CN103316352A - Graphene oxide nano-drug carrier and anti-tumor drug as well as preparation method of anti-tumor drug - Google Patents

Abstract

The invention relates to a graphene oxide drug carrier, an antitumor drug and a preparation method thereof. The graphene oxide drug carrier includes a plurality of nanoparticles, and each nanoparticle includes an inner core formed by graphene oxide and an outer shell formed by pyrenyldithiopolyethylene glycol, and pyrenyldithiopolyethylene glycol passes through pyrene The π-π conjugation effect of the group and graphene oxide adheres to the surface of the graphene oxide. The modification effect of pyrenyl disulfide polyethylene glycol makes the graphene oxide drug carrier have the characteristics of high steric stability and electrostatic stability, and the stability is high.

Description

Graphene oxide nano drug carrier, antitumor drug and preparation method thereof

technical field

The invention relates to the technical field of drug carriers, in particular to a graphene oxide drug carrier, an antitumor drug and a preparation method thereof.

Background technique

Graphene oxide has the characteristics of low toxicity and large surface energy, so it can be used as a drug carrier in the field of biomedicine. Graphene oxide as a drug carrier has incomparable advantages over other carriers, for example, photothermal therapy can be performed by utilizing the properties of graphene oxide itself. At the same time, the graphene oxide drug carrier is much larger than the general drug carrier, and its drug loading is also much larger than the former. However, graphene oxide as a drug carrier also has its own defects. Unmodified graphene oxide has poor stability in the human body, is prone to agglomeration, and cannot be completely metabolized by organisms.

Contents of the invention

Based on this, it is necessary to provide a graphene oxide drug carrier with high stability.

Further provide an antitumor drug containing the graphene oxide drug carrier and a preparation method thereof.

A graphene oxide nano drug carrier, comprising a plurality of nanoparticles, each nanoparticle comprising an inner core formed by graphene oxide and an outer shell formed by pyrenyl disulfide polyethylene glycol; wherein, the pyrenyl disulfide The base polyethylene glycol adheres to the surface of the graphene oxide through the π-π conjugation effect of the pyrene group and the graphene oxide.

In one of the embodiments, the mass ratio of graphene oxide to pyrenyldithiopolyethylene glycol is 1-2:10.

In one embodiment, the particle size of the nanoparticles is 70-100 nanometers.

An anti-tumor drug, comprising a hydrophobic drug with anti-tumor efficacy and the above-mentioned graphene oxide nano drug carrier, the drug is loaded on the inner core of the graphene oxide nano drug carrier through hydrophobic interaction.

In one embodiment, the mass ratio of the drug to the graphene oxide nano drug carrier is 1:11-12.

In one embodiment, the drug is doxorubicin, paclitaxel or camptothecin.

A preparation method of an antineoplastic drug, comprising the steps of:

Adding graphene oxide, pyrenyl dithiopolyethylene glycol and hydrophobic drugs with anti-tumor efficacy into water to obtain a mixture, ultrasonically treating the mixture at room temperature for 2 hours, filtering and freeze-drying to obtain anti-tumor drugs, The anti-tumor drug includes graphene oxide nano drug carrier and hydrophobic drug with anti-tumor effect, the graphene oxide nano drug carrier includes a plurality of nanoparticles, each nano particle includes an inner core formed by graphene oxide and an outer shell formed by adhering pyrenyldithiopolyethylene glycol to the surface of the inner core; wherein the pyrenyldithiopolyethylene glycol is adhered to by the π-π conjugation effect of pyrenyl and graphene oxide Attached to the surface of the graphene oxide to form a shell, the hydrophobic drug with anti-tumor efficacy is loaded on the inner core of the graphene oxide nano drug carrier through hydrophobic interaction.

In one of the embodiments, the mass ratio of graphene oxide, pyrenyldithiopolyethylene glycol and drug is 1-2:10:1.

In one embodiment, the concentration of the graphene oxide in the mixture is 0.1-1 mg/mL.

