CN111548431B - Marine organism polysaccharide grafted pyridine organic micromolecule multicolor adjustable aggregation-induced emission material and preparation method thereof - Google Patents
Marine organism polysaccharide grafted pyridine organic micromolecule multicolor adjustable aggregation-induced emission material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of novel energy materials, in particular to a multicolor adjustable aggregation-induced emission material of pyridine organic micromolecules grafted by marine organism polysaccharide and a preparation method thereof, which adopts pyridine organic micromolecules containing amino groups and oxidized marine organism polysaccharide macromolecules to carry out chemical crosslinking through Schiff base reaction to prepare the multicolor adjustable marine organism polysaccharide material with aggregation-induced emission characteristics, can realize the conversion of solution-state and solid-state emission colors of the pyridine organic micromolecules only by changing the feeding ratio of the pyridine organic micromolecules with weak light emission or non-light emission or simply changing the unit structures of the pyridine organic micromolecules, can relieve the problems of single emission color and low emission efficiency caused by the limitation of the selectivity of multicolor fluorescence molecules at present, provides a novel energy material for realizing a high-efficiency, environment-friendly and good biocompatibility multicolor fluorescence material system, and realizes anti-counterfeiting, biochemical diagnosis, environmental analysis, etc.
Description
Technical Field
The invention belongs to the field of novel energy materials, and particularly relates to a marine organism polysaccharide grafted pyridine organic micromolecule multicolor adjustable aggregation-induced luminescent material and a preparation method thereof.
Background
The multicolor fluorescent material based on the macromolecule has the advantages of good stability and solution-soluble processability, and is widely applied to the fields of luminescent materials, fluorescent sensors, optical equipment and the like. However, the methods for adjusting and controlling the color of light emission by changing the length and size of the copolymerized units in the conjugated polymer are complicated and time-consuming in the prior art, and the organic conjugated polymer generally has high biological toxicity. Therefore, the development of a new type of non-conjugated natural polymer multicolor tunable aggregation-induced emission material is an effective way to alleviate the above problems. The invention aims to combine abundant renewable marine organism polysaccharide with pyridine organic micromolecules containing amino, and the effective regulation and control of the luminous color can be realized by adjusting the adding proportion of the bipyridine micromolecules or slightly adjusting the chemical structure of the bipyridine micromolecules through a chemical bond crosslinking method, so that a multicolor adjustable fluorescent material system is prepared.
The invention prepares the multicolor adjustable aggregation-induced emission material based on the marine organism polysaccharide grafted pyridine organic micromolecules, and provides a novel emission material system for realizing multicolor fluorescent molecules with simple preparation process and environmental protection. The multicolor aggregation-induced fluorescent material with simple preparation process and easily-regulated luminescent color relieves the problem of single luminescent color caused by limited selectivity of a fluorescent emission material, and also solves the problems of high toxicity, difficult processing and the like of the traditional pure organic conjugated macromolecules.
Disclosure of Invention
The invention aims to provide a preparation method of a marine organism polysaccharide grafted pyridine organic micromolecule multicolor adjustable aggregation-induced fluorescent material, which is low in cost, simple in preparation process and environment-friendly.
A marine organism polysaccharide grafted amino-containing pyridine organic micromolecule multicolor adjustable aggregation-induced emission material has the following structural formula:
in the formula, R is a substituent lateral group on a marine organism polysaccharide ring; m is the number of repeating units in the marine organism polysaccharide;
the above-mentioned
Is absent or selected from any one of the following groups:
the invention also provides a preparation method of the marine organism polysaccharide grafted pyridine organic micromolecule multicolor adjustable aggregation-induced emission material, which comprises the following steps:
(1) dissolving the oxidized marine organism polysaccharide in deionized water to prepare an oxidized marine organism polysaccharide solution;
(2) dissolving pyridine organic micromolecules containing amino in an organic solvent to obtain a solution;
(3) slowly dripping the solution obtained in the step (2) into the oxidized marine organism polysaccharide solution obtained in the step (1), stirring and reacting for 0.5-24h (preferably stirring and reacting for 3h at 50-80 ℃ and 400r/min at 50-1000 r/min), adding an acidic substance into the solution for catalysis in the reaction process (preferably adding after reacting for 0.5 h), adding an organic solvent (the volume is 1-5 times of the volume of the reaction liquid) after the reaction is finished, separating out solids, filtering, washing and freeze-drying the obtained solids to obtain the marine organism polysaccharide grafted pyridine organic micromolecule multicolor adjustable aggregation induced luminescent material;
the molar ratio of the oxidized marine organism polysaccharide in the step (3) to the pyridine organic micromolecules containing amino is (1-100000): 1, obtaining luminescent materials with different colors by changing the adding amount of pyridine organic micromolecules containing amino.
