CN108467028B - Preparation method and application of intelligent graphene quantum dot cluster - Google Patents
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Abstract
The invention discloses a preparation method and application of an intelligent graphene quantum dot cluster, wherein concentrated sulfuric acid and concentrated nitric acid are used for heating and refluxing carbon fibers to obtain graphene quantum dot powder; dissolving GQDs powder in dimethyl sulfoxide, reacting with HBTU, HOBT, tert-butyl carbazate and DIPEA in a certain proportion under the protection of nitrogen, and dialyzing to obtain GQDs hydrazide solution; and adding GQDs powder into the GQDs hydrazide solution, simultaneously adding trifluoroacetic acid, reacting to obtain an intelligent GQDs cluster, and dialyzing in deionized water to obtain an aqueous solution of the intelligent GQDs cluster. The method is novel, the yield is high under the condition of controlling experimental conditions, the obtained intelligent GQDs cluster containing hydrazone bonds can realize the controlled release of the GQDs under different pH conditions, and the method has better biological application prospect.
Description
Technical Field
The invention relates to a preparation method and application of graphene quantum dots, in particular to a preparation method and application of a graphene quantum dot cluster, and is applied to the technical field of preparation processes and application of nano materials.
Background
The Graphene Quantum Dots (GQDs) are graphene single-layer sheets smaller than 100nm, and compared with graphene materials, the graphene quantum dots have the characteristics of edge effect and quantum effect, so that the graphene quantum dots have better development potential in the aspects of electrons and photoelectrons than graphene, and can be applied to the aspects of photocatalysts, electrochemical sensors and the like. Meanwhile, the graphene quantum dots also have the characteristics of low toxicity, fluorescence stability, biocompatibility, cell permeability and the like, so that the graphene quantum dots also have wide development prospects in the fields of medicine/gene carrier bands, fluorescent probes and biological imaging.
The existing nano-carrier has the problems of premature release, slow release, difficulty in regulation and control when reaching a tumor part and the like in the transportation process. The graphene quantum dot material prepared by the existing method has limited drug carrying capacity, cannot effectively realize accurate release of the carried drug, and has unsatisfactory biological toxicity, environmental friendliness and intelligence.
Disclosure of Invention
In order to solve the problems of the prior art, the invention aims to overcome the defects in the prior art and provide a preparation method and application of an intelligent graphene quantum dot cluster, wherein GQDs prepared by using mixed acid of concentrated sulfuric acid and concentrated nitric acid contain a large amount of carboxyl and carbonyl, and then GQDs hydrazide is synthesized under the action of a coupling agent; then, carbonyl of the GQDs and GQDs hydrazide react to synthesize a pH-sensitive hydrazone bond, an intelligent GQDs cluster is prepared, and the cluster can be dissociated into dispersed GQDs nano particles under different pH conditions, so that the carried therapeutic drugs can enter tumor cells more accurately and effectively release the drugs, and side effects on non-tumor cells are reduced.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of an intelligent graphene quantum dot cluster comprises the following steps:
a. firstly weighing 4.0g of carbon fiber, adding into a 250mL reaction container, adding a mixture of 135mL of concentrated sulfuric acid with a mass percent concentration of not less than 95 wt.% and 45mL of concentrated nitric acid with a mass percent concentration of not less than 65 wt.%, carrying out ultrasonic treatment for at least 1h under the condition of a normal-temperature water bath, then carrying out heating reflux reaction for at least 24h under the condition of an oil bath with a temperature of not less than 80 ℃, then cooling the mixed solution after reaction to room temperature, diluting with at least 800mL of deionized water, then centrifuging at a rotating speed of not less than 6000rpm for at least 30min by using a centrifuge, separating and removing precipitates at the lower layer, collecting black liquid at the upper layer, treating the black liquid by using a vacuum filtration method, pumping through a filter membrane with a pore size of not more than 0.22 mu m, further removing large-particle substances, finally obtaining an acid solution of graphene quantum dots, and then carrying out dialysis separation and purification for many times in deionized water by using a dialysis bag with a molecular weight of 3500Da, until the dialyzate outside the dialysis bag becomes neutral, evaporating the dialyzed retention solution in the dialysis bag to dryness at a temperature of not less than 60 ℃ by using a rotary evaporator, and grinding to obtain dry graphene quantum dot powder;
b. dissolving 100mg of graphene quantum dot powder prepared in the step a in at least 8mL of deionized water, dialyzing in a solvent in dimethyl sulfoxide for at least 4 times by using a regenerated cellulose dialysis bag with the molecular weight of 1000Da, and replacing dialysate every 4 hours to obtain a DMSO solution of the graphene quantum dots; then taking a DMSO solution containing 50mg of graphene quantum dots to transfer to a single-neck flask, adopting HBTU as a coupling agent, adding 735.3mg of HBTU and 261.48mg of HOBT into the single-neck flask to mix, then adding 383.58mg of tert-butyl carbazate, stirring at normal temperature for at least 30 minutes, and then adding 400 mu L of N, N-diisopropylethylamine to obtain a reactant mixed system solution; then, reacting for at least 48h at room temperature under the condition of nitrogen protection gas, then filling the product solution after the reaction into a regenerated cellulose dialysis bag with the molecular weight of 3500Da, dialyzing for at least two days in a DMSO solution, and replacing dialysate every 8h to obtain GQDs hydrazide solution;
c. taking 50mg of GQDs hydrazide solution prepared in the step b, adding GQDs powder with the mass at least 10 times that of the taken GQDs hydrazide solution, simultaneously adding 0.5mL of trifluoroacetic acid to form a reactant mixed solution system, stirring at room temperature for at least 24h, heating to be not lower than 50 ℃, stirring for at least 48h for reaction to obtain a mixed solution containing intelligent GQDs cluster products, filling the reacted mixed solution into a dialysis bag with the molecular weight of 8000-10000Da, repeatedly dialyzing in deionized water for three days to four days, replacing the dialyzate every 8h, and finally obtaining the aqueous solution of the intelligent GQDs cluster.
