CN108187057B - Porous silicon-coated graphene nano slow-release drug-loading system, preparation method and application thereof, and supported drug and preparation thereof - Google Patents
Porous silicon-coated graphene nano slow-release drug-loading system, preparation method and application thereof, and supported drug and preparation thereof Download PDFInfo
- Publication number
- CN108187057B CN108187057B CN201810030075.2A CN201810030075A CN108187057B CN 108187057 B CN108187057 B CN 108187057B CN 201810030075 A CN201810030075 A CN 201810030075A CN 108187057 B CN108187057 B CN 108187057B
- Authority
- CN
- China
- Prior art keywords
- drug
- pvp
- preparation
- porous silicon
- graphene oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 99
- 238000011068 loading method Methods 0.000 title claims abstract description 40
- 239000003814 drug Substances 0.000 title claims abstract description 36
- 229940079593 drug Drugs 0.000 title claims abstract description 34
- 229910021426 porous silicon Inorganic materials 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 47
- 239000002244 precipitate Substances 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000002356 single layer Substances 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 26
- 229910052681 coesite Inorganic materials 0.000 claims description 25
- 229910052906 cristobalite Inorganic materials 0.000 claims description 25
- 229910052682 stishovite Inorganic materials 0.000 claims description 25
- 229910052905 tridymite Inorganic materials 0.000 claims description 25
- 239000000047 product Substances 0.000 claims description 23
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000006228 supernatant Substances 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000006185 dispersion Substances 0.000 claims description 15
- 238000005530 etching Methods 0.000 claims description 15
- 238000009210 therapy by ultrasound Methods 0.000 claims description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 abstract description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052710 silicon Inorganic materials 0.000 abstract description 8
- 239000010703 silicon Substances 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 5
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 76
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 32
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 23
- 239000000243 solution Substances 0.000 description 11
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 10
- NNJVILVZKWQKPM-UHFFFAOYSA-N Lidocaine Chemical compound CCN(CC)CC(=O)NC1=C(C)C=CC=C1C NNJVILVZKWQKPM-UHFFFAOYSA-N 0.000 description 7
- 229960004194 lidocaine Drugs 0.000 description 7
- 238000005336 cracking Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 4
- 239000007853 buffer solution Substances 0.000 description 4
- 210000003371 toe Anatomy 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 238000000502 dialysis Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004593 Epoxy Chemical group 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 229920003081 Povidone K 30 Polymers 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 210000002390 cell membrane structure Anatomy 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012885 slow-release drug carrier Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
Images
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/02—Inorganic compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
- A61K47/32—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. carbomers, poly(meth)acrylates, or polyvinyl pyrrolidone
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Medicinal Chemistry (AREA)
- Pharmacology & Pharmacy (AREA)
- Epidemiology (AREA)
- Inorganic Chemistry (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Carbon And Carbon Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Medicinal Preparation (AREA)
Abstract
The invention provides a porous silicon-coated graphene nano slow-release drug-loading system, a preparation method and application thereof, a supported drug and preparation thereof. The preparation method disclosed by the invention is simple and convenient in operation process, simple in steps, free of complex post-treatment and suitable for large-scale production of the silicon dioxide protection type graphene oxide material. Meanwhile, the product porous silicon coated graphene nano slow-release drug-loading system obtained by the preparation method has good drug loading performance, and no mesoporous silicon template residue, so that the product porous silicon coated graphene nano slow-release drug-loading system can be further used as a carrier to prepare a loaded drug and has good use safety.
Description
Technical Field
The invention relates to the field of materials, in particular to a porous silicon-coated graphene nano slow-release drug-loading system, a preparation method and application thereof, a supported drug and preparation thereof.
Background
Graphene Oxide (GO) is Graphene oxide obtained by chemically oxidizing graphite powder and then ultrasonically stripping graphite powder, and is sp2A novel monolayer two-dimensional carbon material formed by hybridized carbon atoms. Because a large number of oxygen-containing active functional groups such as carboxyl, hydroxyl, carbonyl, epoxy and the like are attached to the surface of the composite material, the composite material has good water solubility and biocompatibility.
