CN102926272B - Process for preparing biomedical graphene oxide paper - Google Patents

Process for preparing biomedical graphene oxide paper Download PDF

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CN102926272B
CN102926272B CN201210434776.5A CN201210434776A CN102926272B CN 102926272 B CN102926272 B CN 102926272B CN 201210434776 A CN201210434776 A CN 201210434776A CN 102926272 B CN102926272 B CN 102926272B
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graphene oxide
auxiliary material
solid
solvent
medicine
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CN102926272A (en
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李新禄
王皓
邓舒婷
李鸿乂
刘佳
宋宏芳
张勇来
李同涛
钟奇能
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Chongqing Jiabaoxiang Technology Co ltd
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Chongqing University
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Abstract

The invention discloses a process for preparing biomedical graphene oxide paper and belongs to the field of biomedical materials. According to the process, a graphene oxide bought from market serves as a raw material, and a product is obtained through ultrasonic oscillating dispersion, solid-liquid separation and drug loading. The biomedical graphene oxide paper prepared by the process has the advantages of being controllable in thickness, large in specific surface area, abundant in pore structure, good in adsorptivity, strength and flexibility, free from toxicity and bacteria, free from irritation on human bodies and cohesiveness on skin wounds, environment-friendly and the like. The process is simple in technology, convenient to operate, low in production cost, beneficial to popularization and application and the like. The product prepared by the process can be widely applied to medical external application materials which are used for treating skin wounds (such as burns), promoting wound healing and the like, and the product can also be used for electrode materials of super-capacitors and environmental protection materials for adsorption, purification and the like.

