CN103232592A - Preparation of conjugated polymer based signal launch type mercury ion optical probe - Google Patents

Abstract

The present invention is the preparation and application of a signal-opening mercury ion probe based on a fluorescent polymer containing arylamine/carbazole. By adding iodide ions, the polymer-iodide ion complex system whose fluorescence is quenched is obtained, and then the iodine in the polymer-iodide ion system is made use of the strong complexation between mercury ions and iodide ions The ions are extracted and the fluorescent signal is turned on to detect mercury ions. A mercury ion detection test paper based on this polymer can be prepared by simple post-processing, and a fluorescent nanocomposite sensor that can realize probe recycling through magnetic separation can be prepared by compounding with inorganic magnetic nanomaterials. Related sensors based on such fluorescent polymers can achieve high selectivity and high sensitivity detection of mercury ions and achieve the effect of naked eye recognition.

Description

Preparation of Signal-On Mercury Ion Optical Probe Based on Conjugated Polymer

technical field

The invention relates to a fluorescent sensor based on an arylamine/carbazole conjugated polymer, and related color-developing test paper and fluorescent-magnetic dual-functional nanocomposite materials to realize signal-on detection methods and applications of mercury ions. the

Background technique

Mercury ions are one of the heavy metal elements that are extremely threatening and toxic to the human body and the environment. It is of great practical significance to develop a rapid and effective method for the detection of mercury ions. Fluorescence-based detection methods have developed rapidly in recent years. This type of method is fast and effective, has high sensitivity, good selectivity, and is economical and environmentally friendly, making up for many shortcomings of traditional detection methods. But so far, most of the optical probe molecules used for mercury ion detection are fluorescent small molecules. Compared with small molecule fluorescent compounds, the unique signal amplification effect of fluorescent conjugated polymers can further improve the detection sensitivity. Most of the methods reported so far for the detection of mercury ions based on conjugated polymers are in the way of fluorescence signal quenching, and there are few related reports on the detection of mercury ions in the way of fluorescence signal enhancement. the

Wu Shuizhu (B. L. Ma, F. Zeng, F. Y. Zheng and S. Z. Wu, Chem. Eur. J. , 2011, 17 , 14844-14850) and Huang Wei et al. (Z. Y. Zhang, Q. L. Fan, P. F. Sun, L. L. Liu, X. M. Lu , B. Li, Y. W. Quan and W. Huang, Macromol. Rapid Commun., 2010, 31 , 2160-2165), it was reported that the strong complexation between iodide ion and mercury ion was used to achieve the Fluorescent detection. S. Valiyaveettil (M. Vetrichelvan, R. Nagarajan and S. Valiyaveettil, Macromolecules , 2006, 39 , 8303-8310) and Zhang Ming et al (Y. Zhao, L. Yao, M. Zhang and Y. G. Ma, Talanta , 2012 , 97 , 343-348), it was reported that conjugated polymers containing carbazole structures could realize the fluorescence detection of iodide ions. At present, the related methods of using the carbazole/arylamine conjugated polymer-iodide ion composite system to realize the detection of mercury ions have not been applied yet.

In recent years, in order to expand the application range of fluorescence detection technology, people have prepared a wide variety of fluorescent nanocomposites. Fluorescent-magnetic dual-functional nanocomposites are one of the fastest-growing directions. Such materials can be applied to magnetic separation technology, bioimaging technology, drug delivery technology, cancer cell detection and treatment and other technologies. At present, there is no report on the related attempts to use this kind of fluorescent-magnetic nanocomposite materials for the detection of mercury ions. Combining fluorescent conjugated polymers with excellent photochemical stability with magnetic nanomaterials, the easy-to-operate magnetic separation technology can facilitate the recycling of probe materials, thereby further reducing the cost of probe molecules. the