In recent years, graphene oxide has become a biomedical research hotspot, and is mainly focused on the aspects of nano drug loading, tumor treatment, photothermal imaging and the like. However, the graphene currently used has a disadvantage of certain biological toxicity, and since graphene oxide is in a sheet shape, the graphene oxide can damage a cell membrane structure, thereby generating certain biological toxicity.
In order to reduce the biotoxicity of the graphene oxide and improve the application safety of the graphene oxide, researchers modify the graphene oxide by surface modification or coating a material with high compatibility and the like. The surface silicon coating of the graphene oxide is a common coating method, and for example, a CTAB template method can be used to coat mesoporous silicon on the surface of the graphene oxide.
However, CTAB as a template has biological toxicity, and the step of removing CTAB in mesopores is complicated, so that the method is difficult to popularize and apply, and is difficult to realize production and preparation of large-scale products.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a preparation method of a porous silicon-coated graphene nano slow-release drug-loading system, which is simple in process, safe and efficient.
The second purpose of the invention is to provide a graphene nano slow-release drug-loading system obtained by the preparation method.
The third purpose of the invention is to provide an application of the graphene nano slow-release drug-loading system.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
a preparation method of a porous silicon-coated graphene nano slow-release drug-loading system comprises the following steps:
(a) carrying out ultrasonic cracking on the monolayer graphene oxide to obtain nano monolayer graphene oxide;
(b) mixing the obtained nano single-layer graphene oxide with polyvinylpyrrolidone, and performing ultrasonic treatment to obtain nGO-PVP;
(c) under the alkaline condition, the obtained nGO-PVP and tetraethoxysilane are mixed and reacted in an organic solution to obtain nGO-PVP with the surface coated with silicon dioxide, which is recorded as nGO-PVP @ SiO2；
(d) Obtained nGO-PVP @ SiO2Mixing with polyvinylpyrrolidone, reflux reacting, and centrifugingAnd etching the precipitate with sodium hydroxide to obtain the porous silicon-coated graphene nano slow-release drug-carrying system.
Preferably, in the step (a) of the preparation method, micron-sized single-layer graphene oxide is used as a raw material, and the nano single-layer graphene oxide is obtained through ultrasonic cracking;
more preferably, the ultrasonic treatment is carried out under the ice bath condition, and the ultrasonic treatment time is 45-90 min.
Preferably, in the step (b) of the preparation method, the mass ratio of the nano monolayer graphene oxide to the polyvinylpyrrolidone is 1: 3-3: 1;
more preferably, in the step (b), the mass ratio of the nano monolayer graphene oxide to the polyvinylpyrrolidone is 1: 1-3: 1.
Preferably, in the step (c) of the preparation method, the temperature of the mixing reaction is 20-30 ℃ and the time is 1-5 h;
more preferably, in the step (c), the temperature of the mixing reaction is 20-25 ℃ and the time is 2-3 h.
Preferably, in step (d) of the preparation method of the present invention, nGO-PVP @ SiO2The mass ratio of the polyvinylpyrrolidone to the polyvinylpyrrolidone is 1: 3-3: 1;
more preferably, in step (d), nGO-PVP @ SiO2The mass ratio of the polyvinylpyrrolidone to the polyvinylpyrrolidone is 1: 3-1: 1.
Preferably, in the step (d) of the preparation method, the sodium hydroxide is a sodium hydroxide solution, and the concentration of the sodium hydroxide solution is preferably 3-8 mol/L;
and/or the etching time is 5-90 min; more preferably, the etching time is 30-60 min.
Meanwhile, the invention also provides a porous silicon-coated graphene nano slow-release drug-loading system obtained by the preparation method.
Similarly, the invention also provides the application of the porous silicon coated graphene nano slow-release drug-loading system in drug loading;
and/or, the porous silicon-coated graphene nano slow-release drug-loading system is applied to preparation of a loaded drug.
