CN101787123A - Molecular engram polymer and preparation and application thereof - Google Patents
Molecular engram polymer and preparation and application thereof Download PDFInfo
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- CN101787123A CN101787123A CN 201010122775 CN201010122775A CN101787123A CN 101787123 A CN101787123 A CN 101787123A CN 201010122775 CN201010122775 CN 201010122775 CN 201010122775 A CN201010122775 A CN 201010122775A CN 101787123 A CN101787123 A CN 101787123A
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Abstract
The invention relates to a molecular engram polymer, which is used for metal ion detection. The engram and elution objects are metal complex ions; engram geometric dimensioning and combination point location of the polymer are matched with the specificity of the metal complex ions; the polymer is synthesized in-situ on metal membrane surface of a quartz microbalance and a surface plasma resonance device, the metal complex ions are eluted, the metal ions to be detected are processed by complexation and then are selectively absorbed by the molecular engram polymer, and finally the type and content of the metal ions are detected. In the invention, metal ion complexation is adopted to enlarge small changes of metal ion volume by a large extent, template molecular geometric structure memory performance of the molecular engram polymer is utilized to realize high preferential adsorption to improve metal ion detection selectivity effectively, and mass increase and geometric dimensioning enlargement caused by metal ion complexation help further improve sensitivity and antijamming capability of metal ion detection.
Description
Technical field
The present invention relates to a kind ofly prepare the molecularly imprinted polymer of gained with metal complex as template molecule, combine with crystal microbalance or surface plasma resonance technology, the highly sensitive and the highly selective that are used for metal ion detect.The present invention stresses the preparation method of this molecularly imprinted polymer, belongs to the material field.
Background technology
Heavy metal is one of important pollutent of environment and food contamination, has heavy metals such as potential hazardness, particularly mercury, cadmium, lead, chromium and has significant bio-toxicity, and micro-concentrations gets final product toxigenicity.Environment and food safety monitoring need develop real-time, highly sensitive, cheap easy-operating portable heavy metal detection technique and equipment.Crystal microbalance and surface plasma resonance technology are two representative art that can satisfy this demand.A common feature of these two technology is: use the surface of the material of detected object sensitivity being modified its gold and silver or other optional metallic film.
The science and technology progress of present stage is: Casilli etc. detect metal ion at the two pyridine derivates of the metal film electrode surface-coated of crystal microbalance, have obtained the sensitivity of mmole/liter (mmol/l); Ng etc. introduce Polythiophene functional group at surface of metal electrode, have obtained the sensitivity of 10Hz/ppm; Jane and Shih have obtained the sensitivity of 50Hz/ppm with the crown ether modified gold electrode, and detectability has reached 30 micromoles per liter (μ mol/l); Etorki etc. have studied unimolecular film and pb with thiobis mono succinate molecular film modified gold electrode
2+, Cu
2+Isoionic binding ability and selectivity thereof; Usefulness polyaniline modified gold electrodes such as Mirmohseni detect Cr
6+Ion; (Tea Melanin, TM) modified gold electrode detects Hg to Huang etc. with tea melanochrome
2+, Sn
2+, Ge
4+, Li
+, Ag
+, pb
2+, Cd
2+Etc. different kinds of ions, the sensitivity that obtains is between 0.05Hz/ppm～2500Hz/ppm, and relevant detection is limit between 80ppm～5ppb, but selectivity is very undesirable.These surface modification methods all be with the metal bare ion as detected object, in detection sensitivity and optionally desirable not enough aspect the over-all properties, fail to realize practicability.
Another effective means is to utilize the molecularly imprinted polymer material to the gold thin film surface modification, so reference section of the present invention is the patent or the document of template molecule Synthesis of Molecular Imprinting Polymers with metal ion or metal ion complex/inner complex.
With reference to Chinese patent application numbers 200810176455.3; 2008 (division original applying numbers 200380110941.0), the assorted Nas of Carrara agate crith etc. are with metal erbium ion and 5, the mixed ligand ternary complex that 7-dichloro-8-hydroxyquinoline and 4-vinylpridine form is a template molecule, with the methyl methacrylate is function monomer, with γ-radiation or UV radiation or thermochemistry initiated polymerization, the molecularly imprinted polymer of synthesis of selective absorption metal erbium ion, the enrichment that is used for the metal erbium ion with separate.With reference to Chinese patent application numbers 200710079224.6; 2007, Jin Derui etc. are with metal ion and polymer monomer reaction, preparation contains the monomer of metal ion group, the monomer that again this is contained the metal ion group mixes with linking agent and initiator, the reaction of initiated polymerization thing, acquisition contains the molecularly imprinted polymer of this metal ion, and with the metal ion in the nitric acid wash-out polymkeric substance.
