cyclohexane is 0.1-0.2:0.1:15.
Wherein, described in step (4), the volume ratio of APTS and TEOS is 0.03-0.05:0.1-0.2; Described APTS and lambda-cyhalothrin mass ratio are 3-5:1; The described acetone soln adding and whole mixed system equal-volume; Described eluent is the mixed solution of ethanol and acetonitrile, and wherein the volume ratio of ethanol and acetonitrile is 8:2.
Non-molecularly imprinted polymer (CdTe SiO 2synthesizing except not containing template molecule@NIPs), other processes are identical with trace process.
Technological merit of the present invention: using CdTe as fluorescent functional material, utilize reverse microemulsion method to synthesize fluorescence molecule imprinted polymer; Utilize the fluorescence molecule imprinted polymer that the present invention obtains to there is good optical stability, can realize the ability of identification fast and optical detection lambda-cyhalothrin.The preparation of molecular imprinting fluorescent optical sensor is further expanded range of application and the using method of MIPs in analyzing and testing, and the selectivity of MIPs also makes the sensitivity of compound fluorescent probe and selectivity be significantly improved simultaneously.The research of controlling the field that chemistry is new for expanding Environmental Analytical Chemistry and environmental pollution chemistry and environmental pollution provides science reliable foundation.For be further engaged in correlation theory research and practical application as: on-the-spot, fast, selectivity identification analyzes and measures water body with visual detection, the trace/ultra-trace objectionable impurities in food and organism is established solid theory and practice basis.
Accompanying drawing explanation
Fig. 1: CdTe QDs (a, b) and CdTe@SiO 2the transmission electron microscope picture of@MIPs (c, d) and CdTe@SiO 2@MIPs (e) and CdTe@SiO 2the scanning electron microscope (SEM) photograph of@NIPs (f).
Fig. 2: CdTe@SiO 2@NIPs (1), CdTe@SiO 2@LC (2) and CdTe@SiO 2the infared spectrum of@MIPs (3).
Fig. 3: pH value is to CdTe@SiO 2@MIPs(square frame) and CdTe@SiO 2the impact of fluorescence intensity@NIPs(circle).
Fig. 4: CdTe@SiO 2@MIPs(square frame) and CdTe@SiO 2@NIPs(circle) fluorescence time stability.
Fig. 5: CdTe@SiO 2@MIPs and CdTe@SiO 2the response curve of@NIPs to LC.
Fig. 6: under same concentration (60 μmol/L) different pyrethrins are to CdTe@SiO 2@MIPs and CdTe@SiO 2the quencher amount of@NIPs.
 