The preparation method comprises the steps of firstly obtaining the graphene nano slow-release drug-carrying system coated by the porous silicon according to the method, and then mixing the obtained graphene nano slow-release drug-carrying system coated by the porous silicon with a drug in a solution to obtain the supported drug.
Meanwhile, the invention also provides a load type medicine obtained by the preparation method.
Compared with the prior art, the invention has the beneficial effects that:
the preparation method disclosed by the invention is simple and convenient in operation process, simple in steps, free of complex post-treatment and suitable for large-scale production of the silicon dioxide protection type graphene oxide material;
meanwhile, the product porous silicon coated graphene nano slow-release drug-loading system obtained by the preparation method has good drug loading performance and no mesoporous silicon template residue, so that the product porous silicon coated graphene nano slow-release drug-loading system can be further used as a carrier to prepare a loaded drug and has good use safety.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 shows GO-PVP @ SiO before NaOH etching in an embodiment of the invention2An electron microscope image;
FIG. 2 shows GO-PVP @ porous SiO film after NaOH etching according to an embodiment of the present invention2An electron microscope image;
FIG. 3 shows GO-PVP @ porous SiO in an embodiment of the present invention2Cumulative release profile of lidocaine-loaded drug.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
In view of the practical problems that the existing silicon-coated graphene oxide mesoporous material is complex in preparation process and likely to generate biotoxicity due to residual template agent, the invention particularly provides a porous silicon-coated graphene nano slow-release drug-loading system so as to solve various problems in the prior art.
Specifically, the preparation method of the porous silicon-coated graphene nano slow-release drug-loading system provided by the invention has the following steps:
(a) carrying out ultrasonic cracking on the monolayer graphene oxide to obtain nano monolayer graphene oxide;
preferably, in the step, the single-layer graphene oxide serving as the raw material is micron-sized single-layer graphene oxide, and the nano-sized single-layer graphene oxide is obtained by performing ultrasonic cracking on the micron-sized single-layer graphene oxide;
more preferably, in the step, firstly, the raw material monolayer graphene oxide is added into deionized water, wherein the ratio of the mass gram of the monolayer graphene oxide to the volume milliliter of the deionized water is preferably controlled to be 0.2-0.5: 100;
then, carrying out ultrasonic cracking under the ice bath condition, wherein the ultrasonic time is preferably 45-90 min, and more preferably, the ultrasonic time is controlled to be 60-90 min;
after ultrasonic cracking, obtaining nanoscale single-layer graphene oxide nGO dispersed in deionized water, wherein the concentration of the nGO is 0.2-0.5 mg/ml, and the size of the nGO is about 200 nm;
(b) mixing the obtained nano single-layer graphene oxide with polyvinylpyrrolidone, preferably, the polyvinylpyrrolidone is preferably PVP K30;
meanwhile, preferably, the mass ratio of the nano monolayer graphene oxide to the polyvinylpyrrolidone is 1: 3-3: 1; more preferably, in the step (d), the mass ratio of the nano monolayer graphene oxide to the polyvinylpyrrolidone is 1: 3-1: 1;
mixing nano single-layer graphene oxide with polyvinylpyrrolidone, and performing ultrasonic treatment, wherein the ultrasonic treatment time is preferably 30min, and the polyvinylpyrrolidone is allowed to cover the surface of the nano single-layer graphene oxide to obtain nGO-PVP;
(c) mixing the obtained nGO-PVP and tetraethoxysilane in an organic solution for reaction under the alkaline condition;
in this step, it is preferable that the reaction system is made alkaline by adding aqueous ammonia to an organic solvent;
meanwhile, preferably, the organic solvent is ethanol;
