CN108467028A - The preparation method and application of intelligent graphene quantum dot cluster - Google Patents
The preparation method and application of intelligent graphene quantum dot cluster Download PDFInfo
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- CN108467028A CN108467028A CN201810388032.1A CN201810388032A CN108467028A CN 108467028 A CN108467028 A CN 108467028A CN 201810388032 A CN201810388032 A CN 201810388032A CN 108467028 A CN108467028 A CN 108467028A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/48—Preparations in capsules, e.g. of gelatin, of chocolate
- A61K9/50—Microcapsules having a gas, liquid or semi-solid filling; Solid microparticles or pellets surrounded by a distinct coating layer, e.g. coated microspheres, coated drug crystals
- A61K9/51—Nanocapsules; Nanoparticles
- A61K9/5107—Excipients; Inactive ingredients
- A61K9/5115—Inorganic compounds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/32—Size or surface area
Abstract
The invention discloses a kind of preparation method and applications of intelligent graphene quantum dot cluster, are heated to reflux Treatment of Carbon using the concentrated sulfuric acid and concentrated nitric acid, obtain graphene quantum dot powder；GQDs powder is dissolved in dimethyl sulfoxide (DMSO), then is reacted under nitrogen protection with a certain proportion of HBTU, HOBT, tert-butyl carbazate and DIPEA, GQDs hydrazides solution is obtained after dialysis；It adds in GQDs powder to GQDs hydrazides solution, while trifluoroacetic acid is added, intelligent GQDs clusters are obtained after reaction, the aqueous solution of intelligent GQDs clusters is obtained after dialysing in deionized water.The method of the present invention is novel, and in the case where controlling experiment condition, yield is high, and the obtained intelligent GQDs clusters containing hydrazone bond can realize GQDs control releases under condition of different pH, have better biologic applications foreground.
Description
Technical field
The present invention relates to a kind of preparation method and applications of graphene quantum dot, more particularly to a kind of graphene quantum dot
The preparation method and application of cluster is applied to nano material preparation process and applied technical field.
Background technology
The graphene single sheet that graphene quantum dot (GQDs) is less than 100nm has compared to grapheme material
The characteristics of edge effect and quantum effect, these features make it have preferably development than graphene in terms of electronics and photoelectron
Potentiality can be applied to photochemical catalyst, electrochemical sensor etc..Meanwhile graphene quantum dot also has hypotoxicity, fluorescence steady
The characteristics such as qualitative, biocompatibility and Premeabilisation of cells rate, so it is in medicine/gene carrier band, fluorescence probe and bio-imaging neck
Domain equally has extensive development prospect.
Existing nano-carrier, which has release too early in transportational process, discharges slowly and reaches tumor locus, to be difficult to
The problems such as.And the ability of the carrier band drug of the graphene quantum dot material of the preparation of existing method is limited, can't effectively realize
Carry the accurate release of drug, bio-toxicity, environment friendly and intelligent ideal not enough.
Invention content
In order to solve prior art problem, it is an object of the present invention to overcome the deficiencies of the prior art, and to provide one kind
The preparation method and application of intelligent graphene quantum dot cluster, the GQDs being prepared using the nitration mixture of the concentrated sulfuric acid and concentrated nitric acid,
Containing a large amount of carboxyl and carbonyl, then by the effect of coupling agent, GQDs hydrazides has been synthesized；Then by the carbonyl of GQDs with
Hydrazone bond of the GQDs hydrazides reaction synthesis with pH responsive types, prepares intelligence GQDs clusters, which can solve under condition of different pH
From the GQDs nano particles at dispersion, so that the medicine of carrier band is more accurately entered tumour cell and is released effectively drug,
Reduce the side effect to non-tumor cell.
