CN104843686B - Preparation method of carboxymethyl chitosan modified graphene oxide composite material - Google Patents
Preparation method of carboxymethyl chitosan modified graphene oxide composite material Download PDFInfo
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- CN104843686B CN104843686B CN201510177023.4A CN201510177023A CN104843686B CN 104843686 B CN104843686 B CN 104843686B CN 201510177023 A CN201510177023 A CN 201510177023A CN 104843686 B CN104843686 B CN 104843686B
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Abstract
The invention relates to a preparation method of a carboxymethyl chitosan modified graphene oxide composite material; the preparation method includes the steps: (1) under the action of activating agents EDC and NHS, allowing graphene oxide dispersed in water to generate chemical bond connection with CMC, carrying out a reaction for 24 h at room temperature, to obtain a suspension with relatively good micro-particle dispersity, dialyzing, freeze-drying, and thus synthesizing GO-CMC; and (2) dissolving the obtained product in distilled water, adding an appropriate amount of fluorescein FITC; and acetylating the product, carrying out a stirring reaction for 24 h at room temperature, dialyzing, freeze-drying, and thus synthesizing the graphene oxide GO-CMC-FI-Ac composite material. The preparation method is simple to operate, and the product is easy to handle; and the composite material can be applicable to drug sustained release and cell imaging, and the cost is low.
Description
Technical field
The invention belongs to the preparation field of graphene oxide composite material, more particularly to a kind of carboxymethyl chitosan is sugar-modified
The preparation method of graphene oxide composite material.
Background technology
Geim and Novoselov of Univ Manchester UK in 2004 et al. are successfully made first using adhesive tape lift-off technology
It is standby gone out the New Two Dimensional atomic crystal-Graphene being made up of with the monoatomic layer that sp2 hydridization connects carbon atom.This discovery
Overthrown scientists with regard to preferable two dimensional crystal material can not exist at room temperature due to thermodynamic phase it is pre-
Speech.And because Graphene has excellent mechanics, electricity, optical property so that graphite is become based on the composite of Graphene
The focus that alkene application is widely studied, it has in fields such as energy storage, liquid crystal device, electronic device, biomaterials
Wide application prospect.
But because Graphene is difficult to prepare with scale, and surface reaction activity site is less, application is restricted.Oxidation stone
Black alkene GO is in the more Graphene derivative of biomedical sector application.Can be under strong acid and strong oxidizer effect using chemistry
It is prepared by oxidizing process.There is the oxygen-containing functional groups such as substantial amounts of hydroxyl, carboxyl and epoxy radicals in the surface of graphene oxide, can be anti-for chemistry
Reaction site should be provided, while can also improve dissolubility of the GO in polar solvent.
Shitosan is the product of chitin deacetylase base, and its unique biological activity and physiological function cause shitosan making
For pharmaceutical carrier when there is many advantages such as biochemistry and economic benefit.But, shitosan can not be dissolved in water, can only
In being dissolved in some acid aqueous solutions so that the application of shitosan is greatly limited.Special chemical modification can draw
Enter hydrophilic group, improve shitosan dissolubility in aqueous.Wherein, carboxy methylation is the most frequently used and most efficient method it
One.Product carboxymethyl chitosan is a kind of polyampholyte, effectively can carry out complexation with metal ion, nontoxic, tasteless, tool
There are excellent film property, water solublity, moisture absorbability and moisture retentivity, thickening property etc..Compared with shitosan, the water solublity of carboxymethyl chitosan is carried
High, it is possible to dissolve in extensive pH value solution, good biocompatibility, degradable, these enrich and the functional character of uniqueness
Carboxymethyl chitosan is set to be applied in multiple fields such as food, agricultural, daily use chemicals, medicine, water process, such as medical dressing, food
Savor antistaling agent, cosmetic humectant, water treatment flocculant etc..
The content of the invention
The technical problem to be solved is to provide a kind of sugar-modified graphene oxide composite wood of carboxymethyl chitosan
The preparation method of material, the present invention synthesizes the graphene oxide composite material containing carboxymethyl, operation letter using the method for chemical bonding
Single, experiment condition is gentle.