In one of the embodiments, the pyrenyldithiopolyethylene glycol is prepared as follows:

According to the solid-to-liquid ratio of 0.17g:88mg:30mL, cystamine hydrochloride and sodium hydroxide were added to water to obtain the first mixture, and the first mixture was stirred at room temperature for 30 minutes, and then vacuum rotary evaporated at 45°C to remove water , and then add dichloromethane to the first mixture after water removal, filter to remove the precipitate, and then remove the dichloromethane by vacuum rotary evaporation at 30° C. to obtain cystamine;

Mix 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, N-hydroxysuccinimide, carboxymethylated methyl Oxypolyethylene glycol and dichloromethane to obtain a second mixture, after the second mixture was reacted in a nitrogen atmosphere at room temperature for 5 hours, the cystamine was added dropwise to the reacted second mixture, and then React at room temperature for 24 hours to obtain a compound formed by linking polyethylene glycol and amino groups through disulfide bonds;

According to solid-liquid ratio 288mg: 287mg: 178mg: 20mL, pyrene butyric acid, 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride, N-hydroxysuccinimide and bis Chloromethane was mixed and reacted at room temperature for 2 hours, then added the compound formed by linking the polyethylene glycol and amino group through a disulfide bond, and reacted at room temperature for 24 hours to obtain the pyrenyldithiopolyethylene glycol .

The above-mentioned graphene oxide drug carrier includes a plurality of nanoparticles, and each nanoparticle includes an inner core formed by graphene oxide and an outer shell formed by pyrenyl dithiopolyethylene glycol. Among them, pyrenyldithiopolyethylene glycol adheres to the surface of graphene oxide through the π-π conjugation effect of pyrenyl and graphene oxide to form a hydrophilic shell, and the modification of pyrenyldithiopolyethylene glycol The graphene oxide drug carrier has the characteristics of high steric stability and electrostatic stability, and high stability.

Description of drawings

1 is an atomic force microscope (AFM) comparison diagram of graphene oxide and a graphene oxide nano drug carrier according to one embodiment;

Fig. 2 is a sheet height comparison diagram of graphene oxide and a graphene oxide nano-medicine carrier of an embodiment;

3 is a schematic diagram of the phagocytosis and release of antitumor drugs in cells according to one embodiment;

Fig. 4 is the release curve of the antitumor drug of Example 1 in the presence of glutathione and in the absence of glutathione.

Detailed ways

In order to make the above objects, features and advantages of the present invention more comprehensible, specific implementations of the present invention will be described in detail below in conjunction with the accompanying drawings. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. However, the present invention can be implemented in many other ways different from those described here, and those skilled in the art can make similar improvements without departing from the connotation of the present invention, so the present invention is not limited by the specific implementations disclosed below.

The graphene oxide nano drug carrier in one embodiment includes a plurality of nanoparticles, each nanoparticle includes an inner core formed by graphene oxide and an outer shell formed by pyrenyl dithiopolyethylene glycol adhered to the surface of the inner core. The nanoparticles are in the form of flakes.

Pyrenyl dithiopolyethylene glycol is formed by the reaction of pyrene butyric acid, cystamine hydrochloride and carboxymethylated methoxy polyethylene glycol (mPEG-COOH), and the pyrene group is connected with the dithio group to form pyrene Pyrene-S-S-PEG is a compound formed by linking pyrene-S-S-PEG to polyethylene glycol through a dithio-group.

The pyrenyl dithiopolyethylene glycol adheres to the surface of graphene oxide through the π-π conjugation effect of pyrenyl and graphene oxide to form a hydrophilic shell.

Pyrenyl dithiopolyethylene glycol encapsulates graphene oxide with poor stability inside, so that the graphene oxide drug carrier has the advantages of high biocompatibility, low toxicity and high drug loading capacity of graphene oxide , and can overcome the shortcoming of poor stability of graphene oxide, and obtain a nano drug carrier with high biocompatibility and high stability. The graphene oxide nano drug carrier has high steric stability and electrostatic stability, and a long circulation half-life.

Polyethylene glycol (PEG) is located on the surface of the nanoparticles. The polyethylene glycol nanoparticles have the advantages of good biocompatibility, controllable biodegradation and low toxicity of degradation products, which further makes the graphene oxide nano drug carrier have higher biocompatibility.

