CN110668997A - Organelle targeted aggregation-induced emission material and preparation method thereof - Google Patents
Organelle targeted aggregation-induced emission material and preparation method thereof Download PDFInfo
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Abstract
A kind of organelle targeted aggregation-induced emission material and its preparation method, the steps are: 1) triphenylamine borate and aryl bromine compounds are used as raw materials, potassium carbonate solution and ethanol solvent are added after the triphenylamine borate and the aryl bromine compounds are fully and completely dissolved in toluene solution, palladium tetratriphenylphosphine is used as a reaction catalyst, nitrogen gas is used for reaction, and a target material is obtained after extraction, washing, solvent removal and column chromatography purification; when the aryl bromine compound in the first step is 2, 5-dibromopyridine and 2, 5-dibromopyrazine, the product in the first step and iodomethane are used as raw materials, the raw materials are dissolved in toluene, the heating reaction is carried out, after the toluene solvent is removed, sodium hexafluorophosphate and acetonitrile are added to be fully dissolved, and after the raw materials are stirred for 12 to 24 hours at room temperature, the solvent is removed through water washing and decompression, and recrystallization is carried out, the target fluorescent product can also be obtained; the preparation and purification cost is low; the fluorescent probe has excellent fluorescence emission performance and can realize the specific target imaging performance research of a plurality of organelles in cells.
Description
Technical Field
The invention relates to the technical field of organic fluorescent materials and biological imaging thereof, in particular to an organelle targeted aggregation-induced emission material and a preparation method thereof.
Background
Compared with inorganic fluorescent materials, organic fluorescent materials generally have excellent luminous performance and biocompatibility, and show good application prospects in biomedical fields such as cell imaging and the like. Meanwhile, the organic fluorescent material has good structure adjustability, and can provide possibility for further meeting the deep application of the organic fluorescent material in the field of biological imaging. However, it is worth noting that, for the conventional organic fluorescent material, although it can exhibit better luminous efficiency and brightness in a single molecule state such as solution, under a solid state, the luminous brightness thereof usually has a severe quenching phenomenon, i.e. aggregation leads to fluorescence quenching, which severely limits its deep application in the fields of biological imaging and the like. Fortunately, the Tang-Ben-loyd academy team proposed the concept of "aggregation-induced emission", and proposed the theoretical mechanism of molecular rotor motion limitation, and proposed a new idea and method for obtaining high-efficiency emission in the aggregation state. Therefore, the construction of the organic fluorescent material with aggregation-induced emission characteristics undoubtedly lays a tamping foundation for obtaining high-efficiency aggregation state luminescence and high-performance fluorescence imaging thereof.
On the other hand, researches prove that organelles such as lipid droplets, mitochondria, cell membranes, cell nucleuses and the like play an important role in the processes of cell metabolism, cell apoptosis and the like, so that the directional tracking and the visual monitoring of the organelles in the organelles are realized by developing the organelle targeted organic luminescent materials, and a method and a way can be undoubtedly provided for understanding the key processes and behaviors in the cells. Therefore, in summary, how to realize the organic fluorescent material with aggregation-induced emission characteristics and realize the specific targeted imaging of the organic fluorescent material in the cell through molecular design is one of the research hotspots in the field of the preparation of the organic fluorescent material and the cell imaging thereof at present.
