CN106544756B - 一种具有pH诱导与光学检测药物释放行为的上转化发光二氧化硅复合纤维的制备方法 - Google Patents
一种具有pH诱导与光学检测药物释放行为的上转化发光二氧化硅复合纤维的制备方法 Download PDFInfo
- Publication number
- CN106544756B CN106544756B CN201610893376.9A CN201610893376A CN106544756B CN 106544756 B CN106544756 B CN 106544756B CN 201610893376 A CN201610893376 A CN 201610893376A CN 106544756 B CN106544756 B CN 106544756B
- Authority
- CN
- China
- Prior art keywords
- solution
- sio
- added
- caf
- nanofiber
- 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.)
- Active
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000000835 fiber Substances 0.000 title claims abstract description 47
- 239000003814 drug Substances 0.000 title claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 36
- 229940079593 drug Drugs 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000002131 composite material Substances 0.000 title claims abstract description 19
- 230000003287 optical effect Effects 0.000 title claims abstract description 16
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 16
- 238000001514 detection method Methods 0.000 title claims abstract description 13
- 230000006698 induction Effects 0.000 title claims abstract description 10
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 39
- 239000002121 nanofiber Substances 0.000 claims abstract description 27
- 238000004020 luminiscence type Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 13
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 12
- 230000000694 effects Effects 0.000 claims abstract description 7
- 229910052681 coesite Inorganic materials 0.000 claims description 37
- 229910052906 cristobalite Inorganic materials 0.000 claims description 37
- 229910052682 stishovite Inorganic materials 0.000 claims description 37
- 229910052905 tridymite Inorganic materials 0.000 claims description 37
- 239000000243 solution Substances 0.000 claims description 32
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 238000000151 deposition Methods 0.000 claims description 9
- 230000008021 deposition Effects 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- 238000009987 spinning Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- -1 amino modified CaF2 Chemical class 0.000 claims description 7