Pyrene-S-S-PEG adheres to the surface of graphene oxide by π-π conjugation effect to form a hydrophilic shell so that the graphene oxide nano-drug carrier can avoid the recognition of the immune system. When using the graphene oxide nano-carrier to load drugs , can enhance the half-life of drug system circulation and improve curative effect.

Moreover, graphene oxide forms a highly hydrophobic inner core, which can support hydrophobic drugs through hydrophobic interaction.

Preferably, the mass ratio of graphene oxide to pyrenyl dithiopolyethylene glycol is 1 to 2:10, so as to ensure that the above-mentioned graphene oxide nano-medicine carrier has high stability and can give full play to the properties of graphene oxide. The advantage of large drug loading and the advantage of polyethylene glycol is easy to achieve targeted and controlled release.

Each nanoparticle of the above-mentioned graphene oxide nano drug carrier has graphene oxide as the core, and the pyrene group of pyrene-S-S-PEG adheres to the surface of graphene oxide through the π-π conjugation effect to form a hydrophilic shell. In the aqueous environment of the agent, the π-π conjugation effect disappears, so that the inner core and the outer shell of the graphene oxide nano drug carrier are separated, and the hydrophobic drug is released. The above-mentioned graphene oxide nano-drug carrier has reduction responsiveness, and is easy to achieve targeted drug release.

Preferably, the particle size of the nanoparticles with graphene oxide as the inner core and pyrenyldithiopolyethylene glycol as the outer shell is 70-100 nanometers.

Figure 1 is an atomic force microscope (AFM) comparison diagram of graphene oxide and the above-mentioned graphene oxide nano drug carrier. Wherein, A is the atomic force microscope (AFM) picture of graphene oxide, and B is the AFM picture of the above-mentioned graphene oxide nano drug carrier. It can be seen from Fig. 1 that the above graphene oxide nano drug carrier is the same as graphene oxide, with small particle size and large surface energy.

Fig. 2 is a comparison diagram of sheet heights between graphene oxide and the aforementioned graphene oxide nano-drug carrier, wherein C represents graphene oxide, and D represents the aforementioned graphene oxide nano-drug carrier. It can be seen from FIG. 2 that the layer height uniformity of the graphene oxide nano-drug carrier is better, indicating that the graphene oxide nano-drug carrier has higher stability.

An anti-tumor drug according to one embodiment includes the above-mentioned graphene oxide nano-drug carrier and a hydrophobic drug with anti-tumor efficacy. Hydrophobic drugs with anti-tumor efficacy are loaded on the graphene oxide inner core of the graphene oxide nano drug carrier through hydrophobic interaction to form multiple anti-tumor drug nanoparticles.

Preferably, the mass ratio of the hydrophobic drug with anti-tumor efficacy to the graphene oxide is 1:11-12.

Hydrophobic drugs with antitumor efficacy are doxorubicin, paclitaxel or camptothecin.

Since the anti-tumor drug uses the above-mentioned graphene oxide nano-drug carrier as a carrier to load hydrophobic drugs with anti-tumor efficacy, the anti-tumor drug has high steric stability and electrostatic stability, is not easy to agglomerate, and can be well It is metabolized by the human body to exert curative effect. At the same time, this anti-tumor drug can avoid the recognition of the immune system, and has a half-life of circulation in the body and high efficacy.

Moreover, this antitumor drug has the advantages of good biocompatibility, controllable biodegradation and low toxicity of degradation products. This antitumor drug is also reduction-responsive and easy to achieve targeted and controlled release. The release principle of the antineoplastic drug is shown in Figure 3. Adriamycin is an example of a hydrophobic drug with antineoplastic effect. After administration, the antineoplastic drug enters the blood circulation system. There is basically no release. After reaching the tumor site, the antitumor drug enters the cytoplasm through endocytosis, and then the π-π conjugation effect between the pyrene-S-S-PEG shell and the graphene oxide core disappears through reduction response stimulation, and the hydrophilic The pyrene-S-S-PEG shell dissolves in the cytoplasm, thereby releasing hydrophobic drugs with anti-tumor efficacy, which can enable the drugs to be better released at the target site and exert curative effect.

