CN109627464B - Fluorescent probe polymer hydrogel and preparation method thereof - Google Patents

Fluorescent probe polymer hydrogel and preparation method thereof Download PDF

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CN109627464B
CN109627464B CN201811570665.0A CN201811570665A CN109627464B CN 109627464 B CN109627464 B CN 109627464B CN 201811570665 A CN201811570665 A CN 201811570665A CN 109627464 B CN109627464 B CN 109627464B
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rhodamine
lactam
hydroxyethyl hydrazine
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CN109627464A (en
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孟霞
王珍媜
段洪东
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Qilu University of Technology
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Abstract

A fluorescent probe polymer hydrogel and application thereof in detecting 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 capable of being used for selectively detecting mercury ions N-rhodamine 6G lactam-N' -acryloxy hydroxyethyl hydrazine and a preparation method thereof. Firstly, rhodamine 6G and hydroxyethyl hydrazine are used as raw materials to prepare rhodamine 6G hydroxyethyl hydrazine, then the rhodamine 6G hydroxyethyl hydrazine is reacted with acryloyl chloride to obtain N-rhodamine 6G lactam-N '-acryloyloxy hydroxyethyl hydrazine, and then the N-rhodamine 6G lactam-N' -acryloyloxy hydroxyethyl 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 easily controlled reaction conditions. The mercury ion fluorescent probe hydrogel has the characteristics of good selectivity, strong metal ion interference resistance, quick detection response and the like, is a simple, quick and sensitive mercury ion specificity detection material, and can be applied to the field of materials or sensors.

Description

Fluorescent probe polymer hydrogel and preparation method thereof
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 better fluorescence performance, contains C ═ O, N-H functional groups, can provide rich coordination modes, has strong metal coordination capacity and good ion selectivity, and is copolymerized with acrylamide to obtain the hydrogel, so that the problem of recycling of regenerated fluorescent probes is solved.
Background
Probes based on fluorescent signals have been widely studied, and have advantages of low cost, simple synthesis method, high sensitivity, good selectivity, fast response speed, low detection limit, and the like, and can be used for space-time sampling and in-vivo imaging, and thus are widely used for detecting metal ions. In 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 a larger rigid conjugated group, is generally poor in solubility, and cannot be directly used for detecting heavy metal ions in municipal sewage and industrial wastewater; the water solubility can be changed by molecular modification, but the fluorescence property is easy to change. The small molecule fluorescent probe has to have structural units which are sensitive to detected ions to realize the detection of the ions, and the structural units have strong reactivity and poor stability and are easy to react with a plurality of interferents. The small-molecule fluorescent probe is not easy to process, and the application of the small-molecule fluorescent probe in the aspect of detection devices is limited.
The 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 in water. Because the structure has hydrophilic groups (-OH, -COOH, -NH)2，-CONH2，-SO3H) And can absorb water to expand to hundreds of volume increase or even thousands of times volume increase. These properties make them useful in drug delivery systems, antimicrobial materials, sensors, agriculture, matrix tissue engineering materials, catalyst support materials, separations, immobilization, and environmental technologies. According to the method, unsaturated double bonds are introduced into a small-molecular fluorescent probe, and are copolymerized with hydroxyethyl methacrylate, acrylamide and N, N' -methylene bisacrylamide to prepare the high-molecular hydrogel fluorescent probe with high transparency, high hydrophilicity and good mechanical property, so that the problem of recycling of the regenerated fluorescent probe is solved, the workload of synthesis of the fluorescent probe can be greatly reduced, the pollution to the environment and the consumption of energy are reduced, and the fluorescent probe based on a high-molecular material is favorable for being developed into practical application from laboratory research.
The invention content is as follows:
the invention aims to provide a novel fluorescent probe polymer hydrogel aiming at the defects of the prior art, 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, quick detection and the like.
The invention also aims to provide a preparation method of the fluorescent probe monomer.
The invention also aims to provide a preparation method of the fluorescent probe polymer hydrogel.
The invention also aims to provide application of the fluorescent probe polymer hydrogel.
In order to achieve the purpose, the technical scheme of the invention is as follows:
Figure GDA0002959062920000021
the compound is mainly applied to the field of materials or sensors;
a preparation method of a fluorescent probe polymer hydrogel comprises the following steps:
1) preparation of N-rhodamine 6G lactam-N' -hydroxyethyl hydrazine:
weighing rhodamine 6G in a three-necked bottle, adding absolute ethyl alcohol, refluxing and stirring the three-necked bottle for 30min, then dropwise adding hydroxyethyl hydrazine into the solution, after dropwise adding, continuously refluxing and reacting the mixed solution 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' -hydroxyethyl hydrazine;
2) preparation of N-rhodamine 6G lactam-N' -acryloxy hydroxyethyl hydrazine:
weighing triethylamine and the N-rhodamine 6G lactam-N '-hydroxyethyl hydrazine obtained in the step 1) into a three-necked bottle, adding dichloromethane, weighing acryloyl chloride, dropwise adding into the three-necked bottle, performing the dropwise adding process at a constant temperature of-5-0 ℃, heating to room temperature after the dropwise adding is completed, stirring at room temperature for 6-12 h, extracting, drying to remove water, distilling under reduced pressure to remove a solvent, performing column chromatography separation to obtain a pink powdery solid, and performing vacuum drying to obtain the N-rhodamine 6G lactam-N' -acryloyloxy hydroxyethyl hydrazine;
3) preparation of N-rhodamine 6G lactam-N' -acryloxy hydroxyethyl hydrazine polymer hydrogel:
boiling distilled water, sealing and cooling to room temperature to remove oxygen in the water, weighing acrylamide and dissolving the N-rhodamine 6G lactam-N '-acryloyloxy hydroxyethyl hydrazine obtained in the step 2) in distilled water, weighing the N-rhodamine 6G lactam-N' -acryloyloxy hydroxyethyl hydrazine obtained in the step 2) and dissolving the N-rhodamine 6G lactam-N '-acryloyloxy hydroxyethyl hydrazine in dimethyl sulfoxide, mixing the two solutions, vacuumizing and stirring at room 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, sealing the glass mold after ensuring that no bubbles are mixed, placing the hydrogel mold in a constant temperature box at 50-55 ℃ for 3-5 h, carrying out free radical polymerization reaction, cooling and stabilizing for 24h after taking out, opening the glass cover, slowly taking out the formed hydrogel, soaking in the dimethyl sulfoxide solution for 24h, removing the unreacted N-rhodamine 6G lactam-N' -acryloyloxy hydroxyethyl hydrazine, then soaking in distilled water for 24h to remove unreacted acrylamide monomer.
