A far-infrared functional bioluminescent composite material and acupuncture patch prepared therefrom and its application

Abstract

The present invention discloses a far-infrared functional bioluminescent composite material, an acupuncture patch prepared from the composite material, and its application, belonging to the technical field of far-infrared medical materials. The bioluminescent composite material is composed of the following components by weight: 25-45 parts of modified Bianstone, 20-30 parts of medical stone, 10-20 parts of germanium stone, 5-10 parts of silicon dioxide, and 5-10 parts of aluminum oxide. The modified Bianstone is prepared by processes such as bentonite interlayer pore expansion, LaFe perovskite / TiO2 quantum dot intercalation, and Prussian blue analog loading. The composite material has far-infrared emission characteristics and can resonate with human tissue to absorb negative oxygen ions through quantum dot photocatalysis. The porous structure adsorbs inflammatory factors. The LaFe perovskite / TiO2 quantum dot photocatalysis synergizes with the far-infrared radiation of the Bianstone to destroy bacterial cell membranes; the medical stone releases trace elements to inhibit bacterial activity. The prepared acupuncture patch is compounded with a medical pressure-sensitive adhesive through a molding process to generate microcurrent to stimulate the TRPV1 ion channel, achieving the treatment of facial paralysis, hypertension, and diabetes.

Description

Technical Field

[0001] The present invention belongs to the technical field of far-infrared medical materials, and in particular relates to a far-infrared functional biophotonic composite material, an acupuncture patch prepared therefrom, and applications thereof. Background Art

[0002] Far-infrared materials refer to materials that have the property of emitting or absorbing far-infrared radiation. Far-infrared radiation refers to electromagnetic waves with wavelengths between 5.6 and 1000 μm. Studies have shown that far-infrared radiation with a wavelength of 5.6-15 μm can penetrate 3-5 mm of human subcutaneous tissue. This frequency closely matches the resonant absorption frequency of water molecules, generating a thermal effect by stimulating molecular vibrations, promoting local microcirculation and cellular metabolism. Its excellent penetrating power and warming effect can promote blood circulation, accelerate metabolism, and relieve pain. Currently, far-infrared materials are primarily categorized as natural mineral-based (such as Bianstone and tourmaline) and synthetic (such as graphene and carbon fiber). While natural mineral materials offer the advantage of biocompatibility, their emissivity is generally low at room temperature. High-temperature calcination can easily lead to crystal phase transformation and collapse of the porous structure, compromising the sustained release of trace elements. Artificial materials, such as graphene heating films, while offering high emissivity, are costly and have a single function, relying solely on thermal effects and lacking synergistic properties such as antibacterial and adsorption of inflammatory factors.

[0003] By combining far-infrared materials with patch materials to make acupoint patches, the far-infrared materials can be used in acupoint treatment. However, traditional acupoint patches mostly rely on the single thermal effect of far-infrared materials and cannot activate TRPV1 ion channels through microcurrent stimulation, affecting the efficiency of nerve signal conduction. At the same time, they lack the ability to dynamically regulate the local microenvironment. Therefore, it is necessary to propose a far-infrared functional biophotonic composite material with a synergistic effect of multiple materials, which can promote the body's repair and metabolism through the synergistic effect of far-infrared radiation and acupoint stimulation to achieve the purpose of clinical treatment. Summary of the Invention

[0004] In view of the above situation, in order to overcome the defects of the existing technology, the present invention provides a modification of Bianstone to address the key problems of the existing technology, such as the single far-infrared material band, poor functional synergy and insufficient thermal stability, thereby achieving improvements in far-infrared emission performance, antibacterial activity and structural stability, and providing a material basis for acupuncture point treatment of diseases.

[0005] In order to achieve the above-mentioned purpose, the following technical solution is adopted: the present invention provides a far-infrared functional bioluminescent composite material, which is composed of the following components in parts by weight: 25-45 parts of modified Bianstone, 20-30 parts of medical stone, 10-20 parts of germanium stone, 5-10 parts of silicon dioxide and 5-10 parts of aluminum oxide.

[0006] The modified Bianstone is prepared by the following steps:

[0007] S1. Sodium bentonite and deionized water are mixed in a mass ratio of 1:5-1:10 to form a suspension, the pH is adjusted to 4-5 with a 0.3-0.5 mol / L hydrochloric acid solution, a quaternary ammonium salt cationic surfactant is added in an amount of 0.8-1.2 times the mass of the sodium bentonite, and the mixture is stirred and reacted at 60-80°C for 1-3 hours. After the reaction is completed, the mixture is filtered, washed with deionized water, dried, crushed, and passed through a 200 mesh sieve to obtain interlayer expanded pore sodium bentonite;

[0008] S2, mixing a lanthanum source and an iron source in a molar ratio of 1:1-3, adding the mixture to a 30-50 g / L urea solution, and hydrothermally reacting the mixture at 180-200° C. for 12-24 h to obtain a first solution containing nano-LaFe perovskite particles, wherein the total molar ratio of urea to the lanthanum source and the iron source is 3-6:1, mixing tetrabutyl titanate with deionized water in a solid-liquid mass ratio of 1:25-40, and hydrothermally reacting the mixture at 150-180° C. for 6-8 h to obtain a second solution containing nano-TiO2 quantum dots, and dripping the second solution into the first solution in a mass ratio of 1:1-3 to the first solution, uniformly dispersing the mixture by ultrasound, and then adding 5-15% of the total mass of the solution of interlayer expanded pore sodium-based bentonite, stirring the mixture for 24-36 h, centrifuging the mixture, and drying the mixture to obtain LaFe perovskite / TiO2 quantum dot intercalation modified bentonite;

