CN116589757A - Degradable film fluorescence sensor and preparation method and application thereof - Google Patents

Degradable film fluorescence sensor and preparation method and application thereof Download PDF

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CN116589757A
CN116589757A CN202310868478.5A CN202310868478A CN116589757A CN 116589757 A CN116589757 A CN 116589757A CN 202310868478 A CN202310868478 A CN 202310868478A CN 116589757 A CN116589757 A CN 116589757A
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fluorescence sensor
degradable film
formula
preparing
film fluorescence
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CN116589757B (en
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丁兴立
李慧
张革
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Suzhou Bofanxi Technology Co ltd
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    • C08G2261/30Monomer units or repeat units incorporating structural elements in the main chain
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  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)

Abstract

The invention relates to the field of photoelectric devices and discloses a degradable film fluorescence sensor, a preparation method and application thereof, wherein the film fluorescence sensor is prepared from a polymer with a structural formula of 1 and sodium alginate. The invention solves the problems of difficult degradation and high cost of the traditional fluorescent sensor.

Description

Degradable film fluorescence sensor and preparation method and application thereof
Technical Field
The invention relates to the field of photoelectric devices, in particular to a degradable film fluorescence sensor, a preparation method and application thereof.
Background
Environmental, health and safety are closely related to human development and survival, one of the most interesting subjects for people in the 21 st century. With the rapid development of the industrial age, substances discharged into the natural environment by human beings far exceed the bearing capacity of the substances, and a series of crisis is caused. The chromium element is widely applied to industrial processes such as metal smelting, leather tanning, electroplating, dyeing and the like, and most hexavalent chromium generated in the industrial processes is accumulated in soil, so that serious heavy metal pollution is caused, and the environment and human health are endangered. It is particularly important how to formulate a reasonable and feasible heavy metal pollutant treatment scheme and rapidly, conveniently and accurately monitor heavy metal ions in the environment. Fluorescence sensing analysis is a novel trace analysis technique that has been developed and developed to meet these challenges.
As is well known, sensors are widely used in various fields of social development and human life, and the development of the sensors is interdisciplinary and interdisciplinary. The sensitive substance (material) is used as a core component of the sensor, and the innovative preparation of the high-performance sensitive element plays a role. As an important high-end sensor, a film-based fluorescence sensor has gradually developed into a micro-trace substance in-situ rapid detection technology with the most development potential, which is accepted in the industry after the ion mobility spectrometry technology, since industrial application is realized. Recently, international union of pure and applied chemistry has been selected as one of the emerging technologies. Unlike homogeneous fluorescence sensors, the fluorescent molecules of the film sensor can only contact with the object to be measured by the holes or free volume inside the film, and the microstructure of the film is extremely easily affected by the substrate and the preparation process. The fact that the film fluorescence sensor cannot be fully contacted with an object to be detected causes low detection sensitivity and long action time, so that the key scientific problem of the neck of the field is formed. In addition, along with the development of society, the environmental awareness of human beings is gradually improved, and the development of the degradable substrate for constructing the sensitive and rapid-detection thin film sensor can avoid secondary pollution and has very important significance for environmental protection.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a degradable film fluorescence sensor, and a preparation method and application thereof.
The invention adopts the following specific scheme: the degradable film fluorescence sensor is prepared from a polymer with a structural general formula of formula 1 and sodium alginate;
formula 1; wherein n is a natural number between 2 and 50.
In another aspect, the present invention provides a method for preparing a degradable film fluorescence sensor, the method comprising the steps of:
step 1: preparing a formula 1 by adopting potentiostatic polymeric pyrene butyric acid in boron trifluoride diethyl ether solution;
step 2: preparing a cross-linking agent for standby, and dissolving sodium alginate in water;
step 3: dissolving a conjugated polymer with a structural general formula of formula 1 to prepare a fluorescence mother solution;
step 4: adding the fluorescent mother solution in the step 3 into sodium alginate solution, uniformly mixing, injecting into a mould, and drying;
step 5: and (3) dropwise adding a cross-linking agent to the dried mould, taking out the solid in the mould after a period of time, and airing to obtain the degradable film fluorescence sensor.
