生物可降解磁性纳米球的制备与机理研究
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摘要
生物相容和生物可降解磁性纳米球是由具有生物相容性和生物可降解性的物质包覆纳米磁性材料制备而成的,它不但具有高分子磁性纳米球的多功能基团性和强磁性,而且由于其壳层材料是天然绿色的材料,因此它比普通高分子磁性纳米球有更广阔的应用前景,尤其是在医学领域。本文基于磁靶向纳米给药系统,采用两种新颖的、绿色的方法制备出了两种生物相容和生物可降解磁性纳米球,并对制备工艺进行优化,得到各自的较优制备方案,同时还详尽阐述了制备机理,具体内容如下：
(1)以油酸(OA)与十一烯酸(UA)共同修饰的Fe304为磁核,环已烷为中介,牛血清蛋白(BSA)为壳层组分,创新地用超声化学法制备了牛血清蛋白包覆Fe304(Fe3O4/BSA)磁性纳米球。着重探讨了BSA用量、磁流体浓度和用量、超声时间、超声功率、预乳化和水冷等因素对实验的影响,并获得了较优制备方案。在此方案下制备的样品通过FT-IR、TEM、SEM、TG以及VSM等分析手段进行了表征,结果表明纳米球壳层明显,粒径小(约100nm),成球性和分散性好,官能基团多,磁感应性较强(饱和磁化强度为38.5 emu/g),且具有超顺磁性,纳米球中Fe304的含量为57.6%。本文对超声化学法制备Fe3O4/BSA磁性纳米球的形成机理进行了详细分析和阐述,并通过对比实验进行了验证。
(2)对低温水热法制备含碳多聚糖微球和含碳多聚糖包覆Fe3O4(Fe3O4@CP)磁性纳米球的方法进行了改进,以微量NaOH为催化剂,产率和包覆效果都大幅提高。对此本文同样也获得了较优制备方案,在此方案下制备的Fe3O4@CP磁性纳米球,通过VSM分析可知,其饱和磁化强度高达60.629 emu/g;通过红外分析可知,纳米球壳层为含碳多聚糖,具有丰富的羟基和羰基；从热失重曲线可看出,纳米球的Fe304含量很高,达到81.7%；TEM图显示,纳米球的壳层明显,粒径在300nm以下。本文还证明了Fe304纳米粒子粒径较小时(小于20nm),用此法不能制备出以单个Fe304粒子为核的复合球体,而是形成无定型团聚体,并分析了原因。本文对含碳多聚糖微球以及Fe3O4@CP磁性纳米球的形成机理进行了解析,并提出了独到的见解。
Biocompatible and biodegradable magnetic nanospheres are synthesized by coating magnetic materials with biocompatible and biodegradable materials. They not only have surface functionality and high magnetic responsiveness as the polymer nanospheres, but also have shells made from natural and green materials, so their potential applications are much greater than normal polymer nanospheres, especially in medicine field. Magnetic nanospheres synthesized in this paper are based on magnetic targeted nanoparticle drug delivery system. Two kinds of biocompatible and biodegradable magnetic nanospheres were synthesized by two different novel methods in this paper. Their optimal synthesis conditions were got and their formation mechanisms were expounded. The details are described as below:
(1)Fe3O4 modified by OA and UA as the cores, bovine serum albumin (BSA) as the shells and cyclohexane as the agency, Fe3O4/BSA magnetic nanospheres were synthesized by sonochemical method. The effects of various factors in the experiments were studied, including BSA dosage, ferrofluid's concentration and dosage, ultrasonic time, ultrasonic power, pre-emulsification and water cooling. At last, optimal conditions were got. Coating effect and structure of the nanospheres synthesized under the optimal conditions were tested and characterized by FT-IR, TEM, SEM, TG and VSM. The results show that the nanospheres have clear core-shell structure, small size (approximately 100 nm), good sphericity and dispersibility, abundant functional groups, large saturated magnetization (38.5 emu/g) and superparamagnetism, high Fe3O4 content (57.6%).The formation mechanism of Fe3O4/BSA magnetic nanospheres synthesized by sonochemical method was analysed and expounded in detail, and it was proved through contrast experiments.
(2) Low-temperature hydrothermal method was modified by us. With this method, carbonaceous polysaccharide microspheres and carbonaceous polysaccharide coated Fe3O4 (Fe3O4@CP) magnetic nanospheres were synthesized. It was discovered that the yield and coating effect will be improved with the help of little NaOH. The optimal conditions were also found through a lot of experiments. Various properties of the Fe3O4@CP magnetic nanospheres synthesized under the optimal conditions were tested and characterized. They showed high saturated magnetization (60.629 emu/g) in the VSM test, high Fe3O4 content (81.7%) in the TG test. The TEM images show that their particle size is less than 300 nm. It was demonstrated that Fe3O4@CP magnetic nanospheres can not be synthesized with hydrothermal method but unformed agglomerates when small size Fe3O4 particles (less than 20 nm) were used as the cores, and the reasons were analysed. The formation mechanisms of carbonaceous polysaccharide microspheres and Fe3O4@CP magnetic nanospheres were inferred, and unique viewpoints were put forward in the paper.
