Preparation method and application of lanthanide luminescent glass based on tyrosine
Through the low-temperature and normal pressure preparation method of tyrosine lanthanide luminescent glass, the problems of high energy consumption and serious pollution of high-temperature melting method were solved, and high-performance luminescent glass suitable for biomedical and environmentally friendly materials were prepared.
Patent Information
- Application Number
- CN202510446886.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-10
- Publication Date
- 2025-08-01
AI Technical Summary
The existing high-temperature melting method has high energy consumption and serious pollution, making it difficult to prepare luminescent glass with excellent performance and environmentally friendly luminescent glass, especially in the fields of biomedical and environmentally friendly materials.
Tyrosine is used as raw material, and the preparation method under low temperature and normal pressure is used to dissolve tyrosine and lanthanide compounds by using potassium hydroxide to prepare tyrosine lanthanide luminescent glass. The biocompatibility and diversity of tyrosine are used to regulate the glass performance, and multiple strong non-covalent interaction synergies are used to prepare luminescent glass with excellent stability.
It has achieved low energy consumption and pollution-free preparation of luminescent glass, with excellent biocompatibility, optical transparency and adjustable physical and chemical properties, and is suitable for the fields of biomedical and environmentally friendly materials.
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Figure CN120399676A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of luminescent glass materials, and more specifically relates to a preparation method and application of lanthanide luminescent glass based on tyrosine. Background Art
[0002] The high-temperature melting method is a mature, efficient, and flexible luminescent glass preparation technology, with advantages such as wide applicability, composition uniformity, high doping concentration, and large-scale production. These advantages make it one of the most important production methods in the glass industry, especially suitable for preparing high-performance luminescent glass, optoelectronic glass, and other special glass materials. This method prepares glass materials with uniform composition by melting, clarifying, and forming glass raw materials at high temperature.
[0003] The high-temperature melting method requires heating glass raw materials to a high temperature (usually above 1000 °C) and maintaining the high temperature for a certain period to ensure that the raw materials are fully melted and clarified. This process consumes a large amount of energy, resulting in increased production costs and also causing certain pressure on the environment.
[0004] In recent years, with the increasing demand for green and environmentally friendly materials, the development of new, efficient, and environmentally friendly luminescent glass preparation methods has become a research hotspot. How to prepare luminescent glass with excellent performance and environmental friendliness and apply it to fields such as medicine, building materials, chemical engineering, and electronics, including but not limited to tissue engineering, tooth / bone repair, drug release, optical fiber communication, etc., has become a difficult problem that needs to be overcome by those skilled in the art. Summary of the Invention
[0005] The purpose of the present invention is to provide a preparation method and application of lanthanide luminescent glass based on tyrosine to solve the problems existing in the above-mentioned prior art. This glass has excellent biocompatibility and degradability and is suitable for biomedical fields such as drug release and tissue engineering.
[0006] To achieve the above purpose, the present invention provides the following solutions:
[0007] One of the technical solutions of the present invention: Provide a preparation method of lanthanide luminescent glass based on tyrosine, and the steps include:
[0008] Dissolve potassium hydroxide in methanol, then add tyrosine and stir for 10 - 30 min to obtain a tyrosine solution;
[0009] Dissolve lanthanide compounds in methanol to obtain a methanol solution of lanthanide compounds;
[0010] Add the methanol solution of lanthanide compounds to the tyrosine solution and stir for 20 - 40 min to obtain a mixed solution;
[0011] Centrifuge the mixed solution, take the supernatant (glass precursor solution), heat and stir it until it becomes gelatinous, and then cool and solidify it to obtain the lanthanide luminescent glass.
[0012] Further, the concentration of potassium hydroxide in the tyrosine solution is 0.1 M, and the concentration of tyrosine is 100 mg / mL.
[0013] Further, the tyrosine includes at least one of N-acetyl-L-tyrosine, Boc-L-tyrosine, Fmoc-O-tert-butyl-L-tyrosine, and DL-m-tyrosine.
[0014] Further, the concentration of the lanthanide compound methanol solution is 0.02 - 0.05 M.
[0015] Further, the lanthanide compound includes at least one of thulium(III) chloride hexahydrate, lutetium(III) chloride hexahydrate, gadolinium(III) chloride hexahydrate, cerium chloride hexahydrate, neodymium chloride hexahydrate, ytterbium(III) chloride hexahydrate, and dysprosium(III) sulfate octahydrate.
[0016] Further, the volume ratio of the lanthanide compound methanol solution to the tyrosine solution is 1:1.