[0009] S3. Mixing Bianstone powder and ethanol at a mass ratio of 1:10-20, adding 3-5% of a silane coupling agent based on the mass of the Bianstone, adjusting the pH to 4-5 with a 0.5-1.2 mol / L hydrochloric acid solution, subjecting the mixture to a high-speed shear treatment at 10,000-15,000 r / min at 60-80° C. for 2-4 hours, filtering, washing, and drying to obtain amino-functionalized Bianstone;

[0010] S4. The modified Bianstone is mixed with LaFe / TiO2 intercalated modified bentonite in a mass ratio of 1:3-10, and ultrasonically dispersed in deionized water at a solid-liquid mass ratio of 1:30-50. 5-10% of the solution volume of a 0.1-0.3 mol / L potassium ferrocyanide solution and 10-20% of the solution volume of a 0.1-0.3 mol / L transition metal chloride solution are added, wherein the molar ratio of potassium ferrocyanide to transition metal chloride is 1:1-2. The mixture is self-assembled at 25-40°C for 12-24 hours. After centrifugation, washing, and vacuum drying, a modified Bianstone with a surface-loaded Prussian blue analogue is obtained.

[0011] The quaternary ammonium salt type cationic surfactant is one of octadecyltrimethylammonium chloride, dioctadecyldimethylammonium chloride and hexadecyltrimethylammonium bromide.

[0012] The lanthanum source is one of lanthanum nitrate, lanthanum chloride and lanthanum acetate.

[0013] The iron source is one of ferric chloride, ferric nitrate and ferric sulfate.

[0014] The transition metal chloride is one of ferrous chloride, cobalt chloride and nickel chloride.

[0015] The silane coupling agent is a combination of one or more of KH550, KH560, KH562 and KH570.

[0016] The present invention also provides an acupoint patch prepared from a far-infrared functional bioluminescent composite material, which is prepared from the far-infrared functional bioluminescent composite material by the following steps:

[0017] (1) Medical stone, germanium stone, silicon dioxide, and aluminum oxide are added to deionized water to form a slurry with a mass fraction of 30-60%, and then ball milled in a planetary ball mill at a speed of 300-600 r / min for 2-4 hours, and then calcined at 700-900 ° C for 1-3 hours, and then quenched with water;

[0018] (2) Mix the water-quenched raw materials with the modified Bianstone, heat them to 60°C at 5°C / min under nitrogen protection, hold for 0.5h, then heat them to 500-600°C at 3°C / min, hold for 1-3h, and then return to room temperature naturally;

[0019] (3) The mixture obtained in step (2) is mixed with a medical acrylic pressure-sensitive adhesive in a mass ratio of 1:3-5, and a medical acupoint patch with a thickness of 0.5-1.2 mm is obtained by compression molding.

[0020] The present invention also provides the application of an acupuncture patch prepared from the infrared functional biophotonic composite material:

[0021] The patch is a circular structure with a diameter of 10-15 mm, a far-infrared radiation rate of >0.85, and is applied to the acupuncture points for facial paralysis treatment, including Yifeng point, Dicang point, and Jiache point;

[0022] The patch is a circular structure with a diameter of 10-15 mm, a far-infrared radiation rate of >0.85, and is applied to acupuncture points for hypertension treatment, including Yongquan, Taichong, and Quchi points;

[0023] The patch is a circular structure with a diameter of 10-15 mm, a far-infrared radiation rate of >0.85, and is applied to acupuncture points for treating diabetes, including Zusanli, Sanyinjiao, and Pishu points.

[0024] The beneficial effects of the present invention are:

[0025] (1) The present invention modifies the natural far-infrared radiation characteristics of Bianstone itself, and the Prussian blue analogues loaded on its surface and the LaFe perovskite / TiO2 quantum dots intercalated in bentonite can generate a wider spectrum of far-infrared radiation through lattice vibration and electronic transition;

[0026] (2) The porous structure of interlayer expanded pores of bentonite and Prussian blue analogs provides abundant adsorption sites. LaFe perovskite / TiO2 quantum dots have photocatalytic activity and can decompose water molecules and oxygen in the air under light or thermal excitation, releasing negative oxygen ions. The silicate layer of bentonite can adsorb local inflammatory factors through ion exchange, thereby inhibiting the inflammatory response.

[0027] (3) The far-infrared radiation of Bianstone and the active oxygen generation ability of LaFe perovskite can destroy bacterial cell membranes and inhibit the growth of microorganisms. The trace elements such as zinc and selenium released by medical stone can inhibit the activity of bacterial DNA gyrase, and have a physical barrier effect with the silicate layer structure of bentonite to achieve a synergistic antibacterial effect.

