CN108187057A - Graphene nano sustained release medicine-carried system of porous silicon cladding and its preparation method and application and support type drug and preparation - Google Patents
Graphene nano sustained release medicine-carried system of porous silicon cladding and its preparation method and application and support type drug and preparation Download PDFInfo
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- CN108187057A CN108187057A CN201810030075.2A CN201810030075A CN108187057A CN 108187057 A CN108187057 A CN 108187057A CN 201810030075 A CN201810030075 A CN 201810030075A CN 108187057 A CN108187057 A CN 108187057A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 91
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 239000003814 drug Substances 0.000 title claims abstract description 37
- 229940079593 drug Drugs 0.000 title claims abstract description 28
- 238000013268 sustained release Methods 0.000 title claims abstract description 27
- 238000005253 cladding Methods 0.000 title claims abstract description 26
- 229910021426 porous silicon Inorganic materials 0.000 title claims abstract description 26
- 239000012730 sustained-release form Substances 0.000 title claims abstract description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 39
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 12
- 239000010703 silicon Substances 0.000 claims abstract description 12
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 10
- 238000011068 loading method Methods 0.000 claims abstract description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 77
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 47
- 239000002356 single layer Substances 0.000 claims description 31
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 30
- 229910052681 coesite Inorganic materials 0.000 claims description 28
- 229910052906 cristobalite Inorganic materials 0.000 claims description 28
- 229910052682 stishovite Inorganic materials 0.000 claims description 28
- 229910052905 tridymite Inorganic materials 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 239000002159 nanocrystal Substances 0.000 claims description 16
- 238000005530 etching Methods 0.000 claims description 14
- 238000002604 ultrasonography Methods 0.000 claims description 13
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 11
- 230000002459 sustained effect Effects 0.000 claims description 10
- 238000001556 precipitation Methods 0.000 claims description 9
- 239000002994 raw material Substances 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
- 238000005336 cracking Methods 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 4
- -1 polyethylene pyrrole Polymers 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims 1
- 239000010439 graphite Substances 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000011017 operating method Methods 0.000 abstract description 2
- 238000012805 post-processing Methods 0.000 abstract description 2
- 239000006228 supernatant Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 239000006227 byproduct Substances 0.000 description 14
- 238000004064 recycling Methods 0.000 description 12
- 239000002244 precipitate Substances 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 238000012545 processing Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000003643 water by type Substances 0.000 description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 7
- NNJVILVZKWQKPM-UHFFFAOYSA-N Lidocaine Chemical compound CCN(CC)CC(=O)NC1=C(C)C=CC=C1C NNJVILVZKWQKPM-UHFFFAOYSA-N 0.000 description 7
- 239000000908 ammonium hydroxide Substances 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 7
- 229960004194 lidocaine Drugs 0.000 description 7
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product 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
- 239000000463 material Substances 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 239000013049 sediment Substances 0.000 description 4
- 210000003371 toe Anatomy 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 206010001497 Agitation Diseases 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 150000004040 pyrrolidinones Chemical class 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 208000030453 Drug-Related Side Effects and Adverse reaction Diseases 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229920003081 Povidone K 30 Polymers 0.000 description 1
- 206010070863 Toxicity to various agents Diseases 0.000 description 1
- 238000004458 analytical method Methods 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
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 230000000857 drug effect Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 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
- 238000001727 in vivo Methods 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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)
- Medicinal Preparation (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
Graphene nano sustained release medicine-carried system the present invention provides porous silicon cladding and its preparation method and application and support type drug and preparation.Preparation method operating procedure of the present invention is easy, and step is succinct, and without complicated post processing, suitable for the production silica protection type graphene oxide composite material of scale.Simultaneously, there is good drug loading performance by the graphene nano sustained release medicine-carried system of preparation method products therefrom porous silicon of the present invention cladding, it is remained simultaneously without mesoporous silicon template, it is thus possible to be further used as carrier and be used to prepare support type drug, and with good safety in utilization.
Description
Technical field
The present invention relates to Material Field, graphene nano sustained release medicine-carried system in particular to porous silicon cladding and
Preparation method and application and support type drug and preparation.