According to the application of the intelligent graphene quantum dot cluster prepared by the preparation method of the intelligent graphene quantum dot cluster, the intelligent graphene quantum dot cluster can be dissociated into dispersed GQDs nanoparticles under different pH conditions, and the dispersed GQDs nanoparticles are used for pH control release.
In the application of the intelligent graphene quantum dot cluster, the intelligent graphene quantum dot cluster is preferably used for pH control release, so that the therapeutic drug carried by the intelligent graphene quantum dot cluster enters tumor cells for drug release.
In the application of the intelligent graphene quantum dot cluster, the intelligent graphene quantum dot cluster can be preferably dissociated into dispersed GQDs nanoparticles in an environment with the pH value of 5.0-7.4.
Compared with the prior art, the invention has the following obvious and prominent substantive characteristics and remarkable advantages:
1. the method is novel and unique, is environment-friendly under the condition of controlling experimental conditions, has high yield, and the obtained intelligent GQDs cluster containing the hydrazone bond sensitive to the acid can realize the controlled release of the GQDs under different pH conditions, so that the carried therapeutic drugs can more accurately enter tumor cells and effectively release the drugs, the side effects on non-tumor cells are reduced, and the biological application prospect is better;
2. the intelligent GQDs cluster prepared by the method has good water solubility, uniform particle size, high quality and easy control and regulation of purity;
3. the whole system prepared by the invention has lower biotoxicity, simple operation and easy synthesis.
Drawings
FIG. 1 is a TEM photograph of intelligent GQDs cluster containing hydrazone bonds, prepared according to a method of an embodiment of the present invention.
Detailed Description
The above-described scheme is further illustrated below with reference to specific embodiments, which are detailed below:
example one
In this embodiment, referring to fig. 1, a method for preparing an intelligent graphene quantum dot cluster includes the following steps:
a. firstly, weighing 4.0g of carbon fiber by using an electronic balance, adding the carbon fiber into a 250mL round bottom flask, adding a mixture of 135mL of concentrated sulfuric acid with the mass percent concentration of 95 wt.% and 45mL of concentrated nitric acid with the mass percent concentration of 65 wt.%, carrying out ultrasonic treatment for 1h under the condition of a normal-temperature water bath, then heating and refluxing for 24h under the condition of an 80 ℃ oil bath, then cooling the mixed solution after reaction to room temperature, diluting the mixed solution by using 800mL of deionized water, then centrifuging the mixed solution for 30min at 6000rpm by using a centrifuge, separating and removing a lower-layer precipitate, collecting an upper-layer black liquid, treating the black liquid by using a vacuum filtration method, further removing larger-particle substances through a filtration membrane with the pore size of 0.22 mu m, finally obtaining an acid solution of Graphene Quantum Dots (GQDs), and then carrying out multiple dialysis separation and purification in deionized water by using a dialysis bag with the molecular weight of 3500Da, until the dialyzate outside the dialysis bag becomes neutral, evaporating the dialyzed retention solution in the dialysis bag to dryness at 60 ℃ by using a rotary evaporator, and then grinding to obtain dry graphene quantum dot powder;
b. dissolving 100mg of graphene quantum dot powder prepared in the step a in 8mL of deionized water, dialyzing in a solvent in dimethyl sulfoxide (DMSO) for 4 times in a regenerated cellulose dialysis bag with the molecular weight of 1000Da, and replacing the dialysate every 4 hours to obtain a DMSO solution of the graphene quantum dots; then transferring a DMSO solution containing 50mg of graphene quantum dots into a single-neck flask, adopting HBTU as a coupling agent, adding 735.3mg of HBTU and 261.48mg of HOBT into the single-neck flask for mixing, then adding 383.58mg of tert-butyl carbazate, stirring at normal temperature for 30 minutes, and then adding 400 mu L of N, N-Diisopropylethylamine (DIPEA) to obtain a reactant mixed system solution; then reacting for 48 hours at room temperature under the condition of nitrogen protection gas, then putting the product solution after the reaction into a regenerated cellulose dialysis bag with the molecular weight of 3500Da, dialyzing for two days in a DMSO solution, and replacing the dialysate every 8 hours to obtain GQDs hydrazide solution;
c. taking 50mg of GQDs hydrazide solution prepared in the step b, adding GQDs powder with the mass 10 times that of the taken GQDs hydrazide solution, simultaneously adding 0.5mL of trifluoroacetic acid (TFA) to form a reactant mixed solution system, stirring at room temperature for 24h, then heating to 50 ℃, stirring for 48h for reaction to obtain a mixed solution containing intelligent GQDs cluster products, then filling the reacted mixed solution into a dialysis bag with the molecular weight of 8000-10000Da, repeatedly dialyzing in deionized water for three days to four days, and replacing the dialyzate every 8h, thereby finally obtaining the aqueous solution of the intelligent GQDs cluster.