The preparation method of antitumor drug of one embodiment, comprises the steps:

Adding graphene oxide, pyrenyl dithiopolyethylene glycol and hydrophobic drugs with anti-tumor efficacy into water to obtain a mixture, the mixture was ultrasonically treated at room temperature for 2 hours, filtered and freeze-dried to obtain anti-tumor drugs.

Among them, the anti-tumor drugs include graphene oxide nanometer drug carriers and hydrophobic drugs with anti-tumor efficacy. The graphene oxide nano-medicine carrier includes a plurality of nanoparticles, and each nanoparticle includes an inner core formed by graphene oxide and an outer shell formed by adhering pyrenyl disulfide polyethylene glycol to the surface of the inner core. Wherein, pyrenyl dithiopolyethylene glycol adheres to the surface of graphene oxide through the π-π conjugation effect of pyrenyl and graphene oxide to form a shell. Hydrophobic drugs with anti-tumor efficacy are loaded on the inner core of graphene oxide nano drug carrier through hydrophobic interaction.

Hydrophobic drugs with antitumor efficacy are doxorubicin, paclitaxel or camptothecin.

Preferably, the mass ratio of graphene oxide, pyrenyldithiopolyethylene glycol and hydrophobic drug with anti-tumor effect is 1-2:10:1.

When the hydrophobic drug with anti-tumor efficacy is doxorubicin, due to the poor water solubility of doxorubicin, in order to facilitate the preparation, the anti-tumor drug is prepared with doxorubicin hydrochloride as a raw material, in order to neutralize the doxorubicin hydrochloride The hydrochloric acid, add triethylamine in the mixture of graphene oxide, pyrenyl disulfide polyethylene glycol, hydrophobic medicine with antitumor effect and water, to neutralize the hydrochloric acid in the doxorubicin hydrochloride.

The solid-liquid ratio of doxorubicin hydrochloride to triethylamine was 1 mg:1.5 μL.

Preferably, in the mixture of graphene oxide, pyrenyl disulfide polyethylene glycol, hydrophobic drugs with anti-tumor efficacy and water, the concentration of graphene oxide is 0.1～1mg/mL, so that graphene oxide is relatively It can be well dispersed in water and avoid graphene oxide agglomeration, so as to prepare anti-tumor drugs with good dispersion and small particle size.

The above-mentioned pyrenyl dithiopolyethylene glycol is formed by the reaction of pyrene butyric acid, cystamine hydrochloride and carboxymethylated methoxy polyethylene glycol (mPEG-COOH), and the pyrene group is connected with the dithio group Pyrenyl disulfide, a compound formed by linking pyrenyl disulfide to polyethylene glycol through a disulfide group. Pyrenyl dithiopolyethylene glycol is prepared as follows:

According to the solid-to-liquid ratio of 0.17g:88mg:30mL, cystamine hydrochloride and sodium hydroxide were added to water to obtain the first mixture, and the first mixture was stirred at room temperature for 30 minutes, and then the water was removed by vacuum rotary evaporation at 45°C, and then Dichloromethane was added to the first mixture after water removal, the precipitate was removed by filtration, and the dichloromethane was removed by vacuum rotary evaporation at 30° C. to obtain light yellow liquid cystamine.

Mix 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC HCl), N-hydroxysuccinimide ( NHS), methoxypolyethylene glycol carboxylic acid (mPEG-COOH) and dichloromethane to obtain the second mixture, the second mixture was reacted at room temperature for 5 hours in a nitrogen atmosphere, and then added to the reacted second mixture The prepared cystamine was added dropwise, and then reacted at room temperature for 24 hours to obtain a compound formed by linking polyethylene glycol and amino groups through disulfide bonds, expressed as mPEG-SS-NH ₂ . The mass ratio of cystamine to methoxypolyethylene glycol carboxylic acid (mPEG-COOH) was 0.15:1.

EDC·HCl and NHS are used to activate the carboxyl group (-COOH) of methoxypolyethylene glycol carboxylic acid (mPEG-COOH) to increase the activity of the carboxyl group and increase the reaction rate.

