Far-infrared functional photobiotin composite material, acupoint patch prepared from same and application of acupoint patch

Abstract

The invention discloses a far-infrared functional photobiotin composite material, an acupoint patch prepared from the far-infrared functional photobiotin composite material and application of the acupoint patch, and belongs to the technical field of far-infrared medical materials. The photobiotin composite material is prepared from the following components in parts by weight: 25 to 45 parts of modified stone needle, 20 to 30 parts of medical stone, 10 to 20 parts of germanite, 5 to 10 parts of silicon dioxide and 5 to 10 parts of aluminum oxide. The modified stone needle is prepared by processes of bentonite interlayer chambering, LaFe perovskite / TiO2 quantum dot intercalation, Prussian blue analogue loading and the like. The composite material has a far infrared emission characteristic and can generate resonance absorption with human tissues, negative oxygen ions are released through quantum dot photocatalysis, and a porous structure adsorbs inflammatory factors, namely LaFe perovskite / TiO2 quantum dot photocatalysis and cooperates with stone needle far infrared radiation to destroy bacterial cell membranes; and the medical stone releases trace elements to inhibit bacterial activity. The prepared acupoint patch is compounded with a medical pressure-sensitive adhesive through a compression molding process to generate micro-current to stimulate a TRPV1 ion channel, so that the treatment of facial paralysis, hypertension and diabetes mellitus is realized.

Description

Technical Field

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

[0002] Far-infrared materials refer to materials with the property of emitting or absorbing far-infrared rays. Far-infrared rays are electromagnetic waves with wavelengths between 5.6 - 1000 μm. Research shows that far-infrared rays with wavelengths of 5.6 - 15 μm can penetrate 3 - 5 mm into the subcutaneous tissue of the human body, highly matching the resonance absorption frequency of water molecules. By exciting molecular vibrations to generate a thermal effect, it can promote local microcirculation and cell metabolism. It has good penetration and thermal effects, and can promote blood circulation, accelerate metabolism, relieve pain, etc. Currently, far-infrared materials are mainly divided into natural mineral-based (such as bian stone, tourmaline) and synthetic materials (such as graphene, carbon fiber). Although natural mineral materials have the advantage of biocompatibility, their emissivity at room temperature is generally low, and high-temperature calcination easily leads to phase transformation and collapse of the porous structure, affecting the slow-release performance of trace elements. Artificial materials such as graphene heating films have high emissivity, but are costly and have a single function, relying only on the thermal effect and lacking synergistic functions such as antibacterial and adsorbing inflammatory factors.

[0003] By compounding far-infrared materials with patch materials to make acupoint patches, the application of far-infrared materials in acupoint treatment can be realized. However, traditional acupoint patches mostly rely on the single thermal effect of far-infrared materials, cannot activate the TRPV1 ion channel through microcurrent stimulation, affecting the efficiency of nerve signal conduction, and at the same time lacking the ability to dynamically regulate the local microenvironment. Therefore, it is necessary to propose a far-infrared functional bio-photosynthetic composite material with multiple material synergy, through the synergistic effect of far-infrared radiation and acupoint stimulation, to promote body repair and metabolism and achieve the purpose of clinical treatment. Summary of the Invention

[0004] In view of the above situation, to overcome the defects of the prior art, the present invention addresses the key problems in the prior art such as single far-infrared material band, poor functional synergy, and insufficient thermal stability. By modifying bian stone, the improvement of far-infrared emission performance, antibacterial activity, and structural stability is achieved, providing a material basis for acupoint treatment of diseases.

[0005] To achieve the above object, the following technical solution is adopted: The present invention provides a far-infrared functional bio-photosynthetic composite material, which 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.