Embodiment
Below in conjunction with concrete embodiment, the present invention will be further described.
embodiment 1:
30.3 mg sodium borohydrides and 51.04 mg tellurium powder are joined in 5.0 mL syringes, and then add 2.0 mL redistilled waters, syringe is positioned in the container of a filled with water, keeps reaction to spend the night, final white liquid is required presoma NaHTe.
By the presoma NaHTe just the having obtained CdCl that has mercaptosuccinic acid (MSA) to exist that to be injected into the pH of letting nitrogen in and deoxidizing be 10.5 2in the aqueous solution, the CdCl wherein adding 22.5H 2the quality of O and MSA is respectively 182.688 mg and 300.3 mg.Mixing solutions is in nitrogen protection 100 ounder C condition, back flow reaction is 60 minutes, and obtaining required wavelength is 558 nm yellow-green colour quantum dots.
Getting 15 mL hexanaphthenes, 3.2 mL Triton-100,3.2 mL n-hexyl alcohols joins in there-necked flask, stir after 10 min, the CdTe quantum dot aqueous solution that adds 600 μ L to prepare, continue to stir after 15 min, add 100 μ L TEOS and 100 μ L ammoniacal liquor, stir after 1.5 hours, add the cyclohexane solution of 30 μ L APTS and 10 mg lambda-cyhalothrins (LC), sealing is stirred and is spent the night.After reaction finishes, add 22.23 mL acetone breakdowns of emulsion, the precipitation finally obtaining is quantum dot imprinted polymer (CdTe@SiO 2@LC).Eluent ethanol/acetonitrile (v/v, 8:2) by primary template molecule trifluoro Cypermethrin from CdTe@SiO 2in@LC, elute wash-out three times.Remove after template molecule, obtain molecularly imprinted polymer CdTe@SiO 2@MIPs.Non-molecularly imprinted polymer (CdTe SiO 2synthesizing except not containing template molecule@NIPs), other processes are identical with trace process.
embodiment 2:
By 60.6 mg sodium borohydride (NaBH 4) and 51.04 mg tellurium powder join in 5.0 mL syringes, and then add 2.0 mL redistilled waters, syringe is positioned in the container of a filled with water, keep reaction to spend the night, final white liquid is required presoma NaHTe.
By the presoma NaHTe just the having obtained CdCl that has mercaptosuccinic acid (MSA) to exist that to be injected into the pH of letting nitrogen in and deoxidizing be 11.5 2in the aqueous solution, the CdCl wherein adding 22.5H 2the quality of O and MSA is respectively 456.72 mg and 450.45 mg.Mixing solutions is in nitrogen protection 110 ounder C condition, back flow reaction is 20 minutes, and obtaining required wavelength is the green quantum dot of 526nm.
Getting 15 mL hexanaphthenes, 3.6 mL Triton-100,3.6 mL n-hexyl alcohols joins in there-necked flask, stir after 20 min, the CdTe quantum dot aqueous solution that adds 800 μ L to prepare, continue to stir after 30 min, add 200 μ L TEOS and 100 μ L ammoniacal liquor, stir after 2.0 hours, add the cyclohexane solution of 50 μ L APTS and 10 mg lambda-cyhalothrins (LC), sealing is stirred and is spent the night.After reaction finishes, add 23.35 mL acetone breakdowns of emulsion, the precipitation finally obtaining is quantum dot imprinted polymer (CdTe@SiO 2@LC).Eluent ethanol/acetonitrile (v/v, 8:2) by primary template molecule trifluoro Cypermethrin from CdTe@SiO 2in@LC, elute wash-out three times.Remove after template molecule, obtain molecularly imprinted polymer CdTe@SiO 2@MIPs.Non-molecularly imprinted polymer (CdTe SiO 2synthesizing except not containing template molecule@NIPs), other processes are identical with trace process.Fig. 1 is CdTe QDs (a, b) and CdTe@SiO 2the transmission electron microscope picture of@MIPs (c, d) and CdTe@SiO 2@MIPs (e) and CdTe@SiO 2the scanning electron microscope (SEM) photograph of@NIPs (f).From transmission plot, can obtain CdTe QDs and CdTe@SiO 2the size of@MIPs can be found out CdTe@SiO from scanning electron microscope (SEM) photograph 2@MIPs and CdTe@SiO 2the difference of@NIPs, CdTe@SiO 2the surface ratio CdTe@SiO of@MIPs 2the surface of@NIPs is more coarse.Fig. 2 is CdTe@SiO 2@NIPs (1), CdTe@SiO 2@LC (2) and CdTe@SiO 2the infared spectrum of@MIPs (3).1000 ~ 1100 cm that occur in collection of illustrative plates -1the characteristic peak of the corresponding Si-O-Si of broad peak, 790 corresponding Si-O vibrations.Be positioned at 1724 cm -1the peak at place, corresponding to the O-C=O stretching vibration peak of chrysanthemum ester, is positioned at 1489 cm -1the weak peak at place is corresponding to the C=C stretching vibration peak of phenyl ring.Illustrate that lambda-cyhalothrin successfully participates in polyreaction, and remove from polymkeric substance by solvent extraction.
embodiment 3:
By 45 mg sodium borohydride (NaBH 4) and 51.04 mg tellurium powder join in 5.0 mL syringes, and then add 2.0 mL redistilled waters, syringe is positioned in the container of a filled with water, keep reaction to spend the night, final white liquid is required presoma NaHTe.
