CN109133074A - 具有荧光成像和载药双功能的介孔二氧化硅纳米材料的制备方法 - Google Patents
具有荧光成像和载药双功能的介孔二氧化硅纳米材料的制备方法 Download PDFInfo
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 46
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 31
- 239000003814 drug Substances 0.000 title claims abstract description 28
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000000799 fluorescence microscopy Methods 0.000 title claims abstract description 12
- 239000002105 nanoparticle Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 15
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 13
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 52
- 238000003756 stirring Methods 0.000 claims description 31
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 30
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 229960004756 ethanol Drugs 0.000 claims description 18
- 235000019441 ethanol Nutrition 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- CGIHPACLZJDCBQ-UHFFFAOYSA-N acibenzolar Chemical compound SC(=O)C1=CC=CC2=C1SN=N2 CGIHPACLZJDCBQ-UHFFFAOYSA-N 0.000 claims description 14
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 8
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- 230000004913 activation Effects 0.000 claims description 6
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- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 5
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 claims description 5
- 239000007832 Na2SO4 Substances 0.000 claims description 5
- 239000011541 reaction mixture Substances 0.000 claims description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 2
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 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 claims 1
- 238000004140 cleaning Methods 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 229910052814 silicon oxide Inorganic materials 0.000 abstract description 19
- 238000005576 amination reaction Methods 0.000 abstract description 9
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 abstract description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 5
- 239000007850 fluorescent dye Substances 0.000 abstract description 4
- -1 succinimide ester Chemical class 0.000 abstract description 4
- 239000004408 titanium dioxide Substances 0.000 abstract description 4