According to the solid-to-liquid ratio of 288mg:287mg:178mg:20mL, pyrenebutyric acid, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC·HCl), N-hydroxybutanedi Imide (NHS) and dichloromethane were mixed and reacted at room temperature for 2 hours, and then added 0.5 g of polyethylene glycol and amino group connected by disulfide bond (mPEG-SS-NH ₂ ), at room temperature After 24 hours of reaction, pyrenyldithiopolyethylene glycol was obtained.

The aforementioned methoxypolyethylene glycol carboxylic acid (mPEG-COOH) is preferably methoxypolyethylene glycol carboxylic acid (mPEG-COOH) having a weight average molecular weight of 5,000.

The methoxypolyethylene glycol carboxylic acid (mPEG-COOH) with a weight average molecular weight of 5000 is used to prepare pyrenyl dithiopolyethylene glycol, and the obtained pyrenyl dithiopolyethylene glycol is used to prepare graphene oxide Nano-drug carrier, and when the carrier is used to load hydrophobic drugs with anti-tumor efficacy to form anti-tumor drugs, it makes it difficult for the anti-tumor drugs to be taken up by other organs in the blood circulation, so as to facilitate targeted release, and the anti-tumor The particle size of the drug is small.

The preparation method of the above-mentioned antitumor drug is simple and easy, the reaction conditions are mild, and it is convenient for operation and popularization.

The following are specific examples.

Example 1

Weigh 0.17g of cystamine hydrochloride (1.1mmol) and 88mg of NaOH (2.2mmol) into 30mL of water, stir at room temperature for 30min, and then remove water by vacuum rotary evaporation at 45°C. Dichloromethane was added to the above mixture, the precipitate was filtered, and the dichloromethane was removed by vacuum rotary evaporation at 30°C. A pale yellow liquid cystamine was obtained. Take 120mg EDC·HCl (0.62mmol), 28mg NHS (0.23mmol), 1g mPEG-COOH (weight average molecular weight 5000) and 30mL dichloromethane react in _N2 atmosphere at room temperature for 5h, slowly drop 0.15g cystamine , and then reacted at room temperature for 24 hours to obtain a compound (mPEG-SS-NH ₂ ) formed by linking polyethylene glycol and amino groups through disulfide bonds;

Pipette 288 mg of pyrenebutyric acid, 287 mg of EDC·HCl, and 178 mg of NHS in 20 mL of dichloromethane to activate at room temperature for 2 h, add 0.5 g of mPEG-SS-NH ₂ , and react at room temperature for 24 h to obtain pyrenyl disulfide polyethylene glycol;

Pipette 1mg of graphene oxide, 10mg of pyrenyldithiopolyethylene glycol, 1mg of doxorubicin hydrochloride (DXR), 1.5μL of triethylamine, add 10mL of water, and sonicate with an ultrasonic carbon rod for 2 hours at room temperature, allowing the solvent to Volatilize, then filter and freeze-dry to obtain anti-tumor drugs, the anti-tumor drugs include graphene oxide nano drug carrier and doxorubicin, the graphene oxide nano drug carrier includes a plurality of nanoparticles, each nano particle includes graphene oxide The formed inner core and the outer shell formed by pyrenyl dithiopolyethylene glycol adhering to the surface of the inner core, and doxorubicin is loaded on the inner core through hydrophobic interaction.

Above-mentioned antineoplastic drug release curve I in the aqueous solution of glutathione (GSH) that pH value is 5.5,0mM/L, in the aqueous solution of glutathione (GSH) that pH value is 5.5,10mM/L Release curve II, release curve III in an aqueous solution of glutathione (GSH) with a pH value of 7.4 and 0 mM/L, and release curve III in an aqueous solution of glutathione (GSH) with a pH value of 7.4 and 10 mM/L The release curve IV is shown in Figure 4. As can be seen from Figure 4, when the pH value is 5.5 and 7.4 respectively, the above-mentioned antineoplastic drugs can be released well in the aqueous solution of 10mM/L glutathione (GSH), and as time goes on, the released The dose of doxorubicin was gradually increased.

