CN114716999A - Application of sericin as long-afterglow material and preparation of anti-counterfeiting material - Google Patents
Application of sericin as long-afterglow material and preparation of anti-counterfeiting material Download PDFInfo
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- CN114716999A CN114716999A CN202210357729.9A CN202210357729A CN114716999A CN 114716999 A CN114716999 A CN 114716999A CN 202210357729 A CN202210357729 A CN 202210357729A CN 114716999 A CN114716999 A CN 114716999A
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- 108010013296 Sericins Proteins 0.000 title claims abstract description 62
- 239000000463 material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims description 5
- 239000000843 powder Substances 0.000 claims abstract description 17
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 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
- 238000000746 purification Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000006862 quantum yield reaction Methods 0.000 abstract description 6
- 238000004062 sedimentation Methods 0.000 description 6
- 229940039354 sericin 1 Drugs 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 238000004020 luminiscence type Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000005923 long-lasting effect Effects 0.000 description 2
- 230000002688 persistence Effects 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
- 238000003756 stirring Methods 0.000 description 2
- 241000238631 Hexapoda Species 0.000 description 1
- 108010060231 Insect Proteins Proteins 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 238000012984 biological imaging Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 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
- 238000000034 method 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
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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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 application of sericin as a long-afterglow material and application of sericin in preparing an anti-counterfeiting material, wherein the amorphous powder of the sericin can generate a room-temperature long-afterglow phenomenon under a room-temperature condition, and the absolute quantum yield is up to 26.8%. Sericin powder with different long afterglow life can be obtained after processing under different humidity environment. The sericin with the humidity-influenced differential long-afterglow emission ability is matched and used as an anti-counterfeiting material, so that a new field is developed for application of the sericin.
Description
Technical Field
The invention belongs to the field of organic luminescent materials, and particularly relates to a new application of pure organic biomacromolecule sericin as a long afterglow material and an anti-counterfeiting material.
Background
At present, although the long afterglow materials are widely applied to the fields of RMB anti-counterfeiting, biological imaging and the like, the application of the long afterglow materials is greatly limited because many materials can show the long afterglow performance only at low temperature or after being doped with heavy metals such as iridium and platinum. The pure organic molecule long afterglow materials are relatively cheap, the structure is easy to adjust, the materials are relatively safe to the environment and have good processability, so that the materials are more suitable for the preparation of biological engineering, the technical field of medicines, sensors and electronic devices. The atypical luminescent compound has the advantages of simple preparation method, good biocompatibility, low toxicity, environmental friendliness and the like, and is applied to aspects of explosive and ion detection, biological cell imaging, anti-counterfeiting confidentiality and the like. Therefore, it is particularly significant to find a pure organic small-molecule light-emitting compound which is cheap, has high light-emitting efficiency and long afterglow time. The sericin treated by different humidity is not reported to be used as the long-afterglow organic luminescent material.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the application of sericin as a long-afterglow material and the application of sericin in preparing an anti-counterfeiting material.
Aiming at the defects in the prior art, the invention develops an insect macromolecular protein long afterglow material and provides the application of pure organic biological macromolecular sericin as the long afterglow material for the first time. In particular to the application of the materials in preparing organic long afterglow materials, which are characterized by high quantum efficiency and long afterglow time.
The sericin with different molecular weights has long afterglow luminescence property. The sericin is used as a new application of the long-afterglow organic luminescent material, the pure organic room-temperature long-afterglow material is obtained by settling and purifying the sericin sold in the market and is used as an anti-counterfeiting encryption material to prepare the anti-counterfeiting material.
The purpose of dissolution sedimentation is to exclude the long afterglow characteristics caused by impurities contained in commercially available sericin itself. The specific purification method of the pure sericin comprises the following steps: dissolving a sericin raw material in deionized water, dissolving, adding the dissolved sericin raw material into a tetrahydrofuran solvent for sedimentation, carrying out suction filtration washing, and carrying out vacuum drying to obtain purified sericin powder. The purified sericin powder is used as a long afterglow material.
The ratio of the sericin raw material to the amount of deionized water to the amount of tetrahydrofuran is 5-15 g: 25-75 mL: 250-1000 mL, most preferably 10 g: 50mL of: 500 mL.
The vacuum drying conditions are as follows: drying in a vacuum oven at 35-55 ℃ for 18-30 h, and most preferably drying in a vacuum oven at 45 ℃ for 24 h.
The sericin involved in the invention is a first insect protein pure organic animal macromolecular long afterglow material, which can grow afterglow phenomenon under room temperature in amorphous state, the long afterglow life of sericin (sericin-5 thousand) with the average molecular mass of 5000 can reach 455.9ms, and the quantum yield is as high as 22.8%. 10000 sericin (sericin-1 ten thousand) has a long afterglow life of 422.6ms and a quantum yield of 26.4%.
Compared with the prior art, the invention has the following advantages:
the sericin of the invention is used as a new application of the long afterglow material, the amorphous powder of the sericin can generate the room temperature long afterglow phenomenon under the room temperature condition, and the absolute quantum yield reaches up to 26.8 percent. Sericin powder with different long afterglow life can be obtained after processing under different humidity environment. The sericin with the humidity-influenced differential long-afterglow emission ability is matched and used as an anti-counterfeiting material, so that a new field is developed for application of the sericin.
