CN112011098A - Supermolecule luminescent gel system constructed by sulfonated cyclodextrin-bromophenyl picolinate-amino clay and preparation method thereof - Google Patents
Supermolecule luminescent gel system constructed by sulfonated cyclodextrin-bromophenyl picolinate-amino clay and preparation method thereof Download PDFInfo
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Abstract
A supermolecular light-emitting gel system constructed by sulfonated cyclodextrin-bromophenyl picolinate-amino clay and a preparation method thereof are disclosed, wherein the sulfonated cyclodextrin is used as a main body, bromomethyl phenylpyridinate is used as an object, and bromophenyl picoline based on electrostatic interaction and main-object interaction is utilized to successfully construct a novel supermolecular xerogel in which SCD and amino clay are combined in a non-covalent manner. The xerogel network has a rigid structure, can effectively fix the fluorescent powder, limit vibration dissipation and enable the xerogel to emit RTP. In the system, SCD plays a crucial role in maintaining the emission behavior of the monomer, AC provides a layered environment for PYCl through the strong inhibition of the electrostatic gel network structure to the vibration of the fluorescent powder and the radiationless relaxation process, and the supermolecular xerogel can generate a strong RTP signal. In addition, the xerogel has certain responsiveness to humidity, and has potential application prospect in the aspects of organic luminescent materials and humidity sensing.
Description
Technical Field
The invention belongs to the technical field of supramolecular luminescent gel, and particularly relates to a supramolecular luminescent gel system constructed by Sulfonated Cyclodextrin (SCD) -bromophenyl picolinate-amino clay.
Background
Organic Room Temperature Phosphorescence (RTP) has attracted a great deal of attention in recent years, primarily because of their wide range of applications in optoelectronics, photobiology, such as organic light emitting diodes and bioimaging. So far, many organic room temperature phosphorescent materials are organometallic complexes, and considering that the resources of the organic room temperature phosphorescent materials are limited and the price of the organic room temperature phosphorescent materials is high, the development of pure organic (metal-free) room temperature phosphorescent materials is particularly urgent. In addition, the gel material with phosphorescence emission property attracts the wide attention of researchers, and has great potential application value in the fields of material science, chemical sensing, biological imaging, 3D printing, tissue engineering and the like due to the special optical property and mechanical property. However, pure organic molecules have low intersystem crossing efficiency due to inefficient spin coupling, and the emitted phosphorescence is weak. Therefore, great efforts are made to develop new methods for realizing efficient room temperature phosphorescent emission, such as designing special structures (structures containing aromatic ring carbonyl groups, heavy atoms, and the like, which are favorable for intersystem crossing), embedding into suitable matrices (incorporation or covalent modification on polymers, adsorption into inorganic clays, and the like, which inhibit non-radiative transitions), and crystallization (reduction of non-radiative energy dissipation, promotion of intersystem crossing, stabilization of triplet excited states, and the like).
Disclosure of Invention
The invention aims to solve the problems and discloses that after the bromophenyl picolinate is bonded by sulfonated cyclodextrin SCD and forms a supermolecular xerogel with Amino Clay (AC), the phosphorescence of the bromophenyl picolinate can be remarkably improved, and the service life of the bromophenyl picolinate can be prolonged from 5.76 mu s of a monomer to 1.24ms of a compound. One possible explanation for this dramatic enhancement is due to host-guest interactions and the strong suppression of phosphor vibration and suppression of non-radiative relaxation processes by electrostatic gel network structures rather than heavy atom effects. The currently constructed supramolecular luminescent gel has a wide application prospect in the aspect of humidity sensing.
The technical scheme of the invention is as follows:
in particular to a supermolecular light-emitting gel system constructed by Sulfonated Cyclodextrin (SCD) -bromophenyl picolinate-amino clay, wherein the sulfonated cyclodextrin is taken as a host, bromomethyl phenylpyridinate is taken as an object, and the chemical structural formula of the construction unit is as follows:
a preparation method of a supermolecular light-emitting gel system constructed by Sulfonated Cyclodextrin (SCD) -bromophenyl picolinate-amino clay comprises the following steps:
step 3, adding the binary supermolecule nano particle solution obtained in the step 2 into the amino clay aqueous solution prepared in the step 1, stirring, and standing to form gel;
the sulfonated cyclodextrin is a macrocyclic host with 6-position hydroxyl on the cyclodextrin fully substituted by sodium sulfonate, bromophenyl picolinate is a guest phosphorescent compound prepared by simple three-step synthesis, binary supramolecular nanoparticles are constructed by host-guest interaction, supramolecular hydrogel is constructed by electrostatic interaction and amino clay, then the formation of gel is proved by a scanning electron microscope and a rheometer, then the phosphorescence intensity change is monitored by a spectrometry method, and the phosphorescence service life value is calculated.