Disclosure of Invention
In order to solve the problem of poor aggregation state luminescence performance of the traditional organic fluorescent material and realize specific targeting imaging of the traditional organic fluorescent material in cells, the invention aims to provide an organelle targeted aggregation-induced luminescent material and a preparation method thereof; compared with a solution state, the constructed aggregation-induced emission material shows more excellent fluorescence emission performance after forming an aggregate; meanwhile, the material has better biocompatibility, can be better applied to specific target imaging of organelles such as lipid droplets, mitochondria and the like, and provides a reliable method and a way for further dynamically observing the cell state, understanding the interaction between the organelles in the cell and the like.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a gathering induced luminescence material targeted by organelles has the following structural formula:
wherein
Is- - - -H, - -OCH3Or
The preparation method of the aggregation-induced emission material based on the organelle targeting comprises the following steps:
the method comprises the following steps: triphenylamine borate and aryl bromine compounds are used as raw materials, potassium carbonate solution and ethanol solvent are added after the triphenylamine borate and the aryl bromine compounds are fully and completely dissolved in toluene solution, palladium tetratriphenylphosphine is used as a reaction catalyst, the reaction is carried out for 15 to 30 hours under the protection of nitrogen at the temperature of between 80 and 100 ℃, and then water is added for quenching, organic solution is extracted, washing is carried out, solvent is removed, and column chromatography purification is carried out, so that the target organic aggregation-induced luminescent material is obtained.
The triphenylamine borate comprises 4-borate triphenylamine, 4-borate-4 ',4' -dimethoxy triphenylamine or 4-borate-4 ',4' -di-tert-butyl triphenylamine.
The aryl bromine compound comprises 2, 5-dibromopyridine, 2, 5-dibromopyrazine, 4, 7-dibromo-2, 1, 3-benzothiadiazole or 4, 7-dibromo- [1,2,5] thiadiazolo [3,4-c ] pyridine.
The molar ratio of the triphenylamine borate to the aryl bromine compound is (2.1-2.8): 1; the molar ratio of the potassium carbonate to the aryl bromine compound is (5-15): the molar ratio of the 1, tetratriphenylphosphine palladium to the aryl bromine compound is (2-6): 100, the volume ratio of the toluene to the ethanol is (10-40): 1.
when the aryl bromine compound in the first step is 2, 5-dibromopyridine or 2, 5-dibromopyrazine, the aggregation-induced emission material targeted by different organelles can be obtained by the product obtained in the first step through the following steps:
and (3) taking the product obtained in the step one and methyl iodide as raw materials, adding toluene to fully dissolve the product, heating the mixture at the temperature of 80-90 ℃ to react for 12-24 hours, removing the toluene solvent, adding sodium hexafluorophosphate to fully dissolve the product in acetonitrile, stirring the mixture at room temperature for 12-24 hours, washing the mixture with water, removing the solvent under reduced pressure, and recrystallizing the mixture to obtain the target organic aggregation-induced emission material with different targets.
The molar ratio of the product obtained in the first step to the methyl iodide is 1: (1.5-5.0); the molar ratio of the product obtained in the first step to sodium hexafluorophosphate is 1: (5.0-15.0).
The target compound related by the invention has simple synthesis and purification process and lower preparation cost. The obtained target compound can be dissolved in common organic solvents such as dichloromethane, trichloromethane, tetrahydrofuran, dimethyl sulfoxide and the like, and has certain ultraviolet absorption performance and fluorescence emission performance. The constructed target compound has excellent aggregation-induced emission characteristics and shows good solid-state emission performance. Meanwhile, when the target compound is used for cell marking and staining, the target compound can realize good specific imaging performance in organelles such as lipid droplets, mitochondria and the like.
Drawings
FIG. 1 is a diagram showing an ultraviolet absorption spectrum and a fluorescence emission spectrum of a target compound (I) in a tetrahydrofuran solution according to the present invention.
FIG. 2 is a fluorescence emission spectrum of the target compound (I) in a mixed solution of tetrahydrofuran and water at different ratios.
FIG. 3 is a fluorescence emission spectrum of the objective compound (I) in the present invention in a solid state.
FIG. 4 is a schematic diagram of fluorescence confocal imaging of target compounds (I, A) and Nile Red (B) in HeLa cells according to the present invention.
FIG. 5 is a schematic diagram of two-photon fluorescence confocal imaging of the target compound (I) in HeLa cells.
FIG. 6 is a two-dimensional spectrum of excitation and emission of a target compound (II) in a tetrahydrofuran solution according to the present invention.