Background technology
Graphene oxide (Graphene oxide, GO) is through chemical oxidation, then obtained by ultrasound stripping by graphite powder
Graphene oxide, be by sp2A kind of novel single-layer two dimension carbon material that hydbridized carbon atoms are formed.Since its surface has
The oxygen-content actives functional groups such as a large amount of carboxyl, hydroxyl, carbonyl, epoxy group, thus with good water-soluble and biocompatibility.
Graphene oxide has become biomedical research hot spot in recent years, focus primarily on nano drug-carrying, oncotherapy,
Photothermal imaging etc..However, it is had the drawback that with certain bio-toxicity using graphene at present, due to aoxidizing stone
Black alkene in the form of sheets, thus its can to membrane structure generate destruction, so as to generate certain bio-toxicity.
In order to reduce the bio-toxicity of graphene oxide, the safety of its application is improved, researcher employs surface and repaiies
The methods of decorations or cladding compatible high material, is modified graphene oxide.And surface silicon packet is carried out to graphene oxide
It is exactly a kind of common method for coating to cover, such as the method for CTAB templates may be used in surface of graphene oxide mesoporous silicon.
However, due to as template CTAB have bio-toxicity, meanwhile, remove it is mesoporous in CTAB the step of also compared with
To be cumbersome, thus the difficulty that this method is promoted and applied is larger, it is also difficult to realize the production and preparation of scale product.
In view of this, it is special to propose the present invention.
Invention content
The first object of the present invention is to provide a kind of preparation of the graphene nano sustained release medicine-carried system of porous silicon cladding
Method, preparation method simple process of the present invention, and it is safe and efficient.
The second object of the present invention is to provide a kind of by the obtained graphene nano sustained release load of preparation method of the present invention
Medicine body system.
The third object of the present invention is to provide a kind of application of the graphene nano sustained release medicine-carried system.
In order to realize the above-mentioned purpose of the present invention, spy uses following technical scheme：
A kind of preparation method of the graphene nano sustained release medicine-carried system of porous silicon cladding, the preparation method includes as follows
Step：
(a) single-layer graphene oxide ultrasound cracks, and obtains nanocrystal monolayer graphene oxide；
(b) ultrasound after gained nanocrystal monolayer graphene oxide is mixed with polyvinylpyrrolidone, obtains nGO-PVP；
(c) under alkaline condition, by gained nGO-PVP and tetraethoxysilane hybrid reaction in organic solution, table is obtained
The nGO-PVP that face is coated with silicon oxide is denoted as nGO-PVP SiO2；
(d) gained nGO-PVP@SiO2Back flow reaction after being mixed with polyvinylpyrrolidone takes precipitation with hydrogen-oxygen after centrifugation
Change sodium etching and be sustained medicine-carried system to get the graphene nano coated to porous silicon.
Preferably, in preparation method step (a) of the present invention, be using micron order single-layer graphene oxide as raw material,
And obtain nanocrystal monolayer graphene oxide through ultrasound cracking；
It is furthermore preferred that ultrasound carries out under condition of ice bath, the ultrasonic time is 45~90min.
Preferably, in preparation method step step (b) of the present invention, nanocrystal monolayer graphene oxide and polyethylene pyrrole
The mass ratio of pyrrolidone is 1:3~3:1；
It is furthermore preferred that in step (b), the mass ratio of nanocrystal monolayer graphene oxide and polyvinylpyrrolidone is 1:1~
3:1。
Preferably, in preparation method step (c) of the present invention, 20~30 DEG C of the temperature of hybrid reaction, the time 1
~5h；
It is furthermore preferred that in step (c), 20~25 DEG C of the temperature of hybrid reaction, the time is 2~3h.
Preferably, in preparation method step (d) of the present invention, nGO-PVP@SiO2With the matter of polyvinylpyrrolidone
Amount is than being 1:3~3:1；
It is furthermore preferred that in step (d), nGO-PVP@SiO2Mass ratio with polyvinylpyrrolidone is 1:3~1:1.
