Preparation method and application of graphene pain-relieving health-care paste

Abstract

The invention provides a preparation method and application of graphene pain-relieving health-care paste, and the method comprises the following steps: mixing carrageenan with water to obtain a carrageenan solution, and carrying out ionization degradation on the carrageenan solution to obtain a carrageenan oligosaccharide solution; the preparation method comprises the following steps: stirring graphene oxide and a carrageenan oligosaccharide solution, cleaning to obtain a mixed solution, adding sodium alginate into the mixed solution to prepare a gel precursor, and adding an anhydrous calcium chloride solution and effective components into the gel precursor to obtain the pain-relieving gel, and drying the gel to obtain the health-care paste. The health-care ointment has the effects of promoting blood circulation, activating collaterals and inhibiting inflammation, and is suitable for various chronic pains such as rheumatic arthritis and lumbar muscle degeneration and acute pains such as traumatic injury and muscle strain; the composition is also suitable for auxiliary relieving of postoperative pain, and has safety and long-term effect. Due to the thermal conductivity of the graphene oxide in the health-care cream, local skin blood circulation can be accelerated, the permeation efficiency of the herbal extract is improved, and the medicine effect of the effective components is improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of analgesic ointment, in particular to a preparation method and application of a graphene pain-relieving health ointment. BACKGROUND

[0002] Biobased gel is a three-dimensional network material formed by physical or chemical cross-linking of natural biological macromolecules. They can absorb and hold a large amount of water, have good biocompatibility and biodegradability, and have good use effect in biological medicine. It has significant antibacterial, antioxidant and anti-inflammatory capacity, can continuously release the loaded material, promote skin regeneration, and effectively avoid wound infection. The pore structure and water retention of biobased hydrogel are suitable for drug encapsulation and sustained release, and by introducing stimulus-responsive groups, the gel can release drugs under specific conditions or locations, improving drug utilization.

[0003] However, in the prior art, the mechanical properties and thermal conductivity of the biobased gel are poor due to its own characteristics, thereby limiting the practical application of the biobased gel. SUMMARY

[0004] In order to solve the above problems, the present application provides a preparation method and application of a graphene pain-relieving health ointment, which uses natural plant extracts as effective components and combines biobased gel with high thermal conductivity to improve the anti-inflammatory and pain-relieving effects in drug delivery and reduce the problem of low bioactivity of external drugs.

[0005] In order to achieve the above purpose, the technical scheme adopted by the present application is as follows:

[0006] In a first aspect, the present application provides a preparation method of a graphene pain-relieving health ointment, which comprises the following steps: step S1. mixing carrageenan and deionized water at a mass-volume ratio of 1:150-250 to prepare a carrageenan solution with a concentration of 0.5-1wt%, and ionically degrading the carrageenan solution to obtain a carrageenan oligosaccharide solution; step S2. mixing graphene oxide and the carrageenan oligosaccharide solution at a mass ratio of 1:70-120, then ultrasonic cleaning to obtain a mixed solution, adding sodium alginate with a mass ratio of 1:0.03-0.05 to the mixed solution until dissolved to prepare a gel precursor, and adding anhydrous calcium chloride solution with a mass ratio of 1:5 and a concentration of 5wt%, and effective components with a mass ratio of 95:1 to the gel precursor to obtain a pain-relieving gel; step S3. vacuum drying the gel in a freeze-drying machine with a cold trap temperature of-50℃ for 48h to obtain a health ointment.

[0007] In some specific implementations, the effective components include the following components by weight percentage: Heilu Tiger extract 7% to 10%, Angelica extract 6% to 9%, Olibanum extract 5% to 8%, Peony extract 3% to 6%, Sanchi root extract 5% to 8%, Danshen root extract 4% to 7%, Notopterygium extract 4% to 7%, Rhizoma Pruni extract 3% to 6%, Ginseng extract 1% to 4%, Artemisia extract 5% to 9%, Eucommia extract 4% to 7%, Chuanxiong extract 4% to 7%, Bidentata extract 1% to 3%, Crocus extract 1% to 3%, Rhizoma Polygonati extract 1% to 3%, Rhus extract 3% to 6%, Rhizoma Stellariae extract 5% to 9%, Magnolia extract 4% to 7%.

[0008] In some specific implementations, the effective components include the following components by weight percentage: Heilu Tiger extract 9%, Angelica extract 8%, Olibanum extract 6%, Peony extract 5%, Sanchi root extract 6%, Danshen root extract 5%, Notopterygium extract 6%, Rhizoma Pruni extract 4%, Eucommia extract 5%, Ginseng extract 2%, Artemisia extract 8%, Eucommia extract 5%, Chuanxiong extract 5%, Bidentata extract 2%, Crocus extract 2%, Rhizoma Polygonati extract 2%, Rhus extract 5%, Rhizoma Stellariae extract 8%, Magnolia extract 5%.

[0009] In some specific implementations, the ionization degradation takes two electrode sheets as the cathode and anode of the ionization degradation reaction, controls the electrode sheet distance to be 3 cm, the current size to be 10 mA, the air flow rate to be 1 L / min, and the ionization time to be 60 to 300 min.