(1)以油酸(OA)与十一烯酸(UA)共同修饰的Fe304为磁核,环已烷为中介,牛血清蛋白(BSA)为壳层组分,创新地用超声化学法制备了牛血清蛋白包覆Fe304(Fe3O4/BSA)磁性纳米球。着重探讨了BSA用量、磁流体浓度和用量、超声时间、超声功率、预乳化和水冷等因素对实验的影响,并获得了较优制备方案。在此方案下制备的样品通过FT-IR、TEM、SEM、TG以及VSM等分析手段进行了表征,结果表明纳米球壳层明显,粒径小(约100nm),成球性和分散性好,官能基团多,磁感应性较强(饱和磁化强度为38.5 emu/g),且具有超顺磁性,纳米球中Fe304的含量为57.6%。本文对超声化学法制备Fe3O4/BSA磁性纳米球的形成机理进行了详细分析和阐述,并通过对比实验进行了验证。
(2)对低温水热法制备含碳多聚糖微球和含碳多聚糖包覆Fe3O4(Fe3O4@CP)磁性纳米球的方法进行了改进,以微量NaOH为催化剂,产率和包覆效果都大幅提高。对此本文同样也获得了较优制备方案,在此方案下制备的Fe3O4@CP磁性纳米球,通过VSM分析可知,其饱和磁化强度高达60.629 emu/g;通过红外分析可知,纳米球壳层为含碳多聚糖,具有丰富的羟基和羰基；从热失重曲线可看出,纳米球的Fe304含量很高,达到81.7%；TEM图显示,纳米球的壳层明显,粒径在300nm以下。本文还证明了Fe304纳米粒子粒径较小时(小于20nm),用此法不能制备出以单个Fe304粒子为核的复合球体,而是形成无定型团聚体,并分析了原因。本文对含碳多聚糖微球以及Fe3O4@CP磁性纳米球的形成机理进行了解析,并提出了独到的见解。
Biocompatible and biodegradable magnetic nanospheres are synthesized by coating magnetic materials with biocompatible and biodegradable materials. They not only have surface functionality and high magnetic responsiveness as the polymer nanospheres, but also have shells made from natural and green materials, so their potential applications are much greater than normal polymer nanospheres, especially in medicine field. Magnetic nanospheres synthesized in this paper are based on magnetic targeted nanoparticle drug delivery system. Two kinds of biocompatible and biodegradable magnetic nanospheres were synthesized by two different novel methods in this paper. Their optimal synthesis conditions were got and their formation mechanisms were expounded. The details are described as below:
(1)Fe3O4 modified by OA and UA as the cores, bovine serum albumin (BSA) as the shells and cyclohexane as the agency, Fe3O4/BSA magnetic nanospheres were synthesized by sonochemical method. The effects of various factors in the experiments were studied, including BSA dosage, ferrofluid's concentration and dosage, ultrasonic time, ultrasonic power, pre-emulsification and water cooling. At last, optimal conditions were got. Coating effect and structure of the nanospheres synthesized under the optimal conditions were tested and characterized by FT-IR, TEM, SEM, TG and VSM. The results show that the nanospheres have clear core-shell structure, small size (approximately 100 nm), good sphericity and dispersibility, abundant functional groups, large saturated magnetization (38.5 emu/g) and superparamagnetism, high Fe3O4 content (57.6%).The formation mechanism of Fe3O4/BSA magnetic nanospheres synthesized by sonochemical method was analysed and expounded in detail, and it was proved through contrast experiments.
(2) Low-temperature hydrothermal method was modified by us. With this method, carbonaceous polysaccharide microspheres and carbonaceous polysaccharide coated Fe3O4 (Fe3O4@CP) magnetic nanospheres were synthesized. It was discovered that the yield and coating effect will be improved with the help of little NaOH. The optimal conditions were also found through a lot of experiments. Various properties of the Fe3O4@CP magnetic nanospheres synthesized under the optimal conditions were tested and characterized. They showed high saturated magnetization (60.629 emu/g) in the VSM test, high Fe3O4 content (81.7%) in the TG test. The TEM images show that their particle size is less than 300 nm. It was demonstrated that Fe3O4@CP magnetic nanospheres can not be synthesized with hydrothermal method but unformed agglomerates when small size Fe3O4 particles (less than 20 nm) were used as the cores, and the reasons were analysed. The formation mechanisms of carbonaceous polysaccharide microspheres and Fe3O4@CP magnetic nanospheres were inferred, and unique viewpoints were put forward in the paper.
引文
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