- 238000010041 electrostatic spinning Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 239000002105 nanoparticle Substances 0.000 claims description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000003643 water by type Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 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 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- 239000005030 aluminium foil Substances 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 238000000643 oven drying Methods 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 3
- 229940038773 trisodium citrate Drugs 0.000 claims description 3
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims 2
- 230000003760 hair shine Effects 0.000 claims 2
- 230000036571 hydration Effects 0.000 claims 1
- 238000006703 hydration reaction Methods 0.000 claims 1
- 239000011259 mixed solution Substances 0.000 claims 1
- 239000002070 nanowire Substances 0.000 claims 1
- 230000000630 rising effect Effects 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 15
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 5
- 238000012377 drug delivery Methods 0.000 abstract description 4
- 238000003384 imaging method Methods 0.000 abstract description 3
- 229910052769 Ytterbium Inorganic materials 0.000 abstract description 2
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 abstract description 2
- 229920002521 macromolecule Polymers 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 abstract description 2
- 206010028980 Neoplasm Diseases 0.000 abstract 1
- 229920002125 Sokalan® Polymers 0.000 description 26
- 239000004584 polyacrylic acid Substances 0.000 description 14
- 230000008569 process Effects 0.000 description 6
- 238000011068 loading method Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000008055 phosphate buffer solution Substances 0.000 description 4
- AOJJSUZBOXZQNB-TZSSRYMLSA-N Doxorubicin Chemical compound O([C@H]1C[C@@](O)(CC=2C(O)=C3C(=O)C=4C=CC=C(C=4C(=O)C3=C(O)C=21)OC)C(=O)CO)[C@H]1C[C@H](N)[C@H](O)[C@H](C)O1 AOJJSUZBOXZQNB-TZSSRYMLSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- ZHJGWYRLJUCMRT-UHFFFAOYSA-N 5-[6-[(4-methylpiperazin-1-yl)methyl]benzimidazol-1-yl]-3-[1-[2-(trifluoromethyl)phenyl]ethoxy]thiophene-2-carboxamide Chemical compound C=1C=CC=C(C(F)(F)F)C=1C(C)OC(=C(S1)C(N)=O)C=C1N(C1=C2)C=NC1=CC=C2CN1CCN(C)CC1 ZHJGWYRLJUCMRT-UHFFFAOYSA-N 0.000 description 2
