CN112708015B - Rhodamine 6G derivative-based fluorescence sensor and preparation method thereof - Google Patents
Rhodamine 6G derivative-based fluorescence sensor and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a fluorescence sensor based on rhodamine 6G derivatives and a preparation method thereof. Rhodamine 6G is used as a fluorescent group and reacts with 2-thiophene ethylamine to prepare the rhodamine 6G derivative fluorescent probe R6GS. The Hg in the Hg is prepared by taking R6GS as a sensing and identifying functional monomer and using acrylamide and methyl methacrylate in a free radical copolymerization way 2+ A supramolecular hydrogel sensor with responsiveness. The preparation method of the hydrogel sensor material has potential application value in the aspects of establishing monitoring detection modules and systems, including a running water environment detection system, a still water environment detection system and the like.
Description
Technical Field
The application belongs to the field of fluorescent sensors, and particularly relates to a rhodamine 6G derivative-based fluorescent sensor and a preparation method thereof.
Background
Macroscopic supramolecular polymer hydrogels are good matrices for the recognition of sensing materials. Compared with polysaccharide and protein in natural hydrogel, chemical hydrogel is easy to functionalize in the synthesis process, so that the chemical hydrogel is widely researched. Most hydrogels are low in optical background and have certain physical strength, simple synthesis steps, and easy separation from the detection environment. The hydrogel sensor capable of identifying specific heavy metal ions can detect in a microenvironment polluted by heavy metals, and the research of the hydrogel sensor has wide application prospect.
In order to overcome the defects of limited monitoring, detection conditions, human errors and the like of the traditional detection method, the micromolecule functional monomer with the identification sensing performance is fixed on the macroscopic supermolecule hydrogel material matrix, so that the detection operation is more convenient. Therefore, it is very meaningful to design and synthesize a hydrogel sensor having excellent identification sensing performance. Hydrogel sensors are expected to be widely applied and developed in the fields of luminescent patterns, underwater fluorescent devices, sensors, bioengineering and the like.
Based on the situation, the application provides the supramolecular hydrogel sensor with the rhodamine 6G derivative as the fluorescent group.
The invention content is as follows:
in order to solve the defects in the prior art, the application provides a rhodamine 6G derivativeThe supramolecular hydrogel is a sensor of a fluorescent probe carrier and is a fluorescent sensing identification group. The fluorescence sensor is used for Hg 2+ Has good identification performance. The invention aims to provide a synthesis idea and a preparation method of a supramolecular hydrogel sensor aiming at the defects of difficult separation of the existing small-molecule fluorescent probe from the detection environment and continuous monitoring and detection application, and the hydrogel sensor prepared by the method has excellent Hg 2+ Sensing performance is identified.
The invention also aims to provide a preparation method of the R6GS.
The invention also aims to provide a preparation method of the free radical polymerization supramolecular hydrogel sensor.
In order to achieve the above object, the technical means adopted by the present application are as follows:
a fluorescence sensor based on rhodamine 6G derivatives is prepared by taking rhodamine 6G derivative fluorescence probes R6GS as functional recognition monomers and combining the fluorescence probes on supramolecular hydrogel through free radical copolymerization.
The method for preparing the rhodamine 6G derivative-based fluorescence sensor specifically comprises the following steps:
1) Rhodamine 6G and 2-thiophene ethylamine are used as raw materials to obtain a recognition functional monomer R6GS;
2) Acrylamide (AAm), methyl Methacrylate (MMA) and N, N' -Methylene Bisacrylamide (MBA) are used as main raw materials and are subjected to free radical copolymerization with R6GS to obtain the supramolecular hydrogel sensor.