By the presoma NaHTe just the having obtained CdCl that has mercaptosuccinic acid (MSA) to exist that to be injected into the pH of letting nitrogen in and deoxidizing be 11.2 2in the aqueous solution, the CdCl wherein adding 22.5H 2the quality of O and MSA is respectively 365.376 mg and 375.375 mg.Mixing solutions is in nitrogen protection 105 ounder C condition, back flow reaction is 6 hours, and obtaining required wavelength is the red quantum dots of 650 nm.
Getting 15 mL hexanaphthenes, 3.5 mL Triton-100,3.5 mL n-hexyl alcohols joins in there-necked flask, stir after 15 min, the CdTe quantum dot aqueous solution that adds 700 μ L to prepare, continue to stir after 20 min, add 150 μ L TEOS and 100 μ L ammoniacal liquor, stir after 1.8 hours, add the cyclohexane solution of 40 μ L APTS and 10 mg lambda-cyhalothrins (LC), sealing is stirred and is spent the night.After reaction finishes, add 22.99 mL acetone breakdowns of emulsion, the precipitation finally obtaining is quantum dot imprinted polymer (CdTe@SiO 2@LC).Eluent ethanol/acetonitrile (v/v, 8:2) by primary template molecule trifluoro Cypermethrin from CdTe@SiO 2in@LC, elute wash-out three times.Remove after template molecule, obtain molecularly imprinted polymer CdTe@SiO 2@MIPs.Non-molecularly imprinted polymer (CdTe SiO 2synthesizing except not containing template molecule@NIPs), other processes are identical with trace process.
embodiment 4:
In the specific embodiment of the invention, identification and optical detection performance evaluation are carried out by the following method: the target compound ethanolic soln of the aqueous solution of appropriate fluorescent polymer and a series of concentration known is joined in 10 mL colorimetric cylinders, regulating pH value is 7.0 also to use ethanol constant volume, ethanol/water (v/v wherein, 1:1), 10 min that vibrate under room temperature.By molecular fluorescence photometer measurement system, detect the fluorescence intensity of solution.According to Stern-Volmer equation (
Figure 2013107343120100002DEST_PATH_IMAGE001
) to take concentration [c] be X-coordinate, relative intensity of fluorescence ( i max / I)for ordinate zou is drawn fluorescence response curve.Select several structures and kin pyrethrin, material, participates in CdTe@SiO as a comparison 2the research of@MIPs recognition performance.
Test example 1: first investigated pH value on the impact of fluorescence intensity (as shown in Figure 3, prepared fluorescence molecule polymkeric substance is that within the scope of 6.0-11.0, fluorescence intensity keeps stable at pH) and the fluorescence time stability (as shown in Figure 4, prepared fluorescence molecule polymkeric substance has good stability) of resulting polymers.Finally select the solution of the less pH=7.0 of fluorescence intensity impact to do fluorometric investigation experiment.Fluorescence molecule imprinted material is configured to the aqueous solution of 100 mg/L, chrysanthemum ester class target compound is configured as the ethanolic soln of 1 mmol/L.Get the polymers soln of 5 mL and the ethanolic soln of 0-0.6 mL trifluoro Cypermethrin joins in 10 mL colorimetric cylinders, with dilute hydrochloric acid or weak ammonia, regulating pH value is 7.0 also to use ethanol constant volume, ethanol/water (v/v wherein, 1:1), test fluid room temperature 10 min that vibrate, then with spectrophotofluorometer, detect the fluorescence intensity of solution.According to Stern-Volmer equation (
Figure 924733DEST_PATH_IMAGE001
) to take concentration [c] be X-coordinate, relative intensity of fluorescence ( i max / I)for ordinate zou is drawn fluorescence response curve.As shown in Figure 5, along with the rising of LC concentration, fluorescence intensity weakens, according to Stern-Volmer equation (
Figure 585522DEST_PATH_IMAGE001
) to take concentration [c] be X-coordinate, relative intensity of fluorescence ( i max / I)for ordinate zou, draw fluorescence response curve, obtain respectively relation conefficient and be 0.9965 and 0.9918 straight line.Result shows, quantum dot fluorescence molecularly imprinted polymer has the ability of good optical detection LC.
Test example 2: the aqueous solution that fluorescence molecule imprinted material is configured to 100 mg/L, select lambda-cyhalothrin (LC) cyfloxylate (BC), fenvalerate (FE), four kinds of target compounds of bifenthrin (BI), above several pyrethrins are configured as to the ethanolic soln of 1 mmol/L.The ethanolic soln of getting the aqueous solutions of polymers of 5 mL and the pyrethrin of 0.6 mL joins in 10 mL colorimetric cylinders, with dilute hydrochloric acid or weak ammonia, regulating pH value is 7.0 also to use ethanol constant volume, ethanol/water (v/v wherein, 1:1), test fluid room temperature 10 min that vibrate, then with spectrophotofluorometer, detect the fluorescence intensity of solution.As shown in Figure 6, as seen from the figure, LC is to CdTe@SiO 2the quencher amount of@MIPs is maximum, and CdTe@SiO is described 2@MIPs has specific recognition capability to template molecule LC.Result shows, polymkeric substance prepared by the present invention has obvious specific recognition ability to LC, fluorescent quenching amount ( i max / I) higher than other pyrethrin.

