A berberine-based supramolecular fluorescent material, a preparation method and application thereof

Abstract

This invention proposes a supramolecular fluorescent material based on berberine, its preparation method, and its application, belonging to the technical field of fluorescent materials, to solve the problem of narrow fluorescence emission wavelength coverage of berberine dye supramolecular salts. The fluorescent material of this invention is composed of aminosalicylic acid berberine supramolecular salt; the molecular formula of the aminosalicylic acid berberine supramolecular salt is: 8[C 20 H 18 [NO4]·8[C7H6NO3]·H2O; This supramolecular fluorescent material was obtained through ion exchange and recrystallization under the theoretical guidance of crystal engineering, using berberine hydrochloride as the alkali and aminosalicylic acid as the acid, and was obtained by room temperature evaporation. This invention simplifies the preparation method by modifying the solvent recrystallization, resulting in a low cost and a high yield of supramolecular fluorescent material with good large-scale reproducibility. Furthermore, this berberine-based supramolecular fluorescent material exhibits high thermal stability and good UV protection, thus enhancing its dyeing performance as a novel natural fluorescent dye for printed fabrics.

Description

Technical Field

[0001] This invention belongs to the technical field of fluorescent materials, and particularly relates to a supramolecular fluorescent material. Background Technology

[0002] Research in supramolecular chemistry and crystal engineering provides core theoretical support for the design of novel functional materials. Its focus lies in achieving precise molecular recognition and controllable self-assembly through non-covalent interactions (such as electrostatic interactions, hydrogen bonds, π-π stacking, and metal coordination bonds), thereby constructing aggregates with predetermined structures and functions. Electrostatic interactions, due to their directional and tunable intensity, have become a key driving force in constructing supramolecular assemblies. Fluorescent dyes, as functional units, utilize their conjugated double bonds or aromatic ring structures to achieve energy conversion and fluorescence emission through photoexcitation-induced electronic transitions, becoming ideal building blocks for functional materials.

[0003] Natural fluorescent dyes have garnered widespread attention due to their environmental friendliness and biocompatibility, with Phellodendron amurense (extract from the Phellodendron chinense tree) being a representative plant-derived fluorescent dye. Its main active ingredient is berberine, an isoquinoline alkaloid with a planar rigid conjugated system, possessing strong fluorescence, broad-spectrum antibacterial properties, and antioxidant capabilities. Berberine's quaternary ammonium cation structure facilitates its binding to fibers via electrostatic interactions, while its hydrogen bonds and intermolecular forces enable supramolecular fixation onto fabrics. Based on supramolecular principles, berberine can be efficiently integrated into textile matrices through molecular recognition and self-assembly technologies, significantly improving colorfastness and functional durability.

[0004] As a typical application of supramolecular functionalization, luminescent textiles combine fluorescent dyes (such as berberine extract) with textile technology to develop novel smart textiles that possess luminescent properties, UV protection, and biofunctionality. Utilizing supramolecular assembly strategies, natural dyes such as berberine can be stably fixed onto the fiber surface, achieving multifunctional integration of photoluminescence, antibacterial properties, and UV protection. These textiles not only retain flexibility and comfort but also expand application scenarios such as visual interaction and health monitoring, fully demonstrating the interdisciplinary integration of materials science, chemistry, and textile engineering, and providing sustainable solutions for the innovation of green and healthy textiles.

[0005] Patent publication number CN 114702485 A discloses a berberine terephthalate dye supramolecular salt, wherein the molecular formula of the berberine terephthalate dye supramolecular salt is: C 28 H 23NO8: The crystal belongs to the triclinic crystal system, space group P-1, and the cell parameters are: a=9.5975(5), b=10.2268(8), c=12.9835(8); α=102.746(6)°, β=94.140(5)°, γ=108.187(6)°. This dye supramolecular salt has a maximum emission wavelength of 539nm under the maximum excitation wavelength of 346nm. For example, patent publication number CN114560856A discloses a sulfosalicylic acid berberine dye supramolecular salt, the molecular formula of which is: C 27 H 23 NO 10 S: The crystal belongs to the orthorhombic crystal system, space group Pbca, and the unit cell parameters are: a=7.00863(10), b=16.5661(2), c=42.0562(6); α=90°, β=90°, γ=90°. This dye supramolecular salt has a maximum emission wavelength of 520nm under the maximum excitation wavelength of 346nm.