- 101100373011 Drosophila melanogaster wapl gene Proteins 0.000 abstract description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 3
- 210000004483 pasc Anatomy 0.000 abstract description 3
- 229910052710 silicon Inorganic materials 0.000 abstract description 3
- 239000010703 silicon Substances 0.000 abstract description 3
- KZNICNPSHKQLFF-UHFFFAOYSA-N dihydromaleimide Natural products O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 abstract description 2
- 229960002317 succinimide Drugs 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 210000004027 cell Anatomy 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
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- FTALBRSUTCGOEG-UHFFFAOYSA-N Riluzole Chemical compound C1=C(OC(F)(F)F)C=C2SC(N)=NC2=C1 FTALBRSUTCGOEG-UHFFFAOYSA-N 0.000 description 6
- 229960004181 riluzole Drugs 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
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- 239000002246 antineoplastic agent Substances 0.000 description 2
- 229940041181 antineoplastic drug Drugs 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
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- MURGITYSBWUQTI-UHFFFAOYSA-N fluorescin Chemical compound OC(=O)C1=CC=CC=C1C1C2=CC=C(O)C=C2OC2=CC(O)=CC=C21 MURGITYSBWUQTI-UHFFFAOYSA-N 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- NICDRCVJGXLKSF-UHFFFAOYSA-N nitric acid;trihydrochloride Chemical compound Cl.Cl.Cl.O[N+]([O-])=O NICDRCVJGXLKSF-UHFFFAOYSA-N 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 238000004113 cell culture Methods 0.000 description 1
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- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
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- 238000009792 diffusion process Methods 0.000 description 1
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- 238000010579 first pass effect Methods 0.000 description 1
- MHMNJMPURVTYEJ-UHFFFAOYSA-N fluorescein-5-isothiocyanate Chemical compound O1C(=O)C2=CC(N=C=S)=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 MHMNJMPURVTYEJ-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 210000003712 lysosome Anatomy 0.000 description 1
- 230000001868 lysosomic effect Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 229940126701 oral medication Drugs 0.000 description 1
