Application of dehydroabietylamine-based multi-stimuli responsive fluorescent compound in dynamic information decryption

Abstract

The application discloses application of a dehydroabietylamine-based multi-stimulus response fluorescent compound to dynamic information decryption. A dehydroabietylamine-based fluorescent compound as shown in formula (I) is obtained through Schiff base reaction of dehydroabietylamine and 1-pyrene formaldehyde. The compound has simple preparation mode, high yield, aggregation-induced emission performance, multi-stimulus response performance, i.e. mechanochromic and acidochromic performance, and can be applied to dynamic decryption of information, and has application prospect of strengthening protection of information security.

Description

Technical Field

[0001] This invention belongs to the field of biomass-based aggregation-induced emission fluorescent materials and information decryption, and relates to the application of a dehydroafungin-based multi-stimulus responsive fluorescent compound in dynamic information decryption. Background Technology

[0002] Compared to petroleum-based materials, biomass-based materials possess advantages such as renewability and better biocompatibility. However, the molecular structure of biomass is not easily tunable. Derivatization, through controlling the molecular structure, can bring about different performance effects and application potential. Traditional organic light-emitting molecules have a planar conformation, which easily forms π-π stacking in the aggregated state, promoting non-radiative transition losses and thus leading to fluorescence quenching. Aggregation-induced emission materials, due to their twisted molecular structure, are less prone to π-π stacking in the aggregated state, and because of the restricted intramolecular motion, they can emit bright light, overcoming the shortcomings of traditional organic light-emitting materials. Stimulus-responsive optical materials can be viewed as materials that generate changing light signals in response to external stimuli. The high sensitivity, rapid response, and real-time visualization of light signals make stimulus-responsive optical materials potential materials in the field of information decryption.

[0003] This invention synthesizes a dehydroaflavinol fluorescent compound with aggregation-induced emission and multi-stimulus response properties, namely mechanochromic and acid-induced color change, which can realize the dynamic decryption of text and 3D code information. Summary of the Invention

[0004] Purpose of the invention: To address the shortcomings of existing technologies, the purpose of this invention is to provide an application of a dehydroafungin multistimuli-responsive fluorescent compound in dynamic information decryption.

[0005] Technical solution: To achieve the above-mentioned objectives, the technical solution adopted by this invention is as follows:

[0006] The structure of a dehydroaflavinyl multistimuli-responsive fluorescent compound involved in this invention is as follows:

[0007]

[0008] The synthetic route of the dehydroaflavinyl multistimuli-responsive fluorescent compound (I) involved in this invention is as follows:

[0009]

[0010] The present invention relates to a preparation process of a dehydroaflavinyl multistimuli-responsive fluorescent compound comprising the following steps:

[0011] Dehydroabimethamine and 1-pyrenecarboxaldehyde were dissolved in ethanol and heated under reflux at 90°C for 6 hours. After the reaction was completed, the mixture was cooled to room temperature, and a white solid precipitated from the reaction solution. The crude product was obtained by filtration and recrystallization with ethanol to obtain the dehydroabimethamine-based multi-stimulus responsive fluorescent compound (I).

[0012] In the above reaction steps, the molar ratio of dehydroabimethamine to 1-pyrenecarboxaldehyde is 1:1;

[0013] In the above reaction steps, the reaction temperature is 90℃ and the reaction time is 6 hours;

[0014] The application of a dehydroaflavinyl multistimuli-responsive fluorescent compound in dynamic information decryption, as described in this invention, includes the following steps:

[0015] Dynamic decryption based on text and 3D code information:

[0016] Dehydroaflavinol fluorescent compounds in different states (original solid and ground solid) and commercially available fluorescent dyes with similar fluorescence but no stimulus response were filled into different slots. The irregular fluorescence of these compounds prevented them from providing effective information. After sequential treatment with acidic and alkaline solvent vapors, the different compounds produced different fluorescence signals, allowing for the dynamic decryption of text and 3D code information.

