Bis-naphthyl derivative as well as preparation method and application thereof
PA-NPD supramolecular nanoparticles were formed by assembling bis-naphthyl derivatives (NPD) with water-soluble carboxylic acid ammonium columnar aromatics (PA)[5], which solved the problem of covalent bond modification in aqueous phase, achieved efficient energy transfer and light capture, and prepared color-tunable luminescent materials.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- NANTONG UNIV
- Filing Date
- 2023-12-01
- Publication Date
- 2026-04-14
AI Technical Summary
Existing artificial light-harvesting systems mainly rely on covalent bond modification, which makes them difficult to assemble efficiently in water and lacks effective energy transfer and light-harvesting performance.
The design of bis-naphthyl derivatives (NPD) involves the induced assembly of the host molecule, a water-soluble carboxylic acid ammonium column[5] aromatic hydrocarbon (PA), to form a PA-NPD supramolecular amphiphile, which then self-assembles into nanoparticles, encapsulates fluorescent dyes to achieve energy transfer, and forms an aqueous artificial light-harvesting system.
A light-emitting material with a high energy transfer efficiency of 55% and an antenna effect of 15% in aqueous phase was achieved, exhibiting good light-harvesting performance and tunable color.
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Figure CN121850894A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of supramolecular photochemistry, specifically relating to a bisnaphthyl derivative, its preparation method, and its application. Background Technology
[0002] Solar energy, as a continuous and clean energy source, has attracted widespread attention from researchers for its efficient capture and utilization. Green plants and algae in nature can efficiently utilize solar energy through photosynthesis to synthesize necessary chemical substances. To this end, researchers have attempted to design various artificial light-harvesting systems to simulate natural light-harvesting behavior, such as framework materials, gel materials, and polymer materials. However, most designed artificial light-harvesting systems rely on covalent bond modification and are constructed in organic phases, while natural life processes occur in water. Therefore, developing efficient aqueous artificial light-harvesting systems is of great significance. Supramolecular strategies, as a non-covalent assembly strategy, not only avoid complex covalent bond reactions but also enable efficient assembly in water, showing potential applications in the field of artificial light harvesting. Therefore, designing guest molecules suitable for supramolecular assembly and developing novel aqueous supramolecular artificial light-harvesting systems are of great importance for solar energy simulation applications. Summary of the Invention
[0003] In view of this, the present invention aims to provide a bis-naphthyl derivative and its preparation method and application. The bis-naphthyl derivative (NPD) can form a PA-NPD supramolecular amphiphile through the induced assembly of the host molecule, water-soluble carboxylic acid ammonium column [5] aromatic hydrocarbon (PA), and further self-assemble to form PA-NPD supramolecular nanoparticles. Then, energy transfer is achieved by loading fluorescent dyes, obtaining good energy transfer efficiency and antenna effect, and successfully preparing an aqueous artificial light-harvesting system.
[0004] The technical solution adopted in this invention is as follows:
[0005] A bisnaphthyl derivative having the structure shown in the following formula:
[0006]
[0007] Furthermore, the preparation method specifically includes:
[0008] S1. Add 6-hydroxy-2-naphthaldehyde, 1,10-dibromodecane and potassium carbonate to acetonitrile, reflux and stir under nitrogen protection, and separate the product by column chromatography;
[0009] S2. Dissolve the product obtained in step S1 and trimethylamine in 10 mL of chloroform, heat and stir under reflux overnight. After the reaction is complete, concentrate the reaction solution under vacuum to obtain the crude product. Wash the crude product with anhydrous diethyl ether and finally dry it with a forced air to obtain the bisnaphthyl derivative.
[0010] Furthermore, in step S1, the feed ratio of 6-hydroxy-2-naphthaldehyde, 1,10-dibromodecane, potassium carbonate, and acetonitrile is 3 mmol: 6 mmol: 5.2 mmol: 60 mL; the reflux stirring reaction is carried out at a temperature of 85 °C for 48 h.
[0011] Furthermore, the ratio of the product obtained in step S1, trimethylamine, and chloroform is 0.09 mmol: 2 mmol: 10 mL.
[0012] Furthermore, the temperature of the heating, stirring, and reflux is 65-70℃, and the time is 11-13h.
[0013] A method for preparing an aqueous artificial light-harvesting system involves adding water-soluble ammonium carboxylate [5] aromatic hydrocarbon, fluorescent dye PHB, and the bis-naphthyl derivative described in claim 1 to water. The water-soluble ammonium carboxylate [5] aromatic hydrocarbon and the bis-naphthyl derivative self-assemble to form nanoparticles, which are then coated with the fluorescent dye PHB to obtain the aqueous artificial light-harvesting system. The molar ratio of the water-soluble ammonium carboxylate [5] aromatic hydrocarbon to the bis-naphthyl derivative is 20:3, and the molar concentration of the bis-naphthyl derivative is not less than 0.027 mM.