A kind of preparation method of the sugar-modified graphene oxide composite material of carboxymethyl chitosan of the invention, including：
(1) by graphene oxide GO solution, activator EDC and NHS are added, activates 2-3h, be subsequently adding carboxymethyl shell
Polysaccharide CMC solution, reacts at ambient temperature 12-24h, and dialysis, lyophilization obtains GO-CMC；
(2) above-mentioned GO-CMC is dissolved in distilled water, adds fluorescein isothiocyanate FITC solution, reacted under room temperature condition
2-3h, obtains GO-CMC-FI；
(3) triethylamine stirring mixing will be added in above-mentioned GO-CMC-FI, acetic anhydride mixing is subsequently adding, under room temperature condition
Reaction 12-24h, dialysis, lyophilization obtains final product the sugar-modified graphene oxide composite material GO-CMC-FI- of carboxymethyl chitosan
Ac。
Graphene oxide and the mass ratio of carboxymethyl chitosan CMC are 1 in the step (1):1-1:2.
Graphene oxide solution, the solvent of carboxymethyl chitosan CMC solution are distilled water in the step (1).
The solvent of fluorescein isothiocyanate FITC solution is dimethyl sulfoxide DMSO in the step (2).
The mass ratio of GO-CMC and fluorescein isothiocyanate FITC is 40 in the step (2):1-50:1.
Triethylamine stirring incorporation time is added to be 15-30min in the step (3), amino and triethylamine in GO-CMC
Mol ratio is 1:1-1:1.5.
Amino and the mol ratio of acetic anhydride are 1 in GO-CMC in the step (3):5-1:10.
Dialyse in the step (1), (3) and be：First dialyse in the buffer of pH=6-7, then dialyse in water, during dialysis
Between be 3-5d.
Beneficial effect
(1) present invention synthesizes the graphene oxide composite material containing carboxymethyl, preparation method using the method for chemical bonding
Simple to operate, experiment condition is gentle；
(2) graphene oxide composite material of the invention overcomes the problem that Graphene is easily reunited, by carboxymethyl
Modification, reduces the toxicity of graphene oxide and improves the biocompatibility of material, and with using it follow-up related experiment point is done
The potentiality of analysis；
(3) graphene oxide composite material containing carboxymethyl can serve as load and the slow release of medicine, and particular organization determines
To conveying and the fluorescence imaging of cell.
Description of the drawings
Fig. 1 is that the transmission electron microscope of the GO-CMC-FI-Ac of the gained of embodiment 1 shines；.
Fig. 2 is CMC, GO-CMC, GO-CMC-FI-Ac of the gained of embodiment 21H-NMR collection of illustrative plates；Wherein a is for CMC, b
GO-CMC, c are GO-CMC-LA-Ac；
Fig. 3 is GO, GO-CMC and the UV-Vis collection of illustrative plates containing GO-CMC-FI-Ac of the gained of embodiment 3.
Specific embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than restriction the scope of the present invention.In addition, it is to be understood that after the content for having read instruction of the present invention, people in the art
Member can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited
Scope.
Embodiment 1
(1) by graphene oxide GO (50mg), in being dissolved in 10mL water, activator EDC (30mg), NHS (18mg) are added,
Stirring reaction 2h under room temperature.In reaction, aqueous solutions of the 5mL containing CMC (75mg) is added dropwise over, reaction 24h is stirred at room temperature.
After reaction solution is dialysed with bag filter (MW=100,000).With PBS twice after, each volume 2L, then with distillation
Water is dialysed 7 times, each volume 2L, removes impurity and by-product in solution.Products therefrom lyophilization, synthesizes GO-CMC.
(2) GO-CMC that 40mg is taken from above-mentioned product is dissolved in appropriate distilled water, adds 1.2mg fluorescein isothiocyanates
The DMSO solution of FITC, stirring reaction 3h under room temperature.
(3) add 360uL triethylamines to mix in above-mentioned product and add after 30min the mixing of 240uL acetic anhydrides, in room
The lower reaction 24h of temperature.With bag filter, (000) MW=14 is dialysed solution after reaction.With PBS twice after, each volume
2L, then dialysed 7 times with distilled water, each volume 2L removes the impurity and by-product in solution.Products therefrom lyophilization, closes
Into GO-CMC-FI-Ac.
(4) TEM of final product GO-CMC-FI-Ac is characterized as shown in Figure 1, it can be seen that graphene oxide is through work(
Can still keep its laminar structured after modified, i.e. modification occurs over just the surface of graphene oxide, not change oxidation stone
The black alkene structure of itself.