The preparation method of the recognition functional monomer R6GS in the step 1) comprises the following specific steps:
dissolving rhodamine 6G and 2-thiophene ethylamine in ethanol, and heating and refluxing for 6 hours; performing reduced pressure rotary evaporation to remove the solvent, and performing column chromatography purification on the obtained crude product to obtain a fluorescent probe molecule R6GS;
the equivalent ratio of the rhodamine 6G to the 2-thiophene ethylamine is 1.05;
the eluent for column chromatography purification is dichloromethane/ethanol 35/1, v/v;
the preparation method of the supramolecular hydrogel sensor in the step 2) is as follows:
a, mixing acrylamide (AAm), methyl Methacrylate (MMA), R6GS and N, N' -Methylene Bisacrylamide (MBA) (2-6 percent relative to the total monomer amount) and adding the mixture into DMSO;
b, vacuumizing and stirring the mixed solution obtained in the step a at the temperature of between 10 and 15 ℃ until a uniform solution is formed; adding catalyst tetramethyl ethylenediamine (TEMED, 2-6 mu L/mL) and initiator ammonium persulfate (APS, 1.5-3.5% of total monomers) and uniformly dispersing, and keeping the temperature of 10-15 ℃ in the period to form uniform and stable transparent solution;
c, transferring the transparent solution obtained in the step b to a tetrafluoroethylene mold for sealing, and preserving the heat for 12 hours in an oven at the temperature of 35-45 ℃;
d, taking out the prepared hydrogel from the mold, dialyzing with DMSO for 12-36 hours to remove unreacted monomers, dialyzing with distilled water for 12-36 hours to remove DMSO and fully swelling the hydrogel sensor to obtain the supermolecule hydrogel sensor.
In the step a, the mass ratio of acrylamide (AAm), methyl Methacrylate (MMA) and R6GS is 10;
the rhodamine 6G derivative-based fluorescence sensor is applied to the aspect of fluorescence detection of heavy metal ions. Preferably, hg is detected 2+ Application of the aspect.
The reaction principle for preparing R6GS in the invention is as follows:
the reaction principle for preparing the supramolecular hydrogel sensor by a free radical polymerization mode is as follows:
one of the characteristics of the method is that a rhodamine 6G derivative fluorescent probe R6GS is selected as a functional identification monomer of the supramolecular hydrogel sensor, and R6GS and Hg 2+ After combination, the rhodamine 6G inner screw ring is opened, the Photoinduced Electron Transfer (PET) process is forbidden, and the fluorescence is obviously enhanced, so that the Hg is provided for preparing the supermolecule hydrogel sensor 2+ A response characteristic.
The second method is characterized in that a free radical copolymerization mode is selected, a rhodamine 6G derivative fluorescent probe R6GS, acrylamide (AAm) and Methyl Methacrylate (MMA) are mixed in proportion, N' -Methylene Bisacrylamide (MBA) is used as a cross-linking agent, polymerization is initiated through Ammonium Persulfate (APS) under the catalysis of Tetramethylethylenediamine (TEMED), and the supramolecular hydrogel sensor obtained after unreacted monomers are removed through dialysis is simple to use and cannot affect the detection environment in the using process.
Compared with the reported polymer fluorescent hydrogel, the fluorescent hydrogel prepared by the invention has the following outstanding advantages: fluorescent probe molecule R6GS designed based on rhodamine 6G shows excellent Hg 2+ The supramolecular hydrogel sensor prepared by free radical polymerization has obvious identification effect, can judge a detection result by naked eyes without auxiliary instrument and equipment, is easy to separate from an identification environment, and does not influence the detection environment. Due to the characteristics, the prepared supramolecular hydrogel sensor based on the rhodamine 6G derivative is expected to be widely applied and developed in the fields of luminous patterns, underwater fluorescent devices, sensors, biological engineering and the like.
R6GS written in the application is a mark number for identifying a functional monomer, and has no practical significance.
Description of the drawings:
FIG. 1 UV-visible spectrum of R6GS.
FIG. 2 fluorescence emission spectrum of R6GS.
FIG. 3 R6GS and R6GS-Hg 2+ In the infrared spectrum
FIG. 4 R6GS and R6GS-Hg 2+ Nuclear magnetic hydrogen spectrum diagram
FIG. 5 shows free radical copolymerization supramolecular hydrogel sensor and Hg under 365nm ultraviolet lamp 2+ Identification map
FIG. 6 shows free radical copolymerization supramolecular hydrogel sensor and Hg under visible light 2+ Recognition map
The specific implementation mode is as follows:
example 1
(1) Preparation of fluorescent Probe R6GS
0.4790G of rhodamine 6G (1.00 mmol) and 0.1336G of 2-thienylethylamine (1.05 mmol) were dissolved in 20ml of ethanol, and heated under reflux for 6 hours. The solvent was removed by rotary evaporation under reduced pressure, and the resulting residue was purified by column chromatography (eluent: dichloromethane/ethanol 35/1, v/v) to give the desired product R6GS as a white solid (0.3608 g, yield 77%).