- 238000002242 deionisation method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000011664 signaling Effects 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229940009456 adriamycin Drugs 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000003005 anticarcinogenic agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
-
- 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
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K49/00—Preparations for testing in vivo
- A61K49/001—Preparation for luminescence or biological staining
- A61K49/0013—Luminescence
- A61K49/0017—Fluorescence in vivo
- A61K49/0019—Fluorescence in vivo characterised by the fluorescent group, e.g. oligomeric, polymeric or dendritic molecules
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K49/00—Preparations for testing in vivo
- A61K49/001—Preparation for luminescence or biological staining
- A61K49/0013—Luminescence
- A61K49/0017—Fluorescence in vivo
- A61K49/005—Fluorescence in vivo characterised by the carrier molecule carrying the fluorescent agent
- A61K49/0054—Macromolecular compounds, i.e. oligomers, polymers, dendrimers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/025—Other specific inorganic materials not covered by A61L27/04 - A61L27/12
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
- D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Veterinary Medicine (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Textile Engineering (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Dermatology (AREA)
- Pharmacology & Pharmacy (AREA)
- Transplantation (AREA)
- Biomedical Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Luminescent Compositions (AREA)
Abstract
本发明采用表面改性的方法制备出一种具有pH诱导与光学检测药物释放行为的上转换发光二氧化硅复合纤维。采用稀土元素镱和铒的双掺,可实现良好的上转换发光效应方法简便,可操作性强。先将上转换发光二氧化硅复合纤维表面氨基改性,再通过静电结合的方式在纤维的表面加载一层PAA高分子层,改性后的纤维具有强上转换发光性能。所得材料尺寸分布均一、具有较强上转换发光效应的PAA改性二氧化硅复合纤维。所得纳米纤维发光性能良好、产量大,可在实现不同pH环境中的可控肿瘤药物释放行为的同时,达到药物释放动力学的光学检测。该类新型复合纳米材料在药物传递、组织工程、发光器件制备以及生物组织成像等领域有广泛应用前景。
Description
技术领域
本发明属于应用型无机先进纳米材料技术领域,特别涉及一种具有pH诱导与光学检测药物释放行为的上转化发光二氧化硅复合纤维及其制备方法,可应用于药物传递、骨组织工程、发光器件制备、生物组织成像及药物示踪等领域。
背景技术
稀土元素上转换发光材料是一类重要的发光材料,稀土元素拥有丰富的能级,可以由长波段光源激发,激发出较短波段的光。且发出的光可以通过各种条件来控制。光学性能优异,因此得到了广泛关注和研究。
氟化钙的声子能量低、化学稳定性好,其独特的氟化钙结构允许掺杂一定量的稀土元素,适合作为稀土元素的基体材料。二氧化硅作为药物传递材料在生物医学领域已有较多应用,生物相容性良好。因此上转换发光的氟化钙纳米颗粒与二氧化硅的复合纤维是一个研究热点。
由于本发明结合溶胶凝胶法通过静电纺丝制备得到的CaF2:Yb,Er@SiO2纳米纤维直径均匀可控,并通过表面改性的方法得到PAA改性的CaF2:Yb,Er@SiO2纳米纤维,具有pH诱导与光学检测药物释放行为,方法更为简单,产量大,可重复性强。
发明内容