Microscopic experimental observation is carried out on the intelligent GQDs cluster prepared by the invention, referring to fig. 1, the intelligent GQDs cluster containing hydrazone bonds can show that a plurality of single GQDs are in an aggregation state as seen from a transmission electron microscope photo, and the average particle diameter of the single GQDs aggregated into a cluster is measured to be 4.19nm by software, wherein the maximum particle diameter is 28.57nm, and the minimum particle diameter is 1.56 nm.
This example utilizes concentrated sulfuric acid (H)2SO4) And concentrated nitric acid (HNO)3) Heating and refluxing the Carbon Fibers (CF) to obtain Graphene Quantum Dot (GQDs) powder; dissolving GQDs powder in dimethyl sulfoxide (DMSO), reacting with a polypeptide coupling agent O-benzotriazole-tetramethyluronium Hexafluorophosphate (HBTU), a condensing agent 1-Hydroxybenzotriazole (HOBT), tert-butyl carbazate and N, N-Diisopropylethylamine (DIPEA) in a certain proportion under the protection of nitrogen, and dialyzing to obtain a GQDs hydrazide solution; and adding 10 times of GQDs powder into the GQDs hydrazide solution, simultaneously adding trifluoroacetic acid (TFA), reacting the GQDs hydrazide and the GQDs to obtain intelligent GQDs clusters, and dialyzing in deionized water to obtain the aqueous solution of the intelligent GQDs clusters. The method is novel and environment-friendly, the yield is high under the condition of controlling experimental conditions, the prepared whole system has lower biotoxicity, and the obtained intelligent GQDs cluster has good water solubility and uniform particle size.
Example two
This embodiment is substantially the same as the first embodiment, and is characterized in that:
in this embodiment, in an application of the intelligent graphene quantum dot cluster prepared by the method for preparing the intelligent graphene quantum dot cluster according to the embodiment, the intelligent graphene quantum dot cluster can be dissociated into dispersed GQDs nanoparticles under different pH conditions for pH controlled release. The intelligent graphene quantum dot clusters are used for pH control release, so that the therapeutic drugs carried by the intelligent graphene quantum dot clusters enter tumor cells for drug release.
In this embodiment, the smart graphene quantum dot clusters can be respectively dissociated into dispersed GQDs nanoparticles in an acidic environment with a pH of 5.0. Under the conditions that the pH value of the intelligent graphene quantum dot cluster is 7.4, 6.5 and 5.0, the size of GQDs nanoparticles is gradually reduced, which shows that as the environment gradually changes to an acidic condition, the nanocomposite particles begin to dissociate, so that the size gradually decreases, and the controllability is good.
In this embodiment, the GQDs based on the hydrazide modification of the acid-sensitive hydrazone bond mediated GQDs prepared in the first embodiment can be used for pH controlled release, so that the prepared intelligent GQDs cluster can realize the controlled release of the GQDs under different pH conditions, and can realize dissociation under different acidic PHs. Can make the carried therapeutic drug enter tumor cells more accurately and release the drug effectively, and reduce the side effect on non-tumor cells. The whole system prepared in the first embodiment has lower biotoxicity, can realize accurate release of the carried drug, has better application prospect, and effectively solves the problems of premature release, slow release, difficulty in regulation and control of the nano carrier reaching a tumor part and the like in the transportation process.