Claims (6)

1. a preparation method for quantum dot fluorescence imprinted polymer, is characterized in that, according to following steps, carries out:
(1) sodium borohydride and tellurium powder are joined in syringe, and then add redistilled water that solid is dissolved completely; Syringe is positioned in the container of a filled with water, keeps reaction to spend the night, final white liquid is required presoma NaHTe solution;
(2), under the condition of letting nitrogen in and deoxidizing, the presoma NaHTe solution that step (1) is obtained is injected into the CdCl that mercaptosuccinic acid exists 22.5H 2in the O aqueous solution, mixing solutions is under nitrogen protection condition 100 oc-110 oCback flow reaction, according to the difference of return time, obtains the quantum dot of different size;
(3) in there-necked flask, add hexanaphthene, Triton-100 and n-hexyl alcohol, then add the aqueous solution of the CdTe quantum dot of preparation in step (2), continue to stir 15-30 min, then add TEOS and ammoniacal liquor, stir 1.5-2.0 hour;
(4) APTS and lambda-cyhalothrin are dissolved in cyclohexane solution completely, after fully mixing, gained mixing solutions are joined in the mixing solutions of step (3) to sealing and stir and spend the night; After reaction finishes, add acetone soln breakdown of emulsion, be finally precipitated polymkeric substance; With eluent by primary template molecule lambda-cyhalothrin from CdTe@SiO 2in@LC, elute wash-out three times; Remove after template molecule, obtain quantum dot fluorescence imprinted polymer.
2. the preparation method of a kind of quantum dot fluorescence imprinted polymer according to claim 1, is characterized in that, the mol ratio of the sodium borohydride described in step (1) and tellurium powder is 2-4:1.
3. the preparation method of a kind of quantum dot fluorescence imprinted polymer according to claim 1, is characterized in that, the CdCl that has mercaptosuccinic acid (MSA) to exist described in step (2) 22.5H 2the pH of the O aqueous solution is 10.5-11.5; Wherein, CdCl 22.5H 2the mol ratio of O, MSA and NaHTe is 0.4-1:1-1.5:0.2, and wherein the molar weight of NaHTe draws according to the molar weight of tellurium powder in step (1); Described back flow reaction temperature is 100 oc-110 oC.
4. the preparation method of a kind of quantum dot fluorescence imprinted polymer according to claim 1, is characterized in that, the volume ratio of hexanaphthene, Triton-100 and the n-hexyl alcohol described in step (3) is 15:3.2-3.6:3.2-3.6; The aqueous solution of the described CdTe quantum dot adding and hexanaphthene volume ratio are 0.6-0.8:15; The volume ratio of described TEOS, ammoniacal liquor and cyclohexane is 0.1-0.2:0.1:15.
5. the preparation method of a kind of quantum dot fluorescence imprinted polymer according to claim 1, is characterized in that, described in step (4), the volume ratio of APTS and TEOS is 0.03-0.05:0.1-0.2; Described APTS and lambda-cyhalothrin mass ratio are 3-5:1; The described acetone soln adding and whole mixed system equal-volume; Described eluent is the mixed solution of ethanol and acetonitrile, and wherein the volume ratio of ethanol and acetonitrile is 8:2.
6. the preparation method of a kind of quantum dot fluorescence imprinted polymer according to claim 1, is characterized in that, the quantum dot fluorescence imprinted polymer prepared according to claim 1 is applied to optical detection lambda-cyhalothrin.
CN201310734312.0A 2013-12-27 2013-12-27 A kind of preparation method of quantum dot fluorescence imprinted polymer Expired - Fee Related CN103739846B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310734312.0A CN103739846B (en) 2013-12-27 2013-12-27 A kind of preparation method of quantum dot fluorescence imprinted polymer