[0010] In some specific implementations, the graphene oxide is obtained by mixing graphite powder and concentrated sulfuric acid at a mass ratio of 1:37 to 55, sequentially adding phosphorus pentoxide and potassium dichromate in the mixed solution, stirring, and then performing secondary acidification based on the obtained graphene oxide; the mass ratio of the phosphorus pentoxide to the graphite powder is 1:0.5 to 2, and the mass ratio of the potassium dichromate to the graphite powder is 4 to 6:1.

[0011] In some specific implementations, the secondary acidification based on the graphene oxide includes: adding the graphene oxide into concentrated sulfuric acid, again adding potassium dichromate for stirring, and then transferring to an ice bath after stirring, and then performing ion washing to the center and drying to obtain graphene oxide.

[0012] In some specific implementation manners, the method further comprises: obtaining a graphene oxide aqueous dispersion, and dissolving hydroxypropyl cellulose in deionized water to obtain a solution, and mixing the graphene oxide aqueous dispersion with the solution, stirring, and drying to obtain modified graphene oxide; the mass ratio of the hydroxypropyl cellulose to the graphene oxide is 1:2.

[0013] In some specific implementation manners, the method further comprises adding sodium alginate with a mass ratio of 1:0.03-0.05 into the mixed solution until completely dissolved, and adding glycerol into the solution after dissolving and stirring to obtain a gel precursor.

[0014] In some specific implementation manners, the anhydrous calcium chloride solution is prepared by mixing distilled water with a mass ratio of 1:15-20.

[0015] In a second aspect, the application provides an application of the analgesic external dressing prepared by the method in any of the above aspects on a medical dressing.

[0016] In the technical scheme provided in the application, a preparation method of a graphene analgesic health cream and an application thereof are provided, and by dispersing graphene in a gel and adding effective components into the gel, an external dressing with analgesic effect can be obtained. Moreover, by adding extracts of black tiger, frankincense and peony, an anti-inflammatory analgesic effect can be achieved, by adding extracts of notoginseng, salvia miltiorrhiza and radix cyathulae, an effect of activating blood and dredging collaterals can be achieved, by adding extracts of naringenin, angelica sinensis and phellodendri cortex, an effect of removing dampness and strengthening sinews can be achieved, and by adding extracts of ginseng, angelica sinensis and phellodendri cortex, an effect of regulating constitution can be achieved, so that multiple herbal extracts are reused as an external dressing, the effects of the above-mentioned drugs can be achieved, and the activity of the external use of the drugs can be improved by improving the heat conduction. BRIEF DESCRIPTION OF DRAWINGS

[0017] In order to more clearly illustrate the technical scheme in the application, the drawings needed in the following embodiment description will be briefly introduced. Obviously, the drawings in the following description are only some embodiments of the application, and other drawings can be obtained by those skilled in the art without creative effort.

[0018] Figure 1 is a preparation method flowchart of a graphene analgesic external dressing provided in the application.

[0019] Figure 2 is a first schematic diagram of experimental results provided in the application.

[0020] Figure 3is a second schematic diagram of experimental results provided by the invention application. DETAILED DESCRIPTION

[0021] In order to make the purposes, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be described clearly and completely below. If specific conditions are not specified in the embodiments, the conditions are implemented according to conventional conditions or the conditions suggested by the manufacturers. If the reagents or instruments used are not specified by the manufacturers, they are all conventional products that can be purchased in the market. The embodiments described below are part of the embodiments of the present application, but not all the embodiments. All other embodiments obtained by those skilled in the art without creative labor on the basis of the embodiments in the present application all belong to the scope of protection of the present application.

[0022] In one specific embodiment of the present application, a pain-relieving external dressing is provided, the components of which include 97% to 99% base material and 1 to 3% effective components in terms of weight parts. Among them, the base material is the gel structure loaded with effective components in the present embodiment, and the effective components are the composition that produces a direct bacteriostatic effect.

[0023] Among them, the gel in the present embodiment is different from the prior art in that it uses a bio-based gel. Moreover, in order to improve the comprehensive performance of the bio-based gel, compared with the prior art, graphene is added in the gel group to improve the heat conduction and antibacterial performance of the gel, to make an external dressing, and to directly act on the surface of human skin by using the high heat conduction and antibacterial performance of the gel, so that the effective components can effectively penetrate and improve the medicinal and health care effect of the effective components.

[0024] Specifically, the effective components in the present embodiment include 7% to 10% of black tiger extract, 6% to 9% of angelica extract, 5% to 8% of frankincense extract, 3% to 6% of peony extract, 5% to 8% of sanchi root extract, 4% to 7% of salvia miltiorrhiza root extract, 4% to 7% of notopterygium extract, 3% to 6% of angelica pubescens extract, 4% to 7% of phellodendron bark extract, 1% to 4% of ginseng extract, 5% to 9% of artemisia annua extract, 4% to 7% of eucommia ulmoides extract, 4% to 7% of chuanxiong extract, 1% to 3% of caesalpinia japonica extract, 1% to 3% of ligusticum chuanxiong extract, 1% to 3% of crocus sativus extract, 1% to 3% of sparganium extract, 3% to 6% of gallnut extract, 5% to 9% of rhizoma sinodendron extract, and 4% to 7% of magnolia officinalis extract.