Further, the preparation method of the amino clay in the step 1 comprises the following steps:
magnesium chloride hexahydrate (1.68g, 8.30mmol) was dissolved in absolute ethanol (40mL), and a solution of 3-aminopropylethoxysilane (2.59mL, 11.10mmol) in absolute ethanol (10mL) was slowly added dropwise with stirring. Then stirring for 24 hours at room temperature, centrifugally collecting the generated white precipitate, washing the white precipitate with ethanol for three times, then drying the white precipitate in vacuum to obtain the target product, and grinding the target product into powder for later use.1HNMR(400MHz,D2O,298K):(ppm)2.96(t,J＝7.14Hz,2H),1.86-1.58(m,2H),0.79-0.65(m,2H)。
Further, the preparation method of the sulfonated cyclodextrin in the step 2 comprises the following steps:
1) triphenylphosphine (20.2g, 77.0mmol) was dissolved in anhydrous DMF (80mL) and iodine (20.2g, 77.2mmol) was added slowly over 10-15 min under nitrogen. Dried beta-cyclodextrin (5g, 4.4mmol) was then added to the dark brown solution described above, which was stirred well at 70 ℃ under nitrogen for 18 hours. Then, half of the reaction solution was distilled off under reduced pressure. A solution of sodium methoxide in methanol was added thereto under stirring in an ice bath, and the pH of the solution was adjusted to 9 to 10. The mixture was stirred at room temperature for 30 minutes, then the mixture was added to cold methanol (400mL) under vigorous stirring, and the precipitated insoluble matter was filtered and collected, and after washing with methanol, the resulting solid was subjected to soxhlet extraction with methanol until the solvent did not change color to finally obtain the objective product as a white powder (7.70g, 92% yield).
2) The product obtained in 1) (2.66g, 1.40mmol), sodium 2-mercaptoethanesulfonate (4.00g, 24.40mmol) and anhydrous triethylamine (3.40mL, 24.40mmol) were added to anhydrous DMSO (10mL) under a nitrogen atmosphere. And (3) reacting the mixed solution with 60 ℃ for 3 days, cooling to room temperature, dripping the reaction solution into a large amount of acetone (1000mL) to separate out a large amount of white precipitate, filtering and collecting the white precipitate, dissolving the white precipitate in a small amount of water again, dripping the white precipitate into the acetone, repeating the process for three times, collecting the white precipitate, and drying in vacuum to obtain the target product. The yield was 64%.
The preparation method of the sulfonated cyclodextrin-bromophenyl methylpyridine salt solution in the step 2 comprises the following steps:
the sulfonated cyclodextrin-bromophenyl picolinate binary supramolecular nanoparticles are formed by taking sodium sulfonate-substituted beta-cyclodextrin as a main body and bromomethyl phenylpyridinate as an object through the anion-cation bonding effect of the main body and the object; dissolving sodium sulfonate-substituted beta-cyclodextrin and bromophenyl picolinate in water in a molar ratio of 1:1, and uniformly mixing to obtain a binary supramolecular nanoparticle solution.
The invention has the advantages that:
a novel supermolecule xerogel formed by non-covalent combination of SCD and Amino Clay (AC) is successfully constructed by utilizing bromophenyl picoline (PYCl) based on electrostatic interaction and host-guest interaction, and the development of RTP materials is realized. The xerogel network has a rigid structure, can effectively fix the fluorescent powder, limit vibration dissipation and enable the xerogel to emit RTP. The invention has low cost, no toxicity, convenient preparation and convenient processing. In addition, in the system, SCD plays a crucial role in maintaining the emission behavior of the monomer, and AC provides a layered environment for PYCl through strong suppression of phosphor vibration by the electrostatic gel network structure and a radiationless relaxation process, and the supramolecular xerogel can generate a strong RTP signal. In addition, the xerogel has certain responsiveness to humidity, and has potential application prospect in the aspects of organic luminescent materials and humidity sensing.
Drawings
FIG. 1 is a schematic diagram of the synthesis of bromophenyl picolinate.
FIG. 2 is a schematic diagram of a process for synthesizing sulfonated cyclodextrin.
FIG. 3 is a hydrogen spectrum of sulfonated cyclodextrin.
FIG. 4 is a photoluminescence spectrum of the guest and the aqueous solution of the host and guest.
FIG. 5 is a Zeta potential diagram of a sulfonated cyclodextrin-bromophenyl picolinate.