Furthermore, the amino-containing pyridine organic small molecule is T1, T2 or T3, and the structural formulas of T1, T2 and T3 are respectively as follows:
the above-mentioned
As described above.
Further, the marine organism polysaccharide is sodium alginate, chitosan, carrageenan or agar, preferably sodium alginate or chitosan.
Further, the organic solvent is absolute ethyl alcohol, absolute methyl alcohol, acetone, glacial acetic acid, tetrahydrofuran or DMF, and is preferably absolute ethyl alcohol, absolute methyl alcohol or DMF.
Further, the acidic substance is acetic acid, hydrochloric acid, sulfuric acid or nitric acid, preferably (0.005-0.08) mol/L hydrochloric acid, and the addition amount is 0.1-2% of the volume of the reaction solution; or (0.005-0.05) mol/L of acetic acid, and the addition amount is 0.2-1% of the volume of the reaction liquid.
Further, in the step (1), the oxidation of the marine organism polysaccharide is realized by using the reaction of sodium periodate and the marine organism polysaccharide, and the specific steps are as follows: dissolving marine organism polysaccharide in deionized water, adding sodium periodate, reacting completely at normal temperature in the dark, adding water-soluble organic solvent to precipitate, filtering, and freeze drying to obtain oxidized marine organism polysaccharide. The specific reaction formula is as follows:
further, the T1, T2 and T3 may be commercially available products or obtained by Suzuki or Stille coupling reaction, as follows:
carrying out Suzuki reaction by using 2-bromo-3-aminopyridine and bisboron with Ar group as main reactants, or carrying out Stille coupling reaction by using 2-bromo-3-aminopyridine and bistin salt with Ar group as main reactants to obtain T1;
carrying out Suzuki reaction by using 2-bromo-4-aminopyridine and bisboron with Ar group as main reactants, or carrying out Stille coupling reaction by using 2-bromo-4-aminopyridine and bistin salt with Ar group as main reactants to obtain T2;
carrying out Suzuki reaction by using 2-bromo-5-aminopyridine and bisboron with Ar group as main reactants, or carrying out Stille coupling reaction by using 2-bromo-5-aminopyridine and bistin salt with Ar group as main reactants to obtain T3.
Suzuki reaction:
stille reaction:
the invention has the following advantages and application prospects:
the marine organism polysaccharide grafted pyridine organic molecule multicolor adjustable aggregation-induced emission material prepared by the invention has the advantages of simple and efficient synthetic route, wide source, good biocompatibility, good solubility and the like by taking the marine organism polysaccharide as a matrix. The multicolor conversion material only needs to be chemically crosslinked in water, and has the advantages of simple operation, short time consumption and environmental friendliness. The luminescent material prepared by the invention has wide application prospects in the aspects of biochemical diagnosis, anti-counterfeiting, environmental analysis, analytical chemistry and the like. The marine organism polysaccharide and the cross-linked solid of pyridine organic micromolecules containing amino only change the concentration of the micromolecules under the irradiation of a 365nm ultraviolet lamp, and fluorescence can be converted into multiple fluorescence from blue initial fluorescence to green fluorescence and yellow fluorescence. The different kinds of organic micromolecule cross-linked solids can have fluorescence with different colors, can form different patterns and information, and is expected to have application prospects in the aspects of anti-counterfeiting, biochemical diagnosis, environmental analysis and the like.