[0006] Although a series of berberine dye supramolecular salts have been disclosed in existing technologies, different structures and crystal forms exhibit different fluorescence wavelengths. Therefore, to further broaden the application range of natural dyes such as berberine, it is still necessary to further develop berberine dye supramolecular salts with different structures. Specifically, existing berberine dye supramolecular salts still suffer from limited fluorescence emission wavelength coverage, making it difficult to adapt to the needs of diverse application scenarios. The maximum emission wavelength of currently disclosed berberine supramolecular salts is concentrated in the green fluorescence range of 520-539 nm, while fluorescent materials in the blue, yellow, orange, and red bands, which are urgently needed in fields such as smart textiles and fluorescent labeling, remain unavailable. This severely limits the application of berberine-based supramolecular fluorescent materials in high-end application scenarios such as color displays and multi-channel recognition. Based on the shortcomings of the existing technologies, developing a berberine dye supramolecular salt with a novel fluorescence band and a green and compatible preparation process is of great significance for promoting the application upgrade of natural dye supramolecular functional materials in the field of smart textiles and enhancing the core competitiveness of my country's high-end textile materials. Summary of the Invention

[0007] To address the aforementioned technical problems, this invention proposes a supramolecular fluorescent material based on berberine, its preparation method, and its application. This dye supramolecular fluorescent material exhibits emission peaks with maximum emission wavelengths of 395 nm, 594 nm, and 707 nm under a maximum excitation wavelength of 660 nm. The fluorescence peaks are relatively strong, and the luminescence intensity is relatively high.

[0008] To achieve the above objectives, the technical solution of the present invention is implemented as follows:

[0009] A supramolecular fluorescent material based on berberine, wherein the fluorescent material is composed of an aminosalicylic acid berberine supramolecular salt; the molecular formula of the aminosalicylic acid berberine supramolecular salt is: 8[C 20 H 18 NO4]·8[C7H6NO3]·H2O; The structural formula of the repeating structural unit of the aminosalicylic acid berberine supramolecular salt is as follows:

[0010]

[0011] This structural unit is the basic building block of the aminosalicylic acid berberine supramolecular salt.

[0012] The aminosalicylic acid berberine supramolecular salt is a monoclinic crystal with space group C2 / c and cell parameters of: a=26.3±0.2Å, b=10.8±0.3Å, c=15.5±0.2Å; β=92.3±0.5°.

[0013] The cell parameters of the aminosalicylic acid berberine supramolecular salt are: a=26.3227(10)Å, b=10.8429(42)Å, c=15.4566(8)Å; α=90°, β=92.323(4)°, γ=90°.

[0014] A method for preparing a supramolecular fluorescent material based on berberine includes the following steps:

[0015] (1) Berberine hydrochloride was added to solvent I to prepare a berberine hydrochloride solution;

[0016] (2) Prepare an aminosalicylic acid solution by adding aminosalicylic acid to solvent II;

[0017] (3) Add the berberine hydrochloride solution dropwise to the aminosalicylic acid solution, continue stirring the reaction until a precipitate appears, filter, let stand for several days, and then recrystallize to obtain the aminosalicylic acid berberine supramolecular fluorescent material.

[0018] Solvent I is any one or two or more of methanol, ethanol, acetone, tetrahydrofuran, acetonitrile, N,N-dimethylformamide, and water.

[0019] The concentration of berberine hydrochloride in the berberine hydrochloride solution is 0.01-0.05 mmol / mL.

[0020] Solvent II is any one or two or more of methanol, ethanol, acetone, tetrahydrofuran, acetonitrile, N,N-dimethylformamide, and water.

[0021] The concentration of aminosalicylic acid in the aminosalicylic acid solution is 0.01-0.05 mmol / mL.