With reference to United States Patent (USP) the 6th, 248, No. 842; 2001, Singh etc. replace the aliphatics sequestrant with polymerisable functional group, then with itself and metallic ion coordination, add cross-linking monomer again, initiator prepares polymkeric substance, with the metal ion wash-out, obtaining with this metal ion is the molecularly imprinted polymer of template then.Be used for solid phase extractions palladium metal ionic ion imprinted polymer with reference to commentaries such as Rao, the preparation of this polymkeric substance at first allows palladium ion and dimethyl glyoxime and 4-vinylpridine generate ternary complex, be polymerization single polymerization monomer with vinylbenzene and divinylbenzene then, with 2,2 '-azo-bis-isobutyl cyanide is an initiator, and preparation has the ion imprinted polymer of nanoporous, wash-out palladium ion then, stay the trace hole, be used for separating or the enriched palladium ion.Referenced patent application WO99/15707 number; 1999, John etc. are template molecule with the Uranyl ion, are function monomer with complexible substituted fatty acid or aromatic carboxylic acid such as phenylformic acid, and Synthesis of Molecular Imprinting Polymers is used for the Uranyl ionic and detects and enrichment.
Comprehensive above-mentioned and patent or document that other is published are the object Synthesis of Molecular Imprinting Polymers with the metal ion, be template from being that template develops into the metal ion match with the metal bare ion, but the latter's wash-out object are still based on metal ion; The polymeric method then causes based on radiation or chemistry.
Summary of the invention
In view of the defective of above-mentioned prior art, the objective of the invention is to propose the preparation method and the application of a kind of molecularly imprinted polymer and this molecularly imprinted polymer.Stress to improve selectivity, sensitivity and the interference free performance of this detection method from the material aspect, solve crystal microbalance or or surface plasma resonance technology be used for the problem of metal ion rapid detection process exist actually.
One object of the present invention will be achieved through the following technical solutions:
A kind of molecularly imprinted polymer is characterized in that: the trace of described polymkeric substance and wash-out object are the metal complex ion, and the trace geometrical dimension of polymkeric substance, binding site position and metal complex ion specificity are coincide.
Further, aforesaid a kind of molecularly imprinted polymer, wherein metal ion comprises copper, zinc, lead, chromium, cadmium, mercury at least in this metal complex ion;
This complexing agent comprises organic chelate or inorganic inner complex, and one of organic chelate selects for use ethylenediamine tetraacetic acid (EDTA), the concentration ratio of complexing agent and metal ion to satisfy the abundant complexing of metal ion;
This polymer monomer selects to be applicable to the monomer of electrochemical polymerization, at least comprise aniline, O-Phenylene Diamine, mphenylenediamine, Ursol D, adjacent benzene triamine, a benzene triamine, to benzene triamine, Dopamine HCL, pyrroles, indoles, thiophene, and the mixture of two or more arbitrary proportions arbitrarily.
Another object of the present invention, its preparation method can comprise step:
I, select for use metal ion and complexing agent to prepare the metal complex ion, the concentration ratio of complexing agent and metal ion satisfies the abundant complexing of metal ion;
II, be template, adopt electrochemical polymerization, polymer monomer and metal complex ion phase-polymerization with the metal complex ion;
III, with metal complex ion wash-out from polymkeric substance, obtain molecularly imprinted polymer.
Wherein, this electrochemical polymerization comprises optional cyclic voltammetry, potentiostatic method and galvanostatic method at least; Wash-out metal complex ionic method comprises at least regulates pH value, heating, maybe can destroy the chemical reaction of complex structure.
A further object of the present invention, it is in the application that heavy metal ion detects:
Be used for the application of the molecularly imprinted polymer of metal ion detection, it is characterized in that: comprise crystal microbalance and surface plasma resonance device with the technical equipment of described molecularly imprinted polymer coupling, metallic film surface in situ synthetic polymer in described those technical equipment, with described metal complex ion wash-out, be used to detect the metal complex ion again.
In the above-mentioned application scheme, contain one or more metal complex ions in this metallic film surface in situ synthetic polymkeric substance, behind the whole metal complex ions of wash-out, be used to detect more than one metal complex ion; And one of kind of this metallic film is a gold thin film, also can be other metallic film.