(2) Preparation of supramolecular hydrogel sensor based on free radical polymerization
10.00g of acrylamide (AAm), 0.80g of Methyl Methacrylate (MMA), 0.01g of R6GS, and 0.22g of N, N' -Methylenebisacrylamide (MBA) were mixed and added to 30mL of DMSO. Vacuumizing and stirring the mixed solution at the temperature of between 10 and 15 ℃ to (-0.09 MPa to-0.10 MPa) until a uniform solution is formed; then adding 60 mu L of catalyst Tetramethylethylenediamine (TEMED) and 0.17g of initiator Ammonium Persulfate (APS) and uniformly dispersing, keeping the temperature for 10-15 ℃ for a period of time until a uniform and stable transparent solution is formed, pouring the mixed solution into a polytetrafluoroethylene mold for sealing, transferring the polytetrafluoroethylene mold to an oven, keeping the temperature for 12 hours to 45 ℃, taking out the prepared hydrogel sensor from the mold, firstly dialyzing the hydrogel sensor for 12-36 hours by using DMSO to remove unreacted and low molecular weight monomers, then dialyzing the hydrogel sensor for 12-36 hours by using distilled water to remove DMSO and fully swelling the hydrogel sensor.
Example 2
(1) Preparation of fluorescent Probe R6GS
The same as in example 1- (1).
(2) Preparation of supramolecular hydrogel sensor based on free radical polymerization
10.00g of acrylamide (AAm), 0.90g of Methyl Methacrylate (MMA), 0.02g of R6GS, and 0.33g of N, N' -Methylenebisacrylamide (MBA) were mixed and added to 30mL of DMSO. Vacuumizing and stirring the mixed solution at the temperature of between 10 and 15 ℃ to (-0.09 MPa to-0.10 MPa) till a uniform solution is formed; then adding 70 mu L of catalyst Tetramethylethylenediamine (TEMED) and 0.26g of initiator Ammonium Persulfate (APS) and uniformly dispersing, keeping the temperature for 10-15 ℃ until a uniform and stable transparent solution is formed, pouring the mixed solution into a polytetrafluoroethylene mold for sealing, transferring the polytetrafluoroethylene mold to an oven, keeping the temperature for 12 hours to 45 ℃, taking out the prepared hydrogel sensor from the mold, dialyzing by using DMSO for 12-36 hours to remove unreacted and low molecular weight monomers, dialyzing by using distilled water for 12-36 hours to remove DMSO, and fully swelling the hydrogel sensor.
Example 3
(1) Preparation of fluorescent Probe R6GS
The same as in example 1- (1).
(2) Preparation of supramolecular hydrogel sensor based on free radical polymerization
10.00g of acrylamide (AAm), 1.05g of Methyl Methacrylate (MMA), 0.025g of R6GS, and 0.45g of N, N' -Methylenebisacrylamide (MBA) were mixed and added to 30mL of DMSO. Vacuumizing and stirring the mixed solution at the temperature of between 10 and 15 ℃ to (-0.09 MPa to-0.10 MPa) till a uniform solution is formed; then adding 80 mu L of catalyst Tetramethylethylenediamine (TEMED) and 0.35g of initiator Ammonium Persulfate (APS) and uniformly dispersing, keeping the temperature for 10-15 ℃ until a uniform and stable transparent solution is formed, pouring the mixed solution into a polytetrafluoroethylene mold for sealing, transferring the polytetrafluoroethylene mold to an oven, keeping the temperature for 12 hours to 45 ℃, taking out the prepared hydrogel sensor from the mold, dialyzing by using DMSO for 12-36 hours to remove unreacted and low molecular weight monomers, dialyzing by using distilled water for 12-36 hours to remove DMSO, and fully swelling the hydrogel sensor.
Example 4
(1) Preparation of fluorescent Probe R6GS
The same as in example 1- (1).
