CN104803379A - Method for preparing three-dimensional self-assembly graphene implanted with nitrogen ions as well as application of method - Google Patents
Method for preparing three-dimensional self-assembly graphene implanted with nitrogen ions as well as application of method Download PDFInfo
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Abstract
The invention provides a method for preparing three-dimensional self-assembly graphene implanted with nitrogen ions as well as application of the method. The method comprises the following steps: taking three-dimensional self-assembly graphene synthesized according to a hydrothermal method as substrate; conducting form transform on the three-dimensional graphene according to a manner integrating wet slicing and freeze drying; implanting the nitrogen ions onto the three-dimensional self-assembly graphene slices with an ion implanter. The three-dimensional self-assembly graphene implanted with the nitrogen ions has the advantages that on the premise that the spatial structure of three-dimensional graphene is fully utilized, rich binding sites are provided for cells and surfactant protein of the cells. Therefore, the three-dimensional self-assembly graphene implanted with the nitrogen ions can serve as a tissue scaffold and the like and be wildly applied to the field of biomedical materials.
Description
The present invention obtains national natural science fund subsidy project (51272176); Country's high-tech research evolutionary operation(EVOP) item (863, No. SS2015AA030802); The subsidy of country's great scientific research plan Funded Projects (2012CB933600).
Technical field
The new discipline field that the three-dimensional grapheme that the invention belongs to ion modification is applied in bio-medical material.Relate to and use ion implanter by three-dimensional for N~+ implantation self-assembly graphenic surface, make it be applied to the new technology of biomedical sector as tissue stent material to reach.
Background technology
Graphene be a kind of by carbon atom with sp
2hybridized orbital composition hexangle type is the flat film of honeycomb lattice, only has several two-dimensional material to tens carbon atom thickness.Three-dimensional grapheme, as the macroscopic body of two-dimensional graphene material, is formed by two-dimensional graphene is stacking.Three-dimensional grapheme independently completed preparation in 2009 by Vickery and Wang Liang Ge team.Three-dimensional grapheme preparation method conventional is at present divided into self-assembly method and template two class.The present invention selects Hydrothermal Synthesis self-assembly method, utilizes the ionic forces between the H ion in graphene oxide O ion and water and Van der Waals force to form micron order hole, builds three-dimensional grapheme macroscopic body.
Since three-dimensional grapheme comes out, namely its huge specific surface area, micron-sized pore space structure, good machinery, electrical property are subject to pursuing of scientific circles.But to its applied research, then mainly concentrating on energy storage material is at present the electrochemical field of representative, rarely has research to relate to its biology performance.And use ion implantation technique to carry out surfactivity modification to it, and to be applied to this matrix material with organization bracket be that the biomedical sector of representative then has no report.
The present invention utilizes three-dimensional self-assembly Graphene structurally to have the advantage enriching hole, for Growth of Cells and propagation provide abundant solid space; This bio-active group of Nitrogen ion is introduced again by ion implantation mode, the defect of Graphene hydrophobicity, easily reunion, poor biocompatibility is overcome in biological property angle, make the three-dimensional self-assembly Graphene of N~+ implantation have good cell compatibility, the biological applications for three-dimensional grapheme provides initiative guiding.Meanwhile, three-dimensional self-assembly Graphene is by self-assembled molding, and body diameter mean value is 1.2 cm, and height average is the fixing pattern column diameter of 1.7cm.The invention provides a kind of method of it being carried out under condition not destroying its three-dimensional structure to pattern processing, the three-dimensional self-assembly Graphene of the N~+ implantation after the improvement efficient extn Application Areas of three-dimensional grapheme.
Table 1 self-assembly Graphene and the self-assembly Graphene physiologically acceptable experimental result through N~+ implantation
Summary of the invention
An object of the present invention is the preparation method making public for the first time the section of three-dimensional self-assembly Graphene.
Another object of the present invention discloses the technical parameter using ion implantation technique Nitrogen ion successfully to be introduced three-dimensional self-assembly Graphene.
Another object of the present invention is the application in technical field of biological material of the three-dimensional self-assembly Graphene that discloses N~+ implantation.