[0022] In step (3), the molar ratio of berberine hydrochloride to aminosalicylic acid in the berberine hydrochloride solution and the aminosalicylic acid solution is 1:0.5-2.

[0023] The recrystallization steps are as follows: mix and grind polycrystalline aminosalicylic acid berberine with zinc sulfate heptahydrate, then add ethanol, water or a mixture of both and continue grinding, finally filter after stirring, and let stand in a constant temperature incubator until crystals appear and then collect the product.

[0024] Application of a berberine-based supramolecular fluorescent material in fluorescence and printing.

[0025] Berberine-based supramolecular fluorescent materials have shown innovative application potential in the fields of fluorescence and printing: In terms of fluorescence, supramolecular salts can regulate the red shift of fluorescence emission color through electrostatic and π-π stacking interactions, and can be developed into functional fluorescent dyes, such as UV-responsive anti-counterfeiting printing or physiological indicator sensing fabrics; In the field of printing, textiles obtained by screen printing have significant UV protection properties, and combined with their fluorescent properties, it is possible to achieve the intelligent effect of "invisibility in sunlight and visibility in ultraviolet light".

[0026] The beneficial effects of this invention are:

[0027] (1) This invention uses highly polar solvents such as water, ethanol, methanol, and N,N-dimethylformamide to dissolve the raw materials. It can efficiently dissolve two polar raw materials, berberine hydrochloride and aminosalicylic acid, with excellent dissolution effect, which greatly improves the conversion rate of raw materials and the yield of products. At the same time, the selected solvents do not require special purification treatment, and the preparation process does not require high temperature, high pressure or special catalysts. The operation steps are simple and easy to carry out, which not only reduces production energy consumption and cost, but also reduces the environmental and health risks caused by organic solvent residues, providing favorable conditions for industrial-scale production.

[0028] (2) The aminosalicylic acid berberine supramolecular fluorescent material of the present invention has outstanding fluorescence characteristics: at the maximum excitation wavelength of 660 nm, it can simultaneously generate three strong fluorescence emission peaks of 395 nm, 594 nm, and 707 nm, with high fluorescence peak intensity and stable luminescence performance. In addition, the material also has a long fluorescence lifetime, which further improves its adaptability in functional dyes and fluorescence imaging, and significantly broadens the application range of berberine-based natural dye supramolecular materials.

[0029] (3) The experimental PXRD data of the aminosalicylic acid berberine supramolecular salt prepared by this invention has a very high degree of matching with the single crystal structure simulation data, proving that the obtained product is a single crystal phase without any impurity crystal phase mixed in. The high-purity single crystal structure can ensure the consistency and reliability of the core properties of the material such as fluorescence performance and chemical stability, and avoid performance fluctuations caused by the presence of impurity phases, providing a core guarantee for its stable application in fields such as smart textiles.

[0030] (4) The aminosalicylic acid berberine supramolecular fluorescent material of the present invention can exist stably below 150℃ and has good thermal stability. The material of the present invention can withstand the normal temperature of textile printing, dyeing and finishing processes, effectively avoiding the decay or loss of fluorescence performance during processing; at the same time, its excellent thermal stability also enables it to adapt to complex application environments such as outdoor high temperature, further improving the practical value and service life of the material.

[0031] (5) The aminosalicylic acid berberine dye supramolecular fluorescent material of the present invention exhibits unique innovative application potential in the fields of fluorescence and printing. On the one hand, the supramolecular salt can regulate the red shift of fluorescence emission color through electrostatic interaction and stacking interaction, possessing the core advantage of being developed into a functional fluorescent dye. It can be specifically applied to high-end intelligent textile scenarios such as anti-counterfeiting printing with ultraviolet light response and physiological index sensing fabrics, filling the application gap of existing berberine materials in the fields of intelligent sensing and anti-counterfeiting. On the other hand, when it is applied to the screen printing process to prepare textiles, it can not only make the textiles have significant UV protection performance, but also achieve the intelligent effect of "sunlight invisibility and ultraviolet development" by combining its own excellent fluorescence properties. This breaks the limitation of the single function of traditional printing materials, provides a new direction for the innovative development of intelligent printed textiles, and further enhances the market application value and industrial competitiveness of the material. Attached Figure Description

[0032] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0033] Figure 1 This is a structural diagram of a single structural unit in the supramolecular salt of aminosalicylic acid berberine.