The GQDs prepared by the mixed acid of concentrated sulfuric acid and concentrated nitric acid in the embodiment of the invention contain a large amount of carboxyl and carbonyl, and GQDs hydrazide is successfully synthesized in a DMSO solution under the action of a coupling agent; and then, reacting carbonyl of the GQDs with GQDs hydrazide to synthesize a pH-sensitive hydrazone bond, successfully preparing an intelligent GQDs cluster, wherein the cluster can be dissociated into dispersed GQDs nanoparticles under a corresponding pH condition.
The embodiments of the present invention have been described above with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes and modifications can be made according to the purpose of the invention, and any changes, modifications, substitutions, combinations or simplifications made according to the spirit and principle of the technical solution of the present invention shall be equivalent substitution ways, so long as the purpose of the present invention is met, and the present invention shall fall within the protection scope of the present invention as long as the technical principle and inventive concept of the preparation method and the application of the intelligent graphene quantum dot cluster of the present invention are not departed.
Claims (4)
1. A preparation method of an intelligent graphene quantum dot cluster is characterized by comprising the following steps:
a. firstly weighing 4.0g of carbon fiber, adding into a 250mL reaction container, adding a mixture of 135mL of concentrated sulfuric acid with a mass percent concentration of not less than 95 wt.% and 45mL of concentrated nitric acid with a mass percent concentration of not less than 65 wt.%, carrying out ultrasonic treatment for at least 1h under the condition of a normal-temperature water bath, then carrying out heating reflux reaction for at least 24h under the condition of an oil bath with a temperature of not less than 80 ℃, then cooling the mixed solution after reaction to room temperature, diluting with at least 800mL of deionized water, then centrifuging at a rotating speed of not less than 6000rpm for at least 30min by using a centrifuge, separating and removing precipitates at the lower layer, collecting black liquid at the upper layer, treating the black liquid by using a vacuum filtration method, pumping through a filter membrane with a pore size of not more than 0.22 mu m, further removing large-particle substances, finally obtaining an acid solution of graphene quantum dots, and then carrying out dialysis separation and purification for many times in deionized water by using a dialysis bag with a molecular weight of 3500Da, until the dialyzate outside the dialysis bag becomes neutral, evaporating the dialyzed retention solution in the dialysis bag to dryness at a temperature of not less than 60 ℃ by using a rotary evaporator, and grinding to obtain dry graphene quantum dot powder;
b. dissolving 100mg of graphene quantum dot powder prepared in the step a in at least 8mL of deionized water, dialyzing in a solvent in dimethyl sulfoxide for at least 4 times by using a regenerated cellulose dialysis bag with the molecular weight of 1000Da, and replacing dialysate every 4 hours to obtain a DMSO solution of the graphene quantum dots; then taking a DMSO solution containing 50mg of graphene quantum dots to transfer to a single-neck flask, adopting HBTU as a coupling agent, adding 735.3mg of HBTU and 261.48mg of HOBT into the single-neck flask to mix, then adding 383.58mg of tert-butyl carbazate, stirring at normal temperature for at least 30 minutes, and then adding 400 mu L of N, N-diisopropylethylamine to obtain a reactant mixed system solution; then, reacting for at least 48h at room temperature under the condition of nitrogen protection gas, then filling the product solution after the reaction into a regenerated cellulose dialysis bag with the molecular weight of 3500Da, dialyzing for at least two days in a DMSO solution, and replacing dialysate every 8h to obtain GQDs hydrazide solution;
c. taking 50mg of GQDs hydrazide solution prepared in the step b, adding GQDs powder with the mass at least 10 times that of the taken GQDs hydrazide solution, simultaneously adding 0.5mL of trifluoroacetic acid to form a reactant mixed solution system, stirring at room temperature for at least 24h, heating to be not lower than 50 ℃, stirring for at least 48h for reaction to obtain a mixed solution containing intelligent GQDs cluster products, filling the reacted mixed solution into a dialysis bag with the molecular weight of 8000-10000Da, repeatedly dialyzing in deionized water for three days to four days, replacing the dialyzate every 8h, and finally obtaining the aqueous solution of the intelligent GQDs cluster.
2. The application of the intelligent graphene quantum dot cluster prepared by the preparation method of the intelligent graphene quantum dot cluster according to claim 1 is characterized in that: the intelligent graphene quantum dot clusters can be dissociated into dispersed GQDs nanoparticles under different pH conditions, and the dispersed GQDs nanoparticles are used for pH controlled release.
3. The use of the smart graphene quantum dot clusters according to claim 2, wherein: the intelligent graphene quantum dot clusters are used for pH control release, so that the therapeutic drugs carried by the intelligent graphene quantum dot clusters enter tumor cells for drug release.
4. The use of the intelligent graphene quantum dot clusters according to claim 2 or 3, wherein: the intelligent graphene quantum dot cluster can be dissociated into dispersed GQDs nanoparticles in an environment with pH of 5.0-7.4.
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