Preferably, in preparation method step (d) of the present invention, sodium hydroxide used is sodium hydroxide solution, dense
Degree is preferably 3~8mol/L；
And/or the time of the etching is 5~90min；It is furthermore preferred that the time of the etching is 30~60min.
Meanwhile it is received the present invention also provides the graphene by the obtained porous silicon cladding of preparation method of the present invention
Rice sustained release medicine-carried system.
It to be born likewise, present invention provides the graphene nano sustained release medicine-carried systems that the porous silicon coats in drug
Application in load；
And/or application of the graphene nano sustained release medicine-carried system of the porous silicon cladding in carrying medicament is prepared.
Further, the present invention also provides a kind of preparation method of support type drug, in the preparation method, first
The graphene nano sustained release medicine-carried system of hole silicon cladding is obtained according to the method described in the present invention, then again coats gained hole silicon
Graphene nano sustained release medicine-carried system mixed in the solution with drug, obtain support type drug.
Meanwhile the present invention also provides the support type drugs obtained by the preparation method.
Compared with prior art, beneficial effects of the present invention are：
Preparation method operating procedure of the present invention is easy, and step is succinct, and without complicated post processing, suitable for the life of scale
Produce silica protection type graphene oxide composite material；
Meanwhile had by the graphene nano sustained release medicine-carried system of preparation method products therefrom porous silicon of the present invention cladding good
Good drug loading performance, and remained without mesoporous silicon template, it is thus possible to it is further used as carrier and is used to prepare support type medicine
Object, and with good safety in utilization.
Description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, to embodiment or will show below
There is attached drawing needed in technology description to be briefly described.
Fig. 1 is GO-PVP@SiO before NaOH etchings in the embodiment of the present invention2Electron microscope；
Fig. 2 is the porous SiO of GO-PVP of embodiment of the present invention@after NaOH etchings2Electron microscope；
Fig. 3 is the porous SiO of GO-PVP of embodiment of the present invention@2Load lidocaine drug Cumulative release profile.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person, the condition suggested according to normal condition or manufacturer carry out.Reagents or instruments used without specified manufacturer is
The conventional products that can be obtained by commercially available purchase.
In view of existing silicon cladded type graphene oxide mesoporous material preparation process complexity, and can due to template residual
The practical problems such as bio-toxicity can be generated, the graphene nano sustained release the present invention provides a kind of porous silicon cladding carries medicine body
System, it is various in the presence of the prior art to solve the problems, such as.
Specifically, the preparation method step of the graphene nano sustained release medicine-carried system of porous silicon of the present invention cladding can refer to as
Under：
(a) single-layer graphene oxide ultrasound cracks, and obtains nanocrystal monolayer graphene oxide；
Preferably, in this step, the single-layer graphene oxide as raw material is micron order single-layer graphene oxide, and pass through
By its ultrasound cracking, nano level single-layer graphene oxide is obtained；
It is first to add in raw material single-layer graphene oxide in deionized water it is furthermore preferred that in this step, wherein, individual layer
The quality grams of graphene oxide and the ratio of the volume milliliter number of deionized water are preferably controlled 0.2~0.5:100；
Then, ultrasonic cracking is carried out under conditions of ice bath, the ultrasonic time is preferably 45~90min, more preferably
It is in 60~90min by ultrasonic time control；
To get to the nano level single-layer graphene oxide nGO being scattered in deionized water after ultrasound cracking, nGO's is dense
It spends for 0.2~0.5mg/ml, and its size is in 200nm or so；