Description

A kind of preparation method of bio-medical graphene oxide paper
Technical field
The invention belongs to biology medical material technical field, be specifically related to the preparation method of outer compress material bio-medical graphene oxide paper.
Background technology
Graphene (Graphene) refers to the graphite of carbon (C) atomic layer level thickness, by sp between carbon-to-carbon 2covalent linkage is hexagonal network aspect, is considered to the basic structural unit of fullerene, CNT and graphite.Graphene paper is by the material macroscopically in paper-like of Graphene self assembly.There is the features such as high strength, quality is light, absorption property is excellent.The outer compress material of tradition, comprises gauze, bandage etc., although they have water imbibition and heat insulating ability is excellent, heat resistance and feature, the still extensive use in various types of wound so far such as alkali resistance is better.But after their absorption wound exudate, often can cause wound infection because secretion oozes out pollution, and easy adhesion wound etc. when removing outer compress material.In order to solve the outer compress material adhesion wound of tradition, not every bacterium, insulating power difference and stop blooding, the hemagglutinin shortcoming such as bad, people adopt various method to improve the performance of this kind of outer compress material, as dipping, coating and chemistry or physical modification method, but effect is all undesirable.Carbon-based material is because the feature such as good absorption property, nontoxic aseptic, heat resistance is subject to people's extensive concern, and Graphene is considered to have wide practical use in this respect as a kind of characteristic due to its excellence of carbon-based material.
The preparation method of existing medical graphite alkene material, it is the patent of " bacterial cellulose/graphene composite material and preparation method thereof " of 201110063663.4 as application number, disclosed method is: first prepare moistening bacterial cellulose product, again Graphene pulverized, stir and make graphene dispersing solution, then by graphene dispersing solution and bacteria cellulose mixing, then bacterial cellulose/graphene composite material is prepared by Separation of Solid and Liquid.The major defect of the method is: process conditions are complicated, consuming time long, and single with the types of drugs of Graphene compound, are not suitable with the requirement of large-scale production.And for example application number is the patent of " method of using expansion graphite as wound auxiliary material " of 95115437.0, disclosed method is: first prepare expanded graphite pulvis, hybrid medicine in graphite pulvis again, finally applies this mixing powder and is pressed into band-type product at hospital gauze or carbon fiber surface.The major defect of the method is: be only only apply to cause drug powder easily to come off on surface to cause medical value to reduce with expanded graphite based on normal gauze, easily bond with skin wound and cause patient's misery, that fails to make full use of Graphene enriches pore structure and the advantage such as high strength, pliability.
Summary of the invention
The object of the invention is to the deficiency for existing bio-medical grapheme material, a kind of preparation method of bio-medical graphene oxide paper is provided, there is thickness controlled, specific area is large, pore structure is abundant, strong to body fluid adsorptivity, intensity is high, pliability good and skin wound no adhesion, the characteristic such as can be recycled; It is simple, easy to operate that the method has technique, and production cost is low, be suitable for the advantages such as large-scale production.
The technical scheme realizing the object of the invention is: a kind of preparation method of bio-medical graphene oxide paper, using commercial graphene oxide as raw material, through sonic oscillation dispersion, Separation of Solid and Liquid, drug loading and obtain product.The concrete steps of described method are as follows:
(1) sonic oscillation dispersion
With commercial graphene oxide for raw material, quality (g) according to graphene oxide: the quality (g) of auxiliary material: the ratio of the volume (ml) of solvent is the ratio of 1: 0 ~ 1: 20 ~ 100, graphene oxide and auxiliary material are joined in solvent, after stirring, under hyperacoustic power output is 150 ~ 500W, carry out sonic oscillation dispersion 30 ~ 120 minutes, just obtain the dispersion mixed liquor of graphene oxide and auxiliary material.
Wherein: described solvent is absolute ethyl alcohol or deionized water etc.;
Described auxiliary material is CNT or activated carbon fiber or carbon fiber or carbon nano-fiber etc.
(2) Separation of Solid and Liquid
After (1) step completes, the graphene oxide that (1) step is obtained and the dispersion mixed liquor of auxiliary material, adopt 100 ~ 300ml to be with the vacuum filtration instrument of filter membrane to carry out Separation of Solid and Liquid, collect parting liquid (i.e. solvent) and solid residue respectively.Recycling is carried out to the parting liquid (i.e. solvent) collected.
Wherein: the nylon leaching film of described filter membrane or teflon membrane filter etc.
(3) drug loading
After (2) step completes, the solid residue that (2) step is collected uniformly sprays medicament (i.e. Povidone-Iodine Solution or PVP-I or the tincture of iodine) or spraying medicine (i.e. Yunnan Baiyao or ceftriaxone sodium) and obtains the solid residue that load has medicine, then load there is the solid residue of medicine, at temperature is 40 ~ 80 DEG C, drying 0.5 ~ 2 hour, just obtains bio-medical graphene oxide paper.
Wherein: described medicament is povidone-iodine or Povidone-Iodine Solution or the tincture of iodine, and medicine is Yunnan Baiyao or or ceftriaxone sodium.
After the present invention adopts technique scheme, there is following effect:
(1) the inventive method prepare bio-medical graphene oxide paper nontoxic aseptic, to human body nonirritant, absorption property, strong and skin wound can not cause adhesion to be conducive to skin wound healing.
(2) the inventive method prepares the thickness of bio-medical graphene oxide paper between 0.5 ~ 3mm, and aperture is mainly distributed between 6 ~ 50nm, and specific area arrives 100m greatly 2/ more than g, has good pore size distribution$ and absorption property.The fibrous auxiliary material energy well mechanical property be simultaneously evenly distributed, can effectively improve its mechanical strength and pliability.
