氧化硅纳米颗粒的形貌和孔结构的调控及其对药物输运性能影响
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摘要
以阳离子表面活性剂十六烷基三甲基溴化铵(CTAB)和两亲性嵌段共聚物聚苯乙烯-b-聚丙烯酸(PS-b-PAA)为双模板剂,以正硅酸乙酯(TEOS)为硅源,通过精确调控模板剂与硅源之间的界面自组装行为,制备了3种多级孔氧化硅纳米颗粒,包括核壳型双介孔氧化硅纳米颗粒(CS-DMSNs)、嵌入型双介孔氧化硅纳米颗粒(E-DMSNs)及空心型介孔氧化硅纳米颗粒(H-MSNs)。利用透射和扫描电镜、氮气吸附-脱附等表征方法对多级孔氧化硅纳米颗粒形貌和孔结构进行分析,探讨其作为药物输运载体时的形貌和孔结构对载药量、释放性能及细胞存活率的影响规律。
Mesoporous silica nanoparticles have been widely used in biomedicine due to their high surface area,large pore volume and good biocompatibility. However, the precise control of the silica-based particle`s morphology and pore structure is still a great challenge. In this study, by employing cationic surfactant cetyl trimethyl ammonium bromide(CTAB) and amphiphilic block copolymer polystyrene-b-poly(acrylic acid)(PS-b-PAA) as the organic templates, tetraethoxysilane(TEOS) as the silicon source, three kinds of hierarchical porous silica nanoparticles with different morphologies, including core-shell structured dual-mesoporous silica nanospheres(CS-DMSNs), embedded dual-mesoporous silica nanospheres(E-DMSNs) and hollow mesoporous silica nanospheres(H-MSNs), were prepared by precisely controlling the interfacial self-assembly behaviors between the organic templates and the silicon source.The morphologies and pore structures of these samples were characterized by transmission electron microscopy(TEM),field-emission scanning electron microscopy(FE-SEM), N2 absorption-desorption and so on. Results show that both CS-DMSNs and H-MSNs have silica shells distributed with small pores of 1.5 nm, while E-DMSNs have interconnected large mesopores of 11.7 nm and small pores of 1.5 nm in the silica framework. Moreover, the drug loading and delivery performance of these three kinds of hierarchical porous silica nanoparticles was investigated systematically. Especially, as a drug delivery carrier, the effects of particle morphology/pore structure on the loading amounts, release behaviors and in vitro cell viabilities were evaluated. Results indicate that all these three hierarchical porous silica nanoparticles have high drug loading amount and pH-responsive drug releasing behavior. Specifically,compared to the CS-DMSNs and H-MSNs, E-DMSNs display the optimal drug delivery capability in drug loading and cytotoxicity due to their exposed large-mesopore structure and embedded small pores in the silica framework. This study will provide new ideas and methods for the construction of a new type of porous silica nanoparticles for efficient and safe treatment of tumors.
Mesoporous silica nanoparticles have been widely used in biomedicine due to their high surface area,large pore volume and good biocompatibility. However, the precise control of the silica-based particle`s morphology and pore structure is still a great challenge. In this study, by employing cationic surfactant cetyl trimethyl ammonium bromide(CTAB) and amphiphilic block copolymer polystyrene-b-poly(acrylic acid)(PS-b-PAA) as the organic templates, tetraethoxysilane(TEOS) as the silicon source, three kinds of hierarchical porous silica nanoparticles with different morphologies, including core-shell structured dual-mesoporous silica nanospheres(CS-DMSNs), embedded dual-mesoporous silica nanospheres(E-DMSNs) and hollow mesoporous silica nanospheres(H-MSNs), were prepared by precisely controlling the interfacial self-assembly behaviors between the organic templates and the silicon source.The morphologies and pore structures of these samples were characterized by transmission electron microscopy(TEM),field-emission scanning electron microscopy(FE-SEM), N2 absorption-desorption and so on. Results show that both CS-DMSNs and H-MSNs have silica shells distributed with small pores of 1.5 nm, while E-DMSNs have interconnected large mesopores of 11.7 nm and small pores of 1.5 nm in the silica framework. Moreover, the drug loading and delivery performance of these three kinds of hierarchical porous silica nanoparticles was investigated systematically. Especially, as a drug delivery carrier, the effects of particle morphology/pore structure on the loading amounts, release behaviors and in vitro cell viabilities were evaluated. Results indicate that all these three hierarchical porous silica nanoparticles have high drug loading amount and pH-responsive drug releasing behavior. Specifically,compared to the CS-DMSNs and H-MSNs, E-DMSNs display the optimal drug delivery capability in drug loading and cytotoxicity due to their exposed large-mesopore structure and embedded small pores in the silica framework. This study will provide new ideas and methods for the construction of a new type of porous silica nanoparticles for efficient and safe treatment of tumors.
