CN110358114A - Preparation method of porous silicon/gold nanoparticle composite hydrogel and prepared hydrogel - Google Patents
Preparation method of porous silicon/gold nanoparticle composite hydrogel and prepared hydrogel Download PDFInfo
- Publication number
- CN110358114A CN110358114A CN201910506567.9A CN201910506567A CN110358114A CN 110358114 A CN110358114 A CN 110358114A CN 201910506567 A CN201910506567 A CN 201910506567A CN 110358114 A CN110358114 A CN 110358114A
- Authority
- CN
- China
- Prior art keywords
- porous silicon
- gold nano
- solution
- nano grain
- hydrogel
- 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.)
- Pending
Links
- 229910021426 porous silicon Inorganic materials 0.000 title claims abstract description 89
- 239000000017 hydrogel Substances 0.000 title claims abstract description 83
- 239000010931 gold Substances 0.000 title claims abstract description 68
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 59
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002105 nanoparticle Substances 0.000 title abstract description 12
- 229920001661 Chitosan Polymers 0.000 claims abstract description 38
- 239000007788 liquid Substances 0.000 claims abstract description 33
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 13
- 229910004042 HAuCl4 Inorganic materials 0.000 claims abstract description 9
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 8
- 239000005457 ice water Substances 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000002253 acid Substances 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 13
- KANLKAYGXGSUJC-UHFFFAOYSA-N 2,3-dihydroxypropyl dihydrogen phosphate;sodium Chemical compound [Na].OCC(O)COP(O)(O)=O KANLKAYGXGSUJC-UHFFFAOYSA-N 0.000 claims description 10
- AVPCPPOOQICIRJ-UHFFFAOYSA-L sodium glycerol 2-phosphate Chemical compound [Na+].[Na+].OCC(CO)OP([O-])([O-])=O AVPCPPOOQICIRJ-UHFFFAOYSA-L 0.000 claims description 8
- 230000006196 deacetylation Effects 0.000 claims description 6
- 238000003381 deacetylation reaction Methods 0.000 claims description 6
- 239000008280 blood Substances 0.000 claims description 4
- 210000004369 blood Anatomy 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- AMCPECLBZPXAPB-UHFFFAOYSA-N propane-1,2,3-triol;sodium Chemical compound [Na].OCC(O)CO AMCPECLBZPXAPB-UHFFFAOYSA-N 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 42
- 229960002901 sodium glycerophosphate Drugs 0.000 abstract description 15
- REULQIKBNNDNDX-UHFFFAOYSA-M sodium;2,3-dihydroxypropyl hydrogen phosphate Chemical compound [Na+].OCC(O)COP(O)([O-])=O REULQIKBNNDNDX-UHFFFAOYSA-M 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 10
- 239000003814 drug Substances 0.000 abstract description 8
- 238000001727 in vivo Methods 0.000 abstract description 6
- 238000003756 stirring Methods 0.000 abstract description 4
- 239000011259 mixed solution Substances 0.000 abstract description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 41
- 235000013339 cereals Nutrition 0.000 description 31
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 11
- 229910052710 silicon Inorganic materials 0.000 description 11
- 239000010703 silicon Substances 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 239000000499 gel Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 229940079593 drug Drugs 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 239000002114 nanocomposite Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229960000935 dehydrated alcohol Drugs 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 229960004756 ethanol Drugs 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 230000002787 reinforcement Effects 0.000 description 3
- 230000001225 therapeutic effect Effects 0.000 description 3
- 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 2
- 206010028980 Neoplasm Diseases 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000006065 biodegradation reaction Methods 0.000 description 2
- 239000012620 biological material Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011557 critical solution Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000012675 alcoholic extract Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 230000036760 body temperature Effects 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002512 chemotherapy Methods 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 239000002872 contrast media Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 229920006237 degradable polymer Polymers 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 210000004051 gastric juice Anatomy 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000001795 light effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 238000007911 parenteral administration Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000035479 physiological effects, processes and functions Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 108700022290 poly(gamma-glutamic acid) Proteins 0.000 description 1
- 229920002643 polyglutamic acid Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000012890 simulated body fluid Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- 238000000015 thermotherapy Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 210000004881 tumor cell Anatomy 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