Preferably, the molar ratio of rhodamine 6G to hydroxyethyl hydrazine in the step 1) is 2: 13-2: 16; more preferably, the molar ratio of rhodamine 6G to hydroxyethylhydrazine is 2: 15;
preferably, the volume mol ratio of the absolute ethyl alcohol to the rhodamine 6G in the step 1) is 20 mL: 1-4 mmol; more preferably, the volume mol ratio of the absolute ethyl alcohol to the rhodamine 6G is 20 mL: 2mmol of the active carbon;
preferably, the reaction time in the step 1) is 7-10 h; more preferably, the reaction time is 8 h;
preferably, the molar ratio of the N-rhodamine 6G lactam-N' -hydroxyethyl hydrazine to the triethylamine in the step 2) is 1: 1-1: 4; more preferably, the molar ratio of N-rhodamine 6G lactam-N' -hydroxyethyl hydrazine to triethylamine is 1: 2;
preferably, the molar ratio of the N-rhodamine 6G lactam-N' -hydroxyethyl hydrazine to the acryloyl chloride in the step 2) is 1: 1-1: 1.5; more preferably, the molar ratio of the N-rhodamine 6G lactam-N' -hydroxyethyl hydrazine to the acryloyl chloride is 1: 1.3;
preferably, the volume mol ratio of the dichloromethane to the N-rhodamine 6G lactam-N' -hydroxyethyl hydrazine in the step 2) is 40 mL: 1-3 mmol; more preferably, the volume mol ratio of the dichloromethane to the N-rhodamine 6G lactam-N' -hydroxyethyl hydrazine is 40 mL: 1mmol of the active component;
preferably, the dropping temperature in the step 2) is-5-0 ℃; more preferably, the dropping temperature is-3 ℃;
preferably, the reaction time in the step 2) is 8-12 h; more preferably the reaction time is 10 h;
preferably, the crosslinking agent, the initiator and the catalyst in the step 3) are respectively N, N' -methylene-bisacrylamide, ammonium persulfate and tetramethylethylenediamine;
preferably, the mass percentages of the acrylamide, the N-rhodamine 6G lactam-N' -acryloxy hydroxyethyl hydrazine, the cross-linking agent and the initiator in the step 3) in the total solid components are respectively 89-99%, 0.14-9%, 0.4-0.6% and 0.5-0.7%;
preferably, the mass-to-volume ratio of the acrylamide to the distilled water in the step 3) is 1 g: 1-1.2 mL;
preferably, the mass volume ratio of the N-rhodamine 6G lactam-N' -acryloyloxy hydroxyethyl hydrazine to the dimethyl sulfoxide in the step 3) is 0.001G: 0.02-0.8 mL;
preferably, the volume mass ratio of the catalyst to the initiator in the step 3) is 100 μ l: 0.02-0.04 g;
the constant-temperature reaction time in the step 3) is 3-5 hours, and the constant-temperature reaction temperature is 50-55 ℃;
the synthetic route of the fluorescent probe polymer hydrogel is as follows:
Figure GDA0002959062920000041
the invention reacts rhodamine 6G and hydroxyethyl hydrazine to prepare rhodamine 6G hydroxyethyl hydrazine, then the rhodamine 6G hydroxyethyl hydrazine is reacted with acryloyl chloride to obtain N-rhodamine 6G lactam-N ' -acryloxy hydroxyethyl hydrazine, then the N-rhodamine 6G lactam-N ' -acryloxy hydroxyethyl hydrazine is copolymerized with acrylamide to obtain the fluorescent probe hydrogel, and through tests, the N-rhodamine 6G lactam-N ' -acryloxy hydroxyethyl hydrazine and the polymer fluorescent probe hydrogel thereof have good selectivity on metal mercury ions.
In the hydrogel preparation process, the whole stirring process is carried out in a 100mL eggplant-shaped bottle, the eggplant-shaped bottle is erected on a constant-temperature magnetic stirrer, a rubber plug with a hole is plugged at the bottle mouth, and the bottle mouth is connected with a multi-purpose circulating water type vacuum pump through a self-made glass tube and a rubber tube, so that the vacuum pumping can be carried out while stirring to discharge gas in a mixed solution, bubbles are not easily formed during gelling, and the defect rate after hydrogel forming is reduced.
The novel compound can be used as a probe to be applied to the field of ion detection. The compound N-rhodamine 6G lactam-N '-acryloyloxy hydroxyethyl hydrazine and the fluorescent probe hydrogel obtained by copolymerizing the compound N-rhodamine 6G lactam-N' -acryloyloxy hydroxyethyl hydrazine and 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 the nuclear magnetic resonance hydrogen spectrogram of a compound N-rhodamine 6G lactam-N' -acryloxy hydroxyethyl hydrazine.
(2) FIG. 2 is a schematic diagram showing the color change of a mixed solution of N-rhodamine 6G lactam-N' -acryloyloxy hydroxyethyl hydrazine and metal ions under visible light.
(3) FIG. 3 is a graph showing the ultraviolet absorption spectrum of N-rhodamine 6G lactam-N' -acryloyloxy hydroxyethyl hydrazine on different metal ions (the abscissa is the absorption wavelength and the ordinate is the absorption intensity).
(4) FIG. 4 is a fluorescence spectrum of N-rhodamine 6G lactam-N' -acryloxy hydroxyethyl hydrazine on metal ion selectivity (the abscissa is emission wavelength, and the ordinate is fluorescence intensity).
(5) FIG. 5 is a schematic diagram of the color change and regeneration of mercury ions recognized by N-rhodamine 6G lactam-N' -acryloyloxy hydroxyethyl hydrazine polymer fluorescent probe.
The specific implementation mode is as follows:
in order to better understand the technical solution of the present invention, the following detailed description is given by specific examples.