more preferably, in the step, ethanol, nGO-PVP, ammonia water and tetraethoxysilane are used as raw materials for reaction, and the stober growth method is used, so that nGO-PVP is coated with SiO2To obtain a surface coated with SiO2nGO-PVP, i.e. nGO-PVP @ SiO2；
In a further preferred embodiment, the ratio of the volume ml of ethanol, the mass mg of nGO-PVP, the volume ml of ammonia, and the volume ml of tetraethoxysilane is: 50:10:5: 2;
mixing the four raw materials, and reacting at 20-30 ℃ for 1-5 h, preferably at 20-25 ℃ for 2-3 h;
after the reaction is finished, centrifuging a product system, removing supernatant, and recovering the residual precipitate to obtain nGO-PVP @ SiO2；
(d) The obtained nGO-PVP @ SiO2Mixing with polyvinylpyrrolidone, preferably, the polyvinylpyrrolidone used in this step is PVP k15, nGO-PVP @ SiO2The mass ratio of the polyvinylpyrrolidone to the polyvinylpyrrolidone is 1: 3-3: 1, and the polyvinylpyrrolidone is preferably nGO-PVP @ SiO2The mass ratio of the polyvinylpyrrolidone to the polyvinylpyrrolidone is 1: 3-1: 1; further preferred, nGO-PVP @ SiO2The mass ratio of the polyvinylpyrrolidone to the polyvinylpyrrolidone is 1: 1;
mixing the two, and carrying out reflux reaction at the temperature of 90-100 ℃ for about 3 hours; after the reaction, carrying out centrifugal treatment on the product mixed system, removing supernatant, recovering the obtained precipitate, and then dispersing the precipitate in deionized water;
then, etching the product dispersed in the deionized water by using sodium hydroxide, preferably adding 3-8 mol/L sodium hydroxide solution for etching, and more preferably adding 4-5 mol/L sodium hydroxide solution for etching; the etching time is preferably 5-90 min, more preferably 30-60 min;
and then, recovering the solid product by adopting a filtering or centrifuging method to obtain the porous silicon-coated graphene nano slow-release drug-loading system.
The graphene nano slow-release drug carrier system obtained by the method is mainly coated with SiO on the surface2And through further structural etching of the surface covered with silicon dioxide, the medicine can pass through SiO2The holes are loaded on the surface of the graphene, so that the graphene nano slow-release drug-loading system can play a role of a drug carrier.
Meanwhile, compared with the mesoporous silicon graphene carrier obtained by a CTAB method, the graphene nano slow-release drug-loading system provided by the invention has the same drug-loading effect, however, the method is more convenient to operate, and does not generate drug toxic substances such as template residues and the like, so that the method is more suitable for popularization and large-scale production.
Further, the graphene nano slow-release drug-loading system is mixed with the drug solution, so that the drug can be loaded on the graphene nano slow-release drug-loading system, and the loaded drug is formed. The loaded drug entering the body has good biocompatibility, and does not generate irritation to the human body, and meanwhile, the loaded drug can be slowly released in the body due to the good adsorbability of the graphene to the loaded drug, so that the effect of long-acting treatment is achieved.
Example 1
Adding 0.2g of micron-sized single-layer graphene oxide into 100ml of deionized water, carrying out ultrasonic treatment in an ultrasonic crusher under an ice bath condition for 1h to obtain nano graphene oxide aqueous dispersion with the size of about 200 nm;
according to the mass ratio of 1:1, measuring a proper amount of nano graphene oxide aqueous dispersion, mixing the nano graphene oxide aqueous dispersion with a proper amount of PVP k30, and carrying out ultrasonic treatment for 30min to obtain nGO-PVP;
then coating SiO on the surface of the nano graphene oxide by adopting an STOBER growth method2Mixing 50ml of ethanol, 10mg of GO-PVP, 5ml of ammonia water and 2ml of TOES at 25 ℃ for reaction for 3 hours; then, centrifuging the product system at the rotating speed of 12000r/min for 20min, removing supernatant, and recovering precipitate to obtain nGO-PVP @ SiO2I.e. with SiO as outer surface2The structure of the coated nGO-PVP is detected by a scanning electron microscope, and the result is shown in figure 1.