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310734312.0A CN103739846B (en) 2013-12-27 2013-12-27 A kind of preparation method of quantum dot fluorescence imprinted polymer

Publications (2)

Publication Number Publication Date
CN103739846A true CN103739846A (en) 2014-04-23
CN103739846B CN103739846B (en) 2016-04-06

Family

ID=50496923

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310734312.0A Expired - Fee Related CN103739846B (en) 2013-12-27 2013-12-27 A kind of preparation method of quantum dot fluorescence imprinted polymer

Country Status (1)

Country Link
CN (1) CN103739846B (en)

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103965504A (en) * 2014-05-13 2014-08-06 江苏联合化工有限公司 Preparation method of rear earth doped core-shell type fluorescent imprinting polymer
CN104165874A (en) * 2014-07-24 2014-11-26 江苏大学 Quantum dot fluorescent aspirin imprinted sensor and its preparation method and use
CN104403051A (en) * 2014-07-30 2015-03-11 江苏大学 Preparation method of molecularly imprinted material for fluorescent selective recognition of cyhalothrin
CN104744649A (en) * 2015-03-19 2015-07-01 江苏大学 Preparation method of CdTe quantum dot fluorescent cyfluthrin imprinted sensor
CN104877163A (en) * 2015-04-01 2015-09-02 宁波大学 Preparation method for molecularly imprinted-quantum dot polymer of pyrethroid type pesticide
CN104910385A (en) * 2015-06-23 2015-09-16 南华大学 Surface imprinted material capable of selectively adsorbing nordihydroguaiaretic acid and preparation method thereof
CN105062464A (en) * 2015-07-29 2015-11-18 江苏大学 Quantum dot fluorescence printing sensor preparation method based on swelling technology
CN105136758A (en) * 2015-08-28 2015-12-09 合肥学院 Method for preparing Eu3+ labelled molecule imprinted sensor used for pesticide residue detection
CN106198478A (en) * 2016-08-03 2016-12-07 陕西师范大学 The method of molecularly imprinted polymer based on quantum dot ratio fluorescent detection mitoxantrone
CN106442436A (en) * 2016-07-12 2017-02-22 江苏大学 Magnetic quantum dot printing material for detecting trace 4-nitrophenol in water, preparation method and application thereof
CN106872689A (en) * 2017-01-10 2017-06-20 宁波大学 A kind of bionical enzyme-linked immune detection method of quick measure sulfa antibiotics residual
CN108120707A (en) * 2018-01-04 2018-06-05 山西大学 The preparation of molecular engram fluorescent sensing material and its application in high-throughput detection Rogor
CN109021283A (en) * 2018-04-19 2018-12-18 华南师范大学 For detecting the CsPbBr of flolimat3Perovskite quantum dot-molecular engram fluorescent optical sensor and preparation method thereof
CN109406473A (en) * 2018-11-08 2019-03-01 青岛大学 A kind of preparation method of the phycoerythrin ratio fluorescent sensor based on magnetic molecularly imprinted core shell polymer
CN110186884A (en) * 2019-07-09 2019-08-30 南昌大学 A kind of visualization molecular engram nano-sensor and its preparation and application
CN114957667A (en) * 2022-05-19 2022-08-30 济南大学 Preparation method and application of curcumin fluorescent molecularly imprinted polymer

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101265310A (en) * 2008-04-18 2008-09-17 杨挺 Molecular engram polymer of pyrethroid-like pesticide and application thereof
CN101381438A (en) * 2007-09-05 2009-03-11 中国科学院上海微系统与信息技术研究所 Compound material constructed by molecular engram and fluorescent conjugated polymer, preparation and application
CN101644680A (en) * 2009-09-01 2010-02-10 济南大学 Molecular imprinting chemiluminescence sensor for detecting trace amount pesticide residue and application thereof
CN102070739A (en) * 2010-12-02 2011-05-25 浙江大学 Method for preparing cyhalothrin molecular imprinting polymer microspheres
CN102070750A (en) * 2010-12-02 2011-05-25 浙江大学 Method for preparing sumicidin molecularly imprinted polymer microspheres