[0028] (4) The emissivity range of the biophotonic composite material is highly matched with the absorption characteristics of human tissue, and it can penetrate the subcutaneous tissue. The microcurrent stimulation generated can activate TRPV1 ion channels, promote local blood circulation, accelerate tissue metabolism, and promote nerve regeneration. The biophotonic composite material has multiple synergistic antibacterial mechanisms to prevent local infection. Therefore, the acupoint patch prepared by the present invention can be used for the treatment of facial paralysis; the biophotonic composite material releases negative oxygen ions, improves the local microenvironment of the acupoints, activates the nerve endings at these acupoints, regulates nerve reflexes, and thus affects the function of the cardiovascular system, which has the effect of lowering blood pressure. Microcurrent stimulation can It regulates the tension of vascular smooth muscle, dilates blood vessels, reduces peripheral resistance, and thus lowers blood pressure, playing a role in treating hypertension; it activates nerve endings, regulates parasympathetic nerve activity, achieves dynamic balance of blood pressure, and helps treat hypertension; the biophotonic composite material acts on the Zusanli acupoint, Sanyinjiao acupoint, and Pishu acupoint, improves local microcirculation through far-infrared radiation, enhances tissue sensitivity to insulin, and the microcurrent stimulation generated is transmitted through the meridians, regulates organ function, promotes sugar metabolism, and lowers blood sugar levels. By stimulating the Pishu acupoint, it can regulate the endocrine function of the pancreas, make insulin secretion tend to normal, thereby lowering blood sugar and helping to treat diabetes. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 The results of the efficacy evaluation of the acupoint patch prepared by the present invention in the treatment of facial paralysis (case numbers 1-30);

[0030] Figure 2 The results of the efficacy evaluation of the acupoint patch prepared by the present invention in the treatment of facial paralysis (case numbers 31-60);

[0031] Figure 3 Results of efficacy evaluation of the acupoint patch prepared by the present invention in the treatment of hypertension (case numbers 1-30);

[0032] Figure 4 Results of efficacy evaluation of the acupoint patch prepared by the present invention in the treatment of hypertension (case numbers 31-60);

[0033] Figure 5 Results of efficacy evaluation of the acupoint patch prepared by the present invention in the treatment of diabetes (case numbers 1-30);

[0034] Figure 6 These are the results of efficacy evaluation of the acupoint patches prepared according to the present invention in the treatment of diabetes (case numbers 31-60).

[0035] The accompanying drawings are used to provide further understanding of the present invention and constitute a part of the specification. They are used to explain the present invention together with the embodiments of the present invention and do not constitute a limitation of the present invention. DETAILED DESCRIPTION

[0036] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0037] Unless otherwise defined, all technical and scientific terms used herein have the same meanings as those familiar to those skilled in the art. Furthermore, any methods and materials similar or equivalent to those described herein can be applied to the present invention. The preferred embodiments and materials described herein are for illustrative purposes only and are not intended to limit the scope of this application.

[0038] The experimental methods in the following examples, unless otherwise specified, are all conventional methods, and the experimental materials used in the following examples, unless otherwise specified, are all purchased from commercial channels.

[0039] In the preparation process of the acupoint patch, the present invention adopts a QM-3SP2 planetary ball mill for ball milling, which is provided by the Nanjing University Instrument Factory; in the preparation process of the acupoint patch, the present invention adopts an OTF-1200X tubular furnace, which is provided by Hefei Kejing Material Technology Co., Ltd.; in the preparation process of the acupoint patch, the present invention adopts an XLB-D flat plate vulcanizer for molding to obtain the acupoint patch, which is provided by Huzhou Dongfang Machinery Co., Ltd.; in the present invention, an HPZT-200 piezoelectric coefficient tester is used for microcurrent testing, which is provided by Beijing Huace Testing Instrument Co., Ltd. Example 1

[0040] A far-infrared functional bioluminescent composite material is composed of the following components in parts by weight: 25 parts of modified Bianstone, 20 parts of medical stone, 10 parts of germanium stone, 5 parts of silicon dioxide and 5 parts of aluminum oxide.

[0041] The modified Bianstone is prepared by the following steps:

[0042] S1. Sodium bentonite and deionized water were mixed in a mass ratio of 1:5 to form a suspension, the pH was adjusted to 4 with a 0.3 mol / L hydrochloric acid solution, 0.8 times the mass of octadecyltrimethylammonium chloride was added, and the mixture was stirred and reacted at 60°C for 1 hour. After the reaction was completed, the mixture was filtered, washed with deionized water, dried, crushed, and passed through a 200-mesh sieve to obtain interlayer-expanded pore sodium bentonite;

[0043] S2. Lanthanum nitrate and ferric chloride are mixed in a molar ratio of 1:1, added to a 30 g / L urea solution, and hydrothermally reacted at 180°C for 12 hours to obtain a first solution containing nano-LaFe perovskite particles, wherein the total molar ratio of urea to lanthanum source and iron source is 3:1, tetrabutyl titanate and deionized water are mixed in a solid-liquid mass ratio of 1:25, and hydrothermally reacted at 150°C for 6 hours to obtain a second solution containing nano-TiO2 quantum dots, and the second solution is dropped into the first solution in a mass ratio of 1:1 to the first solution, and uniformly dispersed by ultrasound, and then 5% of the total mass of the solution is added with interlayer expanded sodium bentonite, stirred for 24 hours, centrifuged, and dried to obtain LaFe perovskite / TiO2 quantum dot intercalation modified bentonite;

[0044] S3, mixing Bianstone powder and ethanol in a mass ratio of 1:10, adding 3% of the mass of the Bianstone as a silane coupling agent, wherein the silane coupling agent is KH550, adjusting the pH to 4 with a 0.5 mol / L hydrochloric acid solution, and subjecting the mixture to a high-speed shear treatment at 10,000 r / min at 60° C. for 2 h. After filtering, washing, and drying, the amino-functionalized Bianstone is obtained;

[0045] S4. The modified Bianstone was mixed with LaFe / TiO2 intercalated modified bentonite in a mass ratio of 1:3, and ultrasonically dispersed in deionized water at a solid-liquid mass ratio of 1:30. 5% of the solution volume of 0.1 mol / L potassium ferrocyanide solution and 10% of the solution volume of 0.1 mol / L ferrous chloride solution were added, wherein the molar ratio of potassium ferrocyanide to ferrous chloride was 1:1. The mixture was self-assembled at 25°C for 12 h. After centrifugation, washing, and vacuum drying, a modified Bianstone with a surface-loaded Prussian blue analogue was obtained. Example 2

[0046] A far-infrared functional bioluminescent composite material is composed of the following components in parts by weight: 45 parts of modified Bianstone, 30 parts of medical stone, 20 parts of germanium stone, 10 parts of silicon dioxide and 10 parts of aluminum oxide.