Example 2

Weigh 0.17g of cystamine hydrochloride (1.1mmol) and 88mg of NaOH (2.2mmol) into 30ml of water, stir at room temperature for 30min, and then remove water by vacuum rotary evaporation at 45°C. Dichloromethane was added to the above mixture, the precipitate was filtered, and the dichloromethane was removed by vacuum rotary evaporation at 30°C. A pale yellow liquid cystamine was obtained. Take 120mg EDC·HCl (0.62mmol), 28mg NHS (0.23mmol), 1gmPEG-COOH (weight average molecular weight 5000), 30ml methylene chloride and react in _N2 atmosphere at room temperature for 5h, slowly drop 0.15g cystamine and then After reacting at room temperature for 24 hours, mPEG-SS-NH ₂ was obtained

Pipette 288 mg of pyrenebutyric acid, 287 mg of EDC·HCl, and 178 mg of NHS in 20 ml of dichloromethane to activate at room temperature for 2 hours, add 0.5 gmPEG-SS-NH ₂ , and react at room temperature for 24 hours to obtain pyrene-SS-PEG.

Pipette 2mg of graphene oxide, 10mg of pyrene-S-S-PEG, 1mg of DXR, 1.5μl of triethylamine, add 10ml of water, and use an ultrasonic carbon rod to sonicate for 2 hours at room temperature. Drug, the anti-tumor drug includes graphene oxide nano-drug carrier and doxorubicin, the graphene oxide nano-drug carrier includes a plurality of nanoparticles, each nano-particle includes an inner core formed by graphene oxide and pyrenyl disulfide polymer Ethylene glycol adheres to the shell formed on the surface of the inner core, and doxorubicin is loaded on the inner core through hydrophobic interaction. In PBS containing 10mM/L GSH (glutamine) PH=5.5, the antitumor drug has a good release effect in response to reduction stimulation.

Example 3

Weigh 0.34g of cystamine hydrochloride (2.2mmol) and 176mg of NaOH (4.4mmol) into 60mL of water, stir at room temperature for 30min, and then remove water by vacuum rotary evaporation at 45°C. Dichloromethane was added to the above mixture, the precipitate was filtered, and the dichloromethane was removed by vacuum rotary evaporation at 30°C. A pale yellow liquid cystamine was obtained. Take 240mg EDC·HCl (1.24mmol), 56mg NHS (0.46mmol), 2g mPEG-COOH (weight average molecular weight 5000) and 60mL dichloromethane react in _N2 atmosphere at room temperature for 5h, then slowly drop 0.30g cystamine , and then reacted at room temperature for 24 hours to obtain a compound (mPEG-SS-NH ₂ ) formed by linking polyethylene glycol and amino groups through disulfide bonds;

Pipette 288 mg of pyrenebutyric acid, 287 mg of EDC·HCl, and 178 mg of NHS in 20 mL of dichloromethane for 2 h at room temperature, add 1.0 g of mPEG-SS-NH ₂ , and react at room temperature for 24 h to obtain pyrenyl disulfide polyethylene glycol;

Pipette 1mg of graphene oxide, 10mg of pyrenyldithiopolyethylene glycol and 1mg of paclitaxel into 10mL of water, and at room temperature, use an ultrasonic carbon rod to sonicate for 2 hours, during which the solvent is allowed to evaporate, then filtered and freeze-dried to obtain an anti-tumor drug. Antitumor drugs include graphene oxide nano drug carrier and paclitaxel, graphene oxide nano drug carrier includes a plurality of nanoparticles, each nano particle includes an inner core formed by graphene oxide and adhered by pyrenyl disulfide polyethylene glycol In the outer shell formed on the surface of the inner core, paclitaxel is loaded on the inner core through hydrophobic interaction.

The above-mentioned embodiments only express several implementation modes of the present invention, and the descriptions thereof are relatively specific and detailed, but should not be construed as limiting the patent scope of the present invention. It should be noted that those skilled in the art can make several modifications and improvements without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent for the present invention should be based on the appended claims.

Claims (10)

1. a stannic oxide/graphene nano pharmaceutical carrier is characterized in that, comprises a plurality of nano-particle, and each nano-particle comprises the kernel that is formed by graphene oxide and the shell that is formed by pyrenyl disulfide group Polyethylene Glycol; Wherein, described pyrenyl disulfide group Polyethylene Glycol adheres to the surface of described graphene oxide by the π-pi-conjugated effect of pyrenyl and graphene oxide.