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101381438A (en) * 2007-09-05 2009-03-11 中国科学院上海微系统与信息技术研究所 Compound material constructed by molecular engram and fluorescent conjugated polymer, preparation and application
CN101265310A (en) * 2008-04-18 2008-09-17 杨挺 Molecular engram polymer of pyrethroid-like pesticide and application thereof
CN101644680A (en) * 2009-09-01 2010-02-10 济南大学 Molecular imprinting chemiluminescence sensor for detecting trace amount pesticide residue and application thereof
CN102070739A (en) * 2010-12-02 2011-05-25 浙江大学 Method for preparing cyhalothrin molecular imprinting polymer microspheres
CN102070750A (en) * 2010-12-02 2011-05-25 浙江大学 Method for preparing sumicidin molecularly imprinted polymer microspheres

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103965504A (en) * 2014-05-13 2014-08-06 江苏联合化工有限公司 Preparation method of rear earth doped core-shell type fluorescent imprinting polymer
CN103965504B (en) * 2014-05-13 2016-09-14 江苏联合化工有限公司 The preparation method of rear-earth-doped core-shell type fluorescence imprinted polymer
CN104165874A (en) * 2014-07-24 2014-11-26 江苏大学 Quantum dot fluorescent aspirin imprinted sensor and its preparation method and use
CN104403051A (en) * 2014-07-30 2015-03-11 江苏大学 Preparation method of molecularly imprinted material for fluorescent selective recognition of cyhalothrin
CN104744649A (en) * 2015-03-19 2015-07-01 江苏大学 Preparation method of CdTe quantum dot fluorescent cyfluthrin imprinted sensor
CN104744649B (en) * 2015-03-19 2018-06-26 江苏大学 A kind of preparation method of CdTe quantum fluorescence Cyhalothrin trace sensor
CN104877163A (en) * 2015-04-01 2015-09-02 宁波大学 Preparation method for molecularly imprinted-quantum dot polymer of pyrethroid type pesticide
CN104877163B (en) * 2015-04-01 2018-05-18 宁波大学 A kind of preparation method of pyrethroid pesticide molecular engram-quanta polymer
CN104910385A (en) * 2015-06-23 2015-09-16 南华大学 Surface imprinted material capable of selectively adsorbing nordihydroguaiaretic acid and preparation method thereof
CN105062464B (en) * 2015-07-29 2017-06-27 江苏大学 A kind of preparation method of the quantum dot fluorescence trace sensor based on swelling techniques
CN105062464A (en) * 2015-07-29 2015-11-18 江苏大学 Quantum dot fluorescence printing sensor preparation method based on swelling technology
CN105136758B (en) * 2015-08-28 2017-12-08 合肥学院 A kind of Eu to the residual detection of agriculture3+Mark molecule marking transducer production method
CN105136758A (en) * 2015-08-28 2015-12-09 合肥学院 Method for preparing Eu3+ labelled molecule imprinted sensor used for pesticide residue detection
CN106442436B (en) * 2016-07-12 2019-11-05 江苏大学 For detecting magnetic quantum dot imprinted material, the Preparation method and use of underwater trace 4- nitrophenol
CN106442436A (en) * 2016-07-12 2017-02-22 江苏大学 Magnetic quantum dot printing material for detecting trace 4-nitrophenol in water, preparation method and application thereof
CN106198478A (en) * 2016-08-03 2016-12-07 陕西师范大学 The method of molecularly imprinted polymer based on quantum dot ratio fluorescent detection mitoxantrone
CN106198478B (en) * 2016-08-03 2018-12-07 陕西师范大学 The method of molecularly imprinted polymer detection mitoxantrone based on quantum dot ratio fluorescent
CN106872689A (en) * 2017-01-10 2017-06-20 宁波大学 A kind of bionical enzyme-linked immune detection method of quick measure sulfa antibiotics residual
CN108120707A (en) * 2018-01-04 2018-06-05 山西大学 The preparation of molecular engram fluorescent sensing material and its application in high-throughput detection Rogor
CN109021283A (en) * 2018-04-19 2018-12-18 华南师范大学 For detecting the CsPbBr of flolimat3Perovskite quantum dot-molecular engram fluorescent optical sensor and preparation method thereof
CN109021283B (en) * 2018-04-19 2021-01-26 华南师范大学 CsPbBr for detecting omethoate3Perovskite quantum dot-molecularly imprinted fluorescent sensor and preparation method thereof
CN109406473A (en) * 2018-11-08 2019-03-01 青岛大学 A kind of preparation method of the phycoerythrin ratio fluorescent sensor based on magnetic molecularly imprinted core shell polymer
CN109406473B (en) * 2018-11-08 2019-07-30 青岛大学 A kind of preparation method of phycoerythrin ratio fluorescent sensor
US10895536B1 (en) 2018-11-08 2021-01-19 Qingdao University Method for preparing a ratiometric fluorescent sensor for phycoerythrin based on a magnetic molecularly imprinted core-shell polymer
CN110186884A (en) * 2019-07-09 2019-08-30 南昌大学 A kind of visualization molecular engram nano-sensor and its preparation and application
CN114957667A (en) * 2022-05-19 2022-08-30 济南大学 Preparation method and application of curcumin fluorescent molecularly imprinted polymer