- A61K41/0052—Thermotherapy; Hyperthermia; Magnetic induction; Induction heating therapy
-
- 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
- A61K47/36—Polysaccharides; Derivatives thereof, e.g. gums, starch, alginate, dextrin, hyaluronic acid, chitosan, inulin, agar or pectin
-
- 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
- A61K9/06—Ointments; Bases therefor; Other semi-solid forms, e.g. creams, sticks, gels
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P35/00—Antineoplastic agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0831—Gold
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Medicinal Chemistry (AREA)
- Public Health (AREA)
- Animal Behavior & Ethology (AREA)
- Veterinary Medicine (AREA)
- General Health & Medical Sciences (AREA)
- Pharmacology & Pharmacy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Epidemiology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Medicinal Preparation (AREA)
Abstract
The invention provides a preparation method of temperature-sensitive porous silicon/gold nanoparticle composite hydrogel, which comprises the following steps: (1) Adding chitosan into the hydrochloric acid solution, and fully stirring to obtain chitosan hydrochloric acid solution; dissolving beta-sodium glycerophosphate into water to obtain a sodium glycerophosphate solution; uniformly mixing the two solutions in an ice-water bath to obtain a semitransparent liquid which is a hydrogel precursor liquid; (2) adding the porous silicon nano-particles with the porosity of 60-70% into HAuCl4In the solution, uniformly shaking to obtain purple black liquid, carrying out solid-liquid separation to obtain a solid porous silicon/gold nanoparticle compound, and washing the compound with water for later use; (3) and (3) putting the porous silicon/gold nanoparticle composite prepared in the step (2) into the hydrogel precursor solution prepared in the step (1), and carrying out water bath on the mixed solution at the normal temperature of a human body to obtain the porous silicon/gold nanoparticle composite hydrogel. The porous silicon/gold nanoparticle composite hydrogel can realize the slow release of the medicine in vivo; has excellent biodegradability and photothermal effect.
Description
Technical field
The invention belongs to field of material technology, and in particular to a kind of porous silicon/gold nano grain composite hydrogel preparation side
Method and hydrogel obtained.
Background technique
Temperature-sensitive hydrogel is a kind of hydrogel that can crosslink induced transformation in situ after temperature change.Some polymerizations
Object can generate violent changes in solubility with the increase of environment temperature (lower critical solution temperature).This phase transition usually quilt
It is considered what balance and mixture free energy by hydrophilic on polymer chain and hydrophobic part determined.Certain interactions of molecules
The temperature dependency of (such as hydrogen bond and hydrophobic effect) can help the generation of inversion of phases.In lower critical solution temperature, polymer
And water phase interaction is more advantageous than the hydrogen bond between polymer and water, with solvation macromolecular fast dewatering and become hydrophobic
Structure, phase transition will occur.There are also some cases to be, some hydrophilic polymers can carry out self assembly in the solution, due to
Temperature increase when polymer and polymer interaction and show micella accumulation and gel-forming.
Optimal temperature-sensitive hydrogel system be it is a kind of can flow freely at ambient temperature and the liquid of injectable,
It will form gel when it is heated under body temperature environment, and drug or cell can be loaded by the way that mode is simply mixed.
And in parenteral administration, the pH of these systems close to neutrality and is can absorb.
The porous silicon of nanostructure has proved to be a kind of useful biomaterial compared with planar silicon, with existing substitution
Material, which is compared, has many advantages.Its surface area (200-800 meters squared per gram) with higher, mutually ties with pore size control ability
It closes, a series of bioactive substances, including protein, nutriment and drug can be loaded.It has good resistance in vivo
By property and non-inflammation.However, it is that it can be dropped completely in aqueous solution relative to the main advantage of other biological material
Solution is nontoxic silicic acid (Si (OH)4), silicic acid is the principal mode of silicon in human body.And most of degradable polymers, degradation are logical
The fragment of nonabsorable is commonly formed.
Most attracting characteristic first is that the biocompatibility of porous silicon to the dependence of porosity and aperture.In addition in mould
In quasi- gastric juice, highly porous silicon (porosity is more than 70%) is dissolved in all simulated body fluids.However, having medium hole
The porous silicon of gap rate (porosity is lower than 70%) has bioactivity and can slowly biodegrade.The seldom porous silicon of porosity and
The porous silicon of macroporosity is all and the comparable bio-inert material of ordinary silicon.
Gold atom has near infrared light special absorbent properties, and photo-thermal effect is significant.Chinese patent (Publication No.
