Nano particles of Si-O-C type polyether modified polysiloxane entrapped AIE fluorescent molecules, and preparation method and application of nano particles of Si-O-C type polyether modified polysiloxane entrapped AIE fluorescent molecules

Abstract

The invention discloses a nano particle of an amphiphilic Si-O-C type polyether modified polysiloxane entrapped AIE fluorescent molecule as well as a preparation method and application of the nano particle of the amphiphilic Si-O-C type polyether modified polysiloxane entrapped AIE fluorescent molecule. The nano particle is characterized in that a lipophilic AIE fluorescent molecular compound is arranged inside the nano particle, an Si-O-C type polyether modified polysiloxane copolymer is wrapped outside the nano particle, and the structural formula of the lipophilic AIE fluorescent molecular compound is shown in any one of the following formulas. Amphiphilic Si-O-C type polyether modified polysiloxane and novel AIE fluorescent molecules are self-assembled to form oil-in-water type nano particles, so that controllable aggregation among the AIE molecules is improved, and solubility and uniform dispersity of lipophilic AIE fluorescent molecules in a biological environment and a buffer solution are effectively enhanced; therefore, the fluorescence emission intensity and stability of the lipophilic AIE fluorescent molecule are greatly improved, and the application of the lipophilic AIE fluorescent molecule in biological detection and tracing is facilitated. # imgabs0 #

Description

Technical Field

[0001] The invention relates to an application of an organosilicon polymer and an AIE small molecule, and in particular to a Si-OC type polyether modified polysiloxane nanoparticle encapsulating an AIE fluorescent molecule, and a preparation method and application thereof. Background Art

[0002] Traditional fluorescent molecules emit bright fluorescence in dilute solutions, but under conditions of high concentration or high aggregation, fluorescence quenching occurs, which is called aggregation-induced quenching (ACQ). A unique class of fluorescent dyes has aggregation-induced emission (AIE) characteristics, which emit weak or no fluorescence in dilute solutions or in good solvents, and enhance fluorescence in aggregated states or in poor solvents. AIE fluorescent molecules have excellent performance in detection, such as low detection limit, high sensitivity, good specificity, cheap equipment, and easy operation. Therefore, it is of great significance to develop AIE fluorescent molecules with excellent performance for biological detection and imaging.

[0003] Photodynamic therapy (PDT) is an attractive cancer treatment method that can be spatially and temporally controlled by light, is minimally invasive, and has great potential in real-time diagnosis and parallel in situ treatment. It destroys malignant cancer cells by light-induced generation of cytotoxic reactive oxygen species (ROS). Encouragingly, aggregation-induced emission luminogens (AIE) have become useful photosensitizers and are being developed for cancer cell imaging and killing. In addition, AIE fluorescent molecules with near-infrared (NIR) emission can greatly deepen the imaging depth due to low energy loss and low autofluorescence interference in biological tissues.

[0004] At present, fluorescent molecules with AIE properties have made significant progress in many fields and are a hot research area. At the same time, they have a wide range of applications in the detection of biomarkers, drug delivery, and in vivo photodynamic therapy. However, most AIE fluorescent molecules are highly lipid-soluble or water-soluble, and their performance cannot be maximized in a solution system, limiting the application of AIE molecules with excellent performance. Summary of the invention

[0005] Purpose of the invention: The first purpose of the present invention is to provide a Si-OC type polyether-modified polysiloxane-encapsulated AIE fluorescent molecule nanoparticle, the second purpose of the present invention is to provide a method for preparing the Si-OC type polyether-modified polysiloxane-encapsulated AIE fluorescent molecule nanoparticle, the third purpose of the present invention is to provide an application of Si-OC type polyether-modified polysiloxane-encapsulated AIE fluorescent molecule nanoparticle in biological detection or imaging, and to improve the fluorescence emission intensity of fat-soluble / water-soluble AIE small molecules in a solution system by using the amphiphilic Si-OC type polyether-modified polysiloxane self-assembly technology.

[0006] Technical solution: The present invention discloses a Si-OC type polyether-modified polysiloxane nanoparticles encapsulating AIE fluorescent molecules. The nanoparticles contain a lipophilic AIE fluorescent molecule compound inside and are coated with an amphiphilic Si-OC type polyether-modified polysiloxane copolymer on the outside.