In order to achieve the above objectives, the present invention adopts the following technical scheme that：
A kind of preparation method of intelligence graphene quantum dot cluster, includes the following steps：
A. 4.0g carbon fibers are weighed first to be added in the reaction vessel of 250mL, and the mass percent concentration of 135mL is added not
The mass percent concentration of the concentrated sulfuric acid and 45mL less than 95wt.% is not less than the concentrated nitric acid mixture of 65wt.%, in normal-temperature water
At least 1h is ultrasonically treated under the conditions of bath, then under the conditions of the oil bath not less than 80 DEG C, heating reflux reaction at least for 24 hours, then
Mixed liquor after reaction is cooled to room temperature, at least 800mL deionized waters is used in combination to be diluted, then with centrifuge to be not less than
The rotating speed of 6000rpm centrifuges at least 30min, and separation removal lower sediment thing collects upper layer black liquor, uses vacuum filtration
Method handles black liquor, and 0.22 μm of suction filtration film is not more than by pore-size, further removes the substance of larger particles, most
The acid solution of graphene quantum dot is obtained afterwards, is then repeatedly dialysed with the bag filter of molecular weight 3500Da in deionized water
It isolates and purifies, the diffusate outside bag filter after dialysis becomes neutral, then uses the reservation liquid dialysed in bag filter
Rotary Evaporators are evaporated not less than 60 DEG C, then are ground to get to dry graphene quantum dot powder；
B. the graphene quantum dot powder that 100mg is prepared in the step a is taken to be dissolved at least 8mL deionized waters, so
Afterwards with molecular weight be 1000Da regenerated cellulose bag filter in, dialysed in solvent at least 4 times in dimethyl sulfoxide (DMSO), often
4h replaces a dialyzate, obtains the DMSO solution of graphene quantum dot；Then the DMSO of the graphene quantum dot containing 50mg is taken
Solution is transferred in single-necked flask, using HBTU as coupling agent, and the HOBT of the HBTU of 735.3mg and 261.48mg is added
It is mixed in single-necked flask, the tert-butyl carbazate of 383.58mg is then added, after stirring at least 30 minutes at normal temperatures,
The n,N-diisopropylethylamine for adding 400 μ L obtains reactant mixed system solution；Then in room temperature and nitrogen protection gas
Under conditions of reacted at least 48h, then by after reaction reaction mixture be packed into molecular weight be 3500Da regenerated cellulose
It in bag filter, is dialysed in DMSO solution at least two days, a dialyzate is replaced per 8h, obtains GQDs hydrazides solution；
C. the GQDs hydrazides solution that 50mg is prepared in the step b is taken, is then added and is equivalent to taken GQDs acyls
The GQDs powder of at least 10 times quality of hydrazine solution, while the trifluoroacetic acid that 0.5mL is added forms reactant mixture system, in room
The lower stirring of temperature at least for 24 hours, is stirred at least 48h into reaction, is obtained containing intelligence GQDs clusters at being then warming up to not less than 50 DEG C
Then mixed liquor after reaction is fitted into the bag filter that molecular weight is 8000-10000Da, in deionization by the mixed liquor of product
It dialyses repeatedly in water three days to four days, a dialyzate is replaced per 8h, finally obtains the aqueous solution of intelligent GQDs clusters.
A kind of intelligent graphene quantum dot cluster prepared by the preparation method of the intelligent graphene quantum dot cluster of the present invention
Using intelligent graphene quantum dot cluster can be dissociated into the GQDs nano particles of dispersion under condition of different pH, be controlled for pH
Release.
The application of above-mentioned intelligence graphene quantum dot cluster, preferably carries out pH controls by intelligent graphene quantum dot cluster
Release makes the medicine of intelligent graphene quantum dot cluster carrier band enter tumour cell and carries out drug release.
The application of above-mentioned intelligence graphene quantum dot cluster, preferably intelligent graphene quantum dot cluster are 5.0~7.4 in pH
In the environment of can be dissociated into the GQDs nano particles of dispersion.
The present invention compared with prior art, has following obvious prominent substantive distinguishing features and remarkable advantage：
1. the method for the present invention novel and unique, environmental-friendly in the case where controlling experiment condition, yield is high, and what is obtained contains
There are the intelligent GQDs clusters of the hydrazone bond of acid labile, GQDs control releases can be realized under condition of different pH, carrier band can be made
Medicine can more accurately enter tumour cell and be released effectively drug, reduce the side effect to non-tumor cell, have
Better biologic applications foreground；
2. intelligent GQDs clusters prepared by the method for the present invention are water-soluble good, particle size uniformity, quality is high, and purity is easy to
Control and regulation and control；
3. the whole system prepared by the present invention has lower bio-toxicity, and easy to operate, it is readily synthesized.
