Edible organic long-afterglow material as well as preparation method and application thereof

Abstract

The invention discloses an edible organic long-afterglow material as well as a preparation method and application thereof. The preparation method of the edible organic long-afterglow material comprises the following steps: dispersing saccharide micromolecules and amino acid micromolecules in a solvent, and uniformly stirring at 35-55 DEG C to obtain a luminophor mixed solution; and drying the illuminant mixed solution at 80-110 DEG C until the solvent is evaporated to obtain the edible organic long afterglow material. The prepared edible organic material has edibility and excellent afterglow performance and has afterglow emission performance under excitation of ultraviolet light and visible light, and the highest afterglow time is 24 s.

Description

Technical Field

[0001] The present invention belongs to the technical field of methods for preparing organic long afterglow materials, and in particular relates to an edible organic long afterglow material and a preparation method and application thereof. Background Art

[0002] Organic long-persistent luminescence (OLPL) materials have advantages such as facile synthesis, ease of functional modification and processing, and the ability to manipulate room-temperature phosphorescence (RTP) through rational molecular design. They hold potential for application in bioimaging, photodynamic therapy, information storage and anti-counterfeiting, sensing, and security protection. However, most organic compounds and solvents used to prepare OLPL materials have certain biotoxicity, making them virtually unedible. This severely limits their application. Chinese patent publication number CN 113621262A discloses a polysaccharide-based long-persistent luminescence material. This material is made from polysaccharides doped with inorganic salts. High-temperature treatment disrupts the hydrogen bonds between water molecules and polysaccharide chains, promoting the formation of stronger hydrogen bonds and enhancing hydroxyl clusters. This material, in turn, imparts long-lasting luminescence to the polysaccharide. This material avoids the toxicity risks associated with traditional organic luminescent materials, but the introduction of heavy metal inorganic salts still poses a toxicity risk.

[0003] In addition, due to the intersystem crossing phenomenon of singlet and triplet states in organic compounds and the instability of triplet excitons, it is difficult to achieve long-life, high-efficiency long-lasting emission. For the current common preparation methods, it is also difficult to achieve mass production. After large-scale preparation, the luminescence performance of organic long-lasting materials decreases, which is not conducive to the commercial application of organic long-lasting materials. Therefore, it is very necessary to obtain organic long-lasting materials with good luminescence performance, edible properties and scalable mass production through a green and simple preparation method. Summary of the Invention

[0004] In view of the deficiencies of the prior art, the object of the present invention is to provide an edible organic long afterglow material.

[0005] Another object of the present invention is to provide a method for preparing an edible organic long afterglow material.

[0006] Another object of the present invention is to provide an edible organic long afterglow material for use in projection display.

[0007] Another object of the present invention is to provide an edible organic long afterglow material for use in food processing.

[0008] The purpose of the present invention is achieved through the following technical solutions.

[0009] A method for preparing an edible organic long afterglow material comprises the following steps:

[0010] The saccharide small molecules and amino acid small molecules are dispersed in a solvent and stirred at 35-55° C. until uniform, to obtain a luminophore mixed solution; the luminophore mixed solution is dried at 80-110° C. until the solvent evaporates, to obtain an edible organic long afterglow material, wherein the ratio of the saccharide small molecules to the amino acid small molecules is (100-1000):1 by mass.

[0011] In the above technical solution, the ratio of carbohydrate small molecules to amino acid small molecules is (100-300):1 by mass.

[0012] In the above technical solution, the small carbohydrate molecule is one of maltose, sucrose, lactose, glucose, fructose, galactose, xylitol, mannitol, glucuronic acid and stevioside.

[0013] In the above technical solution, the amino acid small molecule is one of tryptophan, phenylalanine, lysine, methionine, threonine, isoleucine, leucine, arginine, histidine, valine, proline, cysteine, tyrosine, alanine, glycine, glutamic acid, serine and aspartic acid.

[0014] In the above technical solution, it is preferred that the small carbohydrate molecule is maltose and the small amino acid molecule is tryptophan.

[0015] In the above technical solution, the solvent is water.

