Fluorescent dynamic anti-counterfeiting method based on donor-acceptor Steinhaus adduct
By mixing the donor-acceptor Steinhaus adduct with F8BT fluorescent molecules, the temporal presentation and disappearance of information are achieved through fluorescence resonance energy transfer, which solves the problem of poor environmental tolerance of existing anti-counterfeiting materials and provides a new approach to dynamic anti-counterfeiting.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2023-10-16
- Publication Date
- 2026-04-03
AI Technical Summary
Existing anti-counterfeiting materials are mainly based on static information, have poor environmental resistance, are easily cracked, and lack dynamic anti-counterfeiting measures with a time dimension.
By mixing donor-acceptor Steinhaus adducts (DASAs) with F8BT fluorescent molecules, fluorescence resonance energy transfer (FRET) is achieved by changing the carbon chain length of the DASA molecules, thus enabling the temporal presentation and disappearance of information under the same illumination.
It provides a dynamic, fast, and reversible anti-counterfeiting solution that enhances information security and anti-counterfeiting effectiveness, with a fast response speed, and is suitable for dynamic anti-counterfeiting of optical materials and devices.
Smart Images
Figure CN117612446B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of advanced electronic materials, and in particular to a fluorescent dynamic anti-counterfeiting method based on donor-acceptor Steinhaus adduct, which can be applied to industries such as optical materials and devices, and dynamic anti-counterfeiting. Background Technology
[0002] Photochromic materials are generally divided into positive photochromic materials and negative photochromic materials. DASAs are a type of negative photochromic material based on furan derivatives. They have a relatively wide spectral response range and can undergo changes in molecular geometry, color, dipole moment and molecular polarity under the stimulation of visible light and near-outer infrared light. They can also return to their previous state under dark or heated conditions.
[0003] Fluorescence resonance energy transfer (FRET), proposed in the 1840s, is a non-radiative energy transition without the involvement of intermediate photons, involving energy transfer between the donor and acceptor groups. Within a certain distance, the donor and acceptor molecules interact via intermolecular electric dipole interactions, transferring fluorescence energy from the donor to the acceptor. This results in a decrease in the fluorescence intensity of the donor molecule and either a higher fluorescence intensity or quenching of the acceptor molecule. The fluorescence lifetime is correspondingly extended or shortened by this process.
[0004] As a resonant energy transfer donor-acceptor pair and fluorescent substance, the following conditions must be met: (1) The excitation light of the acceptor and donor must be sufficiently separated;
[0005] (2) The emission spectrum of the donor molecule and the excitation spectrum of the acceptor molecule should have significant overlap, generally greater than 30%; (3) The distance between the donor molecule and the acceptor molecule should be between 1 and 10 nm.
[0006] Wang Dongsheng's team at the University of Electronic Science and Technology of China has designed a novel method to prepare a dual-security color-changing invisible ink by combining DASAs-sensitive color-changing molecules with oxazolidine. By utilizing OXs, which are opposite to the direction of water-induced isomerization color change of DASAs, the ink displays different colors in multiple states, achieving multi-state anti-counterfeiting of information.
[0007] Current anti-counterfeiting materials primarily focus on static information security, rarely considering the time and dynamic processes involved. This significantly limits the further development of anti-counterfeiting capabilities, especially on paper or solid material surfaces.