Embodiment 2
(1) by graphene oxide GO (100mg), in being dissolved in 25mL water, activator EDC (45mg), NHS (35mg) are added
Stirring reaction 2h under room temperature.In reaction, aqueous solutions of the 20mL containing CMC (200mg) is added dropwise over, reaction is stirred at room temperature
24h.After reaction solution is dialysed with bag filter (MW=100,000).With PBS twice after, each volume 2L, then use
Distilled water is dialysed 7 times, each volume 2L, removes impurity and by-product in solution.Products therefrom lyophilization, synthesizes GO-
CMC。
(2) GO-CMC that 30mg is taken from above-mentioned product is dissolved in appropriate distilled water, adds 1mg fluorescein isothiocyanate FITC
DMSO solution, stirring reaction 3h under room temperature.
(3) add 280uL triethylamines to mix in above-mentioned product and add after 20min the mixing of 160uL acetic anhydrides, in room
The lower reaction 24h of temperature.With bag filter, (000) MW=14 is dialysed solution after reaction.With PBS twice after, each volume
2L, then dialysed 7 times with distilled water, each volume 2L removes the impurity and by-product in solution.Products therefrom lyophilization, closes
Into GO-CMC-FI-Ac.
(4) the 1H-NMR collection of illustrative plates of CMC, GO-CMC, GO-CMC-FI-Ac is not as shown in Fig. 2 because GO has in itself nuclear-magnetism peak,
The proton peak produced in Fig. 2-b is hydrogen atom on CMC, and Fig. 2-c compare Fig. 2-b, and one is occurred in that at δ=1-2 than larger
Peak, that is that methyl peak is defined when acetylizad.Demonstrate success acetylizad to material.
Embodiment 3
(1) by graphene oxide GO (78mg), in being dissolved in 10mL water, activator EDC (45mg), NHS (40mg) are added
Stirring reaction 2.5h under room temperature.In reaction, aqueous solutions of the 20mL containing CMC (120mg) is added dropwise over, reaction is stirred at room temperature
24h.After reaction solution is dialysed with bag filter (MW=100,000).With PBS twice after, each volume 2L, then use
Distilled water is dialysed 7 times, each volume 2L, removes impurity and by-product in solution.Products therefrom lyophilization, synthesizes GO-
CMC。
(2) GO-CMC that 20mg is taken from above-mentioned product is dissolved in appropriate distilled water, adds 0.8mg fluorescein isothiocyanates
The DMSO solution of FITC, stirring reaction 3h under room temperature.
(3) add 200uL triethylamines to mix in above-mentioned product and add after 30min the mixing of 115uL acetic anhydrides, in room
The lower reaction 24h of temperature.With bag filter, (000) MW=14 is dialysed solution after reaction.With PBS twice after, each volume
2L, then dialysed 7 times with distilled water, each volume 2L removes the impurity and by-product in solution.Products therefrom lyophilization, closes
Into GO-CMC-FI-Ac.
(4) the UV-Vis collection of illustrative plates of GO, GO-CMC, GO-CMC-FI-Ac is as shown in figure 3, GO-CMC-FI-Ac is at 501nm
There is absworption peak, the absworption peak is the characteristic absorption peak of FITC, illustrates that FITC has been successfully accessed to graphene oxide composite wood
In material.
Embodiment 4
(1) by graphene oxide GO (200mg), in being dissolved in 40mL water, activator EDC (92mg), NHS (80mg) are added
Stirring reaction 2h under room temperature.In reaction, aqueous solutions of the 35mL containing CMC (325mg) is added dropwise over, reaction is stirred at room temperature
24h.After reaction solution is dialysed with bag filter (MW=100,000).With PBS twice after, each volume 2L, then use
Distilled water is dialysed 7 times, each volume 2L, removes impurity and by-product in solution.Products therefrom lyophilization, synthesizes GO-
CMC。
(2) GO-CMC that 40mg is taken from above-mentioned product is dissolved in appropriate distilled water, adds 1.5mg fluorescein isothiocyanates
The DMSO solution of FITC, stirring reaction 3h under room temperature.
(3) add 360uL triethylamines to mix in above-mentioned product and add after 25min the mixing of 240uL acetic anhydrides, in room
The lower reaction 24h of temperature.With bag filter, (000) MW=14 is dialysed solution after reaction.With PBS twice after, each volume
2L, then dialysed 7 times with distilled water, each volume 2L removes the impurity and by-product in solution.Products therefrom lyophilization, closes
Into GO-CMC-FI-Ac.
(4) the Zeta electric potential collection of illustrative plates of GO, GO-CMC, GO-CMC-FI-Ac is as shown in table 1, it can be found that when negatively charged
Current potential becomes big when connecting positively charged CMC on GO, and current potential diminishes after GO-CMC acetylations, illustrates that CMC is successfully connected
On GO, and successful acetylation.