[0016] In the above technical solution, the mass fraction of the saccharide small molecules and the volume fraction of the solvent are (100-1000): (1-500), the unit of the mass fraction is mg, and the unit of the volume fraction is mL.

[0017] In the above technical solution, the sugar small molecules and amino acid small molecules are dispersed in a solvent and stirred at 35-55° C. for 2-10 minutes until the sugar small molecules and amino acid small molecules are completely dissolved to obtain a luminophore mixed solution.

[0018] In the above technical solution, the drying time is 0.5 to 2 hours.

[0019] The edible organic long afterglow material is obtained by the preparation method.

[0020] The above-mentioned edible organic long afterglow material is used in projection display.

[0021] In the above technical solution, the excitation wavelength of the edible organic long afterglow material is 250 to 430 nm, preferably 365 nm.

[0022] Application of the above-mentioned edible organic long afterglow material in food processing.

[0023] In the above technical solution, the excitation wavelength of the edible organic long afterglow material is 250 to 430 nm, preferably 365 nm.

[0024] Compared with the prior art, the present invention has the following beneficial effects:

[0025] (1) The edible organic material prepared by the present invention has edibility and excellent afterglow performance. It has afterglow emission performance under the excitation of ultraviolet light (365nm) and visible light (405nm), with an afterglow time of up to 24s. The afterglow brightness is high and does not require a completely dark environment.

[0026] (2) The edible organic material prepared by the present invention has good mechanical stability, and its afterglow properties will not be changed after operations such as grinding. It can be used in various forms such as films and powders, which expands the application of long afterglow materials in food processing.

[0027] (3) The amino acid small molecules and sugar small molecules used in the present invention are essential substances for the human body. At the same time, as common materials used in food processing, they have no biological toxicity and have the advantages of being low in price and easy to obtain.

[0028] (4) The method of the present invention has a simple preparation process and mild reaction conditions, and can obtain kilogram-level products through a simple proportional amplification method without causing a decrease in the afterglow performance of the material, which is conducive to the commercial application of long afterglow materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 The UV-visible absorption spectrum, fluorescence emission spectrum and delayed emission spectrum of the edible organic long afterglow material prepared in Example 1;

[0030] Figure 2 This is a macroscopic long afterglow image of the edible organic long afterglow material prepared in Example 1 after being excited by 365nm ultraviolet light;

[0031] Figure 3 This is a macroscopic long afterglow image of the edible organic long afterglow material prepared in Example 4 after being excited by 365nm ultraviolet light;

[0032] Figure 4 This is a macroscopic long afterglow image of the edible organic long afterglow material prepared in Example 5 after being excited by 365nm ultraviolet light;

[0033] Figure 5Macroscopic long afterglow images of the edible organic long afterglow materials prepared in Examples 12, 14, 16, 18-19, and 24 after being excited by 365nm ultraviolet light;

[0034] Figure 6 This is a graph showing the afterglow performance attenuation of the edible organic long afterglow materials prepared in Examples 7, 11, 13, and 15 after being excited by 365nm ultraviolet light;

[0035] Figure 7 This is a graph showing the attenuation of afterglow performance of the edible organic long afterglow materials prepared in Examples 17, 20, and 22 after being excited by 365nm ultraviolet light;

[0036] Figure 8 This is a macroscopic long afterglow image of the edible organic long afterglow material prepared in Example 1 after being excited by 405nm visible light;

[0037] Figure 9 This is a macroscopic long afterglow image of the edible organic long afterglow material prepared in Example 5 after being excited by 405nm visible light;

[0038] Figure 10 This is a graph showing the afterglow performance attenuation of the edible organic long afterglow material prepared in Example 4 after being excited by 405nm visible light;

[0039] Figure 11 This is a macroscopic long afterglow image of the edible organic long afterglow material prepared in Example 28 after being excited by 405nm visible light;

[0040] Figure 12 This is a macroscopic long afterglow image of marshmallows made from the edible organic long afterglow material prepared in Example 28 after being excited by 405nm visible light;

[0041] Figure 13 Schematic diagram of the application of the edible organic long afterglow material prepared in Example 29 in food processing and projection display. DETAILED DESCRIPTION

[0042] The technical solution of the present invention is further described in detail below with reference to the accompanying drawings and embodiments.

