CN116589757A - Degradable film fluorescence sensor and preparation method and application thereof - Google Patents
Degradable film fluorescence sensor and preparation method and application thereof Download PDFInfo
- Publication number
- 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
- Authority
- CN
- China
- Prior art keywords
- fluorescence sensor
- degradable film
- formula
- preparing
- film fluorescence
- 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
Links
- 238000002360 preparation method Methods 0.000 title abstract description 10
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 27
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 26
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 26
- 239000000661 sodium alginate Substances 0.000 claims abstract description 26
- 229920000642 polymer Polymers 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 229920000547 conjugated polymer Polymers 0.000 claims description 10
- 239000003431 cross linking reagent Substances 0.000 claims description 9
- 238000001514 detection method Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 8
- 239000010413 mother solution Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 6
- QXYRRCOJHNZVDJ-UHFFFAOYSA-N 4-pyren-1-ylbutanoic acid Chemical compound C1=C2C(CCCC(=O)O)=CC=C(C=C3)C2=C2C3=CC=CC2=C1 QXYRRCOJHNZVDJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 229940077449 dichromate ion Drugs 0.000 claims description 5
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 230000015556 catabolic process Effects 0.000 abstract description 7
- 238000006731 degradation reaction Methods 0.000 abstract description 7
- 239000010408 film Substances 0.000 description 32
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 108010025899 gelatin film Proteins 0.000 description 13
- 239000000126 substance Substances 0.000 description 9
- 241000282414 Homo sapiens Species 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- 239000000017 hydrogel Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- -1 dichromate ions Chemical class 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- AEMOLEFTQBMNLQ-AZLKCVHYSA-N (2r,3s,4s,5s,6r)-3,4,5,6-tetrahydroxyoxane-2-carboxylic acid Chemical compound O[C@@H]1O[C@@H](C(O)=O)[C@@H](O)[C@H](O)[C@@H]1O AEMOLEFTQBMNLQ-AZLKCVHYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229920001109 fluorescent polymer Polymers 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000001871 ion mobility spectroscopy Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000004454 trace mineral analysis Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
- C08G61/10—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aromatic carbon atoms, e.g. polyphenylenes
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/11—Homopolymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/142—Side-chains containing oxygen
- C08G2261/1426—Side-chains containing oxygen containing carboxy groups (COOH) and/or -C(=O)O-moieties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/18—Definition of the polymer structure conjugated
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
- C08G2261/314—Condensed aromatic systems, e.g. perylene, anthracene or pyrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/40—Polymerisation processes
- C08G2261/44—Electrochemical polymerisation, i.e. oxidative or reductive coupling
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
- C08G2261/52—Luminescence
- C08G2261/522—Luminescence fluorescent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/90—Applications
- C08G2261/94—Applications in sensors, e.g. biosensors
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6432—Quenching
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Immunology (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Optics & Photonics (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- 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
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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310868478.5A CN116589757B (en) | 2023-07-17 | 2023-07-17 | Degradable film fluorescence sensor and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310868478.5A CN116589757B (en) | 2023-07-17 | 2023-07-17 | Degradable film fluorescence sensor and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116589757A true CN116589757A (en) | 2023-08-15 |
| CN116589757B CN116589757B (en) | 2023-09-22 |
Family
ID=87599506
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310868478.5A Active CN116589757B (en) | 2023-07-17 | 2023-07-17 | Degradable film fluorescence sensor and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116589757B (en) |
Citations (4)
| 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 |
-
2023
- 2023-07-17 CN CN202310868478.5A patent/CN116589757B/en active Active
Patent Citations (4)
| 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)
| 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 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116589757B (en) | 2023-09-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Philips et al. | Development of a novel cyano group containing electrochemically deposited polymer film for ultrasensitive simultaneous detection of trace level cadmium and lead | |
| Wang et al. | A luminescent Terbium-Succinate MOF thin film fabricated by electrodeposition for sensing of Cu2+ in aqueous environment | |
| Atta et al. | Palladium nanoclusters-coated polyfuran as a novel sensor for catecholamine neurotransmitters and paracetamol | |
| Chan et al. | Development of a mercury ion-selective optical sensor based on fluorescence quenching of 5, 10, 15, 20-tetraphenylporphyrin | |
| CN107576704B (en) | microcystin-LR molecular imprinting photoelectric chemical sensor and preparation and application thereof | |
| CN104880495B (en) | New spatial steric hindrance regulation type visible ray optical electro-chemistry detects PFOA sensor designs and its application | |
| Nassab et al. | A novel mercury-free stripping voltammetric sensor for uranium based on electropolymerized N-phenylanthranilic acid film electrode | |
| Gong et al. | A novel electrosynthesized polymer applied to molecular imprinting technology | |
| Li et al. | A molecularly imprinted sensor based on an electrochemiluminescent membrane for ultratrace doxycycline determination | |
| Junaid et al. | Fluorenone-based fluorescent and colorimetric sensors for selective detection of I–ions: applications in hela cell imaging and logic gate | |
| Kang et al. | A polyaniline/polyvinyl acetate composite film electrode for highly sensitive electrochemical sensing of pH | |
| Taei et al. | Highly selective determination of ascorbic acid, epinephrine, and uric acid by differential pulse voltammetry using poly (Adizol Black B)-modified glassy carbon electrode | |
| CN116589757B (en) | Degradable film fluorescence sensor and preparation method and application thereof | |
| Yi et al. | Portable AIE hydrogel sensor for rapid and visual field detection of heavy metal residue in food | |
| CN112034025B (en) | Composite modified electrode for chloramphenicol detection and construction and detection methods thereof | |
| Kong et al. | Electrochemical sensor based on a bilayer of PPY–MWCNTs–BiCoPc composite and molecularly imprinted P o AP for sensitive recognition and determination of metolcarb | |
| CN114544730B (en) | Ion sensor and preparation method and application thereof | |
| CN110632144B (en) | All-solid-state ion selective electrode for detecting potassium fertilize and preparation method thereof | |
| CN108426867A (en) | Detection of Fe in Water3+MOF-Cd probe with antibiotic ceftriaxone sodium and preparation method and application thereof | |
| CN113912804B (en) | Construction method and application of electrochemical luminescence system based on extrapolation receptor type covalent organic framework | |
| Ding et al. | Facile fabrication of fluorescent poly (5-cyanoindole) thin film sensor via electropolymerization for detection of Fe3+ in aqueous solution | |
| Abbaspour et al. | Construction of a new selective coated disk electrode for Ag (I) based on modified polypyrrole-carbon nanotubes composite with new lariat ether | |
| Yuan et al. | Molecularly Imprinted Polymer Modified Electrode Prepared by In Situ Polymerization for Specific Determination of Norfloxacin | |
| CN106338540B (en) | A kind of not plasticizer-containing is cross-linked in situ co-polymer membrane and the preparation method and application thereof | |
| Shafiekhani et al. | New optical sensor based on the immobilization of a triazene ligand in PVC membrane for Hg (II) ion |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |