CN115651641A - Water vapor fluorescence sensor and preparation method thereof - Google Patents
Water vapor fluorescence sensor and preparation method thereof Download PDFInfo
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- CN115651641A CN115651641A CN202211156457.2A CN202211156457A CN115651641A CN 115651641 A CN115651641 A CN 115651641A CN 202211156457 A CN202211156457 A CN 202211156457A CN 115651641 A CN115651641 A CN 115651641A
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Abstract
The invention relates to a water vapor fluorescence sensor and a preparation method thereof, wherein the water vapor fluorescence sensor is obtained by compounding a compound M1 and a base material M2, and the water vapor sensor designed by the invention has good water vapor sensing performance. The ether oxygen atom in the M1 molecule and the hydroxyl in the matrix material form a hydrogen bond, so that the ether oxygen atom is dispersed on the surface of the matrix, and monodisperse green fluorescence is emitted; as water molecules are easier to form hydrogen bonds with hydroxyl groups on the matrix, when the water vapor concentration is increased, M1 molecules are dissociated from the matrix material, so that orange associated complex fluorescence is formed. The method has the advantages of simple operation, high sensitivity, convenient preparation, field detection and the like, and provides another choice for the water sensing technology.
Description
Technical Field
The invention relates to the field of fluorescence chemical sensors, in particular to a water vapor fluorescence sensor and a preparation method thereof.
Background
Water is the most common impurity in many organic solvents and its diagnosis is of great importance in many fields such as laboratory chemistry, fine chemistry, biomedical analysis and food processing. The Karl Fischer titration method is a common method for determining the water content in an organic solvent at present. It was originally developed in the 30's of the 20 th century where water reacted with reagents and was converted to a non-conductive substance. Although this technique has the advantages of absolute measurement, high sensitivity, applicability to both liquid and solid samples, low cost, wide application range, etc., it has some non-negligible disadvantages, including the need for specialized equipment and skilled operators, which limit its application. Electrochemical and electrophysical sensors are other sensing mechanisms to quantify water content. They are highly stable and easy to calibrate and use, making them useful in industrial applications. However, these methods are reported to have limitations such as lack of sufficient accuracy and portability, inability to perform real-time analysis, and susceptibility to electromagnetic radiation due to electronic characteristics. Compared with the technology, the optical water sensing technology based on the fluorescence group or chromophore material has the advantages of simplicity in operation, high sensitivity, convenience in preparation, convenience in field detection and the like, and provides another choice for the water sensing technology.
Disclosure of Invention
Based on the above, the invention develops a novel water vapor fluorescence sensor by introducing hydrophilic ether chains to the phenylene ethylene derivatives to endow the phenylene ethylene derivatives with amphiphilic characteristics. The hydrogen bond action among hydroxyl, ether oxygen atoms and water molecules in the silica gel is utilized to induce the sensor molecules to generate association-dissociation phenomena, so that the fluorescent properties with different significance are shown, and the purpose of water vapor sensing is achieved.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
a water vapor fluorescence sensor is obtained by compounding a compound M1 and a base material M2, wherein the compound M1 has the following structural formula:
wherein m ranges from 1 to 3.
The matrix material M2 is one of chitosan, nano-cellulose and silicon dioxide.
The matrix material M2 is a porous structure.
The preparation method of the water vapor fluorescence sensor comprises the following steps:
a) Putting 2, 5-dihydroxy terephthalaldehyde, bromobutane, anhydrous potassium carbonate and solvent N, N-dimethylformamide into a round-bottom flask at one time, and reacting at the constant temperature of 80 ℃ for 48 hours; after the reaction is finished, removing insoluble inorganic salt by vacuum filtration, concentrating the filtrate by a rotary evaporator, and recrystallizing by methanol to obtain a first reactant 1;
b) Putting a first reactant 1, a second reactant 2, an organic base and a tert-butyl alcohol/tetrahydrofuran mixed solvent into a round-bottom flask at one time; stirring and reacting for 20 minutes at a constant temperature of 70 ℃; after the reaction was complete, the reaction was cooled to room temperature, poured into water, extracted with dichloromethane and the organic phase was passed over anhydrous Na 2 SO 4 Drying, concentrating with rotary evaporator, and performing column chromatography to obtain target molecule M1;
c) And c, dissolving the M1 molecules obtained in the step b in a tetrahydrofuran solvent, taking the solution as an impregnation solution to impregnate the matrix M2, and drying the solvent to obtain the final water vapor fluorescence sensor.