(b) gained nanocrystal monolayer graphene oxide is mixed with polyvinylpyrrolidone, it is preferred that polyvinylpyrrolidine used
Ketone is preferably PVP K30；
Likewise it is preferred that, the mass ratio of nanocrystal monolayer graphene oxide and polyvinylpyrrolidone is 1:3~3:1；More
Preferably, in step (d), the mass ratio of nanocrystal monolayer graphene oxide and polyvinylpyrrolidone is 1:3~1:1；
Ultrasound is carried out after nanocrystal monolayer graphene oxide is mixed with polyvinylpyrrolidone, the ultrasonic time is preferably
30min, and polyvinylpyrrolidone is caused to be covered in the surface of nanocrystal monolayer graphene oxide, obtain nGO-PVP；
(c) under alkaline condition, by gained nGO-PVP and tetraethoxysilane hybrid reaction in organic solution；
In this step, cause reaction system in alkalinity preferably by the method for adding in ammonium hydroxide in organic solvent；
Likewise it is preferred that, organic solvent used is ethyl alcohol；
It is further preferred that in this step, carried out by raw material of ethyl alcohol, nGO-PVP, ammonium hydroxide and tetraethoxysilane
Reaction, and pass through stober growth methods, so as in nGO-PVP coated Sis O2, to obtain SiO is coated with to surface2NGO-PVP,
That is nGO-PVP@SiO2；
As above in further preferred scheme, the volume milliliter number of ethyl alcohol, the quality milligram number of nGO-PVP, ammonium hydroxide body
The ratio between volume milliliter number of product milliliter number and tetraethoxysilane is： 50:10:5:2；
After inciting somebody to action as above four kinds of raw materials mixing, 1~5h is reacted under the conditions of 20~30 DEG C, preferably in 20~25 DEG C of items
2~3h under part；
After reaction, by product system centrifugal treating, supernatant is removed, and residue precipitation is recycled, as nGO-
PVP@SiO2；
(d) by gained nGO-PVP@SiO2It is mixed with polyvinylpyrrolidone, it is preferred that in this step, polyethylene used
Pyrrolidones is PVP k15, nGO-PVP@SiO2With the mass ratio 1 of polyvinylpyrrolidone:3~3:1, it is furthermore preferred that nGO-
PVP@SiO2Mass ratio with polyvinylpyrrolidone is 1:3~1:1；It is further preferred that nGO-PVP@SiO2With polyethylene
The mass ratio of pyrrolidones is 1:1；
Back flow reaction after the two is mixed, the temperature of back flow reaction is 90~100 DEG C, and the time control of reaction is on a 3h left sides
It is right；After reaction, by product mixed system carry out centrifugal treating, remove supernatant, by gained precipitate recycle, be then dispersed in from
In sub- water；
Then, the product being scattered in deionized water is etched with sodium hydroxide, it is preferred that be 3~8mol/L of addition
Sodium hydroxide solution performs etching, it is furthermore preferred that being that the sodium hydroxide solution of 4~5mol/L of addition performs etching；Etching when
Between preferably 5~90min, more preferably 30~60min；
Then, using filtering or centrifugal method, solid product is recycled to get the graphene nano coated to porous silicon
It is sustained medicine-carried system.
And it is then mainly that surface is coated with SiO by the obtained graphene nano sustained release medicine-carried system of as above method2Receive
Rice graphene oxide, and the further structure by covering silica for surface etches, but also drug can pass through
SiO2Hole be carried on the surface of graphene, so as to but also graphene nano of the present invention, which is sustained medicine-carried system, can play medicine
The effect of object carrier.
Meanwhile compared to mesoporous silicon graphene carrier obtained by CTAB methods for, graphene nano provided by the present invention delays
It is suitable therewith on drug effect fruit is carried to release medicine-carried system, however, since the method for the present invention operation is more convenient, and template will not be generated
Residual etc. has drug toxicity substance, thus is more suitable for promoting simultaneously large-scale production.
Further, by the way that graphene nano sustained release medicine-carried system is mixed with drug solution, it is also possible that drug energy
It is enough to load thereon, so as to form support type drug.And entering internal support type drug has good biocompatibility, no
Irritation can be generated to human body, simultaneously as graphene has good adsorptivity for the drug loaded, it is also possible that
Carrying medicament can slow release in vivo, so as to play the effect of long-acting treatment.