Also Published As

Publication number Publication date
CN103739846B (en) 2016-04-06

Similar Documents

Publication Publication Date Title
CN103739846B (en) A kind of preparation method of quantum dot fluorescence imprinted polymer
Ge et al. Development of a novel deltamethrin sensor based on molecularly imprinted silica nanospheres embedded CdTe quantum dots
CN105385438A (en) Preparing method of amino carbon quantum dot fluorescence silicon substrate imprint sensor
CN103756004A (en) Preparation method of quantum-dot phosphorescent imprinted polymer
CN104237182B (en) Preparation method and application of Mn-doped ZnS quantum dot imprinted sensor
CN104165874A (en) Quantum dot fluorescent aspirin imprinted sensor and its preparation method and use
CN106967416B (en) The preparation method of titanium dioxide nano-particle fluorescence probe for DDT detection
CN106916159B (en) A kind of switch nanometer porphyrin fluorescence sensor controllable method for preparing
Sun et al. Construction of biomass carbon dots@ molecularly imprinted polymer fluorescent sensor array for accurate identification of 5-nitroimidazole antibiotics
CN102353661A (en) Fluorescent sensor film preparation method based on perylene diimide cholesterol derivative
CN104237183B (en) A kind of preparation method and application of ZnS quantum dot silicon substrate surface molecular engram sensor
CN104359880A (en) Chemical preparation method for CdTe quantum dot fluorescent probe for detecting trace amount of paraquat
CN102012372A (en) Method for detecting medicinal molecules by magnetic imprinting surface enhanced Raman spectroscopy technology
CN105466898A (en) Preparation method of amino CQD (carbon quantum dot) fluorescence and 4-nitrophenol molecularly imprinted sensor
Yang et al. A novel luminescent sensor based on Tb@ UiO-66 for highly detecting Sm3+ and teflubenzuron
CN106124475A (en) A kind of trace pesticide residues Raman spectrum method for detecting surface reinforcement based on aptamer
CN104672476A (en) Preparation method of rare-earth fluorescent molecularly imprinted membrane and application of rare-earth fluorescent molecularly imprinted membrane
CN109283164B (en) Sensor for detecting uric acid by using lanthanide MOF spinning fiber membrane and preparation method thereof
CN104237184B (en) A kind of preparation method of ZnO nanorod molecular engram fluorescent optical sensor
CN103837523A (en) Method and kit for detecting acephate
CN104744649B (en) A kind of preparation method of CdTe quantum fluorescence Cyhalothrin trace sensor
CN110229660A (en) A kind of continuous double ratio two-photon mitochondrias locking fluorescence probes and its preparation method and application of carboxy-lesterase-pH
Zhao et al. Chiral induction in carbazole-conjugated covalent organic frameworks: a supersensitive fluorescence sensing platform for chiral recognition
CN103937487B (en) A kind of phosphorescence fluorion probe and Synthesis and applications thereof
Zhang et al. Perylene imide-based optical chemosensors for vapor detection

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20160406

Termination date: 20161227

CF01 Termination of patent right due to non-payment of annual fee