The cross-linking agent is CaCl 2
The CaCl 2 Is 0.1 mol/l.
The specific operation of dissolving sodium alginate in water in the step 2 is as follows: deionized water is added into a beaker, stirring is carried out at a constant temperature of 40 ℃, and sodium alginate is added into ionized water for a small amount of times.
In the step 3, the conjugated polymer with the structural general formula of formula 1 is dissolved in N, N-dimethylformamide.
The drying condition in the step 4 is that the temperature is 60 ℃ and the drying time is 30 minutes.
In the step 5, caCl is dripped on the dried mould 2 The solution was crosslinked for 2 minutes.
An application of a degradable film fluorescence sensor for dichromate ion detection.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a degradable film fluorescence sensor, which selects conjugated fluorescent polymer with a signal amplifying function as a sensing unit to improve the detection sensitivity of the film sensor. And a film substrate with a porous structure is obtained by selecting non-toxic food-grade sodium alginate for crosslinking, so that a substance to be detected is in quick and full contact with fluorescent molecules, the response time of the film sensor is improved, and the detection sensitivity is further improved. Sodium alginate is rich in resources, easy to obtain and degradable, and is an environment-friendly material. The film fluorescence sensor prepared by the invention has good sensing performance and degradability, can be recycled, and has the advantages of simple preparation method and low cost.
Drawings
FIG. 1 is a linear scan (scan rate 100 mV/s) of a precursor of the present invention (0.01 mol/L) in boron trifluoride etherate system;
FIG. 2 is a flow chart of the preparation of the fluorescent gel film sensor of the present invention;
FIG. 3 is an ultraviolet-visible spectrum of a fluorescent gel film sensor of the present invention;
FIG. 4 is an ion selectivity test chart of a fluorescent gel film sensor of the present invention;
FIG. 5 is a graph showing sensitivity test of the fluorescent gel film sensor of the present invention to response ions;
FIG. 6 is a front-to-back comparison of polymer recovery from immersing a fluorescent gel film sensor of the present invention in ethyl acetate;
FIG. 7 is a graph of fluorescence at 365 nm for ethyl acetate soaked in a fluorescent gel film sensor of the present invention;
FIG. 8 is a graph showing the comparison of the degradation of the fluorescent gel film sensor of the present invention;
FIG. 9 is a graph showing the change of the quality of the fluorescent gel film sensor according to the present invention with degradation time.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the present invention is described below by means of specific embodiments shown in the accompanying drawings. It should be understood that the description is only illustrative and is not intended to limit the scope of the invention. In addition, in the following description, descriptions of well-known structures and techniques are omitted so as not to unnecessarily obscure the present invention.
The invention provides a degradable film fluorescence sensor, which is prepared from a polymer with a structural general formula of formula 1 and sodium alginate by combining with figures 1-9;
formula 1; wherein n is a natural number between 2 and 50.
The polymer with the structural general formula of formula 1 is prepared from a precursor of pyrene butyric acid (formula 2):
2, 2
The invention adopts a potentiostatic method to polymerize a precursor pyrene butyric acid (formula 2) to obtain a conjugated polymer with a structural general formula of formula 1, and the method comprises the following steps: 0.5762 g of formula 2 was dissolved in 20 ml of boron trifluoride diethyl etherate solution, and the conjugated polymer of formula 1 was prepared by a three-electrode method using 0.8V as a polymerization potential. ITO glass is selected as a working electrode, a platinum wire is selected as a counter electrode, and self-made Ag/AgCl is selected as a reference electrode (prepared by electrochemical deposition for 100 seconds in 6 mol/L hydrochloric acid solution at a voltage of 1.5V by using a potentiostatic film forming method). The polymer film was repeatedly washed with anhydrous diethyl ether. Finally, the polymer powder is dried at 60 ℃ for several hours to obtain dried polymer powder which is used for preparing fluorescent mother liquor. Pyrenebutyric acid (formula 2) was purchased from aladine under the trade designation P106902 and 1g.
The invention provides a preparation method of a degradable film fluorescence sensor, which comprises the following steps: step 1: preparing a formula 1 in boron trifluoride diethyl etherate solution by adopting a potentiostatic method; step 2: preparing a cross-linking agent for standby, and dissolving sodium alginate in water; step 3: dissolving a conjugated polymer with a structural general formula of formula 1 to prepare a fluorescence mother solution; step 4: adding the fluorescent mother solution in the step 3 into sodium alginate solution, uniformly mixing, injecting into a mould, and drying; step 5: and (3) dropwise adding a cross-linking agent to the dried mould, taking out the solid in the mould after a period of time, and airing to obtain the degradable film fluorescence sensor.