[0006] The modified bian stone is prepared through the following steps: S1. Mix sodium-based bentonite and deionized water at a mass ratio of 1:5 - 1:10 to form a suspension. Adjust the pH to 4 - 5 with a 0.3 - 0.5 mol / L hydrochloric acid solution. Add a quaternary ammonium salt-type cationic surfactant with a mass 0.8 - 1.2 times that of the sodium-based bentonite. Stir and react at 60 - 80 °C for 1 - 3 h. After the reaction is completed, filter, wash with deionized water, dry, pulverize, and pass through a 200-mesh sieve to obtain interlayer-expanded sodium-based bentonite; S2. Mix a lanthanum source and an iron source at a molar ratio of 1:1 - 3, add them to a 30 - 50 g / L urea solution, and hydrothermally react at 180 - 200 °C for 12 - 24 h to obtain a first solution containing nano-LaFe perovskite particles, where the total molar ratio of urea to the lanthanum source and the iron source is 3 - 6:1. Mix tetrabutyl titanate and deionized water at a solid-liquid mass ratio of 1:25 - 40, and hydrothermally react at 150 - 180 °C for 6 - 8 h to obtain a second solution containing nano-TiO 2 quantum dots. Drop the second solution into the first solution according to a mass ratio of the second solution to the first solution of 1:1 - 3, disperse evenly by ultrasonic wave, then add 5 - 15% of the interlayer-expanded sodium-based bentonite based on the total mass of the solution, stir for 24 - 36 h, centrifuge and separate, and dry to obtain LaFe perovskite / TiO 2 quantum dot intercalated and modified bentonite; S3. Mix bian stone powder and ethanol at a mass ratio of 1:10 - 20, add a silane coupling agent accounting for 3 - 5% of the mass of the bian stone, adjust the pH to 4 - 5 with a 0.5 - 1.2 mol / L hydrochloric acid solution, and perform high-speed shearing treatment at 60 - 80 °C at 10000 - 15000 r / min for 2 - 4 h. After filtering, washing, and drying, obtain amino-functionalized bian stone; S4. Mix the modified bian stone and LaFe / TiO 2 intercalated and modified bentonite at a mass ratio of 1:3 - 10, ultrasonically disperse in deionized water according to a solid-liquid mass ratio of 1:30 - 50, add a 0.1 - 0.3 mol / L potassium ferrocyanide solution accounting for 5 - 10% of the solution volume and a 0.1 - 0.3 mol / L transition metal chloride solution accounting for 10 - 20% of the solution volume, where the molar ratio of potassium ferrocyanide to the transition metal chloride is 1:1 - 2. Perform self-assembly reaction at 25 - 40 °C for 12 - 24 h. After centrifugation, washing, and vacuum drying, obtain modified bian stone with a Prussian blue analogue loaded on the surface.

[0007] The quaternary ammonium salt-type cationic surfactant is one of octadecyl trimethyl ammonium chloride, didodecyl dimethyl ammonium chloride, and cetyl trimethyl ammonium bromide.

[0008] The lanthanum source is one of lanthanum nitrate, lanthanum chloride, and lanthanum acetate.

[0009] The iron source is one of ferric chloride, ferric nitrate, and ferric sulfate.

[0010] The transition metal chloride is one of ferrous chloride, cobalt chloride, and nickel chloride.

[0011] The silane coupling agent is one or a combination of more than one of KH550, KH560, KH562, and KH570.

[0012] The present invention also provides an acupoint patch prepared from the far-infrared functional bio-photonic composite material, which is made from the far-infrared functional bio-photonic composite material through the following steps: (1) Mix medical stone, germanium stone, silicon dioxide, and aluminum oxide with deionized water to form a slurry with a mass fraction of 30 - 60%, then ball mill it for 2 - 4 h with a planetary ball mill at a rotation speed of 300 - 600 r / min, then calcine it at 700 - 900 °C for 1 - 3 h, and then perform water quenching for rapid cooling; (2) Mix the raw materials after water quenching and rapid cooling with modified bian stone, heat it to 60 °C at a rate of 5 °C / min under nitrogen protection, hold for 0.5 h, then heat it to 500 - 600 °C at a rate of 3 °C / min, keep it warm for 1 - 3 h, and then naturally return to room temperature; (3) Mix the mixture obtained in step (2) with a medical acrylate pressure-sensitive adhesive in a mass ratio of 1:3 - 5, and obtain a medical acupoint patch with a thickness of 0.5 - 1.2 mm through die pressing.

[0013] The present invention also provides the application of the acupoint patch prepared from the infrared functional bio-photonic composite material: The patch is a circular structure with a diameter of 10 - 15 mm, the far-infrared emissivity > 0.85, and it is applied to the acupoints for treating facial paralysis, including Yifeng acupoint, Dicang acupoint, and Jiache acupoint; The patch is a circular structure with a diameter of 10 - 15 mm, the far-infrared emissivity > 0.85, and it is applied to the acupoints for treating hypertension, including Yongquan acupoint, Taichong acupoint, and Quchi acupoint; The patch is a circular structure with a diameter of 10 - 15 mm, the far-infrared emissivity > 0.85, and it is applied to the acupoints for treating diabetes, including Zusanli acupoint, Sanyinjiao acupoint, and Yishu acupoint.