[0008] While technology and the economy are developing at breakneck speed, the problems of product counterfeiting and information forgery are becoming increasingly serious. People have higher demands for product quality and personal privacy, so the research on anti-counterfeiting materials remains highly popular in today's information age. One of the current challenges facing anti-counterfeiting materials is that their anti-counterfeiting methods are too simplistic, the environmental resistance of the anti-counterfeiting information is poor, and the confidential information presented is merely the information itself, making it very easy for criminals to predict and crack. Therefore, this patent has invented a novel dynamic anti-counterfeiting material. Its principle is to use donor-acceptor Steinhaus adducts (DASAs) as photosensitive molecules, mix them with F8BT fluorescent molecules to achieve fluorescence resonance energy transfer (FRET), and change the carbon chain length of the DASAs molecules to achieve different imprinting times under the same light, so as to realize the presentation and disappearance of information in the time dimension, thereby achieving dynamic anti-counterfeiting in the time dimension. Summary of the Invention
[0009] To address the problems in the prior art, this application proposes a fluorescent dynamic anti-counterfeiting method based on donor-acceptor Steinhaus adduct, comprising the following steps:
[0010] S1. The Michaelis acid and furfural are heated and stirred to react, and then the mixture is successively washed with water, filtered, extracted, dried, filtered twice, purified by column chromatography and rotary evaporation to obtain the Michaelis acid intermediate.
[0011] S2. The Michaelis acid intermediate obtained in step S1 was added to dichloromethane and stirred to dissolve. Then, N-methylaniline solution was added dropwise. Finally, the product was purified by silica gel chromatography column. The eluent used was a mixed solvent of dichloromethane and ethyl acetate. Finally, the pure final product 1C-DASA-M was obtained.
[0012] S3. The Michaelis acid intermediate obtained in step S1 is added to dichloromethane and dissolved completely. Then, N-propylaniline solution is added dropwise to the Michaelis acid intermediate solution. After the reaction is complete, the product is purified by silica gel column chromatography to obtain the final product 3C-DASA-M. The eluent used is a mixed solvent of ethyl acetate and dichloromethane.
[0013] S4. Add the Michaelis acid intermediate obtained in step S1 to dichloromethane and stir to dissolve. Then add N-dodecylaniline solid powder to the Michaelis acid intermediate solution. After the reaction is complete, the final product 12C-DASA-M is obtained. 12C-DASA-M is purified by chemical chromatography. The eluent is a mixed solvent of dichloromethane and ethyl acetate.
[0014] S5. Using F8BT fluorescent molecules as donors and Steinhaus adduct DASA molecules of three different carbon chain lengths (1C-DASA-M, 3C-DASA-M, and 12C-DASA-M) as donors, DASAs and fluorescent polymer films were prepared by using donor-acceptor Steinhaus adduct DASA molecules of three different carbon chain lengths as donors.
[0015] Preferably, the reaction time of Michaelis-Müller acid with furfural is 4-5 hours and the reaction temperature is 30-40℃.
[0016] Preferably, in step S2, the Michaelis acid intermediate reacts with N-methylaniline at 35 °C for 2 h.
[0017] Preferably, in step S3, the Michaelis acid intermediate reacts with N-propylaniline at 35 °C for 2 h.
[0018] Preferably, in step S4, the Michaelis acid intermediate reacts with N-dodecylaniline at 30 °C and in the dark for 2 h.
[0019] Preferably, in step S5, 1C-DASA-M, 3C-DASA-M and 12C-DASA-M are added to a brown glass bottle, and then a tetrahydrofuran solution of F8BT is added to it. The mixture is stirred under light-protected conditions to ensure complete dissolution. Then, the esterified quartz sheet is taken out and spin-coated using a spin coater. The sheet is then removed and dried to obtain the target DASA-M and polymer FRET film.
[0020] Preferably, different polymer films are used on the same anti-counterfeiting pattern. Under the same light source, different parts of the anti-counterfeiting pattern will show fluorescence in sequence, thereby achieving dynamic anti-counterfeiting in the time dimension.
[0021] The above-mentioned technical features can be combined in various suitable ways or replaced by equivalent technical features, as long as the purpose of the present invention can be achieved.
[0022] The present invention provides a fluorescent dynamic anti-counterfeiting method based on donor-acceptor Steinhaus adduct, which has at least the following advantages compared with the prior art:
[0023] This invention proposes a dynamic, precise, and clean anti-counterfeiting solution that uses light as a stimulus source, providing a new direction in the time-dimensional anti-counterfeiting approach and offering new ideas for information anti-counterfeiting. It also features fast response speed and bidirectional reversibility. Attached Figure Description
[0024] The invention will now be described in more detail with reference to embodiments and the accompanying drawings.