[0007] Furthermore, the structural formula of the lipophilic AIE fluorescent molecule compound is any one of the following:

[0008]

[0009] Furthermore, the maximum absorption wavelength of the TTCN is 495 nm, and the emission wavelength in aqueous solution is 630 nm.

[0010] Furthermore, the maximum absorption wavelength of MTTCN is 515 nm, and the emission wavelength in aqueous solution is 650 nm.

[0011] Furthermore, the amphiphilic Si-OC type polyether-modified polysiloxane is an ABA type structure, and its general structural formula is as follows:

[0012]

[0013] Here, m is 1 to 25, n is 1 to 25, and x is 20 to 100. Preferably, m is 3 to 20, n is 3 to 20, and x is 30 to 50.

[0014] Furthermore, TTCN and MTTCN are synthesized according to the following routes:

[0015]

[0016] Furthermore, the preparation of TTCN comprises the following steps:

[0017] (A1) 4-bromo-N,N-diphenylaniline and (5-formylthiophene-2-yl)boric acid are dissolved in a mixed solvent of methanol and toluene, and potassium carbonate is added. After stirring evenly, the air in the reaction system is removed, and a catalyst of bis(diphenylphosphinothiocene)palladium dichloride is added. Nitrogen is introduced for protection, and the reaction is heated to obtain 5-(4-(diphenylamino)phenyl)thiophene-2-carboxaldehyde.

[0018] (A2) 5-(4-(diphenylamino)phenyl)thiophene-2-carboxaldehyde and 2-(3-cyano-4,5,5-trimethylfuran-2(5H)-ylidene)malononitrile were dissolved in ethanol, pyridine catalyst was added, air was removed, nitrogen was filled for protection, and the reaction was heated.

[0019] Further, the preparation of MTTCN comprises the following steps:

[0020] (B1) dissolving 4-bromo-N,N-bis(4-methoxyphenyl)aniline and (5-formylthiophene-2-yl)boric acid in a mixed solvent of methanol and toluene, adding potassium carbonate, stirring evenly, removing air from the reaction system, adding a catalyst of bis(diphenylphosphinothiocenepalladium)dichloride, filling with nitrogen for protection, and heating the reaction to obtain 5-(4-(bis(4-methoxyphenyl)amino)phenyl)thiophene;

[0021] (B2) Dissolve 5-(4-(bis(4-methoxyphenyl)amino)phenyl)thiophene-2-carboxaldehyde and 2-(3-cyano-4,5,5-trimethylfuran-2(5H)-ylidene)malononitrile in ethanol, add catalyst pyridine, remove air, fill with nitrogen for protection, and heat to react.

[0022] Furthermore, in step (A2) and step (B2), the heating reaction temperature is 80-90°C, and the heating reaction time is 8-12h.

[0023] The preparation method of the nanoparticles of the present invention comprises the following steps: dissolving a lipophilic AIE fluorescent molecule compound in a dimethyl sulfoxide organic solvent to completely dissolve it to form a liquid A, then dissolving an amphiphilic Si-OC type polyether modified polysiloxane in pure water to form a liquid B, mixing the liquid B with the liquid A, ultrasonically treating them, and self-assembling to form nanoparticles with the AIE fluorescent molecule compound inside and the amphiphilic Si-OC type polyether modified polysiloxane outside.

[0024] Furthermore, the Si-OC type polyether-modified polysiloxane is synthesized according to the following route:

[0025]

[0026] Wherein m is 1 to 25, n is 1 to 25, and x is 20 to 100.

[0027] Furthermore, the molar ratio of the amphiphilic Si-OC type polyether-modified polysiloxane to the AIE fluorescent molecule compound is (1.0-1.000):(5-20), preferably (5.0-1000):(10-20).

[0028] Furthermore, the preparation of the Si-OC type polyether-modified polysiloxane comprises the following steps: terminal hydrogen-containing polysiloxane, polyether and catalyst tris(pentafluorophenyl)borane (B(C 6 F 5 ) 3 ) mixed and heated to react.

[0029] Furthermore, the heating reaction temperature is 100-130° C., and the heating reaction time is 2-4 hours.

[0030] The invention discloses an application of Si-OC type polyether modified polysiloxane nanoparticles encapsulating AIE fluorescent molecules in biological detection or imaging.