Drawings
FIG. 1 is a schematic representation of 3,3 '-dinitro-2, 2' -bipyridine of example 11H NMR chart.
FIG. 2 shows 3,3' -diamino-Process for preparing 2,2' -bipyridine1H NMR chart.
FIG. 3 shows fluorescence spectra of oxidized sodium alginate grafted 3,3 '-diamino-2, 2' -bipyridine at different concentrations in example 1, wherein the concentrations from top to bottom are 10mg/L, 7mg/L, 3mg/L, 2mg/L, 1mg/L, 0.5mg/L and 0.2 mg/L.
FIG. 4 is a solid fluorescence photograph of the polysaccharide luminescent material in example 1 at a wavelength of 360nm and fluorescence quantum efficiencies at different molar ratios, where the molar ratio of sodium alginate oxide to 3,3 '-diamino-2, 2' -bipyridine to sodium alginate oxide is 1: 100000,1: 10000,1: 1000,1: 100,1: 10,1: 1, and 3,3 '-diamino-2, 2' -bipyridine.
FIG. 5 shows fluorescence spectra of oxidized sodium alginate grafted 5, 5-diamino-2, 2' -bipyridine at different concentrations in example 2, wherein the concentrations are 10mg/L, 7mg/L, 3mg/L, 2mg/L, 1mg/L, 0.5mg/L and 0.2mg/L from top to bottom.
FIG. 6 is a solid fluorescence photograph of the polysaccharide luminescent material in example 2 at a wavelength of 360nm and fluorescence quantum efficiencies at different molar ratios, from left to right, the molar ratio of sodium alginate oxide to 5,5 '-diamino-2, 2' -bipyridine to sodium alginate oxide is 1: 10000. 1: 1000. 1: 100. 1: 10,1: 2 and 5,5 '-diamino-2, 2' -bipyridine.
FIGS. 7 to 9 are a solid fluorescence photograph at a wavelength of 360nm, a fluorescence spectrum at 3mg/ml, and an ultraviolet-visible absorption spectrum of the oxidized chitosan-grafted 3,3 '-diamino-2, 2' -bipyridine in example 3, respectively.
FIG. 10 shows a1 organic micromolecules in example 41H NMR chart.
FIG. 11 is a solid fluorescence photograph of oxidized sodium alginate grafted a1 organic small molecule at 360nm wavelength in example 4.
FIGS. 12-1-12-3 are the activity safety concentrations of oxidized sodium alginate, oxidized sodium alginate grafted 3,3 '-diamino-2, 2' -bipyridine, and oxidized sodium alginate grafted 5,5 '-diamino-2, 2' -bipyridine in human corneal epithelial cells, respectively, of example 5.
Detailed Description
Embodiment 1 a marine organism polysaccharide grafted pyridine organic small molecule multicolor adjustable aggregation-induced emission material is prepared by the following method:
oxidized sodium alginate is prepared according to the following method
Sodium alginate (2.0g, 10.1mmol) is dissolved in 200mL deionized water, and the solution is stirred at the rotation speed of 350r/min for 3h at room temperature to dissolve the sodium alginate, so as to prepare a 1% solution. Dissolving sodium periodate (4.3g, 20.2mmol) in 30mL deionized water, stirring at 50 ℃ and 350r/min for 20min to completely dissolve the sodium periodate to form a sodium periodate solution, slowly and dropwise adding the sodium periodate solution into the 1% sodium alginate solution, reacting for 24h at room temperature in a dark place, adding ethylene glycol (1.0mL, 20.2mmol) to quench the residual sodium periodate, and stopping the reaction. And finally, adding 400mL of absolute ethyl alcohol into the mixture to separate out the oxidized sodium alginate from the water, and freeze-drying the mixture to obtain white powder, namely the oxidized sodium alginate with the yield of 80%.