FIG. 7 is a fluorescence emission spectrum of the target compound (II) in a mixed solution of tetrahydrofuran and water at different ratios.
FIG. 8 is a diagram showing an ultraviolet absorption spectrum and a fluorescence emission spectrum of the objective compound (III) of the present invention in a tetrahydrofuran solution.
FIG. 9 is a fluorescence emission spectrum of the target compound (III) in a mixed solution of tetrahydrofuran and water at various ratios.
Fig. 10 is a fluorescence emission spectrum of the objective compound (iii) in the present invention in a solid state.
FIG. 11 is a schematic diagram of fluorescence confocal imaging of target compound (III, A) and MitoTracker Red (B) in HeLa cells in accordance with the present invention.
FIG. 12 is a schematic diagram of two-photon fluorescence confocal imaging of a target compound (III) in HeLa cells according to the present invention.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings.
Example one
The organelle targeted aggregation-inducing luminescent material of the present example has the following structural formula (I):
the preparation method of the aggregation-induced emission material of the embodiment includes the following steps:
the method comprises the following steps: 4-boric acid ester triphenylamine and 2, 5-dibromopyridine are used as raw materials, are fully dissolved in a toluene solution, added with a potassium carbonate solution and an ethanol solvent, and reacted for 20 hours under the protection of nitrogen at 90 ℃ by using palladium tetratriphenylphosphine as a reaction catalyst, and then quenched by adding water, extracted by an organic solution, washed, removed of the solvent and purified by column chromatography to obtain the target compound (I).
The mole ratio of the 4-borate triphenylamine to the 2, 5-dibromopyridine is 2.5: 1, the molar ratio of potassium carbonate to 2, 5-dibromopyridine is 6: the molar ratio of 1, tetratriphenylphosphine palladium to 2, 5-dibromopyridine is 3: 100, the volume ratio of toluene to ethanol is 20: 1.
the reaction formula is as follows:
the specific operation is as follows: in a 250mL single-neck flask were added 2, 5-dibromopyridine (2.0g, 8.5mmol) and 4-boronate triphenylamine (7.8g, 21.1mmol), and 70mL of toluene was added to dissolve it sufficiently. After dissolution, 3.5mL of absolute ethanol and 2mol/L of anhydrous potassium carbonate solution (25mL) were added. Thereafter, tetrakistriphenylphosphine palladium (295mg) was added under nitrogen protection. After heating and refluxing for 20 hours, 50mL of deionized water was added to the reaction vessel to quench the reaction, the reaction mixture was extracted three times (3X 100mL) with dichloromethane, the combined organic solutions were washed with water (3X 80mL), and the solvent was removed under reduced pressure to give the crude product. A mixed solvent of petroleum ether and dichloromethane is selected as a developing solvent, and a white product of 3.6g is obtained after column chromatography separation and purification, wherein the yield is 76%.
The nuclear magnetic spectrum of the product is as follows:1H NMR(400MHz,CDCl3)δ8.90(s,1H),7.94-7.90(m,3H),7.74(d,J＝8.3Hz,1H),7.53(d,J＝8.7Hz,2H),7.33-7.28(m,8H),7.20-7.17(m,12H),7.10-7.06(m,4H).
FIG. 1 is a diagram showing an ultraviolet absorption spectrum and a fluorescence emission spectrum of a target compound (I) in a tetrahydrofuran solution according to the present invention. The research result shows that the target compound (I) has good ultraviolet absorption performance (300nm-400nm) and fluorescence emission performance (400nm-500nm) in a solution state; FIGS. 2 and 3 are fluorescence emission spectra of the target compound (I) in the mixed solution of tetrahydrofuran and water at different ratios and in the solid powder state, respectively. Research shows that with the increase of the water content in the mixed solution, nano aggregates of the target compound (I) are gradually formed in the mixed system, the fluorescence intensity of the nano aggregates is gradually improved, and certain aggregation-induced luminescence performance and excellent solid-state luminescence performance are displayed; FIG. 4 is a schematic diagram of fluorescence confocal imaging of the target compound (I) in HeLa cells. The target compound (I) can realize good intracellular lipid drop specific imaging by co-staining with a commercial lipid drop labeling dye Nile Red; FIG. 5 is a schematic diagram of two-photon fluorescence confocal imaging of the target compound (I) in HeLa cells. The results show that the target compound (I) can also realize the specific fluorescence imaging research of intracellular lipid droplets through two-photon excitation.