[0031] Invention mechanism: Water accounts for about 60% to 70% of the human body. Water accounts for the vast majority in both cells and tissues, and cells are cultured in an aqueous environment. Most small molecules with AIE properties are lipophilic small molecules with poor solubility in water. Therefore, most AIE fluorescent molecules with excellent performance cannot exert their excellent performance in biological environments, such as fluorescence imaging, fluorescence sensing and detection, photodynamic therapy, etc. The present invention adds ABA-type amphiphilic Si-OC polyether-modified polysiloxane as a surfactant, wherein the amphiphilic Si-OC polyether-modified polysiloxane contains both lipophilic flexible Si-O-Si long chains and hydrophilic polyether long chains, which can greatly enhance the excellent performance of AIE fluorescent molecules in aqueous environments. The water-in-oil nanoparticles formed by self-assembly of amphiphilic Si-OC polyether-modified polysiloxane and new AIE fluorescent molecules not only improve the controllable aggregation of AIE molecules, but also effectively enhance the solubility and uniform dispersion of lipophilic AIE fluorescent molecules in biological environments and buffer solutions, thereby greatly improving the fluorescence emission intensity and stability of lipophilic AIE fluorescent molecules. On the other hand, nanoparticles of suitable size formed after self-assembly can enter cells through endocytosis and other methods, more effectively realizing cell fluorescence imaging or sensing, which is beneficial to its application in biological detection and tracing.

[0032] At the same time, the formed water-in-oil nanoparticles can reduce the interference of other substances in the body during the delivery process, reduce fluorescence quenching and photobleaching caused by non-radiative relaxation or energy transfer between AIE fluorescent molecules and interfering media, and the formed nanoparticles are also beneficial to cell absorption and delivery, and are very beneficial to biological detection, treatment, imaging and other processes.

[0033] Beneficial effects: Compared with the prior art, the present invention has the following significant advantages:

[0034] The Si-OC polyether-modified polysiloxane of the present invention has excellent biocompatibility and dual hydrophilic and lipophilic properties. Through self-assembly technology, it forms water-in-oil nanoparticles with the above-mentioned lipophilic organic small molecules to maximize the compatibility and dispersibility of lipophilic AIE fluorescent small molecules in biological aqueous solution systems; at the same time, the AIE molecules encapsulated in the nanoparticles are orderly aggregated, thereby greatly enhancing the advantages of aggregation-induced luminescence and improving the application performance of the AIE molecules in biological tracer detection. Compared with patent CN114634811A, the Si-OC polyether-modified polysiloxane encapsulates AIE fat-soluble fluorescent molecules to form nanoparticles, which significantly enhances the gain effect of fluorescent molecules. Description of the Drawings

[0035] Figure 1 1H-NMR spectrum of the hydrogen-terminated polysiloxane prepared in Example 1; 1 1H-NMR spectrum;

[0036] Figure 2 Infrared spectrum of the hydrogen-terminated polysiloxane prepared in Example 1;

[0037] Figure 3 1H-NMR spectrum of the Si-O-C polyether modified polysiloxane prepared in Example 2; 1 1H-NMR spectrum;

[0038] Figure 4 Infrared spectrum of the Si-O-C polyether modified polysiloxane prepared in Example 2;

[0039] Figure 5 1H-NMR spectrum of the intermediate prepared in Example 3; 1 1H-NMR spectrum;

[0040] Figure 6 1H-NMR spectrum of the TTCN prepared in Example 3; 1 1H-NMR spectrum;

[0041] Figure 7 13C-NMR spectrum of the TTCN prepared in Example 3; 13 13C-NMR spectrum;

[0042] Figure 8 1H-NMR spectrum of the intermediate prepared in Example 4; 1 1H-NMR spectrum;

[0043] Fig. 9 1H-NMR spectrum of the MTTCN prepared in Example 4; 1 1H-NMR spectrum;

[0044] Fig.10 13C-NMR spectrum of the MTTCN prepared in Example 4; 13 13C-NMR spectrum;

[0045] Fig.11 Absorption spectra of TTCN and MTTCN in Example 5;

[0046] Fig.12 Fluorescence enhancement spectrum of TTCN in Example 6;

[0047] Fig.13 Fluorescence enhancement spectrum of MTTCN in Example 6;

[0048] Fig.14 Graph for exploring the optimal concentration for fluorescence enhancement of Si-O-C polyether modified polysiloxane in Example 7. Detailed Description of the Invention

[0049] The technical solution of the present invention is further described below in conjunction with the accompanying drawings.