The organic base in the step b) is one or more of potassium tert-butoxide, sodium tert-butoxide, tetrabutylammonium hydroxide, tetramethylguanidine and 1, 8-diaza-bicycloundecen-7-ene.
The concentration of M1 in the impregnation liquid in the step c) is in the range of 0.001-0.005 mol/l, and the impregnation time of the matrix material M2 is 20 minutes or more.
The invention also protects the application of the water vapor fluorescence sensor in the water vapor sensing material.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, a novel water vapor fluorescence sensor is developed by introducing a hydrophilic ether chain to a phenylene ethylene derivative to endow the phenylene ethylene derivative with an amphiphilic characteristic. The hydrogen bond action among hydroxyl, ether oxygen atoms and water molecules in the silica gel is utilized to induce the sensor molecules to generate association-disassociation phenomena, so that the fluorescent properties with different significance are shown, and the purpose of water vapor sensing is achieved. Research results show that when the water vapor sensor molecule is dispersed on a material taking silica gel as a matrix, ether oxygen atoms in the sensor molecule and the silica gel form hydrogen bonds, so that the sensor molecule is dispersed on the surface of the matrix, and monodisperse green fluorescence is emitted; as water molecules are easier to form hydrogen bonds with silicon hydroxyl, when the water vapor concentration is increased, sensor molecules are dissociated from the matrix material to form orange associated complex fluorescence, so that the water vapor sensing performance is good.
The water vapor sensor designed by the invention has good water vapor sensing performance. Ether oxygen atoms in M1 molecules and hydroxyl groups in the matrix material form hydrogen bonds, so that the hydrogen bonds are dispersed on the surface of the matrix, and monodisperse green fluorescence is emitted; as water molecules are easier to form hydrogen bonds with hydroxyl groups on the matrix, when the water vapor concentration is increased, M1 molecules are dissociated from the matrix material, so that orange associated complex fluorescence is formed. The method has the advantages of simple operation, high sensitivity, convenient preparation, field detection and the like, and provides another choice for the water sensing technology.
Drawings
FIG. 1 is a fluorescent photograph of VS-1 at different humidity.
FIG. 2 shows fluorescence spectra of RS-4 before and after standing for 2 hours.
FIG. 3 is a fluorescent and visible photograph of VS-1, VS-2, VS-3 and VS-4.
FIG. 4 is a fluorescent photograph of RS-4 under different humidity conditions.
FIG. 5 shows fluorescence photographs of RS-1, RS-2 and RS-3 at different humidities.
Detailed Description
The above-mentioned contents of the present invention are further described in detail by way of examples below, but it should not be understood that the scope of the above-mentioned subject matter of the present invention is limited to the following examples, and any technique realized based on the above-mentioned contents of the present invention falls within the scope of the present invention.
The water vapor fluorescence sensor prepared by the invention is tested according to the following method:
and (3) measuring a hydrogen spectrum and a carbon spectrum of the nuclear magnetic resonance by using a Bruker AVANCE II nuclear magnetic resonance instrument, wherein tetramethylsilicon is used as an internal standard, and a solvent is deuterated chloroform or deuterated dimethyl sulfoxide. The fluorescence spectra were measured using a Shimadzu RF-5301PC fluorescence spectrophotometer.
Example 1: preparation of water vapor fluorescence sensor VS-1
The preparation route is as follows:
a) 2, 5-dihydroxy terephthalaldehyde (2g, 121mmol), bromobutane (2.41mL, 228mmol), anhydrous potassium carbonate (3.3 g, 239mol) and 30ml N, N-dimethylformamide were put into a round bottom flask in one portion, the oil bath was heated to 80 ℃, the reaction was stirred at constant temperature and refluxed for 48 hours, and the reaction was stopped by detecting the disappearance of the starting material by thin layer chromatography. After the reaction, the insoluble inorganic salt was removed by vacuum filtration, the filter cake was washed three times with N, N-dimethylformamide, and the filtrate was concentrated by a rotary evaporator and recrystallized using methanol as a solvent to obtain a first reactant 1.