Example 1
1) Weighing and dissolving rhodamine 6G 0.9580G (2mmol) in 20mL of hot ethanol, after complete dissolution, dropwise adding hydroxyethyl hydrazine 1.1415G (15mmol), after dropwise adding, refluxing and stirring the mixed solution for 8h until the fluorescence of the solution disappears, checking a dot plate to confirm complete reaction, cooling the reaction solution to room temperature, separating out a precipitate, filtering the precipitate, washing the precipitate with hot ethanol for three times, and recrystallizing the obtained crude product with acetonitrile to obtain a product N-rhodamine 6G lactam-N' -hydroxyethyl hydrazine 0.8473G with the yield of 89.7%;
2) weighing 0.4726G (1mmol) of N-rhodamine 6G lactam-N '-hydroxyethyl hydrazine, dissolving the 0.4726G into 40mL of dichloromethane, dropwise adding 0.2G (2mmol) of triethylamine into the solution, cooling the mixed solution, keeping the temperature stable when the mixed solution is cooled to-3 ℃, starting dropwise adding 0.12G (1.3mmol) of acryloyl chloride, after dropwise adding is finished, heating to room temperature, stirring at room temperature for 10 hours, confirming that the reaction is complete by using a dot plate, extracting, concentrating and performing column chromatography separation to obtain 0.4558G of a product compound, namely N-rhodamine 6G lactam-N' -acryloyloxy hydroxyethyl hydrazine, wherein the yield is 86.6%;
3) boiling distilled water to remove oxygen, sealing and cooling to room temperature for standby, dissolving 0.0073G N-rhodamine 6G lactam-N '-acryloxy hydroxyethyl hydrazine in 5.8mL DMSO, dissolving 5.1480G acrylamide in 6.0mL water, mixing the two solutions, continuously stirring for 30min until the two solutions are completely mixed, dissolving 0.0274, N' -methylene bisacrylamide in the mixed solution, then injecting 100 mu L tetramethyl ethylenediamine into the mixed solution, finally adding 0.0364G ammonium persulfate, stirring uniformly, transferring the solution into a glass mold, covering the glass mold for sealing after no bubbles are mixed, placing the mold in a constant temperature box at 50 ℃ for 5h, 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' -acryloxy hydroxyethyl hydrazine monomer, and then soaking in distilled water for 24h to remove the unreacted acrylamide monomer.
Example 2
1) Weighing and dissolving rhodamine 6G 0.9580G (2mmol) in 20mL of hot ethanol, after complete dissolution, dropwise adding hydroxyethyl hydrazine 1.1415G (15mmol), after dropwise adding, refluxing and stirring the mixed solution for 10h until the fluorescence of the solution disappears, checking a dot plate to confirm complete reaction, cooling the reaction solution to room temperature, separating out a precipitate, filtering the precipitate, washing with hot ethanol for three times (10 mL each time), recrystallizing the obtained crude product with acetonitrile to obtain a product N-rhodamine 6G lactam-N' -hydroxyethyl hydrazine 0.7453G, wherein the yield is 78.9%;
2) weighing 0.4726G (1mmol) of N-rhodamine 6G lactam-N '-hydroxyethyl hydrazine, dissolving the 0.4726G into 40mL of dichloromethane, dropwise adding 0.2G (2mmol) of triethylamine into the solution, cooling the mixed solution, keeping the temperature stable when the mixed solution is cooled to 0 ℃, starting dropwise adding 0.12G (1.3mmol) of acryloyl chloride, after dropwise adding is finished, heating to room temperature, stirring at room temperature for 12 hours, confirming that the reaction is complete by a dot plate, extracting, concentrating, and carrying out column chromatography separation to obtain 0.4032G of a product compound, namely N-rhodamine 6G lactam-N' -acryloyloxy hydroxyethyl hydrazine, wherein the yield is 76.6%;
3) boiling distilled water to remove oxygen, sealing and cooling to room temperature for standby, dissolving 0.0073G N-rhodamine 6G lactam-N '-acryloxy hydroxyethyl hydrazine in 5.8mL DMSO, dissolving 5.1480G acrylamide in 6.0mL water, mixing the two solutions, continuously stirring for 30min until the two solutions are completely mixed, dissolving 0.0274, N' -methylene bisacrylamide in the mixed solution, then injecting 100 mu L tetramethyl ethylenediamine into the mixed solution, finally adding 0.0364G ammonium persulfate, stirring uniformly, transferring the solution into a glass mold, covering the glass mold for sealing after no bubbles are mixed, placing the mold in a constant temperature box at 50 ℃ for 5h, 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' -acryloxy hydroxyethyl hydrazine monomer, and then soaking in distilled water for 24h to remove the unreacted acrylamide monomer.
Example 3
1) Weighing and dissolving rhodamine 6G 0.9580G (2mmol) in 20mL of hot ethanol, after complete dissolution, dropwise adding hydroxyethyl hydrazine 1.1415G (15mmol), after dropwise adding, refluxing and stirring the mixed solution for 10h until the fluorescence of the solution disappears, checking a dot plate to confirm complete reaction, cooling the reaction solution to room temperature, separating out a precipitate, filtering the precipitate, washing with hot ethanol for three times (10 mL each time), recrystallizing the obtained crude product with acetonitrile to obtain a product N-rhodamine 6G lactam-N' -hydroxyethyl hydrazine 0.7755G, wherein the yield is 82.1%;
2) weighing 0.4726G (1mmol) of N-rhodamine 6G lactam-N '-hydroxyethyl hydrazine, dissolving the 0.4726G into 40mL of dichloromethane, dropwise adding 0.2G (2mmol) of triethylamine into the solution, cooling the mixed solution, keeping the temperature stable when the mixed solution is cooled to 0 ℃, starting dropwise adding 0.12G (1.3mmol) of acryloyl chloride, after dropwise adding is finished, heating to room temperature, stirring at room temperature for 12 hours, confirming that the reaction is complete by a dot plate, extracting, concentrating, and carrying out column chromatography separation to obtain 0.4390G of a product compound N-rhodamine 6G lactam-N' -acryloyloxy hydroxyethyl hydrazine, wherein the yield is 83.4%;
3) boiling distilled water to remove oxygen, sealing and cooling to room temperature for standby, dissolving 0.0073G N-rhodamine 6G lactam-N '-acryloxy hydroxyethyl hydrazine in 5.8mL DMSO, dissolving 5.1480G acrylamide in 6.0mL water, mixing the two solutions, continuously stirring for 30min until the two solutions are completely mixed, dissolving 0.0274, N' -methylene bisacrylamide in the mixed solution, then injecting 100 mu L tetramethyl ethylenediamine into the mixed solution, finally adding 0.0364G ammonium persulfate, stirring uniformly, transferring the solution into a glass mold, covering the glass mold for sealing after no bubbles are mixed, placing the mold in a constant temperature box at 50 ℃ for 5h, 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' -acryloxy hydroxyethyl hydrazine monomer, and then soaking in distilled water for 24h to remove the unreacted acrylamide monomer.
