CN104399090A - Poly dopamine-modified reduced graphene oxide and preparation method and application thereof - Google Patents
Poly dopamine-modified reduced graphene oxide and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses poly dopamine-modified reduced graphene oxide and a preparation method and application thereof, the polydopamine-modified reduced graphene oxide includes reduced graphene oxide and poly dopamine, and the poly dopamine is attached to the surface of the reduced graphene oxide in physical adsorption manner. The preparation method comprises the following steps: according to the mass ratio of (1-4): (1-4), weighing graphene oxide and dopamine hydrochloride, adding the graphene oxide and the dopamine hydrochloride into solvent to completely dissolve to prepare a mixed solution; adjusting the pH value of the mixed solution to 8.5-9, and reacting for 12h-24h at the temperature of 55 to 65 DEG C to obtain the poly dopamine-modified reduced graphene oxide. The preparation method is friendly to the environment, low in reduction temperature, in no need of adding a stabilizer, and simple in process, realizes the reduction and stabilization in one step, and is suitable for mass production. The invention also provides the application of the poly dopamine-modified reduced graphene oxide.
Description
Technical field
The present invention relates to new material technology field, particularly relate to redox graphene of a kind of poly-dopamine modification and its preparation method and application.
Background technology
Graphene (Graphene) is a kind of new material of the monolayer laminated structure be made up of carbon atom; Be a kind of by carbon atom with sp
2hybrid orbital composition hexangle type is the flat film of honeycomb lattice, only has the two-dimensional material of a carbon atom thickness.The performances such as the high-modulus that this material has, high strength, good heat conductivity, the carrier mobility of excellence and the specific surface area of super large make it illustrate wide application prospect in fields such as electronic device, sensor, energy storage device and composites.The preparation method of current Graphene mainly comprises micromechanics stripping method, chemical vapour deposition technique, epitaxial growth method, graphene oxide reducing process, organic synthesis method, solvent stripping method and thermal reduction etc.Comparatively speaking, with low cost, the technique of graphene oxide reducing process is simple, is most possibly to realize method prepared by scale, therefore comparatively extensive to its research.
Graphene oxide reducing process is referred to first to be reacted by native graphite plate and strong acid and oxidizing species and generates graphite oxide, prepares graphene oxide through ultrasonic disperse, then by reducing agent (as hydrazine, dimethylhydrazine, NaBH
4, LiAlH
4, vitamin C, tea polyphenols etc.), make the oxygen-containing functional group in graphene oxide (as carboxyl, epoxy radicals and hydroxyl etc.) reduce and obtain Graphene method (due to obtain Graphene still there is certain oxygen-containing functional group, therefore the Graphene obtained by graphene oxide reducing process is called redox graphene by the present invention).But existing graphene oxide reducing process mainly has following shortcoming: utilize hydrazine class reagent (as hydrazine, dimethylhydrazine), NaBH
4, LiAlH
4deng the more supervirulent reagent of tool as reducing agent, to environment, there is larger harm, be unfavorable for large-scale industrial production; During the reducing agent utilizing vitamin C, tea polyphenols etc. environmentally friendly, along with hydrophilic oxy radical is reduced, redox graphene is easily reunited, so will add stabilizing agent when reducing.Therefore, to those skilled in the art, be badly in need of a kind of new reducing agent of research and development, can not produce environment when graphite oxide is reduced and pollute, and without the need to adding stabilizing agent, realize reduction and stablize a step carrying out.
Summary of the invention
For solving the problem, first aspect present invention provides the redox graphene that a kind of poly-dopamine is modified, and the redox graphene that described poly-dopamine is modified has good dispersibility; Second aspect provides the preparation method of the redox graphene that a kind of poly-dopamine is modified, and achieves graphene oxide reduction and a stable step is carried out; Third aspect present invention additionally provides the application of the redox graphene that described poly-dopamine is modified.
First aspect, the invention provides the redox graphene that a kind of poly-dopamine is modified, the redox graphene that described poly-dopamine is modified comprises redox graphene and poly-dopamine, and described poly-dopamine is attached to the surface of described redox graphene in the mode of physical absorption.