[0047] The modified Bianstone is prepared by the following steps:

[0048] S1. Sodium bentonite and deionized water were mixed in a mass ratio of 1:10 to form a suspension, the pH was adjusted to 5 with a 0.5 mol / L hydrochloric acid solution, and 1.2 times the mass of dioctadecyldimethylammonium chloride of the sodium bentonite was added, and the mixture was stirred and reacted at 80°C for 3 hours. After the reaction was completed, the mixture was filtered, washed with deionized water, dried, crushed, and passed through a 200-mesh sieve to obtain interlayer-expanded pore sodium bentonite;

[0049] S2. Lanthanum chloride and ferric sulfate are mixed in a molar ratio of 1:3, added to a 50 g / L urea solution, and hydrothermally reacted at 200°C for 24 hours to obtain a first solution containing nano-LaFe perovskite particles, wherein the total molar ratio of urea to lanthanum source and iron source is 6:1, tetrabutyl titanate and deionized water are mixed in a solid-liquid mass ratio of 1:40, and hydrothermally reacted at 180°C for 8 hours to obtain a second solution containing nano-TiO2 quantum dots, and the second solution is dropped into the first solution in a mass ratio of 1:3 to the first solution, and uniformly dispersed by ultrasound, and then 15% of the total mass of the solution is added with interlayer expanded sodium bentonite, stirred for 36 hours, centrifuged, and dried to obtain LaFe perovskite / TiO2 quantum dot intercalation modified bentonite;

[0050] S3, mixing Bianstone powder with ethanol in a mass ratio of 1:20, adding a silane coupling agent in an amount of 5% by mass of the Bianstone, wherein the silane coupling agent is a combination of KH560 and KH570 in a mass ratio of 1:1, adjusting the pH to 5 with a 1.2 mol / L hydrochloric acid solution, and subjecting the mixture to a high-speed shear treatment at 15,000 r / min at 80° C. for 4 h. After filtering, washing, and drying, the amino-functionalized Bianstone is obtained;

[0051] S4. The modified Bianstone was mixed with LaFe / TiO2 intercalated modified bentonite in a mass ratio of 1:10, and ultrasonically dispersed in deionized water at a solid-liquid mass ratio of 1:50. 10% of the solution volume of 0.3 mol / L potassium ferrocyanide solution and 20% of the solution volume of 0.3 mol / L nickel chloride solution were added, wherein the molar ratio of potassium ferrocyanide to nickel chloride was 1:2. The mixture was self-assembled at 40°C for 24 hours. After centrifugation, washing, and vacuum drying, a modified Bianstone with a surface-loaded Prussian blue analogue was obtained. Example 3

[0052] A far-infrared functional bioluminescent composite material is composed of the following components in parts by weight: 35 parts of modified Bianstone, 25 parts of medical stone, 15 parts of germanium stone, 7.5 parts of silicon dioxide and 7.5 parts of aluminum oxide.

[0053] The modified Bianstone is prepared by the following steps:

[0054] S1. Sodium bentonite and deionized water were mixed in a mass ratio of 1:7.5 to form a suspension, the pH was adjusted to 4.5 with a 0.4 mol / L hydrochloric acid solution, and cetyltrimethylammonium bromide (1 times the mass of the sodium bentonite) was added, and the mixture was stirred and reacted at 70°C for 2 hours. After the reaction was completed, the mixture was filtered, washed with deionized water, dried, crushed, and passed through a 200-mesh sieve to obtain interlayer-expanded pore sodium bentonite;

[0055] S2. Lanthanum acetate and ferric nitrate are mixed in a molar ratio of 1:2, added to a 40 g / L urea solution, and hydrothermally reacted at 190° C. for 18 hours to obtain a first solution containing nano-LaFe perovskite particles, wherein the total molar ratio of urea to lanthanum source and iron source is 4.5:1, tetrabutyl titanate and deionized water are mixed in a solid-liquid mass ratio of 1:32.5, and hydrothermally reacted at 165° C. for 7 hours to obtain a second solution containing nano-TiO2 quantum dots, and the second solution is dropped into the first solution in a mass ratio of 1:2 to the first solution, and uniformly dispersed by ultrasound, and then 10% of the total mass of the solution is added with interlayer expanded sodium bentonite, stirred for 30 hours, centrifuged, and dried to obtain LaFe perovskite / TiO2 quantum dot intercalation modified bentonite;

[0056] S3, mixing Bianstone powder and ethanol in a mass ratio of 1:15, adding 4% of the mass of the Bianstone silane coupling agent, wherein the silane coupling agent is a combination of KH562 and KH570 in a mass ratio of 1:1, adjusting the pH to 4.5 with 0.8 mol / L hydrochloric acid solution, and high-speed shearing treatment at 12500 r / min at 70°C for 3 h, filtering, washing, and drying to obtain amino-functionalized Bianstone;