Implement the technical scheme of molecularly imprinted polymer of the present invention and method for making and application, its beneficial effect is:
The present invention adopts the complexing of molecularly imprinted polymer metal ion from preparation and actual detected process is handled, the slight change of metal ion volume is amplified significantly, utilize the memory performance of molecularly imprinted polymer to the template molecule geometry, the realization highly selective is adsorbed, thereby has effectively improved the selectivity of metal ion detection.Simultaneously, because the quality that causes behind the complexing of metal ion increases and geometrical dimension is amplified, further improved the sensitivity and the immunity from interference of metal ion detection.
Description of drawings
Below in conjunction with specific embodiment and accompanying drawing thereof the present invention being innovated essence is described in further detail:
Fig. 1 is the Cu that the embodiment of the invention is selected
2+-EDTA complexing of metal ion synoptic diagram;
Fig. 2 a be do not add in the embodiment of the invention cupric ion-EDTA complex compound template molecule synthetic polymkeric substance crystal microbalance frequency change response synoptic diagram (reduce～305Hz);
Fig. 2 b be add in the embodiment of the invention cupric ion-EDTA complex compound template molecule synthetic polymkeric substance crystal microbalance frequency change response synoptic diagram (reduce～345Hz);
Fig. 3 a and Fig. 3 b all are x-ray photoelectron power spectrums (XPS) that synthetic of the present invention is enclosed with the polymkeric substance of cupric ion-EDTA complex compound plank molecule, wherein: Cu 2p
1/2,3/2Compose corresponding cupric ion, Cls composes corresponding EDTA and polymkeric substance;
Fig. 4 is a kind of schematic arrangement that the present invention wraps up cupric ion-EDTA metal ion complex plank molecule post polymerization thing;
Fig. 5 is the structural representation that the present invention is modified with the QCM (Quartz Crystal Microbalance) of molecularly imprinted polymer.
Embodiment
The invention provides and a kind ofly prepare the synthetic method of molecularly imprinted polymer as template molecule, and it is combined with crystal microbalance or surface plasma resonance technology, be used for the highly sensitive of metal ion and the method for highly selective detection with metal complex.At first be to select suitable complexing agent in the implementation process with complexing of metal ion to be detected.Complexing agent can be only with the complexing agent of metal ion generation complex reaction to be detected, as with ferric ion bonded oxyphorase, will obtain the selectivity of the best like this.Complexing agent also can be can with the complexing agent of a lot of complexing of metal ion, as EDTA.At this moment, after optionally obtaining will depend on the different metal ion and this complexing agent combines, the size of the geometry of generation and binding site difference.The metal complex ion that generates with this complexing agent is a template molecule synthetic molecularly imprinted polymer, if can realize the metal complex ion highly selective absorption close with character to structure, as Cu
2+-EDTA and Zn
2+-EDTA then can obtain highly selective and detect effect; Otherwise, if the energy indifference adsorption structure metal complex ion close with character then can provide a kind of method that detects these several indifference adsorbing metal ions total amounts.The concentration proportioning of concentration of metal ions and complexing agent guarantees the abundant complexing of metal ionic, and complexing agent/concentration of metal ions is than can being the arbitrary proportion that is equal to or greater than the complexing stoichiometric ratio.
The synthetic method is directly synthetic with electrochemical method on the gold thin film surface of crystal microbalance or surface plasma body resonant vibration device, includes but not limited to cyclic voltammetry, potentiostatic method, optional electrochemical polymerization process such as galvanostatic method.Polymer monomer can be the various monomers that can be used for electrochemical polymerization, includes but not limited to aniline, O-Phenylene Diamine, mphenylenediamine, Ursol D, adjacent benzene triamine, a benzene triamine, to the benzene triamine, Dopamine HCL, pyrroles, indoles, thiophene etc., and any mixture of two or more any ratios between them.Monomer concentration is any monomer concentration that is fit to electrochemical polymerization, and two or more monomeric concentration ratios.
The applying step of the molecularly imprinted polymer of the present invention's preparation is: at gold thin film surface electrochemistry original position synthetic polymer, with the template molecule wash-out of appropriate means, stay the pore space structure that this template molecule is had the specific adsorption ability subsequently with the polymkeric substance parcel.The method of wash-out includes but not limited to polymkeric substance is immersed in the suitable chemical solution, destroys the complex structure that is wrapped, the pH value of regulator solution or heating etc.
Provide an example that application of the present invention is described below.
At first dispose Cu as shown in Figure 1
2+The solution of-EDTA complex ions: with Cu
2+Mixed in 1: 1.1 in molar ratio with EDTA, be dissolved in the 0.2mol/L acetate buffer of pH=6.0, be made into Cu
2+The concentration of-EDTA complex compound is 10～100mmol/L.