CN105664183A γ-PGA the hydrogel of load Au nano particle) is disclosed, but the hydrogel without porous silicon and is suitable for
CT image-forming contrast medium.Chinese patent (Publication No. CN108342043A) discloses a kind of antibacterial thermosensitive polymer hydrogel,
The hydrogel has good biocompatibility, mechanical property and mechanical strength, responds in 37-50 DEG C of section to thermotonus
Rate is high, can be applied to biological slow-released material, fast cooling material etc., but the hydrogel is free of porous silicon and Au nano particle,
And product is external application.
There are various excellent performances and its underexploitation in field of medicaments in view of porous silicon, and urgently it is expected to develop
Hydrogel is made in porous silicon and Au nano-particles reinforcement out, it, can slow releasing medicinal in environment in vivo as pharmaceutical carrier
Object realizes that photo-thermal effect plays therapeutic effect, and ultimate biodegradation.
Summary of the invention
In order to solve the problems, such as that drug is sustained in vivo, realizes photo-thermal effect, and ultimate biodegradation, the present invention provides one
Kind temperature sensitive type porous silicon/gold nano grain composite hydrogel preparation method and temperature sensitive type porous silicon/gold nano grain of preparation
Composite hydrogel.
The preparation method of temperature sensitive type porous silicon/gold nano grain composite hydrogel of the present invention, includes the following steps:
(1) chitosan is added in hydrochloric acid solution and is sufficiently stirred, obtain chitosan salt acid solution；Sodium β-glycerophosphate is dissolved in water
Phosphoglycerol sodium solution is made；In ice-water bath, chitosan salt acid solution is uniformly mixed with phosphoglycerol sodium solution, obtains half
Transparency liquid is hydrogel precursor liquid；
(2) porous silicon nanoparticles that porosity is 60%-70% are added to HAuCl4In solution, atropurpureus liquid is obtained after shaking up
Body be separated by solid-liquid separation obtaining solid porous silicon/gold nano grain compound and stand-by after washing；
(3) porous silicon/gold nano grain compound will be made in step (2) and is put into hydrogel precursor liquid obtained in step (1)
In, then mixed liquor is carried out to the water-bath of blood heat, obtain porous silicon/gold nano grain composite hydrogel.
Further, in the step (1), the deacetylation of the chitosan is 95%, mixing time 12-14h.
Further, in the step (1), the mass ratio of the HCl in chitosan and hydrochloric acid solution is 4-8:1-1.2, salt
Acid solutions are 0.05-0.15mol/L, and the mass percent concentration of sodium β-glycerophosphate solution is 30-42%, chitosan salt
Acid solution and sodium glycero-phosphate liquor capacity ratio are 6-12:1.
Further, in the step (2), porous silicon nanoparticles and HAuCl4Mass ratio be 2-1:1-2, HAuCl4
The concentration of solution is 0.5mg/ml-1.5mg/ml, HAuCl4The temperature of solution is 50-70 DEG C, and washing times are 3 times.
Further, in the step (2), separation of solid and liquid is carried out using centrifuge, revolving speed 13000r/min.
Further, in the step (3), porous silicon/gold nano grain compound and hydrogel precursor liquid mass body
Product is than being 1-3:1.
Further, in the step (3), the time of water-bath is 15-25min.Carry out the water-bath of blood heat
The reason is that needing the medicament-carried investment of temperature sensitive type porous silicon/gold nano grain composite hydrogel in vivo in blood heat
Lower performance therapeutic effect.
The present invention provides a kind of temperature sensitive type porous silicon/gold nano grain composite hydrogel, uses the preparation method system
?.
The utility model has the advantages that the present invention is by the way that porosity for the porous silicon and Au nano-particles reinforcement of 60%-70% and to be prepared into
Hydrogel so that the hydrogel has loose three-dimensional net structure, and has a large amount of perforated holes, and can be medicament-carried
And realize the sustained release of drug in vivo；Since porous silicon has excellent biological degradability, so that the hydrogel finally can be in body
Interior degradation；Due to the photo-thermal effect of Au nano particle, so that the hydrogel shows excellent heating after near infrared light
Effect, to be conducive to treating cancer etc..