Then, GO-PVP @ SiO2And PVP k15 according to the mass ratio of 1:1, mixing, and then carrying out reflux reaction for 3 hours at the temperature of 90 ℃; centrifuging the product system at 12000r/min for 20min, removing supernatant, recovering precipitate, and dispersing the precipitate in 50ml deionized water;
adding 5M sodium hydroxide into deionized water dispersed with the precipitate for etching treatment, wherein the treatment time is 60 min; and then, centrifuging the product system at the rotating speed of 12000r/min for 20min, removing the supernatant, recovering the precipitate, namely the porous silicon-coated graphene nano slow-release drug-loading system of the embodiment 1, and performing scanning electron microscope detection on the system, wherein the result is shown in fig. 2.
As can be seen from FIG. 1, nGO-PVP @ SiO which was not etched by sodium hydroxide2In the method, graphene serving as a reaction raw material is changed into a semitransparent flaky structure coated with a compact silicon layer on the surface from a soft transparent film;
as can be seen from FIG. 2, nGO-PVP @ SiO2After being etched by NaOH for 60min, the surface-coated silicon layer is etched into a porous structure.
Example 2
Adding 0.5g of micron-sized single-layer graphene oxide into 100ml of deionized water, carrying out ultrasonic treatment in an ultrasonic crusher under an ice bath condition for 45min to obtain nano graphene oxide aqueous dispersion with the size of about 200 nm;
according to the mass ratio of 1: 2, measuring a proper amount of nano graphene oxide aqueous dispersion, mixing the nano graphene oxide aqueous dispersion with a proper amount of PVP k30, and carrying out ultrasonic treatment for 30min to obtain nGO-PVP;
mixing 100ml ethanol, 20mg GO-PVP, 10ml ammonia water and 5ml TOES at 30 ℃ for reaction for 5 h; then, centrifuging the product system at the rotating speed of 12000r/min for 20min, removing supernatant, and recovering precipitate to obtain nGO-PVP @ SiO2I.e. with SiO as outer surface2Coated nGO-PVP;
then, GO-PVP @ SiO2And PVP k15 according to the mass ratio of 1: 2, mixing, and then carrying out reflux reaction for 3 hours at the temperature of 95 ℃; centrifuging the product system at 12000r/min for 20min, removing supernatant, recovering precipitate, and dispersing the precipitate in 50ml deionized water;
adding 3M sodium hydroxide into deionized water dispersed with the precipitate for etching treatment, wherein the treatment time is 90 min; and then, centrifuging the product system at the rotating speed of 12000r/min for 20min, removing the supernatant, and recovering the precipitate, so as to obtain the porous silicon-coated graphene nano slow-release drug-loading system of the embodiment 2.
Example 3
Adding 0.3g of micron-sized single-layer graphene oxide into 100ml of deionized water, carrying out ultrasonic treatment in an ultrasonic crusher under an ice bath condition for 90min to obtain nano graphene oxide aqueous dispersion with the size of about 200 nm;
according to the mass ratio of 1:3, measuring a proper amount of nano graphene oxide aqueous dispersion, mixing the nano graphene oxide aqueous dispersion with a proper amount of PVP k30, and carrying out ultrasonic treatment for 30min to obtain nGO-PVP;
mixing 80ml ethanol, 15mg GO-PVP, 10ml ammonia water and 3ml TOES at 20 ℃ for reaction for 5 h; then, centrifuging the product system at the rotating speed of 12000r/min for 20min, removing supernatant, and recovering precipitate to obtain nGO-PVP @ SiO2I.e. with SiO as outer surface2Coated nGO-PVP;
then, GO-PVP @ SiO2And PVP k15 according to the mass ratio of 1:3, mixing, and then carrying out reflux reaction for 3 hours at the temperature of 95 ℃; centrifuging the product system at 12000r/min for 20min, removing supernatant, recovering precipitate, and dispersing the precipitate in 50ml deionized water;
adding 8M sodium hydroxide into deionized water dispersed with the precipitate for etching treatment for 30 min; and then, centrifuging the product system at the rotating speed of 12000r/min for 20min, removing the supernatant, and recovering the precipitate, so as to obtain the porous silicon-coated graphene nano slow-release drug-loading system of the embodiment 3.