[0034] Figure 2 This is a schematic diagram of the supramolecular stacking structure of aminosalicylic acid berberine supramolecular salt in the ab plane.

[0035] Figure 3 This is the PXRD (X-ray powder diffraction pattern) of the supramolecular fluorescent material of this invention.

[0036] Figure 4 This is a thermogravimetric analysis diagram of the supramolecular fluorescent material of the present invention.

[0037] Figure 5 This is the fluorescence spectrum of the supramolecular fluorescent material of the present invention.

[0038] Figure 6 The fluorescence decay curves of the supramolecular fluorescent material of this invention and berberine hydrochloride are shown. Detailed Implementation

[0039] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0040] Example 1

[0041] A supramolecular fluorescent material based on berberine, the preparation method of which includes the following steps:

[0042] (1) Extraction of berberine pigment from Phellodendron bark:

[0043] First, pulverize the Phellodendron bark into a fine powder using a pulverizer to increase the contact area between the Phellodendron bark and CH3CH2OH, thereby increasing the rate at which the Phellodendron pigment dissolves in CH3CH2OH. Accurately weigh 40 g of Phellodendron bark powder into a beaker, add 211 mL of CH3CH2OH and 89 mL of deionized water, and soak at 40℃ for 2 h, then filter. Repeat the soaking and filtration process three times. Combine the three filtrates and evaporate two-thirds of the solvent using a rotary evaporator. Removing the CH3CH2OH solvent increases the solution concentration, facilitating the formation of a supersaturated solution and accelerating solute precipitation. Adjust the pH of the evaporated solution to 9 with 5 mol / L NaOH solution. To remove impurities, let it stand for 3-4 h, then add 3 mol / L HCl solution to adjust the pH to 2. Finally, add 5% (v / v) NaCl solid and stir until the solution becomes turbid. Let it stand for about 8 h, then filter and dry to obtain berberine hydrochloride dye.

[0044] (2) Preparation of aminosalicylic acid berberine supramolecular salt

[0045] Weigh 0.1 mmol of berberine hydrochloride into a small beaker, add 5 mL of methanol solution, place the beaker in a rotor, and stir at 500 rpm on a magnetic stirrer until completely dissolved. Separately weigh 0.1 mmol of aminosalicylic acid into another small beaker, add 8 mL of N,N-dimethylformamide solution, and stir to dissolve in the same manner. Add the dissolved berberine hydrochloride solution dropwise to the aminosalicylic acid solution using a dropper, with a 1:1 ratio of the two solutions. Continue stirring until a precipitate forms. After filtration, allow the mixture to stand at room temperature for approximately 7 days to allow polycrystalline or precipitated crystals to form. Collect the precipitate for later use.

[0046] (3) Preparation of aminosalicylic acid berberine supramolecular fluorescent materials by recrystallization

[0047] Weigh 0.1 mmol of aminosalicylic acid berberine polycrystals and zinc sulfate heptahydrate (ZnSO4·7H2O) and grind them thoroughly in an agate mortar. Add 8 mL of a mixture of ethanol and water and continue grinding, then transfer to a small beaker. After grinding, add 5 mL of ethanol solution to the mortar to wash away any residue, and combine the residue with the mortar in a 50 mL beaker. Place a rotor in the beaker and stir at 500 r / min with plastic wrap sealed on a magnetic stirrer for 2 hours. Filter with filter paper, seal again with plastic wrap, and incubate in a constant temperature incubator. Collect the product after crystallization. The resulting aminosalicylic acid berberine supramolecular fluorescent material is obtained. The molecular formula of the obtained aminosalicylic acid berberine molecular fluorescent material is: 8[C 20 H 18 NO4]·8[C7H6NO3]·H2O.

[0048] The crystallographic parameters of the obtained aminosalicylic acid berberine are detailed in the table below.