[0014] The beneficial effects of the present invention are: (1) Due to the natural far-infrared radiation characteristics of the modified bian stone itself in the present invention, the Prussian blue analog and LaFe perovskite / TiO 2 quantum dots intercalated in bentonite loaded on its surface can generate a broader spectrum of far-infrared radiation through lattice vibration and electron transition; (2) The porous structures of the interlayer-expanded bentonite and the Prussian blue analog provide rich adsorption sites, and LaFe perovskite / TiO2 Quantum dots have photocatalytic activity and can decompose water molecules and oxygen in the air under light irradiation or thermal excitation to release negative oxygen ions. The silicate layer of bentonite can adsorb local inflammatory factors through ion exchange, thereby inhibiting the inflammatory response; (3) The far-infrared radiation of bian stone and the ability of LaFe perovskite to generate reactive oxygen species can damage the bacterial cell membrane and inhibit the growth of microorganisms. 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 play a synergistic antibacterial role; (4) The emissivity range of the bio-photoelement composite material highly matches the absorption characteristics of human tissues and can penetrate under the skin. The generated microcurrent stimulation can activate the TRPV1 ion channel, promote local blood circulation, accelerate tissue metabolism, and promote nerve regeneration. The bio-photoelement composite material has multiple synergistic antibacterial mechanisms to prevent local infection. Therefore, the acupoint patch prepared by the present invention can be applied to the treatment of facial paralysis; by releasing negative oxygen ions through the bio-photoelement composite material, it can improve the local microenvironment of the acupoints, activate the nerve endings at these acupoints, regulate nerve reflexes, and then affect the function of the cardiovascular system to play a role in lowering blood pressure. Through microcurrent stimulation, it can regulate the tension of vascular smooth muscle, dilate blood vessels, reduce peripheral resistance, and thus lower blood pressure to play a role in the treatment of hypertension; activate nerve endings, regulate the activity of the parasympathetic nerve, and achieve dynamic balance of blood pressure, which is helpful for the treatment of hypertension; this bio-photoelement composite material acts on Zusanli acupoint, Sanyinjiao acupoint, and Yishu acupoint. Through far-infrared radiation, it can improve local microcirculation, enhance the sensitivity of tissues to insulin, and the generated microcurrent stimulation is transmitted through the meridians to regulate the functions of the internal organs, promote sugar metabolism, and lower blood sugar levels. By stimulating the Yishu acupoint, it can regulate the endocrine function of the pancreas, make insulin secretion tend to be normal, thereby lowering blood sugar and being helpful for the treatment of diabetes. Description of the Drawings

[0015] Figure 1 Curative effect evaluation results of the acupoint patch prepared by the present invention in the treatment of facial paralysis (case numbers 1 - 30); Figure 2 Curative effect evaluation results of the acupoint patch prepared by the present invention in the treatment of facial paralysis (case numbers 31 - 60); Figure 3 Curative effect evaluation results of the acupoint patch prepared by the present invention in the treatment of hypertension (case numbers 1 - 30); Figure 4 Curative effect evaluation results of the acupoint patch prepared by the present invention in the treatment of hypertension (case numbers 31 - 60); Figure 5 Curative effect evaluation results of the acupoint patch prepared by the present invention in the treatment of diabetes (case numbers 1 - 30); Figure 6Efficacy evaluation results of the acupoint patch prepared for the present invention in the treatment of diabetes (case numbers 31 - 60).

[0016] The accompanying drawings are used to provide a further understanding of the present invention, and constitute a part of the specification. Together with the embodiments of the present invention, they are used to explain the present invention and do not constitute a limitation to the present invention. Detailed implementation manners

[0017] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative work belong to the scope of protection of the present invention.

[0018] Unless otherwise defined, all professional and scientific terms used herein have the same meaning as those familiar to those skilled in the art. In addition, any methods and materials similar or equivalent to the described content can be applied to the present invention. The preferred implementation methods and materials described herein are only for demonstration purposes and do not limit the content of this application.

[0019] The experimental methods in the following embodiments are all conventional methods unless otherwise specified. The test materials used in the following embodiments are all obtained from commercial channels unless otherwise specified.

[0020] In the preparation process of the acupoint patch of the present invention, a QM - 3SP2 planetary ball mill is used for ball milling, provided by Nanjing University Instrument Factory; in the preparation process of the acupoint patch of the present invention, an OTF - 1200X tube furnace type is used, provided by Hefei Kejing Materials Technology Co., Ltd.; the present invention uses an XLB - D flat vulcanizer for molding to obtain the acupoint patch, provided by Huzhou Dongfang Machinery Co., Ltd.; the present invention uses an HPZT - 200 piezoelectric coefficient tester for micro - current testing, provided by Beijing Huace Testing Instruments Co., Ltd. Example 1

[0021] A far - infrared functional bio - photonic composite material is composed of the following components in parts by weight: 25 parts of modified bian stone, 20 parts of medical stone, 10 parts of germanium stone, 5 parts of silicon dioxide, and 5 parts of aluminum oxide.