[0017] The beneficial effects of this invention are:

[0018] Compared with the prior art, the advantages of the dehydroabiamine multi-stimulus responsive fluorescent compound in the present invention for dynamic information decryption are as follows: (1) The preparation conditions of the dehydroabiamine multi-stimulus responsive fluorescent compound are simple, the reaction conditions are mild, and the yield is high; (2) The dehydroabiamine multi-stimulus responsive fluorescent compound has aggregation-induced emission properties; (3) The dehydroabiamine fluorescent compound has multi-stimulus responsive properties, namely mechanochromic properties and acid-induced color change properties, and can provide diverse fluorescence signals under stimulus response; (4) The dehydroabiamine multi-stimulus responsive fluorescent compound can realize dynamic information decryption and enhance information security. Attached Figure Description

[0019] Figure 1 For dehydroaflavin multistimulation responsive fluorescent compound (I) 1 H NMR spectrum.

[0020] Figure 2 The UV-Vis absorption spectrum of dehydroafungin multistimulus responsive fluorescent compound (I) in tetrahydrofuran solvent is shown.

[0021] Figure 3 Fluorescence emission spectra of dehydroafungin multistimulus responsive fluorescent compound (I) in tetrahydrofuran / water mixtures with different water contents.

[0022] Figure 4 The fluorescence emission spectra of dehydroafungin-based multistimuli-responsive fluorescent compound (I) before and after solid grinding are shown.

[0023] Figure 5 The fluorescence emission spectra of dehydroafungin multistimulus responsive fluorescent compound (I) before and after solid acid and alkali fumigation are shown.

[0024] Figure 6 This describes the dynamic decryption process of information by the dehydroafungin multistimuli-responsive fluorescent compound (I). Detailed Implementation

[0025] The present invention will be further illustrated below with specific examples, but these specific examples do not limit the present invention in any way.

[0026] The structure of the compound was determined using nuclear magnetic resonance spectroscopy. The spectral properties of the compound were determined using ultraviolet-visible spectroscopy and fluorescence spectroscopy. The instruments used for the analysis were: a Bruker AVANCE III HD nuclear magnetic resonance spectrometer, a Shimadzu UV-2450 ultraviolet-visible spectrometer, and a Horiba Fluoromax-4 fluorescence spectrometer.

[0027] Example 1

[0028] Dehydroabimethamine (0.5 mmol) and 1-pyrenecarboxaldehyde (0.5 mmol) were dissolved in ethanol and heated under reflux at 90 °C for 6 h. After the reaction was completed, the mixture was cooled to room temperature, and a white solid precipitated from the reaction solution. The crude product was obtained by filtration and recrystallization with ethanol solvent to obtain the dehydroabimethamine-based multi-stimulation responsive fluorescent compound (I) (yield: 80%). 1H NMR (600MHz, Chloroform-d) δ9.26 (s, 1H), 8.99 (d, J = 9.3Hz, 1H), 8.53 (d, J = 7.5Hz, 1H), 8.21 (d, J = 7.6Hz, 2H), 8.17 (t, J = 8.4Hz, 2H ), 8.11 (d, J = 8.8Hz, 1H), 8.06 (d, J = 8.9Hz, 1H), 8.03 (t, J = 7.6Hz, 1H), 7.21 (d, J = 8.2Hz, 1H), 7.00 (d, J = 8.1Hz, 1H), 6.88 (s, 1H), 3. 73 (d, J=11.9Hz, 1H), 3.65 (d, J=11.6Hz, 1H), 2.92 (d, J=5.1Hz, 2H), 2.84-2.79 (m, 1H), 2.32 (d, J=12.6Hz, 1H), 2.08 (s, 1H), 1.89-1 .82 (m, 3H), 1.70 (t, J = 14.2Hz, 2H), 1.61 (d, J = 13.6Hz, 1H), 1.47 (t, J = 11.4Hz, 1H), 1.30 (s, 3H), 1.22 (d, J = 6.9Hz, 6H), 1.17 (s, 3H).

[0029] Example 2

[0030] The UV-Vis absorption spectrum of a tetrahydrofuran solution of dehydroaflecinylamino multistimuli-responsive fluorescent compound (I) was determined. The dehydroaflecinylamino multistimuli-responsive fluorescent compound (I) was dissolved in tetrahydrofuran to prepare a solution with a concentration of 2 × 10⁻⁶. -3 Take 4 × 10 mol / L sample solution. -5 Add 3.96 × 10 L of solution -3 In pure tetrahydrofuran solvent, prepare a solution with a concentration of 2×10⁻⁶. -5 A sample solution with a concentration of mol / L was analyzed. The UV-Vis absorption spectrum of the sample solution was measured; the results are as follows. Figure 2 As shown.