[0049]

[0050] The dye supramolecular salt berberine aminosalicylic acid crystal described in this invention belongs to the monoclinic crystal system, with space group C2 / c and cell parameters a / Å = 26.3227(10), b / Å = 10.8429(4), c / Å = 15.4566(8), α = 90°, β = 92.323(4), and γ = 90°. This molecular structure is composed of cationic berberine and anionic aminosalicylic acid anion, as shown in the figure. Figure 1 As shown, supramolecular forces such as electrostatics and hydrogen bonds exist between cations and anions. Berberine cations and aminosalicylic acid anions are alternately linked and distributed in the ab plane through these supramolecular interactions, as shown in the diagram. Figure 2 As shown.

[0051] from Figure 3 The PXRD (X-ray powder diffraction) analysis results show that the PXRD data obtained from the experiment and the simulation results of its single crystal structure data have a very high degree of matching, indicating that the obtained single crystal is a single phase.

[0052] The aminosalicylic acid berberine of this invention has good stability. Figure 4 The thermogravimetric analysis results show that the supramolecular fluorescent material remains stable at 150℃, indicating that it has good thermal stability below 150℃.

[0053] Fluorescence properties of the dye molecule fluorescent material obtained in Example 1 were detected. The fluorescence properties of the compound were measured at room temperature, such as... Figure 5The aminosalicylic acid berberine samples shown emitted emission peaks at wavelengths of 395 nm, 594 nm, and 707 nm, respectively, when excited at a wavelength of 660 nm. The fluorescence quantum efficiency of aminosalicylic acid berberine was measured to be 0.8%.

[0054] In addition, such as Figure 6 The fluorescence decay curves of aminosalicylic acid berberine obtained with an excitation wavelength of 660 nm and a detection wavelength of 707 nm are shown in the figure. It can be seen from the figure that the fluorescence decay curves conform to the double exponential decay behavior, based on the double exponential function.

[0055] I(t) = A1×exp(-t / τ1)+A2×(-t / τ2) (1)

[0056] In Eq.1, I represents the emission spectral intensity; τ1 and τ2 are the lifetimes of the slow and fast processes in the fluorescence lifetime, respectively; A1 and A2 are the fitting parameters for the slow and fast processes, respectively. The average fluorescence lifetime can be considered as the fluorescence lifetime after combining the contributions of the slow and fast processes. Its value can be calculated according to the formula in Eq.2. From τ1, τ2, A1, and A2, the average fluorescence lifetime is calculated to be 2.31 ns, indicating that this supramolecular salt of dye is a good fluorescent material.

[0057] τ= (A1τ1 2 + A2τ2 2 ) / ( A1τ1 + A2τ2) (2)

[0058] Example 2

[0059] A supramolecular fluorescent material based on berberine, the preparation method of which includes the following steps:

[0060] Weigh 0.1 mmol of berberine hydrochloride into a small beaker, add 10 mL of ethanol solution, place the beaker in a rotor, and stir on a magnetic stirrer at 500 rpm until completely dissolved. Separately weigh 0.1 mmol of aminosalicylic acid into another small beaker, add 10 mL of N,N-dimethylformamide solution, and stir to dissolve in the same manner. Add the dissolved berberine hydrochloride solution dropwise to the aminosalicylic acid solution using a dropper, with a 1:1 ratio of the two solutions. Continue stirring until a precipitate forms. After filtration, allow the mixture to stand at room temperature for approximately 7 days to allow polycrystalline or precipitated crystals to form. Collect the precipitate for later use.

[0061] Weigh 0.1 mmol of polycrystalline berberine aminosalicylic acid and zinc sulfate heptahydrate (ZnSO4·7H2O) and grind them thoroughly in an agate mortar. Add 8 mL of a mixture of ethanol and water and continue grinding, then transfer the mixture to a small beaker. After grinding, add 5 mL of ethanol solution to the mortar to wash away any residue, and combine the residue with the mortar in a 50 mL beaker. Place a rotor in the beaker and stir at 500 r / min with plastic wrap sealed. Stir for 2 hours on a magnetic stirrer. Filter with filter paper, seal again with plastic wrap, and incubate in a constant temperature incubator. Collect the product after crystallization to obtain the supramolecular fluorescent material of berberine aminosalicylic acid.