[0043] In the following examples, maltose (purity: 98 wt%) and stevia (purity: 98 wt%) were purchased from Shanghai Bid Pharmaceutical Technology Co., Ltd.

[0044] Sucrose, lactose, glucose, fructose, galactose, xylitol, mannitol, glucuronic acid, tryptophan, phenylalanine, lysine, methionine, threonine, isoleucine, leucine, arginine, histidine, valine, proline, cysteine, tyrosine, alanine, glycine, glutamic acid, serine, and aspartic acid were purchased from Tianjin Xiens Biochemical Technology Co., Ltd. with a purity of 98 wt%.

[0045] Examples 1 to 27

[0046] A method for preparing an edible organic long afterglow material comprises the following steps:

[0047] A saccharide small molecule (dosage: 300 mg) and an amino acid small molecule were dispersed in a solvent (deionized water) and stirred at 40°C for 2 minutes until the saccharide small molecule and the amino acid small molecule were completely dissolved, thereby obtaining a luminophore mixed solution. The luminophore mixed solution was dried at 90°C for 0.5 hours until the solvent evaporated, thereby obtaining an edible organic long-lasting glow material, wherein the mass ratio of the saccharide small molecule to the amino acid small molecule was 300:1; the mass ratio of the saccharide small molecule to the solvent was 300:2, with the mass ratio being expressed in mg and the volume ratio being expressed in mL.

[0048] The sugar small molecules and amino acid small molecules used in preparing edible organic long afterglow materials in Examples 1 to 27 are shown in Table 1.

[0049] Table 1

[0050]

[0051]

[0052] Example 28

[0053] A method for preparing an edible organic long afterglow material comprises the following steps:

[0054] The sugar small molecules (dosage: 1300 g) and the amino acid small molecules were dispersed in a solvent (the solvent was deionized water), and stirred at 40°C for 10 minutes until the sugar small molecules and the amino acid small molecules were completely dissolved to obtain a luminophore mixed solution. The luminophore mixed solution was dried at 95°C for 2 hours until the solvent evaporated to obtain an edible organic long afterglow material, wherein the sugar small molecule was maltose and the amino acid small molecule was tryptophan. The ratio of the sugar small molecules to the amino acid small molecules was 1300:4.5 by mass; the mass ratio of the sugar small molecules to the solvent was 1.3×10 6: 1400, the unit of mass fraction is mg, the unit of volume fraction is mL. The yield is 98%, yield = edible organic long afterglow material / (the sum of the mass of the sugar small molecules and the amino acid small molecules).

[0055] Example 29

[0056] A method for preparing an edible organic long afterglow material comprises the following steps:

[0057] The sugar small molecules (dosage: 150g) and amino acid small molecules were dispersed in a solvent (the solvent was deionized water) and stirred at 40°C for 5 minutes until the sugar small molecules and amino acid small molecules were completely dissolved to obtain a luminophore mixed solution. The luminophore mixed solution was dried at 90°C for 1.5 hours until the solvent evaporated to obtain an edible organic long afterglow material, wherein the mass ratio of the sugar small molecules to the amino acid small molecules was 300:1; the mass ratio of the sugar small molecules to the solvent was 0.9×10 5 :100, the unit of mass fraction is mg, and the unit of volume fraction is mL.

[0058] Comparative Example 1

[0059] A method for preparing an edible organic material is basically the same as that of Example 1, except that the luminophore mixed solution is placed in a -80°C freeze drying oven and dried for 12 hours to obtain the edible organic material.

[0060] Comparative Example 2

[0061] A method for preparing an edible organic material is basically the same as that of Example 1, except that the luminophore mixed solution in Comparative Example 2 is a mixture of small saccharide molecules (dosage: 300 mg) and deionized water.

[0062] Comparative Example 3

[0063] A method for preparing an edible organic material is basically the same as that of Example 1, except that the sugar small molecule and the amino acid small molecule are different. The sugar small molecule used in Comparative Example 3 is isosorbide, and the amino acid small molecule used is tryptophan.