本发明所要解决的问题是提供一种发光效率和发光强度较大的PAA改性的具有pH诱导与光学检测药物释放行为的上转化发光二氧化硅复合纤维及其制备方法。
本发明的目的是通过以下技术方案实现的:一种具有pH诱导与光学检测药物释放行为的上转化发光二氧化硅复合纤维的制备方法,包括以下步骤:
(1)按照化学通式Ca1-0.18-0.02F2:0.18Yb3+,0.02Er3+中各元素的摩尔计量比,称取四水合硝酸钙、五水合硝酸铒及五水合硝酸镱,总量为4mmol,然后与8mmol的柠檬酸三钠,加入到80毫升去离子水中,混合均匀后得到溶液A。再将8mmol氟硼酸钠加入40毫升去离子水中,得到溶液B。将溶液B逐滴加入到溶液A中,并用氨水调节溶液的pH,使pH=7。将上述混合溶液搅拌30min后,放入水热反应釜中,180℃水热反应24小时。待反应釜冷却至室温后,离心清洗,得到白色沉淀物,并放于80℃烘箱中干燥,即可得到稀土掺杂氟化钙上转换发光纳米颗粒。
(2)配制生物玻璃先驱体溶液:将1.67g正硅酸四乙酯加入含有200微升乙酸和600微升水的10mL乙醇溶液中,加入0.6-1.2g分子量为1300000的PVP。搅拌均匀后,再加入3mL浓度为3mg/mL的稀土掺杂氟化钙上转换发光纳米颗粒的乙醇溶液。继续搅拌1.5h得到纺丝前驱体。
(3)将纺丝先驱体转移到注射器中,利用静电纺丝装置将纺丝先驱体以一定速度纺成纤维状,以接地的带有铝箔的平板作为接收装置,然后放入烘箱干燥12h。最后放入马弗炉中550℃烧结5h,即可得到具有上转换发光效应的氟化钙颗粒与二氧化硅纤维复合材料(即为CaF2:Yb,Er@SiO2纳米纤维)。
(4)氨基改性的CaF2:Yb,Er@SiO2纳米纤维:先将50mg CaF2:Yb,Er@SiO2纳米纤维加入到40mL的DMF,再加入0.4mL的APTES。然后在80℃搅拌反应24小时。反应产物用DMF离心清洗三次,得到白色沉淀物,并放于80℃烘箱中干燥,即可得到氨基改性的CaF2:Yb,Er@SiO2纳米纤维。
(5)PAA改性的CaF2:Yb,Er@SiO2纳米纤维:30mg上述氨基改性的CaF2:Yb,Er@SiO2纳米纤维加入到100mL的水中。再将10mL的PAA(50vol%)水溶液加入上述溶液,室温搅拌24h。最后用离心水洗三次,得到白色沉淀物,并放于37℃烘箱中干燥12h,即可得到PAA改性的CaF2:Yb,Er@SiO2纳米纤维。
进一步地,静电纺丝的流速控制在0.8mL/h,电压值范围为6-8kV
本发明的有益效果在于:本发明在制备过程中利用3-氨丙基三乙氧基硅烷在CaF2:Yb,Er@SiO2纤维表面改性氨基,然后利用氨基与聚丙烯酸的静电作用,最终得到发光性能良好且具有pH诱导与光学检测药物释放性能的聚丙烯酸改性的CaF2:Yb,Er@SiO2纳米纤维。聚丙烯酸改性的CaF2:Yb,Er@SiO2纳米纤维可以实现980nm红外光激发,发射出550-560nm波段的绿光和660-670nm波段的红光。上转换发光效率高,发光强度大,且可以调节光的强度和颜色。生物相容性好,光学信号强,在生物医学中有广泛应用前景,如用作多功能药物传递、组织工程或细胞成像等领域有重要应用。制备方法绿色无污染,可控性强,实现了聚丙烯酸改性的CaF2:Yb,Er@SiO2纳米纤维的制备,且具有pH诱导与光学检测药物释放行为。该制备方法工艺简单,产量大,易于工业化生产。
附图说明
图1为实施例制备的CaF2:Yb,Er@SiO2纤维的扫描电镜照片。可以看出纤维直径约为600nm,且尺寸分布均匀。
图2为实施例制备的氨基改性和聚丙烯酸改性前后的CaF2:Yb,Er@SiO2纤维的红外图谱,纤维改性氨基之后出现1560cm-1的吸收峰,改性PAA后表面出现C=O在1717cm-1处的吸收峰。
图3为实施例制备的氨基改性和聚丙烯酸改性前后的CaF2:Yb,Er@SiO2纤维的ZETA电位图,二氧化硅纤维本身因表面的Si-OH呈现负电性,表面改性氨基后则表现为正电,最后改性PAA后,材料呈现负电。结合红外能够确定纤维表面改性成功。
图4为实施例制备的稀聚丙烯酸改性前后的CaF2:Yb,Er@SiO2纤维的材料的上转换荧光光谱图,可以看出纤维改性前后均呈现上转换发光。
图5为实施例制备的稀聚丙烯酸改性前后的CaF2:Yb,Er@SiO2纤维的材料在不同pH条件下的药物释放曲线。由图可以看出改性后纤维具有pH敏感药物释放功能。
图6为实施例制备的稀聚丙烯酸改性前后的CaF2:Yb,Er@SiO2纤维的材料在药物释放过程中的上转换发光强度变化。(a)和(b)分别为7.4和4.7时,药物释放过程中绿光的变化曲线,(c)为7.4和4.7时药物释放过程中绿光强度与红光强度比值(I550/I660)的变化曲线,由图可看出可以用光来监测药物释放过程中的药物释放性能。药物在释放过程中的释放行为对于治疗效果有很大的影响,而光监测药物释用来调控药物的释放性能,具有重大意义。
具体实施方式
本发明制备出聚丙烯酸改性后的CaF2:Yb,Er@SiO2纤维,并对其进行药物加载,该材料具有很好的pH诱导药物释放性能以及能够用光来监测药物释放行为。图4为制备得到的聚丙烯酸改性前后的CaF2:Yb,Er@SiO2纤维的材料的上转换荧光光谱图,可以看出改性后复合材料在980nm光照射下依然有很强的上转换发光效应。采用稀土元素镱和铒的双掺,可实现良好的上转换发光效应方法简便,可操作性强。先将上转换发光二氧化硅复合纤维表面氨基改性,再通过静电结合的方式在纤维的表面加载一层PAA高分子层,改性后的纤维具有强上转换发光性能。所得材料为平均粒径600nm、尺寸分布均一、且具有较强上转换发光效应的PAA改性二氧化硅复合纤维。