[0025] Among them, the extract of black tiger contains lignans and alkaloids, can inhibit inflammatory factors, promote blood circulation and relieve pain, and has obvious effect on rheumatic pain, sprains and injuries; the extract of frankincense can double inhibit 5-lipoxygenase (5-LO) and human leukocyte elastase (HLE), block the production of leukotrienes, has anti-inflammatory and analgesic effects, and can promote tissue repair and has obvious effect on arthritis and muscle sprain; the extract of angelica can improve dysmenorrhea and joint cold pain; the extract of peony can inhibit COX-2 pathway and reduce PGE2 release, has spasmolysis and analgesic effect, and can assist to relieve muscle spasm and chronic inflammatory pain; the notoginseng saponin in the extract of sanchi can inhibit platelet aggregation, promote microcirculation, has the effect of removing blood stasis, stopping bleeding, detumescence and pain relief, and is suitable for sprains and thrombotic pain; the tanshinone II A in the extract of salvia miltiorrhiza can improve hemodynamics and scavenge free radicals, has the effects of activating blood and dredging channels, and has synergistic effect on pain caused by cardiovascular and cerebrovascular diseases; the ligustrazine in the extract of chuanxiong can dilate blood vessels and increase coronary blood flow, has the effects of ascending to the top of the head and descending to the blood sea, and can treat headache and rheumatic pain; the flavonoid components in the extract of caudate vine activate the ERK signaling pathway, have the effects of tonifying blood, relaxing muscles and collaterals, and can improve limb numbness and menstrual irregularity related pain; the extract of qianghuo and duhuo can inhibit the NF-κB pathway, has the effects of dispelling cold and dampness, and treating rheumatic pain; the extract of eucommia ulmoides can promote bone cell proliferation, has the effects of tonifying liver and kidney and strengthening bones and joints, and can relieve soreness of waist and knees and osteoporosis pain; the alkaloids in the extract of rhizoma sinodendri can relax skeletal muscles, have the effects of relaxing muscles and collaterals, and can eliminate muscle stiffness after exercise; the ginsenosides in the extract of human body can regulate the HPA axis and improve the pain threshold, have the effects of tonifying qi and strengthening the body, enhance the pain tolerance, and relieve chronic fatigue pain; the artesunate in the extract of artemisia can inhibit NLRP3 inflammasome, has the effects of clearing heat and removing pathogenic factors, and can assist to relieve dampness and pain; the berberine in the extract of phellodendron bark can inhibit the secretion of IL-1β and IL-6, has the effects of clearing heat and drying dampness, and treating joint pain caused by damp-heat downward transmission; the extract of crocus can regulate 5-HT receptors, has the effects of activating blood and removing blood stasis, relieving depression and anxiety, and improving mood related pain.

[0026] In the embodiment, the above-mentioned effective components are all extracts of natural plants, and their effects are more gentle than the antibiotics and hormone drugs used in the prior art. Moreover, the combined effects of the effective components provided in the embodiment are not simply analgesic effects. Through the combination of the above-mentioned effective components, different situations can be correspondingly solved. Specifically, the combination of the extracts of frankincense, black tiger and artemisia annua can cover the whole process of inflammation, the combination of the extracts of peony, angelica and chuanqiong can synergistically reduce pain sensitivity; the combination of the extracts of notoginseng and salvia miltiorrhiza can activate blood and remove blood stasis, thereby the combination of the extracts of notoginseng and salvia miltiorrhiza with the extracts of notopterygium and angelica pubescens can achieve the effect of dispelling wind and removing dampness; the extracts of eucommia ulmoides and stretchy grass can relax muscles and strengthen bones, and the combination of the extracts of eucommia ulmoides and stretchy grass with the extracts of caesalpinia diacanthoides can achieve the repair of the damage to the motor system; the extracts of phellodendron amurense and artemisia annua are both cold in nature, and the combination of the extracts of phellodendron amurense and artemisia annua with ginseng and angelica can avoid dryness-heat damaging yin or cold stagnation of blood; the combination of the analgesic effect of the extract of notoginseng and the astringent hemostatic effect of the extract of gallnut can achieve the control of the risk of bleeding.

[0027] From the above, it can be seen that the effective components of the analgesic external dressing provided in the embodiment use a variety of natural plant extracts and the combination of the effective components can improve the realization of the analgesic effect.