The invention combines the fluorescent conjugated polymer with arylamine/carbazole structure in the detection method of mercury ions with technologies such as nanometer materials and detection papers, so as to realize rapid and immediate detection of mercury ions. the

Contents of the invention

Technical problem: The purpose of the present invention is to develop a fluorescent conjugated polymer sensor with an arylamine/carbazole structure, as well as related fluorescent magnetic nanocomposites, color detection test paper and related mercury ion detection technology. The needle has high sensitivity, high selectivity, reusability and the effect of naked-eye recognition of mercury ions. the

Technical solution: The fluorescent chemical sensor for mercury ion detection in the present invention is specifically based on a conjugated polymer with an arylamine/carbazole structure, and the structure of this type of polymer includes four parts A, B, C, and D. The general formula is expressed as follows:

The total molar ratio of each component in the polymer is n ₁ +n ₂ +n ₃ +n ₄ =1;

Among them, (1) A structure is an aromatic amine/carbazole structural component containing non-polar groups, and has one or more of the following structures:

，其中R₁，R₂，R₃可以为一个或多个H、卤原子、C₁─C₂₀的烷基（烷氧基）、C₂—C₂₀卤代烷基、硝基、氰基、酰胺基、酮基、氧膦基、磷酸酯基、磺酸酯基、单取代或多取代的芳基/杂环芳基等；m=1, 2；n=1, 2, 3……； Polyarylamine:

, where R ₁ , R ₂ , R ₃ can be one or more H, halogen atom, C ₁ ─ _{C 20} alkyl (alkoxy), C ₂ —C ₂₀ haloalkyl, nitro, cyano, amide group, keto group, phosphinyl group, phosphate group, sulfonate group, mono-substituted or multi-substituted aryl/heterocyclic aryl, etc.; m=1, 2; n=1, 2, 3……;

，其中R₁可以为一个或多个H、C₁─C₂₀的烷基、烷氧基等；n=1, 2, 3……； Polycarbazole:

, wherein R ₁ can be one or more H, C ₁ ─ C ₂₀ alkyl, alkoxy, etc.; n=1, 2, 3...;

(2) Structure B is an aromatic amine/carbazole structural component containing polar or ionic groups, and has one or more of the following structures:

Polyarylamine: , where R ₁ , R ₂ , R ₃ can be one or more hydroxyl groups, polyethers, sulfonates, carboxylates, phosphates, ammonium salts, and alkyl or alkoxy groups with the above polar or ionic groups at the end Base etc.; m=1, 2; n=1, 2, 3……;

，其中R₁可以为可以为一个或多个羟基、多醚、磺酸盐、羧酸盐、磷酸盐、铵盐及末端为上述极性或离子基团的烷基或烷氧基等；n=1, 2, 3……； Polycarbazole:

, wherein _R can be one or more hydroxyl groups, polyethers, sulfonates, carboxylates, phosphates, ammonium salts, and alkyl or alkoxy groups whose ends are the above-mentioned polar or ionic groups; n =1, 2, 3...;

(3) Group C has one or more of the following structures:

，其中R₁，R₂可以为一个或多个H、C₁─C₂₀的烷基（烷氧基）及末端为羟基、多醚、磺酸盐、羧酸盐、磷酸盐、铵盐等极性或离子基团的烷基（烷氧基）等；n=1, 2, 3……； Polyfluorene:

, where R ₁ , R ₂ can be one or more H, C ₁ ─ _{C 20} alkyl (alkoxy) and the terminal is hydroxyl, polyether, sulfonate, carboxylate, phosphate, ammonium salt, etc. Alkyl (alkoxy) of polar or ionic groups, etc.; n=1, 2, 3……;

，其中R₁，R₂可以为一个或多个H、C₁─C₂₀的烷基（烷氧基）及末端为羟基、多醚、磺酸盐、羧酸盐、磷酸盐、铵盐等极性或离子基团的烷基（烷氧基）等；n=1, 2, 3……； Polyphenylene vinylene:

, where R ₁ , R ₂ can be one or more H, C ₁ ─ _{C 20} alkyl (alkoxy) and the terminal is hydroxyl, polyether, sulfonate, carboxylate, phosphate, ammonium salt, etc. Alkyl (alkoxy) of polar or ionic groups, etc.; n=1, 2, 3……;

，其中R₁，R₂可以为一个或多个H、C₁─C₂₀的烷基（烷氧基）及末端为羟基、多醚、磺酸盐、羧酸盐、磷酸盐、铵盐等极性或离子基团的烷基（烷氧基）等；n=1, 2, 3……； Poly(p-phenylene acetylene):

, where R ₁ , R ₂ can be one or more H, C ₁ ─ _{C 20} alkyl (alkoxy) and the terminal is hydroxyl, polyether, sulfonate, carboxylate, phosphate, ammonium salt, etc. Alkyl (alkoxy) of polar or ionic groups, etc.; n=1, 2, 3……;

Polyphenylene: , where R ₁ , R ₂ can be one or more H, C ₁ ─ _{C 20} alkyl (alkoxy) and the terminal is hydroxyl, polyether, sulfonate, carboxylate, phosphate, ammonium salt, etc. Alkyl (alkoxy) of polar or ionic groups, etc.; n=1, 2, 3……;

，其中R₁，R₂可以为一个或多个H、C₁─C₂₀的烷基（烷氧基）及末端为羟基、多醚、磺酸盐、羧酸盐、磷酸盐、铵盐等极性或离子基团的烷基（烷氧基）等；n=1, 2, 3……； Poly SPIRO-paraphenylene:

, where R ₁ , R ₂ can be one or more H, C ₁ ─ _{C 20} alkyl (alkoxy) and the terminal is hydroxyl, polyether, sulfonate, carboxylate, phosphate, ammonium salt, etc. Alkyl (alkoxy) of polar or ionic groups, etc.; n=1, 2, 3……;

(4) D is a conjugated group with an aromatic amine/carbazole structure in its side chain, and its side chain structure is one or more of the following structures:

，其中R₁，R₂，R₃可以为一个或多个H、C₁─C₂₀的烷基、烷氧基等； Aromatic amine structure:

, wherein R ₁ , R ₂ , R ₃ can be one or more H, C ₁ ─ C ₂₀ alkyl, alkoxy, etc.;

，其中R₁可以为一个或多个H、C₁─C₂₀的烷基、烷氧基等。 Carbazole structure:

, wherein R ₁ can be one or more H, C ₁ ─ C ₂₀ alkyl, alkoxy, etc.

The preparation method of the above-mentioned conjugated polymer with arylamine/carbazole structure includes 2 basic steps:

1. Prepare monomers with four chemical structures : A, B, C, and D ;

2. According to a certain ratio, the corresponding polymer is synthesized through a metal-catalyzed coupling reaction.

The basic steps for the preparation of the colorimetric identification test paper for detecting mercury ions are as follows:

1. Prepare organic/aqueous solutions of conjugated polymers containing arylamine/carbazole units;

2. Immerse the qualitative filter paper into the prepared solution;

3. Place the filter paper strips in a cool place to dry.

The preparation of fluorescent-magnetic nanocomposites for detecting mercury ions includes the following six basic steps:

1. Coat the matrix support material on the surface of the magnetic nano-microspheres, and then coat the fluorescent polymer on it;

2. Directly coat the fluorescent polymer on the surface of magnetic nanospheres;

3. Directly coat the magnetic nanospheres on the surface of the fluorescent polymer;

4. Blend and coat fluorescent polymer and magnetic nanospheres on the surface of the matrix support material;

5. Blend and coat the fluorescent polymer and magnetic nanospheres into the matrix support material;

6. Blend and coat the fluorescent polymer and matrix support material on the surface of the magnetic nanospheres.

Technical advantages:

1. Conjugated polymers containing arylamine/carbazole structures are used to detect mercury ions in a fluorescent signal-enhanced open mode;

2. The supporting materials used in the detection process are iodide ions, which are rich in sources and low in cost.

3. The conjugated polymer solution is colorless. After adding iodide ions, the color of the solution becomes darker and the fluorescence is quenched. After adding mercury ions, the color becomes lighter and the fluorescence recovers. It can be detected by fluorescence and naked eyes;

4. The color recognition test paper is easy to use and can be directly used to detect mercury ions in aqueous solution;

5. Fluorescent magnetic nanomaterials can realize magnetic recovery, can be used repeatedly and maintain good detection performance;

6. The multi-probe systems based on the above polymers have high detection sensitivity and fast detection speed.

Description of drawings

In Fig. 1. embodiment 4, along with the adding of iodide ion aqueous solution, the fluorescence emission spectrum titration figure of the conjugated polymer containing arylamine structure in tetrahydrofuran solution. the

In Fig. 2. embodiment 4, along with the addition of mercury ion aqueous solution, the fluorescence emission spectrum titration diagram of the conjugated polymer containing arylamine structure in tetrahydrofuran solution. the

Figure 3. In Example 5, the selectivity and anti-interference fluorescence emission spectra of the conjugated polymer (tetrahydrofuran solution) containing arylamine structure to various public metal ions (aqueous solution). the

Figure 4. In Example 6, the naked-eye recognition diagram of various metal ions (aqueous solution) by the conjugated polymer containing aromatic amine structure (tetrahydrofuran solution) (the picture has been processed in grayscale). the

In Fig. 5. embodiment 7, in the tetrahydrofuran dispersion liquid of fluorescent magnetic nano material, add the fluorescence emission intensity change figure when iodide ion aqueous solution and mercury ion aqueous solution successively. the

Figure 6. Structural feature map of fluorescent-magnetic nanocomposites. the

Detailed ways

The present invention will be further described below in conjunction with specific examples, but the present invention is not limited to the following examples. the

Embodiment 1, the preparation of the conjugated polymer containing aromatic amine structure:

Weigh 9,9-dioctyl-2,7-diborate fluorene (0.321 g, 0.5 mmol), N , N -bis(4-bromobenzene)-4-(phenylacetylene)amine (0.252 g , 0.5 mmol), 3 milligrams of palladium acetate, 6 milligrams of tricyclohexylphosphine, 3 drops of trioctylmethyl ammonium chloride, 10 milliliters of toluene and 20% potassium carbonate solution were added after feeding nitrogen, and the reaction was carried out under the protection of nitrogen Reflux for 3 days; cool to room temperature, concentrate the reactant, reprecipitate in methanol, filter, purify by silica gel chromatography, concentrate again, and dry under vacuum at 50 ^o C to obtain a solid product.

Embodiment 2, the preparation of the conjugated polymer containing carbazole structure:

Weigh 9,9-dioctyl-2,7-diboronate fluorene (0.321 g, 0.5 mmol), 9-(4-(3-(4-methoxyphenyl)quinoxalinyl) phenyl)-3,6-dibromocarbazole (0.1905 g, 0.3 mmol), 3,6-dibromo-9-(4-triisopropylsilylethynyl)carbazole (0.1905 g, 0.2 mM mol), 3 milligrams of palladium acetate, 6 milligrams of tricyclohexylphosphine, 3 drops of trioctylmethyl ammonium chloride, 10 milliliters of toluene and 20% potassium carbonate solution were added after feeding nitrogen, and the reaction was refluxed for 3 days under nitrogen protection ; Cool to room temperature, concentrate the reactant, reprecipitate in methanol, filter, purify by silica gel chromatography, concentrate again, and dry under vacuum at 50 ^o C to obtain a solid product;

Dissolve the solid obtained above in 10 ml of tetrahydrofuran, add 0.9 ml of tetrabutylammonium fluoride, and reflux for 1 day under nitrogen protection; then cool to room temperature, concentrate the reactant, reprecipitate in methanol, filter, and purify by silica gel chromatography , concentrated again, and dried under vacuum at 50 ^o C to obtain a solid product.