Detailed description of the invention
Fig. 1 is CS-GP(chitosan sodium glycero-phosphate) precursor liquid and CS-GP/PSiNPs/Au(chitosan of the invention/sweet
Oleophosphoric acid sodium/porous silicon/gold) hydrogel infrared spectrogram；
Fig. 2 is environmental scanning electronic microscope (ESEM) photo of CS-GP hydrogel；
Fig. 3 is environmental scanning electronic microscope (ESEM) photo of CS-GP/PSiNPs/Au hydrogel of the invention；
Fig. 4 is CS-GP/PSiNPs/Au hydrogel biodegrade relational graph of the invention；
Fig. 5 is hydrogel photo-thermal heating curve figure.
Specific embodiment
Technical solution of the present invention is described in detail below by embodiment, but protection scope of the present invention is not limited to
In the embodiment.
Porous silicon used in following embodiment is made by following steps:
1. the pretreatment of silicon wafer
Monocrystalline silicon piece is cut into the square of 2 × 2cm, is put into 98% concentrated sulfuric acid and dioxygen water volume ratio as the mixed solution of 3:1
In, 10min is impregnated under the conditions of 80 DEG C, removes the organic pollutant of silicon chip surface.Processed silicon wafer deionized water is anti-
It is multiple to rinse, it is then stored in spare in deionized water.
2. the preparation of porous silicon
Pretreated silicon wafer is fitted into electrolysis unit and fixation is appropriate.A certain amount of dehydrated alcohol is added and has checked whether leakage
Phenomenon continues electrolysis work in next step after ethyl alcohol is sucked out if leaking out without ethyl alcohol.If ethyl alcohol has leaked rapidly, dress is retightened
It sets.
After ready, a certain amount of 20% hydrofluoric acid solution is first added into device and impregnates 1min except oxide layer, after processing
Suck solution.Then the electrolyte prepared with 40% hydrofluoric acid and dehydrated alcohol 3:1 is added.It is padded in previous one in silicon wafer bottom
Enter an aluminium flake, then serves as anode, and serve as cathode with platinum electrode.With electric current of voltage regulation electricity under conditions of 20V, 100mA
Solve 15min.
After the completion of electrolysis, electrolyte is sucked out, and silicon wafer is washed 3 times with dehydrated alcohol.It, will with spoon after standing and drying
The porous silicon on surface, which scrapes, to be fitted into centrifuge tube for use, which is the porous silicon nanoparticles that porosity is 60%-70%
(PSiNPs)。
Embodiment 1
Step 1: taking chitosan 2g (deacetylation >=95%, the limited public affairs of Shanghai Aladdin biochemical technology share of 95% deacetylation
Department), it is added in the 0.1mol/L hydrochloric acid solution of 100ml and stirs 12h, obtain clear 2% chitosan salt acid solution；Take 0.6g
Sodium β-glycerophosphate is dissolved in water, and 37.5% phosphoglycerol sodium solution is made.In ice-water bath, by chitosan salt acid solution 0.9mL
It is mixed evenly with phosphoglycerol sodium solution 0.1mL, obtaining translucent liquid is hydrogel precursor liquid.
Step 2: the HAuCl for being 0.5mg/ml by the concentration that 1.0mg porous silicon nanoparticles are added 1mL60 DEG C4Solution
In, atropurpureus liquid is obtained after shaking up, using centrifuge, (Eppendorf Centrifuge-5418 Germany Ai Bende share is public
Department) it is centrifuged with revolving speed 13000r/min, it obtains solid porous silicon/gold nano grain compound and washes 3 times for use.
Step 3: porous silicon/gold nano grain compound, which is made, in step 2 is put into hydrogel forerunner made from step 1
In liquid, then mixed liquor is put into the thermostat water bath that temperature is 37 DEG C and stands 20min, it is multiple to obtain porous silicon/gold nano grain
Heshui gel 1(CS-GP/PSiNPs/Au).
Embodiment 2
Step 1: taking the chitosan 1.0g of 95% deacetylation, it is added in the 0.05mol/L hydrochloric acid solution of 100ml and stirs 12h, obtain
To clear 1% chitosan salt acid solution；It takes 0.5g sodium β-glycerophosphate to be dissolved in water, 30% phosphoglycerol sodium solution is made.?
In ice-water bath, 0.6mL chitosan salt acid solution and 0.1mL phosphoglycerol sodium solution are mixed evenly, translucent liquid is obtained
Body is hydrogel precursor liquid.