[0017] Further, the temperature of the heating and stirring is 165 °C.
[0018] As a natural biomolecule, tyrosine has rich chemical functional groups and good biocompatibility. Using tyrosine to prepare luminescent glass can not only reduce the toxic and harmful chemicals used in traditional preparation methods, conform to the concept of green environmental protection, but also regulate the optical properties of the luminescent glass through the chemical properties of tyrosine. For example, by changing the content of tyrosine, the luminescence intensity, luminescence wavelength, and luminescence lifetime of the luminescent glass can be regulated.
[0019] The second technical solution of the present invention: Provide a tyrosine-based lanthanide luminescent glass, which is prepared by the above preparation method.
[0020] The third technical solution of the present invention: Provide an application of the above lanthanide luminescent glass in the fields of biomedicine, optical devices, and environmental protection materials.
[0021] The present invention discloses the following technical effects:
[0022] The present invention utilizes the synergistic effect of multiple strong non-covalent interactions existing in the glass precursor solution (supernatant), including hydrogen bonds, metal coordination bonds, and aromatic interactions, and then prepares a tyrosine lanthanide luminescent glass. This tyrosine lanthanide luminescent glass has excellent stability and simultaneously solves the technical problem of environmental pollution in the traditional glass preparation process.
[0023] The preparation steps provided by the present invention are carried out at low temperature and normal pressure, with low energy consumption and simple process. Compared with the traditional preparation of glass, natural tyrosine is used as the raw material, which is renewable and non-toxic, and the preparation process is pollution-free. At the same time, the diversity and modifiability of tyrosine make it easy to regulate the physical, chemical and biological properties of the glass. The tyrosine glass has excellent optical transparency and refractive index, and is suitable for optical applications. Therefore, the glass prepared from tyrosine has significant advantages in terms of biocompatibility, environmental protection, preparation conditions, structural tunability, optical properties and functionality. These characteristics make it have broad application prospects in the fields of biomedicine, optical devices, environmental protection materials, etc., and at the same time meet the requirements of green chemistry and sustainable development. BRIEF DESCRIPTION OF THE DRAWINGS
[0024] The drawings constituting a part of the present invention are used to provide a further understanding of the present invention. The schematic embodiments and descriptions thereof of the present invention are used to explain the present invention and do not constitute an improper limitation of the present invention. In the drawings:
[0025] Figure 1 It is a physical picture of the lanthanide luminescent glass prepared in Example 1.
[0026] Figure 2 It is a physical picture of the lanthanide luminescent glass prepared in Example 2.
[0027] Figure 3 It is a physical picture of the lanthanide luminescent glass prepared in Example 3.
[0028] Figure 4 It is a physical picture of the lanthanide luminescent glass prepared in Example 4.
[0029] Figure 5 It is a physical picture of the lanthanide luminescent glass prepared in Example 5.
[0030] Figure 6 It is a physical picture of the lanthanide luminescent glass prepared in Example 6.
[0031] Figure 7 It is a physical picture of the lanthanide luminescent glass prepared in Example 7.
[0032] Figure 8 It is an optical photograph of the lanthanide luminescent glass prepared in Example 7 when conducting laser as a glass optical fiber.
[0033] Figure 9 It is the DSC test result of the lanthanide luminescent glass prepared in Example 7.
[0034] Figure 10 It is the excitation spectrum of the lanthanide luminescent glass prepared in Example 7.
[0035] Figure 11 The excitation spectrum of the lanthanide luminescent glass prepared in Example 1.
[0036] Figure 12 The excitation spectrum of the lanthanide luminescent glass prepared in Example 5.
[0037] Figure 13 The excitation spectrum of the lanthanide luminescent glass prepared in Example 3.
[0038] Figure 14 The excitation spectrum of the lanthanide luminescent glass prepared in Example 6.
[0039] Figure 15 Physical pictures of the lanthanide luminescent glasses with different dysprosium ion concentrations prepared in Example 7 and Examples 10 - 12.
[0040] Figure 16 The excitation spectra of the lanthanide luminescent glasses with different dysprosium ion concentrations prepared in Example 7 and Examples 10 - 12.
[0041] Figure 17 The degradation photos of the lanthanide luminescent glass prepared in Example 7. Detailed implementation manners
[0042] Now, various exemplary implementation manners of the present invention will be described in detail. This detailed description should not be considered as a limitation to the present invention, but rather as a more detailed description of certain aspects, characteristics, and implementation schemes of the present invention.