[0022] The modified bian stone is prepared through the following steps: S1. Mix sodium-based bentonite and deionized water at a mass ratio of 1:5 to form a suspension. Adjust the pH to 4 with 0.3 mol / L hydrochloric acid solution. Add octadecyltrimethylammonium chloride which is 0.8 times the mass of the sodium-based bentonite. Stir and react at 60 °C for 1 h. After the reaction is completed, filter, wash with deionized water, dry, pulverize, and pass through a 200-mesh sieve to obtain interlayer-expanded sodium-based bentonite; S2. Mix lanthanum nitrate and iron chloride at a molar ratio of 1:1, add them to a 30 g / L urea solution, and hydrothermally react at 180 °C for 12 h to obtain a first solution containing nano-LaFe perovskite particles. The total molar ratio of urea to lanthanum source and iron source is 3:1. Mix tetrabutyl titanate and deionized water at a solid-liquid mass ratio of 1:25, and hydrothermally react at 150 °C for 6 h to obtain a second solution containing nano-TiO 2 quantum dots. Drop the second solution into the first solution at a mass ratio of the second solution to the first solution of 1:1, disperse evenly by ultrasonic wave, then add interlayer-expanded sodium-based bentonite which is 5% of the total mass of the solution, stir for 24 h, centrifuge and separate, and dry to obtain LaFe perovskite / TiO 2 quantum dot intercalated and modified bentonite; S3. Mix bian stone powder and ethanol at a mass ratio of 1:10, add a silane coupling agent which is 3% of the mass of the bian stone. The silane coupling agent is KH550. Adjust the pH to 4 with 0.5 mol / L hydrochloric acid solution, and perform high-speed shearing treatment at 60 °C at 10000 r / min for 2 h. After filtering, washing, and drying, obtain amino-functionalized bian stone; S4. Mix the modified bian stone and LaFe / TiO 2 intercalated and modified bentonite at a mass ratio of 1:3, ultrasonically disperse in deionized water at a solid-liquid mass ratio of 1:30, add 0.1 mol / L potassium ferrocyanide solution which is 5% of the volume of the solution and 0.1 mol / L ferrous chloride solution which is 10% of the volume of the solution. The molar ratio of potassium ferrocyanide to ferrous chloride is 1:1. Perform self-assembly reaction at 25 °C for 12 h. After centrifugation, washing, and vacuum drying, obtain modified bian stone with a surface loaded with Prussian blue analogues. Example 2

[0023] A far-infrared functional bio-photonic composite material is composed of the following components in parts by weight: 45 parts of modified bian stone, 30 parts of medical stone, 20 parts of germanium stone, 10 parts of silicon dioxide, and 10 parts of aluminum oxide.

[0024] The modified bian stone is prepared by the following steps: S1. Mix sodium-based bentonite and deionized water at a mass ratio of 1:10 to form a suspension. Adjust the pH to 5 with 0.5 mol / L hydrochloric acid solution. Add dioctadecyldimethylammonium chloride which is 1.2 times the mass of sodium-based bentonite. Stir and react at 80 °C for 3 h. After the reaction is completed, filter, wash with deionized water, dry, pulverize, and pass through a 200-mesh sieve to obtain interlayer-expanded sodium-based bentonite; S2. Mix lanthanum chloride and iron sulfate at a molar ratio of 1:3, add them to a 50 g / L urea solution, and perform hydrothermal reaction at 200 °C for 24 h to obtain a first solution containing nano-LaFe perovskite particles. The total molar ratio of urea to lanthanum source and iron source is 6:1. Mix tetrabutyl titanate and deionized water at a solid-liquid mass ratio of 1:40, and perform hydrothermal reaction at 180 °C for 8 h to obtain a second solution containing nano-TiO 2 quantum dots. Drop the second solution into the first solution according to the mass ratio of the second solution to the first solution of 1:3, disperse evenly by ultrasonic wave, then add interlayer-expanded sodium-based bentonite which is 15% of the total mass of the solution, stir for 36 h, perform centrifugal separation, and dry to obtain LaFe perovskite / TiO 2 quantum dot intercalated and modified bentonite; S3. Mix bian stone powder and ethanol at a mass ratio of 1:20, add a silane coupling agent which is 5% of the mass of bian stone. The silane coupling agent is a combination of KH560 and KH570 at a mass ratio of 1:1. Adjust the pH to 5 with 1.2 mol / L hydrochloric acid solution, and perform high-speed shearing treatment at 80 °C at 15000 r / min for 4 h. After filtering, washing, and drying, obtain amino-functionalized bian stone; S4. Mix the modified bian stone and LaFe / TiO 2 intercalated and modified bentonite at a mass ratio of 1:10, disperse ultrasonically in deionized water according to the solid-liquid mass ratio of 1:50, add 0.3 mol / L potassium ferrocyanide solution which is 10% of the solution volume and 0.3 mol / L nickel chloride solution which is 20% of the solution volume. The molar ratio of potassium ferrocyanide and nickel chloride is 1:2. Perform self-assembly reaction at 40 °C for 24 h. After centrifugation, washing, and vacuum drying, obtain modified bian stone with Prussian blue analogs loaded on the surface. Example 3

[0025] A far-infrared functional bio-photoelement composite material is composed of the following components in parts by weight: 35 parts of modified bian stone, 25 parts of medical stone, 15 parts of germanium stone, 7.5 parts of silicon dioxide, and 7.5 parts of aluminum oxide.