Example 4
1) Weighing and dissolving rhodamine 6G 0.9580G (2mmol) in 20mL of hot ethanol, after complete dissolution, dropwise adding hydroxyethyl hydrazine 1.1415G (15mmol), after dropwise adding, refluxing and stirring the mixed solution for 10h until the fluorescence of the solution disappears, checking a dot plate to confirm complete reaction, cooling the reaction solution to room temperature, separating out a precipitate, filtering the precipitate, washing with hot ethanol for three times (10 mL each time), recrystallizing the obtained crude product with acetonitrile to obtain a product N-rhodamine 6G lactam-N' -hydroxyethyl hydrazine 0.7547G, wherein the yield is 79.9%;
2) weighing 0.4726G (1mmol) of N-rhodamine 6G lactam-N '-hydroxyethyl hydrazine, dissolving the 0.4726G into 40mL of dichloromethane, dropwise adding 0.2G (2mmol) of triethylamine into the solution, cooling the mixed solution, keeping the temperature stable when the mixed solution is cooled to 0 ℃, starting dropwise adding 0.12G (1.3mmol) of acryloyl chloride, after dropwise adding is finished, heating to room temperature, stirring at room temperature for 12 hours, confirming that the reaction is complete by a dot plate, extracting, concentrating, and carrying out column chromatography separation to obtain 0.4259G of a product compound, namely N-rhodamine 6G lactam-N' -acryloyloxy hydroxyethyl hydrazine, wherein the yield is 80.9%;
3) boiling distilled water to remove oxygen, sealing and cooling to room temperature for standby, dissolving 0.0073G N-rhodamine 6G lactam-N '-acryloxy hydroxyethyl hydrazine in 5.8mL DMSO, dissolving 5.1480G acrylamide in 6.0mL water, mixing the two solutions, continuously stirring for 30min until the two solutions are completely mixed, dissolving 0.0274, N' -methylene bisacrylamide in the mixed solution, then injecting 100 mu L tetramethyl ethylenediamine into the mixed solution, finally adding 0.0364G ammonium persulfate, stirring uniformly, transferring the solution into a glass mold, covering the glass mold for sealing after no bubbles are mixed, placing the mold in a constant temperature box at 50 ℃ for 5h, 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' -acryloxy hydroxyethyl hydrazine monomer, and then soaking in distilled water for 24h to remove the unreacted acrylamide monomer.
Example 5
1) Weighing and dissolving rhodamine 6G 0.9580G (2mmol) in 20mL of hot ethanol, after complete dissolution, dropwise adding hydroxyethyl hydrazine 1.1415G (15mmol), after dropwise adding, refluxing and stirring the mixed solution for 8h until the fluorescence of the solution disappears, checking a dot plate to confirm complete reaction, cooling the reaction solution to room temperature, separating out a precipitate, filtering the precipitate, washing the precipitate with hot ethanol for three times, and recrystallizing the obtained crude product with acetonitrile to obtain a product N-rhodamine 6G lactam-N' -hydroxyethyl hydrazine 0.8473G with the yield of 89.7%;
2) weighing 0.4726G (1mmol) of N-rhodamine 6G lactam-N '-hydroxyethyl hydrazine, dissolving the 0.4726G into 40mL of dichloromethane, dropwise adding 0.2G (2mmol) of triethylamine into the solution, cooling the mixed solution, keeping the temperature stable when the mixed solution is cooled to-3 ℃, starting dropwise adding 0.12G (1.3mmol) of acryloyl chloride, after dropwise adding is finished, heating to room temperature, stirring at room temperature for 10 hours, confirming that the reaction is complete by using a dot plate, extracting, concentrating and performing column chromatography separation to obtain 0.4558G of a product compound, namely N-rhodamine 6G lactam-N' -acryloyloxy hydroxyethyl hydrazine, wherein the yield is 86.6%;
3) boiling distilled water to remove oxygen, sealing and cooling to room temperature for standby, dissolving 0.0412G N-rhodamine 6G lactam-N '-acryloxy hydroxyethyl hydrazine in 26.8mL DMSO, dissolving 5.0470G acrylamide in 6.0mL water, mixing the two solutions, continuously stirring for 30min until the two solutions are completely mixed, dissolving 0.0309G N, N' -methylene bisacrylamide in the mixed solution, then injecting 200 mu L tetramethyl ethylenediamine into the mixed solution, finally adding 0.0361G ammonium persulfate, stirring uniformly, transferring the solution into a glass mold, covering the glass mold for sealing after no bubbles are mixed, placing the mold in a thermostat at 55 ℃ for 5h, 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' -acryloxy hydroxyethyl hydrazine monomer, and then soaking in distilled water for 24h to remove the unreacted acrylamide monomer.