下面结合附图和具体实施例来详细说明本发明的技术方案,但本发明不局限于实施例,本领域技术人员可以根据实际情况进行调整。
实施例1 PAA改性后的复合纤维在不同pH条件下的药物释放性能
(1)按照化学通式Ca1-0.18-0.02F2:0.18Yb3+,0.02Er3+中各元素的摩尔计量比,称取四水合硝酸钙、五水合硝酸铒及五水合硝酸镱,总量为4mmol,然后与8mmol的柠檬酸三钠,加入到80毫升去离子水中,混合均匀后得到溶液A。再将8mmol氟硼酸钠加入40毫升去离子水中,得到溶液B。将溶液B逐滴加入到溶液A中,并用氨水调节溶液的pH,使pH=7。将上述混合溶液搅拌30min后,放入水热反应釜中,180℃水热反应24小时。待反应釜冷却至室温后,离心清洗,得到白色沉淀物,并放于80℃烘箱中干燥,即可得到稀土掺杂氟化钙上转换发光纳米颗粒。
(2)配制生物玻璃先驱体溶液:将1.67g正硅酸四乙酯加入含有200微升乙酸和600微升水的10mL乙醇溶液中,加入0.6g分子量为1300000的PVP。搅拌均匀后,再加入3mL浓度为3mg/mL的稀土掺杂氟化钙上转换发光纳米颗粒的乙醇溶液。继续搅拌1.5h得到纺丝前驱体。
(3)将纺丝先驱体转移到注射器中,利用静电纺丝装置将纺丝先驱体以一定速度纺成纤维状,以接地的带有铝箔的平板作为接收装置,然后放入烘箱干燥12h。静电纺丝的流速控制在0.8mL/h,电压值范围为6-8kV。最后放入马弗炉中550℃烧结5h,即可得到具有上转换发光效应的氟化钙颗粒与二氧化硅纤维复合材料(即为CaF2:Yb,Er@SiO2纳米纤维)。
(4)氨基改性的CaF2:Yb,Er@SiO2纳米纤维:先将50mg CaF2:Yb,Er@SiO2纳米纤维加入到40mL的DMF,再加入0.4mL的APTES。然后在80℃搅拌反应24小时。反应产物用DMF离心清洗三次,得到白色沉淀物,并放于80℃烘箱中干燥,即可得到氨基改性的CaF2:Yb,Er@SiO2纳米纤维。
(5)PAA改性的CaF2:Yb,Er@SiO2纳米纤维:30mg上述氨基改性的CaF2:Yb,Er@SiO2纳米纤维加入到100mL的水中。再将10mL的PAA(50vol%)水溶液加入上述溶液,室温搅拌24h。最后用离心水洗三次,得到白色沉淀物,并放于37℃烘箱中干燥12h,即可得到PAA改性的CaF2:Yb,Er@SiO2纳米纤维。
取50mg的PAA改性的CaF2:Yb,Er@SiO2纳米纤维,加入20mL浓度为1mg/mL的DOX(盐酸阿霉素,一种抗癌药)水溶液中,避光搅拌24h。离心水洗三次后得到载药的纤维。将得到的药物加载后的纤维浸没在20mL的PBS(磷酸缓冲溶液)中,每隔固定时间10mL溶液,并加入10mL新的PBS(磷酸缓冲溶液)。再经过紫外测试吸光度,数据处理得到材料的不同pH条件下的释放曲线。本实施例中pH分别取7.4,5.8和4.7。图5为改性后的复合纤维在这三个不同pH条件下的药物释放曲线。由图可以看出,在释放时间为20h时,pH为7的载药纤维药物释放量约为20%,pH为5.8的载药纤维药物释放量约为50%,而pH为4.7的载药纤维药物释放量则高达约65%。由三条不同pH的释放曲线可以看出,载药纤维在低pH条件下,药物释放率更高。这是由于药物分子表面呈正电,而纤维表面负电性,两者静电结合。低pH条件下,易促使药物分子的释放。基于材料的PH敏感性可知,该材料可通过PH来诱导。本实施示例得到CaF2:Yb,Er@SiO2,并成功对此发光纤维进行聚丙烯酸表面改性。从图1中可以看出,所得纳米纤维形状规则,尺寸均一。图2和图3则从红外和ZETA电位两个方面证实本实验方法成功将聚丙烯酸改性至发光纤维表面。并且从图4中可以看出,所得聚丙烯酸改性后纳米纤维的可以发出很强的红光和绿光信号。
图6为药物释放过程中光学信号的变化情况;(a)和(b)分别为7.4和4.7时,药物释放过程中绿光的变化。可以看出,在药物释放的过程中,随着释放时间的增加,绿光波段光学信号强度逐渐增强,而红光波段光学信号强度基本不变。这是由于DOX会吸收绿光波段的光,而对红光波段的光无吸收。在药物释放的过程中,随着药物的释放,绿光强度会逐渐增加,而红光波段光强不变,因此可以用红绿光比来用检测药物的释放。
Claims (2)
1.一种具有pH诱导与光学检测药物释放行为的上转化发光二氧化硅复合纤维的制备方法,其特征在于,包括以下步骤:
(1)按照化学通式Ca1-0.18-0.02F2:0.18Yb3+,0.02Er3+中各元素的摩尔计量比,称取四水合硝酸钙、五水合硝酸铒及五水合硝酸镱,总量为4mmol,然后与8mmol的柠檬酸三钠,加入到80毫升去离子水中,混合均匀后得到溶液A;再将8mmol氟硼酸钠加入40毫升去离子水中,得到溶液B;将溶液B逐滴加入到溶液A中,并用氨水调节溶液的pH,使pH=7;将上述混合溶液搅拌30min后,放入水热反应釜中,180℃水热反应24小时;待反应釜冷却至室温后,离心清洗,得到白色沉淀物,并放于80℃烘箱中干燥,即可得到稀土掺杂氟化钙上转换发光纳米颗粒;
(2)配制生物玻璃先驱体溶液:将1.67g正硅酸四乙酯加入到含有200微升乙酸和600微升水的10mL乙醇溶液中,加入0.6-1.2g分子量为1300000的PVP;搅拌均匀后,再加入3mL浓度为3mg/mL的稀土掺杂氟化钙上转换发光纳米颗粒的乙醇溶液;继续搅拌1.5h得到纺丝前驱体;
(3)将纺丝先驱体转移到注射器中,利用静电纺丝装置将纺丝先驱体以一定速度纺成纤维状,以接地的带有铝箔的平板作为接收装置,然后放入烘箱干燥12h;最后放入马弗炉中550℃烧结5h,即可得到具有上转换发光效应的CaF2:Yb,Er@SiO2纳米纤维;
