Method for preparing PPEs high-fluorescence nanoparticles

Abstract

The invention discloses a polyphenyl ether (PPEs) fluorescent dye modification technology, and particularly relates to a method for preparing PPEs high-fluorescence nanoparticles. The method comprises the following steps: synthesis of PPEs-OH: mixing and dissolving 2-(2,5-diiodo-4-methyl) phenethyl alcohol, 1,4-diethynyl-2,5-dioctyloxy benzene and piperidine into tetrahydrofuran according to a substance mass ration of (1-3):(1-3):(1-3.3), adding 0.00001-1 equivalent weight of bis (triphenylphosphine) palladium dichloride ((PPh3)2PdCl2) and 0.00001-1 equivalent weight of cuprous iodide (CuI), and performing stirring for 20-28 hours at room temperature. The method firstly synthesizes the PPEs-OH, initiates caprolactone ring opening polymerization by using hydroxyl to obtain PCL-modified PPEs, then self-assembling is carried out on the PCL-modified-PPEs with a block copolymer PEG-PCL to form nano particles, and PCL modification effectively retards PPEs aggregation to improve the fluorescence property of the PPEs, and improve the light stability of the PPEs. According to the invention, the hydrophilicity and biocompatibility of the PPEs are improved, so that the PPEs can be applied more widely.

Description

technical field

[0001] The invention relates to polyphenylene ether (PPEs) fluorescent dye modification technology, in particular to a method for preparing PPEs high-fluorescence nanoparticles. Background technique

[0002] Conjugated polymers, such as polythiophene (PT), polyparaphenylene vinylene (PPV), and polyphenylene ethers (PPEs), are a class of organic semiconducting materials characterized by the presence of large delocalized hydrogen bonds in their polymer backbones. . They exhibit excellent photophysical properties such as high fluorescence and photostability, which are key parameters for various biological applications such as biosensing and cell imaging. The optical properties of conjugated polymers sensitively depend on the chemical composition of the polymer backbone and the physical filling of side chains. Although the theory about the transfer of energy within and between chains is complex and controversial, it has been established that conjugated polymers...

Examples

Embodiment 1

[0029] S1. Synthesis of PPEs-OH

[0030] Add 1.00mmol 2-(2,5-diiodo-4-methyl)phenylethanol, 1.00mmol 1,4-diethynyl-2,5-dioctyloxybenzene and 1.60mL piperazine into a Schlenk flask Pyridine, with 1.60mL tetrahydrofuran (THF), dissolve the three substances, then add 0.1μmol bistriphenylphosphine palladium dichloride ((PPh 3 ) 2 PdCl 2 ), 1.80 μmol cuprous iodide (CuI) mixed, stirred at room temperature for 24h;

[0031] The obtained polymer was extracted with 1ml of dichloromethane each time, extracted 3 times, and the solvent was removed by vacuum evaporation to obtain a solid, which was washed successively with 10% ammonia water and 10% hydrochloric acid; Methane extraction, after extraction 3 times, settling with methanol, filtering to obtain dark green solid P0;

[0032] S2. Synthesis of PPEs-PCL: Take 10 mg of the sample PPEs-OH prepared by S1, dry it under oil pump vacuum at 70 °C, add 0.2 ml ε-caprolactone, heat the mixture to 110 °C until the polymer is dissolved, th...

Embodiment 2

[0036] S1. Synthesis of PPEs-OH

[0037] Add 2.00mmol 2-(2,5-diiodo-4-methyl)phenylethanol, 2.00mmol 1,4-diethynyl-2,5-dioctyloxybenzene and 3.20mL piperazine into a Schlenk flask Pyridine, use 3.20mL tetrahydrofuran (THF), dissolve the three substances, then add 0.2μmol bistriphenylphosphine palladium dichloride ((PPh 3) 2 PdCl 2 ), 3.60 μmol cuprous iodide (CuI) mixed, stirred at room temperature for 24 hours;

[0038] The obtained polymer was extracted with 2ml of dichloromethane each time, extracted 3 times, and the solvent was removed by vacuum evaporation to obtain a solid, which was washed with 10% ammonia water and 10% hydrochloric acid successively; Methane extraction, after extraction 3 times, settling with methanol, filtering to obtain dark green solid P0;

[0039] S2. Synthesis of PPEs-PCL: Take 100 mg of the sample PPEs-OH prepared by S1, dry it under oil pump vacuum at 70 °C, add 2 ml ε-caprolactone, heat the mixture to 110 °C until the polymer is dissolved, ...

Embodiment 3

[0043] A. Synthesis of PPEs-PCL: Take 100 mg of the sample P20 prepared in step S2 in Example 2, dry it under 70°C oil pump vacuum, add 4mlε-caprolactone, heat the mixture to 110°C until the polymer is dissolved, and then After adding stannous octoate (1 mg, 3 mol), the reaction stopped after the mixture solidified. The product was dissolved in chloroform, settled with methanol, filtered, and dried under oil pump vacuum to obtain the product P60.