[0025] Figure 1This is a schematic diagram illustrating the preparation of the Michaelis-Menten acid intermediate.
[0026] Figure 2 A schematic diagram of the preparation of 1C-DASA-M;
[0027] Figure 3 A schematic diagram illustrating the preparation of 3C-DASA-M;
[0028] Figure 4 A schematic diagram of the preparation of 12C-DASA-M;
[0029] Figure 5 Images of three polymer films under a fluorescence microscope;
[0030] Figure 6 shows a schematic diagram of the emission wavelength of F8BT and the absorption wavelength of 3C-DASA-M;
[0031] Figure 7 shows the cyclic graph of fluorescence intensity changes of the mixed solution of DASA-M and polymer F8BT under repeated treatments of light at wavelengths of 420 nm and 520 nm and heating under dark conditions.
[0032] Figure 8 is a schematic diagram of fluorescence regulation of DASAs molecules. Implementation
[0033] The invention will now be further described with reference to the accompanying drawings.
[0034] Example 1: This invention provides a fluorescent dynamic anti-counterfeiting method based on donor-acceptor Steinhaus adduct, comprising the following steps:
[0035] (1) Preparation of Michaelis-Menten acid intermediate: such as Figure 1 As shown, 720 mg (5 mmol) of Michaelis-Menten acid was weighed and added to a pre-prepared 50 mL round-bottom flask. Then, 30 mL of deionized water was added, and the mixture was sonicated for 10 min to dissolve. Next, 415 μL of furfural solution was slowly added dropwise using a pipette. The reaction was carried out at 30 °C with stirring for 2 h, and the reaction was further monitored by TLC. After the reaction was complete, the yellow suspension was filtered using a Buchner funnel. 40 mL of dichloromethane was used to fully dissolve the obtained yellow solid, and then 40 mL of saturated NaHSO3 solution and 40 mL of deionized water were added for extraction, yielding a relatively bright yellow solution. Solid anhydrous magnesium sulfate (MgSO4) was added to the solution to remove water, and the solution was filtered again. Purification was performed using silica gel column chromatography with dichloromethane as the eluent. The pale yellow solid obtained by rotary evaporation was the Michaelis-Menten acid intermediate.
[0036] (2) Preparation of 1C-DASA-M: as follows Figure 2As shown, 222 mg (1 mmol) of the Michaelis-Menten intermediate was weighed and dissolved in 15 mL of dichloromethane by stirring. Then, 108 μL (1 mmol) of N-methylaniline solution was added dropwise, and the reaction was carried out at 35 °C for 2 h under light-protected conditions. The solution changed from pale yellow to red, and the reaction was further detected by TLC. After obtaining the product, it was purified by silica gel column chromatography using a mixed solvent of dichloromethane and ethyl acetate (volume ratio 14:1) as the eluent. The final pure product 1C-DASA-M was obtained, where "-M" indicates that the Michaelis-Menten intermediate is used as the electron acceptor of DASAs.
[0037] (3) Preparation of 3C-DASA-M: such as Figure 3 As shown, 222 mg (1 mmol) of the Michaelis-Menten acid intermediate was weighed and dissolved completely in 15 mL of dichloromethane. Then, 142 μL (1 mmol) of N-propylaniline solution was slowly added dropwise to the Michaelis-Menten acid intermediate solution using a pipette. The reaction was carried out at 35 °C for 2 h, during which the solution gradually changed from pale yellow to red. The reaction was carried out in the dark. The reaction was detected by TLC. After the reaction was completed, the product was purified by silica gel column chromatography to obtain the final product 3C-DASA-M. The eluent used was a mixed solvent of ethyl acetate and dichloromethane (volume ratio 19:1).