(4)氨基改性的CaF2:Yb,Er@SiO2纳米纤维的制备:先将50mg CaF2:Yb,Er@SiO2纳米纤维加入到40mL的DMF,再加入0.4mL的APTES;然后在80℃搅拌反应24小时;反应产物用DMF离心清洗三次,得到白色沉淀物,并放于80℃烘箱中干燥,即可得到氨基改性的CaF2:Yb,Er@SiO2纳米纤维;
(5)PAA改性的CaF2:Yb,Er@SiO2纳米纤维:30mg上述氨基改性的CaF2:Yb,Er@SiO2纳米纤维加入到100mL的水中;再将10mL浓度为50vol%的PAA水溶液加入上述溶液,室温搅拌24h;最后用离心水洗三次,得到白色沉淀物,并放于37℃烘箱中干燥12h,即可得到PAA改性的CaF2:Yb,Er@SiO2纳米纤维。
2.根据权利要求1所述的具有pH诱导与光学检测药物释放行为的上转化发光二氧化硅复合纤维的制备方法,其特征在于,静电纺丝的流速控制在0.8mL/h,电压值范围为6-8kV。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610893376.9A CN106544756B (zh) | 2016-10-13 | 2016-10-13 | 一种具有pH诱导与光学检测药物释放行为的上转化发光二氧化硅复合纤维的制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610893376.9A CN106544756B (zh) | 2016-10-13 | 2016-10-13 | 一种具有pH诱导与光学检测药物释放行为的上转化发光二氧化硅复合纤维的制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN106544756A CN106544756A (zh) | 2017-03-29 |
CN106544756B true CN106544756B (zh) | 2018-12-14 |
Family
ID=58368729
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610893376.9A Active CN106544756B (zh) | 2016-10-13 | 2016-10-13 | 一种具有pH诱导与光学检测药物释放行为的上转化发光二氧化硅复合纤维的制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106544756B (zh) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109106953A (zh) * | 2018-08-16 | 2019-01-01 | 浙江大学 | 一种上转换纳米材料的合成和修饰方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101785862A (zh) * | 2010-02-10 | 2010-07-28 | 吉林大学 | 基于上转换材料的红外光触发可控药物载体及其制备方法 |
CN102380102A (zh) * | 2011-11-02 | 2012-03-21 | 东华大学 | 一种环境响应性介孔硅纳米粒子的制备方法 |
CN105063806A (zh) * | 2015-07-30 | 2015-11-18 | 浙江大学 | 近红外发光钛酸钙多孔纳米纤维的制备方法 |
CN105088418A (zh) * | 2015-09-17 | 2015-11-25 | 吉林大学 | 一种尺寸可控的一维SiO2:Eu3+纤维发光材料的制备方法 |
-
2016
- 2016-10-13 CN CN201610893376.9A patent/CN106544756B/zh active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101785862A (zh) * | 2010-02-10 | 2010-07-28 | 吉林大学 | 基于上转换材料的红外光触发可控药物载体及其制备方法 |
CN102380102A (zh) * | 2011-11-02 | 2012-03-21 | 东华大学 | 一种环境响应性介孔硅纳米粒子的制备方法 |
CN105063806A (zh) * | 2015-07-30 | 2015-11-18 | 浙江大学 | 近红外发光钛酸钙多孔纳米纤维的制备方法 |
CN105088418A (zh) * | 2015-09-17 | 2015-11-25 | 吉林大学 | 一种尺寸可控的一维SiO2:Eu3+纤维发光材料的制备方法 |
Non-Patent Citations (1)
Title |
---|
"Electrospinning Preparation and Drug-Delivery Properties of an up-conversion Luminescent Porous NaYF4:Yb3+,Er3+@Silica Fiber Nanocomposite";Zhiyao Hou 等;《ADVANCED FUNCTIONAL MATERIALS》;20111231;第21卷;第2356-2365页 * |
Also Published As