[0014] Furthermore, the molar ratio of the water-soluble ammonium carboxylate column[5] aromatic hydrocarbon, the fluorescent dye PHB and the bisnaphthyl derivative is 200:30:1.
[0015] The present invention also provides an aqueous artificial light harvesting system prepared by the above-described preparation method, wherein NPD is the energy donor and the fluorescent dye PHB is the energy acceptor.
[0016] The present invention also provides an application of the above-mentioned aqueous artificial light-harvesting system in light-harvesting materials, wherein the light-harvesting material is a color-tunable luminescent material.
[0017] Furthermore, in the above applications, the color control method of the light-harvesting material is as follows: the color is controlled by adjusting the molar ratio of the bis-naphthyl derivative to the fluorescent dye PHB.
[0018] Compared with existing technologies, this invention provides a bis-naphthyl derivative, its preparation method, and its applications. This bis-naphthyl derivative (NPD) can serve as a guest molecule in supramolecular assembly. Through the induced assembly of the host molecule PA, NPD and PA undergo host-guest complexation to form a PA-NPD supramolecular amphiphile. After forming the supramolecular amphiphile, PA-NPD can further self-assemble to form PA-NPD supramolecular nanoparticles. These PA-NPD supramolecular nanoparticles can not only act as energy donors but also encapsulate fluorescent dyes to achieve energy transfer, resulting in an aqueous artificial light-harvesting system. Since the ultraviolet absorption region of the fluorescent dye PHB highly overlaps with the fluorescence emission range of the PA-NPD nanoparticles, after encapsulating PHB dye, PA-NPD can effectively transfer its own energy to PHB, achieving highly efficient energy transfer with an energy transfer efficiency of 55% and an antenna effect of 15, exhibiting excellent light-harvesting performance. This aqueous artificial light-harvesting system can be used to prepare light-harvesting materials, such as luminescent materials, and the color can be controlled according to the amounts of NPD and PHB used. Attached Figure Description
[0019] Figure 1 The photon spectrum of the bisnaphthyl derivative NPD obtained in Example 1 of this invention is shown below.
[0020] Figure 2 The figures show the experimental results of the Tyndall effect and the fluorescence color diagram of Example 2 of this invention.
[0021] Figure 3 This is a graph showing the UV-Vis transmittance experimental results of Example 3 of the present invention;
[0022] Figure 4 The graphs show the PHB UV absorption, PA-NPD fluorescence emission, and energy transfer in the artificial capture system obtained in Example 4 of this invention.
[0023] Figure 5 This is a fluorescence color change diagram of the artificial capture system obtained in Example 4 of the present invention;
[0024] Figure 6 The graph shows the test results of energy transfer efficiency and antenna effect in Embodiment 5 of the present invention. Detailed Implementation
[0025] The present invention can be better understood from the following embodiments. However, those skilled in the art will readily understand that the descriptions in the embodiments are for illustrative purposes only and should not, and will not, limit the invention as detailed in the claims.
[0026] The reagents and instruments used in the embodiments of this invention are as follows: 2-naphthylacetonitrile (98%), Fluorescent Rose B (97%, PHB), 6-hydroxy-2-naphthaldehyde (98%), 1,10-dibromodecane (98%), sodium carbonate (99%), paraformaldehyde (96%), and trimethylamine (2.0M) were purchased from Anaiji Chemical; petroleum ether (AR), acetonitrile (AR), methanol (AR), ethyl acetate (AR), chloroform (AR), and acetone (AR) were purchased from Nanjing Chemical Reagent; 1H NMR (1H NMR spectroscopy) was used. 1 H NMR was performed using a Bruker 400MHz instrument from Switzerland; UV transmittance was measured using a UV-3600 instrument from Japan; and fluorescence spectroscopy was performed using a Hitachi F-7000 instrument from Japan.
[0027] The synthesis of PA was adopted from the literature Sun, G., Cai, L., Zhang, Y., Hu, Y., Zhu, J., Sun, T. and Tang, Y. (2022) Salicylideneaniline-Based Aqueous Supramolecular Artificial Light-Harvesting Platforms with Biocompatibility. Dyes and Pigments, 205, 110577-110584. Prepared according to the method in https: / / doi.org / 10.1016 / j.dyepig.2022.110577.
[0028] Example 1
[0029] S1. 6-Hydroxy-2-naphthaldehyde (0.52 g, 3.0 mmol), 1,10-dibromodecane (1.78 g, 6 mmol) and potassium carbonate (0.72 g, 5.2 mmol) were added to 60 mL of acetonitrile and refluxed at 85 °C for 48 h under nitrogen protection. The mixture was then separated by column chromatography (eluent: petroleum ether / ethyl acetate = 10 / 1) to give the product (0.59 g, 1.5 mmol, 50%).
