CN108744068A - A kind of preparation and application of graphene carried medicine sustained-release electrode material - Google Patents

A kind of preparation and application of graphene carried medicine sustained-release electrode material Download PDF

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CN108744068A
CN108744068A CN201810729710.6A CN201810729710A CN108744068A CN 108744068 A CN108744068 A CN 108744068A CN 201810729710 A CN201810729710 A CN 201810729710A CN 108744068 A CN108744068 A CN 108744068A
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graphene
preparation
electrode material
solution
medicine
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颜洪
姜丽丽
谢俊志
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Chengdu Carborntime Technology Co Ltd
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Chengdu Carborntime Technology Co Ltd
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/14Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L31/145Hydrogels or hydrocolloids
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/02Inorganic materials
    • A61L31/024Carbon; Graphite
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/04Macromolecular materials
    • A61L31/06Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/14Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L31/148Materials at least partially resorbable by the body
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61NELECTROTHERAPY; MAGNETOTHERAPY; RADIATION THERAPY; ULTRASOUND THERAPY
    • A61N1/00Electrotherapy; Circuits therefor
    • A61N1/02Details
    • A61N1/04Electrodes
    • A61N1/0404Electrodes for external use
    • A61N1/0472Structure-related aspects
    • A61N1/0492Patch electrodes
    • A61N1/0496Patch electrodes characterised by using specific chemical compositions, e.g. hydrogel compositions, adhesives
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/20Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials
    • A61L2300/216Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials with other specific functional groups, e.g. aldehydes, ketones, phenols, quaternary phosphonium groups
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/20Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials
    • A61L2300/30Compounds of undetermined constitution extracted from natural sources, e.g. Aloe Vera
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/402Anaestetics, analgesics, e.g. lidocaine
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/45Mixtures of two or more drugs, e.g. synergistic mixtures
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/60Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a special physical form
    • A61L2300/602Type of release, e.g. controlled, sustained, slow

Abstract

The invention discloses a kind of preparation and application of graphene carried medicine sustained-release electrode material, the preparation includes the following steps:Step 1, after the conductive redox graphene after poly-dopamine restores being mixed with Chinese medicine, constant temperature processing certain time, which obtains, under 35 DEG C of temperature conditions carries medicine redox graphene;Step 2, conductive redox graphene carried medicine sustained-release hydrogel electrode material is obtained after the load medicine redox graphene and hydrogel being mixed.Using above-mentioned preparation method obtain graphene carried medicine sustained-release electrode material medical field application.Graphene carried medicine sustained-release electrode material provided by the invention overcomes existing hydrogel in addition to applied to fitting skin and conduction, does not have the unicity problem of more medical functions.

Description

A kind of preparation and application of graphene carried medicine sustained-release electrode material
Technical field
The present invention relates to pharmaceutical technology fields, and in particular to a kind of preparation of graphene carried medicine sustained-release electrode material and answers With.
Background technology
Hydrogel is that one kind is crosslinked by hydrophilic macromolecule or polymer by the effects that covalent bond, hydrogen bond, Van der Waals force The three-dimensional net structure material of formation.Hydrogel properties are soft, can keep certain shape, can absorb a large amount of water.Hydrogel Cell behavior, function of organization can be regulated and controled for the three-dimensional microenvironment of simulation extracellular matrix, be before one kind has very much The biomaterial for organizational project of scape.Has wide application at present.For example, being prepared by poly hydroxy ethyl acrylate Contact lenses, by recombinant protein or albumin formed for surgical operation bonding bioadhesive, by Alginate polysaccharides The wound dressing of preparation has been used for clinic by what hyaluronic acid was formed for filling the hydrogel etc. repaired.In short, hydrogel Have the characteristics that good biocompatibility, easily molded processing, shape size are controllable, is carried in three-dimensional tissue's engineering matrix, drug The biomedical engineering fields such as body, Biocomposite material are with a wide range of applications.In recent years, synthesis or natural polymerization are based on The hydrogel product of object has tens kinds, wherein the conductive hydrogel for electronic stimulation causes because it is widely applied foreground Concern, conductive hydrogel are chiefly used in the biological tissue that nerve, cardiac muscle etc. are related to electric signal.Conductive hydrogel currently on the market It is generally divided into polyelectrolyte class doping type, inorganic conductive ingredient (metal nanoparticle, carbon-based nano particle) addition type, conductive height Several classes such as molecular compound.Traditional conductive hydrogel is mostly the hydrogel of formation based on conducting polymer, common to lead Electric macromolecule includes polypyrrole (Ppy), polyaniline ((PANI), polythiophene (PTH), polyphenylene ethylene (PPV) and its copolymer Or derivative.There is research using the conductive hydrogel that Ppy is base, it is neural thin that cell culture experiments show that the hydrogel can promote The adherency of born of the same parents and the growth of aixs cylinder.PEDOT, which is the conductive hydrogel of base, also similar nerve stimulation reaction.PANI based aquagels It can promote nerve and Myocardial Regeneration under stimulation conditions.However, this kind of conductive hydrogel has one in biomedical applications Fixed limitation:First, the irreversible oxidation of conducting polymer can be caused by electro photoluminescence being repeated several times, to reduce its electric property, Influence service life (irreversible);Secondly, this kind of hydrogel except applied to fitting skin and it is conductive in addition to (medical functions are single), Do not have more medical functions at present;Finally, conducting polymer can introduce some other ions in preparation process, cause (allergic reactions) such as quick reactions.