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
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- C01B33/00—Silicon; Compounds thereof
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- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
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- A61K31/395—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins
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Abstract
本发明公开了一种具有荧光成像和载药双功能的介孔二氧化硅纳米材料的制备方法,用于解决现有荧光二氧化硅纳米材料的制备方法复杂的技术问题。技术方案是以十六烷基三甲基溴化铵为模板,以正硅酸乙酯为硅源,采用溶胶凝胶法制备得到介孔二氧化硅纳米颗粒,再以3‑氨丙基三乙氧基烷基作为氨基化修饰试剂,得到氨基化的介孔二氧化硅,接着利用氯代荧光素琥珀酰亚胺酯与氨基化的介孔二氧化硅反应得到氯代荧光素标记的介孔二氧化硅纳米颗粒。由于通过酰胺键牢固地将荧光染料链接在介孔二氧化硅上,实现了载药和荧光成像双功能。本发明操作简单,且不需要强腐蚀性试剂。
Description
技术领域
本发明涉及一种介孔二氧化硅纳米材料的制备方法,特别涉及一种具有荧光成像和载药双功能的介孔二氧化硅纳米材料的制备方法。
背景技术
介孔二氧化硅纳米颗粒(MSN)是新型的无机高分子,介孔二氧化硅纳米颗粒的优点包括:(1)具有巨大的比表面积(>900m2/g)和孔容(>0.9cm3/g),孔径可调,药物装载量大,包封率较高,且能有效避免药物扩散;(2)MSN可通过胞吞方式进入细胞,避免被溶酶体俘获;(3)良好的生物相容性;(4)通过对其表面进行官能团修饰,可实现主动靶向、药物可控、持续释放的功能。因此,已逐渐成为药物输送的载体。
恶性肿瘤已经成为威胁人类生命健康的主要疾病,治疗肿瘤的口服药物中,某些药物因为口服递送差、水溶性差和肝脏首过效应等因素限制了其应用,导致生物利用度低、受试者间差异性大、治疗窗口狭窄和副作用大。利用MSN运载抗肿瘤药物已经在一定程度上克服药物自身缺点,但是MSN不具有发光团,不能荧光成像,不便于实时监测。
常见的荧光探针包括有机染料、发光纳米颗粒、荧光蛋白等,已经被广泛研究并被应用于环境检测、有毒有害物质分析检测、生物化学检测、肿瘤成像与细胞成像等领域。
人们试图将荧光染料负载到介孔二氧化硅中,再进行修饰,实现材料的载药和荧光可视化双功能。文献“王婷婷博士论文,基于介孔二氧化硅的多功能纳米材料的制备及其在药物输送和荧光成像领域的应用,东北师范大学,2011年,30-33”报道一种可载药可发荧光的金纳米棒包裹的荧光二氧化硅纳米材料。该工艺先将荧光素异硫氰酸酯与3-氨丙基三甲氧基硅氧烷结合,再与正硅酸乙酯和金纳米棒反应,最后用王水刻蚀包裹在外层的金纳米棒,得到空心结构的可载药和可发荧光的纳米材料。实验操作过程繁琐,工艺复杂,而且用到腐蚀性极强的王水。
发明内容
为了克服现有荧光二氧化硅纳米材料的制备方法复杂的不足,本发明提供一种具有荧光成像和载药双功能的介孔二氧化硅纳米材料的制备方法。该方法以十六烷基三甲基溴化铵为模板,以正硅酸乙酯为硅源,采用溶胶凝胶法制备得到介孔二氧化硅纳米颗粒,再以3-氨丙基三乙氧基烷基作为氨基化修饰试剂,得到氨基化的介孔二氧化硅,接着利用氯代荧光素琥珀酰亚胺酯与氨基化的介孔二氧化硅反应得到氯代荧光素标记的介孔二氧化硅纳米颗粒。由于通过酰胺键牢固地将荧光染料链接在介孔二氧化硅上,实现了载药和荧光成像双功能。本发明操作简单,且不需要强腐蚀性试剂。
本发明解决其技术问题所采用的技术方案:一种具有荧光成像和载药双功能的介孔二氧化硅纳米材料的制备方法,其特点是包括以下步骤:
步骤一、将十六烷基三甲基溴化铵溶解在去离子水中,再加入1.0-2.0mol/L的氢氧化钠溶液,60-80℃下剧烈搅拌20-30min。待十六烷基三甲基溴化铵完全溶解后,缓慢加入正硅酸乙酯,继续搅拌1-2小时。静置冷却至室温,离心,依次用去离子水和乙醇洗涤3-5次。最后用含硝酸铵的乙醇溶液回流12-24小时去除模板剂,然后,用去离子水和无水乙醇依次清洗3-5次,在60-80℃真空干燥至恒重,得到介孔二氧化硅纳米粒子粉体。
步骤二、将步骤一制备的介孔二氧化硅纳米粒子粉体放入圆底烧瓶中,加入异丙醇和3-氨丙基三乙氧基烷基,60-80℃下搅拌萃取回流12-24小时,离心,依次用乙醇和去离子水清洗3-5次,在60-80℃真空干燥至恒重,得到氨基化的介孔二氧化硅纳米粒子粉体。
步骤三、在圆底烧瓶中加入三氟乙酸,分批缓慢加入N-羟基琥珀酰亚胺,室温下剧烈搅拌,加料完毕后继续搅拌6-12小时。减压蒸除溶剂,得到无色冰状固体,即为活化酯。将活化酯溶解在二氯甲烷中,加入氯代荧光素和2-6mL吡啶,搅拌2-6小时。反应混合物用稀盐酸洗3-5遍,加无水Na2SO4干燥,减压蒸出溶剂得到粉末状活化的氯代荧光素,再与氨基化的介孔二氧化硅纳米粒子粉体一起加入二氯甲烷,加入2-6mL吡啶,室温下搅拌12-24小时,减压蒸除溶剂,然后放入透析袋除去未反应的活化酯,滤出溶剂,固体物真空干燥,得到荧光标记的介孔二氧化硅纳米材料。