[0030] S2. Dissolve the product obtained in step S1 (50 mg, 0.09 mmol) and trimethylamine (1 mL, 2 mmol) in 10 mL of chloroform. Heat and stir under reflux overnight. After the reaction is complete, concentrate the reaction solution under vacuum to obtain the crude product. Wash the crude product with anhydrous diethyl ether and finally dry it by blowing air to obtain the bis(naphthyl) derivative NPD (55 mg, 0.09 mmol, 99%). The proton NMR spectrum is shown below. Figure 1 As shown, the proton spectrum data are as follows:
[0031] 1H NMR (DMSO-d6, 400MHz) δ (ppm): 8.42 (s, 1H), 8.33 (s, 1H), 8.29 (s, 1H), 8.18 (dd, J = 8. 4,1.2Hz,1H),8.09–8.06(m,2H),8.01–7.92(m,4H),7.60–7.58(m,2H),7.41(d,J=2. 4Hz,1H),7.25(dd,J=8.8,2.4Hz,1H),4.15(t,J=6.4Hz,2H),3.35–3.25(m,2H),3.04 (s,9H),1.84–1.78(m,2H),1.70–1.63(m,2H),1.47–1.44(m,2H),1.36–1.27(m,10H).
[0032] Example 2
[0033] The subject-guest interaction between PA and NPD was analyzed using Tyndall effect experiments and fluorescence color analysis, respectively. The results are as follows: Figure 2 As shown.
[0034] When PA and NPD are added to water simultaneously, they can rapidly assemble into nanoparticles, producing a significant Tyndall effect (e.g., ...). Figure 2 As shown in a), it can emit a significant cyan fluorescence (as shown in a). Figure 2 As shown in c), this indicates that PA and NPD can have significant subject-object interactions.
[0035] When PA, NPD, and the fluorescent dye PHB are added to water, a significant Tyndall effect still exists, see [reference needed]. Figure 2 b indicates that nanoparticles can still be effectively assembled and produced. Simultaneously, the fluorescence color of the nanoparticles changes to yellow fluorescence, see... Figure 2 d indicates that PHB was encapsulated in nanoparticles and a host-guest interaction occurred.
[0036] Example 3
[0037] 0, 24, 48, 72, 96, 120, 144, 168, 192, 216, and 240 μL of water-soluble ammonium carboxylate column [5] aromatic hydrocarbon solution (4.2 × 10⁻⁶) were respectively added to the column. -4 M, solvent is water) and 10 μL of the bis(naphthyl) derivative solution prepared in Example 1 (2 × 10) -2 M (solvent is an organic solvent) was added to water, and the volume was adjusted to 4 mL. After 5 minutes, the transmittance of the PA and NPD mixed solution at 600 nm was measured using a UV-Vis transmittance experiment. The results are as follows: Figure 3 As shown in a. According to Figure 3As shown in Figure a, at 600 nm, without the presence of PA (20:0), the transmittance of NPD is close to 100%, indicating that almost no nanoparticles are assembled. However, when PA is added, the transmittance of the PA / NPD mixture at 600 nm decreases significantly, reaching its lowest point at a 20:3 ratio. Even after continuously increasing the PA ratio to a molar ratio of 20:10, the transmittance of the PA / NPD mixture gradually increases without further decreasing, indicating that the optimal molar ratio for the self-assembly of PA and NPD into nanoparticles is 20:3, at which point the concentration of aromatic hydrocarbons in the ammonium carboxylate column is 7.5 × 10⁻⁶. -6 M, NPD concentration is 5×10 -5 M is the point at which the most nanoparticles are generated.
[0038] Then, keeping the 20:3 molar ratio constant, the molar concentration of NPD was continuously changed (0.005, 0.015, 0.025, 0.05, 0.08, and 0.1 mM), and the transmittance of the PA / NPD mixed solution at 700 nm was measured. The results are as follows: Figure 3 As shown in b, at low NPD concentrations, the transmittance of the PA and NPD mixed solution decreases very slowly. However, when the NPD concentration reaches 0.027 mM, the transmittance of the PA and NPD mixed solution decreases rapidly, indicating that the critical aggregation concentration for PA and NPD to self-assemble into nanoparticles is 0.027 mM.
[0039] Example 4
[0040] In the solution obtained in Example 3, the concentration of ammonium carboxylate column aromatics was 7.5 × 10⁻⁶. -6 M, NPD concentration is 5×10 -5 When M concentration was reached, different volumes (0.1, 0.5, 1, 2, 3, 5 μL) of PHB solution (2 × 10⁻⁶) were added. -4 M (solvent is an organic solvent) was used to obtain an aqueous artificial light-harvesting system. The ultraviolet absorption of PHB and the fluorescence emission of PA-NPD were as follows: Figure 4 As shown in a.