Invention content
The technical problem to be solved by the present invention is to:Existing hydrogel (doctor in addition to applied to fitting skin and conduction Treatment has a single function), do not have more medical functions at present, the present invention provides a kind of graphenes to solve the above problems to carry medicine It is sustained the preparation and application of electrode material.
The present invention is achieved through the following technical solutions:
A kind of preparation method of graphene carried medicine sustained-release electrode material, the preparation include the following steps:
Step 1, after the conductive redox graphene after poly-dopamine restores being mixed with Chinese medicine, in 35 DEG C of temperature strips Constant temperature processing certain time, which obtains, under part carries medicine redox graphene;
Step 2, conductive redox graphene is obtained after the load medicine redox graphene and hydrogel being mixed to carry Medicine sustained-release hydrogel electrode material.
Preferably, the preparation method of the electric conductive oxidation graphene the specific steps are:
Step A, low-temp reaction:The concentrated sulfuric acid of the graphite powder weighed and measurement is added to the container, and container is placed in ice Solution in container be continuously stirring to uniformly under the conditions of bath;It then proceedes to be gradually added weighed height under agitation Potassium manganate obtains mixed solution;
Step B, medium temperature reaction:Container where the mixed solution of gained is placed in 35 DEG C of thermostat water baths and is stirred further After oxidation, takes out container and carry out continuing stirring setting time;
Step C, pyroreaction:Constant temperature after setting water bath with thermostatic control is heated to 85 DEG C;When water bath with thermostatic control initially heats, by institute Container where the mixed solution obtained is placed in water bath, and is gradually added distilled water stirring, after water-bath water temperature reaches 85 DEG C Constant temperature the reaction was continued setting time;
The solution of gained is filtered by step D after pyroreaction, obtains mud block objects;Mud block objects are put Enter that distilled water is added in beaker and obtains the solution of even suspension;
Step E, by obtained aaerosol solution centrifuged electric conductive oxidation graphene aaerosol solution.
Preferably, the quality proportioning of the graphite powder, potassium permanganate and the concentrated sulfuric acid is 1:5:6.5.
Preferably, in the step A, container is placed on the magnetic stirrer with ice bath and carries out stirring operation, and with The charging rate of 25g/h is gradually added potassium permanganate;
In the step B, after container where mixed solution is placed in the further oxidation 0.5h of stirring in 35 DEG C of thermostat water baths, Container is taken out to carry out continuing stirring for 24 hours;
In the step C, constant temperature the reaction was continued the 0.5h after water-bath water temperature reaches 85 DEG C.
Preferably, in the step E, the aaerosol solution of a concentration of 1g/ml of electric conductive oxidation graphene is obtained after centrifugation.
Preferably, the preparation method of the poly-dopamine is:Dopamine powder is dissolved in the alkaline solution of pH=11 And 20min is stirred at 80 DEG C, so that dopamine autohemagglutination in alkalinity, air atmosphere is formed poly-dopamine solution.Alkaline solution can Using sodium hydroxide or potassium hydroxide.