Synthesis of (di) 3,3 '-diamino-2, 2' -bipyridine
The synthetic route is as follows: uniformly mixing 2-chloro-3-nitropyridine (2.0g, 12.7mmol) and copper powder (2.0g, 31.6mmol) under the protection of argon, adding 10ml of anhydrous N, N-dimethylformamide as a solvent, reacting for 3 hours at the temperature of 150 ℃ and the rotating speed of 350r/min, filtering out residual copper powder after the reaction is finished, adding 30ml of 28% concentrated ammonia water into filtrate to remove copper ions, extracting the filtrate for 4 times by using ethyl acetate, removing water by using anhydrous sodium sulfate, performing rotary evaporation to obtain a solid, and recrystallizing the solid in ethyl acetate to obtain a light yellow target product, namely 3,3 '-dinitro-2, 2' -bipyridine with the yield of 48.0%.1H NMR(400MHz,CDCl3) δ 8.89,8.88,8.87,8.60,8.59,8.58,8.57,7.66,7.65,7.64,7.63,7.26. (see fig. 1).
The prepared 3,3 '-dinitro-2, 2' -bipyridyl (1g, 4.1mmol) and stannous chloride dihydrate (8.3g, 36.6mmol) are mixed uniformly, 20ml of 37% concentrated hydrochloric acid is added as a solvent, the mixture reacts for 1h at the temperature of 100 ℃ and the rotating speed of 350r/min, the mixture is extracted for 4 times by ethyl acetate after being filtered, anhydrous sodium sulfate is used for removing water, and the golden yellow 3,3 '-diamino-2, 2' -bipyridyl is obtained by rotary evaporation, wherein the yield is 98.0%.1H NMR(400MHz,CDCl3) δ 7.99,7.98,7.97,7.26,7.06,7.05,7.04,7.03,7.01,6.28 (see fig. 2).
Sodium alginate oxide grafted 3,3 '-diamino-2, 2' -bipyridine
The synthetic route is as follows:
dissolving the oxidized sodium alginate (2.0g, 10.2mmol) in the step (I) in 200mL of deionized water, stirring at the temperature of 40 ℃ and the rotating speed of 400r/min for 3h to dissolve the oxidized sodium alginate to prepare a 1% solution, dissolving the 3,3 '-diamino-2, 2' -bipyridyl (19.0mg, 0.1mmol) in the step (II) in 20mL of absolute ethyl alcohol, stirring at the temperature of 60 ℃ and the rotating speed of 200r/min for 30min to completely dissolve the 3,3 '-diamino-2, 2' -bipyridyl, and obtaining a light brown solution after complete dissolution.
Then slowly dripping the 3,3 '-diamino-2, 2' -bipyridyl solution into the oxidized sodium alginate solution, stirring and reacting for 3h at the temperature of 50 ℃ and the rotating speed of 400r/min, adding 0.5mL and 0.005mol/L acetic acid into the oxidized sodium alginate solution when the reaction is carried out for 0.5h for catalytic reaction, and observing the color change phenomenon of the oxidized sodium alginate solution by irradiating under an ultraviolet lamp with the wavelength of 365nm in the reaction process, wherein the color of the solution is gradually changed to green, yellow green and yellow fluorescence from initial non-fluorescence within 3h along with the reaction. After the reaction is finished, adding 800mL of absolute ethyl alcohol into the reaction solution, precipitating a large amount of solid, filtering, washing the obtained solid with the absolute ethyl alcohol, and freeze-drying to obtain the polysaccharide luminescent material, namely, oxidized sodium alginate grafted 3,3 '-diamino-2, 2' -bipyridine, and testing the fluorescence spectra of the polysaccharide luminescent material at different concentrations, wherein the concentrations from top to bottom are 10mg/L, 7mg/L, 3mg/L, 2mg/L, 1mg/L, 0.5mg/L and 0.2mg/L in sequence as shown in FIG. 3, and the luminous intensity of the polysaccharide luminescent material is gradually enhanced along with the enhancement of the solution concentration, which indicates that the material is a typical aggregation-induced luminescent material.