Table 1
| Sample | Zeta potential (mV) |
| GO | -42.3±1.42 |
| GO-CMC | -37.1±0.3 |
| GO-CMC-FI-Ac | -43.2±0.04 |
Claims (8)
1. the preparation method of the sugar-modified graphene oxide composite material of a kind of carboxymethyl chitosan, including：
(1) by graphene oxide GO solution, activator EDC and NHS are added, activates 2-3h, be subsequently adding carboxymethyl chitosan
CMC solution, reacts at ambient temperature 12-24h, and dialysis, lyophilization obtains GO-CMC；
(2) above-mentioned GO-CMC is dissolved in distilled water, adds fluorescein isothiocyanate FITC solution, under room temperature condition 2- is reacted
3h, obtains GO-CMC-FI；
(3) triethylamine stirring mixing will be added in above-mentioned GO-CMC-FI, is subsequently adding acetic anhydride mixing, reacted under room temperature condition
12-24h, dialysis, lyophilization obtains final product the sugar-modified graphene oxide composite material of carboxymethyl chitosan.
2. the preparation method of the sugar-modified graphene oxide composite material of a kind of carboxymethyl chitosan according to claim 1,
It is characterized in that：Graphene oxide and the mass ratio of carboxymethyl chitosan CMC are 1 in the step (1):1-1:2.
3. the preparation method of the sugar-modified graphene oxide composite material of a kind of carboxymethyl chitosan according to claim 1,
It is characterized in that：Graphene oxide solution, the solvent of carboxymethyl chitosan CMC solution are distilled water in the step (1).
4. the preparation method of the sugar-modified graphene oxide composite material of a kind of carboxymethyl chitosan according to claim 1,
It is characterized in that：The solvent of fluorescein isothiocyanate FITC solution is dimethyl sulfoxide DMSO in the step (2).
5. the preparation method of the sugar-modified graphene oxide composite material of a kind of carboxymethyl chitosan according to claim 1,
It is characterized in that：The mass ratio of GO-CMC and fluorescein isothiocyanate FITC is 40 in the step (2):1-50:1.
6. the preparation method of the sugar-modified graphene oxide composite material of a kind of carboxymethyl chitosan according to claim 1,
It is characterized in that：Triethylamine is added to stir incorporation time for 15-30min in the step (3), amino and triethylamine in GO-CMC
Mol ratio be 1:1-1:1.5.
7. the preparation method of the sugar-modified graphene oxide composite material of a kind of carboxymethyl chitosan according to claim 1,
It is characterized in that：Amino and the mol ratio of acetic anhydride are 1 in GO-CMC in the step (3):5-1:10.
8. the preparation method of the sugar-modified graphene oxide composite material of a kind of carboxymethyl chitosan according to claim 1,
It is characterized in that：Dialyse in the step (1), (3) and be：First dialyse in the buffer of pH=6-7, then dialyse in water, thoroughly
The analysis time is 3-5d.
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| CN105498724A (en) * | 2015-12-03 | 2016-04-20 | 陕西科技大学 | Oxidized graphene/carboxymethyl chitosan magnetic microsphere adsorbent for adsorbing methyl orange dye and preparation method of adsorbent |
| CN107540883B (en) * | 2017-09-08 | 2020-05-12 | 东华大学 | Preparation method of carboxymethyl chitosan/graphene oxide/poly (N-isopropylacrylamide) nano composite hydrogel |
| CN108719317A (en) * | 2018-05-23 | 2018-11-02 | 江南大学 | A kind of preparation method of positive charge nano-graphene anti-biotic material |
| CN110483662A (en) * | 2019-07-05 | 2019-11-22 | 常州大学 | A kind of carboxymethyl chitosan cross-linked gel |
| CN110591830A (en) * | 2019-09-26 | 2019-12-20 | 安徽省聚科石墨烯科技股份公司 | Graphene oxide type degreasing agent and preparation method thereof |
| CN113174090B (en) * | 2021-04-06 | 2022-04-05 | 中科院广州化学有限公司 | Preparation and application of green nano-cellulose high-thermal-conductivity composite film |
| CN113603895B (en) * | 2021-08-16 | 2022-03-29 | 南京工业大学 | Preparation method of chitosan-graphene oxide hybrid material |
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| Adsorbent for chromium removal based on graphene oxide functionalized with magnetic cyclodextrin–chitosan;LeiLei Li et al.;《Colloids and Surfaces B: Biointerfaces》;20130214;第107卷;第77页第2.2部分 * |
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