Preferably, the method for the conductive redox graphene of poly-dopamine reduction is:Electric conductive oxidation graphene is hanged Supernatant liquid is added in the poly-dopamine solution prepared, forms mixed liquor, and stirring makes poly-dopamine and graphite oxide alkene reaction, works as reaction After time is 20min, electric conductive oxidation graphene is completely reduced as redox graphene.
Preferably, in the step 1:By the redox graphene aqueous solution and herb powder of a concentration of 5mg/ml After mixing, the isothermal reaction 1h under 35 DEG C of temperature conditions.
Preferably, in the step 2, by the load medicine redox graphene aqueous solution of hydrogel and a concentration of 5mg/ml into Row mixing, and hydrogel is 25 with the volume ratio for carrying medicine redox graphene aqueous solution:1.
Using above-mentioned preparation method obtain graphene carried medicine sustained-release electrode material medical field application.
Safflower, borneol, frankincense, myrrh, ginger work etc. can be used in Chinese medicine.
The effect of Chinese medicine is with a long history in China, many Chinese herbal medicines has not only withstood the inspection of long term medical practice, and And it is also confirmed by modern scientific research.It can be widely used for prevention and treatment disease and there are the fields such as rehabilitation and health care.
Safron is also known as safflower, west safflower, is a kind of flowering perennial of Iridaceae crocus, is a kind of rare Chinese medicine has powerful physiological activity, and for column cap in Asia and Europe as medicinal, drying column cap is sweet in flavor mild-natured, can live Blood stagnation resolvation dissipates Yu Kaijie, analgesic.For treating troubled thoughts pent-up, chest diaphragm ruffian is bored, spits blood, and typhoid fever is gone mad, and shies and is afraid of in a trance, Fu Nvjing It closes, stasis irregular menstruation, prolonged lochia, hemostasis is had a pain, measles, traumatic injury etc..It is outer to be used as calm, carminative.Promoting blood circulation Stagnation resolvation, removing pattogenic heat from the blood and toxic material from the body, resolving stagnation for tranquilization.Febrile virulent maculae, melancholy ruffian are bored, palpitation with fear is gone mad.Medicinal main component is crocin, sarranine Flower dimethyl phthalate, picrocrocin and volatile oil are mainly safranal etc. in oily.
Borneol also known as piece brain, orange slices, L-Borneol, kapur, MEIHUA BINGPIAN, Dipterocarpus pilosus, plum blossom brain, borneol brain, Mei Bing Deng through steam distillation and being recrystallized and obtained by composite family Blumea balsamifera cauline leaf or canella borneol camphor tree branches and leaves.Also useful turpentine Oil is obtained through a series of chemical method techniques.It can be used for closing card coma, is used for red eye, swell pain, and larynx numbness aphtha swells for sore Bitterly, it is not held back after bursting.
Frankincense is the resin that olive subject plant Boswellia carterii and its congener skin zone ooze out, frankincense resinous 60~70%, Natural gum 27~35%, volatile oil 3~8%.The main component of resin is free α, β-boswellic acid 33%, in conjunction with boswellic acid 1.5%, olibanoresene 33%.Natural gum is the calcium salt and magnesium salts 20% of arabitic acid, bassorin 6%;In addition, still containing hardship Taste matter 0.5%.Volatile oil is in faint yellow, there is fragrance, contains firpene, racemization-limonene and α, β-phellandrene, is demonstrate,proved with hot plate method in mice Bright Olibanum volatile oil has analgesic activity, and the residue extracted after volatile oil is invalid.It is just pungent that analgesia in volatile oil mainly becomes acetic acid Ester, frankincense can promote polynuclear leucocyte to increase, and with the blood cell and cell that phagocytosis is dead, improve metabolism, make to play anti-inflammatory With traumatic injury, sore carbuncle swells.The pungent perfume (or spice) of frankincense is walked to alter, and enters the heart, Liver Channel.Bitter is removed heat by catharsis into blood, can removing blood stasis and analgesics and work Blood disappears carbuncle, putrefaction-removing granulation-promoting, is external wounds key medicine.Control traumatic injury, often match the medicines such as myrrh, dragon's blood, safflower with using, qi depression to blood stasis it Pain is demonstrate,proved.Pungent scatter away of this product is altered, and bitter is removed heat by catharsis, and not only enters blood system, but also enter qi leel, the stagnation of the circulation of vital energy in energy promoting circulation of blood, blood-activating analgetic;Interior energy a surname is logical dirty Internal organs qi and blood, external enwergy reach channels and collaterals, can be used for the pain of all qi depressions to blood stasis thoroughly.
