Preparation method and application of methionine-tyrosine bifunctional porous material
By preparing methionine-tyrosine bifunctional porous materials, the problem of scavenging hydroxyl radicals was solved, achieving a highly efficient antioxidant effect and expanding the application range of the materials.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- NANJING TECH UNIV
- Filing Date
- 2023-09-22
- Publication Date
- 2026-07-14
Smart Images
Figure CN117447706B_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of antioxidant material preparation technology, specifically relating to the preparation method and application of methionine-tyrosine bifunctional porous materials. Background Technology
[0002] Reactive oxygen species (ROS) are oxygen-containing molecules that are unstable and chemically reactive. These ROS participate in a wide variety of complex reaction pathways, sometimes forming molecules and atoms with unpaired electrons, known as free radicals. Small amounts of ROS regulate cell signaling pathways and promote cell proliferation; however, higher concentrations of ROS cannot be neutralized by cellular antioxidants (such as superoxide dismutase or catalase), causing oxidative stress, which can disrupt homeostasis by damaging proteins, liposomes, and DNA. Therefore, developing effective materials to scavenge these free radicals is crucial.
[0003] Amino acids are the basic building blocks of proteins. Methionine exhibits significant antioxidant properties due to the sulfide in its structure being oxidized to sulfones and sulfoxides. Similarly, the phenolic hydroxyl group in tyrosine is a major group with antioxidant activity. By uniformly embedding these two molecules in different proportions into the pore walls of the material, framework functionalization is achieved. The resulting porous material, obtained through framework functionalization, possesses both the properties of amino acids and porous materials, expanding the possibilities for its applications.
[0004] Therefore, the preparation of methionine-tyrosine bifunctional porous materials for scavenging hydroxyl radicals is of certain research significance and is expected to be developed into antioxidant materials with high scavenging rates. Summary of the Invention
[0005] This invention provides a method for preparing a methionine-tyrosine bifunctional porous material for scavenging hydroxyl radicals, thereby addressing the deficiencies of existing technologies.
[0006] To achieve the above objectives, the present invention adopts the following technical solution.
[0007] On the one hand, this application provides a method for preparing a methionine-tyrosine bifunctional porous material, comprising the following steps:
[0008] First, the synthesis of the methionine organosilicon precursor:
[0009] Methionine was used as a raw material. After amino protection by di-tert-butyl dicarbonate, it was hydrazide-hydrated under argon conditions and then reacted with 3-isocyanate-propyltriethoxysilane in tetrahydrofuran solvent to generate an organosilicon precursor of methionine.
[0010] The structural formula of the obtained methionine organosilicon precursor is as follows:
[0011]
[0012] Then, the synthesis of methionine-tyrosine bifunctional porous materials:
[0013] In a mixed solution of template agent, deionized water, and ethanol under alkaline conditions, the mixture was stirred in a water bath for 24 hours. Methionine organosilicon precursors and tyrosine organosilicon precursors in a specific ratio were added to the above solution and reacted for another 24 hours, followed by a period of standing. The mixture was then washed with water and dried overnight. The dried material was placed in a Soxhlet extractor and extracted with anhydrous ethanol and hydrochloric acid for 48 hours to remove the template agent. The material was then dried at room temperature to obtain methionine-tyrosine bifunctional porous materials with varying methionine content.
[0014] Furthermore, the template agent is hexadecyltrimethylammonium bromide (CTAB), the alkaline conditions are 22%-28% concentrated ammonia water, and the water bath temperature is 25℃-35℃.
[0015] Furthermore, the molar ratio of methionine organosilicon precursor to tyrosine organosilicon precursor is 1:3 to 3:1.
[0016] Finally, this application also provides an application of the above-mentioned methionine-tyrosine bifunctional porous material in its antioxidant properties against hydroxyl radicals.
[0017] The methionine-tyrosine bifunctional porous material obtained by this invention exhibits a high scavenging rate in removing hydroxyl radicals, thus fully demonstrating its antioxidant properties.
[0018] Given that the bifunctional porous material obtained by the method of the present invention can efficiently scavenge hydroxyl radicals, it provides an ideal approach for combating hydroxyl radical oxidation. Attached Figure Description
[0019] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the description of the embodiments will be briefly introduced below.
[0020] Figure 1 The result of the 1H NMR spectrum determination of the methionine organosilicon precursor;
[0021] Figure 2 X-ray diffraction (XRD) pattern of a methionine-tyrosine bifunctional porous material containing 25% methionine;
[0022] Figure 3 Nitrogen adsorption-desorption curves for a methionine-tyrosine bifunctional porous material containing 25% methionine.
[0023] Figure 4 X-ray diffraction (XRD) pattern of a methionine-tyrosine bifunctional porous material containing 50% methionine;
[0024] Figure 5 Nitrogen adsorption-desorption curves for a methionine-tyrosine bifunctional porous material containing 50% methionine.