(3) the inventive method adopts sonic oscillation dispersion and Separation of Solid and Liquid and drying etc., and without the need to high-temperature process, energy consumption is low.
(4) the inventive method is without the need to catalyst, can also recycling to the solvent in production process, and without " three wastes " discharge, belong to recycling economy, this can reduce production cost, is conducive to environmental protection again.
(5) present invention process is simple, and easy to operate, production equipment is few, thus reduces costs further, easy to utilize, is suitable for large-scale production.
The bio-medical graphene oxide paper adopting the inventive method to prepare, can be widely used in treatment skin trauma (as burn) and promote that the medical external dressing material of wound healing etc. also can be used for environment conscious material and the electrode material for super capacitor such as absorption, purification.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of the present embodiment 1 bio-medical graphene oxide paper,
In figure: 1 is carrying medicament, 2 is graphene oxide lamella, and 3 is activated carbon fiber.
Detailed description of the invention
Below in conjunction with detailed description of the invention, further illustrate the present invention.
Embodiment 1
The concrete steps of a kind of bio-medical graphene oxide paper preparation method are as follows:
(1) sonic oscillation dispersion
Quality (g) according to graphene oxide: the quality (g) of auxiliary material: the volume (ml) of solvent is than the ratio being 1: 0.5: 50, graphene oxide and auxiliary material are put into solvent, after stirring, under ultrasonic output frequency is 500W, carry out sonic oscillation and disperse 60 minutes, obtain the dispersion mixed liquor of graphene oxide and auxiliary material.
Wherein: described auxiliary material is activated carbon fiber;
Described solvent is absolute ethyl alcohol.
(2) Separation of Solid and Liquid
After (1) step completes, 200ml is adopted to be with the vacuum filtration instrument of teflon membrane filter, the graphene oxide prepare (1) step and the dispersion mixed liquor of auxiliary material activated carbon fiber carry out Separation of Solid and Liquid, collect parting liquid (i.e. anhydrous ethanol solvent) and solid residue respectively, recycling is carried out to the parting liquid (i.e. anhydrous ethanol solvent) collected.
(3) drug loading
After (2) step completes, uniform spraying medicine Yunnan Baiyao on the surface of the solid residue of (2) step collection, just obtain the solid residue that load has medicine, then load there is the solid residue of medicine, under temperature 60 C, drying 60 minutes, just prepares bio-medical graphene oxide paper.
Embodiment 2
Preparation method is with embodiment 1 for one bio-medical graphene oxide paper, wherein:
In (1) step, the quality (g) of graphene oxide: the quality (g) of auxiliary material: the volume (ml) of solvent is than being 1: 1: 100, and ultrasonic frequency is 300W, and the ultrasonic Separation time is 120 minutes.
Wherein: described auxiliary material is CNT;
Described solvent is deionized water.
In (2) step, 300ml is adopted to be with the vacuum filtration instrument of nylon leaching film that the mixed liquor that (1) step is prepared is carried out Separation of Solid and Liquid.
In (3) step, the surface of the solid residue of (2) step collection uniformly sprays the medicament tincture of iodine, just obtains the solid residue that load has medicine, wherein: drying 120 minutes at temperature is 80 DEG C.
Embodiment 3
Preparation method is with embodiment 1 for one bio-medical graphene oxide paper, wherein:
In (1) step, the quality (g) of graphene oxide: the quality (g) of auxiliary material: the volume (ml) of solvent is than being 1: 0: 20, and ultrasonic frequency is 150W, and the ultrasonic Separation time is 80 minutes.
Wherein: described auxiliary material is CNT;
Described solvent is deionized water.
In (2) step, the graphene oxide adopting 100ml to be with the vacuum filtration instrument of teflon membrane filter (1) step to be prepared and the mixed liquor of auxiliary material dispersion carry out Separation of Solid and Liquid.
In (3) step, the surface of the solid residue of (2) step collection uniformly sprays medicament Povidone-Iodine Solution, wherein: drying 30 minutes at temperature is 100 DEG C.
Embodiment 4
Preparation method is with embodiment 1 for one bio-medical graphene oxide paper, wherein:
In (1) step, the quality (g) of graphene oxide: the quality (g) of auxiliary material: the volume (ml) of solvent is than being 1: 0.2: 20, and ultrasonic frequency is 300W, and the ultrasonic Separation time is 30 minutes.
Wherein: described auxiliary material is carbon nano-fiber;
Described solvent is deionized water.
In (2) step, 150ml is adopted to be with the vacuum filtration instrument of nylon leaching film that the mixed liquor that (1) step is prepared is carried out Separation of Solid and Liquid.
In (3) step, the surface of the solid residue of (2) step collection uniformly sprays medicament and gathers iodine dimension ketone, wherein: drying 60 minutes at temperature is 40 DEG C.
Embodiment 5
Preparation method is with embodiment 1 for one bio-medical graphene oxide paper, wherein:
In (1) step, the quality (g) of graphene oxide: the quality (g) of auxiliary material: the volume (ml) of solvent is than being 1: 0.5: 100, and ultrasonic frequency is 300W, and the ultrasonic Separation time is 120 minutes.
Wherein: described auxiliary material is carbon fiber;
Described solvent is absolute ethyl alcohol.
In (2) step, 200ml is adopted to be with the vacuum filtration instrument of teflon membrane filter that the mixed liquor that (1) step is prepared is carried out Separation of Solid and Liquid.
In (3) step, uniform spraying medicine ceftriaxone sodium on the surface of the solid residue of (2) step collection, wherein: drying 60 minutes at temperature is 60 DEG C.
Result of the test
Carry out scanning electron microscopic observation, specific area and pore Structure Analysis, absorption property test to the bio-medical graphene oxide paper that embodiment 1 is prepared, its stereoscan photograph as shown in Figure 1.
From test result analysis, by the graphene-based paper of bio-medical of embodiment 1 gained, thickness is about 3mm, B.E.T. specific area is 158.88m 2/ g; Average pore size is 25.83nm, and aperture is mainly distributed between 10-50nm, good adsorption performance.

