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CN110668997B - A class of organelle-targeted aggregation-induced luminescent materials and preparation methods thereof - Google Patents

A class of organelle-targeted aggregation-induced luminescent materials and preparation methods thereof Download PDF

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CN110668997B
CN110668997B CN201910925169.0A CN201910925169A CN110668997B CN 110668997 B CN110668997 B CN 110668997B CN 201910925169 A CN201910925169 A CN 201910925169A CN 110668997 B CN110668997 B CN 110668997B
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党东锋
胥艳子
王直
申起飞
赵博
孟令杰
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Abstract

一类细胞器靶向的聚集诱导发光材料及其制备方法，步骤为：1)以三苯胺类硼酸酯与芳基溴类化合物为原料，在甲苯溶液中充分完全溶解后，加入碳酸钾溶液及乙醇溶剂，并以四三苯基膦钯为反应催化剂，氮气反应，经加萃取、洗涤、去除溶剂和柱层析纯化后获得目标材料；当步骤一中的芳基溴类化合物为2,5‑二溴吡啶和2,5‑二溴吡嗪时，步骤一产物和碘甲烷为原料，在甲苯中溶解，加热反应，去除甲苯溶剂之后，加入六氟磷酸钠及乙腈使之充分溶解，室温下搅拌12‑24小时之后，经水洗、减压去除溶剂及重结晶后，也可获得目标荧光产物；本发明制备和纯化成本较低；具有优异的荧光发射性能，能够实现在细胞内多个细胞器的特异性靶向成像性能研究。A class of organelle-targeted aggregation-induced luminescent materials and a preparation method thereof. The steps are: 1) using triphenylamine borate and aryl bromide as raw materials, fully and completely dissolving in a toluene solution, adding potassium carbonate solution and Ethanol solvent, and using tetrakistriphenylphosphine palladium as the reaction catalyst, nitrogen reaction, extraction, washing, solvent removal and column chromatography purification to obtain the target material; when the aryl bromide compound in step 1 is 2,5 When the dibromopyridine and 2,5-dibromopyrazine are used, the product of step 1 and methyl iodide are used as raw materials, and the product is dissolved in toluene, heated and reacted. After removing the toluene solvent, sodium hexafluorophosphate and acetonitrile are added to make it fully dissolved. After stirring for 12-24 hours, after washing with water, removing the solvent under reduced pressure and recrystallization, the target fluorescent product can also be obtained; the preparation and purification costs of the invention are low; it has excellent fluorescence emission performance, and can achieve multiple intracellular Organelle-specific targeted imaging performance studies.

Description

Organelle targeted aggregation-induced emission material and preparation method thereof
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:
Figure BDA0002218724520000021
wherein
Figure BDA0002218724520000022
Is- - - -H, - -OCH3Or
Figure BDA0002218724520000023
Figure BDA0002218724520000024
Is composed of
Figure BDA0002218724520000025
Figure BDA0002218724520000031
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):
Figure BDA0002218724520000051
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:
Figure BDA0002218724520000061
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):
Figure BDA0002218724520000071
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:
Figure BDA0002218724520000081
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):
Figure BDA0002218724520000091
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:
Figure BDA0002218724520000101
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 (2)

1. An organelle targeted aggregation-induced emission material having the formula:
Figure FDA0002899590150000011
2. the method for preparing an organelle targeted aggregation-inducing luminescent 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, and after the reaction is carried out for 20 hours under the protection of nitrogen at 90 ℃, water is added for quenching, organic solution is extracted, the solvent is removed, and column chromatography purification is carried out, so that the target organic aggregation-induced emission material is obtained;
the triphenylamine borate is 4-boric acid ester triphenylamine;
the aryl bromine compound is 2, 5-dibromopyridine;
the molar ratio of the triphenylamine borate to the aryl bromine compound is 2.5: 1; the molar ratio of the potassium carbonate to the aryl bromine compound is 6: 1, the molar ratio of the palladium tetratriphenylphosphine to the aryl bromine compound is 3: 100, the volume ratio of toluene to ethanol is 20: 1;
step two, taking the product obtained in the step one and methyl iodide as raw materials, adding toluene to fully dissolve the raw materials, heating the raw materials at 88 ℃ to react for 18 hours, removing the toluene solvent, adding sodium hexafluorophosphate to fully dissolve the raw materials in acetonitrile, stirring the mixture for 18 hours at room temperature, washing the mixture with water, reducing the pressure to remove the solvent, and recrystallizing the mixture to obtain a target product aggregation-induced luminescent material;
the molar ratio of the product obtained in the first step to the methyl iodide is 1: 2.5; the molar ratio of the product obtained in the first step to sodium hexafluorophosphate is 1: 10.
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