Preferably, described poly-dopamine is film like, is evenly attached to redox graphene surface.
Preferably, the redox graphene length that described poly-dopamine is modified is 200nm ~ 600nm, is highly 2.0nm ~ 3.0nm.
The delocalized pi-bond of the redox graphene that poly-dopamine of the present invention is modified is modified, and dispersive property is improved.
Second aspect, the invention provides the preparation method of the redox graphene that a kind of poly-dopamine is modified, comprises the steps:
According to (1 ~ 4): the mass ratio of (1 ~ 4) takes graphene oxide and dopamine hydrochloride, described graphene oxide and described dopamine hydrochloride are joined in solvent and makes it fully dissolve, obtained mixed solution; Regulate pH value to 8.5 ~ 9.0 of described mixed solution, at 55 DEG C ~ 65 DEG C temperature, after reaction 12h ~ 24h, obtain the redox graphene that described poly-dopamine is modified.
Preferably, the number of plies of described graphene oxide is monolayer.
Preferably, the height of described graphene oxide is 0.8 ~ 1.2nm.
Preferably, the mass ratio of described graphene oxide and described dopamine hydrochloride is 2:1.
Preferably, described pH value is 8.5.
Preferably, described temperature is 60 DEG C, and the described response time is 24h.
Preferably, described reaction carries out under the condition of vigorous stirring.
More preferably, described reaction is low whipping speed is carry out under the condition of 600rpm.
Preferably, described mixed solution is stirred ultrasonic 10 minutes in ice-water bath, to activate dopamine hydrochloride, impel it that self-polymerization reaction occurs.
Preferably, described solvent is Tris-Cl solution or PBS buffer.
Dopamine hydrochloride is white or the glossiness crystallization of off-white color, odorless, mildly bitter flavor; Dew is put in air, and it is dark to meet photochromic gradual change; Easily molten in water.In the present invention, under dopamine hydrochloride is placed in alkali condition, dopamine hydrochloride can form dopamine, graphene oxide reduces as reducing agent by dopamine, by its oxygen-containing functional group (as carboxyl, epoxy radicals and hydroxyl etc.) reduction, obtain redox graphene, existing hydroxyl in dopamine molecule, there are again carbon-carbon double bond and conjugated double bond, in the middle of alkaline solution, can self-polymeric reaction be there is in dopamine, the poly-dopamine that its autohemagglutination generates is attached to redox graphene surface in the mode of physical absorption, redox graphene containing poly-dopamine granule, delocalized pi-bond is modified, dispersibility and stability improve greatly.Therefore, the present invention prepares redox graphene without the need to adding other reagent such as stabilizing agent, achieve reduction and stablize a step and carry out, and environment is not produced and pollute, also be convenient to the follow-up redox graphene to generating carry out further functional modification (in such as poly-dopamine carbonyl, carbon-carbon double bond and conjugated double bond can with sulfydryl, amino and quinone structure etc. reacts and forms covalence graft functional material).
The preparation method of the redox graphene that the poly-dopamine that second aspect present invention provides is modified is environmentally friendly, and reduction temperature is low, and without the need to adding stabilizing agent, technique is simple, achieves reduction and stablizes a step and carry out, be applicable to large-scale mass production.
Graphene oxide of the present invention and dopamine hydrochloride all can directly be bought from the market or directly be prepared by prior art.
Third aspect present invention provides the redox graphene of the poly-dopamine modification described in first aspect present invention in photoacoustic ultrasound multi-modality imaging or the application in the photo-thermal therapy medicine of preparation cancer.
The redox graphene that described poly-dopamine is modified has strong optoacoustic effect, can be applied to and prepare photoacoustic tomography probe, have potential using value in fields such as photoacoustic ultrasound multi-modality imagings.In addition, the redox graphene that described poly-dopamine is modified also has certain photo-thermal effect, can be applicable to the photo-thermal therapy medicine preparing cancer.