b) First reactant 1 (100mg, 0.299mmol), second reactant 2 (190mg, 0.719mmol), organic base, 8mL of tert-butanol, 8mL of tetrahydrofuran were placed in a round bottom flask in one portion and the oil bath was heated to 70 ℃. Adding tert-butyl into the round-bottom flaskPotassium alkoxide (36mg, 0.321mmol) and tetrabutylammonium hydroxide (1.8mL, 2.53mmol) were reacted at constant temperature with stirring for 20 minutes, and the reaction was stopped when the starting material disappeared by detection by thin layer chromatography. After completion of the reaction, it was cooled to room temperature, the reaction was poured into water, extracted with dichloromethane and the organic phase was passed over anhydrous Na 2 SO 4 Drying, concentrating with rotary evaporator, and performing column chromatography to obtain target molecule M1.
c) And c, dissolving the M1 molecules obtained in the step b in a tetrahydrofuran solvent, taking the tetrahydrofuran solvent as an impregnation solution to impregnate the matrix M2, and standing and drying at room temperature for 5 hours to obtain the final water vapor fluorescence sensor.
Wherein the M value of the target molecule M1 is 2, the concentration of the M1 impregnation liquid in the step c is 0.003 mol/L, and the matrix M2 is silicon dioxide.
Example 2: preparation of water vapor fluorescence sensor VS-2
The preparation method comprises the following specific steps: the same portions as those in example 1 are not repeated, and the difference from example 1 is that the concentration of the M1 impregnation solution in step c is 0.001 mol/L.
Example 3: preparation of water vapor fluorescence sensor VS-3
The preparation method comprises the following specific steps: the same portions as those in example 1 are not repeated, and the difference from example 1 is that the concentration of the M1 impregnation solution in step c is 0.002 mol/liter.
Example 4: preparation of water vapor fluorescence sensor VS-4
The preparation method comprises the following specific steps: the same portions as those in example 1 are not repeated, and the difference from example 1 is that the concentration of the M1 impregnation solution in step c is 0.004 mol/L.
Comparative example 1: preparation of RS-1
The preparation method comprises the following specific steps: the same parts as those in example 1 are not repeated, and the difference from example 1 is that the base material M2 used in step c is a polyester nonwoven fabric.
Comparative example 2: preparation of RS-2
The preparation method comprises the following specific steps: the same portions as those in example 1 are not described in detail, and the difference from example 1 is that the base material M2 used in step c is a polypropylene nonwoven fabric.
Comparative example 3: preparation of RS-3
The preparation method comprises the following specific steps: the same parts as those in example 1 will not be described again, and the difference from example 1 is that the base material M2 used in step c is filter paper.
Comparative example 4: preparation of RS-4
The preparation method comprises the following specific steps: the same portions as those in example 1 are not repeated, and the difference from example 1 is that the concentration of the M1 impregnation solution in step c is 0.0001 mol/L.
The water vapor fluorescence sensor and the preparation method thereof according to the present invention will be further described with reference to some embodiments.
From the fluorescence photographs of the sensor VS-1 under different moisture (FIG. 1), with moisture from 1g/m 3 Gradually increased to 25g/m 3 The fluorescence color of the system gradually changes from green to orange yellow, and the ratio type fluorescence sensing characteristic is very obvious. The process can be directly observed by the naked eye. The water molecules can form stronger hydrogen bonding action with the hydroxyl on the surface of the silica gel, which can destroy the hydrogen bond formed by the ether oxygen atom and the silicon hydroxyl in the M1 molecule. We therefore preliminarily speculate that the fluorescence colour transition under the action of moisture is due to its induced reaggregation of M1 molecules.