FIG. 6 is an SEM image of sulfonated cyclodextrin-bromophenyl picolinate-amino clay supramolecular xerogel.
FIG. 7 is a one-dimensional nuclear magnetic spectrum of the sulfonated cyclodextrin-bromophenyl picolinate.
FIG. 8 is a two-dimensional nuclear magnetic spectrum of sulfonated cyclodextrin-bromophenyl picolinate.
FIG. 9 shows the bonding ratio spectrum of sulfonated cyclodextrin-bromophenyl picolinate.
FIG. 10 is a graph of the bonding strength of sulfonated cyclodextrin-bromophenyl picolinate.
Fig. 11 is a rheological spectrum of sulfonated cyclodextrin-bromophenyl picolinate-amino clay supramolecular gel.
Fig. 12 is an infrared spectrum of the sulfonated cyclodextrin-bromophenyl picolinate-amino clay supramolecular xerogel and amino clay.
FIG. 13 is a photoluminescence spectrum of sulfonated cyclodextrin-bromophenyl picolinate-amino clay supramolecular xerogel.
Fig. 14 is a phosphorescence lifetime spectrum of the sulfonated cyclodextrin-bromophenyl picolinate-amino clay supramolecular xerogel.
Detailed Description
Example (b):
a supermolecular light-emitting gel system constructed by Sulfonated Cyclodextrin (SCD) -bromophenyl picolinate-amino clay is disclosed, wherein the sulfonated cyclodextrin is used as a host, bromomethyl phenylpyridinate is used as an object, and the chemical structural formula of a construction unit is as follows:
the invention provides a preparation method of a supermolecular luminescent gel system constructed by sulfonated cyclodextrin-bromophenyl picolinate-amino clay, which comprises the following steps:
step 3, adding the binary supermolecule nano particle solution obtained in the step 2 into the amino clay aqueous solution prepared in the step 1, stirring, and standing to form gel;
referring to fig. 1, in the above preparation method, the preparation method of the amino clay in step 1 is as follows:
magnesium chloride hexahydrate (1.68g, 8.30mmol) was dissolved in absolute ethanol (40mL), and a solution of 3-aminopropylethoxysilane (2.59mL, 11.10mmol) in absolute ethanol (10mL) was slowly added dropwise with stirring. Then stirring for 24 hours at room temperature, centrifugally collecting the generated white precipitate, washing the white precipitate with ethanol for three times, then drying the white precipitate in vacuum to obtain the target product, and grinding the target product into powder for later use.1HNMR(400MHz,D2O,298K):(ppm)2.96(t,J＝7.14Hz,2H),1.86-1.58(m,2H),0.79-0.65(m,2H)。
Referring to fig. 2, in the above preparation method, the preparation method of the sulfonated cyclodextrin in step 2 comprises the following steps:
1) triphenylphosphine (20.2g, 77.0mmol) was dissolved in anhydrous DMF (80mL) and iodine (20.2g, 77.2mmol) was added slowly over 10-15 min under nitrogen. Dried beta-cyclodextrin (5g, 4.4mmol) was then added to the dark brown solution described above, which was stirred well at 70 ℃ under nitrogen for 18 hours. Then, half of the reaction solution was distilled off under reduced pressure. A solution of sodium methoxide in methanol was added thereto under stirring in an ice bath, and the pH of the solution was adjusted to 9 to 10. The mixture was stirred at room temperature for 30 minutes, then the mixture was added to cold methanol (400mL) under vigorous stirring, the precipitated insoluble matter was filtered and collected, after washing with methanol, and the resulting solid was subjected to soxhlet extraction with methanol until the solvent did not change color, to finally obtain the objective product as a white powder (7.70g, yield 92%);
2) the product obtained in 1) (2.66g, 1.40mmol), sodium 2-mercaptoethanesulfonate (4.00g, 24.40mmol) and anhydrous triethylamine (3.40mL, 24.40mmol) were added to anhydrous DMSO (10mL) under a nitrogen atmosphere. And (3) reacting the mixed solution with 60 ℃ for 3 days, cooling to room temperature, dripping the reaction solution into a large amount of acetone (1000mL) to separate out a large amount of white precipitate, filtering and collecting the white precipitate, dissolving the white precipitate in a small amount of water again, dripping the white precipitate into the acetone, repeating the process for three times, collecting the white precipitate, and drying in vacuum to obtain the target product. The yield was 64%.
FIG. 3 is a hydrogen spectrum of sulfonated cyclodextrin. The figure shows that: the synthesized sulfonated cyclodextrin has correct structure.