Example 6
1) Weighing and dissolving rhodamine 6G 0.9580G (2mmol) in 20mL of hot ethanol, after complete dissolution, dropwise adding hydroxyethyl hydrazine 1.1415G (15mmol), after dropwise adding, refluxing and stirring the mixed solution for 8h until the fluorescence of the solution disappears, checking a dot plate to confirm complete reaction, cooling the reaction solution to room temperature, separating out a precipitate, filtering the precipitate, washing the precipitate with hot ethanol for three times, and recrystallizing the obtained crude product with acetonitrile to obtain a product N-rhodamine 6G lactam-N' -hydroxyethyl hydrazine 0.8473G with the yield of 89.7%;
2) weighing 0.4726G (1mmol) of N-rhodamine 6G lactam-N '-hydroxyethyl hydrazine, dissolving the 0.4726G into 40mL of dichloromethane, dropwise adding 0.2G (2mmol) of triethylamine into the solution, cooling the mixed solution, keeping the temperature stable when the mixed solution is cooled to-3 ℃, starting dropwise adding 0.12G (1.3mmol) of acryloyl chloride, after dropwise adding is finished, heating to room temperature, stirring at room temperature for 10 hours, confirming that the reaction is complete by using a dot plate, extracting, concentrating and performing column chromatography separation to obtain 0.4558G of a product compound, namely N-rhodamine 6G lactam-N' -acryloyloxy hydroxyethyl hydrazine, wherein the yield is 86.6%;
3) boiling distilled water to remove oxygen, sealing and cooling to room temperature for standby, taking 0.0859G N-rhodamine 6G lactam-N '-acryloxy hydroxyethyl hydrazine to dissolve in 42.9mL DMSO, taking 4.8985G acrylamide to dissolve in 5.4mL water, mixing the two solutions, continuously stirring for 30min until the mixing is complete, dissolving 0.0253G N, N' -methylene bisacrylamide in the mixed solution, then injecting 150 muL tetramethyl ethylene diamine into the mixed solution, finally adding 0.0303G ammonium persulfate, stirring uniformly, transferring the solution into a glass mold, covering the glass mold for sealing after ensuring that no air bubbles are mixed, placing the mold in a thermostat at 50 ℃ for 4.5h for free radical polymerization, taking out and cooling 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' -acryloxy hydroxyethyl hydrazine monomer, and then soaking in distilled water for 24h to remove the unreacted acrylamide monomer.
Example 7
1) Weighing and dissolving rhodamine 6G 0.9580G (2mmol) in 20mL of hot ethanol, after complete dissolution, dropwise adding hydroxyethyl hydrazine 1.1415G (15mmol), after dropwise adding, refluxing and stirring the mixed solution for 8h until the fluorescence of the solution disappears, checking a dot plate to confirm complete reaction, cooling the reaction solution to room temperature, separating out a precipitate, filtering the precipitate, washing the precipitate with hot ethanol for three times, and recrystallizing the obtained crude product with acetonitrile to obtain a product N-rhodamine 6G lactam-N' -hydroxyethyl hydrazine 0.8473G with the yield of 89.7%;
2) weighing 0.4726G (1mmol) of N-rhodamine 6G lactam-N '-hydroxyethyl hydrazine, dissolving the 0.4726G into 40mL of dichloromethane, dropwise adding 0.2G (2mmol) of triethylamine into the solution, cooling the mixed solution, keeping the temperature stable when the mixed solution is cooled to-3 ℃, starting dropwise adding 0.12G (1.3mmol) of acryloyl chloride, after dropwise adding is finished, heating to room temperature, stirring at room temperature for 10 hours, confirming that the reaction is complete by using a dot plate, extracting, concentrating and performing column chromatography separation to obtain 0.4558G of a product compound, namely N-rhodamine 6G lactam-N' -acryloyloxy hydroxyethyl hydrazine, wherein the yield is 86.6%;
3) boiling distilled water to remove oxygen, sealing and cooling to room temperature for standby, dissolving 0.1733G N-rhodamine 6G lactam-N '-acryloxy hydroxyethyl hydrazine in 60.4mL DMSO, dissolving 4.7025G acrylamide in 5.2mL water, mixing the two solutions, continuously stirring for 30min until the mixture is complete, dissolving 0.0248G N, N' -methylene bisacrylamide in the mixed solution, injecting 150 mu L tetramethyl ethylenediamine into the mixed solution, finally adding 0.0297G ammonium persulfate, stirring uniformly, transferring the solution into a glass mold, sealing by covering a glass cover after ensuring that no air bubbles are mixed, placing the mold in a thermostat at 54 ℃ for 4h, 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' -acryloxy hydroxyethyl hydrazine monomer, and then soaking in distilled water for 24h to remove the unreacted acrylamide monomer.
Example 8
1) Weighing and dissolving rhodamine 6G 0.9580G (2mmol) in 20mL of hot ethanol, after complete dissolution, dropwise adding hydroxyethyl hydrazine 1.1415G (15mmol), after dropwise adding, refluxing and stirring the mixed solution for 8h until the fluorescence of the solution disappears, checking a dot plate to confirm complete reaction, cooling the reaction solution to room temperature, separating out a precipitate, filtering the precipitate, washing the precipitate with hot ethanol for three times, and recrystallizing the obtained crude product with acetonitrile to obtain a product N-rhodamine 6G lactam-N' -hydroxyethyl hydrazine 0.8473G with the yield of 89.7%;
2) weighing 0.4726G (1mmol) of N-rhodamine 6G lactam-N '-hydroxyethyl hydrazine, dissolving the 0.4726G into 40mL of dichloromethane, dropwise adding 0.2G (2mmol) of triethylamine into the solution, cooling the mixed solution, keeping the temperature stable when the mixed solution is cooled to-3 ℃, starting dropwise adding 0.12G (1.3mmol) of acryloyl chloride, after dropwise adding is finished, heating to room temperature, stirring at room temperature for 10 hours, confirming that the reaction is complete by using a dot plate, extracting, concentrating and performing column chromatography separation to obtain 0.4558G of a product compound, namely N-rhodamine 6G lactam-N' -acryloyloxy hydroxyethyl hydrazine, wherein the yield is 86.6%;
3) boiling distilled water to remove oxygen, sealing and cooling to room temperature for standby, dissolving 0.2571G N-rhodamine 6G lactam-N '-acryloxy hydroxyethyl hydrazine in 51.4mL DMSO, dissolving 4.5105G acrylamide in 5.0mL water, mixing the two solutions, continuously stirring for 30min until the mixture is complete, dissolving 0.0243G N, N' -methylene bisacrylamide in the mixed solution, injecting 150 mu L tetramethyl ethylenediamine into the mixed solution, finally adding 0.0291G ammonium persulfate, stirring uniformly, transferring the solution into a glass mold, sealing the glass cover after ensuring that no air bubbles are mixed, placing the mold in a constant temperature box at 53 ℃ for 3h for free radical polymerization, taking out the mold, 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' -acryloxy hydroxyethyl hydrazine monomer, and then soaking in distilled water for 24h to remove the unreacted acrylamide monomer.