[0026] The modified bian stone is prepared through the following steps: S1. Mix sodium-based bentonite and deionized water at a mass ratio of 1:7.5 to form a suspension. Adjust the pH to 4.5 with 0.4 mol / L hydrochloric acid solution. Add cetyltrimethylammonium bromide which is 1 time the mass of sodium-based bentonite. Stir and react at 70 °C for 2 h. After the reaction is completed, filter, wash with deionized water, dry, crush, and pass through a 200-mesh sieve to obtain interlayer-expanded sodium-based bentonite; S2. Mix lanthanum acetate and iron nitrate at a molar ratio of 1:2, add them to a 40 g / L urea solution, and carry out a hydrothermal reaction at 190 °C for 18 h to obtain a first solution containing nano-LaFe perovskite particles. The total molar ratio of urea to lanthanum source and iron source is 4.5:1. Mix tetrabutyl titanate and deionized water at a solid-liquid mass ratio of 1:32.5, and carry out a hydrothermal reaction at 165 °C for 7 h to obtain a second solution containing nano-TiO 2 quantum dots. Drop the second solution into the first solution according to a mass ratio of the second solution to the first solution of 1:2, disperse evenly by ultrasonic wave, then add interlayer-expanded sodium-based bentonite which is 10% of the total mass of the solution, stir for 30 h, centrifuge and separate, and dry to obtain LaFe perovskite / TiO 2 quantum dot intercalated and modified bentonite; S3. Mix bian stone powder and ethanol at a mass ratio of 1:15, add a silane coupling agent which is 4% of the mass of bian stone. The silane coupling agent is a combination of KH562 and KH570 at a mass ratio of 1:1. Adjust the pH to 4.5 with 0.8 mol / L hydrochloric acid solution, and carry out high-speed shearing treatment at 70 °C at 12500 r / min for 3 h. After filtering, washing, and drying, obtain amino-functionalized bian stone; S4. Mix the modified bian stone and LaFe / TiO 2 intercalated and modified bentonite at a mass ratio of 1:6.5, disperse ultrasonically in deionized water according to a solid-liquid mass ratio of 1:40, add a 0.2 mol / L potassium ferrocyanide solution which is 7.5% of the solution volume and a 0.2 mol / L cobalt chloride solution which is 15% of the solution volume. The molar ratio of potassium ferrocyanide and cobalt chloride is 1:1.5. Carry out a self-assembly reaction at 32.5 °C for 18 h. After centrifugation, washing, and vacuum drying, obtain modified bian stone with Prussian blue analogs loaded on the surface. Example 4

[0027] The difference between this comparative example and Example 3 is that the weight portion of the modified bian stone is 30 portions and the weight portion of medical stone is 22 portions, and the rest are the same as in Example 3. Example 5

[0028] The difference between this comparative example and Example 3 is that in step S1, the mass ratio of sodium-based bentonite to deionized water is 1:6, and the stirring reaction time is 1.5 h, and the rest are the same as in Example 3. Example 6

[0029] The difference between this comparative example and Example 3 is that in step S2, the molar ratio of lanthanum source to iron source is changed to 1:1.5, and the concentration of urea solution is changed to 35 g / L, and the rest are the same as in Example 3. Example 7

[0030] The difference between this comparative example and Example 3 is that in step S3, the mass ratio of bian stone powder to ethanol is 1:12, and the dosage of silane coupling agent is 3.5% of the mass of bian stone, and the rest are the same as in Example 3. Example 8

[0031] The difference between this comparative example and Example 3 is that in step S4, the mass ratio of modified bian stone to LaFe / TiO 2 intercalated modified bentonite is changed to 1:4, and the self-assembly reaction temperature is changed to 30 °C, and the rest are the same as in Example 3. Example 9

[0032] The far-infrared emissivity of the bio-photonic composite materials prepared in Examples 1-8 was tested in accordance with GB / T 30127-2013 "Testing and Evaluation of the Far-Infrared Performance of Textiles".

[0033] The micro-current of the bio-photonic composite materials prepared in Examples 1-8 was tested using an HPZT-200 piezoelectric coefficient tester.

[0034] The antibacterial rates of the bio-photonic composite materials prepared in Examples 1-8 against Candida albicans and Staphylococcus aureus were tested in accordance with GB / T 21510-2008 "Testing Methods for the Antibacterial Properties of Nano-Inorganic Materials".

[0035] The above test results are shown in Table 1.

[0036] It can be seen from the data in Table 1 that the emissivity of all examples is ≥0.82 (the standard GB / T 30127-2013 requires ≥0.80 to be qualified), which indicates that the synergistic effect of modified bian stone and LaFe / TiO 2 quantum dots and Prussian blue analogues significantly improves the far-infrared radiation performance. Micro-currents 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 ionic migration current, activate the TRPV1 channel, and the antibacterial rates against Candida albicans and Staphylococcus aureus are both >98.5%, far exceeding the national standard (>90%).