Embodiment 1
0.2g micron order single-layer graphene oxides are taken, are added in 100ml deionized waters, and the Ultrasonic Pulverization under condition of ice bath
In machine, and 1h is ultrasonically treated, obtains the nano graphene oxide aqueous dispersions that size is 200 rans；
According to mass ratio 1：1 ratio measures proper amount of nano graphene oxide aqueous dispersions, and is mixed with appropriate PVP k30
It closes, is ultrasonically treated 30min, obtains nGO-PVP；
Then using STOBER growth methods in nano graphene oxide surface coated Si O2, i.e., by 50ml ethyl alcohol, 10mg
GO-PVP, 5ml ammonium hydroxide and 2ml TOES the hybrid reaction 3h under the conditions of 25 DEG C；Then, it is in rotating speed by product system
Centrifugal treating 20min under 12000r/min removes supernatant, recycling precipitation, as nGO-PVP@SiO2, i.e., outer surface is with SiO2
The nGO-PVP of cladding is detected its structure using scanning electron microscope, and the results are shown in Figure 1.
Then, by GO-PVP@SiO2With PVP k15 according to mass ratio 1：1 mixes, then the back flow reaction under the conditions of 90 DEG C
3h；Then it is centrifugal treating 20min under 12000r/min by product system rotating speed, removes supernatant, recycling precipitates, and will be heavy
Shallow lake is scattered in 50ml deionized waters；
The sodium hydroxide that 5M is added in into the deionized water for be dispersed with sediment performs etching processing, and the time of processing is
60min；Then, it is centrifugal treating 20min under 12000r/min by product system rotating speed, removes supernatant, recycling precipitates, as
The graphene nano sustained release medicine-carried system of the porous silicon cladding of embodiment 1, is scanned it Electronic Speculum detection, as a result such as Fig. 2 institutes
Show.
As shown in Figure 1, the nGO-PVP@SiO not etched by sodium hydroxide2In, the graphene as reaction raw materials is by softness
Transparent membrane become laminated structure translucent, that surface is coated with fine and close silicon layer；
And as shown in Figure 2, nGO-PVP@SiO2After 60min is etched by NaOH, surface coated silicon layer is etched to more
Pore structure.
Embodiment 2
0.5g micron order single-layer graphene oxides are taken, are added in 100ml deionized waters, and the Ultrasonic Pulverization under condition of ice bath
In machine, and 45min is ultrasonically treated, obtains the nano graphene oxide aqueous dispersions that size is 200 rans；
According to mass ratio 1：2 ratio measures proper amount of nano graphene oxide aqueous dispersions, and is mixed with appropriate PVP k30
It closes, is ultrasonically treated 30min, obtains nGO-PVP；
By 100ml ethyl alcohol, 20mg GO-PVP, 10ml ammonium hydroxide and 5ml TOES under the conditions of 30 DEG C hybrid reaction 5h；So
Afterwards, it is centrifugal treating 20min under 12000r/min in rotating speed by product system, removes supernatant, recycling precipitation, as nGO-
PVP@SiO2, i.e., outer surface is with SiO2The nGO-PVP of cladding；
Then, by GO-PVP@SiO2With PVP k15 according to mass ratio 1：2 mix, then the back flow reaction under the conditions of 95 DEG C
3h；Then it is centrifugal treating 20min under 12000r/min by product system rotating speed, removes supernatant, recycling precipitates, and will precipitation
It is scattered in 50ml deionized waters；
The sodium hydroxide that 3M is added in into the deionized water for be dispersed with sediment performs etching processing, and the time of processing is
90min；Then, it is centrifugal treating 20min under 12000r/min by product system rotating speed, removes supernatant, recycling precipitates, i.e.,
The graphene nano that porous silicon for embodiment 2 coats is sustained medicine-carried system.