Claims (1)

1. a preparation method for bio-medical graphene oxide paper, is characterized in that the concrete steps of described method are as follows:
(1) sonic oscillation dispersion
With commercial graphene oxide for raw material, quality according to graphene oxide: the quality of auxiliary material: the ratio of the volume of solvent is the ratio of 1g: 0 ~ 1g: 20 ~ 10ml, graphene oxide and auxiliary material are joined in solvent, after stirring, under ultrasonic power output is 150 ~ 500W condition, carries out sonic oscillation dispersion 30 ~ 120 minutes and just obtain the dispersion mixed liquor of graphene oxide and auxiliary material;
(2) Separation of Solid and Liquid
After (1) step completes, the graphene oxide obtain (1) step and the dispersion mixed liquor of auxiliary material, adopt 100 ~ 300m1 to be with the vacuum filtration instrument of filter membrane to carry out Separation of Solid and Liquid, collect parting liquid and solid residue respectively;
(3) drug loading
After (2) step completes, even application medicament or spray medicine and obtain the solid residue that load has medicine on the solid residue that (2) step obtains, then load there is the solid residue of medicine, at temperature is 40 ~ 80 DEG C, drying 0.5 ~ 2 hour, just obtains bio-medical graphene oxide paper;
Described solvent is absolute ethyl alcohol or deionized water;
Described auxiliary material is CNT or activated carbon fiber or carbon fiber or carbon nano-fiber;
Described filter membrane is nylon leaching film or teflon membrane filter;
Described medicament is povidone-iodine or Povidone-Iodine Solution or the tincture of iodine, and medicine is Yunnan Baiyao or ceftriaxone sodium.
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CN103449421B (en) * 2013-08-23 2015-10-28 上海二工大资产经营有限公司 A kind of preparation method of heat conductive insulating graphene oxide paper
CN103482621B (en) * 2013-09-11 2016-01-20 黄镇东 Oxidation or reduced graphene base macroscopic material and preparation method thereof
CN103482620B (en) * 2013-09-11 2016-01-20 黄镇东 Oxidation or reduced graphene base net grid material and preparation method thereof
CN104977194B (en) * 2014-04-10 2018-08-14 北京雷根生物技术有限公司 A method of addition graphene accelerates sample process
CN104129779A (en) * 2014-06-27 2014-11-05 桂林浩新科技服务有限公司 Preparation method of graphene-containing nano paper
CN105544306B (en) * 2015-11-26 2017-06-13 张建刚 A kind of preparation method containing graphene oxide antibiotic mildew-proof wallpaper
CN108421082A (en) * 2018-04-23 2018-08-21 闫金银 The preparation method of graphene oxide wound dressing with antibacterial anti-scar double action
CN109331780B (en) * 2018-11-29 2021-03-30 长沙学院 Preparation method of activated carbon fiber/graphene tube composite material
CN113652885A (en) * 2021-07-19 2021-11-16 南京信息工程大学 Preparation method and application of bacterial cellulose-reinforced graphene oxide paper

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CN1145257A (en) * 1995-09-15 1997-03-19 清华大学 Method of using expansion graphite as wound dressing
CN102066245A (en) * 2007-10-19 2011-05-18 卧龙岗大学 Process for the preparation of graphene
CN101670108A (en) * 2009-08-13 2010-03-17 苏州纳米技术与纳米仿生研究所 Medicine carrying system based on nano graphene oxide
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