本发明的有益效果是:该方法以十六烷基三甲基溴化铵为模板,以正硅酸乙酯为硅源,采用溶胶凝胶法制备得到介孔二氧化硅纳米颗粒,再以3-氨丙基三乙氧基烷基作为氨基化修饰试剂,得到氨基化的介孔二氧化硅,接着利用氯代荧光素琥珀酰亚胺酯与氨基化的介孔二氧化硅反应得到氯代荧光素标记的介孔二氧化硅纳米颗粒。由于通过酰胺键牢固地将荧光染料链接在介孔二氧化硅上,实现了载药和荧光成像双功能。本发明操作简单,且不需要强腐蚀性试剂。
具体的,本发明制备的荧光标记的介孔二氧化硅纳米材料,比表面积大。比表面积为900-1200m2·g-1;粒子的孔径为2-5nm,孔容积为3-5m3·g-1,大的孔容积能够负载大量的药物,载药性能好。最大荧光发射波长在530-560nm,荧光性能好。
细胞实验证明,本发明荧光标记的介孔二氧化硅纳米材料与细胞培养生物相容性好。体外载药实验说明,本发明荧光标记的介孔二氧化硅纳米材料载药量大,释放缓慢,缓释效果好。
下面结合附图和具体实施方式对本发明作详细说明。
附图说明
图1是本发明实施例1制得荧光纳米粒子(MSN-FL)的扫描电镜图;
图2是本发明实施例1制得纳米粒子(MSN)的粒度分布图;
图3是本发明实施例1制得荧光纳米粒子(MSN-FL)的粒度分布图;
图4是本发明实施例1制得荧光纳米粒子(MSN-FL)的荧光发射图;
图5是本发明应用实施例2荧光纳米粒子(MSN-FL)的药物释放曲线;
图6是本发明应用实施例3荧光纳米粒子(MSN-FL)被MCF-7细胞摄取明场图;
图7是本发明应用实施例3荧光纳米粒子(MSN-FL)被MCF-7细胞摄取荧光成像。
具体实施方式
以下实施例参照图1-7。
实施例1:
步骤一、介孔二氧化硅纳米颗粒的制备。
称取250mg十六烷基三甲基溴化铵溶解在120mL去离子水中,再加入0.87mL的1.0mol/L的氢氧化钠溶液,60℃下剧烈搅拌20min。待十六烷基三甲基溴化铵完全溶解后,缓慢加入1.0mL正硅酸乙酯,继续搅拌1小时。反应后产物静置冷却至室温,离心,依次用去离子水和乙醇洗涤3次。最后用质量体积比为5g/L的含硝酸铵的乙醇溶液回流12小时来去除模板剂,依次用去离子水和乙醇清洗3次,在60℃真空干燥至恒重,得到介孔二氧化硅纳米粒子,代号为MSN。
步骤二、介孔二氧化硅纳米颗粒表面进行氨基化修饰。
称取100mg步骤一中合成的介孔二氧化硅纳米粒粉体放入圆底烧瓶中,加入100mL异丙醇和0.2mL的3-氨丙基三乙氧基烷基,60℃下搅拌萃取回流12小时,离心,依次用乙醇和去离子水清洗3次,在60℃真空干燥至恒重,得到氨基化的介孔二氧化硅纳米粒子,代号为MSN-NH2。
步骤三、表面氨基化的介孔二氧化硅接荧光素。
在圆底烧瓶中加入100mL三氟乙酸,分批加入30g的N-羟基琥珀酰亚胺室温下剧烈搅拌,加料完毕后继续搅拌6小时。减压蒸除溶剂,得到无色冰状固体,即活化酯。将生成的活化酯溶解在60mL的二氯甲烷中,加入氯代荧光素,2mL吡啶,搅拌2小时。反应混合物用稀盐酸洗3遍,加无水Na2SO4干燥,减压蒸出溶剂得到粉末状活化氯代荧光素,与适量的MSN-NH2一起加入100mL二氯甲烷,加入2mL吡啶,室温下搅拌12小时,减压蒸除溶剂,然后放入透析袋除去未反应的活化酯。滤掉溶剂,固体物真空干燥,得到荧光标记的介孔二氧化硅纳米材料,代号为MSN-FL。
将实施例1得到的MSN和MSN-FL进行粒度分布测试,MSN-FL进行扫描电镜测试、荧光光谱测试和细胞实验。
由图1荧光介孔二氧化硅纳米粒子(代号MSN-FL)的扫描电镜图可见,得到的纳米颗粒呈现球形,粒径比较均匀,分散性好。由图2可知MSN的粒径分布情况,经过粒径仪器测定,粒径分布在120-300nm之间。由图3可知MSN-FL的粒径分布情况,粒径分布在150-300nm之间。由图4可知,MSN-FL纳米颗粒的最大荧光发射波长为540nm,相对荧光强度最高值为820。
实施例2:
步骤一、介孔二氧化硅纳米颗粒的制备。
称取300mg十六烷基三甲基溴化铵溶解在120mL去离子水中,再加入0.98mL的1.5mol/L的氢氧化钠溶液,70℃下剧烈搅拌25min。待十六烷基三甲基溴化铵完全溶解后,缓慢加入1.5mL正硅酸乙酯,继续搅拌1.5小时。反应后产物静置冷却至室温,离心,依次用去离子水和乙醇洗涤4次。最后用质量体积比为6g/L的含硝酸铵的乙醇溶液回流18小时来去除模板剂,依次用去离子水和无水乙醇清洗4次,在70℃真空干燥至恒重,得到介孔二氧化硅纳米粒子,代号为MSN。
步骤二、介孔二氧化硅纳米颗粒表面进行氨基化修饰。
称取150mg步骤一中合成的介孔二氧化硅纳米粒粉体放入圆底烧瓶中,加入120mL异丙醇和0.4mL的3-氨丙基三乙氧基烷基,70℃下搅拌萃取回流18小时,离心,依次用乙醇和去离子水清洗4次,在70℃真空干燥至恒重,得到氨基化的介孔二氧化硅纳米粒子,代号为MSN-NH2。
步骤三、表面氨基化的介孔二氧化硅接荧光素