For achieving the above object, the invention provides following technology contents:
A three-dimensional self-assembly Graphene for N~+ implantation, is characterized in that its pore size scope is at 5 ~ 15 μm, and 2 μm of magnitudes can see obvious Graphene sheet structure under observing.The preparation method of the three-dimensional self-assembly Graphene of described N~+ implantation, is characterized in that, carry out as follows:
(1) by the three-dimensional self-assembly Graphene direct slicing of hygrometric state, slice thickness 2-3.2 mm; Then surface-moisture freezing 12 more than h below 0 DEG C are blotted; Last at-40 DEG C to-80 DEG C, be less than lyophilize 10-48 h under the condition of 10 Pa;
(2) the injection density of Nitrogen ion is 1 × 10
16-1 × 10
20individual/cm
2; Ion energy is 5-25keV; In described material, the percentage ratio of N is 0.6%-4.24%.
The three-dimensional self-assembly Graphene that the present invention further discloses N~+ implantation is as the application in organization bracket biomaterial, application wherein as organization bracket biomaterial aspect refers to: improve the growth of l cell at material surface, improve wetting ability and the protein adsorption of material, improve the application of the biocompatibility of material.
The present invention is more detailed to be described below:
The three-dimensional self-assembly Graphene of N~+ implantation, is characterized in that injecting nitrogen ion on the self-assembly Graphene after section; Wherein the injection density of Nitrogen ion is respectively 1 × 10
16individual/cm
2, 1 × 10
18individual/cm
2with 1 × 10
20individual/cm
2; Ion energy is 5-25 keV; In described material, the percentage ratio of N is 4.24% ~ 0.6%.
Self-assembly Graphene of the present invention, be at room temperature mixed with deionized water (concentration is 2 mg/mL) by the graphite oxide powder of drying, be injected in hydrothermal reaction kettle subsequently, setting working temperature is 180 DEG C, reaction times is 12 h, sends in baking oven and carries out self-assembling reaction.After shaping self-assembly Graphene cylinder section lyophilize, ion implanter is used to carry out N~+ implantation to it; In the process, adopt nitrogen as ion source, first carry out high temperature evaporation to nitrogen and accelerate electronics bombardment making its ionization, electron beam current density controls at 3 μ A/cm
2below; The air pressure of injection process middle chamber is 7.510
-3pa, temperature is room temperature, and ion energy is 2-25 keV.
The three-dimensional self-assembly Graphene sample of the present invention to three-dimensional self-assembly Graphene and N~+ implantation has carried out scanning electron microscope (SEM), fourier transform infrared spectroscopy instrument (FT-IR) and X-ray diffraction (XPS) and has carried out structural analysis and compare.Self-assembly Graphene after adopting CAM KSV021733 contact angle measurement effects on surface before modified carries out wetting ability and measures.
Fig. 1 is the SEM photo of self-assembly Graphene and the self-assembly Graphene through N~+ implantation, the surface topography of material can be observed intuitively by this figure, the pore size scope of self-assembly Graphene is at 3 ~ 10 μm, obvious Graphene sheet structure can be seen under 2 μm of magnitudes are observed, itself pattern of self-assembly Graphene after ion implantation does not change, prove that ion implantation mode can not have an impact to the porous three-dimensional structure of material, for it provides possibility as biological tissue's support.
Table 1 checks self-assembly Graphene for XPS and through self-assembly Graphene C, the O of N~+ implantation material surface, the content of N element, ion implantation concentration is 1 × 10
20individual/cm
2condition under, in sample, N content is the highest, reaches 4.24%.
Table 2 self-assembly Graphene and the self-assembly graphenic surface constituent content (%) through N~+ implantation
Fig. 2 is the XPS spectrum line chart of the self-assembly Graphene of self-assembly Graphene and injecting nitrogen ion, and as seen from the figure, C and O element is all obtained by spy in without ion implantation self-assembly Graphene sample, and N element does not then exist.
(1) by C
1Scompare with the spectral line without ion implantation self-assembly Graphene through ion implantation, self-assembly Graphene has peak value at 286.6 eV, the corresponding C-O key of this peak value and O-C-O key, and through the Graphene peak value of N~+ implantation at 285.5 eV, what this peak value was corresponding is C-N key, can find out the existence of Nitrogen ion;
(2) it is 1 × 10 that reference ion of reaching the same goal injects density
16individual/cm
2, 1 × 10
18individual/cm
2with 1 × 10
20individual/cm
2material spectrogram can find out: C
1Sin spectrum various dose injecting material in the peak area of C-N increase gradually, the increase along with ion implantation density can be found, increasing containing n of group in material.N
1Sin spectrum along with but the increase of ion implantation content, sp
2the peak area of C-N reduces sp gradually
3the peak area of C-N increases gradually, can find but ion implantationly to increase gradually.
Above phenomenon shows, along with the increase of N~+ implantation density, and more surfaces being present in self-assembly Graphene containing n of group.
