A fluorescent multicolor control polymer and its preparation method, control method and application
By attaching perylene diamide and pyrene groups to highly branched polyethyleneimine, a fluorescent multicolor regulated polymer was prepared, which solved the problem of poor signal stability of fluorescent markers and achieved multicolor regulation of fluorescence intensity and color, making it suitable for pH probes and supramolecular interactions.
Patent Information
- Application Number
- CN202411083457.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2024-08-08
- Publication Date
- 2025-09-16
- Estimated Expiration
- 2044-08-08
AI Technical Summary
The luminescence of existing fluorescent markers is easily affected by multiple factors, resulting in poor signal stability and difficulty in achieving multi-color fluorescence regulation in different solvent environments.
By attaching perylene diamide and pyrene as luminescent groups to highly branched polyethyleneimine (HPEI), a fluorescent multicolor regulated polymer was prepared, and the fluorescence color and intensity were regulated by changing the pH value and solvent composition.
The fluorescence intensity increases with decreasing pH, producing pink fluorescence changes, and exhibits changes in various fluorescence colors in different solvent environments. It is suitable for pH probes and supramolecular interactions, and improves the stability of the fluorescence signal and the multi-color regulation capability.
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Figure CN118994568B_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of luminescent materials, and in particular to a fluorescent multicolor controllable polymer and a preparation method, a control method and an application thereof. Background Art
[0002] Smart luminescent materials have attracted widespread attention because their luminescent signals, which can be detected by the naked eye in response to perceived stimuli, are emitting luminescent signals that can be detected by the naked eye. Dynamically tunable luminescent systems often exhibit sensitive modulation of luminescence properties in response to various external stimuli, such as light, temperature, magnetism, mechanical force, chemistry, electric fields, and pH. Consequently, they have attracted considerable attention and have been widely applied in fields such as information encryption, bioimaging, detection, sensing, diagnosis, and therapy. Over the past decade, scientists have reported numerous stimuli-responsive luminescent materials that exhibit multicolor luminescence and luminescence switching effects in response to external stimuli.
[0003] Supramolecular assemblies are defined as multimolecular groups formed by non-covalent bonds, and can be as simple as two molecules. They can be spherical, rod-shaped, or sheet-like. Their sizes range from nanometers to micrometers. Two or more molecules are bound together to form complex, organized aggregates that maintain a certain degree of integrity, resulting in well-defined microstructures and macroscopic properties. The relationship between molecules and supramolecular structures and intermolecular interactions is similar to the relationship between atoms and molecules and covalent bonds.
[0004] Aggregation-induced quenching (AIQ) is a physical phenomenon that describes the quenching of fluorescence or luminescence signals caused by the formation of molecular or macroscopic aggregates in solutions or solid-state materials. This occurs because aggregate formation leads to close contact between molecules, altering the internal electronic energy levels of the molecules and disrupting the luminescence pathway of the fluorescent marker, thereby reducing or completely extinguishing the luminescence. This phenomenon is widely used in chemical and biological diagnostics, particularly for the detection and imaging of fluorescent markers. The specificity and high sensitivity of fluorescent markers make them ideal tools for detecting and imaging biomolecules. However, the luminescence of fluorescent markers is often affected by many factors, such as ultraviolet radiation, ambient temperature, and chemical reactions, resulting in poor stability of the fluorescence signal. The application of the AIQ phenomenon can effectively reduce this interference, thereby improving the accuracy and reliability of detection and imaging. In AIQ applications, researchers often exploit the physical and chemical properties of fluorescent molecules and the aggregation ability of materials to design novel molecular structures or material compositions to achieve efficient, rapid, and sensitive detection and imaging. For example, researchers can use intramolecular oxygen-sensitive fluorescent dyes to design new oxygen molecular probes, thereby expanding their applications in medical and biomolecular detection. Furthermore, by manipulating the aggregation state of the material, they can achieve highly sensitive detection of certain substances, such as soluble organic molecules, metal ions, and environmental pollutants.