[0037] Table 1 Test results of far-infrared emissivity, micro-current and antibacterial properties of Examples 1-8 Serial number Far-infrared emissivity Microcurrent (mA) Inhibitory rate against Candida albicans Inhibitory rate against Staphylococcus aureus 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% 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 bio-photoelement composite material prepared in Example 6 was used to prepare acupoint patches in Examples 10 - 13. Example 10

[0038] An acupoint patch prepared from a far-infrared functional bio-photoelement composite material is made from the far-infrared functional bio-photoelement composite material through the following steps: (1) Mix medical stone, germanium stone, silicon dioxide, and aluminum oxide with deionized water to form a slurry with a mass fraction of 30%, then ball-mill it for 2 h using a planetary ball mill with a rotation speed of 300 r / min, then calcine it at 700 °C for 1 h, and then quench it rapidly with water. (2) Mix the raw materials after rapid water quenching with modified bian stone, heat it to 60 °C at a rate of 5 °C / min under nitrogen protection, hold for 0.5 h, then heat it to 500 °C at a rate of 3 °C / min, keep it warm for 1 h, and then naturally return to room temperature. (3) Mix the mixture obtained in step (2) with a medical acrylate pressure-sensitive adhesive in a mass ratio of 1:3, and obtain a medical acupoint patch with a thickness of 0.5 mm through die pressing. Example 11

[0039] An acupoint patch prepared from a far-infrared functional bio-photoelement composite material is made from the far-infrared functional bio-photoelement composite material through the following steps: (1) Mix medical stone, germanium stone, silicon dioxide, and aluminum oxide with deionized water to form a slurry with a mass fraction of 60%, then ball-mill it for 4 h using a planetary ball mill with a rotation speed of 600 r / min, then calcine it at 900 °C for 3 h, and then quench it rapidly with water. (2) Mix the raw materials after rapid water quenching with modified bian stone, heat it to 60 °C at a rate of 5 °C / min under nitrogen protection, hold for 0.5 h, then heat it to 600 °C at a rate of 3 °C / min, keep it warm for 3 h, and then naturally return to room temperature. (3) Mix the mixture obtained in step (2) with a medical acrylate pressure-sensitive adhesive in a mass ratio of 1:5, and obtain a medical acupoint patch with a thickness of 1.2 mm through die pressing. Example 12

[0040] An acupoint patch prepared from a far-infrared functional bio-photoelement composite material is made from the far-infrared functional bio-photoelement composite material through the following steps: (1) Mix medical stone, germanium stone, silicon dioxide, and aluminum oxide with deionized water to form a slurry with a mass fraction of 40%, then ball-mill it for 3 h using a planetary ball mill with a rotation speed of 500 r / min, then calcine it at 800 °C for 2 h, and then quench it rapidly with water. (2) Mix the raw materials after water quenching and rapid cooling with modified bian stone, heat it to 60°C at a rate of 5°C / min under nitrogen protection, hold for 0.5 h, then heat it to 550°C at a rate of 3°C / min, keep it warm for 2 h, and then naturally return to room temperature; (3) Mix the mixture obtained in step (2) with a medical acrylate pressure-sensitive adhesive in a mass ratio of 1:4, and obtain a medical acupoint patch with a thickness of 1.0 mm by molding. Example 13

[0041] The difference between this comparative example and Example 11 is that the mixture and the medical acrylate 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, and the rest are the same as in Example 11. Example 14

[0042] Conduct far-infrared emissivity test, microcurrent test and antibacterial test on the acupoint patches prepared in Examples 10-13, and the results are shown in Table 2.

[0043] It can be seen from the data in Table 2 that the thickness of all patches meets the medical patch standard, and the microcurrent is > 0.2 mA, which can meet the requirement of activating the nerve endings of acupoints. Among them, Example 12 shows higher emissivity, microcurrent and antibacterial rates against Candida albicans and Staphylococcus aureus, and has the potential for clinical transformation, proving that the present invention realizes the synergistic improvement of far-infrared performance, microcurrent stimulation and antibacterial function through material modification and process optimization. Therefore, the acupoint patch prepared in Example 12 is used in Examples 15-17.

[0044] Table 2 Results of far-infrared emissivity test, microcurrent test and antibacterial test of Examples 10-13 Example 15

[0045] In the outpatient and inpatient departments of neurology in multiple hospitals, 60 patients with facial paralysis were screened according to the diagnostic criteria for facial paralysis in "Neurology" (9th edition). The age range of the patients is between 18 and 60 years old. Exclude facial paralysis caused by other clear etiologies such as brain tumors and trauma, as well as pregnant or lactating women and patients with serious diseases of important organs such as the heart, liver and kidneys.

[0046] The acupoint patches prepared by the present invention are applied to the Yifeng acupoint, Dicang acupoint and Jiache acupoint of the patients by trained medical staff. Before application, first disinfect the acupoint skin with 75% alcohol cotton balls, and apply the patch after the skin is dry. The application time of each acupoint patch is 12 h, changed once a day, and continuous application for 8 weeks is a course of treatment.

[0047] Before treatment, at the end of the 4th and 8th weeks of treatment, two experienced neurologists independently evaluated the facial expression function of the patients according to the facial paralysis grading scale, which ranges from grade I (normal) to grade VI (complete paralysis), and recorded the grading changes of the patients before and after treatment.