Example 4
Adding 0.4g of micron-sized single-layer graphene oxide into 100ml of deionized water, carrying out ultrasonic treatment in an ultrasonic crusher under an ice bath condition for 75min to obtain nano graphene oxide aqueous dispersion with the size of about 200 nm;
according to the mass ratio of 1:1, measuring a proper amount of nano graphene oxide aqueous dispersion, mixing the nano graphene oxide aqueous dispersion with a proper amount of PVP k30, and carrying out ultrasonic treatment for 30min to obtain nGO-PVP;
mixing 30ml ethanol, 5mg GO-PVP, 3ml ammonia water and 1ml TOES at 25 ℃ for reaction for 2 h; then, centrifuging the product system at the rotating speed of 12000r/min for 20min, removing supernatant, and recovering precipitate to obtain nGO-PVP @ SiO2I.e. with SiO as outer surface2Coated nGO-PVP;
then, GO-PVP @ SiO2And PVP k15 according to the mass ratio of 2: 1, mixing, and then carrying out reflux reaction for 3 hours at the temperature of 100 ℃; centrifuging the product system at 12000r/min for 20min, removing supernatant, recovering precipitate, and dispersing the precipitate in 50ml deionized water;
adding 5M sodium hydroxide into deionized water dispersed with the precipitate for etching treatment for 45 min; and then, centrifuging the product system at the rotating speed of 12000r/min for 20min, removing the supernatant, and recovering the precipitate, so as to obtain the porous silicon-coated graphene nano slow-release drug-loading system of the embodiment 4.
Experimental example 1
The porous silicon-coated graphene nano slow-release drug-loading system prepared in example 1 is used as an experimental material, and drug loading and release tests are performed, wherein the experimental method is as follows:
a certain amount of precisely weighed lidocaine is taken to prepare a standard solution, an ultraviolet spectrophotometer is used for measuring a peak value at 262nm, and a standard curve is drawn.
10mg of the product of example 1 was precisely weighed, mixed with 2ml of a lidocaine solution of a predetermined concentration, magnetically stirred for 24 hours, and centrifuged to measure the ultraviolet absorption peak at 262nm of the supernatant. Substituting the standard curve to obtain the concentration of lidocaine in the supernatant after drug loading, and multiplying the concentration difference by the volume to calculate the drug loading amount;
the precipitate obtained after centrifugation is nGO @ porous SiO2The lidocaine-loaded drug mixture is precisely weighed nGO @ porous SiO after being vacuumized for 8 hours2And (4) adding the libo dispersed in 5ml of PBS buffer solution into a dialysis bag with two ends closed by a clamp, then putting the dialysis bag into 95ml of PBS buffer solution to meet the condition of a leak tank, magnetically stirring at 37 ℃, and sucking 5ml of PBS buffer solution in the large system for ultraviolet absorption test at 0.5, 1, 2, 4, 6, 8, 16, 24, 32 and 48 hours respectively while supplementing 5ml of PBS buffer solution. In another dialysis system, a cumulative release profile was plotted against a stock solution of lidocaine. The results of the experiment are shown in FIG. 3.
From the results in FIG. 3, it can be seen that nGO @ porous SiO2The cumulative release of the lidocaine load reaches 62.5 percent, and the release time reaches 48 hours. Therefore, the porous silicon-coated graphene nano slow-release drug-carrying system has better drug loading capacity and can play a role in slow-controlled release of drugs, so that the porous silicon-coated graphene nano slow-release drug-carrying system becomes a new-generation drug slow-release carrier material with good application prospect.
While particular embodiments of the present invention have been illustrated and described, it would be obvious that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.