[0062] Example 3

[0063] A supramolecular fluorescent material based on berberine, the preparation method of which includes the following steps:

[0064] Weigh 0.5 mmol of berberine hydrochloride into a small beaker, add 10 mL of ethanol solution, place the beaker in a rotor, and stir on a magnetic stirrer at 500 rpm until completely dissolved. Separately weigh 0.5 mmol of aminosalicylic acid into another small beaker, add 10 mL of ethanol solution, and stir to dissolve in the same manner. Add the dissolved berberine hydrochloride solution dropwise to the aminosalicylic acid solution using a dropper, with a ratio of 1:2. Continue stirring until a precipitate forms. After filtration, allow to stand at room temperature for approximately 7 days to allow polycrystalline or precipitated crystals to form. Collect the precipitate for later use.

[0065] Weigh 0.1 mmol of polycrystalline berberine aminosalicylic acid and zinc sulfate heptahydrate (ZnSO4·7H2O) and grind them thoroughly in an agate mortar. Add 8 mL of a mixture of ethanol and water and continue grinding, then transfer the mixture to a small beaker. After grinding, add 5 mL of ethanol solution to the mortar to wash away any residue, and combine the residue with the mortar in a 50 mL beaker. Place a rotor in the beaker and stir at 500 r / min with plastic wrap sealed. Stir for 2 hours on a magnetic stirrer. Filter with filter paper, seal again with plastic wrap, and incubate in a constant temperature incubator. Collect the product after crystallization to obtain the supramolecular fluorescent material of berberine aminosalicylic acid.

[0066] Example 4

[0067] A supramolecular fluorescent material based on berberine, the preparation method of which includes the following steps:

[0068] Weigh 0.3 mmol of berberine hydrochloride into a small beaker, add 10 mL of ethanol solution, place the beaker in a rotor, and stir on a magnetic stirrer at 500 rpm until completely dissolved. Separately weigh 0.3 mmol of aminosalicylic acid into another small beaker, add 10 mL of ethanol solution, and stir to dissolve in the same manner. Add the dissolved berberine hydrochloride solution dropwise to the aminosalicylic acid solution using a dropper, with a ratio of 2:1. Continue stirring until a precipitate forms. After filtration, allow to stand at room temperature for approximately 7 days to allow polycrystalline or precipitated crystals to form. Collect the precipitate for later use.

[0069] Weigh 0.1 mmol of polycrystalline berberine aminosalicylic acid and zinc sulfate heptahydrate (ZnSO4·7H2O) and grind them thoroughly in an agate mortar. Add 8 mL of a mixture of ethanol and water and continue grinding, then transfer the mixture to a small beaker. After grinding, add 5 mL of ethanol solution to the mortar to wash away any residue, and combine the residue with the mortar in a 50 mL beaker. Place a rotor in the beaker and stir at 500 r / min with plastic wrap sealed. Stir for 2 hours on a magnetic stirrer. Filter with filter paper, seal again with plastic wrap, and incubate in a constant temperature incubator. Collect the product after crystallization to obtain the supramolecular fluorescent material of berberine aminosalicylic acid.

[0070] Application Example 1

[0071] Application of the supramolecular fluorescent dye material obtained in Example 1 on printed cotton and silk fabrics: Weigh 3 g of sodium alginate into a 150 mL beaker, and measure 100 mL of water into a 250 mL beaker using a graduated cylinder. Turn on the electric stirrer to stir the water, and while stirring, add the sodium alginate powder evenly to avoid clumping caused by adding it too quickly. Observe the change in the viscosity of the original paste and adjust the stirrer speed as needed. After the sodium alginate is completely dissolved, add 0.1 g of sodium carbonate and 0.5 g of urea and stir until uniform. Weigh 0.1 g of aminosalicylic acid berberine into a 150 mL beaker, add deionized water and stir until the dye dissolves. Then pour it into the stirred original paste and continue stirring for 1 min before use.