Embodiment 3
0.3g micron order single-layer graphene oxides are taken, are added in 100ml deionized waters, and the Ultrasonic Pulverization under condition of ice bath
In machine, and 90min is ultrasonically treated, obtains the nano graphene oxide aqueous dispersions that size is 200 rans；
According to mass ratio 1：3 ratio measures proper amount of nano graphene oxide aqueous dispersions, and is mixed with appropriate PVP k30
It closes, is ultrasonically treated 30min, obtains nGO-PVP；
By 80ml ethyl alcohol, 15mg GO-PVP, 10ml ammonium hydroxide and 3ml TOES under the conditions of 20 DEG C hybrid reaction 5h；So
Afterwards, it is centrifugal treating 20min under 12000r/min in rotating speed by product system, removes supernatant, recycling precipitation, as nGO-
PVP@SiO2, i.e., outer surface is with SiO2The nGO-PVP of cladding；
Then, by GO-PVP@SiO2With PVP k15 according to mass ratio 1：3 mix, then the back flow reaction under the conditions of 95 DEG C
3h；Then it is centrifugal treating 20min under 12000r/min by product system rotating speed, removes supernatant, recycling precipitates, and will be heavy
Shallow lake is scattered in 50ml deionized waters；
The sodium hydroxide that 8M is added in into the deionized water for be dispersed with sediment performs etching processing, and the time of processing is
30min；Then, it is centrifugal treating 20min under 12000r/min by product system rotating speed, removes supernatant, recycling precipitates, i.e.,
The graphene nano that porous silicon for embodiment 3 coats is sustained medicine-carried system.
Embodiment 4
0.4g micron order single-layer graphene oxides are taken, are added in 100ml deionized waters, and the Ultrasonic Pulverization under condition of ice bath
In machine, and 75min is ultrasonically treated, obtains the nano graphene oxide aqueous dispersions that size is 200 rans；
According to mass ratio 1：1 ratio measures proper amount of nano graphene oxide aqueous dispersions, and is mixed with appropriate PVP k30
It closes, is ultrasonically treated 30min, obtains nGO-PVP；
By 30ml ethyl alcohol, 5mg GO-PVP, 3ml ammonium hydroxide and 1ml TOES under the conditions of 25 DEG C hybrid reaction 2h；Then,
By product system, in the case where rotating speed is 12000r/min, centrifugal treating 20min, removing supernatant, recycling precipitate, as nGO-PVP@
SiO2, i.e., outer surface is with SiO2The nGO-PVP of cladding；
Then, by GO-PVP@SiO2With PVP k15 according to mass ratio 2：Then 1 mixing flows back anti-under the conditions of 100 DEG C
Answer 3h；Then it is centrifugal treating 20min under 12000r/min by product system rotating speed, removes supernatant, recycling precipitates, and will
Precipitation is scattered in 50ml deionized waters；
The sodium hydroxide that 5M is added in into the deionized water for be dispersed with sediment performs etching processing, and the time of processing is
45min；Then, it is centrifugal treating 20min under 12000r/min by product system rotating speed, removes supernatant, recycling precipitates, i.e.,
The graphene nano that porous silicon for embodiment 4 coats is sustained medicine-carried system.
Experimental example 1
The graphene nano coated using the porous silicon prepared by embodiment 1 is sustained medicine-carried system as experiment material, and carries out
Drug loading and release test, test method are as follows：
A certain amount of lidocaine of precision weighing is taken, is configured to standard solution, using ultraviolet specrophotometer, in 262nm
Place surveys peak value, draws standard curve.
1 product of precision weighing 10mg embodiments mixes it with the certain density lidocaine solutions of 2ml, magnetic agitation
24 hours, supernatant 262nm ultraviolet absorption peaks are surveyed after centrifugation.Standard curve is substituted into, obtains and carries after medicine that lidocaine is dense in supernatant
Degree, concentration difference are multiplied by volume and calculate drugloading rate；
The precipitation obtained after centrifugation is the porous SiO of nGO@2It loads lidocaine and carries medicine mixture, vacuumized 8h
Afterwards, the porous SiO of precision weighing nGO@2- lido, after being scattered in 5mlPBS buffer solutions, be added to both ends closed with clip it is saturating
It analyses in bag, then, bag filter is put into PBS 95ml buffer solutions, meet sink conditions, 37 DEG C of magnetic agitations, respectively at 0.5,
1st, 5mlPBS buffer solutions in big system are drawn within 2,4,6,8,16,24,32,48 hours and carry out UV absorption test, are supplemented simultaneously
5mlPBS buffer solutions.Using lidocaine stoste as control in another dialysis system, Cumulative release profile is drawn.Experimental result is such as
Shown in Fig. 3.