[0028] The substrate in the embodiment is used to load, transfer and release the above-mentioned effective components. The substrate is a biological gel. Commonly used raw materials of biological gel include sodium alginate, chitosan, gelatin, collagen and the like. These materials are widely available, renewable and pollution-free, and have high application value in biomedicine. However, biological gel still faces many technical problems in practical application. The heat conduction and antibacterial properties of biological gel are poor, and if it is used as a material for the above-mentioned effective components and as a dressing, it is easy to cause problems such as incomplete release of effective components due to low temperature and inactivation of effective components due to external bacterial interference when directly used externally.

[0029] Therefore, in the use scenario of the embodiment, the substrate is an improved biological gel. Specifically, in the embodiment, the heat conduction effect and stability are improved by adding graphene into the biomass gel, so that the biological gel is combined with the effective components, and the gel is used as an analgesic external dressing.

[0030] Specifically, referring to Figure 1 , a preparation method for preparing a graphene analgesic external dressing is provided. The preparation method comprises the following steps:

[0031] Step S11. A carrageenan solution with a concentration of 0.5-1 wt% is prepared by mixing carrageenan with deionized water at a mass-volume ratio of 1:150-250, and the carrageenan solution is ionically degraded to obtain a carrageenan oligosaccharide solution.

[0032] Step S12. A mixed solution is obtained by magnetically stirring graphene oxide and the carrageenan oligosaccharide solution at a mass ratio of 1:70-120, and then ultrasonic cleaning, and sodium alginate is added to the mixed solution at a mass ratio of 1:0.03-0.05 until dissolved to prepare a gel precursor, and a 5 wt% anhydrous calcium chloride solution at a mass ratio of 1:5 and the effective component at a mass ratio of 95:1 are added to the gel precursor to obtain a pain-relieving gel.

[0033] Step S13. The gel is placed in a freeze dryer with a cold trap temperature of -50°C and vacuum dried for 48 h to obtain a health care paste.

[0034] In this embodiment, the ionically degradation of the carrageenan solution is performed in a free radical stripping device, specifically, a direct current is used as the power source, two electrode sheets are used as the cathode and anode for the free radical reaction, the distance between the electrode sheets is controlled to be 30 cm, the current size is 10 mA, the air flow rate is 1.0 L / min, and the electrolysis time is 60-300 min. Then the degraded solution is centrifuged at 10,000 rpm / min for 10 min to obtain the carrageenan oligosaccharide solution. The carrageenan is a high molecular sulfated polysaccharide extracted from marine red algae, and the low molecular weight carrageenan oligosaccharide has higher solubility, biological activity and functional properties, such as antioxidant, antibacterial, and immune regulation effects. In this embodiment, the low molecular weight carrageenan oligosaccharide can be directly obtained by free radical degradation.

[0035] In this embodiment, the graphene oxide is obtained by mixing graphite powder with concentrated sulfuric acid at a mass ratio of 1:37-55, and then adding phosphorus pentoxide and potassium dichromate in sequence to the stirred solution, and slowly stirring in a 80°C water bath for 4 h. After filtration and drying, the graphene oxide is obtained. The mass ratio of phosphorus pentoxide to graphite powder is 1:0.5-2, and the mass ratio of potassium dichromate to graphite powder is 4-6:1. Then, concentrated sulfuric acid is added to the graphene oxide, followed by the addition of the same amount of potassium dichromate, and slowly stirring at 35°C for 2 h. After the reaction is completed, the solution is transferred to an ice bath, and a 30% hydrogen peroxide solution is added dropwise, and washed by centrifugation until neutral, and dried to obtain graphene oxide.

[0036] It is worth noting that the interlayer interaction of graphene oxide is balanced by electrostatic repulsion, π-π interplanar attraction, hydrogen bonding and van der Waals force, which hinders the dispersion of graphene oxide in the polymer gel solution. The stretched polymer chain not only occupies the effective space of the solution, but also has rich functional groups which are easy to hydrolyze and change the solution environment, resulting in unbalanced interaction between graphene oxide layers. Strong π-π interaction causes regional stacking, which hinders the dispersion of graphene oxide in the solution.

[0037] Therefore, in the present embodiment, the obtained graphene oxide is also modified. Specifically, the graphene oxide is added to deionized water, stirred at room temperature for 30 min using a magnetic stirrer, and then dispersed for 30 min using an ultrasonic cleaner until a uniform graphene oxide water dispersion is obtained. At the same time, hydroxypropyl cellulose is added to the graphene oxide water dispersion for dissolution, wherein the mass ratio of hydroxypropyl cellulose to graphene oxide water dispersion is 1:2. After stirring at room temperature, the modified graphene oxide is obtained after standing and defoaming, and is dried to obtain graphene oxide powder.

[0038] The graphene oxide treated by the above method is mixed with carrageenan oligosaccharide solution at a mass ratio of 1:70-120, stirred on a magnetic stirrer for 1 h, and then placed in an ultrasonic cleaner for ultrasonic treatment at an ultrasonic power of 420 W and an ultrasonic time of 4 h to obtain a mixed solution. Sodium alginate with a mass ratio of 1:0.03-0.05 is added to the mixed solution until it is completely dissolved, and glycerol with a mass ratio of 1:0.05 is added to the dissolved solution and stirred to obtain a gel precursor. Anhydrous calcium chloride with a mass ratio of 1:15-20 is mixed with distilled water to obtain a 5wt% anhydrous calcium chloride solution, and then the effective components are added to the anhydrous calcium chloride solution. The gel precursor is laid on a polytetrafluoroethylene flat plate and soaked in the anhydrous calcium chloride solution, and after standing for 12 h, a pain-relieving gel is formed.