在圆底烧瓶中加入150mL三氟乙酸,分批加入40g的N-羟基琥珀酰亚胺室温下剧烈搅拌,加料完毕后继续搅拌10小时。减压蒸除溶剂,得到无色冰状固体,即活化酯。将生成的活化酯溶解在100mL的二氯甲烷中,加入氯代荧光素,4mL吡啶,搅拌3小时。反应混合物用稀盐酸洗4遍,加无水Na2SO4干燥,减压蒸出溶剂得到粉末状活化氯代荧光素,与适量的MSN-NH2一起加入130mL二氯甲烷,加入4mL吡啶,室温下搅拌18小时,减压蒸除溶剂,然后放入透析袋除去未反应的活化酯。滤掉溶剂,固体物真空干燥,得到荧光标记的介孔二氧化硅纳米材料,代号为MSN-FL。
经过测试,MSN-FL的粒径为80-180nm,比表面积为980m2·g-1,孔径为2-4nm,孔容积为3-4m3·g-1,最大荧光发射波长在530-540nm。
实施例3:
步骤一、介孔二氧化硅纳米颗粒的制备。
称取350mg十六烷基三甲基溴化铵溶解在200mL去离子水中,再加入1.85mL的2.0mol/L的氢氧化钠溶液,80℃下剧烈搅拌30min。待十六烷基三甲基溴化铵完全溶解后,缓慢加入3.0mL正硅酸乙酯,继续搅拌2小时。反应后产物静置冷却至室温,离心,依次用去离子水和乙醇洗涤5次。最后用质量体积比为7g/L的含硝酸铵的乙醇溶液回流24小时来去除模板剂,依次用去离子水和无水乙醇清洗5次,在80℃真空干燥至恒重,得到介孔二氧化硅纳米粒子,代号为MSN。
步骤二、介孔二氧化硅纳米颗粒表面进行氨基化修饰。
称取200mg步骤一中合成的介孔二氧化硅纳米粒粉体放入圆底烧瓶中,加入150mL异丙醇和0.6mL的3-氨丙基三乙氧基烷基,80℃下搅拌萃取回流24小时,离心,用乙醇和去离子水分别清洗5次,在80℃真空干燥至恒重,得到氨基化的介孔二氧化硅纳米粒子,代号为MSN-NH2。
步骤三、表面氨基化的介孔二氧化硅接荧光素。
在圆底烧瓶中加入180mL三氟乙酸,分批加入55g的N-羟基琥珀酰亚胺室温下剧烈搅拌,加料完毕后继续搅拌12小时。减压蒸除溶剂,得到无色冰状固体,即活化酯。将生成的活化酯溶解在150mL的二氯甲烷中,加入氯代荧光素,6mL吡啶,搅拌6小时。反应混合物用稀盐酸洗5遍,加无水Na2SO4干燥,减压蒸出溶剂得到粉末状活化氯代荧光素,与适量的MSN-NH2一起加入150mL二氯甲烷,加入6mL吡啶,室温下搅拌24小时,减压蒸除溶剂,然后放入透析袋除去未反应的活化酯。滤掉溶剂,固体物真空干燥,得到荧光标记的介孔二氧化硅纳米材料,代号为MSN-FL。
经过测试,粒径为120-200nm,比表面积为1100m2·g-1,孔径为3-5nm,孔容积为4-5m3·g-1,最大荧光发射波长在540-560nm。
为说明本发明的有益效果,给出应用实施例。
应用实施例1:荧光介孔二氧化硅负载抗肿瘤药物利鲁唑的载药实验。
取100mg荧光介孔二氧化硅与等质量的利鲁唑加入圆底烧瓶中,加入100mL乙醇溶剂,搅拌24小时,使荧光介孔二氧化硅充分吸附药物,然后用乙醇洗三遍,除去未吸附的药物,真空干燥至恒重。
应用实施例2:载利鲁唑的介孔二氧化硅的体外释放曲线。
取10mg载利鲁唑的荧光介孔二氧化硅,分散在含2mL PBS的透析袋中,然后放到含20mL PBS的离心管中,在37℃下恒温震荡进行体外释放实验。在不同时间点依次取1mL透析液,同时补充1mL的PBS。用紫外分光光度计测定透析液药物浓度。
由图5负载有利鲁唑的荧光介孔二氧化硅的药物释放曲线可见,在开始0.5小时,药物利鲁唑的释放量达到总量的25%,12小时后,释放曲线平缓,载药体系仍持续缓慢释放利鲁唑,累积释放量趋于平缓。
应用实施例3:细胞摄取荧光介孔二氧化硅实验。
取5mg制得的MSN-FL加入5mL培养液中,制MSN-FL悬液,稀释后得到不同浓度的悬浊液,分别与MCF-7细胞进行共培养。由图6可见,明场下细胞呈现圆形,呈现MCF-7细胞的正常形态。由图7可见,对应明场部分的细胞发出明亮的荧光,荧光图像呈现出细胞的轮廓,说明MSN-FL能够在细胞表面附着,在荧光显微镜下呈现明亮的荧光。
Claims (1)
1.一种具有荧光成像和载药双功能的介孔二氧化硅纳米材料的制备方法,其特征在于包括以下步骤:
步骤一、将十六烷基三甲基溴化铵溶解在去离子水中,再加入1.0-2.0mol/L的氢氧化钠溶液,60-80℃下剧烈搅拌20-30min;待十六烷基三甲基溴化铵完全溶解后,缓慢加入正硅酸乙酯,继续搅拌1-2小时;静置冷却至室温,离心,依次用去离子水和乙醇洗涤3-5次;最后用含硝酸铵的乙醇溶液回流12-24小时去除模板剂,然后,用去离子水和无水乙醇依次清洗3-5次,在60-80℃真空干燥至恒重,得到介孔二氧化硅纳米粒子粉体;
步骤二、将步骤一制备的介孔二氧化硅纳米粒子粉体放入圆底烧瓶中,加入异丙醇和3-氨丙基三乙氧基烷基,60-80℃下搅拌萃取回流12-24小时,离心,依次用乙醇和去离子水清洗3-5次,在60-80℃真空干燥至恒重,得到氨基化的介孔二氧化硅纳米粒子粉体;
步骤三、在圆底烧瓶中加入三氟乙酸,分批缓慢加入N-羟基琥珀酰亚胺,室温下剧烈搅拌,加料完毕后继续搅拌6-12小时;减压蒸除溶剂,得到无色冰状固体,即为活化酯;将活化酯溶解在二氯甲烷中,加入氯代荧光素和2-6mL吡啶,搅拌2-6小时;反应混合物用稀盐酸洗3-5遍,加无水Na2SO4干燥,减压蒸出溶剂得到粉末状活化的氯代荧光素,再与氨基化的介孔二氧化硅纳米粒子粉体一起加入二氯甲烷,加入2-6mL吡啶,室温下搅拌12-24小时,减压蒸除溶剂,然后放入透析袋除去未反应的活化酯,滤出溶剂,固体物真空干燥,得到荧光标记的介孔二氧化硅纳米材料。
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