Step 2: 0.5mg porous silicon nanoparticles to be added to the HAuCl of 0.5mL50 DEG C of 1.0mg/ml4In solution, shake
Atropurpureus liquid is obtained after even, using centrifuge (Eppendorf AG, Eppendorf Centrifuge-5418 Germany) to turn
Fast 13000r/min is centrifuged, and obtains solid porous silicon/gold nano grain compound and washes 3 times for use.
Step 3: porous silicon/gold nano grain compound, which is made, in step 2 is put into hydrogel forerunner made from step 1
In liquid, then mixed liquor is put into the thermostat water bath that temperature is 37 DEG C and stands 15min, it is multiple to obtain porous silicon/gold nano grain
Heshui gel 2.
Embodiment 3
Step 1: taking the chitosan 3.0g of 95% deacetylation, it is added in the 0.15mol/L hydrochloric acid solution of 100ml and stirs 12h, obtain
To clear 3% chitosan salt acid solution；It takes 0.7g sodium β-glycerophosphate to be dissolved in water, 42% phosphoglycerol sodium solution is made.?
In ice-water bath, 1.2mL chitosan salt acid solution and 0.1mL phosphoglycerol sodium solution are mixed evenly, translucent liquid is obtained
Body is hydrogel precursor liquid.
Step 2: 1.5mg porous silicon nanoparticles to be added to the HAuCl of 1.5mL70 DEG C of 1.5mg/ml4In solution, shake
Atropurpureus liquid is obtained after even, using centrifuge (Eppendorf AG, Eppendorf Centrifuge-5418 Germany) to turn
Fast 13000r/min is centrifuged, and obtains solid porous silicon/gold nano grain compound and washes 3 times for use.
Step 3: porous silicon/gold nano grain compound, which is made, in step 2 is put into hydrogel forerunner made from step 1
In liquid, then mixed liquor is put into the thermostat water bath that temperature is 37 DEG C and stands 25min, it is multiple to obtain porous silicon/gold nano grain
Heshui gel 3.
Hereinafter, being tested for the property to porous silicon/gold nano grain composite hydrogel 1 obtained in embodiment 1.
Infrared and electron microscope analysis
Using ultraviolet/visible/near infrared spectrophotometer (Lambda950, Perkinelmer Inc., Britain), to porous silicon/gold
Porous silicon/gold nano grain composite hydrogel 1 after hydrogel precursor liquid and formation before the formation of nano-particles reinforcement hydrogel 1
Infrared spectrum analysis is carried out, as a result as shown in Figure 1.After forming gel, it is located at 3426cm originally-1Neighbouring amino and hydroxyl
Red shift has occurred in the stretching vibration absworption peak of N-H and O-H overlap peak, becomes 3275cm-1, this shows have between amino and phosphate radical
Interaction, forms coordinate bond.Due to the formation of coordinate bond, the electron cloud of N electronics is migrated in amino, leads to N-H
Weaken so that the energy of stretching vibration and bending vibration reduce, therefore the absorption peak of N-H with sodium β-glycerophosphate addition to
Low frequency direction is mobile.Meanwhile 2935cm-1The C-H stretching vibration absworption peak and another 1388cm at place-1Place=CH2Absorption peak
It disappears, 1089cm-1The absorption peak of the alcoholic extract hydroxyl group at place becomes more sharp, illustrates that the gel is formed by physical crosslinking mode
Plural gel.
In addition, by chitosan/sodium glycero-phosphate and porous silicon/gold nano grain composite hydrogel 1(chitosan/glycerol phosphorus
Sour sodium/porous silicon/gold nano composite hydrogel) freeze-drying after with environmental scanning electron microscope (LS55 Quanta200, beauty
EFI company, state) carry out its microcosmic pattern, as shown in Figure 2,3.Fig. 2 be CS-GP(chitosan/sodium glycero-phosphate) hydrogel ESEM
Photo, Fig. 3 are chitosan/sodium glycero-phosphate/porous silicon/gold nano composite hydrogel ESEM photo, be can see from Fig. 2,3
Three-dimensional network structure is presented in two kinds of hydrogels, and has perforative hole.With CS-GP(chitosan/sodium glycero-phosphate) water
Gel is compared, and chitosan/sodium glycero-phosphate/porous silicon/gold nano composite hydrogel structure is more loose, and hole is more, this
Sample is conducive to drug package and release.