[0005] The present application aims to provide a fluorescent multicolor controllable polymer and its preparation method, control method and application, so as to achieve multicolor fluorescence control in different solvent environments. Summary of the Invention
[0006] To address these issues, the present invention provides a fluorescent multicolor controllable polymer, its preparation method, control method, and application. Its fluorescence intensity increases with decreasing pH, producing a pink fluorescent color change. This molecule can also interact supramolecularly with cyclodextrin to produce yellow fluorescence, and induces molecular structural changes at the molecular level, thereby achieving multicolor fluorescence control.
[0007] The technical solution adopted in the present invention is:
[0008] A fluorescent multicolor regulating polymer, whose chemical formula is shown below:
[0009]
[0010] Specifically, the average relative molecular mass of the polymer is 25,000;
[0011] The fluorescent multicolor regulation polymer has a multicolor fluorescence regulation function by attaching two luminescent groups to HPEI (highly branched polyethyleneimine).
[0012] Furthermore, the amount of the two luminescent groups attached is 40 mg of perylene diamide and 10 mg of pyrene per 1 g of PEI.
[0013] Based on the same inventive concept, the present application also provides a method for preparing the above-mentioned fluorescent multicolor controllable polymer, comprising the following steps:
[0014] S1. PEI was dissolved in DMF (dimethylformamide) and mixed with perylenetetracarboxylic dianhydride. After heating for reaction, the mixture was cooled to room temperature, and most of the DMF solvent was evaporated. Water was then added to dissolve the perylenetetracarboxylic dianhydride-modified PEI. The mixture was filtered, the filtrate was dialyzed, and the liquid in the dialysis bag was lyophilized to obtain Compound 1.
[0015] S2. The prepared compound 1 is dissolved in methanol, and 1-pyrene formaldehyde is added, and the mixture is heated to produce a Schiff base reaction. After that, a large amount of methanol is evaporated off, deionized water is added, and the mixture is filtered. The filtrate is dialyzed, and the liquid in the dialysis bag is freeze-dried to obtain compound 2, which is a fluorescent multicolor controllable polymer.
[0016] Furthermore, in step S1 and step S2, dialysis bags with a molecular weight cut-off of 3500 are used respectively and ionized water is used as the dialysis fluid for 3 to 4 times, and then the liquid in the dialysis bag is freeze-dried.
[0017] Furthermore, in step S1, the temperature of the heating reaction is 85-95°C, and the reaction time is 46-50 hours; in step S2, the temperature of the heating reaction is 85-95°C, and the reaction time is 22-25 hours.
[0018] Based on the same inventive concept, the present application also provides a method for regulating the above-mentioned fluorescent multicolor regulatory polymer, wherein the fluorescent multicolor regulatory polymer is configured into a solution with a concentration of 1 mg / ml, which responds to a pH range of 1 to 7. As the pH decreases, the fluorescent color of the solution turns pink and the fluorescence intensity increases.
[0019] Furthermore, the concentration of the fluorescent multicolor controllable polymer solution was set at 1 mg / ml, and the content of water and organic solvent in the solvent was changed. As the organic solvent increased, the fluorescent color of the compound changed, and the change trend was cyan-purple-pink;
[0020] Wherein, the organic solvent is at least one of dimethyl sulfoxide, N,N-dimethylformamide, acetonitrile and tetrahydrofuran.
[0021] Furthermore, when the concentration of the fluorescent multicolor regulating polymer solution is 1 mg / ml and γ-CD (γ-cyclodextrin) is added, the color of the solution changes to orange-yellow; when Fe 3+ , the compound fluorescence is quenched.
[0022] Based on the same inventive concept, the present application also provides an application of the above-mentioned fluorescent multicolor regulating polymer incorporated into a film or forming a hydrogel with a polymer in pH monitoring or pH probe.
[0023] Based on the same inventive concept, the present application also provides an application of the above-mentioned fluorescent multicolor controllable polymer as a fluorescent ink.