Claims (3)
1. The application of the porous silicon-coated graphene nano slow-release drug-loading system in drug loading and/or drug loading;
the preparation method of the porous silicon-coated graphene nano slow-release drug-loading system comprises the following steps:
(a) adding 0.2g of micron-sized single-layer graphene oxide into 100ml of deionized water, carrying out ultrasonic treatment in an ultrasonic crusher under an ice bath condition for 1h to obtain nano graphene oxide aqueous dispersion with the size of about 200 nm;
(b) and the mass ratio of 1:1, measuring a proper amount of the nano graphene oxide aqueous dispersion obtained in the step (a), mixing the nano graphene oxide aqueous dispersion with a proper amount of PVPk30, and carrying out ultrasonic treatment for 30min to obtain nGO-PVP;
(c) then coating SiO on the surface of the nano graphene oxide by adopting an STOBER growth method2Mixing 50ml of ethanol, 10mg of GO-PVP obtained in the step (b), 5ml of ammonia water and 2ml of TEOS at 25 ℃ for reaction for 3 hours; then, centrifuging the product system at the rotating speed of 12000r/min for 20min, removing supernatant, and recovering precipitate to obtain nGO-PVP @ SiO2I.e. with SiO as outer surface2Coated nGO-PVP;
(d) and (c) adding GO-PVP @ SiO obtained in the step (c)2And PVP k15 according to the mass ratio of 1:1, mixing, and then carrying out reflux reaction for 3 hours at the temperature of 90 ℃; centrifuging the product system at 12000r/min for 20min, removing supernatant, recovering precipitate, and dispersing the precipitate in 50ml deionized water;
adding 5M sodium hydroxide into deionized water dispersed with the precipitate for etching treatment, wherein the treatment time is 60 min; and then, centrifuging the product system at the rotating speed of 12000r/min for 20min, removing supernatant, and recovering the precipitate to obtain the porous silicon-coated graphene nano slow-release drug-carrying system.
2. The preparation method of the supported drug is characterized in that in the preparation method, firstly, the graphene nano slow-release drug-carrying system coated by the porous silicon is obtained according to the method of claim 1, and then the obtained graphene nano slow-release drug-carrying system coated by the porous silicon is mixed with the drug in a solution to obtain the supported drug.
3. The supported drug obtained by the production method according to claim 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810030075.2A CN108187057B (en) | 2018-01-12 | 2018-01-12 | Porous silicon-coated graphene nano slow-release drug-loading system, preparation method and application thereof, and supported drug and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810030075.2A CN108187057B (en) | 2018-01-12 | 2018-01-12 | Porous silicon-coated graphene nano slow-release drug-loading system, preparation method and application thereof, and supported drug and preparation thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108187057A CN108187057A (en) | 2018-06-22 |
| CN108187057B true CN108187057B (en) | 2020-05-22 |
Family
ID=62588837
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810030075.2A Expired - Fee Related CN108187057B (en) | 2018-01-12 | 2018-01-12 | Porous silicon-coated graphene nano slow-release drug-loading system, preparation method and application thereof, and supported drug and preparation thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108187057B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108862245B (en) * | 2018-04-27 | 2022-06-14 | 辽宁大学 | Large-aperture foam silicon-reduced graphene oxide-based electrochemical modification material and preparation method and application thereof |
| CN110623943B (en) * | 2019-11-14 | 2022-03-01 | 吉林大学第一医院 | Medicine carrying application of flexible hollow mesoporous organic silicon oxide |
| CN112147210A (en) * | 2020-09-25 | 2020-12-29 | 复旦大学 | Preparation method, product and application of boric acid functionalized mesoporous graphene-silicon dioxide composite material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106268630A (en) * | 2015-05-13 | 2017-01-04 | 中国石油天然气股份有限公司 | Silicon dioxide-graphene composite material, preparation method thereof and treatment method for removing dye pollutants in water |