[0039] Finally, the gel is placed in a freeze dryer with a cold trap temperature of -50°C and vacuum dried for 48 h to obtain a health care paste.

[0040] Example 1

[0041] The embodiment of the present application provides a graphene analgesic external dressing, which comprises 97% of a base material and 3% of an effective component by weight. The effective component comprises the following components by weight: 7% of black tiger extract, 6% of angelica extract, 5% of frankincense extract, 3% of peony root extract, 5% of sanchi root extract, 7% of salvia miltiorrhiza root extract, 7% of notopterygium root extract, 6% of radix angelicae pubescentis extract, 4% of phellodendron bark extract, 4% of ginseng extract, 5% of artemisia vulgaris extract, 4% of eucommia ulmoides oliver extract, 4% of cnidium officinale extract, 3% of morinda officinalis extract, 3% of saffron extract, 3% of sparganium stoloniferum extract, 6% of gallnut extract, 9% of rhizoma camphorati extract and 6% of magnolia officinalis extract.

[0042] The embodiment of the present application also provides a preparation method of the graphene analgesic external dressing, which comprises the following steps:

[0043] Preparation of graphene oxide:

[0044] Step S11. 100g of graphite powder is mixed and stirred with 3700ml of concentrated sulfuric acid, and 50g of diphosphorus pentoxide and 400g of potassium dichromate are sequentially added to the stirred solution, and slowly stirred in a 80℃ water bath for 4h. After filtration and drying, 60g of graphene oxide is obtained.

[0045] Step S12. Then, 400g of potassium dichromate is added to the concentrated sulfuric acid, and slowly stirred at 35℃ for 2h. After the reaction is completed, the solution is transferred to an ice bath, and a 30% hydrogen peroxide solution is added dropwise. Finally, the solution is washed to neutral by centrifugation, and dried to obtain 50g of graphene oxide.

[0046] Step S13. 50g of graphene oxide is added to deionized water, and stirred at room temperature for 30min using a magnetic stirrer. Then, the solution is ultrasonically dispersed for 30min using an ultrasonic cleaner until a uniform graphene oxide aqueous dispersion is obtained. Then, hydroxypropyl cellulose is added to the graphene oxide aqueous dispersion for dissolution, and stirred at room temperature. After standing and defoaming, modified graphene oxide is obtained, and dried to obtain 50g of graphene oxide powder.

[0047] Preparation of carrageenan oligosaccharide:

[0048] Step S21. 20g of carrageenan is mixed with 30L of deionized water to prepare a 0.5wt% carrageenan solution, which is heated and stirred at 70℃ using a heat collecting constant temperature magnetic stirrer until completely dissolved.

[0049] Step S22. The prepared carrageenan solution is added to a free radical stripping device for degradation. A direct current is used as a power source, and two electrode sheets are used as a cathode and an anode for free radical reaction. The distance between the electrode sheets is controlled to be 3cm, the current size is 10mA, the air flow rate is 1L / min, and the electrolysis time is 60min.

[0050] Step S23. Centrifuge the degraded solution at 10000 rpm / min for 10 min to obtain a 5000 g carrageenan oligosaccharide solution after degradation.

[0051] Preparation of the dressing:

[0052] Step S31. Mix 50 g of graphene oxide powder with 5 Kg of carrageenan oligosaccharide solution, stir for 1 h on a magnetic stirrer, then set the ultrasonic power to 420 W in an ultrasonic cleaner and ultrasonicate for 4 h to obtain a mixed solution, and add 200 g of sodium alginate to the mixed solution in batches until completely dissolved, and add 250 ml of glycerol and stir for 5 h to obtain a gel precursor.

[0053] Step S32. Weigh 1250 g of anhydrous calcium chloride and 23750 g of distilled water to prepare a 5 wt% anhydrous calcium chloride solution, and add the effective components to the anhydrous calcium chloride solution, and lay the gel precursor on a polytetrafluoroethylene plate, and immerse the gel precursor in the anhydrous calcium chloride solution with the effective components, and stand for 12 h to form a gel.

[0054] Step S33. Place the gel in a freeze dryer with a cold trap temperature of -50°C and vacuum dry for 48 h to obtain a health care paste.

[0055] Example 2

[0056] The example of the present application provides a graphene analgesic external dressing, which differs from example 1 in that the example includes the following components by weight: 98% substrate and 2% effective component, and the effective component includes the following components by weight: black tiger extract 9%, angelica extract 8%, frankincense extract 6%, peony extract 5%, sanchi root extract 6%, danshen root extract 5%, notopterygium extract 6%, rhizoma lumbry extract 4%, phellodendron bark extract 5%, ginseng extract 2%, artemisia annua extract 8%, eucommia extract 5%, chuanxiong extract 5%, kudzu vine extract 2%, inula extract 2%, saffron extract 2%, sparganium extract 2%, gallnut extract 5%, rhizoma sinodendron extract 8%, magnolia extract 5%.