The present invention further discloses self-assembly Graphene and the application of self-assembly grapheme material in biomaterial through N~+ implantation.Adopt the cytocompatibility of Apoptosis L929 test material, observation in vitro is in a growth cycle, and the self-assembly grapheme material of self-assembly Graphene and N~+ implantation is to the experiment of cell adhesion and growth.Control group uses 24 orifice plates being specifically designed to cell cultures, and sample sets is the self-assembly grapheme material of self-assembly Graphene implantation concentration different from three kinds.
As seen from Figure 4, control group and sample sets are between the 1 to 7 day, the l cell number adhering to material surface increases all gradually, reaching maximum value at the cell number of the 7th day blank group starts on a declining curve, be illustrated as after fibrocyte density acquires a certain degree and start to enter the paracme, and the cell number on experimental group material still increases gradually; Be 1 × 10 to the 8th day experimental group intermediate ion implantation concentration
20individual/cm
2cell number exceeded the peak-peak of control group, its excess-three group experimental group surface inoblast is also rising tendency and is greater than blank group at the 8th day cell number.Control group self character is just very suitable for cell adhesion thereon and growth, therefore the results show: the 3-D solid structure of three-dimensional self-assembly Graphene can increase cells survival space, extend cell growth time and step back the paracme, and the self-assembly Graphene after N~+ implantation turn increases various containing n of group, the increase along with nitrogen injection rate can be found out by growth curve, growth and the adhesion situation of cell all increase, and ion implantation concentration is 1 × 10
20individual/cm
2time, cell interlinking is best.Imply that this material, can be used as the candidate materials of organization bracket have Research Significance and using value widely in technical field of biological material.
Accompanying drawing explanation
Fig. 1: self-assembly Graphene and the SEM through the self-assembly Graphene of N~+ implantation scheme: wherein (a) is self-assembly Graphene; (b) for ion implantation concentration be 1 × 10
16individual/cm
2self-assembly Graphene; (c) for ion implantation concentration be 1 × 10
18individual/cm
2self-assembly Graphene; (d) for ion implantation concentration be 1 × 10
20individual/cm
2self-assembly Graphene.
Fig. 2: the C of self-assembly Graphene and the self-assembly Graphene through N~+ implantation
1sxPS spectrum line chart: wherein (a) is self-assembly Graphene; (b) for ion implantation concentration be 1 × 10
16individual/cm
2self-assembly Graphene; (c) for ion implantation concentration be 1 × 10
18individual/cm
2self-assembly Graphene; (d) for ion implantation concentration be 1 × 10
20individual/cm
2self-assembly Graphene.
Fig. 3: the N of self-assembly Graphene and the self-assembly Graphene through N~+ implantation
1sxPS spectrum line chart: wherein (a) for ion implantation concentration be 1 × 10
16individual/cm
2self-assembly Graphene; (b) for ion implantation concentration be 1 × 10
18individual/cm
2self-assembly Graphene; (c) for ion implantation concentration be 1 × 10
20individual/cm
2self-assembly Graphene.
Fig. 4: l cell is at the growth curve of self-assembly Graphene and the self-assembly graphenic surface through N~+ implantation.
Fig. 5: N~+ implantation self-assembly Graphene process schematic.
Fig. 6: the schematic arrangement of self-assembly Graphene and the self-assembly Graphene through N~+ implantation: (a) is self-assembly Graphene; B () is ion implantation self-assembly Graphene.
Fig. 7: self-assembly Graphene is at structural changes microcosmic schematic diagram before and after N~+ implantation.
Below in conjunction with embodiment, the present invention is described, the scheme of embodiment described here, do not limit the present invention, one of skill in the art can make improvements and change according to spirit of the present invention, these described improvement and change all should be considered as within the scope of the invention, and scope of the present invention and essence are limited by claim.
Embodiment
For content of the present invention, Characteristic can be understood further, be described as follows:
embodiment 1
The preparation of three-dimensional self-assembly Graphene section:
Prepare graphite oxide with Hummers, the powder of drying is mixed with deionized water (concentration is 2 mg/mL), through ultrasonic disperse, put into self-assembly 12 h under hydrothermal reaction kettle 180 DEG C of conditions, obtain self assembled three-dimensional Graphene hydrogel.
1) due to the weak easy distortion of self-assembly Graphene anti-pressure ability under moisture state, for preventing destroying its interior three-dimensional cavernous structure, adsorption surface moisture on filter paper after taking out moistening cylinder with spoon, is put in.