Changing the dosage of 3,3 '-diamino-2, 2' -bipyridyl and changing the molar ratio of the 3,3 '-diamino-2, 2' -bipyridyl to sodium alginate oxide in the reaction to 1: 100000, 1: 10000. 1: 1000. 1: 100. 1: 10 and 1: 1, reacting, keeping other conditions unchanged, and obtaining the luminescent colors and the fluorescence quantum efficiencies of the polysaccharide luminescent materials under different molar ratios as shown in figure 4 (excitation wavelength of 430nm), wherein the adding proportions (molar ratios) of sodium alginate oxide, 3 '-diamino-2, 2' -bipyridine and sodium alginate oxide are respectively 1: 100000,1: 10000,1: 1000,1: 100,1: 10 and 1: 1 and 3,3 '-diamino-2, 2' -bipyridine.
Embodiment 2 a marine organism polysaccharide grafted pyridine organic molecule multicolor adjustable aggregation-induced emission material is prepared by the following method:
oxidized sodium alginate was prepared as in example 1 by dissolving oxidized sodium alginate (1.8g, 9.2mmol) in 100ml of deionized water, stirring at a temperature of 40 ℃ and a speed of 400r/min for 3 hours to dissolve oxidized sodium alginate to give a 1.8% oxidized sodium alginate solution, dissolving the isomer of 3,3 '-diamino-2, 2' -bipyridine-5, 5 '-diamino-2, 2' -bipyridine (17.1mg, 0.09mmol) in 15ml of anhydrous methanol, and stirring at a temperature of 60 ℃ and a speed of 200r/min for 30 minutes to completely dissolve it to give a 5,5 '-diamino-2, 2' -bipyridine solution.
Slowly dripping a 5,5 '-diamino-2, 2' -bipyridyl solution into an oxidized sodium alginate solution, stirring for 3h at the temperature of 50 ℃ and the rotating speed of 400r/min, adding 0.5ml and 0.05mol/L of acetic acid into the oxidized sodium alginate solution for catalysis when the reaction is carried out for 0.5h, irradiating under a 365nm ultraviolet lamp in the reaction process, and gradually converting the color of the solution into light blue, blue and indigo blue fluorescence from initial non-fluorescence within 3h along with the reaction. After the reaction is finished, 200mL of anhydrous methanol is added into the solution, a large amount of solid is precipitated, the solution is filtered, the obtained solid is washed by the anhydrous methanol and then is frozen and dried, and an aggregation-inducing solid luminescent material, namely, the oxidized sodium alginate grafted 5,5 '-diamino-2, 2' -bipyridyl is obtained, the fluorescence spectra of the aggregation-inducing solid luminescent material at different concentrations are tested, as shown in FIG. 5, the concentrations of the aggregation-inducing solid luminescent material are 10mg/L, 7mg/L, 3mg/L, 2mg/L, 1mg/L, 0.5mg/L and 0.2mg/L from top to bottom in sequence, and the luminescent intensity is gradually enhanced along with the enhancement of the solution concentration, which indicates that the material is a typical aggregation-inducing luminescent material.
Changing the dosage of 5,5 '-diamino-2, 2' -bipyridyl and changing the molar ratio of the 5,5 '-diamino-2, 2' -bipyridyl to sodium alginate oxide in the reaction to 1: 10000. 1: 1000. 1: 100. 1: 10 and 1: 2, reacting, keeping other conditions unchanged, and obtaining the luminescent colors and the fluorescence quantum efficiencies (excitation wavelength 410nm) of the polysaccharide luminescent materials under different molar ratios, wherein the polysaccharide luminescent materials sequentially comprise sodium alginate oxide, 5 '-diamino-2, 2' -bipyridine and sodium alginate oxide according to the addition ratio (molar ratio) of 1: 10000,1: 1000,1: 100,1: 10 and 1: 2 and 5,5 '-diamino-2, 2' -bipyridine.
