CN114716999B - Sericin as long afterglow material and application for preparing anti-fake material - Google Patents

Abstract

The invention discloses the use of sericin as a long afterglow material and the application of sericin in preparing anti-counterfeiting materials. Its amorphous powder can produce room temperature long afterglow phenomenon under room temperature conditions, and the absolute quantum yield is as high as 26.8%. Sericin powders with different long afterglow lifetimes can be obtained after processing in different humidity environments. The present invention uses sericin with humidity-influenced differential long afterglow emission capability as an anti-counterfeiting material, opening up a new field for the application of sericin.

Description

Application of sericin as long afterglow material and preparation of anti-counterfeiting materials

Technical field

The invention belongs to the field of organic luminescent materials, and specifically relates to the new use of pure organic biological macromolecule sericin as a long afterglow material and the preparation of anti-counterfeiting materials.

Background technique

At present, although long afterglow materials have been widely used in fields such as RMB anti-counterfeiting and bioimaging, many materials often only show long afterglow performance at low temperatures or doped with heavy metals such as iridium and platinum, which limits the application of long afterglow materials. been greatly restricted. Pure organic molecule long-afterglow materials are relatively cheap, easy to adjust their structures, relatively safe for the environment, and have good processability, which makes them more suitable for bioengineering, medical technology, and the preparation of sensors and electronic devices. Atypical luminescent compounds have been used in explosives and ion detection, biological cell imaging, and anti-counterfeiting and confidentiality because of their simple preparation methods, good biocompatibility, low toxicity, and environmental friendliness. Therefore, it is particularly meaningful to look for pure organic small molecule luminescent compounds that are cheap, have high luminous efficiency and have long afterglow time. The use of sericin treated with different humidity as a long-afterglow organic luminescent material has not been reported before.

Contents of the invention

The purpose of the present invention is to provide an application of sericin as a long afterglow material and an application of sericin in the preparation of anti-counterfeiting materials in order to overcome the above-mentioned defects in the prior art.

The present invention is aimed at the deficiencies existing in the prior art. The present invention is aimed at the deficiencies existing in the prior art and develops a type of insect macromolecule protein long afterglow material, and for the first time provides the use of pure organic biological macromolecule sericin as a long afterglow material. . It specifically involves the use of these materials in the preparation of organic long-afterglow materials, which are characterized by high quantum efficiency and long afterglow time.

The sericin proteins of different molecular weights all have long afterglow luminescence properties. Sericin is a new use of long afterglow organic luminescent materials. Commercially available sericin is purified through sedimentation to obtain pure organic room temperature long afterglow materials and used as anti-counterfeiting encryption materials to prepare anti-counterfeiting materials.

The purpose of dissolution and sedimentation is to eliminate the long afterglow characteristics caused by the impurities contained in commercially available sericin itself. The specific purification method of pure sericin is as follows: Dissolve the sericin raw material in deionized water, then add it to tetrahydrofuran solvent for sedimentation, then suction filtration and washing, and vacuum drying to obtain purified sericin powder. The purified sericin powder is used as a long afterglow material.

The dosage ratio of the sericin raw material, deionized water and tetrahydrofuran is 5-15g: 25-75mL: 250-1000mL, most preferably 10g: 50mL: 500mL.

The vacuum drying conditions are: drying in a vacuum oven at 35°C to 55°C for 18 to 30 hours, and most preferably drying in a vacuum oven at 45°C for 24 hours.

The sericin involved in the present invention is the first example of an insect protein pure organic animal macromolecule long afterglow material. Its amorphous form can produce a long afterglow phenomenon at room temperature. The sericin (sericin) with an average molecular weight of 5000 Protein-5K) has a long afterglow lifetime of up to 455.9ms and a quantum yield as high as 22.8%. The long afterglow lifetime of 10000 sericin (sericin-10000) can be as long as 422.6ms, and the quantum yield is as high as 26.4%.

Compared with the prior art, the present invention has the following advantages:

The sericin of the present invention has a new use as a long afterglow material. Its amorphous powder can produce room temperature long afterglow phenomenon under room temperature conditions, and the absolute quantum yield is as high as 26.8%. Sericin powders with different long afterglow lifetimes can be obtained after processing in different humidity environments. The present invention uses sericin with humidity-influenced differential long afterglow emission capability as an anti-counterfeiting material, opening up a new field for the application of sericin.