[0048] Before treatment, at the end of the 4th and 8th weeks of treatment, a laser Doppler flowmeter was used to detect the microcirculation blood perfusion volume of the skin around the Yifeng acupoint, Dicang acupoint, and Jiache acupoint of the patients. During the measurement, the probe was vertically placed on the skin surface of the acupoint and kept stable, and the average blood perfusion value (PU) within 30 seconds was recorded.

[0049] The above test results are shown in Figure 1-2 . From the above test results, it can be seen that in the clinical trial of 60 patients with facial paralysis (grades III-V), after 8 weeks of application to the Yifeng acupoint, Dicang acupoint, and Jiache acupoint: the marked effective rate was 61.7% (37 / 60): the improvement of facial paralysis grading was ≥2 grades, and some patients recovered completely; the effective rate was 38.3% (23 / 60): the improvement was ≥1 grade. The blood perfusion volume around the acupoints increased, confirming that far-infrared radiation promoted local blood circulation. It was proved that the acupoint patch prepared by the present invention could effectively promote facial blood circulation, accelerate tissue metabolism. At the same time, the microcurrent generated by the biophotonic composite material could activate the TRPV1 ion channel and improve the function of the facial nerve. Example 16

[0050] From the outpatient department of cardiology and the physical examination center, 60 patients with essential hypertension were selected according to the diagnostic criteria of "Chinese Guidelines for the Prevention and Treatment of Hypertension (2018 Revised Edition)". The systolic blood pressure of the patients was between 140-180 mmHg, the diastolic blood pressure was between 90-110 mmHg, and the age range was 30-70 years. Patients with secondary hypertension, hypertensive crisis, severe arrhythmia, hepatic and renal insufficiency, and mental diseases were excluded.

[0051] Professional trained medical staff guided the patients to apply the acupoint patch on the Yongquan acupoint, Taichong acupoint, and Quchi acupoint by themselves. Before application, the acupoint skin was cleaned with warm water and waited to dry before application. Each acupoint patch was applied for 24 hours and replaced every 3 days, and observed continuously for 12 weeks. During the treatment, the patients maintained normal daily routines and eating habits, and avoided strenuous exercise and emotional excitement.

[0052] Before treatment, at the end of the 4th, 8th, and 12th weeks of treatment, 24-hour ambulatory blood pressure monitoring was performed on the patients using an ambulatory blood pressure monitor. The monitoring started at 8:00 am and continuously recorded the blood pressure values every 15 - 30 minutes within 24 hours. Calculate 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 blood pressure circadian rhythm.

[0053] The above test results are shown in Figure 3-4 . From the above test results, it can be seen that during the 12-week application treatment of 60 patients with essential hypertension, the acupoint patches were applied to Yongquan acupoint, Taichong acupoint, and Quchi acupoint, showing a significant antihypertensive effect: the marked effective rate was about 66.7% (40 / 60), the 24-hour mean systolic blood pressure (24hSBP) of the patients decreased by ≥15 mmHg, and the diastolic blood pressure (24hDBP) decreased by ≥10 mmHg, and the blood pressure circadian rhythm returned to normal; the effective rate was 33.3% (20 / 60), the blood pressure was significantly improved (SBP decreased by 10 - 14 mmHg, DBP decreased by 5 - 9 mmHg), and the circadian rhythm of some patients recovered. It shows that the patch has a positive effect on regulating the autonomic nerve function. This is because the local microcirculation of the acupoint is improved through far-infrared radiation, promoting vasodilation and activating the nerve endings of the acupoint. Example 17

[0054] In the outpatient and inpatient departments of the endocrinology departments of multiple hospitals, 60 patients with type 2 diabetes were screened according to the diagnostic criteria for type 2 diabetes formulated by the World Health Organization (WHO) in 1999. The patients' ages were between 35 - 75 years old, and their glycated hemoglobin (HbA1c) was between 7.0% - 10.0%. Exclude patients with type 1 diabetes, gestational diabetes, acute diabetic complications (such as diabetic ketoacidosis, hyperglycemic hyperosmolar syndrome), severe hepatic and renal insufficiency, and malignant tumors.

[0055] Professional medical staff applied acupoint patches to Zusanli acupoint, Sanyinjiao acupoint, and Yishu acupoint for the patients. Before application, the acupoint skin was disinfected with iodophor and waited to dry before application. Each acupoint patch was applied for 8 hours and replaced once a day. Continuous application for 16 weeks was regarded as one course of treatment. During the treatment period, the patients followed the principles of diabetic diet and exercised moderately.

[0056] Before treatment, at the end of the 4th, 8th, 12th, and 16th weeks of treatment, fasting venous blood of the patients was collected, and fasting blood glucose (FPG) was detected by the glucose oxidase method; at the same time, 2 hours after the patients orally took 75 g of anhydrous glucose, venous blood was collected to detect 2-hour postprandial blood glucose (2hPG).

[0057] Before treatment and at the end of the 16th week of treatment, the level of glycated hemoglobin (HbA1c) in patients was detected by high performance liquid chromatography.