[0025] Figure 6 X-ray diffraction (XRD) pattern of a methionine-tyrosine bifunctional porous material containing 75% methionine;
[0026] Figure 7 Nitrogen adsorption-desorption curves for a methionine-tyrosine bifunctional porous material containing 75% methionine.
[0027] Figure 8 This is a schematic diagram of the preparation process for methionine-tyrosine bifunctional porous materials. Detailed Implementation
[0028] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0029] Example 1: Preparation of methionine organosilicon precursor.
[0030] (1) Synthesis of N-tert-butoxycarbonylmethionine hydrazide: 0.05 mol of methionine was dissolved in 50 mL of sodium hydroxide solution. Under ice bath conditions, 50 mL of tetrahydrofuran solution containing 7.5 g of ditert-butyl dicarbonate was slowly added. After stirring overnight at room temperature, the solvent was evaporated under reduced pressure to obtain crude N-tert-butoxycarbonylmethionine (9.88 g). N-tert-butoxycarbonylmethionine was added to a 250 mL round-bottom flask, and excess 80% hydrazine hydrate was added under argon atmosphere. The mixture was stirred at room temperature for 24 h, followed by reduced pressure distillation to remove excess hydrazine hydrate. The residue was purified by silica gel chromatography using methanol:dichloromethane = 1:30 as the eluent to obtain an oily N-tert-butoxycarbonylmethionine hydrazide (8.43 g). (2) N-tert-butoxycarbonyl methionine hydrazide was dissolved in 5 mL of acetyl chloride at 0°C to obtain methionine hydrazide. Under argon protection, it was dissolved in 50 mL of anhydrous tetrahydrofuran, and 10 g of 3-isocyanate-propyltriethoxysilane (IPTES) was added. The mixture was stirred overnight at room temperature. After the reaction was complete, the mixture was distilled under reduced pressure, washed with anhydrous n-hexane to remove impurities, filtered, and dried to obtain a white solid, which was the methionine organosilicon precursor. See [link to relevant documentation]. Figure 1The NMR spectrum results are as follows: 1H NMR (400MHz, DMSO) 9.67(s, 1H), 7.69(s, 1H), 6.41(s, 1H), 6.19(s, 1H), 6.07(s, 1H), 4.09(s, 1H), 3.73(s, 12H), 2.96(s, 4H), 2.45(s, 2H), 2.04(s, 3H), 1.79(s, 2H), 1.43(s, 4H), 1.15(s, 18H), 0.52(s, 4H).
[0031] Example 2: Preparation of a methionine-tyrosine bifunctional porous material with 25% methionine.
[0032] Step (1) Dissolve 0.78g of the template agent cetyltrimethylammonium bromide (CTAB), 88ml of deionized water, 33mL of ethanol and 0.5mL of 25% ammonia in a mixture and stir at room temperature for 1 hour.
[0033] Step (2): Based on the ratio of methionine organosilicon precursor to mixed organosilicon precursor (the sum of methionine organosilicon precursor and tyrosine organosilicon precursor) of 25%, 0.345g of methionine organosilicon precursor and 0.9501g of tyrosine organosilicon precursor dissolved in 5ml of ethanol were slowly added to the system. The reaction was carried out for 24h, and then allowed to stand overnight at room temperature. After the reaction was completed, the material was collected by centrifugation, washed with deionized water and ethanol, dried at 60℃, and the dried material was placed in a Soxhlet extractor and extracted with anhydrous ethanol and hydrochloric acid (50:1) for 48h to remove the template agent. The material was then dried at room temperature.
[0034] Step (3) Disperse 10 mg of methionine-tyrosine bifunctional porous material containing 25% methionine in 10 mL of 0.2 mol / L phosphate buffer solution (pH 7.4) to prepare a sample solution with a concentration of 1 mg / mL. Take 1 mL of this sample solution and mix it with 1 mL of 0.75 mmol / L o-phenanthroline solution and 2 mL of 0.2 mol / L phosphate buffer solution (pH 7.4). Add 1 mL of 0.75 mmol / L ferrous sulfate solution and 1 mL of 0.01% hydrogen peroxide solution to the above mixture. Mix and react in a shaker at 37°C for 60 min. Take it out and measure its absorbance at 536 nm. The hydroxyl scavenging rate can be calculated to be 52.68%.
[0035] Figure 2 XRD pattern of methionine-tyrosine bifunctional porous material (25% Met-Tyr-BMO) containing 25% methionine obtained by this method: From Figure 2 As can be seen, there is a strong diffraction peak at a diffraction angle of 2.4, which is a (d100) crystal plane diffraction peak; and a diffraction peak at a diffraction angle of 4.2, which is a (d110) crystal plane diffraction peak.
[0036] Figure 3 The nitrogen adsorption-desorption curve of the methionine-tyrosine bifunctional porous material (25% Met-Tyr-BMO) containing 25% methionine obtained by this method belongs to type IV. Figure 3 It can be seen that there is a sudden jump between P / P0 of 0.2 and 1.0, and the overall hysteresis loop exhibits an H3-type hysteresis loop, indicating the presence of mesoporous capillary condensation.