Embodiment 3, the preparation of fluorescent-magnetic nanocomposite material:

Add the prepared azide-modified silica-coated iron ferric oxide nanospheres (5 mg) and the conjugated polymer containing carbazole structure (5 mg) into a 100 ml three-necked bottle , add 5 mg of tris(triphenylphosphine) cuprous bromide, 10 ml of tetrahydrofuran, and ultrasonic for 20 minutes, at 40 ^o C, mechanically stir overnight; the reactant is ultrasonically cleaned 3 times with tetrahydrofuran, vacuum at 50 ^o C A solid product was obtained after drying.

Embodiment 4, titration experiment:

Conjugate the conjugated polymer containing aromatic amine structure into a tetrahydrofuran solution of about 1×10 ^-5 M, pipette 3 ml of the prepared solution into a cuvette, and add increasing concentrations of iodide ion aqueous solution to the cuvette , until the degree of fluorescence quenching reaches equilibrium; test data show that with the addition of iodide ions, the emission peak at about 432 nm in the fluorescence emission spectrum of the polymer gradually weakens (as shown in Figure 1). Then, the mercury ion aqueous solution with increasing concentration was added dropwise to the above-mentioned equilibrium solution until the degree of fluorescence recovery reached equilibrium; the test data showed that with the addition of mercury ions, the emission peak at about 432 nm in the fluorescence emission spectrum of the polymer gradually Enhanced (as shown in Figure 2), its lowest detection limit was ~2.4×10 ^-7 M.

Embodiment 5, the selective interfering experiment of different metal ions:

Conjugate the conjugated polymer containing arylamine structure into a tetrahydrofuran solution of about 1×10 ^-5 M, pipette 3 ml of the prepared solution into a cuvette, and add 7 microliters of 1× 10 ^-1 M iodide ion aqueous solution, until the degree of fluorescence quenching reaches equilibrium, and then drop 2.5 microliters of 1×10 ^-3 M metal ions (Cu ²⁺ , Co ²⁺ , Mg ²⁺ , Ni ²⁺ , Pb ²⁺ , Sn ²⁺ , Sr ²⁺ , Cd ²⁺ , Ag ⁺ , Ba ²⁺ , Al ³⁺ , Zn ²⁺ , Ca ²⁺ , Fe ³⁺ ) aqueous solution, measured respectively Fluorescence emission spectra of 2.5 microliters of 1×10 ^-3 M mercury ion aqueous solution without adding metal ions, adding metal ions, and adding metal ions (as shown in Figure 3); the test data show that only when the added metal ions The intensity of the emission spectrum will be significantly enhanced when it is mercury ions, but there is no obvious change in the emission spectrum when adding other metal ions except mercury ions; when adding metal ions and then adding mercury ions, the emission spectrum will change significantly. It shows that this fluorescent chemical sensor has high selectivity and anti-interference.

Embodiment 6, naked-eye recognition experiment:

Prepare the conjugated polymer containing aromatic amine structure into about 1×10 ^-5 M tetrahydrofuran solution, then immerse qualitative filter paper strips in the solution for 5 minutes, take them out and dry them, and drop 7 microliters on 15 filter papers respectively. Liter 1×10 ^-1 M iodide ion aqueous solution, after 5 minutes all the filter paper strips turn yellow, then add 2.5 μl 1×10 ^-3 M metal ions (Cu ²⁺ , Co ²⁺ , Mg ²⁺ , Ni ²⁺ , Pb ²⁺ , Sn ²⁺ , Sr ²⁺ , Cd ²⁺ , Ag ⁺ , Ba ²⁺ , Al ³⁺ , Zn ²⁺ , Ca ²⁺ , Fe ³⁺ , Hg ²⁺ ) aqueous solution, and then take pictures to obtain metal ion selectivity experimental photos; the photos show that only when the added metal ions are mercury ions, the color of the solution changes from yellow to colorless, while adding other metal ions except mercury ions The color of the solution did not change much (as shown in Figure 4).