[0050] Example 1

[0051] Preparation of terminal hydrogen-containing polysiloxane: In a reflux condenser equipped with a thermometer, a stirrer, and a N 2 In a 100ml four-necked flask with a gas guide tube, add D 4 37.25g, tetramethyl disiloxane 3.35g, acid clay catalyst dosage is 2% of the total mass of the material, reaction temperature is 60°C, reaction time is 6h, through D 4 The terminal hydrogen-containing polysiloxane is formed by ring-opening polymerization. After the reaction is completed, the product is filtered to obtain a clear and transparent product.

[0052] The hydrogen-terminated polysiloxane prepared in this example was analyzed by nuclear magnetic resonance spectroscopy. The results are as follows: Figure 1 shown.

[0053] Depend on Figure 1 The structural formula of the hydrogen-terminated polysiloxane is as follows:

[0054]

[0055] The hydrogen-terminated polysiloxane prepared in this example was analyzed by infrared spectroscopy. Figure 2 shown.

[0056] Depend on Figure 2 Available at 1097cm -1 、1020cm -1 The long chain -Si-O-Si- stretching vibration absorption peak appears at 2130cm -1 It is the characteristic absorption peak of Si-H deformation vibration.

[0057] Example 2

[0058] Preparation of Si-OC polyether modified polysiloxane: equipped with a thermometer, a stirrer, a reflux condenser (equipped with N 2 The hydrogen-terminated polysiloxane and polyether prepared in Example 1 (ratio of 1:1.2) were added into a 100ml four-necked flask with an air guide tube, and tri(pentafluorophenyl)borane was added as a catalyst (the catalyst amount was 0.5% of the total mass). The reaction temperature was set to 120°C and the reaction time was 3h. After the reaction was completed, the reaction solution was filtered to obtain a clear and transparent Si-OC polyether-modified polysiloxane product.

[0059] The Si-OC polyether-modified polysiloxane prepared in this example was analyzed by nuclear magnetic resonance hydrogen spectrum, and the results are as follows: Figure 3 shown.

[0060] Depend on Figure 3 It can be obtained that the structural formula of Si-OC polyether modified polysiloxane is as follows:

[0061]

[0062] The Si-OC polyether-modified polysiloxane prepared in this example was analyzed by infrared spectroscopy. Figure 4 As shown. Figure 4 Available, 2130cm -1 The characteristic absorption peak of Si-H deformation vibration disappears.

[0063] Example 3

[0064] Preparation of AIE fluorescent molecule TTCN:

[0065] Prepared according to the following route:

[0066]

[0067] (1) 1mmol 4-bromo-N,N-diphenylaniline and 1mmol (5-formylthiophene-2-yl)boric acid were dissolved in a mixed solvent of 10ml methanol and 10ml toluene, and potassium carbonate (5mmol) was added. After stirring evenly, the air in the reaction system was removed, and then 0.1mmol of catalyst bis(diphenylphosphinothiocene)palladium dichloride was added. The air in the container was removed again, nitrogen was filled in for protection, the temperature was raised to 85°C, and the reaction was continued for 12h. After the reaction was completed, potassium carbonate was filtered out, the solvent was removed by rotary evaporation, and the reaction mixture was eluted and purified with a mixed liquid of petroleum ether: ethyl acetate = 100:1. After elution, the eluent was removed by rotary evaporation to obtain 0.43g of yellow solid product 5-(4-(diphenylamino)phenyl)thiophene-2-carboxaldehyde (yield 82%).

[0068] The prepared 5-(4-(diphenylamino)phenyl)thiophene-2-carboxaldehyde was analyzed by nuclear magnetic hydrogen spectrum, and the results were as follows:

[0069] 1 H NMR (600MHz, DMSO) δ8.00–7.80 (m, 2H), 7.63 (s, 2H), 4.60 (s, 2H), 3.88 (s, 4H), 2.83 (s, 3H), 2.50 (s, 5H), 1.55 (s, 6H). The spectrum is shown in Figure 5 shown.