Description of the drawings
Fig. 1 is that the transmission electron microscope of the intelligent GQDs clusters containing hydrazone bond prepared by one method of the embodiment of the present invention shines
Piece.
Specific implementation mode
Said program is described further below in conjunction with specific examples of the implementation, the preferred embodiment of the present invention is described in detail such as
Under：
Embodiment one
In the present embodiment, referring to Fig. 1, a kind of preparation method of intelligence graphene quantum dot cluster includes the following steps：
A. 4.0g carbon fibers are weighed with electronic balance first to be added in the round-bottomed flask of 250mL, the quality hundred of 135mL is added
Divide the concentrated nitric acid mixture that the mass percent concentration for the concentrated sulfuric acid and 45mL that specific concentration is 95wt.% is 65wt.%, in room temperature
1h is ultrasonically treated under water bath condition, then under the conditions of 80 DEG C of oil bath, heating reflux reaction for 24 hours, then will be mixed after reaction
It closes liquid and is cooled to room temperature, 800mL deionized waters is used in combination to be diluted, then centrifuge is used to be centrifuged with the rotating speed of 6000rpm
30min, separation removal lower sediment thing, collects upper layer black liquor, handles black liquor using the method for vacuum filtration, passes through
The suction filtration film that pore-size is 0.22 μm further removes the substance of larger particles, finally obtains graphene quantum dot (GQDs)
Acid solution, then in deionized water with the bag filter of molecular weight 3500Da carry out repeatedly dialyse isolate and purify, until dialysis
The diffusate outside bag filter afterwards becomes neutral, then by the reservation liquid Rotary Evaporators dialysed in bag filter 60 DEG C into
Row is evaporated, then is ground to get to dry graphene quantum dot powder；
B. it takes the graphene quantum dot powder that 100mg is prepared in the step a to be dissolved in 8mL deionized waters, then uses
Molecular weight is to carry out dialysis 4 times in solvent in dimethyl sulfoxide (DMSO) (DMSO) in the regenerated cellulose bag filter of 1000Da, per 4h
A dialyzate is replaced, the DMSO solution of graphene quantum dot is obtained；Then take the DMSO of the graphene quantum dot containing 50mg molten
Liquid is transferred in single-necked flask, using HBTU as coupling agent, and list is added in the HOBT of the HBTU of 735.3mg and 261.48mg
It is mixed in mouth flask, the tert-butyl carbazate of 383.58mg is then added, after stirring 30 minutes at normal temperatures, added
The n,N-diisopropylethylamine (DIPEA) of 400 μ L, obtains reactant mixed system solution；Then in room temperature and nitrogen protection gas
Reaction 48h is carried out under conditions of body, it is saturating that the reaction mixture after reaction is then packed into the regenerated cellulose that molecular weight is 3500Da
It analyses in bag, dialysis two days is carried out in DMSO solution, a dialyzate is replaced per 8h, obtains GQDs hydrazides solution；
C. the GQDs hydrazides solution that 50mg is prepared in the step b is taken, is then added and is equivalent to taken GQDs acyls
The GQDs powder of 10 times of quality of hydrazine solution, while the trifluoroacetic acid (TFA) that 0.5mL is added forms reactant mixture system,
It stirs at room temperature for 24 hours, is then warming up at 50 DEG C and stirs 48h into reaction, obtain the mixed liquor containing intelligence GQDs cluster products,
Then the mixed liquor after reaction is fitted into the bag filter that molecular weight is 8000-10000Da, dialyses three repeatedly in deionized water
It replaced a dialyzate per 8h, and finally obtained the aqueous solution of intelligent GQDs clusters by four days.
Intelligent GQDs clusters prepared by the present invention carry out microcosmos experiment observation and pass through the intelligence containing hydrazone bond referring to Fig. 1
The transmission electron microscope photos of GQDs clusters is measured by software it is found that it shows the state of many single GQDs aggregations
The average grain diameter for assembling pockets of single GQDs is 4.19nm, wherein maximum 28.57nm, minimum 1.56nm.