By Fig. 3 results it is found that the porous SiO of nGO@2Load lidocaine adds up release up to 62.5%, and release time is up to 48
Hour.It can be seen that the graphene nano sustained release medicine-carried system of porous silicon cladding of the present invention not only has preferable drug loading
Ability, while also be able to play the effect of medicine sustained and controlled release is put, and this also becomes a new generation with applications well prospect
Slow releasing carrier of medication material.
Although illustrate and describing the present invention with specific embodiment, it will be appreciated that without departing substantially from the present invention's
Many other change and modification can be made in the case of spirit and scope.It is, therefore, intended that in the following claims
Including belonging to all such changes and modifications in the scope of the invention.
Claims (10)
- A kind of 1. preparation method of the graphene nano sustained release medicine-carried system of porous silicon cladding, which is characterized in that the preparation side Method includes the following steps：(a) single-layer graphene oxide ultrasound cracks, and obtains nanocrystal monolayer graphene oxide；(b) ultrasound after gained nanocrystal monolayer graphene oxide is mixed with polyvinylpyrrolidone, obtains nGO-PVP；(c) under alkaline condition, by gained nGO-PVP and tetraethoxysilane hybrid reaction in organic solution, surface packet is obtained The nGO-PVP of silica is covered with, is denoted as nGO-PVP@SiO2；(d) gained nGO-PVP@SiO2Back flow reaction after being mixed with polyvinylpyrrolidone takes precipitation to be carved with sodium hydroxide after centrifugation It loses and is sustained medicine-carried system to get the graphene nano coated to porous silicon.
- 2. preparation method according to claim 1, which is characterized in that be with micron order mono-layer graphite oxide in step (a) Alkene is raw material, and obtains nanocrystal monolayer graphene oxide through ultrasound cracking；Preferably, ultrasound carries out under condition of ice bath, and the ultrasonic time is 45~90min.
- 3. preparation method according to claim 1, which is characterized in that in step (b), nanocrystal monolayer graphene oxide is with gathering The mass ratio of vinylpyrrolidone is 1:3~3:1；Preferably, in step (b), the mass ratio of nanocrystal monolayer graphene oxide and polyvinylpyrrolidone is 1:1~3:1.
- 4. preparation method according to claim 1, which is characterized in that in step (c), the temperature 20~30 of hybrid reaction DEG C, the time is 1~5h；Preferably, in step (c), 20~25 DEG C of the temperature of hybrid reaction, the time is 2~3h.
- 5. preparation method according to claim 1, which is characterized in that in step (d), nGO-PVP@SiO2With polyethylene pyrrole The mass ratio of pyrrolidone is 1:3~3:1；Preferably, in step (d), nGO-PVP@SiO2Mass ratio with polyvinylpyrrolidone is 1:3~1:1.
- 6. preparation method according to claim 1, which is characterized in that in step (d), sodium hydroxide used is sodium hydroxide Solution, concentration are preferably 3~8mol/L；And/or the time of the etching is 5~90min；Preferably, the time of the etching is 30~60min.
- 7. the graphene nano sustained release of the obtained porous silicon cladding of preparation method according to any one of claim 1-6 Medicine-carried system.
- 8. application of the graphene nano sustained release medicine-carried system of the porous silicon cladding described in claim 7 in drug loading；And/or the graphene nano of the porous silicon cladding described in claim 7 is sustained medicine-carried system in carrying medicament is prepared Using.
- 9. a kind of preparation method of support type drug, which is characterized in that in the preparation method, first, in accordance with claim 1-6 Any one of described in method obtain the graphene nano sustained release medicine-carried system of hole silicon cladding, then again by gained hole silicon cladding Graphene nano sustained release medicine-carried system mixes in the solution with drug, obtains support type drug.
- 10. the support type drug that preparation method according to claim 9 obtains.
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