[0024] The beneficial effects of the present invention are as follows:
[0025] The fluorescent multicolor regulation polymer provided by the present invention can achieve multicolor fluorescence regulation intelligent molecules for different solvent environments. The molecule of the compound is divided into a hydrophilic carrier polymer PEI and hydrophobic fluorescent groups pyrene and perylene. When the hydrophobic fluorescent groups pyrene and perylene are dispersed in an organic solvent, thereby changing the intermolecular force, and then showing a variety of fluorescence color changes according to the content of water and organic solvent in the solvent; the polymer can also be used as a pH fluorescent probe, and its fluorescence intensity increases with decreasing pH and produces pink fluorescence color changes; the polymer can also produce supramolecular effects with cyclodextrin to produce yellow fluorescence and produce changes in molecular structure at the molecular level. It can have the ability to perceive pH, organic solvents, and cyclodextrin, and show changes in fluorescence color and intensity, thereby realizing the application of fluorescent multicolor regulation. BRIEF DESCRIPTION OF THE DRAWINGS
[0026] Figure 1 is the UV absorption spectrum of the compound prepared in the examples of this application in aqueous solution;
[0027] Figure 2 is the NMR spectrum of the compound prepared in the examples of this application;
[0028] Figure 3 The fluorescence spectra of the compound solutions prepared in the examples of this application at different pH values are shown;
[0029] Figure 4 The UV absorption spectra of the compound solutions prepared in the examples of this application under different pH conditions;
[0030] Figure 5 The fluorescence spectra of the compounds prepared in the examples of this application in different DMSO:H2O contents are shown;
[0031] Figure 6 The fluorescence spectra of the compounds prepared in the examples of this application in different DMF:H2O contents are shown;
[0032] Figure 7 The fluorescence spectra of the compounds prepared in the examples of this application in different ACN:H2O contents;
[0033] Figure 8 The fluorescence spectra of the compounds prepared in the examples of this application in different THF:H2O contents;
[0034] Figure 9 The UV absorption spectra of the compounds prepared in the examples of this application in different DMSO:H2O contents;
[0035] Figure 10 The UV absorption spectra of the compounds prepared in the examples of this application in different DMF:H2O contents;
[0036] Figure 11 The UV absorption spectra of the compounds prepared in the examples of this application in different ACN:H2O contents;
[0037] Figure 12 The UV absorption spectra of the compounds prepared in the examples of this application in different THF:H2O contents;
[0038] Figure 13 The fluorescence spectra of the compounds prepared in the examples of this application in solutions containing different γ-CD are shown;
[0039] Figure 14 The UV absorption spectra of the compounds prepared in the examples of this application in solutions containing different γ-CD are shown. DETAILED DESCRIPTION
[0040] To facilitate understanding of the present invention, the present invention will be described more fully below through examples, with preferred embodiments of the present invention provided below. However, the present invention can be implemented in a variety of different forms and is not limited to the embodiments described herein. Any other embodiments obtained by modifying or equivalently replacing the technical solution of the present invention without inventive results are within the scope of protection of the present invention.
[0041] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used in the specification of the present invention are only for describing specific embodiments and are not intended to limit the present invention.
[0042] The numerical values disclosed in the embodiments of the present invention are approximate values, not definite values. Where errors or experimental conditions permit, all values within the error range may be included without being limited to the specific numerical values disclosed in the embodiments of the present invention.
[0043] Unless otherwise specified, various raw materials, reagents, instruments and equipment used in the present invention can be purchased from the market or prepared by existing methods.
[0044] This embodiment provides a method for preparing a fluorescent multicolor controllable polymer, and the synthesis route is as follows:
[0045]
[0046] Specifically, it can be prepared according to the following steps:
[0047] S1. 1 g of polyethyleneimine (PEI) was dissolved in 10 ml of DMF and mixed with 40 mg of perylenetetracarboxylic dianhydride. The mixture was heated to 90°C for 48 h, cooled to room temperature, and most of the DMF solvent was removed by rotary evaporation. A large amount of water was then added to dissolve the perylenetetracarboxylic dianhydride-modified PEI. The mixture was filtered and the filtrate was dialyzed using a 3500 molecular weight cutoff dialysis bag with deionized water as the dialyzate for 3 to 4 cycles. The liquid in the dialysis bag was then lyophilized to obtain Compound 1.