Embodiment 3 a marine organism polysaccharide grafted pyridine organic molecule multicolor adjustable aggregation-induced emission material is prepared by the following method:
oxidized chitosan was prepared according to the method of step (one) of example 1: chitosan (2.0g, 10.5mmol) was dissolved in 200ml of 3% acetic acid and stirred at 350r/min at room temperature for 3 hours to dissolve chitosan and prepare a 1% solution. Dissolving sodium periodate (4.4g, 21.0mmol) in 30mL deionized water, stirring at 50 ℃ and 350r/min for 20min to completely dissolve the sodium periodate to form a sodium periodate solution, slowly and dropwise adding the sodium periodate solution into the 1% chitosan solution, reacting for 24h in a dark place, adding ethylene glycol (1.1mL, 21.0mmol) to quench the residual sodium periodate, and stopping the reaction. Finally, 400mL of absolute ethyl alcohol is added into the mixture to separate the oxidized chitosan from the water, and the mixture is frozen and dried to obtain light yellow powder, namely the oxidized chitosan with the yield of 75%.
Then dissolving oxidized chitosan (3.36g, 10mmol) in 336ml deionized water, stirring for 5h at 80 ℃ and 500r/min to dissolve the oxidized chitosan to prepare 1% oxidized chitosan solution, dissolving 3,3 '-diamino-2, 2' -bipyridyl (19.0mg, 0.1mmol) in 20ml absolute ethyl alcohol, and stirring for 30min at 60 ℃ and 200r/min to completely dissolve the 3,3 '-diamino-2, 2' -bipyridyl to form 3,3 '-diamino-2, 2' -bipyridyl solution.
And then slowly dripping the 3,3 '-diamino-2, 2' -bipyridyl solution into the oxidized chitosan solution, stirring and reacting for 3 hours at the temperature of 80 ℃ and the rotating speed of 400r/min, adding 0.5ml of 0.005mol/L hydrochloric acid for catalysis after the reaction is carried out for 0.5 hour, irradiating under a 365nm ultraviolet lamp in the reaction process, observing the color change in the reaction process, and gradually converting the solution from initial non-fluorescence to green fluorescence and yellow-green fluorescence within 3 hours along with the reaction. After the reaction is finished, 672mL of absolute ethyl alcohol is added, a large amount of solid is separated out, the obtained solid is filtered, washed by the absolute ethyl alcohol and freeze-dried, and the aggregation-induced solid luminescent material, namely the oxidized chitosan grafted 3,3 '-diamino-2, 2' -bipyridyl (shown in figure 7) is obtained. The fluorescence spectrum (see fig. 8, where the triangle is labeled oxidized chitosan, the square is labeled oxidized chitosan-grafted 3,3 '-diamino-2, 2' -bipyridine, and the circle is labeled 3,3 '-diamino-2, 2' -bipyridine) and the uv-visible absorption spectrum (see fig. 9, where the triangle is labeled oxidized chitosan, the circle is labeled 3,3 '-diamino-2, 2' -bipyridine, and the square is labeled oxidized chitosan-grafted 3,3 '-diamino-2, 2' -bipyridine) were tested at a concentration of 3 mg/ml. The ultraviolet and fluorescence spectra show that the absorption and emission positions of the synthesized fluorescent material are changed, and the fluorescence intensity is higher than that of the raw material.