Myrrh (Commiphora myrrha Eng1.) also known as myrrh, there is also bright myrrh, myrrh, stir-baked MYRRHA with vinegar, Vinegar-fried myrrh, Myrrha, raw bright myrrh etc. are also known as.For olive subject plant Chinese violet tree or the dry resin of Ha Didingshu.Main product in The ground such as African Somalia, Ethiopia and India.The white oleo-gum-resin oozed out by bark crack is acquired, in air Become rufous and hard round block.After smashing, fry to coke black application.Cure mainly chest and abdomen stasis caused pain, dysmenorrhoea, Amenorrhea, abdominal mass, bruise Damage, carbuncle swells sore, acute appendicitis, red eye, swell pain.Myrrh is fine to treat wound, dermatitis effect, to bronchitis, coughs, carefully Bacterium infects and the infection of Hui bacterium is helpful.There are promoting blood circulation and stopping pain, detumescence and promoting granulation and other effects.It is a kind of promoting blood circulation, stagnation resolvation, only in east Bitterly, the Chinese medicine of stomach invigorating.《Northern history》In it is i.e. on the books, say be come from Western Regions mortise state.In west, it is said that myrrh, which is one kind, magical treatment The drug of effect.Myrrh branch is fabricated to various aromatic, preservative and analgesic by Hebrew.
Rhizoma Et Radix Notopterygii (scientific name:Notopterygium incisum Ting ex H.T.Chang) be Umbelliferae, Notopterygium for many years Raw herbaceous plant, high up to 120 centimetres, rhizome is sturdy, and stem is upright, cylindrical, band purple.Basal leaf and the lower portion of the stem leaf have handle, Blade three goes out formula three and returns pinnate compound leaf, and edge incises that shape is shallow to be split to pinniform drastic crack;Leaf sheath film quality is grown and embraces stem.Universal umbel, Side survivor Chang Buyu;Phyllary is linear, caducous;Involucel piece is linear, spends majority, calyx tooth ovate triangle, petal is white, oval Oval, the anther yellow to long round shape, ellipse, style base concora crush slightly swell.The mitogenetic long round shape of fruit, blooms July, 8-9 month results. It is distributed in Shaanxi, China, Sichuan, Gansu, Qinghai, Tibet.It is grown in border and the shrubbery of 2000-4000 meters of height above sea level.This kind of root Stem and root are medicinal, warm-natured, dispellieg cold and dampness, for catching cold, headache and adiapneustia, cold-dampness numbness, upper limb arthritis pain
All there is these Chinese medicines throe, the main functions such as promoting blood circulation can be used for medical care effect in tcm theory.
The present invention has the advantage that and advantageous effect:
The present invention will use carbon material to substitute the conductive compositions in original conductive hydrogel, and will carry medicine body using carbon material System is introduced into hydrogel, while enhancing hydrogel mechanical strength, electric conductivity, makes hydrogel in electronic stimulation engineering Slow releasing pharmaceutical realizes the functionalization medical applications such as analgesia.This method utilizes the larger specific surface area of graphene and excellent conduction Performance successfully prepares conductive medicine-carried system, and the slow releasing function of drug is realized by electro photoluminescence, while the material is added to water In the forming process of gel, the hydrogel electrode slice with health-care effects such as throes has been obtained, under electro photoluminescence effect, poly- DOPA Amine decompose, promote the traditional Chinese medicine ingredients made it combine it is evenly dispersed enter hydrogel in, by hydrogel uniformly, sustained release enter human body in, Play long-acting drug action.Using dopamine reduction GO and Chinese medicine compound system, dopamine gathers during reduced graphene Conjunction forms poly-dopamine, equally has certain pharmacological action, is conducive to application of this kind of electrode material in medical field.The present invention Using method, operation is simple, progress at low cost, being conducive to large-scale production.
Specific implementation mode
To make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiment, the present invention is made Further to be described in detail, exemplary embodiment of the invention and its explanation are only used for explaining the present invention, are not intended as to this The restriction of invention.