At lower M1 concentrations, there was no significant shift in the fluorescence spectra before and after standing, and RS-4 showed bright green fluorescence (FIG. 2). The main reason for this is that at low concentrations of M1, the molecules are essentially in a dispersed state and do not undergo aggregation-hydrogen bond-induced dispersion. When the M1 loading concentration reaches 0.004M/L, because the concentration is too high, the hydrogen bonds on the surface of the silica gel are not enough to induce all M1 molecules to disperse on the surface, so that the VS-4 system shows more obvious aggregation orange-yellow fluorescence after standing, and the blue shift degree of the fluorescence spectrum is reduced (FIG. 3). The control RS-4 did not exhibit significant moisture fluorescence sensing characteristics. As can be seen from FIG. 4, when the concentration of the M1 solution is as low as 0.0001M/L, the concentration of the M1 solution is 1g/M with the generation of water vapor 3 Raised to 25g/m 3 The fluorescence color of the system did not change significantly.This phenomenon further confirms our presumed moisture sensing mechanism.
Composites prepared with Polyester (PET) and polypropylene (PP) nonwovens as the impregnated substrates did not exhibit significant moisture sensing properties (fig. 5). At a water content of 1g/m, respectively 3 、10g/m 3 、25g/m 3 And then, the fluorescence colors of the RS-1, RS-2 and RS-3 systems are not obviously changed, and orange yellow fluorescence is shown. The main reason for this is the different content of groups on the surface of the substrate. The surfaces of PET and PP do not contain hydroxyl, so that the M1 molecules cannot be induced to disperse on the surface of the base material through hydrogen bond action. The filter paper is prepared from cellulose, but the cellulose has strong crystallinity, and the hydroxyl content on the surface of the fiber is lower than that of porous silica gel, so the filter paper does not have obvious water vapor sensing characteristic.
Therefore, the moisture fluorescence sensor provided by the invention can perform sensing response in a wider humidity range. The technical route has the advantages of simple operation, high sensitivity, convenient preparation, field detection and the like, and provides another choice for the water sensing technology.
The above description is only a preferred embodiment of the present invention, and should not be taken as limiting the invention in any way, and any person skilled in the art can make any simple modification, equivalent replacement, and improvement on the above embodiment without departing from the technical spirit of the present invention, and still fall within the protection scope of the technical solution of the present invention.
Claims (7)
1. The water vapor fluorescence sensor is characterized by being obtained by compounding a compound M1 and a base material M2, wherein the compound M1 has the following structural formula:
wherein m ranges from 1 to 3.
2. The aqueous vapor fluorescence sensor according to claim 1, wherein the matrix material M2 is one of chitosan, nanocellulose and silica.
3. The aqueous vapor fluorescence sensor according to claim 2, wherein the matrix material M2 is a porous structure.
4. The method for preparing the water vapor fluorescence sensor according to any one of claims 1 to 3, which is characterized by comprising the following steps:
a) Putting 2, 5-dihydroxy terephthalaldehyde, bromobutane, anhydrous potassium carbonate and solvent N, N-dimethylformamide into a round-bottom flask at one time, and reacting at the constant temperature of 80 ℃ for 48 hours; after the reaction is finished, carrying out vacuum filtration to remove insoluble inorganic salt, concentrating the filtrate by using a rotary evaporator, and recrystallizing by using methanol to obtain a first reactant 1;
b) Putting a first reactant 1, a second reactant 2, an organic base and a tert-butyl alcohol/tetrahydrofuran mixed solvent into a round-bottom flask at one time; stirring and reacting for 20 minutes at a constant temperature of 70 ℃; after completion of the reaction, it was cooled to room temperature, the reaction was poured into water, extracted with dichloromethane and the organic phase was passed over anhydrous Na 2 SO 4 Drying, concentrating with rotary evaporator, and performing column chromatography to obtain target molecule M1;
c) And c, dissolving the M1 molecules obtained in the step b in a tetrahydrofuran solvent, taking the solution as an impregnation solution to impregnate the matrix M2, and drying the solvent to obtain the final water vapor fluorescence sensor.
5. The method for preparing the water vapor fluorescence sensor according to claim 4, wherein the organic base in the step b) is one or more of potassium tert-butoxide, sodium tert-butoxide, tetrabutylammonium hydroxide, tetramethylguanidine and 1, 8-diazabicycloundecen-7-ene.
6. The method for preparing the water vapor fluorescence sensor according to claim 4, wherein the concentration of M1 in the dipping solution in the step c) is in the range of 0.001-0.005 mol/L, and the dipping time of the matrix material M2 is more than 20 minutes.
7. Use of the moisture fluorescent sensor according to any one of claims 1 to 3 in a moisture sensing material.
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