The configuration of electrolyte solution: take by weighing a certain amount of O-Phenylene Diamine and be dissolved in the above-mentioned solution, the concentration that makes O-Phenylene Diamine is 1～50mmol/L.
Electrolyzer is described: (AT-cut 7.995MHz) is fixed in the tetrafluoroethylene electrolyzer by rubber seal the gold-plated quartz crystal slice in two sides, and its one side and the electrolyte solution in the electrolyzer contact, and simultaneously contact with air.
Electrochemical polymerization process is described: with the golden film on the quartz crystal slice is working electrode, and platinum filament is a supporting electrode, and saturated calomel electrode is a reference electrode, contains O-Phenylene Diamine and Cu in above-mentioned configuration
2+Utilize electrochemical cyclic voltammetry to prepare Cu in the electrolyte solution of-EDTA
2+The imprinted polymer of-EDTA, scanning current potential 0～0.8V, scanning speed 30～50mV/s, scanning hop count 30～50.Carrying out along with reaction formed the one layer of polymeric film on the golden film of quartz crystal slice.
The description of electrochemical polymerization film performance: the polymeric film for preparing as stated above is embedded with Cu
2+-EDTA complex compound, this is from being confirmed with the building-up process of crystal microbalance in-situ monitoring polymkeric substance with the synthetic polymkeric substance that obtains of XPS analysis.As shown in Figure 2, under same electrolytic condition, add Cu
2+The weight ratio of the polymeric film that obtains behind-EDTA the complex compound does not add Cu
2+The many 10-15% of the weight of the polymkeric substance that-EDTA complex compound obtains.Part is the Cu that is embedded in the polymkeric substance in the quality that has more
2+-EDTA complex compound causes.As shown in Figure 3, XPS analysis shows, adds Cu in the polyelectrolyte
2+Contain Cu in the-EDTA complex compound synthetic polymkeric substance
2+Ion and EDTA.This explanation, the preparation of aforesaid synthetic method success may structure as shown in Figure 4 be the molecularly imprinted polymer of template with the metal complex ion.XPS result shows also that further the poly-o-phenylenediamine film is to Cu
2+Bare ion has tangible non-specific adsorption, and to Cu
2+The non-specific adsorption of-EDTA bare ion can be ignored in the detection limit of XPS.Simultaneously, Cu
2+Main interaction between-EDTA complex compound template molecule and the poly-o-phenylenediamine is not an electrostatic interaction, and may be hydrogen bond action.
The sulphuric acid soln that utilizes 0.1～0.5mol/L is with Cu
2+-EDTA is wash-out from polymeric film, has just stayed and Cu in polymeric film like this
2+The hole that-EDTA complex compound space and point of application are complementary, such hole is to Cu
2+-EDTA has special absorption property.Utilize the molecularly imprinted polymer of method for preparing, with itself and QCM (Quartz Crystal Microbalance) technology coupling (as shown in Figure 5), by simple linear relationship between the variation of polymkeric substance to absorption of metal complex ionic and quartz crystal oscillation frequency, can come to determine metal complex ionic concentration in the sample, thereby also just obtain the concentration of metal ion indirectly.This device can be used for real-time on-site and monitor the pollution of heavy metal ion in the water body apace.
The present invention in sum specifically implements example, and protection scope of the present invention is not constituted any limitation.All employing equivalents or equivalence are replaced and the technical scheme of formation; perhaps use different technology according to the technical scheme preparation that is subjected to this invention patent protection with the molecularly imprinted polymer of metal complex ion as template; and with crystal microbalance or surface plasma resonance or other based on molecular recognition with metallic film as the combining of molecular recognition material support technology, all drop within the rights protection scope of the present invention.
Claims (9)
1. molecularly imprinted polymer, it is characterized in that: the trace of described polymkeric substance and wash-out object are the metal complex ion, and the trace geometrical dimension of polymkeric substance, binding site position and metal complex ion specificity are coincide.
2. a kind of molecularly imprinted polymer according to claim 1 is characterized in that: metal ion comprises copper, zinc, lead, chromium, cadmium, mercury at least in the described metal complex ion; Described complexing agent comprises organic chelate or inorganic inner complex, and wherein one of organic chelate is selected ethylenediamine tetraacetic acid (EDTA) for use, and the concentration ratio of complexing agent and metal ion satisfies the abundant complexing of metal ion.