[0070] From the above results, it can be seen that the structure of 5-(4-(diphenylamino)phenyl)thiophene-2-carboxaldehyde is as follows:

[0071]

[0072] (2) 1 mmol of 5-(4-(diphenylamino)phenyl)thiophene-2-carboxaldehyde and 1 mmol of 2-(3-cyano-4,5,5-trimethylfuran-2(5H)-ylidene)malononitrile were dissolved in 20 ml of ethanol, and 0.1 mmol of catalyst pyridine was added. The air in the container was removed, nitrogen was filled in for protection, the temperature was raised to 85°C, and the reaction was continued for 12 hours. The solvent was removed by rotary evaporation, and the reaction mixture was eluted and purified with a mixed liquid of dichloromethane:methanol=100:1. After elution, the eluent was removed by rotary evaporation to obtain 0.47 g of a red-black solid product (E)-2-(3-cyano-4-(2-(5-(4-(diphenylamino)phenyl)thiophen-2-yl)vinyl)-5,5-dimethylfuran-2(5H)-ylidene)malononitrile (yield 82%).

[0073] The prepared black solid product was subjected to nuclear magnetic hydrogen spectrum and carbon spectrum analysis, and the results were as follows:

[0074] 1 H NMR (600MHz, DMSO) δ8.61 (s, 1H), 7.92 (s, 1H), 7.70 (s, 3H), 7.38 (s, 4H), 7.13 (s, 6H), 7.06 (dd, J=18.7, 7.3Hz, 1H), 6.96 (s, 2H), 1.33 (s, 6H). The spectrum is shown in Figure 6 shown.

[0075] 13 C NMR (151 MHz, DMSO) δ 156.04, 152.88, 149.68, 146.64, 143.25, 133.48, 130.30, 130.07, 128.24, 125.78, 125.02, 124.93, 124.78, 124.57, 121.63, 115.34, 114.58, 73.76, 40.54, 40.42, 40.28, 40.14, 40.00, 39.87, 39.73, 39.59. The spectrum is shown in Figure 7 shown.

[0076] From the above results, it can be seen that the structure of the red-black solid product is as follows:

[0077]

[0078] Example 4

[0079] Preparation of AIE fluorescent molecule MTTCN:

[0080] Prepared according to the following route:

[0081]

[0082] (1) 1mmol 4-bromo-N,N-bis(4-methoxyphenyl)aniline and 1mmol (5-formylthiophene-2-yl)boric acid were dissolved in a mixed solvent of 10ml methanol and 10ml toluene, and potassium carbonate (5mmol) was added. After stirring evenly, the air in the reaction system was removed, and then 0.1mmol of catalyst bis(diphenylphosphinothiocene)palladium dichloride was added. The air in the container was removed again, nitrogen was filled in for protection, and the temperature was raised to 85°C. The reaction was continued for 12h. After the reaction was completed, potassium carbonate was filtered out, the solvent was removed by rotary evaporation, and the reaction mixture was eluted and purified with a mixed liquid of petroleum ether: ethyl acetate = 100:1. After elution, the eluent was removed by rotary evaporation to obtain a yellow solid product 5-(4-(bis(4-methoxyphenyl)amino)phenyl)thiophene-2-carboxaldehyde (yield 53%).

[0083] The prepared yellow solid product was subjected to nuclear magnetic hydrogen spectrum analysis, and the results were as follows:

[0084] product 1 H NMR (600MHz, DMSO) δ9.84 (s, 1H), 7.97 (s, 1H), 7.59 (s, 2H), 7.53 (d, J=4.0Hz, 1H), 7.11 (s, 4H), 6.95 (s, 4H), 6.74 (s, 2H), 3.76 (s, 6H). The spectrum is shown in Figure 8 shown.

[0085] From the above results, it can be seen that the structure of the yellow solid product is as follows:

[0086]

[0087] (2) 1 mmol of 5-(4-(bis(4-methoxyphenyl)amino)phenyl)thiophene-2-carboxaldehyde and 1 mmol of 2-(3-cyano-4,5,5-trimethylfuran-2(5H)-ylidene)malononitrile were dissolved in 20 ml of ethanol, and 0.1 mmol of catalyst pyridine was added. The air in the container was removed, nitrogen was filled in for protection, the temperature was raised to 85°C, and the reaction was continued for 12 hours. The solvent was removed by rotary evaporation, and the reaction mixture was eluted and purified with a mixed liquid of dichloromethane:methanol=100:1. After elution, the eluent was removed by rotary evaporation to obtain a black solid product (E)-2-(4-(2-(5-(4-(bis(4-methoxyphenyl)amino)phenyl)thiophen-2-yl)vinyl)-3-cyano-5,5-dimethylfuran-2(5H)-ylidene)malononitrile (49%).