[0057] The example of the present application also provides a preparation method of a graphene analgesic external dressing, which includes the following steps:

[0058] Preparation of graphene oxide:

[0059] Step S11. Mix 100 g of graphite powder with 4500 ml of concentrated sulfuric acid and stir, and then add 100 g of phosphorus pentoxide and 500 g of potassium dichromate to the stirred solution, and slowly stir in a 80°C water bath for 4 h, and then filter and dry to obtain 65 g of graphene oxide.

[0060] Step S12. Then add 500g of potassium dichromate in concentrated sulfuric acid, slowly stirring at 35℃ for 2h, after the reaction is completed, transfer to ice bath, drop 30% concentration of hydrogen peroxide solution, finally washed to neutral by centrifugation, dry to obtain 60g of graphene oxide.

[0061] Step S13. 60g of graphene oxide is added to deionized water, stirred at room temperature for 30min using a magnetic stirrer, and then ultrasonically dispersed for 30min using an ultrasonic cleaner until a uniform graphene oxide aqueous dispersion is obtained; then add hydroxypropyl cellulose to the graphene oxide aqueous dispersion for dissolution, stir at room temperature, then stand to defoam to obtain modified graphene oxide, and dry to obtain 60g of graphene oxide powder.

[0062] Preparation of carrageenan oligosaccharide:

[0063] Step S21. Mix 20g of carrageenan with 40L of deionized water to prepare a carrageenan solution with a concentration of 0.7wt%, and heat and stir in a heat collecting constant temperature magnetic stirrer at 70℃ until completely dissolved.

[0064] Step S22. Add the prepared carrageenan solution to the radical peeling device for degradation, use direct current as the power source, take two electrode sheets as the cathode and anode of the radical reaction, control the distance between the electrode sheets to be 3cm, the current size to be 10mA, the air flow rate to be 1L / min, and the electrolysis time to be 200min.

[0065] Step S23. Centrifuge the degraded solution at 10000rpm / min for 10min to obtain 5200g of degraded carrageenan oligosaccharide solution.

[0066] Preparation of dressing:

[0067] Step S31. Mix 60g of graphene oxide powder with 5.2Kg of carrageenan oligosaccharide solution, stir for 1h on a magnetic stirrer, then set the ultrasonic power to 420W in an ultrasonic cleaner, ultrasonically for 4h to obtain a mixed solution, and then add 300g of sodium alginate to the mixed solution in batches until completely dissolved, and add 400ml of glycerol and stir for 5h to obtain a gel precursor.

[0068] Step S32. Weigh 1250g of anhydrous calcium chloride and 23750g of distilled water to prepare a 5wt% anhydrous calcium chloride solution, and add the above effective components to the anhydrous calcium chloride solution, and then lay the gel precursor on a polytetrafluoroethylene plate, and immerse the gel precursor in the anhydrous calcium chloride solution with the effective components, and stand for 12h to form a gel.

[0069] Step S33. The gel is placed in a freeze dryer with a cold trap temperature of -50℃ and vacuum dried for 48h to obtain the health care paste.

[0070] Example 3

[0071] The embodiment of the present application provides a graphene analgesic external dressing, which is different from the embodiment 1 in that the embodiment comprises the following components by weight: 98.4% of the base material and 1.6% of the effective component. The effective component comprises the following components by weight: 10% of the extract of black tiger, 9% of the extract of angelica, 8% of the extract of frankincense, 6% of the extract of peony root, 8% of the extract of sanchi root, 7% of the extract of salvia miltiorrhiza root, 7% of the extract of notopterygium, 6% of the extract of radix angelicae pubescentis, 6% of the extract of phellodendron, 1% of the extract of ginseng, 5% of the extract of artemisia annua, 4% of the extract of eucommia ulmoides, 4% of the extract of chuanxiong, 1% of the extract of caesalpinia, 1% of the extract of inula, 1% of the extract of saffron, 1% of the extract of sparganium, 3% of the extract of gallnut, 5% of the extract of rhizoma sinodendri, and 7% of the extract of magnolia officinalis.

[0072] The embodiment of the present application further provides a preparation method of the graphene analgesic external dressing, which comprises the following steps.

[0073] Preparation of graphene oxide:

[0074] Step S11. 100g of graphite powder is mixed and stirred with 4500ml of concentrated sulfuric acid, and 100g of diphosphorus pentoxide and 500g of potassium dichromate are sequentially added to the stirred solution, and slowly stirred in a 80℃ water bath for 4h. After filtration and drying, 65g of graphene oxide is obtained.

[0075] Step S12. Then 500g of potassium dichromate is added to the concentrated sulfuric acid, and slowly stirred at 35℃ for 2h. After the reaction is completed, the solution is transferred to an ice bath and a 30% hydrogen peroxide solution is added dropwise. Finally, the solution is washed to neutral by centrifugation, and dried to obtain 60g of graphene oxide.