FIG. 4 is a photoluminescence spectrum of the guest and the aqueous solution of the host and guest. The figure shows that: the aqueous solution of the guest and the host-guest complex has only fluorescence and no phosphorescence emission.
In step 2 of the preparation method, the preparation of the sulfonated cyclodextrin-bromophenyl methylpyridine salt solution comprises the following steps:
the sulfonated cyclodextrin-bromophenyl picolinate binary supramolecular nanoparticles are prepared by taking sodium sulfonate-substituted beta-cyclodextrin as a main body and bromomethyl phenylpyridinate as an object through the anion-cation bonding effect of the main body and the object. Dissolving sodium sulfonate-substituted beta-cyclodextrin and bromophenyl picolinate in water in a molar ratio of 1:1, and uniformly mixing to obtain a binary supramolecular nanoparticle solution.
FIG. 5 is a Zeta potential diagram of a sulfonated cyclodextrin-bromophenyl picolinate. The figure shows that: the Zeta potential of the supermolecule nano-particle constructed by the sulfonated cyclodextrin-bromophenyl picolinate is-12.95V.
FIG. 6 is an SEM image of sulfonated cyclodextrin-bromophenyl picolinate-amino clay supramolecular xerogel. The figure shows that: the sulfonated cyclodextrin-bromophenyl picolinate-amino clay supermolecular xerogel forms a net structure.
FIG. 7 is a one-dimensional nuclear magnetic spectrum of the sulfonated cyclodextrin-bromophenyl picolinate. The figure shows that: the sulfonated cyclodextrin has an effect with bromophenyl picolinate.
FIG. 8 is a two-dimensional nuclear magnetic spectrum of sulfonated cyclodextrin-bromophenyl picolinate. The figure shows that: the sulfonated cyclodextrin and bromophenyl picolinate have a host-guest interaction.
FIG. 9 shows the bonding ratio spectrum of sulfonated cyclodextrin-bromophenyl picolinate. The figure shows that: the bonding ratio of the sulfonated cyclodextrin-bromophenyl methylpyridine salt is 1: 1.
FIG. 10 is a graph of the bonding strength of sulfonated cyclodextrin-bromophenyl picolinate. The figure shows that: sulfonated ringThe dextrin-bromophenyl picolinate bond strength was 5.8X104。
Fig. 11 is a rheological spectrum of sulfonated cyclodextrin-bromophenyl picolinate-amino clay supramolecular gel. The figure shows that: the sulfonated cyclodextrin-bromophenyl picolinate-amino clay forms a gel.
Fig. 12 is an infrared spectrum of the sulfonated cyclodextrin-bromophenyl picolinate-amino clay supramolecular xerogel and amino clay. The figure shows that: the structure of the sulfonated cyclodextrin-bromophenyl picolinate-amino clay supermolecular xerogel and amino clay.
FIG. 13 is a photoluminescence spectrum of sulfonated cyclodextrin-bromophenyl picolinate-amino clay supramolecular xerogel. The figure shows that: the sulfonated cyclodextrin-bromophenyl picolinate-amino clay supermolecular xerogel has a good photoluminescence emission peak.
Fig. 14 is a phosphorescence lifetime spectrum of the sulfonated cyclodextrin-bromophenyl picolinate-amino clay supramolecular xerogel. The figure shows that: the millisecond lifetime demonstrated that the emission peak in fig. 13 was a phosphorescence emission peak.
Claims (8)
1. A supermolecular light-emitting gel system constructed by sulfonated cyclodextrin-bromophenyl picolinate-amino clay is characterized in that: the sulfonated cyclodextrin is used as a main body, the bromomethyl phenyl pyridinium is used as an object, and the chemical structural formula of the building unit is as follows:
2. a preparation method of a supermolecule luminescent gel system constructed by sulfonated cyclodextrin-bromophenyl picolinate-amino clay is characterized by comprising the following steps:
step 1, preparing an amino clay aqueous solution;
step 2, preparing a sulfonated cyclodextrin-bromophenyl methyl pyridinium binary supramolecular nanoparticle solution;
step 3, adding the binary supermolecule nano particle solution obtained in the step 2 into the amino clay aqueous solution prepared in the step 1, stirring, and standing to form gel; the binary supermolecule fluorescent nano-particles are used as an energy donor, Nile red is used as an energy receptor, then the fluorescence of the donor is monitored by a fluorescence spectroscopy method to be gradually reduced, the fluorescence of the receptor is gradually increased, and the efficiency of fluorescence resonance energy transfer, the antenna effect value and the corresponding ratio of the donor to the receptor are calculated.