The present embodiment utilizes the concentrated sulfuric acid (H2SO4) and concentrated nitric acid (HNO3) it is heated to reflux Treatment of Carbon (CF), after processing
Obtain graphene quantum dot (GQDs) powder；GQDs powder is dissolved in dimethyl sulfoxide (DMSO) (DMSO), then with it is a certain proportion of more
Peptide coupling agent O- benzotriazole-tetramethylurea hexafluorophosphate (HBTU), condensing agent I-hydroxybenzotriazole (HOBT), diazanyl
T-butyl formate and n,N-diisopropylethylamine (DIPEA) are reacted under nitrogen protection, and it is molten that GQDs hydrazides is obtained after dialysis
Liquid；It adds in the GQDs powder to GQDs hydrazides solution of 10 times of quality, while trifluoroacetic acid (TFA) is added, pass through GQDs acyls
Intelligent GQDs clusters are obtained after hydrazine and GQDs phase reactions, and the aqueous solution of intelligent GQDs clusters is obtained after dialysing in deionized water.
The present embodiment method is novel, environmental-friendly, and in the case where controlling experiment condition, yield is high, and prepared whole system has
Lower bio-toxicity, obtained intelligent GQDs clusters are water-soluble good, particle size uniformity.
Embodiment two
The present embodiment and embodiment one are essentially identical, are particular in that：
In the present embodiment, the intelligence that prepared by a kind of preparation method using the intelligent graphene quantum dot cluster of embodiment one
The application of graphene quantum dot cluster, the GQDs that intelligent graphene quantum dot cluster can be dissociated into dispersion under condition of different pH receive
Rice grain, for pH control releases.PH control releases are carried out by intelligent graphene quantum dot cluster, make intelligent graphene quantum
The medicine of point cluster carrier band enters tumour cell and carries out drug release.
In the present embodiment, intelligent graphene quantum dot cluster can dissociate ingredient respectively in the case where pH is 5.0 acidic environment
Scattered GQDs nano particles.This intelligent graphene quantum dot cluster is under conditions of pH is 7.4,6.5,5.0, GQDs nano particles
Size be gradually reduced, illustrate that, with environment gradual oxytropism condition variation, nano-complex particle starts to dissociate, thus size by
Gradual change is small, and controllability is good.
In the present embodiment, the hydrazone bond based on acid-sensitive that prepared by embodiment one mediates the GQDs of GQDs hydrazides modification that can use
It controls and discharges in pH so that the intelligent GQDs clusters of preparation realize GQDs control releases under condition of different pH, may be implemented
It is dissociated under different acidity PH.The medicine of carrier band can be enable more accurately to enter tumour cell and be released effectively drug, subtracted
Few side effect to non-tumor cell.Whole system prepared by embodiment one has lower bio-toxicity, and may be implemented
The accurate release of drug is carried, there is preferable application prospect, nano-carrier is effectively solved and there is premature disconnection in transportational process
It puts, discharge slowly and reach the problems such as tumor locus is difficult to.
The GQDs that the above embodiment of the present invention is prepared using the nitration mixture of the concentrated sulfuric acid and concentrated nitric acid contains a large amount of carboxyl
And carbonyl successfully synthesizes GQDs hydrazides by the effect of coupling agent in DMSO solution；Then, by the carbonyl of GQDs with
Hydrazone bond of the GQDs hydrazides reaction synthesis with pH responsive types, is successfully prepared intelligent GQDs clusters, the cluster is in corresponding pH items
The GQDs nano particles of dispersion can be dissociated under part.
Above in conjunction with saying that the embodiment of the present invention is illustrated in attached drawing, but the present invention is not limited to the above embodiments, may be used also
A variety of variations, the Spirit Essence and principle of all technical solutions according to the present invention are made with the purpose of innovation and creation according to the present invention
Under change, modification, replacement, combination or the simplification made, equivalent substitute mode is should be, as long as meeting the invention mesh of the present invention
, the technical principle without departing from the preparation method and application of intelligent graphene quantum dot cluster of the invention and inventive concept,
Belong to protection scope of the present invention.