[0038] (4) Preparation of 12C-DASA-M: as follows Figure 4 As shown, 222 mg (1 mmol) of the Michaelis-Menten acid intermediate was added to 15 mL of dichloromethane and stirred to dissolve. Then, 130.72 mg (1 mmol) of N-dodecylaniline solid powder was weighed and added to the Michaelis-Menten acid intermediate solution. The reaction was carried out at 30 °C in the dark for 2 h. The reaction was further detected by TLC. After the reaction was completed, the final product 12C-DASA-M was obtained. 12C-DASA-M was purified by chemical chromatography using a mixed solvent of dichloromethane and ethyl acetate (volume ratio 40:1).
[0039] (5) Preparation of DASAs and fluorescent polymer films: such as Figure 5 As shown, 5 mg of 1C-DASA-M, 3C-DASA-M, and 12C-DASA-M were weighed and added to a brown glass bottle. Then, 1 mL of a 10 mg / mL tetrahydrofuran solution of F8BT was added. The mixture was stirred under light-protected conditions to ensure complete dissolution. The esterified quartz wafer was then removed and spin-coated using a spin coater for 60 s at 1000 rpm. After drying, the target DASA-M and polymer FRET film were obtained.
[0040] (6) Dynamic anti-counterfeiting study of DASA polymer films: A 200-mesh copper mesh was used as a photolithography template and covered on the surface of DASA-M and F8BT films, and then irradiated with light of a certain wavelength. Figure 5 The image showcases images of the fluorescence intensity modulation of DASA-M and F8BT films using fluorescence microscopy based on the FRET principle. By examining photographs of films with different alkyl chain lengths (1C-DASA-M, 3C-DASA-M, 12C-DASA-M) and polymer F8BT, it is clear that shorter alkyl chains result in higher fluorescence brightness and reach maximum fluorescence in the shortest time. Conversely, longer alkyl chains result in lower maximum fluorescence brightness and take the longest time. Therefore, by applying different polymer films to the same anti-counterfeiting pattern under the same light source, different parts of the anti-counterfeiting pattern will sequentially fluoresce, thus achieving dynamic anti-counterfeiting over time.
[0041] like Figure 6 As shown, the absorption spectrum of 3C-DASA-M and the emission spectrum of the selected fluorescent molecule F8BT are highly overlapping, which is a prerequisite for the FRET effect between the two.
[0042] like Figure 7 The figure shows a cyclic graph of fluorescence intensity changes in a mixed solution of 3C-DASA-M and polymer F8BT under repeated treatments of illumination at wavelengths of 420 nm and 520 nm and heating under dark conditions. This indicates that the mixed solution has repeatability and fatigue resistance.
[0043] like Figure 8 The diagram illustrates the FRET effect between DASAs and the fluorescent molecule F8BT: When the mixture is irradiated with light of a specific wavelength, the F8BT fluorescent molecule emits fluorescence at another wavelength. As mentioned above, the emission spectrum of the F8BT fluorescent molecule highly overlaps with the absorption spectrum of the DASAs; therefore, the fluorescence is absorbed by the DASAs, and the mixture does not exhibit fluorescence. However, as absorption continues, the DASA molecules undergo isomerization into cyclic DASAs, which no longer absorb fluorescence, and the mixture then exhibits fluorescence. This isomerization process is directly related to the distance between the two molecules.
[0044] In one embodiment, barbiturate intermediate (-B) or 1,3-indanedione intermediate (-I) is used instead of mifepristone intermediate (-M) as the electron acceptor for DASAs, and the rest of the method is the same as in Example 1.
[0045] While the invention has been described herein with reference to specific embodiments, it should be understood that these embodiments are merely examples of the principles and applications of the invention. Therefore, it should be understood that many modifications can be made to the exemplary embodiments, and other arrangements can be designed without departing from the spirit and scope of the invention as defined by the appended claims. It should be understood that different dependent claims and features described herein can be combined in ways different from those described in the original claims. It is also understood that features described in conjunction with individual embodiments can be used in other described embodiments.