(2) Preparation of supramolecular hydrogel sensor based on free radical polymerization
10.00g of acrylamide (AAm), 1.15g of Methyl Methacrylate (MMA), 0.03g of R6GS and 0.45g of N, N' -Methylenebisacrylamide (MBA) were mixed and added to 30mL of DMSO. Vacuumizing and stirring the mixed solution at the temperature of between 10 and 15 ℃ to (-0.09 MPa to-0.10 MPa) until a uniform solution is formed; then adding 80 mu L of catalyst Tetramethylethylenediamine (TEMED) and 0.35g of initiator Ammonium Persulfate (APS) and uniformly dispersing, keeping the temperature for 10-15 ℃ until a uniform and stable transparent solution is formed, pouring the mixed solution into a polytetrafluoroethylene mold for sealing, transferring the polytetrafluoroethylene mold to an oven, keeping the temperature for 12 hours to 45 ℃, taking out the prepared hydrogel sensor from the mold, dialyzing by using DMSO for 12-36 hours to remove unreacted and low molecular weight monomers, dialyzing by using distilled water for 12-36 hours to remove DMSO, and fully swelling the hydrogel sensor.
Example 5
(1) Preparation of fluorescent Probe R6GS
The same as in example 1- (1).
(2) Preparation of supramolecular hydrogel sensor based on free radical polymerization
10.00g of acrylamide (AAm), 1.20g of Methyl Methacrylate (MMA), 0.035g of R6GS, and 0.45g of N, N' -Methylenebisacrylamide (MBA) were mixed and added to 30mL of DMSO. Vacuumizing and stirring the mixed solution at the temperature of between 10 and 15 ℃ to (-0.09 MPa to-0.10 MPa) until a uniform solution is formed; then adding 80 mu L of catalyst Tetramethylethylenediamine (TEMED) and 0.35g of initiator Ammonium Persulfate (APS) and uniformly dispersing, keeping the temperature for 10-15 ℃ until a uniform and stable transparent solution is formed, pouring the mixed solution into a polytetrafluoroethylene mold for sealing, transferring the polytetrafluoroethylene mold to an oven, keeping the temperature for 12 hours to 45 ℃, taking out the prepared hydrogel sensor from the mold, dialyzing by using DMSO for 12-36 hours to remove unreacted and low molecular weight monomers, dialyzing by using distilled water for 12-36 hours to remove DMSO, and fully swelling the hydrogel sensor.
Example 6
(1) Preparation of fluorescent Probe R6GS
The same as in example 1- (1).
(2) Preparation of supramolecular hydrogel sensor based on free radical polymerization
10.00g of acrylamide (AAm), 1.35g of Methyl Methacrylate (MMA), 0.04g of R6GS, and 0.57g of N, N' -Methylenebisacrylamide (MBA) were mixed and added to 30mL of DMSO. Vacuumizing and stirring the mixed solution at the temperature of between 10 and 15 ℃ to (-0.09 MPa to-0.10 MPa) till a uniform solution is formed; then adding 90 mu L of catalyst Tetramethylethylenediamine (TEMED) and 0.44g of initiator Ammonium Persulfate (APS) and uniformly dispersing, keeping the temperature for 10-15 ℃ until a uniform and stable transparent solution is formed, pouring the mixed solution into a polytetrafluoroethylene mold for sealing, transferring the polytetrafluoroethylene mold to an oven, keeping the temperature for 12 hours to 45 ℃, taking out the prepared hydrogel sensor from the mold, dialyzing by using DMSO for 12-36 hours to remove unreacted and low molecular weight monomers, dialyzing by using distilled water for 12-36 hours to remove DMSO, and fully swelling the hydrogel sensor.
Example 7
(1) Preparation of fluorescent Probe R6GS
The same as in example 1- (1).
(2) Preparation of supramolecular hydrogel sensor based on free radical polymerization
10.00g of acrylamide (AAm), 1.50g of Methyl Methacrylate (MMA), 0.05g of R6GS, and 0.69g of N, N' -Methylenebisacrylamide (MBA) were mixed and added to 30mL of DMSO. Vacuumizing and stirring the mixed solution at the temperature of between 10 and 15 ℃ to (-0.09 MPa to-0.10 MPa) until a uniform solution is formed; then adding 100 mu L of catalyst Tetramethylethylenediamine (TEMED) and 0.53g of initiator Ammonium Persulfate (APS) and uniformly dispersing, keeping the temperature for 10-15 ℃ for a period of time until a uniform and stable transparent solution is formed, pouring the mixed solution into a polytetrafluoroethylene mold for sealing, transferring the polytetrafluoroethylene mold to an oven, keeping the temperature for 12 hours to 45 ℃, taking out the prepared hydrogel sensor from the mold, firstly dialyzing the hydrogel sensor for 12-36 hours by using DMSO to remove unreacted and low molecular weight monomers, then dialyzing the hydrogel sensor for 12-36 hours by using distilled water to remove DMSO and fully swelling the hydrogel sensor.