Example 9
1) Weighing and dissolving rhodamine 6G 0.9580G (2mmol) in 20mL of hot ethanol, after complete dissolution, dropwise adding hydroxyethyl hydrazine 1.1415G (15mmol), after dropwise adding, refluxing and stirring the mixed solution for 8h until the fluorescence of the solution disappears, checking a dot plate to confirm complete reaction, cooling the reaction solution to room temperature, separating out a precipitate, filtering the precipitate, washing the precipitate with hot ethanol for three times, and recrystallizing the obtained crude product with acetonitrile to obtain a product N-rhodamine 6G lactam-N' -hydroxyethyl hydrazine 0.8473G with the yield of 89.7%;
2) weighing 0.4726G (1mmol) of N-rhodamine 6G lactam-N '-hydroxyethyl hydrazine, dissolving the 0.4726G into 40mL of dichloromethane, dropwise adding 0.2G (2mmol) of triethylamine into the solution, cooling the mixed solution, keeping the temperature stable when the mixed solution is cooled to-3 ℃, starting dropwise adding 0.12G (1.3mmol) of acryloyl chloride, after dropwise adding is finished, heating to room temperature, stirring at room temperature for 10 hours, confirming that the reaction is complete by using a dot plate, extracting, concentrating and performing column chromatography separation to obtain 0.4558G of a product compound, namely N-rhodamine 6G lactam-N' -acryloyloxy hydroxyethyl hydrazine, wherein the yield is 86.6%;
3) boiling distilled water to remove oxygen, sealing and cooling to room temperature for standby, dissolving 0.3420G N-rhodamine 6G lactam-N '-acryloxy hydroxyethyl hydrazine in 17.1mL DMSO, dissolving 4.3225G acrylamide in 4.3mL water, mixing the two solutions, continuously stirring for 30min until the two solutions are completely mixed, dissolving 0.0190G N and N' -methylene bisacrylamide in the mixed solution, then injecting 200 mu L tetramethyl ethylenediamine into the mixed solution, finally adding 0.0238G ammonium persulfate, stirring uniformly, transferring the solution into a glass mold, covering the glass mold for sealing after no bubbles are mixed, placing the mold in a thermostat at 52 ℃ for 3.5h for free radical polymerization, taking out the mold, cooling and stabilizing for 24h, opening the glass cover, slowly taking out the formed hydrogel, soaking the hydrogel in dimethyl sulfoxide solution for 24h, removing unreacted N-rhodamine 6G lactam-N' -acryloxy hydroxyethyl hydrazine monomer, and then soaking in distilled water for 24h to remove the unreacted acrylamide monomer.
Example 10
1) Weighing and dissolving rhodamine 6G 0.9580G (2mmol) in 20mL of hot ethanol, after complete dissolution, dropwise adding hydroxyethyl hydrazine 1.1415G (15mmol), after dropwise adding, refluxing and stirring the mixed solution for 8h until the fluorescence of the solution disappears, checking a dot plate to confirm complete reaction, cooling the reaction solution to room temperature, separating out a precipitate, filtering the precipitate, washing the precipitate with hot ethanol for three times, and recrystallizing the obtained crude product with acetonitrile to obtain a product N-rhodamine 6G lactam-N' -hydroxyethyl hydrazine 0.8473G with the yield of 89.7%;
2) weighing 0.4726G (1mmol) of N-rhodamine 6G lactam-N '-hydroxyethyl hydrazine, dissolving the 0.4726G into 40mL of dichloromethane, dropwise adding 0.2G (2mmol) of triethylamine into the solution, cooling the mixed solution, keeping the temperature stable when the mixed solution is cooled to-3 ℃, starting dropwise adding 0.12G (1.3mmol) of acryloyl chloride, after dropwise adding is finished, heating to room temperature, stirring at room temperature for 10 hours, confirming that the reaction is complete by using a dot plate, extracting, concentrating and performing column chromatography separation to obtain 0.4558G of a product compound, namely N-rhodamine 6G lactam-N' -acryloyloxy hydroxyethyl hydrazine, wherein the yield is 86.6%;
3) boiling distilled water to remove oxygen, sealing and cooling to room temperature for standby, dissolving 0.4185G N-rhodamine 6G lactam-N '-acryloxy hydroxyethyl hydrazine in 10.5mL DMSO, dissolving 4.1385G acrylamide in 4.1mL water, mixing the two solutions, continuously stirring for 30min until the mixture is complete, dissolving 0.0186G N, N' -methylene bisacrylamide in the mixed solution, then injecting 100 mu L tetramethyl ethylenediamine into the mixed solution, finally adding 0.0233G ammonium persulfate, stirring uniformly, transferring the solution into a glass mold, sealing by covering a glass cover after no bubbles are mixed, placing the mold in a thermostat at 51 ℃ for 4.5h, 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' -acryloxy hydroxyethyl hydrazine monomer, and then soaking in distilled water for 24h to remove the unreacted acrylamide monomer.
N-rhodamine 6G lactam-N' -acryloxy hydroxyethyl hydrazine elemental analysis: c31H34N4O4: % C: 73.27 (73.26); % H: 6.93 (6.92); % N: 9.16 (9.15); % O: 10.64(10.67) (measurement in brackets).