2) measuring material with vernier callipers, to obtain mean length be 1.7 cm, be that the slim blade of 0.1 mm carries out 7 grades to material and divides cutting by thinness, every equal portions thickness range is between 2-3.2 mm, verify by experiment, easily there is obvious powder phenomenon-tion in the section exceeding this scope after lyophilize.
3) the lamella self-assembly Graphene filter paper adsorption surface moisture will cut, is put in watch-glass, seals up for safekeeping with preservative film, freezing 12 more than h below 0 DEG C, ensure that it fully freezes, otherwise in drying process, liquid boiling situation can occur, destroy the surface topography of material.
4) material freezed to be put in the freeze drier of (model) within the scope of-40 DEG C to-80 DEG C, under the condition of the atmospheric pressure of 10 below Pa, between lyophilize 10-48 h, biological detection is for subsequent use, and the self-assembly grapheme material exceeding this scope has more serious powder phenomenon-tion equally.
Instrument needed for the preparation of the three-dimensional self-assembly Graphene section of table 3
Medicine needed for the preparation of the three-dimensional self-assembly Graphene section of table 4
embodiment 2
The preparation of the self-assembly Graphene of N~+ implantation:
Ion implanter is used to carry out N~+ implantation to self-assembly Graphene; In the process, adopt nitrogen as ion source, first carry out high temperature evaporation to nitrogen and accelerate electronics bombardment making its ionization, electron beam current density controls at 3 μ A/cm
2below; The air pressure of injection process middle chamber is 1 × 10
-3pa, temperature is room temperature, and ion energy is 5-25 keV.
Wherein Nitrogen ion be injected to 1 × 10
16individual/cm
2; The percentage ratio of Sauerstoffatom is 0.6%.
Wherein Nitrogen ion be injected to 1 × 10
18individual/cm
2; The percentage ratio of Sauerstoffatom is 0.73%.
Wherein Nitrogen ion be injected to 1 × 10
20individual/cm
2; The percentage ratio of Sauerstoffatom is 4.24%.
Ion implantation preparation parameter:
1) adopt nitrogen as ion source, sample is placed on and hides indoor, temperature of reaction room temperature, extract preliminary vacuum value and control to be 1 × 10
-3pa;
2) continue adjusting cabin house vacuum degree, regulate vacuum pressure to 7.5 × 10
-4pa;
3) electron beam current density controls at 3 μ A/cm
2below, controlling Nitrogen ion ion energy is 2-25 keV.Carry out high temperature evaporation to nitrogen and accelerate electronics bombardment making its ionization;
4) injection process ensures that atmospheric pressure value is 7.5 × 10
-4pa, change injection length correlation parameter according to injection density as shown in table 2, injection process as shown in Figure 4.
Table 5 self-assembly Graphene and the self-assembly graphenic surface constituent content (%) through N~+ implantation
Instrument and material needed for table 6 N~+ implantation
embodiment 3
L cell adheres to and propagation behavior case study:
Different for N~+ implantation content three kinds of self-assembly grapheme materials and each 32 of untreated self-assembly grapheme material are placed in 24 orifice plates respectively, are divided into 4 groups (repeating experiment for 4 times).By cultivating 48 h, to make cell concn be 1 × 10 to eugonic L929 cell
4the cell suspension (cell survival rate 96%) of individual/mL, uses liquid-transfering gun equivalent (700 μ L) to drip at sample surfaces, and another inoculation 8 blank well as a control group.When 1 d, 3 d, 4 d, 5 d, 6 d, 7 d, 8 d and 9 d, with the cell proliferation curve on mtt assay test material.Test was often organized sample and was got 1 hole the same day, injected the 3-(4 of 170 μ L, 5-dimethylthiazole-2)-2,5-diphenyltetrazolium bromide bromine salt (MTT) staining fluids dye to viable cell, at the CO of 37 DEG C
2after hatching 4 h in incubator, sucking-off nutrient solution adds dimethyl sulfoxide (DMSO) (DMSO) and cultivates 30 min, liquid-transfering gun equivalent (70 μ L) sucking liquid is used to transfer in 96 orifice plates, use Biotek ELx808 type absorb light microplate reader to be that 490 nm places measure light absorption value in absorbancy, draw growth curve.
Table 7 l cell adheres to required instrument and consumables associated therewith with propagation
Table 8 l cell adheres to the required medicine with propagation
embodiment 4
Bovine serum albumin is to the protein adsorption experiment of the self-assembly Graphene of self-assembly Graphene and injecting nitrogen ion
1) with bovine serum albumin (BSA) solution, measure the absorbancy of this solution, to absorbancy be y=3.1x+0.6, R2=0.841 to the relation curve of BSA concentration.