Claims (4)
1. a kind of preparation method of intelligence graphene quantum dot cluster, which is characterized in that include the following steps：
A. it weighs 4.0g carbon fibers first to be added in the reaction vessel of 250mL, the mass percent concentration that 135mL is added is not less than
The concentrated sulfuric acid of 95wt.% and the mass percent concentration of 45mL are not less than the concentrated nitric acid mixture of 65wt.%, in room temperature water-bath item
At least 1h is ultrasonically treated under part, then under the conditions of the oil bath not less than 80 DEG C, heating reflux reaction at least for 24 hours, then will be anti-
Mixed liquor after answering is cooled to room temperature, and at least 800mL deionized waters is used in combination to be diluted, then with centrifuge to be not less than
The rotating speed of 6000rpm centrifuges at least 30min, and separation removal lower sediment thing collects upper layer black liquor, uses vacuum filtration
Method handles black liquor, and 0.22 μm of suction filtration film is not more than by pore-size, further removes the substance of larger particles, most
The acid solution of graphene quantum dot is obtained afterwards, is then repeatedly dialysed with the bag filter of molecular weight 3500Da in deionized water
It isolates and purifies, the diffusate outside bag filter after dialysis becomes neutral, then uses the reservation liquid dialysed in bag filter
Rotary Evaporators are evaporated not less than 60 DEG C, then are ground to get to dry graphene quantum dot powder；
B. it takes the graphene quantum dot powder that 100mg is prepared in the step a to be dissolved at least 8mL deionized waters, then uses
Molecular weight is to be dialysed in solvent at least 4 times in dimethyl sulfoxide (DMSO) in the regenerated cellulose bag filter of 1000Da, more per 4h
A dialyzate is changed, the DMSO solution of graphene quantum dot is obtained；Then the DMSO solution of the graphene quantum dot containing 50mg is taken
It is transferred in single-necked flask, using HBTU as coupling agent, and single port is added in the HOBT of the HBTU of 735.3mg and 261.48mg
It is mixed in flask, the tert-butyl carbazate of 383.58mg is then added, after stirring at least 30 minutes at normal temperatures, then added
The n,N-diisopropylethylamine for entering 400 μ L obtains reactant mixed system solution；Then in the item of room temperature and nitrogen protection gas
At least 48h is reacted under part, the reaction mixture after reaction, which is then packed into the regenerated cellulose that molecular weight is 3500Da, dialyses
It in bag, is dialysed in DMSO solution at least two days, a dialyzate is replaced per 8h, obtains GQDs hydrazides solution；
C. the GQDs hydrazides solution that 50mg is prepared in the step b is taken, it is molten to be equivalent to taken GQDs hydrazides for then addition
The GQDs powder of at least 10 times quality of liquid, while the trifluoroacetic acid that 0.5mL is added forms reactant mixture system, at room temperature
Stirring at least for 24 hours, is stirred at least 48h into reaction, is obtained containing intelligence GQDs cluster products at being then warming up to not less than 50 DEG C
Mixed liquor, then by the mixed liquor after reaction be fitted into molecular weight be 8000-10000Da bag filter in, in deionized water
It dialyses three days to four days repeatedly, a dialyzate is replaced per 8h, finally obtains the aqueous solution of intelligent GQDs clusters.
2. the intelligent graphene quantum dot group that described in a kind of claim 1 prepared by the preparation method of intelligent graphene quantum dot cluster
The application of cluster, it is characterised in that：Intelligent graphene quantum dot cluster can be dissociated into the GQDs nanometers of dispersion under condition of different pH
Particle, for pH control releases.
3. the application of intelligent graphene quantum dot cluster according to claim 2, it is characterised in that：Pass through intelligent graphene amount
Son point cluster carries out pH control releases, so that the medicine of intelligent graphene quantum dot cluster carrier band is entered tumour cell and carries out medicine
Object discharges.
4. according to the application of intelligent graphene quantum dot cluster described in Claims 2 or 3, it is characterised in that：Intelligent graphene amount
Son point cluster can be dissociated into the GQDs nano particles of dispersion in the environment of pH is 5.0~7.4.
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| CN113651319A (en) * | 2021-08-25 | 2021-11-16 | 深圳华算科技有限公司 | Preparation method of graphene quantum dot nanocluster |
| CN113788479A (en) * | 2021-10-29 | 2021-12-14 | 凯盛石墨碳材料有限公司 | Preparation method of graphite-based quantum dots |
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| CN113788479A (en) * | 2021-10-29 | 2021-12-14 | 凯盛石墨碳材料有限公司 | Preparation method of graphite-based quantum dots |
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| CN108467028B (en) | 2021-10-12 |
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