[0041] like Figure 4 As shown in Figure a, because the ultraviolet absorption region of the fluorescent dye PHB highly overlaps with the fluorescence emission range of PA-NPD, after encapsulating PHB, not only is the spatial distance between NPD and PHB in the PA-NPD-PHB nanoparticles effectively shortened, but the energy of NPD itself can also be efficiently transferred to PHB through the fluorescence resonance energy transfer process, realizing a reliable artificial light capture process. As the energy acceptor, PHB, with its molar ratio gradually increasing, shows that the characteristic fluorescence emission of the energy donor NPD gradually decreases, while the characteristic fluorescence emission of PHB significantly increases, indicating that the energy of NPD is effectively transferred to PHB, realizing the artificial light capture process.Figure 4 b) Furthermore, the fluorescence color of the system gradually changed from cyan to yellow, further confirming the occurrence of energy transfer and artificial light capture processes. Figure 5 ).
[0042] Example 5
[0043] To further analyze the capabilities of the PA-NPD-PHB artificial light-harvesting system, the fluorescence intensity of PA-NPD (molar ratio NPD:PA = 20:3) and PA-NPD-PHB (molar ratio NPD:PA:PHB = 200:30:1) nanoparticles at 490 nm was tested. Based on the fluorescence quenching at this point (490 nm) characteristic of NPD, the energy transfer efficiency of the PA-NPD-PHB nanoparticles was calculated to be 55%. Figure 6 a). Furthermore, through normalized calculations of PA-NPD nanoparticles at 490 nm and the emission spectrum of PA-NPD-PHB nanoparticles at 520 nm, the antenna effect of PA-NPD-PHB nanoparticles was found to be 15, indicating that PA-NPD-PHB possesses good artificial light-harvesting performance. Figure 6 b).
Claims
1. A bisnaphthyl derivative, characterized in that, The bisnaphthyl derivative has the structure shown in the following formula:
2. The method for preparing the bisnaphthyl derivative according to claim 1, characterized in that, The preparation method includes the following steps: S1. Add 6-hydroxy-2-naphthaldehyde, 1,10-dibromodecane and potassium carbonate to acetonitrile, reflux and stir under nitrogen protection, and separate the product by column chromatography; S2. Dissolve the product obtained in step S1 and trimethylamine in 10 mL of chloroform, heat and stir under reflux overnight. After the reaction is complete, concentrate the reaction solution under vacuum to obtain the crude product. Wash the crude product with anhydrous diethyl ether and finally dry it with a forced air to obtain the bisnaphthyl derivative.
3. The preparation method according to claim 2, characterized in that, In step S1, the feed ratio of 6-hydroxy-2-naphthaldehyde, 1,10-dibromodecane, potassium carbonate and acetonitrile is 3.0 mmol: 6 mmol: 5.2 mmol: 60 mL; the reflux stirring reaction temperature is 85 °C and the reaction time is 48 h.
4. The preparation method according to claim 2, characterized in that, In step S2, the ratio of the product obtained in step S1, trimethylamine, and chloroform is 0.09 mmol: 2 mmol: 10 mL.
5. The preparation method according to claim 2, characterized in that, In step S2, the temperature of the heating, stirring, and reflux is 65-70℃, and the reaction time is 11-13h.
6. A method for preparing an aqueous artificial light-harvesting system, characterized in that: A water-soluble ammonium carboxylate column[5] aromatic hydrocarbon, fluorescent dye PHB, and the bis-naphthyl derivative described in claim 1 were added to water. The water-soluble ammonium carboxylate column[5] aromatic hydrocarbon and the bis-naphthyl derivative self-assembled to form nanoparticles, which were then loaded with fluorescent dye PHB to obtain an aqueous artificial light-harvesting system. The molar ratio of the water-soluble ammonium carboxylate column[5] aromatic hydrocarbon to the bis-naphthyl derivative was 20:
3. The molar concentration of the bis-naphthyl derivative was not less than 0.027 mM.
7. The preparation method according to claim 6, characterized in that, The molar ratio of water-soluble ammonium carboxylate column[5] aromatic hydrocarbon, fluorescent dye PHB and the bisnaphthyl derivative is 200:30:
1.
8. The aqueous artificial light-harvesting system prepared by the method of claim 6.
9. The application of the aqueous artificial light-harvesting system of claim 8 in light-harvesting materials, wherein the light-harvesting material is a color-tunable luminescent material.
10. The application according to claim 9, wherein the color control method of the light-harvesting material is: controlling the color by adjusting the molar ratio of the bis-naphthyl derivative of claim 1 to the fluorescent dye PHB.