[0076] Step S13. 60g of graphene oxide is added to deionized water and stirred at room temperature for 30min using a magnetic stirrer. Then, an ultrasonic cleaner is used for ultrasonic dispersion for 30min until a uniform graphene oxide aqueous dispersion is obtained. Then, hydroxypropyl cellulose is added to the graphene oxide aqueous dispersion and dissolved. After stirring at room temperature, the modified graphene oxide is obtained after standing and defoaming, and dried to obtain 60g of graphene oxide powder.

[0077] Preparation of carrageenan oligosaccharide:

[0078] Step S21. 20g of carrageenan is mixed with 30L of deionized water to prepare a 1wt% carrageenan solution, and heated and stirred at 70℃ using a heat collecting constant temperature magnetic stirrer until completely dissolved.

[0079] Step S22. The prepared carrageenan solution was added to the radical stripping device for degradation, with direct current as the power source, two electrode sheets as the cathode and anode of the radical reaction, the distance between the electrode sheets controlled at 3 cm, the current size at 10 mA, the air flow rate at 1 L / min, and the electrolysis time at 300 min.

[0080] Step S23. The degraded solution was centrifuged at 10,000 rpm / min for 10 min to obtain 5,500 g of the degraded carrageenan oligosaccharide solution.

[0081] Preparation of the dressing:

[0082] Step S31. 60 g of graphene oxide powder was mixed with 5.5 Kg of the carrageenan oligosaccharide solution, stirred on a magnetic stirrer for 1 h, then placed in an ultrasonic cleaning machine, set at an ultrasonic power of 420 W, and ultrasonically treated for 4 h to obtain a mixed solution, and 400 g of sodium alginate was added to the mixed solution in batches until completely dissolved, and 500 ml of glycerol was added and stirred for 5 h to obtain a gel precursor.

[0083] Step S32. 1250 g of anhydrous calcium chloride and 23750 g of distilled water were weighed to prepare a 5wt% anhydrous calcium chloride solution, and the effective components were added to the anhydrous calcium chloride solution, and the gel precursor was laid on a polytetrafluoroethylene plate and soaked in the anhydrous calcium chloride solution with effective components, and a gel was formed after standing for 12 h.

[0084] Step S33. The gel was placed in a freeze dryer with a cold trap temperature of -50°C and vacuum dried for 48 h to obtain a health care paste.

[0085] Experimental Example 1

[0086] The graphene pain-relieving external dressing corresponding to Examples 1-3 was subjected to heat dissipation performance test, and the heat dissipation effects corresponding to different examples were obtained by infrared thermal imaging at different times. For the results, see Figure 2 . Among them, Figure 2 -a, Figure 3 -b and Figure 2 -c are the heat dissipation effect diagrams corresponding to Example 1, Example 2, and Example 3, respectively.

[0087] From the results, it can be seen that graphene can form a three-dimensional network structure in the gel, which increases the specific surface area and porosity of the gel, and provides more heat conduction channels.

[0088] Experimental Example 2

[0089] The gels corresponding to Examples 1-3 are selected as direct experimental materials for this experimental example, and the antibacterial circle method is used to obtain the bacterial distribution images of each example by adding the same concentration of E. coli in Examples 1-3, respectively. See Figure 3 -a, Figure 3 -b and Figure 3 c, are the antibacterial circle images corresponding to Examples 1-3, respectively. It can be seen from the above images that the gels corresponding to Examples 1-3 have antibacterial effects.

[0090] In summary, the preparation method and application of the graphene pain-relieving health cream provided in the embodiments of the present application can obtain an external application dressing with pain-relieving effect by dispersing graphene in the gel and adding effective components in the gel. The effective components can achieve anti-inflammatory analgesic effect by adding black tiger extract, frankincense extract and peony extract, can achieve blood-activating meridian-unblocking effect by adding notoginseng extract, salvia miltiorrhiza extract and chuanxiong extract, can achieve dampness-removing and muscle-strengthening effect by adding naringenin extract, angelica extract, eucommia extract and stretchy grass extract, and can achieve constitution-regulating effect by adding ginseng extract, angelica extract and phoebe extract, so that multiple herbal extracts are reused as external application dressing, which can achieve the effects of the above-mentioned drugs themselves and improve the activity of external application of the drugs by improving the thermal conductivity.

[0091] The above only describes the preferred embodiments of the present application and is not intended to limit the present application. Any modification, equivalent replacement and improvement within the principles of the present application shall be included in the protection scope of the present application.