[0088] The prepared black solid product was subjected to nuclear magnetic hydrogen spectrum and carbon spectrum analysis, and the results were as follows:

[0089] product 1H NMR (600MHz, DMSO) δ8.57 (s, 1H), 7.90 (s, 1H), 7.64 (s, 4H), 7.14 (s, 4H), 6.96 (s, 6H), 6.74 (s, 2H), 3.74 (s, 6H), 1.22 (s, 6H). The spectrum is shown in Fig. 9 shown.

[0090] 13 C NMR (151 MHz, DMSO) δ 157.12, 156.83, 152.68, 150.80, 143.39, 139.26, 132.90, 128.15, 124.10, 122.90, 118.17, 115.63, 115.48, 114.71, 72.92, 55.77, 40.56, 40.44, 40.30, 40.16, 40.02, 39.89, 39.75, 39.61. The spectrum is shown in Fig.10 shown.

[0091] From the above results, it can be seen that the structure of the black solid product is as follows:

[0092]

[0093] Example 5

[0094] Absorption spectra of TTCN and MTTCN:

[0095] 10 μmol / L TTCN and MTTCN solutions were prepared with water, and 3 ml of each solution was placed in a four-way cuvette for absorption spectrum measurement. The ultraviolet spectrophotometer was Shimadzu UV2600, with a wavelength range of 190-900 nm and an integrating sphere wavelength range of 190-1400 nm. The results are shown in Figure 2. Fig.11 As shown, the maximum absorption peaks of TTCN and MTTCN are at 495nm and 515nm.

[0096] Example 6

[0097] Preparation of amphiphilic Si-OC polyether-modified polysiloxane nanoparticles encapsulating AIE fluorescent molecules and test of the fluorescence enhancement effect of Si-OC polyether-modified polysiloxane on TTCN and MTTCN:

[0098] TTCN mother solution and MTTCN mother solution were prepared with dimethyl sulfoxide to a concentration of 1 mmol / L, and then the TTCN mother solution and MTTCN mother solution were diluted with water to 15 μmol / L to obtain TTCN solution and MTTCN solution. 5 mL of 15 μmol / L TTCN solution and MTTCN solution were taken respectively, and the ABA structure type Si-OC polyether modified polysiloxane prepared in Example 2 was slowly added until it was prepared to a concentration of 1×10 -3 mol / L solution, and then ultrasonicated it with an ultrasonic cleaning machine for 15 minutes. The solution became clear and transparent, and the nanoparticles of amphiphilic Si-OC polyether-modified polysiloxane encapsulating AIE fluorescent molecules were obtained. Then 3 ml was taken and placed in a cuvette for fluorescence analysis. The fluorescence spectrophotometer was Shimadzu RF-6000, the TTCN excitation wavelength was 495, the MTTCN excitation wavelength was 515, and the bandwidth was 5nm. -3 mol / L) is pure TTCN or MTTCN for comparison. The results are as follows Figure 12-13 As shown. Fig.12 and Fig.13 It can be seen that Si-OC polyether-modified polysiloxane has a very strong effect on increasing the fluorescence of small molecule AIE fluorescent molecules in water or water buffer solution, increasing the fluorescence intensity of TTCN by 10.8 times and the fluorescence intensity of MTTCN by 11.3 times. This shows that amphiphilic Si-OC polyether-modified polysiloxane can significantly enhance the fluorescence emission intensity of AIE small molecule fluorescent molecules.

[0099] Example 7

[0100] The fluorescence enhancement effect of different concentrations of amphiphilic Si-OC polyether modified polysiloxane on TTCN and MTTCN was tested: The experimental process was the same as Example 6. The experimental effect of adding different concentrations of Si-OC polyether modified polysiloxane on fluorescence enhancement was investigated. -6 mol / L、5.0×10 -6 mol / L、1.0×10 -5 mol / L、5.0×10 -5 mol / L、1.0×10 -4 mol / L、5.0×10 -4 mol / L、7.5×10 -4 mol / L、1.0×10 -3 mol / L concentration to explore the best fluorescence enhancement effect. The results are as follows Fig.14 shown.