[0064] Comparative Example 4

[0065] A method for preparing an edible organic material is basically the same as that of Example 1, except that the carbohydrate small molecule and the amino acid small molecule are different. In Comparative Example 4, the carbohydrate small molecule used is isosorbide, and the amino acid small molecule used is phenylalanine.

[0066] Comparative Example 5

[0067] A method for preparing an edible organic material is basically the same as that of Example 1, except that the luminophore mixed solution is dried in a vacuum drying oven at 40° C. for 0.5 h until the solvent evaporates, thereby obtaining an edible organic long-afterglow material.

[0068] At room temperature, the UV-visible absorption spectrum of the edible organic long afterglow material prepared in Example 1 was measured using a Shimadzu UV-2700 UV-visible spectrophotometer. Figure 1 As shown in the “UV-visible absorption” Figure 1 It can be seen that it has an absorption peak in the range of 250 to 500 nm, indicating that the edible organic long afterglow material prepared in Example 1 can be excited under both ultraviolet light and visible light.

[0069] The fluorescence emission spectrum of the edible organic long afterglow material prepared in Example 1 under 365nm ultraviolet light excitation was measured using an Edinburgh FLS1000 photoluminescence spectrometer. Figure 1 Then test the delayed emission spectrum after 1s of 365nm ultraviolet light excitation, as shown in the "Fluorescence Emission" in the figure. Figure 1 The “delayed emission” in the figure shows that the edible organic long afterglow material prepared in Example 1 can emit afterglow under ultraviolet light.

[0070] The edible organic long afterglow material prepared in Example 1 was excited for 1 second with visible light with a peak of 405nm and natural light with a peak of 430nm emitted by a flashlight. After excitation, the excitation light source was turned off. It was found that after excitation with 405nm visible light, the material emitted an afterglow, while after excitation with 430nm natural light, the afterglow was weak and the luminescence was almost invisible. In summary, the excitation light source of the edible organic long afterglow material is between 250 and 430nm.

[0071] Example 30

[0072] Afterglow test: At room temperature of 20-25℃, use 365nm ultraviolet light or 405nm visible light emitted by an ultraviolet lamp (power is 35W) as the light source to excite the organic long afterglow material for 5s. After 5s of excitation, turn off the excitation light source and use the Ocean Optics multi-band spectrometer to detect the afterglow of the organic long afterglow material to obtain the afterglow performance attenuation diagram (such as Figures 6-7 and Figure 10 ) and afterglow time (as shown in Table 2), and at the same time, take a photo in the dark after the excitation light source is turned off to obtain a macroscopic long afterglow picture (as shown in Table 2). Figures 2 to 5 and Figures 8-9 ), wherein the organic long afterglow material is one of the edible organic long afterglow materials prepared in Examples 1 to 27 and the edible organic materials prepared in Comparative Examples 1 to 5.

[0073] The macroscopic long afterglow picture of organic long afterglow material after being excited by 365nm ultraviolet light is as follows Figures 2 to 5 As shown, Figure 2 For Example 1, Figure 3 For Example 4, Figure 4 For Example 5, Figure 5 They are Example 12, Example 14, Example 16, Examples 18-19 and Example 24.

[0074] The afterglow performance attenuation of organic long afterglow materials after being excited by 365nm ultraviolet light is shown in the figure below. Figures 6-7 As shown. Among them, Figure 6 For Example 7, Example 11, Example 13 and Example 15, Figure 7 These are Example 17, Example 20 and Example 22.

[0075] The macroscopic long afterglow images of Example 1 and Example 5 after being excited by 405nm visible light are as follows: Figures 8-9 As shown in the figure, the afterglow performance attenuation diagram of Example 4 after being excited by 405nm visible light is as follows Figure 10 shown.

[0076] Table 2

[0077]

[0078]

[0079] In Table 2, “-” means no afterglow time

[0080] Depend on Figure 2 As shown in Table 2, the edible organic long afterglow material prepared in Example 1 can maintain its afterglow for 24 seconds after being excited by 365nm ultraviolet light. After being excited by 405nm visible light, its afterglow can be maintained for 22 seconds. The edible organic long afterglow material prepared in Example 1 has the best afterglow performance.