[0037] Example 3: Preparation of a methionine-tyrosine bifunctional porous material with 50% methionine.
[0038] Step (1) in this implementation is the same as step (1) in Example 2.
[0039] Step (2) is basically the same as step (2) in Example 2, except that the proportion of the added methionine organosilicon precursor to the mixed organosilicon precursor (the sum of methionine organosilicon precursor and tyrosine organosilicon precursor) is 50%.
[0040] Step (3) is basically the same as step (3) in Example 2, except that the methionine-tyrosine bifunctional porous material with 50% methionine can scavenge 58.24% of hydroxyl radicals.
[0041] Figure 4 XRD pattern of methionine-tyrosine bifunctional porous material (50% Met-Tyr-BMO) containing 50% methionine obtained by this method: From Figure 4 As can be seen, there is a strong and relatively sharp diffraction peak at a diffraction angle of 2.38, which is the (d100) crystal plane diffraction peak.
[0042] Figure 5 The nitrogen adsorption-desorption curve of the methionine-tyrosine bifunctional porous material (50% Met-Tyr-BMO) containing 50% methionine obtained by this method belongs to type IV. Figure 5 It can be seen that there is a sudden jump between P / P0 of 0.7 and 1.0, and the overall hysteresis loop exhibits an H3-type hysteresis loop, indicating the presence of mesoporous capillary condensation.
[0043] Example 4: Preparation of a methionine-tyrosine bifunctional porous material with 75% methionine.
[0044] Steps (1) and (2) are the same as step (1) in Example 2.
[0045] Step (2) is basically the same as step (2) in Example 2, except that the proportion of the added methionine organosilicon precursor to the mixed organosilicon precursor (the sum of the methionine organosilicon precursor and the tyrosine organosilicon precursor) is 75%.
[0046] Step (3) is basically the same as step (3) in Example 2, except that the methionine-tyrosine bifunctional porous material with 75% methionine can scavenge 71.08% of hydroxyl radicals.
[0047] Figure 6 XRD pattern of 75% methionine-tyrosine bifunctional porous material (75% Met-Tyr-BMO) obtained by this method: From Figure 6 As can be seen, there is a relatively strong and slightly broad diffraction peak at a diffraction angle of 2.32, which is the (d100) crystal plane diffraction peak.
[0048] Figure 7 The nitrogen adsorption-desorption curve of the methionine-tyrosine bifunctional porous material (75% Met-Tyr-BMO) containing 75% methionine obtained by this method belongs to type IV. Figure 7 It can be seen that there is a sudden jump between P / P0 of 0.5 and 1.0, and the overall hysteresis loop exhibits an H3-type hysteresis loop, indicating the presence of mesoporous capillary condensation.
[0049] In summary, the increased content of methionine organosilicon precursor leads to a decrease in the ordered structure and orderliness of the material, resulting in a lower hydroxyl radical scavenging rate. However, the material still retains its mesoporous channel structure characteristics and exhibits good antioxidant properties.
[0050] Figure 8 This is a schematic diagram of the preparation process for methionine-tyrosine bifunctional porous materials.
[0051] The above description is merely a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.
Claims
1. A method for preparing a methionine-tyrosine bifunctional porous material, characterized in that, Includes the following steps: 1) Methionine was used as a raw material and hydrazide-treated, followed by reaction with 3-isocyanate-propyltriethoxysilane to obtain an organosilicon precursor of methionine; 2) Mix the methionine organosilicon precursor and the tyrosine organosilicon precursor in a certain proportion, and slowly add them dropwise to the template agent in an ethanol-deionized water mixture under alkaline conditions. Incubate overnight in a water bath, filter, wash with water, and dry at room temperature. 3) Methionine-tyrosine porous materials with different ratios were obtained by removing the template agent using a Soxhlet extractor in anhydrous ethanol and hydrochloric acid mixture and drying at room temperature. The mixing ratio of the methionine organosilicon precursor to the tyrosine organosilicon precursor is 1:3 to 3:1 in molar ratio.
2. The preparation method according to claim 1, characterized in that, The structural formula of the methionine organosilicon precursor is as follows: 。 3. The preparation method according to claim 1, characterized in that, The temperature for overnight water bathing as described in step 2) is 25℃~35℃.
4. The preparation method according to claim 1, characterized in that, The template agent is hexadecyltrimethylammonium bromide.
5. The preparation method according to claim 1, characterized in that, The alkaline conditions are 22%-28% concentrated ammonia water.
6. A methionine-tyrosine bifunctional porous material, characterized in that, It is prepared by any one of the preparation methods described in claims 1-5.
7. The application of the methionine-tyrosine bifunctional porous material prepared by any one of the preparation methods described in claims 1-5 in scavenging hydroxyl radicals and resisting oxidation.