Embodiment 7, recovery experiment:

Prepare the prepared fluorescent-magnetic nanomaterials into a tetrahydrofuran dispersion of about 5 μg/ml, pipette 3 ml into a cuvette, and add 2.31×10 ^-4 M iodide ion aqueous solution and 8.25×10 ^-5 For the mercury ion aqueous solution of M, test its fluorescence emission spectrum. After each group is measured, it is magnetically recovered and cleaned, and the test is repeated 10 times. The test data shows that the emission peak intensity at about 418 nm is weakened when iodide ion aqueous solution is added, and the emission peak intensity at about 418 nm is enhanced when mercury ion aqueous solution is added (as shown in Figure 5), indicating that this fluorescent magnetic nanosensor has good Resilience, can be reused.

Claims (6)

1. based on the unblanking type mercury ion optical probe of conjugated polymers, it is characterized in that:

(1) this type of conjugated polymers is the fluorescent conjugated polymer that contains arylamine/carbazoles structural constituent;

(2) the detection principle of this type of conjugated polymers is the specific function between N atom primitive and the iodide ion of containing that utilizes in the polymkeric substance, by adding iodide ion, obtain fluorescence by the polymkeric substance of cancellation-iodide ion compound system, and then utilize strong complexing action between mercury ion and the iodide ion that iodide ion in polymkeric substance-iodide ion system is detached and realize that fluorescent signal opens to detect mercury ion;

(3) based on this type of conjugated polymers, prepare the difunctional nano combined sensor of fluorescence-magnetic that a class fluorescent method detects mercury ion;

(4) based on this type of conjugated polymers, prepare the detection test paper of class colour developing identification mercury ion.

The conjugated polymers that contains arylamine/carbazole structure class component according to claim 1 can by A, B, C, DFour parts are formed, and have following structure:

The total molar ratio of each component in polymers is n ₁+ n ₂+ n ₃+ n ₄=1;

Wherein, (1) AStructure is the arylamine/carbazole structure class component that contains non-polar group, has following one or more structures:

Polyarylamine:

, R wherein ₁, R ₂, R ₃Can be one or more H, halogen atom, C ₁-C ₂₀Alkyl (alkoxyl group), C ₂-C ₂₀Haloalkyl, nitro, cyano group, amide group, ketone group, phosphinyl, phosphate-based, sulfonate group, the single replacement or polysubstituted aryl/heterocyclic aryl etc.; M=1,2; N=1,2,3

Polycarbazole:

, R wherein ₁Can be one or more H, C ₁-C ₂₀Alkyl, alkoxyl group etc.; N=1,2,3

(2) BStructure is the arylamine/carbazole structure class component that contains polarity or ionic group, has following one or more structures:

Polyarylamine:

, R wherein ₁, R ₂, R ₃Can be the alkyl of above-mentioned polarity or ionic group or alkoxyl group etc. for one or more hydroxyls, polyether, sulfonate, carboxylate salt, phosphoric acid salt, ammonium salt and end; M=1,2; N=1,2,3

Polycarbazole: , R wherein ₁Can be for can being the alkyl of above-mentioned polarity or ionic group or alkoxyl group etc. for one or more hydroxyls, polyether, sulfonate, carboxylate salt, phosphoric acid salt, ammonium salt and end; N=1,2,3

(3) CComponent is for having following one or more structures:

Poly-fluorenes:

, R wherein ₁, R ₂Can be one or more H, C ₁-C ₂₀Alkyl (alkoxyl group) and the end alkyl (alkoxyl group) that is hydroxyl, polyether, sulfonate, carboxylate salt, phosphoric acid salt, ammonium salt isopolarity or ionic group etc.; N=1,2,3

The p-phenylene vinylene:

, R wherein ₁, R ₂Can be one or more H, C ₁-C ₂₀Alkyl (alkoxyl group) and the end alkyl (alkoxyl group) that is hydroxyl, polyether, sulfonate, carboxylate salt, phosphoric acid salt, ammonium salt isopolarity or ionic group etc.; N=1,2,3

Polyparaphenylene's acetylene:

, R wherein ₁, R ₂Can be one or more H, C ₁-C ₂₀Alkyl (alkoxyl group) and the end alkyl (alkoxyl group) that is hydroxyl, polyether, sulfonate, carboxylate salt, phosphoric acid salt, ammonium salt isopolarity or ionic group etc.; N=1,2,3

Poly-to benzene: , R wherein ₁, R ₂Can be one or more H, C ₁-C ₂₀Alkyl (alkoxyl group) and the end alkyl (alkoxyl group) that is hydroxyl, polyether, sulfonate, carboxylate salt, phosphoric acid salt, ammonium salt isopolarity or ionic group etc.; N=1,2,3

The poly-benzene of SPIRO-:

, R wherein ₁, R ₂Can be one or more H, C ₁-C ₂₀Alkyl (alkoxyl group) and end be the alkyl (alkoxyl group) of hydroxyl, polyether, sulfonate, carboxylate salt, phosphoric acid salt, ammonium salt isopolarity or ionic group; N=1,2,3

(4) DFor side chain contains the conjugation group of arylamine/carbazole structure, its side-chain structure is following one or more structures:

The arylamine class formation:

, R wherein ₁, R ₂, R ₃Can be one or more H, C ₁-C ₂₀Alkyl, alkoxyl group etc.;

The carbazoles structure:

, R wherein ₁Can be one or more H, C ₁-C ₂₀Alkyl, alkoxyl group etc.

3. detect the difunctional nano combined sensor of fluorescence-magnetic of mercury ion according to a kind of fluorescent method described in the claim 1, its constitutional features as shown in Figure 6, the complex method of the nano material of fluorescence magnetic shown in the figure has 6 classes, and wherein the inorganic nano magneticsubstance is: contain iron-based, Ni-based, cobalt-based and alloy thereof; Magnetic such as rare earth alloy, ferritic alloy nano material; The matrix propping material is: but organo-siloxane, the polymkeric substance that contains modification group and organic molecule, polymer dielectric etc.; Fluorescent polymer is the polymkeric substance described in the claim 2.

4. the difunctional nano combined sensor of fluorescence-magnetic that detects for mercury ion fluorescent according to claim 1, it is as follows that it detects step:

(1) dispersion liquid of certain density this nano composite material of preparation;

(2) in dispersion liquid, drip the detection substrate that the iodide ion aqueous solution obtains fluorescent quenching;

(3) in above-mentioned dispersion liquid, drip the mercury ion aqueous solution and its fluorescence Recovery Process is carried out signal tracking again;

(4) the above-mentioned mixed solution of ultrasonic cleaning, the magnetic recovery nano composite material also recycles.

5. the preparation method of the colour developing identification test paper for detection of mercury ion according to claim 1, its characteristics are at first to be mixed with organic fluorescent conjugated polymer described in the claim 2 or the aqueous solution, the qualitative filter paper bar is immersed wherein, be placed into the cool place and locate to dry to get final product.

6. according to the application method of the fluorescence chemical sensor that is used for mercury ion detecting described in the claim 1, it is characterized in that such fluorescence chemical sensor can form the combined probe system with iodide ion and detect for the fluorescent signal open type of mercury ion, and it has stronger immunity from interference to other common metal ions, and can realize bore hole identification and recycle.

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