CN114716999B - Sericin as long afterglow material and application for preparing anti-fake material - Google Patents
Sericin as long afterglow material and application for preparing anti-fake material Download PDFInfo
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- CN114716999B CN114716999B CN202210357729.9A CN202210357729A CN114716999B CN 114716999 B CN114716999 B CN 114716999B CN 202210357729 A CN202210357729 A CN 202210357729A CN 114716999 B CN114716999 B CN 114716999B
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- afterglow material
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- 108010013296 Sericins Proteins 0.000 title claims abstract description 54
- 239000000463 material Substances 0.000 title claims abstract description 38
- 239000000843 powder Substances 0.000 claims abstract description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000004062 sedimentation Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000006862 quantum yield reaction Methods 0.000 abstract description 6
- 230000004069 differentiation Effects 0.000 abstract description 2
- 229940039354 sericin 1 Drugs 0.000 description 5
- 230000005284 excitation Effects 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000000103 photoluminescence spectrum Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 241000238631 Hexapoda Species 0.000 description 1
- 108010060231 Insect Proteins Proteins 0.000 description 1
- 238000012984 biological imaging Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
- G09F3/02—Forms or constructions
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Theoretical Computer Science (AREA)
- Luminescent Compositions (AREA)
- Peptides Or Proteins (AREA)
Abstract
The invention discloses an application of sericin as a long afterglow material and an application of sericin in preparing an anti-counterfeiting material, wherein the amorphous powder can generate a long afterglow phenomenon at room temperature, and the absolute quantum yield is as high as 26.8%. After being treated under different humidity environments, the sericin powder with different long afterglow service lives can be obtained. The sericin with humidity influence differentiation long afterglow emission capability is matched and then used as an anti-counterfeiting material, so that a new field is developed for the application of the sericin.
Description
Technical Field
The invention belongs to the field of organic luminescent materials, and in particular relates to a novel application of pure organic biomacromolecule sericin as a long afterglow material and a preparation method of an anti-counterfeiting material.
Background
At present, although the long afterglow material is widely applied to the fields of RMB anti-counterfeiting, biological imaging and the like, the long afterglow material is limited in application because a plurality of materials can only show long afterglow performance at low temperature or doped with heavy metals such as iridium and platinum. The pure organic molecule long afterglow materials are relatively cheap, easy to adjust in structure, relatively safe to environment and good in processability, so that the pure organic molecule long afterglow materials are more suitable for the preparation of bioengineering, medical technical fields, sensors and electronic devices. Atypical luminescent compounds are applied to the aspects of explosive and ion detection, biological cell imaging, anti-counterfeiting confidentiality and the like because of the advantages of simple preparation method, good biocompatibility, low toxicity, environmental friendliness and the like. Therefore, the method has the advantages of low price, high luminous efficiency and long afterglow. The sericin after different humidity treatments is used as a long afterglow organic luminescent material, which is not reported.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide an application of sericin as a long afterglow material and an application of sericin in preparing an anti-counterfeiting material.
Aiming at the defects in the prior art, the invention develops a class of insect macromolecular protein long afterglow materials and provides the application of the pure organic biological macromolecular sericin as the long afterglow materials for the first time. In particular to the application of the materials in preparing organic long afterglow materials, which is characterized by high quantum efficiency and long afterglow time.
The sericin proteins with different molecular weights have long afterglow luminescence property. The sericin is used as a novel long-afterglow organic luminescent material, and the commercially available sericin is subjected to sedimentation and purification to obtain a pure organic room-temperature long-afterglow material which is used as an anti-counterfeiting encryption material to prepare the anti-counterfeiting material.
The purpose of the dissolution sedimentation is to eliminate the long afterglow characteristic caused by impurities contained in the sericin itself on the market. The specific purification method of the pure sericin comprises the following steps: dissolving the sericin raw material in deionized water, adding the solution into tetrahydrofuran solvent for sedimentation, filtering and washing, and drying in vacuum 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 5-15 g: 25-75 mL:250 to 1000mL, most preferably 10g:50mL:500mL.
The vacuum drying conditions are as follows: drying in a vacuum oven at 35-55deg.C for 18-30 h, most preferably in a vacuum oven at 45deg.C for 24h.
The sericin related in the invention is a first instance of insect protein pure organic mobile macromolecular long afterglow material, the amorphous form of the sericin can generate long afterglow under the condition of room temperature, the long afterglow life of the sericin (sericin-5 thousand) with the average molecular weight of 5000 can reach 455.9ms, and the quantum yield is as high as 22.8 percent. The long afterglow life of 10000 sericin (sericin-1 ten thousand) can reach 422.6ms, and the quantum yield is as high as 26.4%.
Compared with the prior art, the invention has the following advantages:
the sericin of the present invention has the new use as long afterglow material, and the amorphous powder may have long afterglow at room temperature, and the absolute quantum yield is as high as 26.8%. After being treated under different humidity environments, the sericin powder with different long afterglow service lives can be obtained. The sericin with humidity influence differentiation long afterglow emission capability is matched and then used as an anti-counterfeiting material, so that a new field is developed for the application of the sericin.
Drawings
FIG. 1 is a graph showing the observation of (a) PL spectrum, (b) long afterglow lifetime and (c) long afterglow time change of sericin-5 thousand at room temperature.
FIG. 2 is a graph showing the observation of (a) PL spectrum, (b) long afterglow lifetime, and (c) long afterglow time change of sericin-1W at room temperature.
Fig. 3 shows the application of the combined anti-counterfeiting effect of the sericin powder treated under different humidity.
Detailed Description
The technical scheme of the present invention is described in further detail below in conjunction with specific embodiments. It will be appreciated by those skilled in the art that the following examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
Sericin powder of different molecular weights used in the following examples is commercially available and was subjected to dissolution, sedimentation and purification before use.