Embodiment 1
A kind of preparation method of graphene carried medicine sustained-release electrode material is as follows successively:
First, the preparation of graphene oxide is carried out:
A) 10g graphite powders are weighed, 50g potassium permanganate measures the 230ml concentrated sulfuric acids;
B) low-temp reaction:
By the 230ml concentrated sulfuric acids of the 10g graphite powders and measurement that weigh to entering in beaker, it is placed on the magnetic agitation with ice bath It is stirred on machine.Then the potassium permanganate that gradually a small amount of addition is weighed again, 50g potassium permanganate is equably added in 2h, is obtained To mixed solution.
C) medium temperature is reacted:
The mixed solution of gained is placed in 35 DEG C of thermostat water bath after stirring further oxidation 0.5h, 0.5h and is taken out Beaker is placed on magnetic stirrer and stirs for 24 hours.
D) pyroreaction:
Constant temperature after setting thermostat water bath is heated to 85 DEG C;It is when thermostat water bath initially heats, the mixing of gained is molten Liquid is placed in water-bath, and is gradually added distilled water and is stirred to 1000ml, the isothermal reaction after water-bath water temperature reaches 85 DEG C 0.5h。
E) solution of gained is filtered twice after pyroreaction, obtains mud block objects;Mud block objects are put Enter to be added distilled water in beaker to 1000ml, obtains the solution of even suspension.
F) obtained aaerosol solution in 4000n/min centrifuges is carried out to the centrifugation of 10min, repeat this operation centrifugation two It is secondary, obtain the aaerosol solution of graphene oxide (being named as GO) a concentration of 1g/ml.
Secondly, it restores GO using dopamine and surface modification is carried out to it:
A) dopamine pre-polymerization:Dopamine (DA) powder is dissolved in alkaline solution (pH=11) and is stirred at 80 DEG C 20min makes dopamine autohemagglutination in alkalinity, air atmosphere form poly-dopamine (PDA).
B) poly-dopamine (PDA) restores GO:The graphene oxide aaerosol solution prepared addition step is prepared In PDA solution, mixed liquor is formed, stirring makes PDA be reacted with GO.When being 20min between when reacted, GO is completely reduced as reduction Graphene oxide is denoted as rGO.At this moment graphene medicine-carried system has just been obtained.
Then, the amine-modified rGO of DOPA and traditional Chinese medicine ingredients are compound:
After mixing by the redox graphene aqueous solution of a concentration of 5mg/ml and herb powder, in 35 DEG C of temperature Isothermal reaction 1h under the conditions of degree.
Finally, conductive rGO carried medicine sustained-releases electrode material.
5ml hydrogels are carried medicine redox graphene aqueous solution with the 200ml of a concentration of 5mg/ml to mix, are obtained A kind of conduction rGO carried medicine sustained-release hydrogel electrode materials.
Embodiment 2
Conductive rGO carried medicine sustained-releases hydrogel electrode material prepared by embodiment 1 be used for hip joint, knee joint, shoulder joint, Elbow joint, ankle-joint, wrist joint, remporomandibular joint, hip joint, knee joint, shoulder joint, elbow joint, ankle-joint, wrist joint, temporo The arthropathies such as mandibular joint, effect characterization analgesia, anti-inflammatory for a long time.
First, graphene is a kind of material with excellent heat conducting performance, which, can will be due to electricity when human body The heat that resistance generates acts on completely carries medicine ingredient and skin interface.In theory of traditional Chinese medical science, heat can dredge the channels, and promote blood Flowing promotes absorption of the skin to drug, the foster afflicted area of temperature.Secondly, modified electrode material traditional Chinese medicine ingredients are by graphene and more Bar amine package, in the case where electric heating is used, dopamine slowly decomposes, and discharges traditional Chinese medicine ingredients, realizes the sustained release of traditional Chinese medicine ingredients.Finally, Hydrogel is that have fabulous biocompatible materials, has tack to skin, can be placed directly against on skin, enhances electrode The comfort of material.And traditional Chinese medicine ingredients are completely encapsulated in electrode material by solid-state hydrogel, extend medicine carrying material usage time.
Above-described specific implementation mode has carried out further the purpose of the present invention, technical solution and advantageous effect It is described in detail, it should be understood that the foregoing is merely the specific implementation mode of the present invention, is not intended to limit the present invention Protection domain, all within the spirits and principles of the present invention, any modification, equivalent substitution, improvement and etc. done should all include Within protection scope of the present invention.