引文
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[15]SINGH R K,KIM T H,MAHAPATRA C,et al.Preparation of self-activated fluorescence mesoporous silica hollow nanoellipsoids for theranostics[J].Langmuir,2015,31(1):11344-11352.
[16]KWON S,SINGH R K,KIM T H,et al.Luminescent mesoporous nanoreservoirs for the effective loading and intracellular delivery of therapeutic drugs[J].Acta Biomaterialia,2014,10(3):1431-1442.
[2]JIN C Z, WANG Y J, WEI H W, et al. Magnetic iron oxide nanoparticles coated by hierarchically structured silica:A highly stable nanocomposite system and ideal catalyst support[J]. Journal of Materials Chemistry A, 2014, 2(29):11202-11208.
[3]DU X, ZHAO C X, ZHOU M Y, et al. Hollow carbon nanospheres with tunable hierarchical pores for drug, gene, and photothermal synergistic treatment[J]. Small, 2017, 13(6):1602592.
[4]付华,胡静,章弘扬,等.以甲酸溶液为介质的磁性介孔硅纳米材料的制备及其吸附性能[J].华东理工大学学报(自然科学版),2017,43(2):207-212.
[5]LI Y S,SHI J L,HUA Z L,et al.Hollow spheres of mesoporous aluminosilicate with a three-dimensional pore network and extraordinarily high hydrothermal stability[J].Nano Letters,2003,3(5):609-612.
[6]CHEN Y,WANG Q H,WANG T M.Facile large-scale synthesis of brain-like mesoporous silica nanocomposites via a selective etching process[J].Nanoscale,2015,7(39):16442-16450.
[7]D U X,QIAO S Z.Dendritic silica particles with center-radial pore channels:Promising platforms for catalysis and biomedical applications[J].Small,2015,11(4):392-413.
[8]SEL O,KUANG D,THOMMES M,et al.Principles of hierarchical meso-and macropor architectures by liquid crystalline and polymer colloid templating[J].Langmuir,2006,22(5):2311-2322.
[9]RYOO R,KO C H,KRUK M,et al.Block-copolymer-templated ordered mesoporous silica:Array of uniform mesopores or mesopore-micropore network?[J].The Journal of Physical Chemistry B,2000,104(48):11465-11471.
[10]NIU D C,MA Z,LI Y S,et al.Synthesis of core-shell structured dual-mesoporous silica spheres with tunable pore size and controllable shell thickness[J].Journal of the American Chemical Society,2010,132(43):15144-15147.
[11]LI N,NIU D C,JIANG Y,et al.Morphology evolution and spatially selective functionalization of hierarchically porous silica nanospheres for improved multidrug delivery[J].Chemistry of Materials,2017,29(24):10377-10385.
[12]KANG Y J,TATON T A.Core/shell gold nanoparticles by self-assembly and crosslinking of micellar,block-copolymer shells[J].Angewandte Chemie,2005,117(3):413-416.
[13]NIU D C,LIU Z J,LI Y S,et al.Monodispersed and ordered large-poremesoporous silica nanospheres with tunable pore structure for magnetic functionalization and gene delivery[J].Advanced Materials,2014,26(29):4947-4953.
[14]CHEN Z T,NIU D C,LI Y S,et al.One-step approach to synthesize hollow mesoporous silica spheres co-templated by an amphiphilic block copolymer and cationic surfactant[J].RSC Advances,2013,3(19):6767-6770.
[15]SINGH R K,KIM T H,MAHAPATRA C,et al.Preparation of self-activated fluorescence mesoporous silica hollow nanoellipsoids for theranostics[J].Langmuir,2015,31(1):11344-11352.
[16]KWON S,SINGH R K,KIM T H,et al.Luminescent mesoporous nanoreservoirs for the effective loading and intracellular delivery of therapeutic drugs[J].Acta Biomaterialia,2014,10(3):1431-1442.
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