[0048] S2. The prepared compound 1 was dissolved in methanol and reacted at a ratio of 1 g of compound 1 to 10 mg of 1-pyrene formaldehyde. The temperature was heated to 90°C to cause a Schiff base reaction. The reaction was carried out for 24 hours. A large amount of methanol was evaporated and a large amount of deionized water was added. The mixture was filtered and the filtrate was dialyzed using a dialysis bag with a molecular weight cutoff of 3500 and deionized water as the dialysis fluid. After dialysis 3 to 4 times, the liquid in the dialysis bag was freeze-dried to obtain compound 2, which is a fluorescent multicolor controllable polymer.
[0049] The UV absorption spectrum of this fluorescent multicolor regulated polymer can be found in Figure 1 As shown, 500nm is the characteristic absorption peak of perylene, and 350nm is the characteristic absorption peak of pyrene. Its nuclear magnetic spectrum is shown in Figure 2, where the chemical shift of 8.03 is the characteristic peak of perylene and pyrene, 2.65 is the peak of H of the unmodified part of PEI, and 3.43 is the peak of the modified part. The successful preparation of the compound can be characterized by UV absorption spectrum and nuclear magnetic spectrum.
[0050] The fluorescent multicolor control polymer prepared in the above examples was tested for its pH perception and response to the environment in which it was located:
[0051] ① Weigh the prepared compound and dissolve it in deionized water to prepare a 1 mg / mL aqueous solution. Adjust the pH of the solution to 6, 5, 4, 3, 2, and 1 with dilute hydrochloric acid solution. Observe the fluorescence color changes of the aqueous solutions of the compound at different pH under ultraviolet light. Figure 3 The fluorescence spectra of the compound solution under different pH conditions are shown in Figure 4 As shown, it is the UV absorption spectrum of the compound solution under different pH conditions. Figure 3It can be seen that as the pH decreases, the fluorescent color of the solution gradually turns pink. By testing the fluorescence spectra of the compound aqueous solutions under different pH environments, it can be seen that as the pH decreases, the emission peak intensities at 592nm and 430nm increase accordingly.
[0052] ② The prepared compound was weighed and dissolved in solvents containing different contents of DMSO (dimethyl sulfoxide) and H2O, where the content of the compound was 1 mg / mL. The fluorescence color change caused by the solvent effect of the compound in solvents with different contents of DMSO and H2O was observed. It was found that the color change pattern was cyan-blue-pink-yellow. Its fluorescence emission spectrum is shown as follows Figure 5 As shown, the organic solvent can be selected from DMF (dimethylformamide), ACN (acetonitrile), THF (tetrahydrofuran), where the fluorescence emission spectra of DMF, ACN, and THF solvents correspond to Figure 6 , 7, 8, and the UV spectra used for characterization are Figure 9 ,10,11,12.
[0053] ③ Weigh the prepared compound and dissolve it in solvents containing different contents of γ-CD, where the content of the compound is 1 mg / mL. Observe the fluorescence color change caused by the supramolecular effect of the compound in solvents with different contents of γ-CD. When the concentration of γ-CD reaches a certain level, the fluorescence color turns yellow, and its fluorescence emission spectrum corresponds to Figure 13 , its UV spectrum is Figure 14 .
[0054] In summary, the fluorescent multicolor regulation polymer prepared in this embodiment can achieve multicolor fluorescence regulation intelligent molecules for different solvent environments. The molecules of this compound are divided into hydrophilic carrier polymer PEI and hydrophobic fluorescent groups pyrene and perylene. When in an organic solvent, the hydrophobic fluorescent groups pyrene and perylene will disperse and change the intermolecular force, thereby showing changes in the content of water and organic solvent in the solvent, thereby showing changes in various fluorescent colors; it can also be used as a pH fluorescent probe, and its fluorescence intensity will increase with decreasing pH and produce pink fluorescent color changes; this molecule can also produce supramolecular effects with cyclodextrin, produce yellow fluorescence, and produce changes in molecular structure at the molecular level. It can have the ability to perceive pH, organic solvents, and cyclodextrin, and show changes in fluorescence color and intensity, thereby realizing the application of fluorescent multicolor regulation.