Compared with prior art, the present invention has following beneficial effect:
1, the preparation method of the redox graphene of poly-dopamine modification provided by the invention is by using dopamine hydrochloride as reducing agent redox graphene, environmentally friendly, reduction temperature is low, and without the need to adding stabilizing agent, technique is simple, achieve reduction and stablize a step and carry out, be applicable to large-scale mass production;
2, the redox graphene photoacoustic signal that poly-dopamine provided by the invention is modified strengthens greatly, optoacoustic effect significantly improves, photo-thermal effect also significantly improves, and the redox graphene that described poly-dopamine is modified has good using value at photoacoustic ultrasound multi-modality imaging or in the photo-thermal therapy medicine of preparation cancer.
Accompanying drawing explanation
Fig. 1 is the preparation process schematic diagram that the embodiment of the present invention 1 gathers the redox graphene that dopamine is modified;
Fig. 2 is the ultraviolet-visible-near-infrared figure of the redox graphene of poly-dopamine modification prepared by the embodiment of the present invention 1;
Fig. 3 is x-ray photoelectron power spectrum (XPS) figure of the redox graphene of poly-dopamine modification prepared by the embodiment of the present invention 1;
Fig. 4 is atomic force microscope (AFM) figure of the redox graphene of poly-dopamine modification prepared by the embodiment of the present invention 1;
Fig. 5 is that the stability of the redox graphene of poly-dopamine modification prepared by graphene oxide and embodiment 1 compares;
Fig. 6 is the photo-thermal therapy design sketch of redox graphene in mouse breast cancer tumour model of poly-dopamine modification prepared by graphene oxide and embodiment 1;
Fig. 7 is the photoacoustic imaging design sketch of the redox graphene of poly-dopamine modification prepared by embodiment 1.
Detailed description of the invention
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearly understand, below in conjunction with accompanying drawing and preferred embodiment, the present invention is described in further detail.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not used in restriction the present invention.
Embodiment 1:
A preparation method for the redox graphene that poly-dopamine is modified, comprises the steps:
(1) first take 10mg graphene oxide (GO) add be equipped with 20mL pH be 8.5 concentration be in the round-bottomed flask of 10mMTris-Cl solution, and by this round-bottomed flask in ice-water bath ultrasonic 10 minutes, make graphene oxide be dissolved completely in Tris-Cl solution;
(2) in above-mentioned round-bottomed flask, add the dopamine hydrochloride (DA) of 5mg, then this round-bottomed flask is stirred in ice-water bath ultrasonic 10 minutes to activate dopamine hydrochloride, obtain yellowish-brown reaction mixture;
(3) under above-mentioned reaction mixture being placed in the condition of 60 DEG C, vigorous stirring reacts 24h;
(4) to above-mentioned reaction mixture, by centrifuge washing, (rotating speed is set to 10,000rpm/min, each washing 20min, washs 8 times altogether) mode removes free dopamine hydrochloride, obtains the redox graphene (PDA-RGO) that poly-dopamine is modified.
Fig. 1 is the preparation process schematic diagram that the embodiment of the present invention 1 gathers the redox graphene that dopamine is modified; As can be seen from Figure 1, through dopamine, (chemical formula is graphene oxide (in figure, " 1 " represents)
) after reduction, the oxygen-containing functional group (in figure shown in arrow) in graphene oxide reduces, after reduction, dopamine autohemagglutination generates poly-dopamine, and (chemical formula is
), poly-dopamine is attached to redox graphene surface in the mode of physical absorption, obtains the redox graphene (in figure, " 2 " represent) that poly-dopamine is modified.
Fig. 2 is the ultraviolet-visible-near-infrared figure of the redox graphene of poly-dopamine modification prepared by the embodiment of the present invention 1; As can be seen from Figure 2, graphene oxide (GO) has obvious characteristic ultraviolet absorption peak at 228nm and 300nm place, after being modified by dopamine reduction, the 228nm ultraviolet absorption peak of PDA-RGO still exists, and 300nm ultraviolet absorption peak weakens disappearance, illustrate that the PDA-RGO reducing and obtain is modified in graphene oxide success by dopamine, most of oxygen-containing functional group is reduced.