Drawings
FIG. 1 is a graph showing the observation of (a) PL spectrum, (b) long afterglow life, and (c) long afterglow with time at 5 kg room temperature of sericin.
FIG. 2 is a graph showing the observation of (a) PL spectrum, (b) long afterglow life, and (c) long afterglow with time of sericin-1W at room temperature.
Fig. 3 is a diagram showing the application of the sericin powder combination anti-counterfeiting effect after treatment under different humidities.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the following specific examples. It will be understood 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 powders of different molecular weights used in the following examples were commercially available and were purified by dissolution sedimentation before use.
The purpose of dissolution sedimentation is to exclude the long afterglow characteristics caused by impurities contained in commercially available sericin itself. Dissolving sericin in deionized water, dissolving, pouring into 10-20 times of tetrahydrofuran solvent for sedimentation, performing suction filtration and washing, and performing vacuum drying at normal temperature to obtain purified sericin powder.
Example 1
10g sericin-5 thousand (Dali silk) solid powder was weighed into a 100mL two-necked flask, 50mL deionized water was added thereto, and dissolved by stirring, and then the sericin solution was dropped into 500mL tetrahydrofuran solution to be precipitated. And drying the sample obtained after suction filtration and washing in a vacuum oven at 45 ℃ for 24h to obtain a purified sericin-5 thousand sample.
Sericin-5 kilo luminescence property as shown in FIG. 1 (a) fluorescence at 340nm and long-lasting persistence spectrum (t)d0.01 s): PL and long afterglow emission peaks excited at 312nm are 372 and 512nm, respectively. (b) The lifetime test found that at 512nm (. lamda.)ex340nm) was 455.9 ms. The total quantum yield of DHU at 340nm excitation was 22.8%.
Example 2
Weighing 10g sericin-1 ten thousand (Dali silk) solid powder into a 100mL two-necked flask, adding 50mL deionized water, stirring to dissolve, and dropping the sericin solution into 500mL tetrahydrofuran solution for sedimentation. And drying the sample obtained after suction filtration in a vacuum oven at 45 ℃ for 24h to obtain a purified sericin-1 ten thousand sample.
Luminescence of sericin-1 ten thousandFIG. 2 (a) shows fluorescence at 340nm and a long-lasting afterglow spectrum (t)d0.01 s): the PL and long persistence emission peaks at 312nm excitation were 475 and 525nm, respectively. (b) The lifetime test found that at 525nm (lambda)ex340nm) was monitored for 422.6 ms. The total quantum yield of DHU at 340nm excitation was 26.4%.
Example 3
The purified Dahli silk sericin-1 ten thousand powder is placed in a constant temperature and humidity box with the humidity of 80% and the temperature of 25 ℃ for half an hour and then taken out, then the powder and the powder which is not placed form a smiling face pattern, the ultraviolet lamp is switched off after being excited for 1 minute at 312nm, and the disappearance of the long afterglow emission of the mouth in the middle of the smiling face which is faster than that of the other parts can be seen, because of the humidity response, the purified Dahli silk sericin-1 ten thousand powder has the anti-counterfeiting encryption function (figure 3).
Claims (9)
1. The application of sericin as a long-afterglow material.
2. The use of sericin as a long-afterglow material according to claim 1, wherein the sericin is in a solid state.
3. The use of sericin as a long-afterglow material according to claim 1, wherein the sericin is obtained by purification.
4. The use of sericin as a long-afterglow material according to claim 3, wherein the purification comprises the following steps:
dissolving a sericin raw material in deionized water for dissolving, then adding the dissolved sericin raw material into a tetrahydrofuran solvent for settling, then carrying out suction filtration and washing, and carrying out vacuum drying to obtain purified sericin powder.
5. The use of sericin as a long-afterglow material according to claim 4, wherein the purified sericin powder is used as a long-afterglow material.
6. The application of the sericin as a long-afterglow material according to claim 4, wherein the ratio of the sericin raw material, deionized water and tetrahydrofuran is 5-15 g: 25-75 mL: 250-1000 mL.
7. The use of sericin as a long-afterglow material according to claim 4, wherein the vacuum drying conditions are as follows: drying for 18-30 h in a vacuum oven at 35-55 ℃.
8. Application of sericin in preparing anti-counterfeiting materials.
9. The use of sericin according to claim 8 in the preparation of a security material, wherein the security material comprises sericin with different humidity.
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 |
|---|---|---|---|
| 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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| Publication Number | Publication Date |
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| CN114716999A true CN114716999A (en) | 2022-07-08 |
| CN114716999B CN114716999B (en) | 2023-10-31 |
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Citations (5)
| 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 |
| US20190003113A1 (en) * | 2015-07-14 | 2019-01-03 | Silk Therapeutics, Inc. | Silk Performance Apparel and Products and Methods of Preparing the Same |
| CN113185972A (en) * | 2021-03-25 | 2021-07-30 | 清华大学 | Multi-mode luminescent carbon dot and preparation method and application thereof |
-
2022
- 2022-04-06 CN CN202210357729.9A patent/CN114716999B/en active Active
Patent Citations (5)
| 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 |
| US20190003113A1 (en) * | 2015-07-14 | 2019-01-03 | Silk Therapeutics, Inc. | Silk Performance Apparel and Products and Methods of Preparing the Same |
| 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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| CN114716999B (en) | 2023-10-31 |
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