Example two
The organelle targeted aggregation-inducing luminescent material of the present example has the following structural formula (ii):
the preparation method of the aggregation-induced emission material of the embodiment includes the following steps:
the method comprises the following steps: 4-borate ester-4 ',4' -dimethoxy triphenylamine and 4, 7-dibromo-2, 1, 3-benzothiadiazole are used as raw materials, are fully dissolved in a toluene solution, added with a potassium carbonate solution and an ethanol solvent, reacted for 24 hours at 85 ℃ under the protection of nitrogen by using palladium tetratriphenylphosphine as a reaction catalyst, quenched by adding water, extracted by an organic solution, washed, subjected to solvent removal and purified by column chromatography to obtain a target compound (II).
The molar ratio of the 4-borate ester-4 ',4' -dimethoxy triphenylamine to the 4, 7-dibromo-2, 1, 3-benzothiadiazole is 2.5: 1, molar ratio of potassium carbonate to 4, 7-dibromo-2, 1, 3-benzothiadiazole 6: the molar ratio of 1, tetratriphenylphosphine palladium to 4, 7-dibromo-2, 1, 3-benzothiadiazole was 3: 100, the volume ratio of toluene to ethanol is 20: 1.
the reaction formula is as follows:
the specific operation is as follows: in a 100mL single-neck flask were added 4, 7-dibromo-2, 1, 3-benzothiadiazole (1.0g, 3.4mmol) and 4-boronate-4 ',4' -dimethoxytriphenylamine (3.6g, 8.5mmol) in this order, and 50mL of toluene was added to dissolve them sufficiently. Thereafter, 2.5mL of anhydrous ethanol and 2mol/L anhydrous potassium carbonate solution (10mL) were further added. Thereafter, tetrakistriphenylphosphine palladium (118mg) was added under nitrogen protection. After heating and reacting at 85 ℃ for 24 hours, deionized water (10mL) is added into the reaction system to quench the reaction, chloroform is selected to extract the reaction mixed liquid (3X 100mL), and the combined organic layers are washed by water (3X 80mL) and the solvent is removed under reduced pressure to obtain a crude product. A mixed solvent of petroleum ether and dichloromethane is selected as a developing solvent, and a red product 1.6g is obtained after column chromatography separation and purification, wherein the yield is 65%.
The nuclear magnetic spectrum of the product is as follows:1H NMR(400MHz,CDCl3)δ7.83(d,J＝8.8Hz,4H),7.72(s,2H),7.17(d,J＝9.0Hz,8H),7.08(d,J＝8.8Hz,4H),6.89(d,J＝9.0Hz,8H),3.84(s,12H).
FIG. 6 is a two-dimensional spectrum of excitation and emission of a target compound (II) in a tetrahydrofuran solution according to the present invention. Research shows that the target compound (II) can generate obvious red fluorescence at the excitation wavelength of 250nm-450nm, and the maximum emission wavelength of the target compound (II) is about 670 nm. FIG. 7 is a fluorescence emission spectrum of the target compound (II) in a mixed solution of tetrahydrofuran and water at different ratios. Researches show that the fluorescence emission intensity of the target compound (II) is obviously improved along with the increase of the water content in the mixed system. In particular, the target compound (ii) showed better fluorescence emission properties in the aggregated state with a water content of 90% compared to the solution state, demonstrating its excellent aggregation-induced emission properties.