[0057] S4. The modified Bianstone was mixed with LaFe / TiO2 intercalated modified bentonite in a mass ratio of 1:6.5, and ultrasonically dispersed in deionized water at a solid-liquid mass ratio of 1:40. 7.5% of the solution volume of 0.2 mol / L potassium ferrocyanide solution and 15% of the solution volume of 0.2 mol / L cobalt chloride solution were added, wherein the molar ratio of potassium ferrocyanide to cobalt chloride was 1:1.5. The mixture was self-assembled at 32.5°C for 18 h. After centrifugation, washing, and vacuum drying, a modified Bianstone with a surface-loaded Prussian blue analogue was obtained. Example 4

[0058] The difference between this comparative example and Example 3 is that the weight portion of the modified Bianstone is 30 parts, the weight portion of medical stone is 22 parts, and the rest is the same as Example 3. Example 5

[0059] The difference between this comparative example and Example 3 is that in step S1, the mass ratio of sodium bentonite to deionized water is 1:6, and the stirring reaction time is 1.5 h. The rest is the same as Example 3. Example 6

[0060] The difference between this comparative example and Example 3 is that the molar ratio of the lanthanum source to the iron source in step S2 is changed to 1:1.5, the concentration of the urea solution is changed to 35 g / L, and the rest is the same as Example 3. Example 7

[0061] The difference between this comparative example and Example 3 is that in step S3, the mass ratio of Bianstone powder to ethanol is 1:12, the amount of silane coupling agent used is 3.5% of the mass of Bianstone, and the rest is the same as Example 3. Example 8

[0062] The difference between this comparative example and Example 3 is that in step S4, the mass ratio of modified Bianstone to LaFe / TiO2 intercalated modified bentonite is changed to 1:4, and the self-assembly reaction temperature is changed to 30° C., and the rest is the same as Example 3. Example 9

[0063] The far-infrared emissivity of the bioluminescent composite materials prepared in Examples 1-8 was tested according to GB / T 30127-2013 “Testing and evaluation of far-infrared properties of textiles”.

[0064] The microcurrent test was performed on the biophotonic composite materials prepared in Examples 1-8 using an HPZT-200 piezoelectric coefficient tester.

[0065] The antibacterial rates of the bioluminescent composite materials prepared in Examples 1-8 against Candida albicans and Staphylococcus aureus were tested according to GB / T 21510-2008 “Test methods for antibacterial properties of nano-inorganic materials”.

[0066] The above test results are shown in Table 1.

[0067] As can be seen from the data in Table 1, the emissivity of all examples was ≥0.82 (the standard GB / T 30127-2013 requires ≥0.80 to be qualified), indicating that the synergistic effect of the modified Bianstone with LaFe / TiO2 quantum dots and Prussian blue analogues significantly improved the far-infrared radiation performance. Microcurrents of 0.16-0.28 mA were detected in all examples, confirming that the self-assembled structure of Prussian blue analogues and transition metals can generate ion migration currents and activate TRPV1 channels. In addition, the antibacterial rates against Candida albicans and Staphylococcus aureus were both >98.5%, far exceeding the national standard (>90%).

[0068] Table 1 Far infrared emissivity test, microcurrent test and antibacterial test results of Examples 1-8

[0069] Serial number Far infrared emissivity Microcurrent (mA) Candida albicans inhibition rate Staphylococcus aureus inhibition rate Example 1 0.82 0.18 98.7% 99.0% Example 2 0.85 0.22 99.1% 99.2% Example 3 0.82 0.16 98.5% 99.1% Example 4 0.88 0.20 99.2% 99.3% Example 5 0.90 0.23 99.4% 99.4% Example 6 0.91 0.28 99.6% 99.8% Example 7 0.89 0.23 99.3% 99.2% Example 8 0.84 0.22 99.0% 99.5%

[0070] As can be seen from Table 1, Example 6 has the highest emissivity, the highest microcurrent, and the highest antibacterial rate against Candida albicans and Staphylococcus aureus. Therefore, the biophotonic composite material prepared in Example 6 was used to prepare acupoint patches in Examples 10-13. Example 10

[0071] An acupoint patch prepared from a far-infrared functional biophotonic composite material is prepared from the far-infrared functional biophotonic composite material by the following steps:

[0072] (1) Medical stone, germanium stone, silicon dioxide, and aluminum oxide were added to deionized water to form a slurry with a mass fraction of 30%, and then ball milled in a planetary ball mill at a speed of 300 r / min for 2 h, and then calcined at 700 °C for 1 h, and then quenched with water;

[0073] (2) The raw material after water quenching and rapid cooling was mixed with the modified Bianstone, and the temperature was raised to 60°C at 5°C / min under nitrogen protection, maintained for 0.5h, then raised to 500°C at 3°C / min, maintained for 1h, and then naturally returned to room temperature;

[0074] (3) The mixture obtained in step (2) is mixed with a medical acrylic pressure-sensitive adhesive in a mass ratio of 1:3, and a medical acupoint patch with a thickness of 0.5 mm is obtained by molding. Example 11

[0075] An acupoint patch prepared from a far-infrared functional biophotonic composite material is prepared from the far-infrared functional biophotonic composite material by the following steps:

[0076] (1) Medical stone, germanium stone, silicon dioxide, and aluminum oxide were added to deionized water to form a slurry with a mass fraction of 60%, and then ball milled in a planetary ball mill at a speed of 600 r / min for 4 h, and then calcined at 900 °C for 3 h, and then quenched with water;

[0077] (2) Mix the water-quenched raw material with the modified Bianstone, heat it to 60°C at 5°C / min under nitrogen protection, hold it for 0.5h, then heat it to 600°C at 3°C / min, hold it for 3h, and then return it to room temperature naturally;