Fig. 3 is graphene oxide (x-ray photoelectron power spectrum (XPS) figure of the redox graphene (Fig. 3 b) that the poly-dopamine that Fig. 3 a) is prepared with the embodiment of the present invention 1 is modified; As can be seen from Fig. 3 a, in graphene oxide, C atom has three kinds of covalent bond existences, the corresponding C-C of 284.8eV in conjunction with energy, 286.8eV be C-O in conjunction with energy, 288.4eV be then C=O in conjunction with energy.After poly-dopamine is modified, as can be seen from Fig. 3 b, C-C, C-O, and the combination of C=O can be still corresponding with graphene oxide, but the combination of C-O can obviously reduce, and illustrates that oxygen-containing functional group is reduced by dopamine.In addition, in the redox graphene that poly-dopamine is modified, also there is C-N key (285.8eV), also prove that poly-dopamine is successfully attached to redox graphene surface.The slotting XPS figure seeking for N 1s in figure b.
Fig. 4 is atomic force microscope (AFM) figure of the redox graphene of poly-dopamine modification prepared by the embodiment of the present invention 1.4a and 4b is respectively AFM shape appearance figure and the AFM high-level schematic (height at the white dashed line place in a figure) of graphene oxide, 4c and 4d is respectively AFM shape appearance figure and the AFM high-level schematic (height at the white dashed line place in c figure) of the redox graphene that poly-dopamine is modified, as can be seen from the figure, redox graphene is after poly-dopamine reduction is modified, height is increased to 2.74nm from about 0.86nm, illustrates that poly-dopamine is successfully modified on the surface of redox graphene.
Fig. 5 is that the stability of the redox graphene of poly-dopamine modification prepared by graphene oxide and embodiment 1 compares.As can be seen from the figure, graphene oxide (GO) solution in placement after ten days, graphene oxide aggregate and precipitate in solution, solution becomes clarification, and dispersibility is poor; Redox graphene (PDA-RGO) water solublity that poly-dopamine prepared by this method is modified is better, disperses homogeneous, and after placing ten days, still has good aqueous dispersion.Stability, the favorable dispersibility of the redox graphene that poly-dopamine prepared by the embodiment of the present invention is modified are described.
Embodiment 2:
A preparation method for the redox graphene that poly-dopamine is modified, comprises the steps:
(1) first take 10mg graphene oxide add be equipped with 20mLpH be 9.0 concentration be in the round-bottomed flask of 10mMTris-Cl solution, and by this round-bottomed flask in ice-water bath ultrasonic 10 minutes, make graphene oxide be dissolved completely in Tris-Cl solution;
(2) in above-mentioned round-bottomed flask, add the dopamine hydrochloride of 2.5mg, then this round-bottomed flask is stirred in ice-water bath ultrasonic 10 minutes to activate dopamine hydrochloride, obtain yellowish-brown reaction mixture;
(3) under above-mentioned reaction mixture being placed in the condition of 65 DEG C, vigorous stirring reacts 12h;
(4) by centrifuge washing (rotating speed is set to 10,000rpm/min, washs 20min, washs 8 times altogether) mode at every turn, free dopamine hydrochloride is removed to above-mentioned reaction mixture, obtain the redox graphene that poly-dopamine is modified.
Embodiment 3:
A preparation method for the redox graphene that poly-dopamine is modified, comprises the steps:
(1) first take 10mg graphene oxide add be equipped with 20mLpH be 8.5 concentration be in the round-bottomed flask of 10mMTris-Cl solution, and by this round-bottomed flask in ice-water bath ultrasonic 10 minutes, make graphene oxide be dissolved completely in Tris-Cl solution;
(2) in above-mentioned round-bottomed flask, add the dopamine hydrochloride of 10mg, then this round-bottomed flask is stirred in ice-water bath ultrasonic 10 minutes to activate dopamine hydrochloride, obtain yellowish-brown reaction mixture;
(3) under above-mentioned reaction mixture being placed in the condition of 55 DEG C, vigorous stirring reacts 24h;
(4) by centrifuge washing (rotating speed is set to 10,000rpm/min, washs 20min, washs 8 times altogether) mode at every turn, free dopamine hydrochloride is removed to above-mentioned reaction mixture, obtain the redox graphene that poly-dopamine is modified.