Nuclear magnetic analysis (nuclear magnetic spectrum shown in figure 1) of the final product N-rhodamine 6G lactam-N' -acryloyloxy hydroxyethyl hydrazine:1h NMR (400MHz, DMSO) δ 7.65(d, J ═ 6.6Hz,1H),7.42 to 7.35(m,2H),6.86(d, J ═ 6.7Hz,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 ═ 5.7Hz,2H),3.0 to 2.97(m,4H),2.62(d, J ═ 5.8Hz,2H),1.72(s,6H),1.07(t, J ═ 7.1Hz, 6H). One of the compounds has 34 hydrogens, with peaks at 4.87ppm and 4.94ppm for the signal of hydrogen on the C ═ C double bond, at 7.40ppm for the signal of secondary amine (-NH), at 3.65ppm, 3.00ppm, 2.63ppm for the signal of methylene hydrogen, at 1.72ppm and 1.07ppm for methyl hydrogen, and at 7.65ppm, 6.87ppm, 6.11ppm, 5.96ppm and 5.77ppm for the signal of hydrogen on the benzene ring. Through the comparison analysis of the hydrogen and the chemical shift and peak area of the hydrogen, the structure of the compound is consistent with the information on a spectrogram, so that the compound N-rhodamine 6G lactam-N' -acryloxy hydroxyethyl hydrazine can be successfully synthesized.
The invention relates to a fluorescent probe and application of polymer hydrogel thereof
Experimental example 1
Taking N-rhodamine 6G lactam-N' -acryloxy hydroxyethyl hydrazine as a fluorescent probe monomer prepared in example 1, dissolving in dimethyl sulfoxide: distilled water 1:1 to obtain a mixed solution of 1X 10-3mol/L stock solution, 1mL of the stock solution was taken out of the stock solution and put into a 100mL measuring flask, and 1mL of an aluminum ion standard solution (1X 10)-3mol/L) with dimethyl sulfoxide: distilled water 1:1 to obtain the mixed solution with the volume of 1.0 multiplied by 10-51:1 mixed solution of mol/L compound and metal ions, 1.0X 10-5The color change of the mixed solution of the mol/L compound and the metal ions can be observed under visible light, as shown in figure 2, which shows that the compound N-rhodamine 6G lactam-N' -acryloyloxy hydroxyethyl hydrazine can visually detect Hg2+。
Experimental example 2
Taking N-rhodamine 6G lactam-N' -acryloxy hydroxyethyl hydrazine as a fluorescent probe monomer prepared in example 1, dissolving in dimethyl sulfoxide: distilled water 1:1 to obtain a mixed solution of 1X 10-3mol/L stock solution, 1mL of the stock solution was taken out of the stock solution and put into a 100mL measuring flask, and 1mL of an aluminum ion standard solution (1X 10)-3mol/L) with dimethyl sulfoxide: distilled water 1:1 to obtain the mixed solution with the volume of 1.0 multiplied by 10-5The compound and metal ion solution are tested for ultraviolet absorption spectrum (see figure 3) when mol/L compound and metal ion 1:1 mixed solution is added into the solution, and we find that when equivalent Mg is added into the solution2+，Cu2+，Co2+，Cr2+，Al3+，Ni2+，Zn2+And Cd2+Then, the fluorescence spectrum has no obvious change, and only Hg is added2+And then, the ultraviolet spectrum is enhanced to a certain degree, 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' -acryloxy hydroxyethyl hydrazine, and reacting the monomer with dimethyl sulfoxide: distilled water 1:1 mixed solutionDissolving and diluting the solution to 1.0 × 10-5measuring the ultraviolet absorption spectrogram of a sample by using an ultraviolet-visible spectrophotometer, measuring the fluorescence excitation wavelength of a compound by using an F-4600 fluorescence spectrophotometer according to the maximum ultraviolet absorption wavelength of the measured compound, measuring the fluorescence emission spectrum of the compound, and then respectively adding equivalent different metal ions Al into the solution3+，Ag+，Co2+，Mg2+，Cu2+，Ni2+，Pb2+And Zn2 +Measuring the fluorescence emission spectrum of the fluorescent probe molecule in the presence of each metal ion (see the result in figure 4);
we have found that the fluorescence intensity of the compound itself is so weak that it is difficult to observe it in the figure when no metal ion is added, but when an equivalent amount of Mg is added to the solution2+，Cu2+，Co2+，Cr2+，Al3+，Ni2+，Zn2+And Cd2 +Then, the fluorescence spectra are enhanced to some extent, and only when Hg is added2+And then, the fluorescence spectrum generates very remarkable enhancement, the characteristic has important significance for rapidly identifying metal aluminum ions, and the synthesized fluorescent probe has better selectivity on mercury ions (II).
Experimental example 4
The acrylamide hydrogel can not be used as a visual sensor to detect any metal ions through tests, but when N-rhodamine 6G lactam-N' -acryloxy hydroxyethyl hydrazine is copolymerized with acrylamide as a monomer to form the hydrogel, the hydrogel has the function of detecting Hg2+The hydrogel was passed through Hg as shown in FIG. 5(a)2+Soaking the solution to obtain pink color, soaking the hydrogel with EDA solution of 1mol/L to recover the original color, as shown in figure 5(b), under 365nm ultraviolet irradiation, performing corresponding color change and regeneration process, passing through Hg2+The hydrogel soaked in the solution turns yellow under an ultraviolet lamp, and then can recover the original color after being soaked in 1mol/L EDA aqueous solution.