Biological degradability
By porous silicon/gold nano grain composite hydrogel 1(chitosan/sodium glycero-phosphate/porous silicon/gold nano composite hydrogel)
It is immersed in 1mlPBS buffer, keeps the temperature 37 DEG C.Section takes supernatant in different times, with molybdenum blue colorimetric method analytical solution with
As a result the element silicon reaction degraded in supernatant, porous silicon are shown in Fig. 4 as control.Fig. 4 indicates porous silicon/gold nano
The figure of Particles dispersed hydrogel (CS-GP/PSiNPs/Au) biodegrade relationship；Fig. 4 (a) is porous silicon and porous silicon/gold nano
The figure of Particles dispersed hydrogel normalization UV absorption intensity；Fig. 4 (b) is porous silicon and porous silicon/gold nano grain Compound Water
The photo that gel degrades over time；Fig. 4 (c) is the figure of porous silicon/gold nano grain composite hydrogel weight loss；Fig. 4 (d)
For porous silicon/gold nano grain composite hydrogel degradation front and back photo.In 4(a), 4(b) in, be not dispersed in chitosan/glycerol
Degradation in porous silicon first day in sodium phosphate hydrogel rapidly, degrades 95% in two days.And it is dispersed in chitosan/sodium glycero-phosphate
Porous silicon in hydrogel is due to the protection of chitosan/sodium glycero-phosphate hydrogel, and degradation rate is slower than porous silicon, but in physiology
It is still degradable under environment.Over time, chitosan/sodium glycero-phosphate hydrogel gradually disintegrates, and disperses in hydrogel
Porous silicon is slowly degraded.Chitosan/sodium glycero-phosphate/porous silicon/Jenner after it can be seen that 28 days in Fig. 4 (c) and Fig. 4 (d)
Rice composite hydrogel weight loss reaches 83%.This biodegradable characteristics make it in drug release, internal chemotherapy, photo-thermal
The fields such as treatment more have application prospect.
Photo-thermal effect
1ml porous silicon/gold nano grain composite hydrogel 1(chitosan/sodium glycero-phosphate/porous silicon/gold nano grain is compound
Hydrogel) be placed in the plastic centrifuge tube that volume is 1.5ml, be irradiated using 1.6W near-infrared laser, and with it is infrared it is hot at
As instrument (TiS40, Fiuke Co., Ltd, the U.S.) monitoring temperature variations, as a result as shown in Figure 5.
Fig. 5 is the photo-thermal heating curve figure of hydrogel.By Fig. 5 it can be found that simple CS-GP aquogel system is without photo-thermal
Characteristic, and after addition porous silicon obtains CS-GP/PSiNPs hydrogel, temperature is slowly increased to 25 DEG C or so from room temperature, rises
Warm Δ T, which is about 8 DEG C, can produce photo-thermal effect, but ineffective.And it is porous when being added in simple CS-GP aquogel system
After silicon/gold nano grain obtains CS-GP/PSiNPs/Au composite hydrogel, then there is the change of matter in photo-thermal effect, close
20 DEG C or more are increased under the irradiation of infrared laser in 5min, is increased steadily until 48 DEG C backward.Since tumour cell is at 42 DEG C
Left and right can both be killed, thus this material has certain development prospect in therapeutic field of tumor.It can be seen from the above, porous silicon material
Material possesses good photo-thermal effect, and future can be used as a kind for the treatment of means of thermotherapy.And since gold atom is near infrared light
Special absorbent properties, after being compounded with gold nano grain, the photo-thermal effect of material becomes highly significant.
As described above, must not be explained although the present invention has been indicated and described referring to specific preferred embodiment
For the limitation to invention itself.It without prejudice to the spirit and scope of the invention as defined in the appended claims, can be right
Various changes can be made in the form and details for it.
Claims (8)
1. a kind of preparation method of temperature sensitive type porous silicon/gold nano grain composite hydrogel, which is characterized in that including walking as follows
It is rapid:
(1) chitosan is added in hydrochloric acid solution and is sufficiently stirred, obtain chitosan salt acid solution；Sodium β-glycerophosphate is dissolved in water
Phosphoglycerol sodium solution is made；In ice-water bath, chitosan salt acid solution is uniformly mixed with phosphoglycerol sodium solution, obtains half
Transparency liquid is hydrogel precursor liquid；
(2) porous silicon nanoparticles that porosity is 60%-70% are added to HAuCl4In solution, atropurpureus liquid is obtained after shaking up,
Be separated by solid-liquid separation obtaining solid porous silicon/gold nano grain compound and stand-by after washing；
(3) porous silicon/gold nano grain compound will be made in step (2) and is put into hydrogel precursor liquid obtained in step (1)
In, then mixed liquor is carried out to the water-bath of blood heat, obtain porous silicon/gold nano grain composite hydrogel.