| CN106492221A (en) * | 2016-11-21 | 2017-03-15 | 吉林大学 | A kind of reduction responsive nano graphene oxide cladding carries medicine mesoporous silicon dioxide nano particle and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101618556B1 (en) * | 2014-11-07 | 2016-05-09 | 기초과학연구원 | Mesoporous silica coated graphene oxide hybrid structure and development of drug delivery system using phase change material and drug delivery system using thereof |
-
2018
- 2018-01-12 CN CN201810030075.2A patent/CN108187057B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106268630A (en) * | 2015-05-13 | 2017-01-04 | 中国石油天然气股份有限公司 | Silicon dioxide-graphene composite material, preparation method thereof and treatment method for removing dye pollutants in water |
| CN106492221A (en) * | 2016-11-21 | 2017-03-15 | 吉林大学 | A kind of reduction responsive nano graphene oxide cladding carries medicine mesoporous silicon dioxide nano particle and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 氧化石墨烯对盐酸利多卡因的高效装载和缓释性能及其经皮给药的渗透性研究;申玉坤等;《科学技术与工程》;20150831;第15卷(第23期);参见摘要 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108187057A (en) | 2018-06-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Teng et al. | Mesoporous organosilica hollow nanoparticles: synthesis and applications | |
| CN108187057B (en) | Porous silicon-coated graphene nano slow-release drug-loading system, preparation method and application thereof, and supported drug and preparation thereof | |
| Madni et al. | Graphene-based nanocomposites: synthesis and their theranostic applications | |
| Li et al. | Anisotropic encapsulation-induced synthesis of asymmetric single-hole mesoporous nanocages | |
| CN107936266B (en) | Cellulose/black phosphorus nanosheet composite hydrogel and preparation method thereof | |
| Xu et al. | Group IV nanodots: synthesis, surface engineering and application in bioimaging and biotherapy | |
| CN108524941B (en) | Enzyme-driven bottle-shaped nano motor and preparation method thereof | |
| Yoncheva et al. | Functionalized mesoporous silica nanoparticles for oral delivery of budesonide | |
| CN108545761B (en) | Macroporous prussian blue nanoparticles and preparation method thereof | |
| AU2020101112A4 (en) | Carborane-modified mesoporous silica nanosphere (msn) and preparation method thereof | |
| Zeng et al. | Controlled architecture of hybrid polymer nanocapsules with tunable morphologies by manipulating surface-initiated ARGET ATRP from hydrothermally modified polydopamine | |
| CN112619666A (en) | Preparation method and application of central radial-diplopore nano composite material | |
| CN109453136B (en) | Antioxidant microcapsule containing fullerene and preparation method thereof | |
| CN108084451B (en) | Water-soluble fullerene nano material and preparation method and application thereof | |
| Qu et al. | A redox responsive controlled release system using mesoporous silica nanoparticles capped with Au nanoparticles | |
| CN116492289A (en) | Folic acid grafted polydopamine@thermosensitive polymer core-shell microgel, preparation method and application thereof in preparation of in-vitro drug controlled release drug | |
| Sun et al. | Bowl-shaped polydopamine nanocapsules: control of morphology via template-free synthesis | |
| Yu et al. | Interface assembly to magnetic mesoporous organosilica microspheres with tunable surface roughness as advanced catalyst carriers and adsorbents | |
| CN113332426B (en) | Preparation method of nano therapeutic agent loaded with iron monoatomic atom in silicon carrier, nano therapeutic agent obtained by preparation method and application of nano therapeutic agent | |
| CN110604817A (en) | Preparation method of transferrin-folic acid multiple modified double-targeting mesoporous silica coated gold nanorod | |
| CN111467509B (en) | Phase-change nano diagnosis and treatment agent composite material, preparation method and application thereof | |
| CN113181361A (en) | Phase-change nano composite material with bubbles promoting drug release, preparation method and application | |
| Li et al. | Preparation of superparamagnetic β-cyclodextrin-functionalized composite nanoparticles with core–shell structures | |
| CN106581688A (en) | Medicine carrier based on graphene and preparation method of same | |
| CN108478793B (en) | Stannous sulfide nano-grade photo-thermal agent and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200522 |