[0043] It should be understood that the terms described in the present invention are only for describing specific implementation manners and are not used to limit the present invention. Additionally, for the numerical ranges in the present invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Each intermediate value within any stated value or stated range, as well as each smaller range between any other stated value or intermediate value within the stated range, is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded from the range.
[0044] Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the art to which the present invention pertains. Although the present invention only describes preferred methods and materials, any methods and materials similar or equivalent to those described herein can also be used in the implementation or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials related to the documents. In case of conflict with any incorporated document, the content of this specification shall prevail.
[0045] Without departing from the scope or spirit of the present invention, various improvements and changes can be made to the specific embodiments of the specification of the present invention, which are obvious to those skilled in the art. Other embodiments obtained from the specification of the present invention are obvious to those skilled in the art. The specification and examples of the present invention are merely exemplary.
[0046] Regarding "comprising", "including", "having", "containing", etc. used herein, they are all open-ended terms, meaning including but not limited to.
[0047] Those aspects not described in detail in the present invention are all conventional operating means in the art and are not the focus of the present invention.
[0048] The raw materials and reagents used in the specific embodiments of the present invention are all commercially available products.
[0049] In the specific embodiments of the present invention, room temperature and normal temperature both refer to 20 - 30 °C.
[0050] Example 1
[0051] The preparation steps of the tyrosine-based lanthanide luminescent glass include:
[0052] S1. Dissolve thulium(III) chloride hexahydrate in methanol to obtain a lanthanide compound methanol solution with a concentration of 0.02 M;
[0053] S2. Dissolve KOH in methanol to obtain a potassium hydroxide methanol solution, then add N-acetyl-L-tyrosine and stir for 10 min to obtain a tyrosine solution, wherein the concentration of KOH is 0.1 M and the concentration of N-acetyl-L-tyrosine is 100 mg / mL;
[0054] S3. Add the lanthanide compound methanol solution obtained in step S1 to the tyrosine solution obtained in step S2 (equal volume ratio), stir for 30 min, centrifuge to take the supernatant, heat and stir (165 °C) until it becomes colloidal, pour it into a mold, and cool and shape it to obtain the lanthanide luminescent glass.
[0055] Figure 1 Figure of the lanthanide luminescent glass prepared for Example 1.
[0056] Example 2
[0057] The preparation steps of the tyrosine-based lanthanide luminescent glass include:
[0058] S1. Dissolve lutetium(III) chloride hexahydrate in methanol to obtain a lanthanide compound methanol solution with a concentration of 0.02 M;
[0059] S2. Dissolve KOH in methanol to obtain a potassium hydroxide methanol solution, then add N-acetyl-L-tyrosine and stir for 10 min to obtain a tyrosine solution, where the concentration of KOH is 0.1 M and the concentration of N-acetyl-L-tyrosine is 100 mg / mL;
[0060] S3. Add the lanthanide compound methanol solution obtained in step S1 to the tyrosine solution obtained in step S2 (equal volume ratio), stir for 30 min, centrifuge to take the supernatant, heat and stir (165 °C) until it becomes gelatinous, pour it into a mold, and cool and solidify to obtain a lanthanide luminescent glass.
[0061] Figure 2 It is a physical picture of the lanthanide luminescent glass prepared in Example 2.
[0062] Example 3
[0063] The preparation steps of the lanthanide luminescent glass based on tyrosine include:
[0064] S1. Dissolve gadolinium(III) chloride hexahydrate in methanol to obtain a lanthanide compound methanol solution with a concentration of 0.02 M;
[0065] S2. Dissolve KOH in methanol to obtain a potassium hydroxide methanol solution, then add N-acetyl-L-tyrosine and stir for 10 min to obtain a tyrosine solution, where the concentration of KOH is 0.1 M and the concentration of N-acetyl-L-tyrosine is 100 mg / mL;
[0066] S3. Add the lanthanide compound methanol solution obtained in step S1 to the tyrosine solution obtained in step S2 (equal volume ratio), stir for 30 min, centrifuge to take the supernatant, heat and stir (165 °C) until it becomes gelatinous, pour it into a mold, and cool and solidify to obtain a lanthanide luminescent glass.
[0067] Figure 3 It is a physical picture of the lanthanide luminescent glass prepared in Example 3.