Claims (10)

1. a kind of preparation method of graphene carried medicine sustained-release electrode material, which is characterized in that the preparation method includes following step Suddenly:
Step 1, after the conductive redox graphene after poly-dopamine restores being mixed with Chinese medicine, under 35 DEG C of temperature conditions Constant temperature handles certain time acquisition and carries medicine redox graphene;
Step 2, conductive redox graphene load medicine is obtained after the load medicine redox graphene and hydrogel being mixed to delay Release hydrogel electrode material.
2. a kind of preparation method of graphene carried medicine sustained-release electrode material according to claim 1, which is characterized in that described The preparation method of electric conductive oxidation graphene the specific steps are:
Step A, low-temp reaction:The concentrated sulfuric acid of the graphite powder weighed and measurement is added to the container, and container is placed in ice bath item Solution in container be continuously stirring to uniformly under part;It then proceedes to be gradually added weighed permanganic acid under agitation Potassium obtains mixed solution;
Step B, medium temperature reaction:Container where the mixed solution of gained is placed in 35 DEG C of thermostat water baths and stirs further oxidation Afterwards, container is taken out to carry out continuing stirring setting time;
Step C, pyroreaction:Constant temperature after setting water bath with thermostatic control is heated to 85 DEG C;When water bath with thermostatic control initially heats, by gained Container where mixed solution is placed in water bath, and is gradually added distilled water stirring, the constant temperature after water-bath water temperature reaches 85 DEG C Setting time that the reaction was continued;
The solution of gained is filtered by step D after pyroreaction, obtains mud block objects;Mud block objects are put into burning Distilled water is added in cup and obtains the solution of even suspension;
Step E, by obtained aaerosol solution centrifuged electric conductive oxidation graphene aaerosol solution.
3. a kind of preparation method of graphene carried medicine sustained-release electrode material according to claim 2, which is characterized in that described Graphite powder, potassium permanganate and concentrated sulfuric acid quality proportioning are 1:5:6.5.
4. a kind of preparation method of graphene carried medicine sustained-release electrode material according to claim 2, which is characterized in that described In step A, container is placed on the magnetic stirrer with ice bath and carries out stirring operation, and gradually with the charging rate of 25g/h Potassium permanganate is added;
In the step B, after container where mixed solution is placed in the further oxidation 0.5h of stirring in 35 DEG C of thermostat water baths, take out Container carries out continuing stirring for 24 hours;
In the step C, constant temperature the reaction was continued the 0.5h after water-bath water temperature reaches 85 DEG C.
5. a kind of preparation method of graphene carried medicine sustained-release electrode material according to claim 2, which is characterized in that described In step E, the aaerosol solution of a concentration of 1g/ml of electric conductive oxidation graphene is obtained after centrifugation.
6. a kind of preparation method of graphene carried medicine sustained-release electrode material according to claim 1, which is characterized in that described The preparation method of poly-dopamine is:Dopamine powder is dissolved in the alkaline solution of pH=11 and stirs 20min at 80 DEG C, Dopamine autohemagglutination in alkalinity, air atmosphere is set to form poly-dopamine solution.
7. a kind of preparation method of graphene carried medicine sustained-release electrode material according to claim 6, which is characterized in that described The method of the conductive redox graphene of poly-dopamine reduction is:Electric conductive oxidation graphene suspension is added to the poly- DOPA prepared In amine aqueous solution, formed mixed liquor, stirring make poly-dopamine and graphite oxide alkene reaction, when reacted between be 20min after, conductive oxygen Graphite alkene is completely reduced as redox graphene.
8. a kind of preparation method of graphene carried medicine sustained-release electrode material according to claim 1, which is characterized in that described In step 1:After mixing by the redox graphene aqueous solution of a concentration of 5mg/ml and herb powder, in 35 DEG C of temperature Isothermal reaction 1h under the conditions of degree.
9. a kind of preparation method of graphene carried medicine sustained-release electrode material according to claim 1, which is characterized in that described In step 2, hydrogel is mixed with the load medicine redox graphene aqueous solution of a concentration of 5mg/ml, and hydrogel and load The volume ratio of medicine redox graphene aqueous solution is 25:1.
10. the graphene carried medicine sustained-release electrode material based on the acquisition of claim 1 to 9 any one of them preparation method is in medical treatment The application in field.
CN201810729710.6A 2018-07-05 2018-07-05 A kind of preparation and application of graphene carried medicine sustained-release electrode material Pending CN108744068A (en)

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