2) add material with the protein solution of the PH=6.9 of 200 μ L, at room temperature deposit 24 h, protein concn is C
0=4.0 mg/mL.
3) add and pipette with liquid-transfering gun one group of BSA solution that 50 ul prepare respectively, add the Xylene Brilliant Cyanine G (CBB) of 200 ul.After leaving standstill 10 min, record the absorbancy of the solution of this group BSA with spectrophotometer.
4) bring numerical value into 1) in the equation that calculates to solution protein concentration be C
1.
5) then the adsorptive capacity of albumen is Qa=40 (C
0-C
1)/S.
6) through measuring, self-assembly Graphene protein adsorption quantity increases along with N ionic concn and is rendered as up-trend, as shown in table 3, illustrate that the injection of nitrogen particle can improve the protein adsorption quantity of material surface, protein adsorption quantity is larger, platelet adhesion effect is lower, thus the anticoagulation function of testimonial material is better, and then reaches the object improving Biocompatibility.
Table 9 self-assembly Graphene and the self-assembly Graphene bovine serum albumin adsorptive capacity through N~+ implantation
The required instrument of table 10 bovine serum albumin absorption and consumables associated therewith
The required medicine of table 11 bovine serum albumin absorption
After the preferred embodiment described in detail, be familiar with this technology personage can be well understood to, do not departing under above-mentioned claim and spirit and can carry out various change and amendment, all above embodiment is done according to technical spirit of the present invention any simple modification, equivalent variations and modification, all belong to the scope of technical solution of the present invention.And the present invention is not also by the limit of example embodiment in specification sheets.
Claims (4)
1. the three-dimensional self-assembly Graphene of N~+ implantation, is characterized in that its pore size scope is at 5 ~ 15 μm, and 2 μm of magnitudes can see obvious Graphene sheet structure under observing, and nitrogen content is between 0.6%-4.24%.
2. the preparation method of the three-dimensional self-assembly Graphene of N~+ implantation described in claim 1, is characterized in that, carry out as follows:
(1) by the three-dimensional self-assembly Graphene direct slicing of hygrometric state, slice thickness 2-3.2 mm; Then surface-moisture freezing 12 more than h below 0 DEG C are blotted; Last at-40 DEG C to-80 DEG C, be less than lyophilize 10-48 h under the condition of 10 Pa;
(2) the injection density of Nitrogen ion is 1 × 10
16-1 × 10
20individual/cm
2; Ion energy is 5-25keV; In described material, the percentage ratio of nitrogen-atoms is 0.6%-4.24%.
3. the three-dimensional self-assembly Graphene of N~+ implantation described in claim 1 is being prepared as the application in organization bracket biomaterial.
4. application according to claim 3, the application wherein as organization bracket biomaterial aspect refers to: improve cell in the adhesion of material surface and growth; Improve hydrophilicity and the protein adsorption performance of material; Improve the biocompatibility of material itself.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107248581A (en) * | 2017-06-30 | 2017-10-13 | 燕山大学 | The composite and preparation method of a kind of N doping three-dimensional grapheme loading nano silvery |
| CN113069597A (en) * | 2021-06-07 | 2021-07-06 | 中南大学湘雅医院 | Method for preparing titanium dioxide doped ceramic film by sol-gel method |
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| CN102486993A (en) * | 2010-12-02 | 2012-06-06 | 国家纳米科学中心 | Preparation method of doped graphene and application of doped graphene |
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| CN102486993A (en) * | 2010-12-02 | 2012-06-06 | 国家纳米科学中心 | Preparation method of doped graphene and application of doped graphene |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107248581A (en) * | 2017-06-30 | 2017-10-13 | 燕山大学 | The composite and preparation method of a kind of N doping three-dimensional grapheme loading nano silvery |
| CN107248581B (en) * | 2017-06-30 | 2020-02-04 | 燕山大学 | Nitrogen-doped three-dimensional graphene nano-silver-loaded composite material and preparation method thereof |
| CN113069597A (en) * | 2021-06-07 | 2021-07-06 | 中南大学湘雅医院 | Method for preparing titanium dioxide doped ceramic film by sol-gel method |
| CN113069597B (en) * | 2021-06-07 | 2021-08-06 | 中南大学湘雅医院 | Method for preparing titanium dioxide doped ceramic film by sol-gel method |
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Application publication date: 20150729 |