[0068] Example 4
[0069] The preparation steps of the lanthanide luminescent glass based on tyrosine include:
[0070] S1. Dissolve cerium(III) chloride hexahydrate in methanol to obtain a lanthanide compound methanol solution with a concentration of 0.02 M;
[0071] S2. Dissolve KOH in methanol to obtain a potassium hydroxide methanol solution, then add N-acetyl-L-tyrosine and stir for 10 min to obtain a tyrosine solution, where the concentration of KOH is 0.1 M and the concentration of N-acetyl-L-tyrosine is 100 mg / mL;
[0072] S3. Add the lanthanide compound methanol solution obtained in step S1 to the tyrosine solution obtained in step S2 (equal volume ratio), stir for 30 min, centrifuge to obtain the supernatant, heat and stir (165 °C) until it becomes gelatinous, pour it into a mold, and cool and solidify to obtain the lanthanide luminescent glass.
[0073] Figure 4 It is a physical picture of the lanthanide luminescent glass prepared in Example 4.
[0074] Example 5
[0075] The preparation steps of the lanthanide luminescent glass based on tyrosine include:
[0076] S1. Dissolve neodymium(III) chloride hexahydrate in methanol to obtain a lanthanide compound methanol solution with a concentration of 0.02 M;
[0077] S2. Dissolve KOH in methanol to obtain a potassium hydroxide methanol solution, and then add N-acetyl-L-tyrosine, stir for 10 min to obtain a tyrosine solution, wherein the concentration of KOH is 0.1 M and the concentration of N-acetyl-L-tyrosine is 100 mg / mL;
[0078] S3. Add the lanthanide compound methanol solution obtained in step S1 to the tyrosine solution obtained in step S2 (equal volume ratio), stir for 30 min, centrifuge to obtain the supernatant, heat and stir (165 °C) until it becomes gelatinous, pour it into a mold, and cool and solidify to obtain the lanthanide luminescent glass.
[0079] Figure 5 It is a physical picture of the lanthanide luminescent glass prepared in Example 5.
[0080] Example 6
[0081] The preparation steps of the lanthanide luminescent glass based on tyrosine include:
[0082] S1. Dissolve ytterbium(III) chloride hexahydrate in methanol to obtain a lanthanide compound methanol solution with a concentration of 0.02 M;
[0083] S2. Dissolve KOH in methanol to obtain a potassium hydroxide methanol solution, and then add N-acetyl-L-tyrosine, stir for 10 min to obtain a tyrosine solution, wherein the concentration of KOH is 0.1 M and the concentration of N-acetyl-L-tyrosine is 100 mg / mL;
[0084] S3. Add the lanthanide compound methanol solution obtained in step S1 to the tyrosine solution obtained in step S2, stir for 30 min, centrifuge to obtain the supernatant, heat and stir (165 °C) until it becomes gelatinous, pour it into a mold, and cool and solidify to obtain the lanthanide luminescent glass.
[0085] Figure 6The physical picture of the lanthanide luminescent glass prepared in Example 6.
[0086] Example 7
[0087] The preparation steps of the tyrosine-based lanthanide luminescent glass include:
[0088] S1. Dissolve dysprosium(III) sulfate octahydrate in methanol to obtain a lanthanide compound methanol solution with a concentration of 0.02 M;
[0089] S2. Dissolve KOH in methanol to obtain a potassium hydroxide methanol solution, and then add N-acetyl-L-tyrosine and stir for 10 min to obtain a tyrosine solution, where the concentration of KOH is 0.1 M and the concentration of N-acetyl-L-tyrosine is 100 mg / mL;
[0090] S3. Add the lanthanide compound methanol solution obtained in step S1 to the tyrosine solution obtained in step S2 (equal volume ratio), stir for 30 min, centrifuge to take the supernatant, heat and stir (165 °C) until it becomes gelatinous, pour it into a mold, and cool and solidify to obtain the lanthanide luminescent glass.
[0091] Figure 7 The physical picture of the lanthanide luminescent glass prepared in Example 7.
[0092] Figure 8 The optical photograph of the lanthanide luminescent glass of Example 7 when prepared into an optical fiber for laser conduction.
[0093] Example 8
[0094] Compared with Example 1, the only difference is that N-acetyl-L-tyrosine is replaced with an equal amount of Boc-L-tyrosine.
[0095] Example 9
[0096] Compared with Example 1, the only difference is that N-acetyl-L-tyrosine is replaced with an equal amount of DL-m-tyrosine.
[0097] Example 10
[0098] Compared with Example 7, the only difference is that the concentration of dysprosium(III) sulfate octahydrate in the solution in step S1 is adjusted to 0.03 M.
[0099] Example 11
[0100] Compared with Example 7, the only difference is that the concentration of dysprosium(III) sulfate octahydrate in the solution in step S1 is adjusted to 0.04 M.
[0101] Example 12
[0102] Compared with Example 7, the only difference is that the concentration of dysprosium(III) octahydrate in the solution in step S1 is adjusted to 0.05 M.