[0072] Cut four pieces of cotton and silk fabric of appropriate sizes. Pour the prepared color paste evenly onto the top of a sieve. Tilt the scraper at 45° and scrape back and forth twice from top to bottom with slight force. Then remove the sieve and take out the fabric to check if the pattern is complete. Place the printed fabric in an 80°C oven to dry. After drying, fix the fabric flat and place it in a steam oven for steaming at 102°C for 5 minutes.

[0073] The fabric exhibits a noticeable fluorescent effect under ultraviolet light. Under 365nm ultraviolet light, aminosalicylic acid berberine fluoresces with a blue-green light, and the fluorescence effect on silk is generally better than that on cotton. The ultraviolet protection performance of the above-mentioned printed and dyed fabrics was tested. According to the national standard GB / T 18830-2009 "Evaluation of Ultraviolet Protection Performance of Textiles," sun-protective textiles must meet the core indicator of a UPF value > 40. The silk fabric treated with aminosalicylic acid berberine supramolecular fluorescent material achieved a UPF value of 44.27, exceeding the lower limit of the national standard. This result indicates that this type of supramolecular fluorescent material system has the potential to be developed into a natural-source sun-protective functional dye, providing a new direction for green sun-protective textiles.

[0074] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A supramolecular fluorescent material based on berberine, characterized in that, The fluorescent material is composed of an aminosalicylic acid berberine supramolecular salt; the molecular formula of the aminosalicylic acid berberine supramolecular salt is: 8[C 20 H 18 NO4]·8[C7H6NO3]·H2O; The structural formula of the repeating structural unit of the aminosalicylic acid berberine supramolecular salt is as follows: This structural unit is the basic building block of the aminosalicylic acid berberine supramolecular salt.

2. The supramolecular fluorescent material based on berberine according to claim 1, characterized in that, The aminosalicylic acid berberine supramolecular salt is a crystal belonging to the monoclinic crystal system, with space group C2 / c and unit cell parameters of: a=26.3±0.2Å, b=10.8±0.3Å, c=15.5±0.2Å; β=92.3±0.5°.

3. The supramolecular fluorescent material based on berberine according to claim 2, characterized in that, The cell parameters of the aminosalicylic acid berberine supramolecular salt are: a=26.3227(10)Å, b=10.8429(42)Å, c=15.4566(8)Å; α=90°, β=92.323(4)°, γ=90°.

4. The method for preparing the supramolecular fluorescent material based on berberine according to any one of claims 1-3, characterized in that, Includes the following steps: (1) Berberine hydrochloride was added to solvent I to prepare a berberine hydrochloride solution; (2) Prepare an aminosalicylic acid solution by adding aminosalicylic acid to solvent II; (3) Add the berberine hydrochloride solution dropwise to the aminosalicylic acid solution, stir until a precipitate is formed, filter, let stand, and recrystallize to obtain the aminosalicylic acid berberine supramolecular fluorescent material.

5. The method for preparing supramolecular fluorescent materials based on berberine according to claim 4, characterized in that, Solvent I is any one or two or more of methanol, ethanol, acetone, tetrahydrofuran, acetonitrile, N,N-dimethylformamide, and water.

6. The method for preparing supramolecular fluorescent materials based on berberine according to claim 5, characterized in that, The concentration of berberine hydrochloride in the berberine hydrochloride solution is 0.01-0.05 mmol / mL.

7. The method for preparing supramolecular fluorescent materials based on berberine according to claim 4, characterized in that, Solvent II is any one or two or more of methanol, ethanol, acetone, tetrahydrofuran, acetonitrile, N,N-dimethylformamide, and water.

8. The method for preparing supramolecular fluorescent materials based on berberine according to claim 7, characterized in that, The concentration of aminosalicylic acid in the aminosalicylic acid solution is 0.01-0.05 mmol / mL.

9. The method for preparing supramolecular fluorescent materials based on berberine according to claim 4, characterized in that, In step (3), the molar ratio of berberine hydrochloride to aminosalicylic acid in the berberine hydrochloride solution and the aminosalicylic acid solution is 1:0.5-2.

10. The application of the berberine-based supramolecular fluorescent material according to any one of claims 1-3 in fluorescence and printing.

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