The cross-linking agent is CaCl 2 . The CaCl 2 Is 0.1 mol/l. The specific operation of dissolving sodium alginate in water in the step 2 is as follows: deionized water is added into a beaker, stirring is carried out at a constant temperature of 40 ℃, and sodium alginate is added into the deionized water for a small amount of times. In the step 3, the conjugated polymer with the structural general formula of formula 1 is dissolved in N, N-dimethylformamide. The drying condition in the step 4 is that the temperature is 60 ℃ and the drying time is 30 minutes. In the step 5, caCl is dripped on the dried mould 2 The solution was crosslinked for 2 minutes.
Sodium alginate can rapidly form gel under extremely mild conditions, and has Ca 2+ 、Sr 2+ Na on alpha-L-guluronic acid (G) unit in sodium alginate structure in the presence of plasma cation + Ion exchange reaction with divalent cations occurs, and G units are piled up to form a cross-linked network structure, so that hydrogel is formed.
In another aspect of the invention, there is provided the use of a degradable film fluorescence sensor for dichromate ion detection.
Example 1
The degradable film fluorescence sensor is prepared from a polymer with a structural general formula of formula 1 and sodium alginate;
formula 1; wherein n is a natural number between 2 and 50.
Referring to fig. 2, the method for preparing the degradable film fluorescence sensor comprises the following steps: 200 ml of 0.1 mol/l CaCl was prepared 2 The solution was ready for use. 22 ml of deionized water is added into a beaker, and the mixture is stirred at a constant temperature of 40 ℃ and 0.66 g of sodium alginate is added into the solution for a small amount of times so as to prevent the sodium alginate from caking. The conjugated polymer obtained by electrodeposition was dissolved in N, N-dimethylformamide to prepare 11 ml of a fluorescent mother liquor of 0.1 g/L. Adding the fluorescence mother solution into sodium alginate solution, and mixing. Sucking when it is hotThe mixed solution is taken and injected into a die (the die is a cuboid groove with the length of 45 mm, the width of 10 mm and the depth of 1 mm, and each injection of the mixed solution is 0.6 ml), and the die is taken out after being dried for 30 minutes at the temperature of 60 ℃. Dropwise adding CaCl to the dried mould 2 And (3) crosslinking the solution for 2 minutes, clamping the solid in the groove by using tweezers, and slightly airing to obtain the degradable film fluorescence sensor.
The degradable film fluorescence sensor described above is used for dichromate ion detection applications.
Referring to FIG. 3, it can be seen from the UV-visible spectrum of the fluorescent hydrogel film prepared according to the present invention that the maximum absorption peaks of the fluorescent gel film are 280 nm and 350 nm. As can be seen from the experimental plot of ion selectivity of the fluorescent gel film prepared by the present invention in combination with FIG. 4, the dichromate ion has a specific and strong quenching effect on the fluorescence of the conjugated polymer gel film.
Referring to fig. 5, it can be seen from the sensitivity test chart of the fluorescent hydrogel film prepared according to the present invention to dichromate ions, the fluorescent hydrogel film can immediately detect dichromate ions of micromolar scale.
The method for recycling the degradable film fluorescence sensor prepared by the invention comprises the following steps: referring to fig. 6, when the fluorescent gel film sensor prepared by the present invention is soaked in an organic solvent (ethyl acetate), the polymer non-covalently bonded in the sodium alginate gel network oozes out, and the insoluble substance does not fluoresce under the irradiation of 365 nm ultraviolet lamp, thus being sodium alginate solid.
Referring to fig. 7, the ethyl acetate solution of the fluorescent gel film sensor prepared by the method shows strong blue fluorescence under 365 nm ultraviolet lamp irradiation, and is a polymer formula 1, so that the polymer and sodium alginate can be recycled.
The degradation treatment method for the degradable film fluorescence sensor prepared by the invention comprises the following steps: the degradable film fluorescence sensor prepared by the method is soaked in ethyl acetate solution, and insoluble substances are degraded after being dried, and the specific method is as follows: the insoluble substances are placed in HCl solution with pH=1-2, the rotating speed is kept at 600-900 r/min at 65 ℃ and stirred for 2-24 hours, the insoluble substances in the solution are filtered out at intervals of several hours, and the drying oven is dried for 20-40 minutes at 60 ℃. After weighing, the solid is poured into the original solution to be maintained in the solution, and heating and stirring are continued. The above steps are repeated until the insoluble matter amount is substantially unchanged, in conjunction with fig. 8. And (3) drawing the degradation time according to the mass after degradation by combining with the figure 9, so as to obtain the degradation condition of the membrane.
The foregoing drawings and description are only one embodiment of the present invention, but the specific scope of the present invention is not limited to the above description, and any simple replacement or modification within the scope of the technical idea disclosed in the present invention and according to the technical scheme of the present invention should be within the scope of the present invention.