The purpose of the dissolution sedimentation is to eliminate the long afterglow characteristic caused by impurities contained in the sericin itself on the market. Dissolving sericin in deionized water, pouring into tetrahydrofuran solvent 10-20 times for sedimentation, filtering, washing, and vacuum drying at normal temperature to obtain purified sericin powder.
Example 1
10g of sericin-5 kilo (dali silk) solid powder was weighed into a 100mL two-necked flask, 50mL of deionized water was added, and the solution was stirred and dissolved, and then the sericin solution was dropped into 500mL of tetrahydrofuran solution to settle. And drying the sample obtained after suction filtration and washing in a vacuum oven at 45 ℃ for 24 hours to obtain a purified sericin-5-thousand sample.
Sericin-5 thousand has luminescent properties as shown in FIG. 1 (a) fluorescence at 340nm and long afterglow spectrum (t d =0.01 s) as shown in: the PL and long afterglow emission peaks at 312nm excitation were 372 and 512nm, respectively. (b) Life test found that at 512nm (lambda ex =340 nm) is monitored at 455.9ms. The total quantum yield of DHU at 340nm excitation was 22.8%.
Example 2
10g of sericin-1 ten thousand (Dali silk) solid powder was weighed into a 100mL double-necked flask, 50mL of deionized water was added, and the solution was stirred and dissolved, then the sericin solution was dropped into 500mL of tetrahydrofuran solution and settled. And drying the sample obtained after suction filtration in a vacuum oven at 45 ℃ for 24 hours to obtain the purified sericin-1 ten thousand samples.
Sericin-1 ten thousand luminous properties are shown as (a) fluorescence at 340nm and long afterglow spectrum (t d =0.01 s) as shown in: the PL and long afterglow emission peaks at 312nm excitation were 475 and 525nm, respectively. (b) Life test found that at 525nm (lambda ex =340 nm) is 422.6ms. The total quantum yield of DHU at 340nm excitation was 26.4%.
Example 3
The purified dary silk sericin-1 ten thousand powder is placed in a constant temperature and humidity box with the humidity of 80 percent and the temperature of 25 ℃ for half an hour, then is taken out, forms smiling face patterns with the powder which is not placed, and is turned off after being excited for 1 minute by a 312nm ultraviolet lamp, so that the mouth in the middle of the smiling face can be seen to disappear more quickly than the long afterglow emission of other parts, and the smiling face has an anti-counterfeiting encryption function due to the humidity response (figure 3).
Claims (7)
1. The sericin is used as a long afterglow material.
2. The use of sericin according to claim 1 as a long afterglow material, wherein the state of sericin is solid.
3. The use of sericin according to claim 1 as a long afterglow material, wherein the sericin is obtained after purification.
4. The use of sericin as claimed in claim 3 as a long afterglow material, wherein the purification comprises the steps of:
dissolving the sericin raw material in deionized water, adding the solution into tetrahydrofuran solvent for sedimentation, filtering and washing, and drying in vacuum to obtain purified sericin powder.
5. The use of sericin according to claim 4 as a long afterglow material, wherein the purified sericin powder is used as a long afterglow material.
6. The use of sericin according to claim 4 as a long afterglow material, wherein the ratio of the amount of sericin raw material, deionized water and tetrahydrofuran is 5 to 15g: 25-75 mL: 250-1000 mL.
7. The use of sericin according to claim 4 as a long afterglow material, wherein the vacuum drying conditions are as follows: and drying in a vacuum oven at 35-55 ℃ for 18-30 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210357729.9A CN114716999B (en) | 2022-04-06 | 2022-04-06 | Sericin as long afterglow material and application for preparing anti-fake material |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210357729.9A CN114716999B (en) | 2022-04-06 | 2022-04-06 | Sericin as long afterglow material and application for preparing anti-fake material |
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| CN114716999A CN114716999A (en) | 2022-07-08 |
| CN114716999B true CN114716999B (en) | 2023-10-31 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09208600A (en) * | 1995-11-30 | 1997-08-12 | Otsuka Chem Co Ltd | Functional protein raw material |
| CN104789225A (en) * | 2015-03-16 | 2015-07-22 | 浙江理工大学 | Quantum dots-fibroin gel fluorescence nanometer anti-fake material and preparation method thereof |
| CN106334192A (en) * | 2015-07-10 | 2017-01-18 | 华中科技大学同济医学院附属协和医院 | Sericin hydrogel, preparation method and application thereof |
| CN113185972A (en) * | 2021-03-25 | 2021-07-30 | 清华大学 | Multi-mode luminescent carbon dot and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EA201890289A1 (en) * | 2015-07-14 | 2018-08-31 | Силк Терапьютикс, Инк. | CLOTHES AND PRODUCTS WITH SILK CHARACTERISTICS AND METHODS OF THEIR PREPARATION |
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- 2022-04-06 CN CN202210357729.9A patent/CN114716999B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09208600A (en) * | 1995-11-30 | 1997-08-12 | Otsuka Chem Co Ltd | Functional protein raw material |
| CN104789225A (en) * | 2015-03-16 | 2015-07-22 | 浙江理工大学 | Quantum dots-fibroin gel fluorescence nanometer anti-fake material and preparation method thereof |
| CN106334192A (en) * | 2015-07-10 | 2017-01-18 | 华中科技大学同济医学院附属协和医院 | Sericin hydrogel, preparation method and application thereof |
| CN113185972A (en) * | 2021-03-25 | 2021-07-30 | 清华大学 | Multi-mode luminescent carbon dot and preparation method and application thereof |
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