[0058] Before treatment and at the end of the 16th week of treatment, 5 ml of fasting venous blood was collected from patients, and the levels of total cholesterol (TC), triglyceride (TG), high density lipoprotein cholesterol (HDL-C), and low density lipoprotein cholesterol (LDL-C) were detected by an automatic biochemical analyzer.

[0059] Before treatment and at the end of the 16th week of treatment, fasting venous blood was collected from patients to detect the levels of fasting plasma glucose (FPG) and fasting insulin (FINS), and the insulin resistance index was calculated by the homeostasis model assessment method.

[0060] The above test results are shown in Figure 5-6 . It can be seen from the test results that during the 16-week application treatment of 60 patients with type 2 diabetes, the acupoint patch was applied to Zusanli, Sanyinjiao, and Yishu acupoints, showing significant blood glucose regulation effects: the marked effective rate was 93.3% (56 / 60), the fasting plasma glucose (FPG) of patients decreased by ≥1.4 mmol / L, the 2-hour postprandial blood glucose (2hPG) decreased by ≥2.9 mmol / L, and the glycated hemoglobin (HbA1c) decreased by ≥1.2%. The effective rate was 6.7% (4 / 60), and the blood glucose indexes were partially improved. The homeostasis model assessment (HOMA-IR) showed that the insulin resistance index of patients decreased significantly, confirming that the patch could enhance insulin sensitivity. It was proved that the present invention had a significant curative effect on type 2 diabetes, could effectively reduce blood glucose, improve insulin resistance, and had good safety.

[0061] Although the embodiments of the present invention have been shown and described, it will be understood by those of ordinary skill in the art that various changes, modifications, substitutions, and variations can be made to these embodiments without departing from the principles and spirit of the present invention, and the scope of the present invention is defined by the appended claims and their equivalents.

[0062] The present invention and its embodiments have been described above. Such description is not restrictive. What is shown in the drawings is only one of the embodiments of the present invention, and the actual application is not limited thereto. Generally speaking, if those of ordinary skill in the art are inspired by it and design similar ways and embodiments to this technical solution without creative efforts without departing from the purpose of the present invention, they shall fall within the protection scope of the present invention.

Claims

1. A far-infrared functional bioluminescent composite material, characterized in that: 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 Bian stone is prepared by the following steps: S1. Mix sodium bentonite and deionized water in a mass ratio of 1:5-1:10 to form a suspension, adjust the pH to 4-5 with a 0.3-0.5 mol / L hydrochloric acid solution, add a quaternary ammonium salt cationic surfactant in an amount of 0.8-1.2 times the mass of the sodium bentonite, stir and react at 60-80°C for 1-3h, filter after the reaction is completed, wash with deionized water, dry, crush, and pass 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 hours 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 hours 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 sodium bentonite, stirring the mixture for 24-36 hours, 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 the mass of Bianstone to a silane coupling agent, 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 10000-15000 r / min for 2-4 h at 60-80°C, 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 in a solid-liquid mass ratio of 1:30-50, and 0.1-0.3 mol / L potassium ferrocyanide solution of 5-10% by volume of the solution and 0.1-0.3 mol / L transition metal chloride solution of 10-20% by volume of the solution are added, wherein the molar ratio of potassium ferrocyanide to transition metal chloride is 1:1-2, and self-assembly reaction is carried out at 25-40°C for 12-24h. After centrifugation, washing, and vacuum drying, a modified Bianstone with a surface loaded with a Prussian blue analogue is obtained.

2. The far-infrared functional bioluminescent 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 bioluminescent 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 bioluminescent 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 bioluminescent 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 bioluminescent 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 acupuncture point patch made of a far-infrared functional bioluminescent composite material, characterized in that: The far-infrared functional bioluminescent composite material according to any one of claims 1 to 6 is prepared by the following steps: (1) Adding medical stone, germanium stone, silicon dioxide and aluminum oxide to deionized water to form a slurry with a mass fraction of 30-60%, then milling it in a planetary ball mill at a speed of 300-600 r / min for 2-4 hours, then calcining it at 700-900°C for 1-3 hours, and then quenching it with water; (2) Mix the water-quenched raw material with the modified Bian stone, heat it to 60°C at 5°C / min under nitrogen protection, keep it for 0.5h, then heat it to 500-600°C at 3°C / min, keep it 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 acupuncture point patch having a thickness of 0.5-1.2 mm is obtained by compression molding.

8. The use of the acupuncture patch prepared from the infrared functional bioluminescent composite material as claimed in claim 7, 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 acupuncture points for treating facial paralysis, including Yifeng point, Dicang point, and Jiache point.

9. The use of the acupuncture patch prepared from the infrared functional bioluminescent composite material according to claim 7, 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 acupuncture points for hypertension treatment, including Yongquan point, Taichong point, and Quchi point.

10. The use of the acupuncture patch prepared from the infrared functional bioluminescent composite material according to claim 7, 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 diabetes treatment acupuncture points, including Zusanli, Sanyinjiao, and Pishu points.

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