[0031] Example 3

[0032] The fluorescence emission spectra of dehydroafungin multistimuli-responsive fluorescent compound (I) in tetrahydrofuran / water mixtures with different water contents were determined, where water was a poor solvent. Following the steps shown in Example 2, a concentration of 2 × 10⁻⁶ was first prepared. -3 A sample solution of mol / L was prepared. The sample solution was added to tetrahydrofuran / water mixtures with varying water contents to obtain a sample concentration of 2 × 10⁻⁶ mol / L. -5 A tetrahydrofuran / water mixed solution with a concentration of mol / L and a water content of 0%–99% was prepared. Its fluorescence emission spectrum was then measured, and the results are as follows: Figure 3 As shown.

[0033] Example 4

[0034] The mechanochromic performance of the dehydroabietylamine-based multi-stimuli responsive fluorescent compound (I) was determined, and its fluorescence emission spectra before and after grinding were measured. 20 mg of the fluorescent compound (I) was taken and fully ground in a mortar. A fluorescence spectrometer was used to measure the solid fluorescence emission spectra before and after grinding, and the results are shown in Figure 4 .

[0035] Example 5

[0036] The acidochromic performance of the dehydroabietylamine-based multi-stimuli responsive fluorescent compound (I) was determined, and its fluorescence emission spectra before and after acid fumigation were measured. 20 mg of the fluorescent compound (I) was taken and fumigated at the mouth of a beaker containing trifluoroacetic acid, and the fluorescence emission spectrum was measured after complete fumigation. Then the compound was fumigated at the mouth of a beaker containing triethylamine, and the fluorescence emission spectrum was measured after complete fumigation. The results are shown in Figure 5 .

[0037] Example 6

[0038] Dynamic information decryption process of the dehydroabietylamine-based multi-stimuli responsive fluorescent compound (I) described in the present invention. The steps are as follows: the original dehydroabietylamine-based multi-stimuli responsive fluorescent compound (I), the ground fluorescent compound (I) and a commercial fluorescent material are filled into clamping grooves at different positions. Wherein the fluorescence of the commercial fluorescent material is not affected by force and acid stimulation. Therefore, the chaotic fluorescence signal cannot provide effective information. At this time, the fluorescent compound (I) exhibits blue fluorescence, and the ground fluorescent compound (I) exhibits green fluorescence. After being treated with trifluoroacetic acid vapor, both the fluorescent compound (I) and the ground fluorescent material (I) are affected, exhibiting strong red fluorescence intensity. According to the sorting of new fluorescence signals, the decrypted information can be the Chinese character "Tian". After further treatment with triethylamine vapor, the fluorescence of the fluorescent compound (I) in both states is restored to blue, and the decrypted text information becomes the Chinese character "Wang" again, achieving the dynamic decryption effect for information. Similarly, a 3D code is composed of these fluorescent compounds (I) in different states and commercial fluorescent materials. Under three treatment conditions: original state, trifluoroacetic acid fumigation and triethylamine fumigation, 3D codes with different fluorescence signals are formed, and different information can be presented after scanning with a 3D code APP. The above dynamic decryption effect is shown in Figure 6 .

Claims

1. The application of a dehydroafungin multistimuli-responsive fluorescent compound in dynamic information decryption, characterized in that, The compound is shown in formula (I): 。 2. The application of the dehydroaflavinyl multistimulus responsive fluorescent compound according to claim 1 in dynamic information decryption, characterized in that, The compound is used for the dynamic decryption of text and 3D code information; after being subjected to acid and alkali treatment in sequence, the compound material dynamically achieves the decryption of text and 3D code information.

3. A method for preparing a dehydroafungin multistimuli-responsive fluorescent compound as described in claim 1, characterized in that, The compound is prepared by using dehydroabimethamine and 1-pyrenecarboxaldehyde as raw materials, and generating a dehydroabimethamine-based fluorescent compound through a Schiff base reaction.

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