Claims (9)

1. The degradable film fluorescence sensor is characterized by being prepared from a polymer with a structural general formula of formula 1 and sodium alginate;
formula 1; wherein n is a natural number between 2 and 50.
2. A method of making a degradable film fluorescence sensor according to claim 1, said method comprising the steps of:
step 1: preparing a formula 1 by adopting potentiostatic polymeric pyrene butyric acid in boron trifluoride diethyl ether solution;
step 2: preparing a cross-linking agent for standby, and dissolving sodium alginate in water;
step 3: dissolving a conjugated polymer with a structural general formula of formula 1 to prepare a fluorescence mother solution;
step 4: adding the fluorescent mother solution in the step 3 into sodium alginate solution, uniformly mixing, injecting into a mould, and drying;
step 5: and (3) dropwise adding a cross-linking agent to the dried mould, taking out the solid in the mould after a period of time, and airing to obtain the degradable film fluorescence sensor.
3. The method for preparing the degradable film fluorescence sensor according to claim 2, wherein the cross-linking agent is CaCl 2
4. The method for preparing a degradable film fluorescence sensor according to claim 3, wherein the CaCl 2 Is 0.1 mol/l.
5. The method for preparing the degradable film fluorescence sensor according to claim 2, wherein the specific operation of dissolving sodium alginate in water in step 2 is as follows: deionized water is added into a beaker, stirring is carried out at a constant temperature of 40 ℃, and sodium alginate is added into ionized water for a small amount of times.
6. The method for preparing a degradable film fluorescence sensor according to claim 2, wherein the conjugated polymer having a structural formula of formula 1 is dissolved in N, N-dimethylformamide in the step 3.
7. The method for preparing the degradable film fluorescence sensor according to claim 2, wherein the drying condition in the step 4 is that the temperature is 60 ℃ for 30 minutes.
8. The method for preparing a degradable film fluorescence sensor according to claim 2, wherein CaCl is added dropwise to the dried mold in step 5 2 The solution was crosslinked for 2 minutes.
9. Use of the degradable film fluorescence sensor of claim 1 for dichromate ion detection.
CN202310868478.5A 2023-07-17 2023-07-17 Degradable film fluorescence sensor and preparation method and application thereof Active CN116589757B (en)

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Citations (4)

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Publication number Priority date Publication date Assignee Title
US5019350A (en) * 1986-02-13 1991-05-28 Pfizer Hospital Products, Inc. Fluorescent polymers
CN102702546A (en) * 2012-05-10 2012-10-03 陕西师范大学 Preparation method of perylene bisimide cholesterol polymer gel fluorescent sensing film, and application thereof
US20120282705A1 (en) * 2011-04-01 2012-11-08 University Of Connecticut Explosives Detection Substrate and Methods of Using the Same
CN115160598A (en) * 2022-07-26 2022-10-11 武汉纺织大学 Preparation method and application of calcium alginate-based gel material with fluorescence reversible effect

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5019350A (en) * 1986-02-13 1991-05-28 Pfizer Hospital Products, Inc. Fluorescent polymers
US20120282705A1 (en) * 2011-04-01 2012-11-08 University Of Connecticut Explosives Detection Substrate and Methods of Using the Same
CN102702546A (en) * 2012-05-10 2012-10-03 陕西师范大学 Preparation method of perylene bisimide cholesterol polymer gel fluorescent sensing film, and application thereof
CN115160598A (en) * 2022-07-26 2022-10-11 武汉纺织大学 Preparation method and application of calcium alginate-based gel material with fluorescence reversible effect

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ZHAO LU ET AL.: ""Layer-by-Layer Deposited Multilayer Films of Oligo(pyrenebutyric acid) and a Perylene Diimide Derivative: Structure and Photovoltaic Properties"", 《 LANGMUIR》, vol. 24, no. 8, pages 4380 - 4387 *

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