Embodiment 4:
A preparation method for the redox graphene that poly-dopamine is modified, comprises the steps:
(1) first take 5mg graphene oxide add be equipped with 20mLpH be 8.5 concentration be in the round-bottomed flask of 10mMTris-Cl solution, and by this round-bottomed flask in ice-water bath ultrasonic 10 minutes, make graphene oxide be dissolved completely in Tris-Cl solution;
(2) in above-mentioned round-bottomed flask, add the dopamine hydrochloride of 10mg, then this round-bottomed flask is stirred in ice-water bath ultrasonic 10 minutes to activate dopamine hydrochloride, obtain yellowish-brown reaction mixture;
(3) under above-mentioned reaction mixture being placed in the condition of 60 DEG C, vigorous stirring reacts 12h;
(4) by centrifuge washing (rotating speed is set to 10,000rpm/min, washs 20min, washs 8 times altogether) mode at every turn, free dopamine hydrochloride is removed to above-mentioned reaction mixture, obtain the redox graphene that poly-dopamine is modified.
Embodiment 5:
A preparation method for the redox graphene that poly-dopamine is modified, comprises the steps:
(1) first take 2.5mg graphene oxide add be equipped with 20mLpH be 8.5 concentration be in the round-bottomed flask of 10mMTris-Cl solution, and by this round-bottomed flask in ice-water bath ultrasonic 10 minutes, make graphene oxide be dissolved completely in Tris-Cl solution;
(2) in above-mentioned round-bottomed flask, add the dopamine hydrochloride of 10mg, then this round-bottomed flask is stirred in ice-water bath ultrasonic 10 minutes to activate dopamine hydrochloride, obtain yellowish-brown reaction mixture;
(3) under above-mentioned reaction mixture being placed in the condition of 65 DEG C, vigorous stirring reacts 12h;
(4) by centrifuge washing (rotating speed is set to 10,000rpm/min, washs 20min, washs 8 times altogether) mode at every turn, free dopamine hydrochloride is removed to above-mentioned reaction mixture, obtain the redox graphene that poly-dopamine is modified.
Comparative example
The redox graphene that the poly-dopamine embodiment of the present invention 1 ~ 5 obtained is modified carries out the investigation of external photoacoustic imaging effect.
1, photoacoustic imaging platform (photoacoustic imaging platform is U.S. Nexus 128 (680-950nm) photoacoustic imaging system) is built;
2, agarose gel model is built; Make simple gel respectively, the redox graphene agarose gel nahlock model that the poly-dopamine that the graphene oxide of 0.05mg/mL and the embodiment 1 ~ 5 of 0.05mg/mL obtain is modified;
3, the investigation of external photoacoustic imaging signal; Be all the agarose gel model of the redox graphene that the graphene oxide of 0.05mg/mL and the obtained poly-dopamine of embodiment 1 ~ 5 are modified from concentration and detect photoacoustic signal.Relatively photoacoustic signal is known, and the graphene oxide external photoacoustic signal of embodiment 1 ~ 5 after reduction strengthens greatly compared to graphene oxide, and optoacoustic effect significantly improves.Illustrate that the redox graphene that poly-dopamine is modified has good optoacoustic effect.