Description of the drawings

Figure 1 shows (a) PL spectrum, (b) long afterglow lifetime and (c) long afterglow changes with time of sericin-5k at room temperature.

Figure 2 shows (a) PL spectrum, (b) long afterglow lifetime and (c) long afterglow changes with time of sericin-1W at room temperature.

Figure 3 shows the application of the anti-counterfeiting effect of the sericin powder combination after treatment under different humidity.

Detailed ways

The technical solution of the present invention will be described in further detail below with reference to specific embodiments. Those skilled in the art should understand that the following examples are only for illustration and are not intended to limit the scope of the invention.

The sericin powders of different molecular weights used in the following examples are commercially available products, and were dissolved, sedimented and purified before use.

The purpose of dissolution and sedimentation is to eliminate the long afterglow characteristics caused by the impurities contained in commercially available sericin itself. Dissolve sericin in deionized water, then pour into 10 to 20 times of tetrahydrofuran solvent to settle, then filter and wash with suction, and vacuum dry at room temperature to obtain purified sericin powder.

Example 1

Weigh 10g of sericin-5K (Dali Silk) solid powder into a 100mL double-necked flask, add 50mL of deionized water, stir to dissolve, and then drop the sericin solution into 500ml of tetrahydrofuran solution to settle. The sample obtained after suction filtration and washing was dried in a vacuum oven at 45°C for 24 hours to obtain a purified sericin-5K sample.

The luminescent properties of sericin-5K are shown in Figure 1 (a) Fluorescence and long afterglow spectra at 340 nm (t _d = 0.01 s): the PL and long afterglow emission peaks excited at 312 nm are 372 and 512 nm, respectively. . (b) Lifetime test found that 455.9ms was monitored at 512nm (λ _ex =340nm). The total quantum yield of DHU under 340nm excitation is 22.8%.

Example 2

Weigh 10g of sericin-10,000 (Dali Silk) solid powder into a 100mL double-necked flask, add 50mL of deionized water, stir to dissolve, and then drop the sericin solution into 500ml of tetrahydrofuran solution to settle. The sample obtained after suction filtration was dried in a vacuum oven at 45°C for 24 hours to obtain a purified sericin-10,000 sample.

The luminescent properties of sericin-10,000 are shown in Figure 2 (a) Fluorescence and long afterglow spectra at 340 nm (t _d = 0.01 s): the PL and long afterglow emission peaks excited at 312 nm are 475 and 525 nm, respectively. . (b) Lifetime test found that 422.6ms was monitored at 525nm (λ _ex =340nm). The total quantum yield of DHU under 340nm excitation is 26.4%.

Example 3

The purified Dali silk sericin-10,000 powder was placed in a constant temperature and humidity box with a humidity of 80% and a temperature of 25°C for half an hour. Then it was taken out and then combined with the unplaced powder to form a smiley face pattern. Under 312nm UV When the UV light is turned off after 1 minute of light excitation, you can see that the mouth in the middle of the smile disappears faster than the long afterglow emission of other parts. This is because the humidity response also makes it have an anti-counterfeiting encryption function (Figure 3).

Claims (7)

1. Application of sericin as long afterglow material. 2. Application of sericin as a long afterglow material according to claim 1, characterized in that the state of the sericin is solid. 3. The application of sericin as a long afterglow material according to claim 1, characterized in that the sericin is obtained after purification. 4. The application of sericin as a long afterglow material according to claim 3, characterized in that the purification includes the following steps: Dissolve the sericin raw material in deionized water, then add it to tetrahydrofuran solvent to settle, then filter and wash with suction, and vacuum dry to obtain purified sericin powder. 5. Application of sericin as a long afterglow material according to claim 4, characterized in that the purified sericin powder is used as a long afterglow material. 6. The application of sericin as a long afterglow material according to claim 4, characterized in that the dosage ratio of the sericin raw material, deionized water and tetrahydrofuran is 5~15g:25~75mL:250 ~1000mL. 7. The application of sericin as a long afterglow material according to claim 4, characterized in that the vacuum drying conditions are: drying in a vacuum oven at 35°C to 55°C for 18 to 30 hours.