[0078] (3) The mixture obtained in step (2) was mixed with a medical acrylic pressure-sensitive adhesive in a mass ratio of 1:5, and a medical acupoint patch with a thickness of 1.2 mm was obtained by compression molding. Example 12

[0079] An acupoint patch prepared from a far-infrared functional biophotonic composite material is prepared from the far-infrared functional biophotonic composite material by the following steps:

[0080] (1) Medical stone, germanium stone, silicon dioxide, and aluminum oxide were added to deionized water to form a slurry with a mass fraction of 40%, and then ball milled in a planetary ball mill at a speed of 500 r / min for 3 h, and then calcined at 800 °C for 2 h, and then quenched with water;

[0081] (2) The raw material after water quenching and rapid cooling was mixed with the modified Bianstone, and the temperature was raised to 60°C at 5°C / min under nitrogen protection, maintained for 0.5h, and then raised to 550°C at 3°C / min, maintained for 2h, and then naturally returned to room temperature;

[0082] (3) The mixture obtained in step (2) is mixed with a medical acrylic pressure-sensitive adhesive in a mass ratio of 1:4, and a medical acupoint patch with a thickness of 1.0 mm is obtained by compression molding. Example 13

[0083] The difference between this comparative example and Example 11 is that the mixture and the medical acrylic pressure-sensitive adhesive are mixed in a mass ratio of 1:3, and a medical acupoint patch with a thickness of 1.0 mm is obtained by molding. The rest is the same as Example 11. Example 14

[0084] The acupoint patches prepared in Examples 10-13 were subjected to far-infrared emissivity test, microcurrent test and antibacterial test. The results are shown in Table 2.

[0085] It can be seen from the data in Table 2 that the thickness of all patches meets the standards for medical patches, and the microcurrents are all greater than 0.2 mA, which can meet the needs of activating acupuncture nerve endings. Among them, Example 12 shows higher emissivity, microcurrent, and antibacterial rates of Candida albicans and Staphylococcus aureus, and has clinical transformation potential, proving that the present invention achieves synergistic improvements in far-infrared performance, microcurrent stimulation, and antibacterial function through material modification and process optimization. Therefore, the acupuncture patch prepared in Example 12 was used in Examples 15-17.

[0086] Table 2 Far infrared emissivity test, microcurrent test and antibacterial test results of Examples 10-13

[0087] Example 15

[0088] Sixty patients with facial palsy were screened from outpatient and inpatient neurology departments at multiple hospitals using the diagnostic criteria for facial palsy in the 9th edition of Neurology. Patients ranged in age from 18 to 60 years old, and patients with other clear causes of facial palsy, such as brain tumors or trauma, as well as pregnant or lactating women and those with severe heart, liver, or kidney diseases were excluded.

[0089] Professionally trained medical staff applied the acupoint patches prepared in this invention to the patient's Yifeng, Dicang, and Jiache acupoints. Before application, the skin at the acupoints was routinely disinfected with a 75% alcohol cotton ball and then applied after the skin dried. Each patch was applied for 12 hours, with patches replaced daily. A course of treatment consisted of eight weeks of continuous application.

[0090] Before treatment, at the end of the fourth and eighth weeks of treatment, two experienced neurologists independently evaluated the patients' facial expression function according to the facial paralysis grading scale, which ranges from grade I (normal) to grade VI (complete paralysis), and recorded the changes in the patients' grades before and after treatment.

[0091] Laser Doppler flowmetry was used to measure microcirculatory blood perfusion around the Yifeng, Dicang, and Jiache acupoints before treatment, at the end of the fourth and eighth weeks. The probe was placed vertically and steadily on the skin surface at the acupoints, and the average perfusion value (PU) was recorded over 30 seconds.

[0092] The above test results can be found in Figure 1-2 . From the above test results, it can be seen that in a clinical trial of 60 patients with facial paralysis (grades III-V), after 8 weeks of application on the Yifeng acupoint, Dicang acupoint, and Jiache acupoint: the significant efficacy was 61.7% (37 / 60): the facial paralysis grade improved by ≥2 levels, and some patients recovered completely; the effective rate was 38.3% (23 / 60): improvement by ≥1 level. The blood perfusion around the acupoints increased, confirming that far-infrared radiation promotes local blood circulation. It is proven that the acupoint patch prepared by the present invention can effectively promote facial blood circulation and accelerate tissue metabolism. At the same time, the microcurrent generated by the biophotonic composite material can activate the TRPV1 ion channel and improve the function of the facial nerve. Example 16

[0093] Sixty patients with essential hypertension were selected from cardiology clinics and physical examination centers according to the diagnostic criteria of the "Guidelines for the Prevention and Treatment of Hypertension in China (2018 Revised Edition)." Patients had systolic blood pressures between 140 and 180 mmHg and diastolic blood pressures between 90 and 110 mmHg, and were aged 30 to 70 years. Patients with secondary hypertension, hypertensive crisis, severe arrhythmias, hepatic and renal insufficiency, or psychiatric illness were excluded.

[0094] Professionally trained medical staff instructed patients to apply the acupoint patches to the Yongquan, Taichong, and Quchi acupoints. Before application, the skin at the acupoints should be cleaned with warm water and allowed to dry before application. Each patch should be applied for 24 hours, replaced every three days, for 12 weeks. During treatment, patients should maintain a normal lifestyle and diet, and avoid strenuous exercise and emotional excitement.