Embodiment 4 a marine organism polysaccharide grafted pyridine organic molecule multicolor adjustable aggregation-induced emission material is prepared by the following method:
2-chloro-3-nitropyridine (20.0mg, 0.115mmol), 2, 7-bis (4,4,5, 5-tetramethyl-1, 3-dioxo-2-boryl) -9, 9-dioctylfluorene (37.1mg, 0.0578mmol) and tetrakis (triphenylphosphine) palladium are uniformly mixed under the protection of argon, 5ml of anhydrous tetrahydrofuran is added as a solvent, the mixture reacts for 0.5h under the conditions that the temperature is 70 ℃ and the rotating speed is 350r/min, and then 2ml of 2M K is added2CO3And (3) continuing the reaction of the solution for 24 hours, after the reaction is finished, extracting the solution for 4 times by using dichloromethane, removing water by using anhydrous sodium sulfate, performing rotary evaporation to obtain a solid, and performing chromatographic column chromatography on the solid by using a mixed solvent of dichloromethane and ethyl acetate in a volume ratio of 5:1 to obtain a yellowish-brown target product a1 organic micromolecule with a yield of 85%.1H NMR(400MHz,CDCl3) δ 8.23,8.22,7.89,7.87,7.87,7.77,7.76,7.74,7.72,7.69,7.68,7.67,7.66,7.65,7.64,7.64,7.62,7.49,7.48,7.47,7.47,7.26,7.10,7.09,7.08,7.07.) (see fig. 10).
Dissolving oxidized sodium alginate (1.96g, 10mmol) in 196mL deionized water, stirring at the temperature of 40 ℃ and the rotation speed of 400r/min for 3h to dissolve the oxidized sodium alginate to obtain a 1% oxidized sodium alginate solution, dissolving a1 organic micromolecule (56.0mg, 0.1mmol) in 10mL DMF, and stirring at the temperature of 100 ℃ and the rotation speed of 200r/min for 1h to completely dissolve a1 organic micromolecule. Then slowly dripping the sodium alginate solution into an oxidized sodium alginate solution, stirring for 3 hours at the temperature of 70 ℃ and the rotating speed of 400r/min, adding 3mL of 0.08mol/L hydrochloric acid for catalysis after the reaction is carried out for 0.5 hour, irradiating under a 365nm ultraviolet lamp in the reaction process, observing the color change in the reaction process, and gradually changing the solution from the original light yellow to orange yellow and orange red fluorescence within 3 hours along with the reaction. After the reaction is finished, 400mL of DMF is added into the mixture, a large amount of solid is precipitated, the solid is filtered, the obtained solid is washed by anhydrous DMF, and freeze drying is carried out, so as to obtain the aggregation-induced solid luminescent material, namely the oxidized sodium alginate grafted a1 organic micromolecule (as shown in figure 11).
Comparing fig. 4, 6 and 11, it can be seen that the fluorescence shows multiple changes from blue to green, yellow and orange-red fluorescence by changing the concentration of 3,3 '-diamino-2, 2' -bipyridine or 5,5 '-diamino-2, 2' -bipyridine or replacing the 3,3 '-diamino-2, 2' -bipyridine with a1 organic small molecule.
Example 5
The cell biological activity detection is carried out on oxidized sodium alginate, 3 '-diamino-2, 2' -bipyridyl grafted by the oxidized sodium alginate and 5,5 '-diamino-2, 2' -bipyridyl grafted by the oxidized sodium alginate in human corneal epithelial cells by using a CCK8 detection method (shown in figures 12-1, 12-2 and 12-3 respectively), the oxidized sodium alginate can maintain the cell biological activity in a concentration range of 10-400 mu g/mL when the cells are treated for 12h and 24h, and the cell toxicity begins to appear and is concentration-dependent when the concentration is increased to 800 mu g/mL; when it was used to treat cells for 48h and 72h, the safe concentration was increased to 800. mu.g/mL. The oxidized sodium alginate grafted 3,3 '-diamino-2, 2' -bipyridyl can maintain the cell proliferation activity state when the concentration is 10-200 mu g/mL after the cells are treated for 12h and 24h, and the safe concentration is increased to 400 mu g/mL when the cells are treated for 48h and 72 h. And after the oxidized sodium alginate grafted 5,5 '-diamino-2, 2' -bipyridyl treats the cells for 12h and 24h, the safe concentration range for maintaining the cell proliferation activity is 10-100 mu g/mL, and after the cells are treated for 48h and 72h, the safe concentration range of the compound is not obviously changed, which indicates that the corneal epithelial cells do not interfere the biological proliferation activity of the corneal epithelial cells to the catabolism of the corneal epithelial cells. The CCK8 experiment results show that the upper limit of the safe concentration of the oxidized sodium alginate introduced with the bipyridyl micromolecules in the human corneal epithelial cells is 100-400 mu g/mL, which indicates that the safe concentration of the sodium alginate grafted by the pyridyl micromolecules is close to that of the pure sodium alginate, does not cause strong cytotoxicity and can be used for cell imaging application.