[0055] The above-described embodiments merely illustrate several implementations of the present invention, and while their descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the present invention. It should be noted that a person skilled in the art would be able to make numerous variations and improvements without departing from the spirit of the present invention, all of which fall within the scope of protection of the present invention. Therefore, the scope of protection of the present invention shall be determined by the appended claims.
Claims
1. A fluorescent multicolor regulating polymer, characterized in that: Its chemical structure is shown below: The fluorescent multicolor regulation polymer has a multicolor fluorescence regulation function by attaching two luminescent groups to HPEI.
2. The fluorescent multicolor controllable polymer according to claim 1, characterized in that: The amount of the two luminescent groups attached was 40 mg of perylene diamide and 10 mg of pyrene per 1 g of PEI.
3. A method for preparing a fluorescent multicolor controllable polymer according to claim 1 or 2, characterized in that: The following steps are included: S1. PEI was dissolved in DMF and mixed with perylenetetracarboxylic dianhydride. After heating for reaction, the mixture was cooled to room temperature, and most of the DMF solvent was evaporated. Water was then added to dissolve the perylenetetracarboxylic dianhydride-modified PEI. The mixture was filtered, the filtrate was dialyzed, and the liquid in the dialysis bag was lyophilized to obtain compound 1. S2. The prepared compound 1 is dissolved in methanol, and 1-pyrene formaldehyde is added, and the mixture is heated to produce a Schiff base reaction. After that, a large amount of methanol is evaporated off, deionized water is added, and the mixture is filtered. The filtrate is dialyzed, and the liquid in the dialysis bag is freeze-dried to obtain compound 2, which is a fluorescent multicolor controllable polymer.
4. The method for preparing a fluorescent multicolor controllable polymer according to claim 3, characterized in that: In step S1 and step S2, dialysis bags with a molecular weight cut-off of 3500 were used respectively and ionized water was used as the dialysis fluid for 3 to 4 times, and then the liquid in the dialysis bag was freeze-dried.
5. The method for preparing a fluorescent multicolor controllable polymer according to claim 3, characterized in that: In step S1, the heating reaction temperature is 85-95° C. and the reaction time is 46-50 h; in step S2, the heating reaction temperature is 85-95° C. and the reaction time is 22-25 h.
6. A method for controlling a fluorescent multicolor controllable polymer according to claim 1 or 2, characterized in that: The fluorescent multicolor regulating polymer is configured into a solution with a concentration of 1 mg / ml, which responds to pH values between 1 and 7. As the pH value decreases, the fluorescent color of the solution changes to pink and the fluorescence intensity increases.
7. The method for controlling a fluorescent multicolor controllable polymer according to claim 6, wherein: The concentration of the fluorescent multicolor controllable polymer solution was set at 1 mg / ml. The content of water and organic solvent in the solvent was changed. As the organic solvent increased, the fluorescent color of the compound changed from cyan to purple to pink. Wherein, the organic solvent is at least one of dimethyl sulfoxide, N,N-dimethylformamide, acetonitrile and tetrahydrofuran.
8. The method for controlling fluorescent multicolor control polymers according to claim 6, characterized in that: The concentration of the fluorescent multicolor control polymer solution is 1 mg / ml. When γ-CD is added, the color of the solution changes to orange-yellow. When Fe is added, 3+ , the compound fluorescence is quenched.
9. Use of the fluorescent multicolor controllable polymer according to claim 1 or 2 in a film or in forming a hydrogel with a polymer, in pH monitoring or pH probe.
10. Use of the fluorescent multicolor controllable polymer according to claim 1 or 2 as fluorescent ink.
Citation Information
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