Publication number | Publication date |
---|---|
CN106544756A (zh) | 2017-03-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Liu et al. | NIR‐triggered anticancer drug delivery by upconverting nanoparticles with integrated azobenzene‐modified mesoporous silica | |
Gu et al. | Upconversion composite nanoparticles for tumor hypoxia modulation and enhanced near-infrared-triggered photodynamic therapy | |
Xiao et al. | Novel multifunctional NaYF4: Er 3+, Yb 3+/PEGDA hybrid microspheres: NIR-light-activated photopolymerization and drug delivery | |
Yang et al. | A single 808 nm near-infrared light-mediated multiple imaging and photodynamic therapy based on titania coupled upconversion nanoparticles | |
Xie et al. | Luminescence enhanced Eu3+/Gd3+ co-doped hydroxyapatite nanocrystals as imaging agents in vitro and in vivo | |
Abdukayum et al. | Functional near infrared-emitting Cr3+/Pr3+ co-doped zinc gallogermanate persistent luminescent nanoparticles with superlong afterglow for in vivo targeted bioimaging | |
Chen et al. | Multifunctional mesoporous nanoellipsoids for biological bimodal imaging and magnetically targeted delivery of anticancer drugs | |
CN108192590A (zh) | 一种基于稀土上转换材料的聚偶氮苯多功能纳米粒子的制备方法 | |
CN103540310A (zh) | 用于多形貌稀土上转换发光纳米晶表面直接介孔修饰的制备方法 | |
CN102782573A (zh) | 在治疗和诊断中应用的稀土掺杂上转换纳米颗粒 | |
CN108130069A (zh) | 稀土上转换纳米诊疗剂及其制备方法 | |
CN111978556B (zh) | 一种硒化zif-67的制备方法及应用 | |
CN102942935B (zh) | 一步合成DNA功能化Zn掺杂CdTe量子点的方法 | |
Fu et al. | pH-triggered SrTiO3: Er nanofibers with optically monitored and controlled drug delivery functionality | |
Ran et al. | Rhythm Mild‐Temperature Photothermal Therapy Enhancing Immunogenic Cell Death Response in Oral Squamous Cell Carcinoma | |
CN106512000B (zh) | 一种近红外光触发释放化疗药物的纳米载体及其制备方法 | |
CN104629761A (zh) | 一种钛酸钙上转换发光纳米颗粒及其制备方法 | |
CN109498807B (zh) | 上转换纳米粒子非氧依赖性光动力学诊疗探针及制备方法 | |
CN105602566B (zh) | 一种稀土掺杂NaGdF4上转换纳米晶及其制备方法 | |
CN106544756B (zh) | 一种具有pH诱导与光学检测药物释放行为的上转化发光二氧化硅复合纤维的制备方法 | |
CN103980434A (zh) | 一种两亲性聚合物、其制备方法、复合纳米药物载体及其制备方法 | |
CN106753323A (zh) | 具有上转换发光效应的CaF2:Yb,Er@SiO2复合纤维材料的制备方法 | |
CN108728098B (zh) | 同时实现近红外光动力学治疗和荧光成像的上转换纳米粒子和石墨烯量子点复合材料及制法 | |
CN104473902B (zh) | 一种光、热调控的纳米超分子囊泡及其制备方法和应用 | |
Qu et al. | Poly (p-phenylenevinylene) functionalized fluorescent mesoporous silica nanoparticles for drug release and cell imaging |
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 |