The embodiment is as follows:
hg of R6GS 2+ Recognition performance testing
Dissolving the prepared R6GS in DMSO, diluting with distilled water to obtain 10-concentration solution -4 Probe solution of M (DMSO/H) 2 O=9/1,v/v)。
Respectively measuring ultraviolet absorption spectrum of sample with ultraviolet-visible spectrophotometer to find its maximum ultraviolet absorption wavelength, taking it as fluorescence excitation wavelength, measuring fluorescence spectrum with fluorescence spectrophotometer (see the results in figures 1-2), and measuring R6GS and R6GS-Hg 2+ The infrared spectrum and nuclear magnetic hydrogen spectrum of the compound are tested.
The results show that: r6GS has mercury ion selectivity.
2. Hg of supramolecular hydrogel sensor 2+ Recognition performance testing
Placing the fully swollen supramolecular hydrogel sensor at 10 -4 ~10 -8 Hg of M concentration 2+ In an aqueous solution of (a).
Observing the color change of the supramolecular hydrogel sensor under visible light and a 365nm ultraviolet lamp, wherein the color of the visible hydrogel under the visible light is along with Hg 2+ The concentration is gradually changed into red, and the color of the visible hydrogel under a 365nm ultraviolet lamp is along with Hg 2+ The fluorescence gradually increased with increasing concentration. (the results are shown in FIGS. 5 to 6)
The results show that: the supramolecular hydrogel sensor has the sensing characteristic of mercury ion recognition.
Claims (6)
1. A fluorescence sensor based on rhodamine 6G derivatives is characterized in that the fluorescence sensor is prepared by taking the rhodamine 6G derivatives as recognition monomers and combining a fluorescence probe on supramolecular hydrogel through copolymerization;
the method for preparing the rhodamine 6G derivative-based fluorescence sensor specifically comprises the following steps:
1) Rhodamine 6G and 2-thiophene ethylamine are used as raw materials to obtain a recognition functional monomer R6GS;
2) Acrylamide, methyl methacrylate and N, N' -methylene-bisacrylamide are used as main raw materials and are subjected to free radical copolymerization with R6GS to obtain the supramolecular hydrogel sensor.
2. The rhodamine 6G derivative-based fluorescence sensor as defined in claim 1, wherein the preparation method of the functional monomer R6GS for recognition in step 1) is as follows:
dissolving rhodamine 6G and 2-thiophene ethylamine in ethanol, and heating and refluxing for 6 hours; and (3) carrying out reduced pressure rotary evaporation to remove the solvent, and carrying out column chromatography purification on the obtained crude product to obtain the fluorescent probe molecule R6GS.
3. The rhodamine 6G derivative based fluorescence sensor of claim 2 wherein the reaction equivalence ratio of rhodamine 6G and 2-thiopheneethylamine is 1.05.
4. The rhodamine 6G derivative based fluorescence sensor as claimed in claim 2, wherein the eluent for column chromatography purification is a dichloromethane/ethanol mixed solution with a volume ratio of 35/1.
5. The rhodamine 6G derivative-based fluorescence sensor of claim 1, wherein the preparation method of the supramolecular hydrogel sensor in step 2) is specifically as follows:
a, mixing acrylamide, methyl methacrylate, R6GS and N, N' -methylene bisacrylamide and adding the mixture into DMSO;
b, vacuumizing and stirring the mixed solution obtained in the step a at the temperature of 10-15 ℃ until a uniform solution is formed; adding catalyst tetramethyl ethylenediamine and initiator ammonium persulfate, and uniformly dispersing, wherein the temperature is kept at 10-15 ℃ during the period to form uniform and stable transparent solution;
c, transferring the transparent solution obtained in the step b into a tetrafluoroethylene mold, sealing, and preserving heat for 12 hours in an oven at the temperature of 35-45 ℃;
d, taking out the prepared hydrogel from the mold, dialyzing with DMSO for 12-36 hours to remove unreacted monomers, dialyzing with distilled water for 12-36 hours to remove DMSO and fully swelling the hydrogel sensor to obtain the supermolecule hydrogel sensor.
6. The rhodamine 6G derivative based fluorescence sensor as set forth in claim 5, wherein the mass ratio of acrylamide, methyl methacrylate and R6GS in step a is from 10.8 to 1.5.
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