[0095] Patients underwent 24-hour ambulatory blood pressure monitoring using an ambulatory blood pressure monitor before treatment and at the end of the fourth, eighth, and 12th weeks of treatment. Monitoring began at 8:00 AM, and blood pressure values ​​were continuously recorded every 15-30 minutes for 24 hours. The 24-hour mean systolic blood pressure (24hSBP), 24-hour mean diastolic blood pressure (24hDBP), daytime mean systolic blood pressure (dSBP), daytime mean diastolic blood pressure (dDBP), nighttime mean systolic blood pressure (nSBP), nighttime mean diastolic blood pressure (nDBP), and circadian rhythm of blood pressure were calculated.

[0096] The above test results can be found in Figure 3-4 The above test results show that in 60 patients with essential hypertension, acupoint patches applied to the Yongquan, Taichong, and Quchi acupoints demonstrated significant blood pressure-lowering effects during 12 weeks of treatment: Significant efficacy was achieved in approximately 66.7% (40 / 60), with patients experiencing a decrease in their 24-hour average systolic blood pressure (24hSBP) by ≥15 mmHg and a decrease in their diastolic blood pressure (24hDBP) by ≥10 mmHg, and normalization of their circadian rhythm. Effectiveness was achieved in 33.3% (20 / 60), with significant improvement in blood pressure (SBP decreased by 10-14 mmHg and DBP decreased by 5-9 mmHg), and some patients experienced restoration of their circadian rhythm. This suggests that the patch has a positive effect on regulating autonomic nervous system function. This is due to the far-infrared radiation improving local microcirculation at the acupoints, promoting vasodilation, and activating nerve endings at the acupoints. Example 17

[0097] Sixty patients with type 2 diabetes were screened from outpatient and inpatient endocrinology departments of multiple hospitals according to the diagnostic criteria for type 2 diabetes established by the World Health Organization (WHO) in 1999. Patients were aged 35-75 years, with glycated hemoglobin (HbA1c) levels between 7.0% and 10.0%. Patients with type 1 diabetes, gestational diabetes, acute complications of diabetes (e.g., diabetic ketoacidosis, hyperosmolar hyperglycemic syndrome), severe hepatic and renal insufficiency, and malignant tumors were excluded.

[0098] Professional medical staff applied acupuncture patches to the Zusanli, Sanyinjiao, and Pishu acupoints. Before application, the skin at the acupoints was disinfected with iodine and allowed to dry before application. Each patch was applied for 8 hours, with daily changes. A course of 16 weeks was considered a treatment course. During treatment, patients adhered to a diabetic diet and exercised regularly.

[0099] Before treatment, and at the end of the 4th, 8th, 12th, and 16th weeks of treatment, fasting venous blood was collected from the patients, and fasting blood glucose (FPG) was measured using the glucose oxidase method. At the same time, venous blood was collected 2 hours after the patients orally took 75 g of anhydrous glucose to measure 2-hour postprandial blood glucose (2hPG).

[0100] The glycated hemoglobin (HbA1c) levels of the patients were measured by high performance liquid chromatography before treatment and at the end of the 16th week of treatment.

[0101] Before treatment and at the end of the 16th week of treatment, 5 ml of fasting venous blood was collected from the patients, and the levels of total cholesterol (TC), triglyceride (TG), high-density lipoprotein cholesterol (HDL-C), and low-density lipoprotein cholesterol (LDL-C) were measured using an automatic biochemical analyzer.

[0102] Before treatment and at the end of the 16th week of treatment, fasting venous blood was collected from the patients to measure fasting plasma glucose (FPG) and fasting insulin (FINS) levels, and the insulin resistance index was calculated using the homeostasis model assessment method.

[0103] The above test results can be found in Figure 5-6 . The test results show that in the 16-week patch treatment of 60 patients with type 2 diabetes, the acupoint patches applied to Zusanli, Sanyinjiao and Pishu points showed significant blood sugar regulation effects: significant efficacy: 93.3% (56 / 60), the patients' fasting blood glucose (FPG) decreased by ≥1.4mmol / L, 2h postprandial blood glucose (2hPG) decreased by ≥2.9mmol / L, and glycosylated hemoglobin (HbA1c) decreased by ≥1.2%. Effective rate: 6.7% (4 / 60), and blood sugar indicators were partially improved. The homeostasis model assessment (HOMA-IR) showed that the patient's insulin resistance index was significantly reduced, confirming that the patch can enhance insulin sensitivity. It is proved that the present invention has significant therapeutic effects on type 2 diabetes, can effectively lower blood sugar, improve insulin resistance, and has good safety.

[0104] While embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions, and variations may be made to these embodiments without departing from the principles and spirit of the invention, and that the scope of the invention is defined by the appended claims and their equivalents.

[0105] The present invention and its embodiments are described above. Such description is not restrictive. The drawings show only one embodiment of the present invention, and actual applications are not limited thereto. In short, if a person skilled in the art is inspired by the above, and does not deviate from the purpose of the present invention, any method and embodiment similar to the technical solution without creative design shall fall within the scope of protection of the present invention.