[0101] like Fig.14When the concentration of Si-OC polyether modified polysiloxane reaches 7.5×10 -4 mol / L, and the fluorescence intensity was the highest, and further increasing the concentration had no significant effect on the fluorescence enhancement. Therefore, based on the above experiments, the optimal concentration range was 2.5×10 -4 ~1.0×10 -3 mol / L, and 7.5×10 -4 mol / L is the optimal concentration.

Claims

1. An amphiphilic Si-OC type polyether-modified polysiloxane nanoparticle containing AIE fluorescent molecules, characterized in that: The nanoparticles contain lipophilic AIE fluorescent molecular compounds inside and are coated with amphiphilic Si-OC type polyether modified polysiloxane copolymers outside.

2. The nanoparticle according to claim 1, characterized in that The structural formula of the lipophilic AIE fluorescent molecular compound is shown as any one of the following:

3. The nanoparticle according to claim 2, characterized in that The maximum absorption wavelength of the TTCN is 495 nm, and the emission wavelength in aqueous solution is 630 nm; the maximum absorption wavelength of the MTTCN is 515 nm, and the emission wavelength in aqueous solution is 650 nm.

4. The nanoparticle according to claim 1, characterized in that The amphiphilic Si-OC type polyether modified polysiloxane has an ABA type structure, and its general structural formula is as follows: Among them, m is 1 to 25, n is 1 to 25, and x is 20 to 100.

5. The nanoparticles according to claim 2 or 3, characterized in that TTCN and MTTCN were synthesized according to the following routes:

6. The nanoparticle according to claim 5, characterized in that The preparation of TTCN includes the following steps: (A1) dissolving 4-bromo-N,N-diphenylaniline and (5-formylthiophene-2-yl)boric acid in a mixed solvent of methanol and toluene, adding potassium carbonate, stirring evenly, removing air from the reaction system, adding a catalyst of bis(diphenylphosphinothiocene)palladium dichloride, filling with nitrogen for protection, and heating for reaction to obtain 5-(4-(diphenylamino)phenyl)thiophene-2-carboxaldehyde; (A2) 5-(4-(diphenylamino)phenyl)thiophene-2-carboxaldehyde and 2-(3-cyano-4,5,5-trimethylfuran-2(5H)-ylidene)malononitrile were dissolved in ethanol, pyridine catalyst was added, air was removed, nitrogen was filled for protection, and the reaction was heated.

7. The nanoparticle according to claim 5, characterized in that The preparation of MTTCN includes the following steps: (B1) dissolving 4-bromo-N,N-bis(4-methoxyphenyl)aniline and (5-formylthiophene-2-yl)boric acid in a mixed solvent of methanol and toluene, adding potassium carbonate, stirring evenly, removing air from the reaction system, adding a catalyst of bis(diphenylphosphinothiocenepalladium)dichloride, filling with nitrogen for protection, and heating the reaction to obtain 5-(4-(bis(4-methoxyphenyl)amino)phenyl)thiophene; (B2) Dissolve 5-(4-(bis(4-methoxyphenyl)amino)phenyl)thiophene-2-carboxaldehyde and 2-(3-cyano-4,5,5-trimethylfuran-2(5H)-ylidene)malononitrile in ethanol, add catalyst pyridine, remove air, fill with nitrogen for protection, and heat to react.

8. The method for preparing nanoparticles according to any one of claims 1 to 7, characterized in that: The following steps are involved: The lipophilic AIE fluorescent molecule compound is dissolved in a dimethyl sulfoxide organic solvent to completely dissolve it to form a liquid A, and then the amphiphilic Si-OC type polyether modified polysiloxane is dissolved in pure water to form a liquid B. The liquid B is mixed with the liquid A, and ultrasonic treatment is performed to self-assemble to form nanoparticles with the AIE fluorescent molecule compound inside and the amphiphilic Si-OC type polyether modified polysiloxane outside.

9. The preparation method according to claim 8, characterized in that: The molar ratio of the amphiphilic Si-OC type polyether modified polysiloxane to the AIE fluorescent molecule compound is (1.0-1000): (5-20).

10. Use of the nanoparticles of the amphiphilic Si-OC type polyether-modified polysiloxane carrying AIE fluorescent molecules according to any one of claims 1 to 7 in biological detection or imaging.

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