3. a kind of molecularly imprinted polymer according to claim 1, it is characterized in that: described polymer monomer is the monomer that is applicable to electrochemical polymerization, at least comprise aniline, O-Phenylene Diamine, mphenylenediamine, Ursol D, adjacent benzene triamine, a benzene triamine, to benzene triamine, Dopamine HCL, pyrroles, indoles, thiophene, and the mixture of two or more arbitrary proportions arbitrarily.
4. the method for making of the described a kind of molecularly imprinted polymer of claim 1 is characterized in that comprising step:
I, select for use metal ion and complexing agent to prepare the metal complex ion, the concentration ratio of complexing agent and metal ion satisfies the abundant complexing of metal ion;
II, be template, adopt electrochemical polymerization, polymer monomer and metal complex ion phase-polymerization with the metal complex ion;
III, with metal complex ion wash-out from polymkeric substance, obtain molecularly imprinted polymer.
5. the method for making of a kind of molecularly imprinted polymer according to claim 4, it is characterized in that: described electrochemical polymerization comprises optional cyclic voltammetry, potentiostatic method and galvanostatic method at least.
6. the method for making of a kind of molecularly imprinted polymer according to claim 4 is characterized in that: described wash-out metal complex ionic method comprises at least regulates pH value, heating, maybe can destroy the chemical reaction of complex structure.
7. the application of the described a kind of molecularly imprinted polymer of claim 1, it is characterized in that: comprise crystal microbalance and surface plasma resonance device with the technical equipment of described molecularly imprinted polymer coupling, metallic film surface in situ synthetic polymer in described those technical equipment, again with described metal complex ion wash-out, use the molecularly imprinted polymer selective adsorption after the complexing of metal ionization to the needs detection, detect the kind and the content of metal ion.
8. the application of a kind of molecularly imprinted polymer according to claim 7, it is characterized in that: contain one or more metal complex ions in the described metallic film surface in situ synthetic polymkeric substance, behind the whole metal complex ions of wash-out, be used to detect more than one metal complex ion.
9. according to the application of claim 7 or 8 described a kind of molecularly imprinted polymers, it is characterized in that one of kind of described metallic film is a gold thin film.
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2010
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| CN102675506B (en) * | 2012-06-12 | 2013-12-11 | 福州大学 | 6-kinetin molecularly imprinted polymer and application thereof |
| CN103073685A (en) * | 2013-01-18 | 2013-05-01 | 肇庆学院 | Spirulina magnetic porous Pb2+ and Cd2+ double-template imprinting polymer micro-sphere |
| CN103760208A (en) * | 2013-01-23 | 2014-04-30 | 南京医科大学 | Preparation method of gold nanoparticle-doped molecular imprinting electrochemistry sensor for dopamine detection |
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| CN104062331A (en) * | 2014-06-23 | 2014-09-24 | 安徽师范大学 | Imprinted sensor based on gold nanoparticles, preparation method and application thereof |
| CN104062331B (en) * | 2014-06-23 | 2016-06-15 | 安徽师范大学 | Trace sensor based on golden nanometer particle and its preparation method and application |
| CN104844758B (en) * | 2015-04-16 | 2017-03-01 | 浙江普正检测技术有限公司 | A kind of mercury ion imprinted polymer and preparation method thereof |
| CN107570125A (en) * | 2017-09-15 | 2018-01-12 | 哈尔滨工业大学深圳研究生院 | A kind of EDTA Ni molecular engram materials and preparation method thereof and its application |
| CN108318693A (en) * | 2017-12-15 | 2018-07-24 | 北京大学 | Abasic magnetic molecularly imprinted nano particle of endonuclease and its preparation method and application |
| CN108318693B (en) * | 2017-12-15 | 2020-09-22 | 北京大学 | Dealkalized endonuclease magnetic molecularly imprinted nano-particle as well as preparation method and application thereof |
| CN108993416A (en) * | 2018-08-10 | 2018-12-14 | 太原理工大学 | A kind of preparation method of copper ion blotting membrane |
| CN112179878A (en) * | 2019-07-02 | 2021-01-05 | 南京工业大学 | Method for detecting dopamine based on copper ion catalytic reaction in-situ fluorescence |
| CN112179878B (en) * | 2019-07-02 | 2022-11-08 | 南京工业大学 | Method for detecting dopamine based on copper ion catalytic reaction in-situ fluorescence |
| CN110344247A (en) * | 2019-07-18 | 2019-10-18 | 晋江瑞碧科技有限公司 | A kind of preparation method of copper ion trace nano fibrous membrane |
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| CN114425310A (en) * | 2020-10-29 | 2022-05-03 | 伊斯拓通用设备江苏有限公司 | Modified polyaniline adsorbent and preparation method and application thereof |
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