2. the preparation method of temperature sensitive type porous silicon/gold nano grain composite hydrogel according to claim 1, feature exist
In in the step (1), the deacetylation of the chitosan is 95%, mixing time 12-14h.
3. the preparation method of temperature sensitive type porous silicon/gold nano grain composite hydrogel according to claim 1, feature exist
In in the step (1), the mass ratio of the HCl in chitosan and hydrochloric acid solution is 4-8:1-1.2, and concentration of hydrochloric acid solution is
0.05-0.15mol/L, the mass percent concentration of sodium β-glycerophosphate solution are 30-42%, chitosan salt acid solution and glycerol
Sodium radio-phosphate,P-32 solution volume ratio is 6-12:1.
4. the preparation method of temperature sensitive type porous silicon/gold nano grain composite hydrogel according to claim 1, feature exist
In, in the step (2), porous silicon nanoparticles and HAuCl4Mass ratio be 2-1:1-2, HAuCl4The concentration of solution is
0.5mg/ml-1.5mg/ml, HAuCl4The temperature of solution is 50-70 DEG C, and washing times are 3 times.
5. the preparation method of temperature sensitive type porous silicon/gold nano grain composite hydrogel according to claim 1, feature exist
In in the step (2), separation of solid and liquid is carried out using centrifuge, revolving speed 13000r/min.
6. the preparation method of temperature sensitive type porous silicon/gold nano grain composite hydrogel according to claim 1, feature exist
In in the step (3), the mass volume ratio of porous silicon/gold nano grain compound and hydrogel precursor liquid is 1-3:1.
7. the preparation method of temperature sensitive type porous silicon/gold nano grain composite hydrogel according to claim 1, feature exist
In in the step (3), the time of water-bath is 15-25min.
8. a kind of temperature sensitive type porous silicon/gold nano grain composite hydrogel, which is characterized in that using any in claim 1 to 7
Preparation method described in is made.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910506567.9A CN110358114A (en) | 2019-06-12 | 2019-06-12 | Preparation method of porous silicon/gold nanoparticle composite hydrogel and prepared hydrogel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910506567.9A CN110358114A (en) | 2019-06-12 | 2019-06-12 | Preparation method of porous silicon/gold nanoparticle composite hydrogel and prepared hydrogel |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110358114A true CN110358114A (en) | 2019-10-22 |
Family
ID=68216025
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910506567.9A Pending CN110358114A (en) | 2019-06-12 | 2019-06-12 | Preparation method of porous silicon/gold nanoparticle composite hydrogel and prepared hydrogel |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110358114A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114870412A (en) * | 2022-04-02 | 2022-08-09 | 深圳大学 | Solar evaporator and preparation method and application thereof |
| CN116854939A (en) * | 2023-06-02 | 2023-10-10 | 宁波大学 | Nisin nanoparticle-loaded hydrogel and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110286925A1 (en) * | 2010-05-20 | 2011-11-24 | Sophie Lerouge | Embolizing Sclerosing Hydrogel |
| CN106492220A (en) * | 2016-11-01 | 2017-03-15 | 东华大学 | There is the preparation method of the mesoporous nano silicon composite aquogel of control-release function |
| CN107583049A (en) * | 2017-10-30 | 2018-01-16 | 江南大学 | A kind of preparation method of the syringeability hydrogel with light thermal property |
| CN109260472A (en) * | 2018-09-28 | 2019-01-25 | 上海理工大学 | Multi-functional temperature sensitive aquagel of one kind and its preparation method and application |
-
2019
- 2019-06-12 CN CN201910506567.9A patent/CN110358114A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110286925A1 (en) * | 2010-05-20 | 2011-11-24 | Sophie Lerouge | Embolizing Sclerosing Hydrogel |
| CN106492220A (en) * | 2016-11-01 | 2017-03-15 | 东华大学 | There is the preparation method of the mesoporous nano silicon composite aquogel of control-release function |
| CN107583049A (en) * | 2017-10-30 | 2018-01-16 | 江南大学 | A kind of preparation method of the syringeability hydrogel with light thermal property |