Claims
1. A fluorescent dynamic anti-counterfeiting method based on donor-acceptor Steinhaus adduct, characterized in that, Includes the following steps: S1. The Michaelis acid and furfural are heated and stirred to react, and then washed with water, filtered, extracted, dried, filtered twice, purified by column chromatography and rotary evaporation to obtain the Michaelis acid intermediate. S2. The Michaelis acid intermediate obtained in step S1 was added to dichloromethane and stirred to dissolve. Then, N-methylaniline solution was added dropwise. Finally, the product was purified by silica gel chromatography column. The eluent used was a mixed solvent of dichloromethane and ethyl acetate. Finally, the pure final product 1C-DASA-M was obtained. S3. The Michaelis acid intermediate obtained in step S1 is added to dichloromethane and dissolved completely. Then, N-propylaniline solution is added dropwise to the Michaelis acid intermediate solution. After the reaction is complete, the product is purified by silica gel column chromatography to obtain the final product 3C-DASA-M. The eluent used is a mixed solvent of ethyl acetate and dichloromethane. S4. Add the Michaelis acid intermediate obtained in step S1 to dichloromethane and stir to dissolve. Then add N-dodecylaniline solid powder to the Michaelis acid intermediate solution. After the reaction is complete, the final product 12C-DASA-M is obtained. 12C-DASA-M is purified by chemical chromatography. The eluent is a mixed solvent of dichloromethane and ethyl acetate. S5. Using F8BT fluorescent molecules as donors and Steinhaus adduct DASA molecules of three different carbon chain lengths (1C-DASA-M, 3C-DASA-M, and 12C-DASA-M) as donors, DASAs and fluorescent polymer films were prepared by using donor-acceptor Steinhaus adduct DASA molecules of three different carbon chain lengths as donors.
2. The fluorescent dynamic anti-counterfeiting method based on donor-acceptor Steinhaus adduct according to claim 1, characterized in that, The reaction time of Michaelis-Müller acid with furfural is 4-5 hours, and the reaction temperature is 30-40℃.
3. The fluorescent dynamic anti-counterfeiting method based on donor-acceptor Steinhaus adduct according to claim 1, characterized in that, In step S2, the Michaelis acid intermediate reacts with N-methylaniline at 35 °C for 2 h.
4. The fluorescent dynamic anti-counterfeiting method based on donor-acceptor Steinhaus adduct according to claim 1, characterized in that, In step S3, the Michaelis acid intermediate reacts with N-propylaniline at 35 °C for 2 h.
5. The fluorescent dynamic anti-counterfeiting method based on donor-acceptor Steinhaus adduct according to claim 1, characterized in that, In step S4, the Michaelis acid intermediate reacts with N-dodecylaniline at 30 °C in the dark for 2 h.
6. The fluorescent dynamic anti-counterfeiting method based on donor-acceptor Steinhaus adduct according to claim 1, characterized in that, In step S5, 1C-DASA-M, 3C-DASA-M and 12C-DASA-M are added to a brown glass bottle, and then a tetrahydrofuran solution of F8BT is added. The mixture is stirred under light-protected conditions to ensure complete dissolution. Then, the esterified quartz sheet is removed and spin-coated using a spin coater. The sheet is then removed and dried to obtain the target DASA-M and polymer FRET film.
7. The fluorescent dynamic anti-counterfeiting method based on donor-acceptor Steinhaus adduct according to claim 1, characterized in that, By applying different polymer films to the same anti-counterfeiting pattern, different parts of the anti-counterfeiting pattern will sequentially show fluorescence under the same light source, thus achieving dynamic anti-counterfeiting over time.
8. The fluorescent dynamic anti-counterfeiting method based on donor-acceptor Steinhaus adduct according to claim 1, characterized in that, Barbiturate intermediate was used instead of mifepristone intermediate as the electron acceptor for DASAs.
9. The fluorescent dynamic anti-counterfeiting method based on donor-acceptor Steinhaus adduct according to claim 1, characterized in that, The 1,3-indanedione intermediate was used instead of the mifepristone acid intermediate as the electron acceptor for DASAs.