[0081] Example 31

[0082] The edible organic long afterglow material prepared in Example 28 was used as the "organic long afterglow material" to perform the afterglow test in Example 30 using 405nm visible light to obtain a macroscopic long afterglow image, as shown in FIG. Figure 11 As shown. Figure 11 It can be seen that it still has a bright afterglow under kilogram-scale preparation, and the afterglow time is 22s, indicating that the present invention can achieve kilogram-scale macro-preparation using sugar small molecules and amino acid small molecules, and emit afterglow after visible light excitation, and the afterglow performance remains unchanged after macro-scale preparation.

[0083] The edible organic long afterglow material prepared in Example 28 was ground into powder in a mortar for 10 minutes and then made into cotton candy using a cotton candy machine. The cotton candy was excited with 405nm visible light for 5 seconds. After 5 seconds of excitation, the excitation light source was turned off and the afterglow was observed in the dark. The macroscopic long afterglow picture is as follows: Figure 12 As shown by Figure 12 It can be seen that the afterglow performance remains unchanged when it is further applied to food processing.

[0084] Example 32

[0085] Take 100g of the edible organic long afterglow material prepared in Example 29 and mix it with 10mL of water to obtain a viscous mixture. Apply the mixture on the surface of the cake and dry it naturally at room temperature to form a transparent afterglow film with a thickness of 3mm. Figure 13 As shown, 405nm visible light is used as the light source. The light source is filtered by a film with a pattern (as a filter) and then irradiated onto the surface of the cake and excited for 5s. Among them, the patterns formed in the transparent area of ​​the film are "Tianjin", "Apple" and "Grape" respectively.

[0086] After 5 seconds of excitation, the light source was turned off. A cyan-blue pattern of "Tianjin," "apple," and "grape" could be clearly seen on the cake surface. The light was uniform, the pattern was clear, and the resolution was high. The edible organic long-afterglow material of the present invention can be further applied in projection displays, imparting enhanced performance to processed food products without altering their original properties.

[0087] The above is an exemplary description of the present invention. It should be noted that, without departing from the core of the present invention, any simple deformation, modification or other equivalent replacement that can be made by other skilled in the art without expending creative labor falls within the scope of protection of the present invention.

Claims

1. A method for preparing an edible organic long afterglow material, characterized in that: The following steps are involved: Dispersing the sugar small molecules and the amino acid small molecules in a solvent and stirring until uniform to obtain a luminophore mixed solution; The luminophore mixed solution is dried at 80-110° C. until the solvent evaporates to obtain an edible organic long afterglow material, wherein the ratio of sugar small molecules to amino acid small molecules is (100-1000):1 by mass, and the sugar small molecules are a mixture of one or more of maltose, sucrose, lactose, glucose, fructose, galactose, xylitol, mannitol, glucuronic acid and stevioside.

2. The preparation method according to claim 1, characterized in that The amino acid small molecule is a mixture of one or more of tryptophan, phenylalanine, lysine, methionine, threonine, isoleucine, leucine, arginine, histidine, valine, proline, cysteine, tyrosine, alanine, glycine, glutamic acid, serine and aspartic acid.

3. The preparation method according to claim 1, characterized in that The solvent is water.

4. The preparation method according to claim 1, characterized in that The mass fraction of the saccharide small molecules and the volume fraction of the solvent are (100-1000): (1-500), the unit of the mass fraction is mg, and the unit of the volume fraction is mL.

5. The preparation method according to claim 1, characterized in that The drying time is 0.5 to 2 hours.

6. An edible organic long afterglow material obtained by the preparation method according to any one of claims 1 to 5.

7. Application of edible organic long afterglow materials in luminescent displays.

8. The use according to claim 7, characterized in that The excitation wavelength of the edible organic long afterglow material is 250 to 430 nm.

9. A food, characterized in that The food is loaded with edible organic long-lasting glow material.

10. The food according to claim 9, characterized in that The edible organic long afterglow material emits light under the excitation of 250 to 430 nm.

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