Claims (8)
1. A marine organism polysaccharide grafted amino-containing pyridine organic micromolecule multicolor adjustable aggregation-induced emission material has the following structural formula:
in the formula, R is a substituent lateral group on a marine organism polysaccharide ring; m is the number of repeating units in the marine organism polysaccharide;
the above-mentioned
Is absent or selected from any one of the following groups:
2. the preparation method of the marine organism polysaccharide grafted amino-containing pyridine organic small molecule multicolor adjustable aggregation-induced emission material as claimed in claim 1, which is characterized by comprising the following steps:
(1) dissolving the oxidized marine organism polysaccharide in deionized water to prepare an oxidized marine organism polysaccharide solution;
(2) dissolving pyridine organic micromolecules containing amino in an organic solvent to obtain a solution;
(3) slowly dripping the solution obtained in the step (2) into the oxidized marine organism polysaccharide solution obtained in the step (1), stirring and reacting for 0.5-24h under the conditions that the temperature is 20-100 ℃ and the rotating speed is 50-1000r/min, adding an acidic substance into the solution for catalysis in the reaction process, adding an organic solvent into the solution after the reaction is finished, separating out a solid, filtering, washing the obtained solid, and freeze-drying the solid to obtain the marine organism polysaccharide grafted amino-containing pyridine organic micromolecule multicolor adjustable aggregation induced luminescent material;
the molar ratio of the oxidized marine organism polysaccharide to the pyridine organic micromolecules containing amino in the step (3) is (1-100000): 1.
3. the preparation method of claim 2, wherein the amino-containing pyridine organic small molecule is T1, T2 or T3, and the structural formulas of T1, T2 and T3 are as follows:
4. the preparation method according to claim 2, wherein the marine organism polysaccharide is sodium alginate or chitosan.
5. The method according to claim 2, wherein the organic solvent used in steps (2) and (3) is absolute ethanol, absolute methanol, acetone, glacial acetic acid, tetrahydrofuran or DMF.
6. The method according to claim 2, wherein the acidic substance is acetic acid, hydrochloric acid, sulfuric acid, or nitric acid.
7. The preparation method according to claim 2, wherein the step (1) comprises the following steps of reacting sodium periodate with marine polysaccharide to oxidize the marine polysaccharide: dissolving marine organism polysaccharide in deionized water, adding sodium periodate, reacting completely at normal temperature in the dark, adding water-soluble organic solvent to precipitate, filtering, and freeze drying to obtain oxidized marine organism polysaccharide.
8. The preparation method according to claim 3, wherein the T1, T2 and T3 are commercially available products or obtained by Suzuki or Stille coupling reaction, and are as follows:
carrying out Suzuki reaction by using 2-bromo-3-aminopyridine and bisboron with Ar group as main reactants, or carrying out Stille coupling reaction by using 2-bromo-3-aminopyridine and bistin salt with Ar group as main reactants to obtain T1;
carrying out Suzuki reaction by using 2-bromo-4-aminopyridine and bisboron with Ar group as main reactants, or carrying out Stille coupling reaction by using 2-bromo-4-aminopyridine and bistin salt with Ar group as main reactants to obtain T2;
carrying out Suzuki reaction by using 2-bromo-5-aminopyridine and bisboron with Ar group as main reactants, or carrying out Stille coupling reaction by using 2-bromo-5-aminopyridine and bistin salt with Ar group as main reactants to obtain T3.
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