Claims

1. A far-infrared functional bioluminescent composite material, characterized by: The invention is composed of the following components in parts by weight: 25-45 parts of modified Bian stone, 20-30 parts of medical stone, 10-20 parts of germanium stone, 5-10 parts of silicon dioxide and 5-10 parts of aluminum oxide; The modified Bianstone is prepared by the following steps: S1. Sodium bentonite and deionized water are mixed in a mass ratio of 1:5-1:10 to form a suspension, the pH is adjusted to 4-5 with a 0.3-0.5 mol / L hydrochloric acid solution, a quaternary ammonium salt cationic surfactant is added in an amount of 0.8-1.2 times the mass of the sodium bentonite, and the mixture is stirred and reacted at 60-80°C for 1-3 hours. After the reaction is completed, the mixture is filtered, washed with deionized water, dried, crushed, and passed through a 200 mesh sieve to obtain interlayer expanded pore sodium bentonite; S2, mixing a lanthanum source and an iron source in a molar ratio of 1:1-3, adding the mixture to a 30-50 g / L urea solution, and hydrothermally reacting the mixture at 180-200° C. for 12-24 h to obtain a first solution containing nano-LaFe perovskite particles, wherein the total molar ratio of urea to the lanthanum source and the iron source is 3-6:1, mixing tetrabutyl titanate with deionized water in a solid-liquid mass ratio of 1:25-40, and hydrothermally reacting the mixture at 150-180° C. for 6-8 h to obtain a second solution containing nano-TiO2 quantum dots, and dripping the second solution into the first solution in a mass ratio of 1:1-3 to the first solution, uniformly dispersing the mixture by ultrasound, and then adding 5-15% of the total mass of the solution of interlayer expanded pore sodium-based bentonite, stirring the mixture for 24-36 h, centrifuging the mixture, and drying the mixture to obtain LaFe perovskite / TiO2 quantum dot intercalation modified bentonite; S3. Mixing Bianstone powder and ethanol at a mass ratio of 1:10-20, adding 3-5% of a silane coupling agent based on the mass of the Bianstone, adjusting the pH to 4-5 with a 0.5-1.2 mol / L hydrochloric acid solution, subjecting the mixture to a high-speed shear treatment at 10,000-15,000 r / min at 60-80° C. for 2-4 hours, filtering, washing, and drying to obtain amino-functionalized Bianstone; S4. The modified Bianstone is mixed with LaFe / TiO2 intercalated modified bentonite in a mass ratio of 1:3-10, and ultrasonically dispersed in deionized water at a solid-liquid mass ratio of 1:30-50. 5-10% of the solution volume of a 0.1-0.3 mol / L potassium ferrocyanide solution and 10-20% of the solution volume of a 0.1-0.3 mol / L transition metal chloride solution are added, wherein the molar ratio of potassium ferrocyanide to transition metal chloride is 1:1-2. The mixture is self-assembled at 25-40°C for 12-24 hours. After centrifugation, washing, and vacuum drying, a modified Bianstone with a surface-loaded Prussian blue analogue is obtained.

2. The far-infrared functional biophotonic composite material according to claim 1, characterized in that: The quaternary ammonium salt type cationic surfactant is one of octadecyltrimethylammonium chloride, dioctadecyldimethylammonium chloride and hexadecyltrimethylammonium bromide.

3. The far-infrared functional biophotonic composite material according to claim 1, characterized in that: The lanthanum source is one of lanthanum nitrate, lanthanum chloride and lanthanum acetate.

4. The far-infrared functional biophotonic composite material according to claim 1, characterized in that: The iron source is one of ferric chloride, ferric nitrate and ferric sulfate.

5. The far-infrared functional biophotonic composite material according to claim 1, characterized in that: The transition metal chloride is one of ferrous chloride, cobalt chloride and nickel chloride.

6. The far-infrared functional biophotonic composite material according to claim 1, characterized in that: The silane coupling agent is a combination of one or more of KH550, KH560, KH562 and KH570.

7. An acupoint patch made of a far-infrared functional bioluminescent composite material, characterized by: The far-infrared functional biophotonic composite material according to any one of claims 1 to 6 is prepared by the following steps: (1) Medical stone, germanium stone, silicon dioxide, and aluminum oxide are added to deionized water to form a slurry with a mass fraction of 30-60%, and then ball milled in a planetary ball mill at a speed of 300-600 r / min for 2-4 hours, and then calcined at 700-900 ° C for 1-3 hours, and then quenched with water; (2) Mix the water-quenched raw materials with the modified Bianstone, heat them to 60°C at 5°C / min under nitrogen protection, hold for 0.5h, then heat them to 500-600°C at 3°C / min, hold for 1-3h, and then return to room temperature naturally; (3) The mixture obtained in step (2) is mixed with a medical acrylic pressure-sensitive adhesive in a mass ratio of 1:3-5, and a medical acupoint patch with a thickness of 0.5-1.2 mm is obtained by compression molding.

8. Use of the acupoint patch prepared from the infrared functional biophotonic composite material according to claim 7 in preparing a patch for treating facial paralysis, characterized in that: The patch is a circular structure with a diameter of 10-15 mm, a far-infrared radiation rate>0.85, and is applied to the acupuncture points for treating facial paralysis, including the Yifeng point, the Dicang point, and the Jiache point.

9. Use of the acupoint patch prepared from the infrared functional biophotonic composite material according to claim 7 in preparing a patch for treating hypertension, characterized in that: The patch is a circular structure with a diameter of 10-15 mm, a far-infrared radiation rate of >0.85, and is applied to acupuncture points for treating hypertension, including Yongquan acupoint, Taichong acupoint, and Quchi acupoint.

10. Use of the acupoint patch prepared from the infrared functional biophotonic composite material according to claim 7 in preparing a patch for treating diabetes, characterized in that: The patch is a circular structure with a diameter of 10-15 mm, a far-infrared radiation rate of >0.85, and is applied to acupuncture points for treating diabetes, including Zusanli, Sanyinjiao, and Pishu points.

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