Application Example
1, the photo-thermal therapy effect of the redox graphene of poly-dopamine modification;
Fig. 6 is the photo-thermal therapy design sketch of GO and PDA-RGO in mouse breast cancer tumour model, matched group is PBS, and experimental group is GO and PDA-RGO, injects the PBS of 35uL in tumor respectively, the PDA-RGO of GO and 0.8mg/mL of 0.8mg/mL, at 808nm@1W/cm
2irradiate under condition after five minutes and carry out infrared thermal imaging.Result shows, the mouse tumor position of injection PDA-RGO is irradiated through laser, temperature obviously raises, reach 45.2 DEG C, 3.2 DEG C are exceeded than tumor photo-thermal treatment critical temperature 42.0 DEG C, this is because the high grade of transparency of single-layer graphene oxide causes its specific absorbance lower, and the redox graphene in the PDA-RGO obtained after reduction is attached with poly-dopamine on the surface, redox graphene specific absorbance is significantly improved, thus make PDA-RGO have higher photothermal conversion efficiency, illustrate that PDA-RGO can as potential mouse tumor photo-thermal therapy reagent.GO group tumor temperature after laser irradiates is only 39.8 DEG C, and PBS group tumor temperature after laser irradiates is almost constant, and therefore, PAD-RGO can significantly improve the light thermal property of GO, can be used as potential photo-thermal therapy medicinal application in the treatment of cancer.
2, the photoacoustic imaging effect of the redox graphene of poly-dopamine modification;
Detect the photoacoustic signal of the agarose gel nahlock model of the redox graphene modified containing the poly-dopamine that embodiment 1 is obtained.Fig. 7 is the photoacoustic imaging design sketch of PDA-RGO, and as can be seen from the figure, along with PDA-RGO concentration raises, its photoacoustic signal progressively strengthens, at 0.5 μ g mL
-1time photoacoustce signal intensity be 972, when concentration raise be 4.0 μ g mL
-1time, photoacoustic signal enhances 2.5 times, along with concentration progressively increases to 64 μ g mL
-1, photoacoustce signal intensity reaches 11581, and photoacoustic signal enhances 11 times.This illustrates, PDA-RGO has good photoacoustic imaging function, can be applicable to photoacoustic ultrasound multi-modality imaging field.
Should be understood that, the above-mentioned statement for present pre-ferred embodiments is comparatively detailed, and therefore can not think the restriction to scope of patent protection of the present invention, scope of patent protection of the present invention should be as the criterion with claims.
Claims (10)
1. the redox graphene of a poly-dopamine modification, it is characterized in that, the redox graphene that described poly-dopamine is modified comprises redox graphene and poly-dopamine, and described poly-dopamine is attached to the surface of described redox graphene in the mode of physical absorption.
2. a preparation method for the redox graphene of poly-dopamine modification, is characterized in that, comprise the steps:
According to (1 ~ 4): the mass ratio of (1 ~ 4) takes graphene oxide and dopamine hydrochloride, described graphene oxide and described dopamine hydrochloride are joined in solvent and makes it fully dissolve, obtained mixed solution; Regulate pH value to 8.5 ~ 9.0 of described mixed solution, at 55 DEG C ~ 65 DEG C temperature, after reaction 12h ~ 24h, obtain the redox graphene that described poly-dopamine is modified.
3. the preparation method of the redox graphene of poly-dopamine modification according to claim 2, it is characterized in that, the mass ratio of described graphene oxide and described dopamine hydrochloride is 2:1.
4. the preparation method of the redox graphene of poly-dopamine modification according to claim 2, it is characterized in that, described pH value is 8.5.
5. the preparation method of the redox graphene of poly-dopamine modification according to claim 2, it is characterized in that, described temperature is 60 DEG C, and the described response time is 24h.
6. the preparation method of the redox graphene of poly-dopamine modification according to claim 2, it is characterized in that, described reaction carries out under the condition of vigorous stirring.
7. the preparation method of the redox graphene of poly-dopamine modification according to claim 6, it is characterized in that, described reaction is low whipping speed is carry out under the condition of 600rpm.
8. the preparation method of the redox graphene of poly-dopamine modification according to claim 2, it is characterized in that, described solvent is Tris-Cl solution or PBS buffer.
9. the preparation method of the redox graphene of poly-dopamine modification according to claim 2, is characterized in that, after obtained mixed solution, described mixed solution is stirred ultrasonic 10 minutes in ice-water bath.
10. the redox graphene of poly-dopamine modification according to claim 1 is in photoacoustic ultrasound multi-modality imaging or the application in the photo-thermal therapy medicine of preparation cancer.
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