EXAMPLE III
The organelle targeted aggregation-inducing luminescent material of the present example has the following structural formula (iii):
the preparation method of the aggregation-induced emission material of the embodiment includes the following steps:
the product of the first example and methyl iodide were used as raw materials, toluene was added to dissolve them sufficiently, and the reaction was heated at 88 ℃ for 18 hours. After removal of the toluene solvent, sodium hexafluorophosphate was added and sufficiently dissolved in acetonitrile. After stirring for 18 hours at room temperature, the target fluorescent product (III) is obtained after washing with water, removal of the solvent under reduced pressure and recrystallization.
The molar ratio between the product of the first example and methyl iodide is 1: 2.5; example one product to sodium hexafluorophosphate molar ratio was 1: 10.
the reaction formula is as follows:
the specific operation is as follows: a50 mL single-neck flask was charged with the product of example (0.6g, 1.0mmol) and methyl iodide (0.38g, 2.5mmol), and 20mL of toluene was added to dissolve it sufficiently, and the reaction was heated at 88 ℃ for 18 hours. Thereafter, the toluene solvent was removed, and sodium hexafluorophosphate (1.6g, 10.0mmol) was added to the reaction vessel, and 200mL of acetonitrile was added thereto to be sufficiently dissolved. After stirring at room temperature for 18 hours, the reaction was washed with water (3X 50mL) and the solvent was removed under reduced pressure to give the crude product. The crude product was recrystallized from acetonitrile to yield 3.6g of the orange target product in 76% yield.
The nuclear magnetic spectrum of the product is as follows:1H NMR(600MHz,d6-DMSO):δ＝9.39(s,1H),8.80(d,J＝8.4Hz,1H),8.07(d,J＝8.4Hz,1H),7.82(d,J＝8.4Hz,2H),7.57(d,J＝8.4Hz,2H),7.44-7.38(m,8H),7.23-7.02(m,16H)ppm。
FIG. 8 is a diagram showing an ultraviolet absorption spectrum and a fluorescence emission spectrum of the objective compound (III) of the present invention in a tetrahydrofuran solution. The research result shows that the target compound (III) has good ultraviolet absorption performance and fluorescence emission performance in a solution state, the absorption spectrum range is between 250nm and 500nm, and the emission spectrum is between 450nm and 750 nm; fig. 9 and 10 are fluorescence emission spectrograms of the target compound (iii) in the mixed solution of tetrahydrofuran and water at different ratios and in the solid powder state, respectively. Research results show that the fluorescence intensity of the mixed system is gradually improved along with the increase of the water content in the mixed system, and the excellent aggregation-induced emission performance is shown. It is to be noted that the target compound (III) exhibits extremely excellent fluorescence emission properties in an aggregated state with a water content of 90% and a solid state. FIG. 11 is a schematic view of fluorescence confocal imaging of target compound (III) in HeLa cells according to the present invention. The co-staining with a commercial MitoTracker Red dye shows that the target compound (III) can realize good intracellular mitochondrion specificity imaging; FIG. 12 is a schematic diagram of two-photon fluorescence confocal imaging of a target compound (III) in HeLa cells according to the present invention. The results show that the target compound (III) can also realize the specific fluorescence imaging research of mitochondria in cells through two-photon excitation.
Example four
The organelle targeted aggregation-inducing luminescent material with the structure shown as (III) can also be prepared by the following steps:
the product of the first example and methyl iodide were used as raw materials, toluene was added to dissolve them sufficiently, and the reaction was heated at 80 ℃ for 12 hours. After the toluene solvent was removed, sodium hexafluorophosphate and acetonitrile were added to be sufficiently dissolved. After stirring for 12 hours at room temperature, the target fluorescent product (III) is obtained after washing with water, removal of the solvent under reduced pressure and recrystallization.
The molar ratio between the product of the first example and methyl iodide is 1: 1.5; example one product to sodium hexafluorophosphate molar ratio was 1: 5.
the method for preparing the organelle targeted aggregation-induced emission material with the structure shown as (III) is simple, the purification cost is low, and the yield is 50.1%.