Claims (4)

1. A fluorescent probe polymer hydrogel characterized by: the hydrogel is prepared by copolymerizing N-rhodamine 6G lactam-N' -acryloxy hydroxyethyl hydrazine fluorescent probe monomer and acrylamide, and is applied to the field of materials or sensors, and the specific structure and the preparation method are as follows:
Figure 140072DEST_PATH_IMAGE001
1) preparation of N-rhodamine 6G lactam-N' -hydroxyethyl hydrazine:
weighing rhodamine 6G in a three-necked bottle, adding absolute ethyl alcohol, refluxing and stirring the three-necked bottle for 30min, then dropwise adding hydroxyethyl hydrazine into the solution, after dropwise adding, continuously refluxing and reacting the mixed solution 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' -hydroxyethyl hydrazine;
2) preparation of N-rhodamine 6G lactam-N' -acryloxy hydroxyethyl hydrazine:
weighing triethylamine and the N-rhodamine 6G lactam-N '-hydroxyethyl hydrazine obtained in the step 1) into a three-necked bottle, adding dichloromethane, weighing acryloyl chloride, dropwise adding into the three-necked bottle, performing the dropwise adding process at a constant temperature of-5-0 ℃, heating to room temperature after the dropwise adding is completed, stirring at room temperature for 6-12 h, extracting, drying to remove water, distilling under reduced pressure to remove a solvent, performing column chromatography separation to obtain a pink powdery solid, and performing vacuum drying to obtain the N-rhodamine 6G lactam-N' -acryloyloxy hydroxyethyl hydrazine;
3) preparation of N-rhodamine 6G lactam-N' -acryloxy hydroxyethyl hydrazine polymer hydrogel:
boiling distilled water, sealing and cooling to room temperature to remove oxygen in the water, weighing acrylamide and dissolving the N-rhodamine 6G lactam-N '-acryloyloxy hydroxyethyl hydrazine obtained in the step 2) in distilled water, weighing the N-rhodamine 6G lactam-N' -acryloyloxy hydroxyethyl hydrazine obtained in the step 2) and dissolving the N-rhodamine 6G lactam-N '-acryloyloxy hydroxyethyl hydrazine in dimethyl sulfoxide, mixing the two solutions, vacuumizing and stirring at room temperature, continuously stirring for 30min until the two solutions are completely mixed, sequentially adding a crosslinking agent N, N' -methylene bisacrylamide, a catalyst tetramethyl ethylenediamine and an initiator ammonium persulfate into the mixed solution, stirring uniformly, transferring the solution into a glass mold, covering a glass cover for sealing after ensuring that no bubbles are mixed, placing the hydrogel mold in a thermostat at 50-55 ℃ for 3-5 h for carrying out free radical polymerization reaction, taking out, cooling and stabilizing for 24h, opening the glass cover, and slowly taking out the, soaking in dimethyl sulfoxide solution for 24h to remove unreacted N-rhodamine 6G lactam-N' -acryloxy hydroxyethyl hydrazine monomer, and then soaking in distilled water for 24h to remove unreacted acrylamide monomer;
the mass percentages of the acrylamide, the N-rhodamine 6G lactam-N' -acryloxy hydroxyethyl hydrazine, the cross-linking agent and the initiator in the step 3) in the total solid components are respectively 89-99%, 0.14-9%, 0.4-0.6% and 0.5-0.7%.
2. The fluorescent probe polymer hydrogel of claim 1, wherein: the molar ratio of rhodamine 6G to hydroxyethyl hydrazine in the step 1) is 2: 13-2: 16; the volume mol ratio of the absolute ethyl alcohol to the rhodamine 6G in the step 1) is 20 ml: 1 to 4 mmol.
3. The fluorescent probe polymer hydrogel of claim 1, wherein: the molar ratio of the N-rhodamine 6G lactam-N' -hydroxyethyl hydrazine to triethylamine in the step 2) is 1: 1-1: 4; the molar ratio of the N-rhodamine 6G lactam-N' -hydroxyethyl hydrazine to the acryloyl chloride is 1: 1-1: 1.5; the volume mol ratio of the dichloromethane to the N-rhodamine 6G lactam-N' -hydroxyethyl hydrazine is 40 ml: 1 to 3 mmol.
4. The fluorescent probe polymer hydrogel of claim 1, wherein: the mass volume ratio of the acrylamide to the distilled water is 1 g: 1-1.2 ml; the mass volume ratio of the N-rhodamine 6G lactam-N' -acryloyloxy hydroxyethyl hydrazine to the dimethyl sulfoxide is 0.001G: 0.02-0.8 ml; the volume mass ratio of the catalyst to the initiator is 100 mu l: 0.02-0.04 g.
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CN110483682B (en) * 2019-08-28 2021-03-16 济南大学 Polymer fluorescent probe for detecting viscosity and preparation method and application thereof
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102295726A (en) * 2011-05-23 2011-12-28 中国药科大学 Inorganic fluorescent quantum dot-rhodamine composite block thermo sensitive hydrogel
WO2012080218A1 (en) * 2010-12-17 2012-06-21 Eyesense Ag Competitive biosensor having elevated sensitivity
CN103242328A (en) * 2013-04-11 2013-08-14 天津师范大学 p-N-methyl acetamidophenyl rhodamine 6G pH fluorescence molecular probe as well as preparation method and use thereof
CN104341347A (en) * 2014-10-21 2015-02-11 苏州福来兹检测科技有限公司 Organic compound for preparing wide pH fluorescence probes and application thereof
CN104804115A (en) * 2015-04-21 2015-07-29 天津大学 High-strength supramolecular hydrogel and preparation method and application thereof
CN104910392A (en) * 2015-06-03 2015-09-16 西安交通大学 Dual-network poly(N-acryloyl-L-alpha-amino acid)/hyaluronic acid composite hydrogel and preparation method thereof
CN106978163A (en) * 2017-03-24 2017-07-25 河南省农业科学院农业质量标准与检测技术研究所 A kind of Cu of the red sulphonyl structure containing rhodamine2+Fluorescence probe and its preparation method and application

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012080218A1 (en) * 2010-12-17 2012-06-21 Eyesense Ag Competitive biosensor having elevated sensitivity
CN102295726A (en) * 2011-05-23 2011-12-28 中国药科大学 Inorganic fluorescent quantum dot-rhodamine composite block thermo sensitive hydrogel
CN103242328A (en) * 2013-04-11 2013-08-14 天津师范大学 p-N-methyl acetamidophenyl rhodamine 6G pH fluorescence molecular probe as well as preparation method and use thereof
CN104341347A (en) * 2014-10-21 2015-02-11 苏州福来兹检测科技有限公司 Organic compound for preparing wide pH fluorescence probes and application thereof
CN104804115A (en) * 2015-04-21 2015-07-29 天津大学 High-strength supramolecular hydrogel and preparation method and application thereof
CN104910392A (en) * 2015-06-03 2015-09-16 西安交通大学 Dual-network poly(N-acryloyl-L-alpha-amino acid)/hyaluronic acid composite hydrogel and preparation method thereof
CN106978163A (en) * 2017-03-24 2017-07-25 河南省农业科学院农业质量标准与检测技术研究所 A kind of Cu of the red sulphonyl structure containing rhodamine2+Fluorescence probe and its preparation method and application

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"Rhodamine based reusable and colorimetric naked-eye hydrogel sensors for Fe3+ ion";Hava Ozay等;《Chemical Engineering Journal》;20130809;第232卷;364-371 *

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