| CN109260472A (en) * | 2018-09-28 | 2019-01-25 | 上海理工大学 | Multi-functional temperature sensitive aquagel of one kind and its preparation method and application |
Non-Patent Citations (3)
| Title |
|---|
| BING XIA等: ""Multifunctional Chitosan/Porous Silicon@Au Nanocomposite Hydrogels for Long-Term and Repeatedly Localized Combinatorial Therapy of Cancer via a Single Injection"", 《ACS BIOMATER. SCI. ENG.》 * |
| 彭飞等: ""一种新颖的硅量子点-金复合纳米粒子的制备和表征"", 《纳米加工工艺》 * |
| 郭萍等: ""多孔硅颗粒在微波加热诱导下荧光增强效果研究"", 《硅酸盐通报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114870412A (en) * | 2022-04-02 | 2022-08-09 | 深圳大学 | Solar evaporator and preparation method and application thereof |
| CN114870412B (en) * | 2022-04-02 | 2024-04-30 | 深圳大学 | Solar evaporator and preparation method and application thereof |
| CN116854939A (en) * | 2023-06-02 | 2023-10-10 | 宁波大学 | Nisin nanoparticle-loaded hydrogel and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Jalani et al. | Seeing, targeting and delivering with upconverting nanoparticles | |
| Yang et al. | A single 808 nm near-infrared light-mediated multiple imaging and photodynamic therapy based on titania coupled upconversion nanoparticles | |
| Zhu et al. | Responsive fluorescent Bi2O3@ PVA hybrid nanogels for temperature-sensing, dual-modal imaging, and drug delivery | |
| Sounderya et al. | Use of core/shell structured nanoparticles for biomedical applications | |
| Sui et al. | Nanocomposite hydrogels based on carbon dots and polymers | |
| Hou et al. | Electrospun upconversion composite fibers as dual drugs delivery system with individual release properties | |
| CN104592702B (en) | Organic matter capable of self-healing/inorganic nano particle hybridization material and preparation method thereof | |
| CN105271174B (en) | Super carbon nano dot with strong near infrared absorption and preparation method and application | |
| CN104911819B (en) | A kind of preparation method of supported noble metal nanometer rods temperature stimuli-responsive nano fibrous membrane | |
| CN110358114A (en) | Preparation method of porous silicon/gold nanoparticle composite hydrogel and prepared hydrogel | |
| CN107865822A (en) | A kind of preparation method and application for the pharmaceutical hydrogel slow releasing carrier material for mixing mesoporous nano silicon dioxide | |
| CN107456439B (en) | Injectable hybrid hydrogel with near-infrared light response property and preparation method and application thereof | |
| ITRM20120169A1 (en) | RELEASE DEVICE FOR CHEMICAL SPECIES WITH OPTICAL CONTROL | |
| CN107583049A (en) | A kind of preparation method of the syringeability hydrogel with light thermal property | |
| Gulino et al. | An innovative route to prepare in situ graded crosslinked PVA graphene electrospun mats for drug release | |
| CN104800845A (en) | Preparation method of hepatoma carcinoma cell targeted molybdenum disulfide drug-loaded nano tablets | |
| CN106729770A (en) | A kind of nano material and preparation method thereof for tumor imaging and treatment | |
| CN107308462A (en) | A kind of environment-friendly preparation method thereof of sea urchin shape nanogold and its application in tumor imaging and treatment | |
| Özkan et al. | Nanocarriers used most in drug delivery and drug release: nanohydrogel, chitosan, graphene, and solid lipid | |
| CN104436193A (en) | Preparation method of folic acid coupled gold nano-rod/polypyrrole/ferroferric oxide multifunctional composite nano diagnosis and treatment agent | |
| CN106916266A (en) | A kind of preparation and its application of quadruple responsive nano compound | |
| Yoon et al. | Multifunctional nanomaterial-alginate drug delivery and imaging system for cancer therapy | |
| CN110542671B (en) | Organic two-photon fluorescent probe, preparation and application thereof | |
| CN103540311A (en) | Synthetic method of cysteine modified rare earth up-conversion luminescent nanocrystallines | |
| CN104069087B (en) | Microcapsule for microwave tumor sensitization treatment and preparation method and application 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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20191022 |
|
| RJ01 | Rejection of invention patent application after publication |