EXAMPLE five
The organelle targeted aggregation-inducing luminescent material with the structure shown as (III) can also be prepared by the following steps:
the product of the first example and methyl iodide were used as raw materials, toluene was added to dissolve them sufficiently, and the reaction was heated at 90 ℃ for 24 hours. After the toluene solvent was removed, sodium hexafluorophosphate and acetonitrile were added to be sufficiently dissolved. After stirring for 24 hours at room temperature, the target fluorescent product (III) is obtained after washing with water, removing the solvent under reduced pressure and recrystallizing.
The molar ratio between the product of the first example and methyl iodide is 1: 5; example one product to sodium hexafluorophosphate molar ratio was 1: 15.
the method for preparing the organelle targeted aggregation-induced emission material with the structure shown as (III) is simple, but more excessive methyl iodide exists, the removal and purification cost is high, and the yield is 63.5%.
Claims (6)
1. A organelle targeted aggregation-induced emission material is characterized by having the following structural formula:
wherein
Is- - - -H, - -OCH3Or
2. The preparation method of the organelle targeted aggregation-induced emission material according to claim 1, comprising the following steps:
the method comprises the following steps: triphenylamine borate and aryl bromine compounds are used as raw materials, potassium carbonate solution and ethanol solvent are added after the triphenylamine borate and the aryl bromine compounds are fully and completely dissolved in toluene solution, palladium tetratriphenylphosphine is used as a reaction catalyst, the reaction is carried out for 15 to 30 hours under the protection of nitrogen at the temperature of between 80 and 100 ℃, and then water is added for quenching, organic solution is extracted, washing is carried out, solvent is removed, and column chromatography purification is carried out, so that the target organic aggregation-induced luminescent material is obtained.
3. The preparation method of the organelle targeted aggregation-induced emission material according to claim 2, wherein the triphenylamine borate comprises 4-borate triphenylamine, 4-borate-4 ',4' -dimethoxy triphenylamine or 4-borate-4 ',4' -di-tert-butyl triphenylamine; the aryl bromine compound comprises 2, 5-dibromopyridine, 2, 5-dibromopyrazine, 4, 7-dibromo-2, 1, 3-benzothiadiazole or 4, 7-dibromo- [1,2,5] thiadiazolo [3,4-c ] pyridine.
4. The preparation method of the organelle targeted aggregation-induced emission material according to claim 2, wherein the molar ratio of the triphenylamine borate to the aryl bromide compound is (2.1-2.8): 1; the molar ratio of the potassium carbonate to the aryl bromine compound is (5-15): the molar ratio of the 1, tetratriphenylphosphine palladium to the aryl bromine compound is (2-6): 100, the volume ratio of the toluene to the ethanol is (10-40): 1.
5. the preparation method of organelle targeted aggregation-induced emission material according to claim 2, wherein when the aryl bromide compound in the step one is 2, 5-dibromopyridine or 2, 5-dibromopyrazine, the product obtained in the step one is subjected to the following steps to obtain different organelle targeted aggregation-induced emission materials, specifically:
and (3) taking the product obtained in the step one and methyl iodide as raw materials, adding toluene to fully dissolve the product, heating the mixture at the temperature of 80-90 ℃ to react for 12-24 hours, removing the toluene solvent, adding sodium hexafluorophosphate to fully dissolve the product in acetonitrile, stirring the mixture at room temperature for 12-24 hours, washing the mixture with water, removing the solvent under reduced pressure, and recrystallizing the mixture to obtain the target organic aggregation-induced emission material with different targets.
6. The method for preparing an organelle targeted aggregation-induced emission material according to claim 5, wherein the molar ratio of the product obtained in the first step to methyl iodide is 1: (1.5-5.0); the molar ratio of the product obtained in the first step to sodium hexafluorophosphate is 1: (5.0-15.0).
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