Claims

1. A method for preparing a graphene analgesic health cream, characterized in that, The method comprises the following steps: Step S1. Mixing carrageenan and deionized water at a mass-volume ratio of 1:150-250 to prepare a carrageenan solution with a concentration of 0.5-1 wt%, and ionically degrading the carrageenan solution to obtain a carrageenan oligosaccharide solution; Step S2. Mixing graphene oxide and the carrageenan oligosaccharide solution at a mass ratio of 1:70-120, and then performing ultrasonic cleaning to obtain a mixed solution, adding sodium alginate at a mass ratio of 1:0.03-0.05 to the mixed solution until the sodium alginate is dissolved to prepare a gel precursor, and adding anhydrous calcium chloride solution at a mass ratio of 1:5 and with a concentration of 5 wt%, and effective components at a mass ratio of 95:1 to the gel precursor to obtain a pain-relieving gel; Step S3. Placing the gel in a freeze dryer with a cold trap temperature of -50°C, and vacuum drying for 48 h to obtain a health-care paste.

2. The method of claim 1, wherein the graphene pain-relieving health cream is prepared by mixing graphene oxide, water, and a surfactant, and then reducing the graphene oxide to graphene. The effective components comprise the following components in parts by weight: black tiger extract 7-10%, angelica extract 6-9%, frankincense extract 5-8%, peony extract 3-6%, notoginseng root extract 5-8%, salvia miltiorrhiza root extract 4-7%, notopterygium extract 4-7%, radix angelicae pubescentis extract 3-6%, phoebe bark extract 4-7%, ginseng extract 1-4%, artemisia extract 5-9%, eucommia extract 4-7%, cnidium extract 4-7%, lycium barbarum extract 1-3%, inula extract 1-3%, crocus extract 1-3%, sparganium extract 1-3%, gallnut extract 3-6%, rhizoma sinodendri extract 5-9%, magnolia extract 4-7%.

3. The method of claim 2, wherein the graphene pain-relieving health cream is prepared by mixing graphene oxide, water, and a surfactant, and then reducing the graphene oxide to graphene. The effective components comprise the following components in parts by weight: black tiger extract 9%, angelica extract 8%, frankincense extract 6%, peony extract 5%, notoginseng root extract 6%, salvia miltiorrhiza root extract 5%, notopterygium extract 6%, radix angelicae pubescentis extract 4%, phoebe bark extract 5%, ginseng extract 2%, artemisia extract 8%, eucommia extract 5%, cnidium extract 5%, lycium barbarum extract 2%, inula extract 2%, crocus extract 2%, sparganium extract 2%, gallnut extract 5%, rhizoma sinodendri extract 8%, magnolia extract 5%.

4. The method of claim 1, wherein the graphene pain-relieving health cream is prepared by mixing graphene oxide, water, and a surfactant, and then reducing the graphene oxide. The ionically degrading uses two electrode sheets as cathode and anode of the ionically degrading reaction, controls the distance between the electrode sheets to be 3 cm, the current size to be 10 mA, the air flow rate to be 1 L / min, and the electrolysis time to be 60-300 min.

5. The method of claim 1, wherein the graphene pain-relieving health cream is prepared by mixing graphene oxide, water, and a surfactant, and then reducing the graphene oxide to graphene. The graphene oxide is obtained by mixing graphite powder and concentrated sulfuric acid at a mass ratio of 1:37-55, sequentially adding phosphorus pentoxide and potassium dichromate to the mixed solution, stirring, and then performing secondary acidification based on the graphene oxide; the mass ratio of the phosphorus pentoxide to the graphite powder is 1:0.5-2, and the mass ratio of the potassium dichromate to the graphite powder is 4-6:

1.

6. The method of claim 5, wherein the graphene pain-relieving health cream is prepared by mixing graphene oxide, water, and a surfactant, and then reducing the graphene oxide to graphene. The secondary acidification based on the oxidized graphite includes: adding the oxidized graphite into concentrated sulfuric acid, and adding potassium dichromate again for stirring, and transferring into an ice bath after stirring for low concentration of 30% hydrogen peroxide, and drying after ion washing to the center to obtain graphene oxide.

7. The method of claim 6, wherein the graphene pain relief health cream is prepared by mixing graphene oxide, water, and a surfactant, and then reducing the graphene oxide to graphene. The method further includes: obtaining a graphene oxide aqueous dispersion, dissolving hydroxypropyl cellulose in deionized water to obtain a dissolution solution, mixing the graphene oxide aqueous dispersion with the dissolution solution, stirring, and drying to obtain modified graphene oxide; the mass ratio of the hydroxypropyl cellulose to the graphene oxide is 1:

2.

8. The method of claim 1, wherein the graphene pain relief health cream is prepared by mixing graphene oxide, water, and a surfactant, and then reducing the graphene oxide to graphene. The method further includes adding sodium alginate with a mass ratio of 1:0.03-0.05 in the mixed solution until completely dissolved, and adding glycerol in the dissolved solution for stirring to obtain a gel precursor.

9. The method of claim 1, wherein the graphene pain relief health cream is prepared by mixing graphene oxide, water, and a surfactant, and then reducing the graphene oxide to graphene. The anhydrous calcium chloride solution is prepared by mixing distilled water with a mass ratio of 1:15-20.

10. Use of the analgesic external dressing prepared by the method of any one of claims 1-9 on a medical dressing.

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