[0044] B. PPEs-PCL and PCL 2K -PEG 5K Co-assembly: 1.00mgPPEs-PCL and 11mgPCL prepared in step A 2K -PEG 5K (purchased from the market) was dissolved in 1 ml, and the mixture was dripped into 15 ml of deionized water for 1 h under vortex, then dialyzed with a dialysis bag to remove tetrahydrofuran, and freeze-dried at -50°C to obtain a yellow powder.

[0045] According to the above fluorescence detection method, the fluorescence quantum yield of the target object prepared in Example 3 was 0.78.

technical field

[0001] The invention relates to polyphenylene ether (PPEs) fluorescent dye modification technology, in particular to a method for preparing PPEs high-fluorescence nanoparticles. Background technique

[0002] Conjugated polymers, such as polythiophene (PT), polyparaphenylene vinylene (PPV), and polyphenylene ethers (PPEs), are a class of organic semiconducting materials characterized by the presence of large delocalized hydrogen bonds in their polymer backbones. . They exhibit excellent photophysical properties such as high fluorescence and photostability, which are key parameters for various biological applications such as biosensing and cell imaging. The optical properties of conjugated polymers sensitively depend on the chemical composition of the polymer backbone and the physical filling of side chains. Although the theory about the transfer of energy within and between chains is complex and controversial, it has been established that conjugated polymers...

Examples

Embodiment 1

[0029] S1. Synthesis of PPEs-OH

[0030] Add 1.00mmol 2-(2,5-diiodo-4-methyl)phenylethanol, 1.00mmol 1,4-diethynyl-2,5-dioctyloxybenzene and 1.60mL piperazine into a Schlenk flask Pyridine, with 1.60mL tetrahydrofuran (THF), dissolve the three substances, then add 0.1μmol bistriphenylphosphine palladium dichloride ((PPh 3 ) 2 PdCl 2 ), 1.80 μmol cuprous iodide (CuI) mixed, stirred at room temperature for 24h;

[0031] The obtained polymer was extracted with 1ml of dichloromethane each time, extracted 3 times, and the solvent was removed by vacuum evaporation to obtain a solid, which was washed successively with 10% ammonia water and 10% hydrochloric acid; Methane extraction, after extraction 3 times, settling with methanol, filtering to obtain dark green solid P0;

[0032] S2. Synthesis of PPEs-PCL: Take 10 mg of the sample PPEs-OH prepared by S1, dry it under oil pump vacuum at 70 °C, add 0.2 ml ε-caprolactone, heat the mixture to 110 °C until the polymer is dissolved, th...

Embodiment 2

[0036] S1. Synthesis of PPEs-OH

[0037] Add 2.00mmol 2-(2,5-diiodo-4-methyl)phenylethanol, 2.00mmol 1,4-diethynyl-2,5-dioctyloxybenzene and 3.20mL piperazine into a Schlenk flask Pyridine, use 3.20mL tetrahydrofuran (THF), dissolve the three substances, then add 0.2μmol bistriphenylphosphine palladium dichloride ((PPh 3) 2 PdCl 2 ), 3.60 μmol cuprous iodide (CuI) mixed, stirred at room temperature for 24 hours;

[0038] The obtained polymer was extracted with 2ml of dichloromethane each time, extracted 3 times, and the solvent was removed by vacuum evaporation to obtain a solid, which was washed with 10% ammonia water and 10% hydrochloric acid successively; Methane extraction, after extraction 3 times, settling with methanol, filtering to obtain dark green solid P0;

[0039] S2. Synthesis of PPEs-PCL: Take 100 mg of the sample PPEs-OH prepared by S1, dry it under oil pump vacuum at 70 °C, add 2 ml ε-caprolactone, heat the mixture to 110 °C until the polymer is dissolved, ...

Embodiment 3

[0043] A. Synthesis of PPEs-PCL: Take 100 mg of the sample P20 prepared in step S2 in Example 2, dry it under 70°C oil pump vacuum, add 4mlε-caprolactone, heat the mixture to 110°C until the polymer is dissolved, and then After adding stannous octoate (1 mg, 3 mol), the reaction stopped after the mixture solidified. The product was dissolved in chloroform, settled with methanol, filtered, and dried under oil pump vacuum to obtain the product P60.

[0044] B. PPEs-PCL and PCL 2K -PEG 5K Co-assembly: 1.00mgPPEs-PCL and 11mgPCL prepared in step A 2K -PEG 5K (purchased from the market) was dissolved in 1 ml, and the mixture was dripped into 15 ml of deionized water for 1 h under vortex, then dialyzed with a dialysis bag to remove tetrahydrofuran, and freeze-dried at -50°C to obtain a yellow powder.

[0045] According to the above fluorescence detection method, the fluorescence quantum yield of the target object prepared in Example 3 was 0.78.

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