CN109400800B - N-rhodamine 6G lactam-N' -acryloyloxy hydrazine fluorescent probe polymer hydrogel and preparation method thereof - Google Patents
N-rhodamine 6G lactam-N' -acryloyloxy hydrazine fluorescent probe polymer hydrogel and preparation method thereof Download PDFInfo
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Abstract
A fluorescent probe polymer hydrogel and application thereof in detection of mercury ions relate to a fluorescent probe polymer hydrogel with remarkably enhanced fluorescence in the presence of mercury ions. The invention provides a fluorescent probe polymer hydrogel for selectively detecting mercury ions, namely N-rhodamine 6G lactam-N' -acryloyloxy hydrazine and a preparation method thereof. Firstly, rhodamine 6G and hydroxyethyl hydrazine are used as raw materials to prepare rhodamine 6G hydrazine hydrate, then the rhodamine 6G hydrazine hydrate is reacted with acryloyl chloride to obtain N-rhodamine 6G lactam-N '-acryloyloxy hydrazine, and then the N-rhodamine 6G lactam-N' -acryloyloxy hydrazine is copolymerized with acrylamide to obtain the fluorescent probe hydrogel. The process has the advantages of low synthesis cost, high yield, simple product purification and easy control of reaction conditions. The mercury ion fluorescent probe hydrogel has the characteristics of good selectivity, strong metal ion interference resistance, rapid detection response and the like, is a simple, rapid and sensitive mercury ion specific detection material, and can be applied to the field of materials or sensors.
Description
Technical Field
The invention relates to a fluorescent probe polymer hydrogel and a preparation method thereof, wherein the fluorescent probe has a conjugated and rigid planar structure, shows good fluorescent performance, contains C=O and N-H functional groups, can provide rich coordination modes, has strong metal coordination capability and good ion selectivity, and is copolymerized with acrylamide to obtain the hydrogel, so that the recycling problem of a regenerated fluorescent probe is solved.
Background
Probes based on fluorescent signals have been widely studied, and have the advantages of low cost, simple synthesis method, high sensitivity, good selectivity, high response speed, low detection limit, and can be used for space-time sampling, in vivo imaging and the like, thereby being widely used for detecting metal ions. During the course of research, small molecule fluorescent probes have been found to have a number of disadvantages that are difficult to overcome. The small molecular fluorescent probe generally has larger rigid conjugated groups, has poor solubility, and cannot be directly used for detecting heavy metal ions in urban sewage and industrial wastewater; the water solubility can be changed by molecular modification, but the fluorescence property is easily changed. Small molecule fluorescent probes must have structural units that are sensitive to the ions being detected to achieve ion detection, and these structural units are generally more reactive, less stable, and more prone to react with many interferents. The small molecular fluorescent probe is not easy to process, and the application of the small molecular fluorescent probe in detection devices is limited.
Hydrogel, as an intelligent material, is formed by chemical (covalent bond) or physical (non-covalent interaction) crosslinking, and has a three-dimensional structure which swells when meeting water. Because of the hydrophilic groups (-OH, -COOH, -NH2, -CONH2, -SO 3H) in the structure, the water can expand to hundreds or thousands of times of volume increase. These properties allow their use in drug delivery systems, antimicrobial materials, sensors, agriculture, matrix tissue engineering materials, catalyst support materials, separation, immobilization, and environmental technologies. The unsaturated double bond is introduced into the micromolecular fluorescent probe, and the micromolecular fluorescent probe is copolymerized with acrylamide to prepare the macromolecule hydrogel fluorescent probe with high transparency, high hydrophilicity and good mechanical property, so that the recycling problem of the regenerated fluorescent probe is solved, the research result can greatly reduce the synthetic workload of the fluorescent probe, thereby reducing the environmental pollution and the energy consumption, and the fluorescent probe based on the macromolecule material is beneficial to the practical application from laboratory research.
The invention comprises the following steps:
aiming at the defects of the prior art, the invention provides a novel fluorescent probe polymer hydrogel, and the fluorescent probe monomer has a special conjugated structure and good chemical coordination performance, and the synthesis process has the advantages of simple operation, high yield, low cost, rapid detection and the like.
The invention also aims at providing a preparation method of the fluorescent probe monomer.
Another object of the present invention is to provide a method for preparing the fluorescent probe polymer hydrogel.
It is another object of the present invention to provide the use of said fluorescent probe polymer hydrogel.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the compound is mainly applied to the field of materials or sensors;
a preparation method of fluorescent probe polymer hydrogel comprises the following steps:
1) Preparation of N-rhodamine 6G lactam-N' -hydrazine hydrate:
weighing rhodamine 6G in a three-mouth bottle, adding absolute ethyl alcohol, refluxing and stirring the three-mouth bottle for 30min, dropwise adding hydrazine hydrate into the solution, continuously refluxing and reacting the mixed solution for 5-10 h after the dropwise adding, cooling to room temperature, carrying out suction filtration, recrystallizing with absolute ethyl alcohol, and carrying out vacuum drying to obtain N-rhodamine 6G lactam-N' -hydrazine hydrate;
2) Preparation of N-rhodamine 6G lactam-N' -acryloyloxy hydrazine:
weighing triethylamine and the N-rhodamine 6G lactam-N '-hydrazine hydrate obtained in the step 1) into a three-mouth bottle, adding methylene dichloride, weighing and dripping acrylic chloride into the three-mouth bottle, performing constant temperature of-5-0 ℃ in the dripping process, heating to room temperature after the dripping is finished, stirring for 6-12 hours at room temperature, extracting, drying, removing water, distilling under reduced pressure to remove a solvent, separating by column chromatography to obtain pink powdery solid, and drying in vacuum to obtain the N-rhodamine 6G lactam-N' -acryloyloxy hydrazine;
3) Preparation of N-rhodamine 6G lactam-N' -acryloyloxy hydrazine polymer hydrogel:
boiling distilled water, sealing and cooling to room temperature to remove oxygen in the water, weighing acrylamide, dissolving acrylamide in distilled water, weighing N-rhodamine 6G lactam-N ' -acryloyloxy hydrazine obtained in the step 2), dissolving in dimethyl sulfoxide, mixing the two solutions, vacuumizing and stirring at normal temperature, continuously stirring for 30min until the two solutions are completely mixed, sequentially adding a cross-linking agent, a catalyst and an initiator into the mixed solution, uniformly stirring, transferring the solution into a glass mold, ensuring that no bubbles are mixed, sealing a glass cover, placing the hydrogel mold in an incubator at 50-55 ℃ for 3-5 h, performing free radical polymerization, taking out, cooling and stabilizing for 24h, opening the glass cover, slowly taking out the formed hydrogel, soaking in dimethyl sulfoxide solution for 24h, removing unreacted N-rhodamine 6G lactam-N ' -acryloyloxy hydrazine monomer, and then soaking in distilled water for 24h, and removing unreacted N-rhodamine 6G lactam-N ' -acryloyloxy hydrazine
Reacted acrylamide monomer.
Preferably, the molar ratio of rhodamine 6G to hydrazine hydrate in the step 1) is 2:13-2:16; more preferably, the molar ratio of rhodamine 6G to hydrazine hydrate is 2:15;
preferably, the volume molar ratio of absolute ethanol to rhodamine 6G described in step 1) is 20mL: 1-4 mmol; more preferably, the volume molar ratio of absolute ethanol to rhodamine 6G is 20mL:2mmol;
preferably, the reaction time in step 1) is 7 to 10 hours; more preferably, the reaction time is 8 hours;
preferably, the molar ratio of the N-rhodamine 6G lactam-N' -hydrazine hydrate to the triethylamine in the step 2) is 1:1-1:2; more preferably, the molar ratio of the N-rhodamine 6G lactam-N' -hydrazine hydrate to the triethylamine is 1:1.5;
preferably, the molar ratio of the N-rhodamine 6G lactam-N' -hydrazine hydrate to the acryloyl chloride in the step 2) is 1:1-1:2; more preferably, the molar ratio of the N-rhodamine 6G lactam-N' -hydrazine hydrate to the acryloyl chloride is 1:1;
preferably, the volume mole ratio of the dichloromethane to the N-rhodamine 6G lactam-N' -hydrazine hydrate in the step 2) is 20-30 mL:1mmol; more preferably, the volume molar ratio of dichloromethane to N-rhodamine 6G lactam-N' -hydrazine hydrate is 24mL:1mmol;
preferably, the dropping temperature in the step 2) is between-5 and 0 ℃; more preferably, the dropping temperature is-2 ℃;
preferably, the reaction time in step 2) is 10 to 12 hours; more preferred reaction time is 12 hours;
the cross-linking agent, the initiator and the catalyst in the step 3) are respectively N, N' -methylene bisacrylamide, ammonium persulfate and tetramethyl ethylenediamine;
the mass percentages of the acrylamide, the N-rhodamine 6G lactam-N' -acryloyloxy hydrazine, the cross-linking agent and the initiator in the step 3) accounting for 89 to 99 percent, 0.14 to 9 percent, 0.4 to 0.6 percent and 0.5 to 0.7 percent of the total solid components respectively;
the mass volume ratio of the acrylamide to the distilled water in the step 3) is 1g:1 to 1.2 mL;
the mass volume ratio of the N-rhodamine 6G lactam-N' -acryloyloxy hydrazine to the dimethyl sulfoxide in the step 3) is 0.001G: 0.04-1.6 mL;
the volume to mass ratio of the catalyst to the initiator in step 3) is 100. Mu.L: 0.02-0.04 g;
the constant temperature reaction time in the step 3) is 3-5 h, and the constant temperature reaction temperature is 50-55 ℃;
the synthetic route of the fluorescent probe polymer hydrogel is as follows:
the invention reacts rhodamine 6G with hydrazine hydrate to prepare rhodamine 6G hydrazine hydrate, then reacts with acryloyl chloride to obtain N-rhodamine 6G lactam-N '-acryloyloxy hydrazine, then copolymerizes the N-rhodamine 6G lactam-N' -acryloyloxy hydrazine with acrylamide to obtain fluorescent probe hydrogel, and tests,
the N-rhodamine 6G lactam-N' -acryloyloxy hydrazine and the polymer fluorescent probe hydrogel thereof have good selectivity to metal mercury ions.
In the preparation process of the hydrogel, the whole stirring process is carried out in a 100mL eggplant-shaped bottle, the eggplant-shaped bottle is supported on a constant-temperature magnetic stirrer, a rubber plug with a hole is plugged at the bottle mouth, and the rubber plug is connected with a multipurpose circulating water type vacuum pump through a self-made glass pipe and a rubber pipe, so that the stirring and the vacuum pumping can be carried out simultaneously so as to conveniently discharge the gas in the mixed solution, the bubble formation is not easy to occur during the gel formation, and the defect rate of the formed hydrogel is reduced.
The novel compound can be used as a probe in the field of ion detection. The compound N-rhodamine 6G lactam-N' -acryloyloxy hydrazine and the fluorescent probe hydrogel obtained by copolymerizing the same with acrylamide have the characteristics of good selectivity, strong metal ion interference resistance, quick detection response and the like, are simple, quick and sensitive mercury ion specificity detection materials, and can be applied to the field of materials or sensors.
Description of the drawings:
(1) FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of the compound N-rhodamine 6G lactam-N' -acryloyloxy hydrazine.
(2) FIG. 2 is a schematic representation of the color change of a mixed solution of the compound N-rhodamine 6G lactam-N' -acryloyloxyhydrazine and metal ions under visible light.
(3) FIG. 3 is a graph of the ultraviolet absorbance spectra (absorption wavelength on the abscissa and absorption intensity on the ordinate) of N-rhodamine 6G lactam-N' -acryloyloxy hydrazine for different metal ions.
(4) FIG. 4 is a fluorescence spectrum (emission wavelength on the abscissa and fluorescence intensity on the ordinate) of N-rhodamine 6G lactam-N' -acryloyloxy hydrazine to metal ion selectivity.
(5) FIG. 5 is a schematic representation of the color change and regeneration of a fluorescent probe of N-rhodamine 6G lactam-N' -acryloyloxy hydrazine polymer to recognize mercury ions.
The specific embodiment is as follows:
in order to better understand the technical solution of the present invention, the following description is further given in detail by way of specific examples.
Example 1
1) Weighing rhodamine 6G 0.9580G (2 mmol) and dissolving in 20mL of hot ethanol, dropwise adding 0.7509G (15 mmol) of hydrazine hydrate after complete dissolution, refluxing and stirring the mixed solution after the completion of dropwise adding for 8 hours until the fluorescence of the solution disappears, confirming the completion of the reaction by a dot plate, cooling the reaction solution to room temperature, separating out a precipitate, filtering the precipitate and washing the precipitate with hot ethanol, and recrystallizing the obtained crude product with acetonitrile to obtain 0.7344G of the product N-rhodamine 6G lactam-N' -hydrazine hydrate with the yield of 85%;
2) Weighing 0.4285G (1 mmol) of N-rhodamine 6G lactam-N ' -hydrazine hydrate, dissolving the N-rhodamine 6G lactam-N ' -hydrazine hydrate into 24mL of dichloromethane, dropwise adding 0.1518G (1.5 mmol) of triethylamine into the solution, cooling the mixed solution to-3 ℃, keeping the temperature stable, beginning dropwise adding 0.0905G (1 mmol) of acryloyl chloride, heating to room temperature after the dropwise adding is finished, stirring at room temperature for 12h, carrying out extraction, concentration and column chromatography separation after the spot plate confirmation reaction is complete, and obtaining 0.3915G of a product compound N-rhodamine 6G lactam-N ' -acryloyloxy hydrazine, wherein the yield is 81%;
3) Boiling distilled water to remove oxygen, sealing, cooling to room temperature for standby, dissolving 0.0073G of N-rhodamine 6G lactam-N ' -acryloyloxy hydrazine in 11.7mL of DMSO, dissolving 5.1480G of acrylamide in 5.1mL of water, mixing the two solutions, continuously stirring for 30min until the two solutions are completely mixed, dissolving 0.0312G N, N ' -methylenebisacrylamide in the mixed solution, injecting 100 mu L of tetramethyl ethylenediamine into the mixed solution, finally adding 0.0364G of ammonium persulfate, stirring uniformly, transferring the solution into a glass mold, ensuring that no bubbles are mixed, sealing by a glass cover, placing the mold in a constant temperature oven at 50 ℃ for 5h, performing free radical polymerization, cooling for 24h after the mold is taken out, opening the glass cover, slowly taking out the formed hydrogel, soaking in dimethyl sulfoxide solution for 24h, removing unreacted N-rhodamine 6G lactam-N ' -acryloyloxy hydrazine monomer, and then soaking in distilled water for 24h, and removing unreacted acrylamide monomer.
Example 2
1) Weighing rhodamine 6G 0.9580G (2 mmol) and dissolving in 40mL of hot ethanol, dropwise adding 0.6508G (13 mmol) of hydrazine hydrate after complete dissolution, refluxing and stirring the mixed solution after the completion of dropwise adding for 7 hours until the fluorescence of the solution disappears, confirming the completion of the reaction by a dot plate, cooling the reaction solution to room temperature, separating out a precipitate, filtering the precipitate and washing the precipitate with hot ethanol, and recrystallizing the obtained crude product with acetonitrile to obtain 0.5530G of the product N-rhodamine 6G lactam-N' -hydrazine hydrate with the yield of 64%;
2) Weighing 0.4285G (1.0 mmol) of N-rhodamine 6G lactam-N ' -hydrazine hydrate, dissolving the N-rhodamine 6G lactam-N ' -hydrazine hydrate into 20mL of dichloromethane, dropwise adding 0.1012G (1.1 mmol) of triethylamine into the solution, cooling the mixed solution to 0 ℃, keeping the temperature stable, starting dropwise adding 0.0905G (1.0 mmol) of acryloyl chloride after the mixed solution is cooled to 0 ℃, heating to room temperature after the dropwise adding is finished, stirring for 9h at room temperature, carrying out extraction, concentration and column chromatography separation after the spot plate confirmation reaction is complete, and obtaining 0.3625G of a product compound N-rhodamine 6G lactam-N ' -acryloyloxy hydrazine, wherein the yield is 75%;
3) Boiling distilled water to remove oxygen, sealing, cooling to room temperature for standby, dissolving 0.0073G of N-rhodamine 6G lactam-N ' -acryloyloxy hydrazine in 11.7mL of DMSO, dissolving 5.1480G of acrylamide in 5.1mL of water, mixing the two solutions, continuously stirring for 30min until the two solutions are completely mixed, dissolving 0.0312G N, N ' -methylenebisacrylamide in the mixed solution, injecting 100 mu L of tetramethyl ethylenediamine into the mixed solution, finally adding 0.0364G of ammonium persulfate, stirring uniformly, transferring the solution into a glass mold, ensuring that no bubbles are mixed, sealing by a glass cover, placing the mold in a constant temperature oven at 50 ℃ for 5h, performing free radical polymerization, cooling for 24h after the mold is taken out, opening the glass cover, slowly taking out the formed hydrogel, soaking in dimethyl sulfoxide solution for 24h, removing unreacted N-rhodamine 6G lactam-N ' -acryloyloxy hydrazine monomer, and then soaking in distilled water for 24h, and removing unreacted acrylamide monomer.
Example 3
1) Weighing rhodamine 6G 0.9580G (2 mmol) and dissolving in 60mL of hot ethanol, dropwise adding 0.7008G (14 mmol) of hydrazine hydrate after complete dissolution, refluxing and stirring the mixed solution after the completion of dropwise adding for 9 hours until the fluorescence of the solution disappears, confirming the completion of the reaction by a dot plate, cooling the reaction solution to room temperature, separating out a precipitate, filtering the precipitate and washing the precipitate with hot ethanol, and recrystallizing the obtained crude product with acetonitrile to obtain 0.6912G of the product N-rhodamine 6G lactam-N' -hydrazine hydrate with the yield of 80%;
2) Weighing 0.4285G (1 mmol) of N-rhodamine 6G lactam-N ' -hydrazine hydrate, dissolving the N-rhodamine 6G lactam-N ' -hydrazine hydrate into 28mL of dichloromethane, dropwise adding 0.1012G (1.0 mmol) of triethylamine into the solution, cooling the mixed solution to-2 ℃, keeping the temperature stable, beginning dropwise adding 0.1358G (1.5 mmol) of acryloyl chloride, heating to room temperature after the dropwise addition is finished, stirring for 10 hours at room temperature, carrying out extraction, concentration and column chromatography separation after the spot plate confirmation reaction is complete, and obtaining 0.3770G of a product compound N-rhodamine 6G lactam-N ' -acryloyloxy hydrazine, wherein the yield is 78%;
3) Boiling distilled water to remove oxygen, sealing, cooling to room temperature for standby, dissolving 0.0073G of N-rhodamine 6G lactam-N ' -acryloyloxy hydrazine in 11.7mL of DMSO, dissolving 5.1480G of acrylamide in 5.1mL of water, mixing the two solutions, continuously stirring for 30min until the two solutions are completely mixed, dissolving 0.0312G N, N ' -methylenebisacrylamide in the mixed solution, injecting 100 mu L of tetramethyl ethylenediamine into the mixed solution, finally adding 0.0364G of ammonium persulfate, stirring uniformly, transferring the solution into a glass mold, ensuring that no bubbles are mixed, sealing by a glass cover, placing the mold in a constant temperature oven at 50 ℃ for 5h, performing free radical polymerization, cooling for 24h after the mold is taken out, opening the glass cover, slowly taking out the formed hydrogel, soaking in dimethyl sulfoxide solution for 24h, removing unreacted N-rhodamine 6G lactam-N ' -acryloyloxy hydrazine monomer, and then soaking in distilled water for 24h, and removing unreacted acrylamide monomer.
Example 4
1) Weighing rhodamine 6G 0.9580G (2 mmol) and dissolving in 80mL of hot ethanol, dropwise adding 0.8010G (16 mmol) of hydrazine hydrate after complete dissolution, refluxing and stirring the mixed solution after the completion of dropwise adding for 10 hours until the fluorescence of the solution disappears, confirming the completion of the reaction by a dot plate, cooling the reaction solution to room temperature, separating out a precipitate, filtering the precipitate and washing the precipitate with hot ethanol, and recrystallizing the obtained crude product with acetonitrile to obtain 0.6566G of the product N-rhodamine 6G lactam-N' -hydrazine hydrate with the yield of 76%;
2) Weighing 0.4285G (1 mmol) of N-rhodamine 6G lactam-N ' -hydrazine hydrate, dissolving the N-rhodamine 6G lactam-N ' -hydrazine hydrate into 30mL of dichloromethane, dropwise adding 0.1810G (2.0 mmol) of triethylamine into the solution, cooling the mixed solution to-3 ℃, keeping the temperature stable, beginning dropwise adding 0.2024 (2.0 mmol) of acryloyl chloride, heating to room temperature after the dropwise addition is completed, stirring for 8 hours at room temperature, carrying out extraction, concentration and column chromatography separation after the completion of the spot plate confirmation reaction, and obtaining 0.3721G of a product compound N-rhodamine 6G lactam-N ' -acryloyloxy hydrazine, wherein the yield is 77%;
3) Boiling distilled water to remove oxygen, sealing, cooling to room temperature for standby, dissolving 0.0073G of N-rhodamine 6G lactam-N ' -acryloyloxy hydrazine in 11.7mL of DMSO, dissolving 5.1480G of acrylamide in 5.1mL of water, mixing the two solutions, continuously stirring for 30min until the two solutions are completely mixed, dissolving 0.0312G N, N ' -methylenebisacrylamide in the mixed solution, injecting 100 mu L of tetramethyl ethylenediamine into the mixed solution, finally adding 0.0364G of ammonium persulfate, stirring uniformly, transferring the solution into a glass mold, ensuring that no bubbles are mixed, sealing by a glass cover, placing the mold in a constant temperature oven at 50 ℃ for 5h, performing free radical polymerization, cooling for 24h after the mold is taken out, opening the glass cover, slowly taking out the formed hydrogel, soaking in dimethyl sulfoxide solution for 24h, removing unreacted N-rhodamine 6G lactam-N ' -acryloyloxy hydrazine monomer, and then soaking in distilled water for 24h, and removing unreacted acrylamide monomer.
Example 5
1) Weighing rhodamine 6G 0.9580G (2 mmol) and dissolving in 20mL of hot ethanol, dropwise adding 0.7509G (15 mmol) of hydrazine hydrate after complete dissolution, refluxing and stirring the mixed solution after the completion of dropwise adding for 8 hours until the fluorescence of the solution disappears, confirming the completion of the reaction by a dot plate, cooling the reaction solution to room temperature, separating out a precipitate, filtering the precipitate and washing the precipitate with hot ethanol, and recrystallizing the obtained crude product with acetonitrile to obtain 0.5530G of the product N-rhodamine 6G lactam-N' -hydrazine hydrate with the yield of 64%;
2) Weighing 0.4285G (1 mmol) of N-rhodamine 6G lactam-N ' -hydrazine hydrate, dissolving the N-rhodamine 6G lactam-N ' -hydrazine hydrate into 24mL of dichloromethane, dropwise adding 0.1518G (1.5 mmol) of triethylamine into the solution, cooling the mixed solution to-3 ℃, keeping the temperature stable, beginning dropwise adding 0.0905G (1 mmol) of acryloyl chloride, heating to room temperature after the dropwise adding is finished, stirring at room temperature for 12h, carrying out extraction, concentration and column chromatography separation after the spot plate confirmation reaction is complete, and obtaining 0.3625G of a product compound N-rhodamine 6G lactam-N ' -acryloyloxy hydrazine, wherein the yield is 75%;
3) Boiling distilled water to remove oxygen, sealing, cooling to room temperature for standby, dissolving 0.0412G of N-rhodamine 6G lactam-N ' -acryloyloxy hydrazine in 53.7mL of DMSO, dissolving 5.0470G of acrylamide in 5.0mL of water, mixing the two solutions, continuously stirring for 30min until the two solutions are completely mixed, dissolving 0.0309G of N, N ' -methylenebisacrylamide in the mixed solution, injecting 200 mu L of tetramethyl ethylenediamine into the mixed solution, finally adding 0.0361G of ammonium persulfate, stirring uniformly, transferring the solution into a glass mold, ensuring that no bubbles are mixed, sealing by a glass cover, placing the mold in a constant temperature box at 55 ℃ for 4.5h, carrying out free radical polymerization, cooling for 24h after taking out, opening the glass cover, slowly taking out the formed hydrogel, soaking in dimethyl sulfoxide solution for 24h, removing unreacted N-rhodamine 6G lactam-N ' -acryloyloxy monomer, and then soaking in distilled water for 24h, and removing unreacted acrylamide monomer.
Example 6
1) Weighing rhodamine 6G 0.9580G (2 mmol) and dissolving in 20mL of hot ethanol, dropwise adding 0.7509G (15 mmol) of hydrazine hydrate after complete dissolution, refluxing and stirring the mixed solution after the completion of dropwise adding for 8 hours until the fluorescence of the solution disappears, confirming the completion of the reaction by a dot plate, cooling the reaction solution to room temperature, separating out a precipitate, filtering the precipitate and washing the precipitate with hot ethanol, and recrystallizing the obtained crude product with acetonitrile to obtain 0.5530G of the product N-rhodamine 6G lactam-N' -hydrazine hydrate with the yield of 64%;
2) Weighing 0.4285G (1 mmol) of N-rhodamine 6G lactam-N ' -hydrazine hydrate, dissolving the N-rhodamine 6G lactam-N ' -hydrazine hydrate into 24mL of dichloromethane, dropwise adding 0.1518G (1.5 mmol) of triethylamine into the solution, cooling the mixed solution to-3 ℃, keeping the temperature stable, beginning dropwise adding 0.0905G (1 mmol) of acryloyl chloride, heating to room temperature after the dropwise adding is finished, stirring at room temperature for 12h, carrying out extraction, concentration and column chromatography separation after the spot plate confirmation reaction is complete, and obtaining 0.3625G of a product compound N-rhodamine 6G lactam-N ' -acryloyloxy hydrazine, wherein the yield is 75%;
3) Boiling distilled water to remove oxygen, sealing, cooling to room temperature for standby, dissolving 0.0859G of N-rhodamine 6G lactam-N ' -acryloyloxy hydrazine in 85.9mL of DMSO, dissolving 4.8985G of acrylamide in 4.9mL of water, mixing the two solutions, continuously stirring for 30min until the two solutions are completely mixed, dissolving 0.0253G of N, N ' -methylenebisacrylamide in the mixed solution, injecting 150 mu L of tetramethyl ethylenediamine into the mixed solution, finally adding 0.0303G of ammonium persulfate, stirring uniformly, transferring the solution into a glass mould, covering a glass cover for sealing after ensuring that no bubbles are mixed, placing the mould in a constant temperature box at 54 ℃ for 3.5h, carrying out free radical polymerization, cooling for 24h after taking out, opening the glass cover, slowly taking out the formed solution, soaking in dimethyl sulfoxide solution for 24h, removing unreacted N-rhodamine 6G lactam-N ' -acryloyloxy monomer, and then soaking in distilled water for 24h, and removing unreacted acrylamide monomer.
Example 7
1) Weighing rhodamine 6G 0.9580G (2 mmol) and dissolving in 20mL of hot ethanol, dropwise adding 0.7509G (15 mmol) of hydrazine hydrate after complete dissolution, refluxing and stirring the mixed solution after the completion of dropwise adding for 8 hours until the fluorescence of the solution disappears, confirming the completion of the reaction by a dot plate, cooling the reaction solution to room temperature, separating out a precipitate, filtering the precipitate and washing the precipitate with hot ethanol, and recrystallizing the obtained crude product with acetonitrile to obtain 0.5530G of the product N-rhodamine 6G lactam-N' -hydrazine hydrate with the yield of 64%;
2) Weighing 0.4285G (1 mmol) of N-rhodamine 6G lactam-N ' -hydrazine hydrate, dissolving the N-rhodamine 6G lactam-N ' -hydrazine hydrate into 24mL of dichloromethane, dropwise adding 0.1518G (1.5 mmol) of triethylamine into the solution, cooling the mixed solution to-3 ℃, keeping the temperature stable, beginning dropwise adding 0.0905G (1 mmol) of acryloyl chloride, heating to room temperature after the dropwise adding is finished, stirring at room temperature for 12h, carrying out extraction, concentration and column chromatography separation after the spot plate confirmation reaction is complete, and obtaining 0.3625G of a product compound N-rhodamine 6G lactam-N ' -acryloyloxy hydrazine, wherein the yield is 75%;
3) Boiling distilled water to remove oxygen, sealing, cooling to room temperature for standby, dissolving 0.1733G N-rhodamine 6G lactam-N '-acryloyloxy hydrazine in 121.28mL of LDMSO, dissolving 4.7030G acrylamide in 4.7 mL of water, mixing the two solutions, continuously stirring for 30min until the mixing is complete, dissolving 0.0248G N, N' -methylenebisacrylamide in the mixed solution, injecting 150 mu L of tetramethyl ethylenediamine into the mixed solution, finally adding 0.0297G of ammonium persulfate, stirring uniformly, transferring the solution into a glass mold, covering a glass cover for sealing after no air bubbles are mixed, placing the mold in a constant temperature oven at 53 ℃ for 4h, performing free radical polymerization, taking out, cooling and stabilizing for 24h, opening the glass cover, and slowly shaping hydrogel
Slowly taking out, soaking in dimethyl sulfoxide solution for 24 hr, removing unreacted N-rhodamine 6G lactam-N' -acryloyloxy hydrazine monomer, and soaking in distilled water for 24 hr to remove unreacted acrylamide monomer.
Example 8
1) Weighing rhodamine 6G 0.9580G (2 mmol) and dissolving in 20mL of hot ethanol, dropwise adding 0.7509G (15 mmol) of hydrazine hydrate after complete dissolution, refluxing and stirring the mixed solution after the completion of dropwise adding for 8 hours until the fluorescence of the solution disappears, confirming the completion of the reaction by a dot plate, cooling the reaction solution to room temperature, separating out a precipitate, filtering the precipitate and washing the precipitate with hot ethanol, and recrystallizing the obtained crude product with acetonitrile to obtain 0.5530G of the product N-rhodamine 6G lactam-N' -hydrazine hydrate with the yield of 64%;
2) Weighing 0.4285G (1 mmol) of N-rhodamine 6G lactam-N ' -hydrazine hydrate, dissolving the N-rhodamine 6G lactam-N ' -hydrazine hydrate into 24mL of dichloromethane, dropwise adding 0.1518G (1.5 mmol) of triethylamine into the solution, cooling the mixed solution to-3 ℃, keeping the temperature stable, beginning dropwise adding 0.0905G (1 mmol) of acryloyl chloride, heating to room temperature after the dropwise adding is finished, stirring at room temperature for 12h, carrying out extraction, concentration and column chromatography separation after the spot plate confirmation reaction is complete, and obtaining 0.3625G of a product compound N-rhodamine 6G lactam-N ' -acryloyloxy hydrazine, wherein the yield is 75%;
3) Boiling distilled water to remove oxygen, sealing, and cooling to room temperature for use. 0.2571G of N-rhodamine 6G lactam-N ' -acryloyloxy hydrazine is dissolved in 102.8mL of LDMSO, 4.5105 acrylamide is dissolved in 4.5mL of water, the two solutions are mixed and continuously stirred for 30min until the mixture is complete, 0.0243N, N ' -methylenebisacrylamide is dissolved in the mixed solution, 150 mu L of tetramethyl ethylenediamine is injected into the mixed solution, 0.0291G of ammonium persulfate is finally added, stirring is uniform, the solution is transferred to a glass mold, after no air bubbles are mixed, a glass cover is covered for sealing, the mold is placed in a constant temperature box at 52 ℃ for 3h, free radical polymerization reaction is carried out, cooling and stabilization are carried out for 24h after the mold is taken out, the glass cover is opened, the formed hydrogel is slowly taken out, the hydrogel is soaked in dimethyl sulfoxide solution for 24h, unreacted N-rhodamine 6G lactam-N ' -acryloyloxy hydrazine monomer is removed, and the unreacted acrylamide monomer is removed after the solution is soaked in distilled water for 24 h.
Example 9
1) Weighing rhodamine 6G 0.9580G (2 mmol) and dissolving in 20mL of hot ethanol, dropwise adding 0.7509G (15 mmol) of hydrazine hydrate after complete dissolution, refluxing and stirring the mixed solution after the completion of dropwise adding for 8 hours until the fluorescence of the solution disappears, confirming the completion of the reaction by a dot plate, cooling the reaction solution to room temperature, separating out a precipitate, filtering the precipitate and washing the precipitate with hot ethanol, and recrystallizing the obtained crude product with acetonitrile to obtain 0.5530G of the product N-rhodamine 6G lactam-N' -hydrazine hydrate with the yield of 64%;
2) Weighing 0.4285G (1 mmol) of N-rhodamine 6G lactam-N ' -hydrazine hydrate, dissolving the N-rhodamine 6G lactam-N ' -hydrazine hydrate into 24mL of dichloromethane, dropwise adding 0.1518G (1.5 mmol) of triethylamine into the solution, cooling the mixed solution to-3 ℃, keeping the temperature stable, beginning dropwise adding 0.0905G (1 mmol) of acryloyl chloride, heating to room temperature after the dropwise adding is finished, stirring at room temperature for 12h, carrying out extraction, concentration and column chromatography separation after the spot plate confirmation reaction is complete, and obtaining 0.3625G of a product compound N-rhodamine 6G lactam-N ' -acryloyloxy hydrazine, wherein the yield is 75%;
3) Boiling distilled water to remove oxygen, sealing, and cooling to room temperature for use. Dissolving 0.3420G of N-rhodamine 6G lactam-N ' -acryloyloxy hydrazine in 34.2mL of DMSO, dissolving 4.3225G of acrylamide in 4.3mL of water, mixing the two solutions, continuously stirring for 30min until the two solutions are completely mixed, dissolving 0.0190G of N, N ' -methylenebisacrylamide in the mixed solution, injecting 200 mu L of tetramethyl ethylenediamine into the mixed solution, finally adding 0.0238G of ammonium persulfate, stirring uniformly, transferring the solution into a glass mold, ensuring that no bubbles are mixed, covering a glass cover for sealing, placing the mold in a constant temperature oven at 51 ℃ for 5h, performing free radical polymerization, cooling and stabilizing for 24h after taking out the glass cover, slowly taking out the formed hydrogel, soaking in dimethyl sulfoxide solution for 24h, removing unreacted N-rhodamine 6G lactam-N ' -acryloyloxy hydrazine monomer, and then soaking in distilled water for 24h, and removing unreacted acrylamide monomer.
Example 10
1) Weighing rhodamine 6G 0.9580G (2 mmol) and dissolving in 20mL of hot ethanol, dropwise adding 0.7509G (15 mmol) of hydrazine hydrate after complete dissolution, refluxing and stirring the mixed solution after the completion of dropwise adding for 8 hours until the fluorescence of the solution disappears, confirming the completion of the reaction by a dot plate, cooling the reaction solution to room temperature, separating out a precipitate, filtering the precipitate and washing the precipitate with hot ethanol, and recrystallizing the obtained crude product with acetonitrile to obtain 0.5530G of the product N-rhodamine 6G lactam-N' -hydrazine hydrate with the yield of 64%;
2) Weighing 0.4285G (1 mmol) of N-rhodamine 6G lactam-N ' -hydrazine hydrate, dissolving the N-rhodamine 6G lactam-N ' -hydrazine hydrate into 24mL of dichloromethane, dropwise adding 0.1518G (1.5 mmol) of triethylamine into the solution, cooling the mixed solution to-3 ℃, keeping the temperature stable, beginning dropwise adding 0.0905G (1 mmol) of acryloyl chloride, heating to room temperature after the dropwise adding is finished, stirring at room temperature for 12h, carrying out extraction, concentration and column chromatography separation after the spot plate confirmation reaction is complete, and obtaining 0.3625G of a product compound N-rhodamine 6G lactam-N ' -acryloyloxy hydrazine, wherein the yield is 75%;
3) Boiling distilled water to remove oxygen, sealing, cooling to room temperature for standby, dissolving 0.4185G of N-rhodamine 6G lactam-N ' -acryloyloxy hydrazine in 16.7mL of LDMSO, dissolving 4.1385G of acrylamide in 4.1mL of water, mixing the two solutions, continuously stirring for 30min until the two solutions are completely mixed, dissolving 0.0186G of N, N ' -methylenebisacrylamide in the mixed solution, injecting 100 mu L of tetramethyl ethylenediamine into the mixed solution, finally adding 0.0233G of ammonium persulfate, stirring uniformly, transferring the solution into a glass mold, ensuring that no bubbles are mixed, sealing by a glass cover, placing the mold in a constant temperature box at 50 ℃ for 5h, carrying out free radical polymerization, cooling for 24h after taking out, opening the glass cover, slowly taking out the formed hydrogel, soaking in dimethyl sulfoxide solution for 24h, removing unreacted N-rhodamine 6G lactam-N ' -acryloyloxy hydrazine monomer, and then soaking in distilled water for 24h, and removing unreacted acrylamide monomer.
N-rhodamine 6G lactam-N' -acryloyloxy hydrazine elemental analysis: c3 1 H3 4 N4 O4: % C:
7.2.1 5 (72.18); % H:6.25 (6.27); % N:9.97 (9.95); % O:11.63 (11.60) (measurement values in brackets).
Nuclear magnetic analysis (nuclear magnetic spectrum chart is shown in figure 1) of the final product N-rhodamine 6G lactam-N' -acryloyloxy hydrazine: 1H NMR (400 MHz, DMSO). Delta.7.65 (d, J6.6Hz, 1H), 7.42-7.35 (m, 2H), 6.86 (d, J=6.7 Hz, 1H), 6.11 (s, 3H), 5.95 (s, 3H), 5.77 (s, 1H), 4.87 (dt, J=10.2, 5.6Hz, 3H), 3.65 (t, J=5.7 Hz, 2H), 3.0-2.97 (m, 4H), 2.62 (d, J5.8Hz, 2H), 1.72 (s, 6H), 1.07 (t, J=7.1 Hz, 6H). One of the compounds had 30 hydrogen peaks at 4.22ppm and 3.15ppm for hydrogen on the C=C double bond, 5.00ppm for the secondary amine (-NH-) and 3.13ppm for methylene hydrogen, 1.87ppm and 1.21ppm for methyl hydrogen and 6.10ppm, 6.27ppm, 6.93ppm, 7.45ppm and 7.76ppm for hydrogen on the benzene ring. The structure of the compound was consistent with the information on the spectra by the above comparative analyses of each hydrogen and their chemical shifts and peak areas, and it was found that the compound N-rhodamine 6G lactam-N' -acryloyloxyhydrazine was successfully synthesized.
The fluorescent probe and the application of the polymer hydrogel thereof
Experimental example 1
The fluorescent probe monomer N-rhodamine 6G lactam-N' -acryloyloxy hydrazine prepared in example 1 is taken and dissolved in dimethyl sulfoxide: distilled water = 4:1 to prepare a stock solution of 1X 10-3 mol/L, taking 1mL out of the stock solution, adding the stock solution to a 100mL measuring flask, and adding 1mL of an aluminum ion standard solution (1X 10-3 mol/L) to the flask with dimethyl sulfoxide: distilled water = 4:1 to prepare a 1:1 mixed solution of 1.0X10-5 mol/L compound and metal ions, wherein the mixed solution of 1.0X10-5 mol/L compound and metal ions can observe color change under visible light, and as shown in figure 2, the compound N-rhodamine 6G lactam-N' -acryloyloxy hydrazine can visually detect Hg < 2+ >.
Experimental example 2
The fluorescent probe monomer N-rhodamine 6G lactam-N' -acryloyloxy hydrazine prepared in example 1 is taken and dissolved in dimethyl sulfoxide: distilled water = 4:1 to prepare a stock solution of 1X 10-3 mol/L, taking 1mL out of the stock solution, adding the stock solution to a 100mL measuring flask, and adding 1mL of an aluminum ion standard solution (1X 10-3 mol/L) to the flask with dimethyl sulfoxide: distilled water = 4:1 to prepare a 1.0x10 < -5 > mol/L mixed solution of a compound and metal ions in a ratio of 1:1, and testing the ultraviolet absorption spectrum of the compound and metal ion solution (the result is shown in figure 3), the inventor finds that when the equivalent amount of Mg2+, cu2+, co2+, cr2+, al3+, ni2+, zn2+ and Cd2+ are added into the solution, the fluorescence spectrum does not change obviously, and only after Hg < 2+ > is added, the ultraviolet spectrum is enhanced to a certain extent, so that the synthesized fluorescent probe has better selectivity on mercury ions (II).
Experimental example 3
Taking the purified fluorescent probe monomer N-rhodamine 6G lactam-N' -acryloyloxy hydrazine, and utilizing dimethyl sulfoxide: distilled water = 4:1, preparing a sample solution of 1.0x10 < -5 > mol/L by dissolving and diluting the mixed solution, measuring an ultraviolet absorption spectrum of the sample by using an ultraviolet visible spectrophotometer, measuring the fluorescence excitation wavelength of the compound by using an F-4600 fluorescence spectrophotometer according to the maximum ultraviolet absorption wavelength of the compound, measuring the fluorescence emission spectrum of the compound, and then respectively adding equivalent amounts of different metal ions Al < 3+ >, ag < + >, co < 2 >, mg < 2+ >, cu < 2+ >, ni < 2+ >, pb < 2+ > and Zn < 2+ > into the solution, and measuring the fluorescence emission spectrum of a fluorescent probe molecule in the presence of each metal ion (the result is shown in figure 4);
the fluorescence intensity of the compound is very weak when no metal ion is added, so that the compound is difficult to observe in a graph, but when the equivalent Mg2+, cu2+, co2+, cr2+, al3+, ni2+, zn2+ and Cd2+ are added into the solution, the fluorescence spectrum is enhanced to a certain extent, and only after Hg < 2+ > is added, the fluorescence spectrum is enhanced remarkably, which has important significance for quickly identifying metal aluminum ions, and the synthesized fluorescent probe has better selectivity for mercury ions (II).
Experimental example 4
Through tests, the acrylamide hydrogel cannot be used as a visual sensor to detect any metal ions, but when N-rhodamine 6G lactam-N' -acryloyloxy hydrazine is used as a monomer to be copolymerized with acrylamide to form the hydrogel, the hydrogel has the capability of detecting Hg < 2+ >, as shown in figure 5, the hydrogel turns into pink after being soaked in Hg < 2+ > solution, and then the hydrogel after being combined with metal ion color change can be soaked in 1mol/L EDA aqueous solution, so that the original color can be recovered.
Claims (5)
1. An N-rhodamine 6G lactam-N' -acryloyloxy hydrazine fluorescent probe polymer hydrogel, which is characterized in that: the hydrogel is prepared by copolymerizing an N-rhodamine 6G lactam-N' -acryloyloxy hydrazine fluorescent probe and acrylamide, and has the following structural formula:
the preparation method of the fluorescent probe polymer hydrogel comprises the following specific steps:
1) Preparation of N-rhodamine 6G lactam-N' -hydrazine hydrate:
weighing rhodamine 6G in a three-mouth bottle, adding absolute ethyl alcohol, stirring the three-mouth bottle at the constant temperature of 60-80 ℃ for 30min, then dripping hydrazine hydrate into the solution, continuing to react for 5-10 h, cooling to room temperature, carrying out suction filtration, recrystallizing with absolute ethyl alcohol, and carrying out vacuum drying to obtain N-rhodamine 6G lactam-N' -hydrazine hydrate;
2) Preparation of N-rhodamine 6G lactam-N' -acryloyloxy hydrazine:
weighing triethylamine and the N-rhodamine 6G lactam-N '-hydrazine hydrate obtained in the step 1) into a three-mouth bottle, adding methylene dichloride, weighing and dripping acrylic chloride into the three-mouth bottle, performing constant temperature of-5-0 ℃ in the dripping process, slowly heating to room temperature after the dripping is finished, stirring for 6-12 hours at the room temperature, extracting, drying, removing water, distilling under reduced pressure to remove a solvent, separating by column chromatography to obtain pink powdery solid, and drying in vacuum to obtain the N-rhodamine 6G lactam-N' -acryloyloxy hydrazine;
3) Preparation of N-rhodamine 6G lactam-N' -acryloyloxy hydrazine polymer hydrogel:
boiling distilled water, sealing and cooling to room temperature to remove oxygen in the water, weighing acrylamide, dissolving the acrylamide in the distilled water, weighing N-rhodamine 6G lactam-N '-acryloyloxy hydrazine obtained in the step 2), dissolving the two solutions in dimethyl sulfoxide, vacuumizing and stirring at normal temperature, continuously stirring for 30min until the two solutions are completely mixed, sequentially adding a cross-linking agent, a catalyst and an initiator into the mixed solution, uniformly stirring, transferring the solution into a glass mold, ensuring that no bubbles are mixed, sealing a glass cover, placing the hydrogel mold in an incubator at 50-55 ℃ for 3-5 h, carrying out free radical polymerization, taking out, cooling and stabilizing for 24h, opening the glass cover, slowly taking out the formed hydrogel, soaking in dimethyl sulfoxide solution for 24h, removing unreacted N-rhodamine 6G lactam-N' -acryloyloxy hydrazine monomer, and then soaking in distilled water for 24h, and removing unreacted acrylamide monomer;
the mass percentages of the acrylamide, the N-rhodamine 6G lactam-N' -acryloyloxy hydrazine, the cross-linking agent and the initiator in the step 3) accounting for 89 to 99 percent, 0.14 to 9 percent, 0.4 to 0.6 percent and 0.5 to 0.7 percent of the total solid components are 100 percent respectively; the mass volume ratio of the acrylamide to the distilled water is 1g: 1-2 mL; the mass volume ratio of the N-rhodamine 6G lactam-N' -acryloyloxy hydrazine to the dimethyl sulfoxide is 0.001G: 0.04-1.6 mL; the volume-mass ratio of the catalyst to the initiator is 100 mu L: 0.02-0.04 g.
2. The N-rhodamine 6G lactam-N' -acryloyloxy hydrazine fluorescent probe polymer hydrogel of claim 1, characterized by: the molar ratio of rhodamine 6G to hydrazine hydrate in the step 1) is 2:13-2:16; the volume mole ratio of the absolute ethyl alcohol to the rhodamine 6G in the step 1) is 20mL:1 to 4mmol.
3. The N-rhodamine 6G lactam-N' -acryloyloxy hydrazine fluorescent probe polymer hydrogel of claim 1, characterized by: the molar ratio of the N-rhodamine 6G lactam-N' -hydrazine hydrate to the triethylamine in the step 2) is 1:1-1:2; the molar ratio of the N-rhodamine 6G lactam-N' -hydrazine hydrate to the acryloyl chloride is 1:1-1:2; the volume molar ratio of the dichloromethane to the N-rhodamine 6G lactam-N' -hydrazine hydrate is 20-30 mL:1mmol.
4. The N-rhodamine 6G lactam-N' -acryloyloxy hydrazine fluorescent probe polymer hydrogel of claim 1, characterized by: the cross-linking agent, the initiator and the catalyst in the step 3) are respectively N, N' -methylene bisacrylamide, ammonium persulfate and tetramethyl ethylenediamine.
5. Use of the fluorescent probe polymer hydrogel according to claim 1 in the material field or in the sensor field.
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