[0103] Figure 15 Figures of the lanthanide luminescent glasses with different concentrations of dysprosium ions prepared in Example 7 and Examples 10 - 12.
[0104] Figure 16 Excitation spectra of the lanthanide luminescent glasses with different concentrations of dysprosium ions prepared in Example 7 and Examples 10 - 12.
[0105] Comparative Example 1
[0106] Compared with Example 7, the only difference is that N - acetyl - L - tyrosine in step S3 is adjusted to N - acetyl - L - glutamic acid.
[0107] Test Example 1
[0108] The luminescence intensities of the lanthanide luminescent glasses prepared in Examples 1, 3, 5, 6, and 7 were detected, and the results are as Figures 10 to 14 shown.
[0109] Luminescence intensity detection method: Use a steady - state and transient fluorescence spectrometer FLS1000 to test its excitation spectrum.
[0110] Figure 10 Excitation spectrum of the lanthanide luminescent glass prepared in Example 7.
[0111] Figure 11 Excitation spectrum of the lanthanide luminescent glass prepared in Example 1.
[0112] Figure 12 Excitation spectrum of the lanthanide luminescent glass prepared in Example 5.
[0113] Figure 13 Excitation spectrum of the lanthanide luminescent glass prepared in Example 3.
[0114] Figure 14 Excitation spectrum of the lanthanide luminescent glass prepared in Example 6.
[0115] It can be seen from Figures 10 - 14 that the lanthanide luminescent glass prepared by this method has good luminescence properties.
[0116] Test Example 2
[0117] The biodegradability of the lanthanide luminescent glass prepared in Example 7 was tested, and the results are as Figure 17 shown.
[0118] Degradation experiment procedure: Place the prepared glass in pure water for the degradation experiment.
[0119] Figure 17 Degradation photo of the lanthanide luminescent glass prepared in Example 7.
[0120] From Figure 17 It can be seen that the lanthanide luminescent glass has degradability.
[0121] In this specification, each embodiment is described in a progressive manner. The key point of each embodiment is to illustrate the differences from other embodiments. For the same or similar parts among the embodiments, reference can be made to each other.
[0122] The above description of the disclosed embodiments enables those skilled in the art to implement or use the present invention. Various modifications to these embodiments will be obvious to those skilled in the art. The general principles defined herein can be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to these embodiments shown herein, but will be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims
1. A preparation method of a tyrosine-based lanthanide luminescent glass, characterized in that the steps Comprising: Dissolve potassium hydroxide in methanol, then add tyrosine and stir for 10 - 30 min to obtain a tyrosine solution; Dissolve the lanthanide compound in methanol to obtain a lanthanide compound methanol solution; Add the lanthanide compound methanol solution to the tyrosine solution and stir for 20 - 40 min to obtain a mixed solution; Centrifuge the mixed solution, take the supernatant, heat and stir it to a gel state, and cool and shape it to obtain the lanthanide luminescent glass.
2. The preparation method according to claim 1, characterized in that, The concentration of potassium hydroxide in the tyrosine solution is 0.1 M.
3. The preparation method according to claim 1, characterized in that, The concentration of tyrosine in the tyrosine solution is 100 mg / mL.
4. The preparation method according to claim 1, characterized in that, The tyrosine includes at least one of N-acetyl-L-tyrosine, Boc-L-tyrosine, Fmoc-O-tert-butyl-L-tyrosine, and DL-m-tyrosine.
5. The preparation method according to claim 1, characterized in that, The concentration of the lanthanide compound methanol solution is 0.02 - 0.05 M.
6. The preparation method according to claim 1, characterized in that, The lanthanide compound includes at least one of thulium(III) chloride hexahydrate, lutetium(III) chloride hexahydrate, gadolinium(III) chloride hexahydrate, cerium chloride hexahydrate, neodymium chloride hexahydrate, ytterbium(III) chloride hexahydrate, and dysprosium(III) sulfate octahydrate.
7. The preparation method according to claim 1, characterized in that, The volume ratio of the lanthanide compound methanol solution to the tyrosine solution is 1:
1.
8. The preparation method according to claim 1, characterized in that, The temperature of the heating and stirring is 165 °C.
9. A tyrosine-based lanthanide luminescent glass, characterized in that, The lanthanide luminescent glass based on tyrosine is prepared by the preparation method according to any one of claims 1 - 8.
10. Use of the lanthanide luminescent glass according to claim 9 in the fields of biomedicine, optical devices, and environmental protection materials.