2. stannic oxide/graphene nano pharmaceutical carrier according to claim 1 is characterized in that, the mass ratio of described graphene oxide and pyrenyl disulfide group Polyethylene Glycol is 1～2:10.

3. stannic oxide/graphene nano pharmaceutical carrier according to claim 1 is characterized in that, the particle diameter of described nano-particle is 70～100 nanometers.

4. antitumor drug, it is characterized in that, comprise hydrophobic medicine and each described stannic oxide/graphene nano pharmaceutical carrier of claim 1～3 with antitumor curative effect, described medicine is carried on the kernel of described stannic oxide/graphene nano pharmaceutical carrier by hydrophobic interaction.

5. antitumor drug according to claim 4 is characterized in that, the mass ratio of described medicine and described stannic oxide/graphene nano pharmaceutical carrier is 1:11～12.

6. antitumor drug according to claim 4 is characterized in that, described medicine is amycin, paclitaxel or camptothecine.

7. a preparing anti-tumor medicine method is characterized in that, comprises the steps:

With graphene oxide, pyrenyl disulfide group Polyethylene Glycol and hydrophobic medicine with antitumor curative effect are added to the water and obtain mixture, with described mixture supersound process 2 hours under room temperature, filter, obtain antitumor drug after the lyophilizing, described antitumor drug comprises stannic oxide/graphene nano pharmaceutical carrier and hydrophobic medicine with antitumor curative effect, described stannic oxide/graphene nano pharmaceutical carrier comprises a plurality of nano-particle, and each nano-particle comprises the kernel that formed by graphene oxide and adheres to the shell that the surface of described kernel forms by pyrenyl disulfide group Polyethylene Glycol; Wherein, the surface that the π-pi-conjugated effect of described pyrenyl disulfide group Polyethylene Glycol by pyrenyl and graphene oxide adheres to described graphene oxide forms shell, and described hydrophobic medicine with antitumor curative effect is carried on the kernel of described stannic oxide/graphene nano pharmaceutical carrier by hydrophobic interaction.

8. preparing anti-tumor medicine method according to claim 7 is characterized in that, the mass ratio of described graphene oxide, pyrenyl disulfide group Polyethylene Glycol and medicine is 1～2:10:1.

9. preparing anti-tumor medicine method according to claim 7 is characterized in that, in the described mixture, the concentration of described graphene oxide is 0.1～1mg/mL.

10. preparing anti-tumor medicine method according to claim 7 is characterized in that, described pyrenyl disulfide group Polyethylene Glycol prepares as follows:

By solid-to-liquid ratio 0.17g:88mg:30mL cystamine hydrochlorate and sodium hydroxide are added to the water and obtain first mixture, described first mixture was stirred under room temperature 30 minutes, revolve to steam in 45 ℃ of following vacuum again and dewater, add methylene chloride then and add in first mixture after described the dewatering, remove by filter precipitation, revolve in 30 ℃ of vacuum again and steam except dichloromethane, obtain cystamine;

Obtain second mixture by solid-to-liquid ratio 120mg:28mg:1g:30mL mixing 1-ethyl-(3-dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate, N-maloyl imines, carboxy methylation methoxy poly (ethylene glycol) and dichloromethane, with the reaction after 5 hours in nitrogen atmosphere, under the room temperature of described second mixture, in described reacted second mixture, splash into described cystamine, under room temperature, reacted 24 hours again, obtain Polyethylene Glycol and the amino chemical compound that is connected to form by disulfide bond;

By solid-to-liquid ratio 288mg:287mg:178mg:20mL pyrene butanoic acid, 1-ethyl-(3-dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate, N-maloyl imines and dichloromethane are mixed and to be incorporated under the room temperature reaction 2 hours, add described Polyethylene Glycol and the amino chemical compound that is connected to form by disulfide bond then, reaction is 24 hours under room temperature, obtains described pyrenyl disulfide group Polyethylene Glycol.

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