3. The method for preparing the supramolecular luminescent gel system constructed by the sulfonated cyclodextrin-bromophenyl picolinate-amino clay according to claim 2, wherein the preparation method of the amino clay in the step 1 is as follows:
dissolving magnesium chloride hexahydrate in absolute ethyl alcohol, and slowly dripping an absolute ethyl alcohol solution containing 3-aminopropyl ethoxysilane under stirring; then stirring for 24 hours at room temperature, centrifugally collecting the generated white precipitate, washing the white precipitate with ethanol for three times, then carrying out vacuum drying to obtain a target product, and grinding the target product into powder for later use;1H NMR(400MHz,D2O,298K):(ppm)2.96(t,J＝7.14Hz,2H),1.86-1.58(m,2H),0.79-0.65(m,2H)。
4. the method for preparing the supramolecular luminescent gel system constructed by the sulfonated cyclodextrin-bromophenyl picolinate-amino clay as claimed in claim 2, wherein the method for preparing the sulfonated cyclodextrin in step 2 is as follows:
1) dissolving triphenylphosphine in anhydrous DMF, and slowly adding iodine under nitrogen protection for 10-15 min; then adding the dried beta-cyclodextrin into the dark brown solution, and fully stirring the dark brown solution for 18 hours at 70 ℃ under the nitrogen atmosphere; then evaporating half of the reaction solution under the condition of reduced pressure; adding a methanol solution of sodium methoxide into the solution under the condition of ice bath and stirring, and then adjusting the pH of the solution to 9-10; the mixture was stirred at room temperature for 30 minutes, then the mixture was added to cold methanol under vigorous stirring, the precipitated insoluble matter was filtered and collected, and after washing with methanol, the resulting solid was subjected to soxhlet extraction with methanol until the solvent did not change color, and finally the objective product was obtained as a white powder.
2) Adding the product prepared in the step 1), 2-mercaptoethanesulfonic acid sodium salt and anhydrous triethylamine into anhydrous DMSO in a nitrogen atmosphere; reacting the mixed solution with 60 ℃ for 3 days, cooling to room temperature, dripping the reaction solution into a large amount of acetone to separate out a large amount of white precipitate, filtering, collecting the white precipitate, dissolving the white precipitate in a small amount of water again, dripping the white precipitate into the acetone, repeating the process for three times, collecting the white precipitate, and drying in vacuum to obtain the target product.
5. The method for preparing the supramolecular luminescent gel system constructed by the sulfonated cyclodextrin-bromophenyl picolinate-amino clay as claimed in claim 2, which is characterized in that the sulfonated cyclodextrin-bromophenyl picolinate solution is prepared in step 2 by the following steps:
the sulfonated cyclodextrin-bromophenyl picolinate binary supramolecular nanoparticles are formed by taking sodium sulfonate-substituted beta-cyclodextrin as a main body and bromomethyl phenylpyridinate as an object through the anion-cation bonding effect of the main body and the object; dissolving sodium sulfonate-substituted beta-cyclodextrin and bromophenyl picolinate in water in a molar ratio of 1:1, and uniformly mixing to obtain a binary supramolecular nanoparticle solution.
6. The method for preparing the supramolecular luminescent gel system constructed by the sulfonated cyclodextrin-bromophenyl picolinate-amino clay as claimed in claim 3, which is characterized in that: the dosage of the magnesium chloride hexahydrate is 1.68g and 8.30 mmol; the dosage of the absolute ethyl alcohol is 40 mL; the dosage of the 3-aminopropyl ethoxy silane is 2.59mL and 11.10 mmol; the amount of the absolute ethanol solution is 10 mL.
7. The method for preparing the supramolecular luminescent gel system constructed by the sulfonated cyclodextrin-bromophenyl picolinate-amino clay as claimed in claim 4, which is characterized in that: the dosage of the triphenylphosphine in the step 1) is 20.2g, 77.0 mmol; the dosage of anhydrous DMF is 80 mL; the dosage of iodine is 20.2g, 77.2 mmol; the amount of dried beta-cyclodextrin was 5g, 4.4 mmol; the amount of cold methanol used was 400 mL.
8. The method for preparing the supramolecular luminescent gel system constructed by the sulfonated cyclodextrin-bromophenyl picolinate-amino clay as claimed in claim 4, which is characterized in that: the dosage of the product in the step 2) is 2.66g and 1.40 mmol; the dosage of the 2-mercaptoethanesulfonic acid sodium salt is 4.00g, 24.40 mmol; the dosage of the anhydrous triethylamine is 3.40mL and 24.40 mmol; the dosage of the anhydrous DMSO is 10 mL; the amount of acetone used was 1000 mL.
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