刺激响应性有机硅杂化纳米颗粒的制备及性能研究

发布时间：2018-01-26 13:51

本文关键词： APTS 亲核加成/开环缩合反应纳米颗粒温度响应性 pH响应性　出处：《郑州大学》2015年硕士论文　论文类型：学位论文

【摘要】：当受到外部刺激如温度、p H、光等,响应性纳米颗粒的性能、尺寸、结构或相互作用会发生变化,从而使得颗粒发生重排或聚集相发生变化,这使得响应性纳米颗粒具有独特的物理和化学性能,因此其在油回收、传感器和药物传输方面具有潜在应用。聚醚中聚乙二醇(PEO)结构中的醚键与水之间具有氢键作用,使其具有温度响应性;此外,PEO具有毒性小、生物相容性好等优点,因此选用PEO来制备响应性纳米颗粒。然而,单独的PEO结构机械稳定性较差,而含有硅氧烷的无机组分的加入能够改善此种状况。本课题利用氨基和环氧基团之间的亲核加成/开环缩合反应制备有机硅杂化纳米颗粒,此合成方法与原子转移自由基聚合(ATRP)和可逆加成-断裂链转移聚合(RAFT)方法相比,具有简便、绿色、无污染等特点。本课题利用该合成方法成功制备出了有机硅杂化纳米颗粒,通过透射电镜(TEM)、动态光散射(DLS)和浊点(CP)等研究表明,该纳米颗粒为具有核壳结构的球状结构,且具有温度和p H刺激响应性能。具体研究内容及结果如下:1、以聚乙二醇二缩水甘油醚(PEO-DE)和氨丙基三乙氧基硅烷(APTS)为原料成功制备出了中间产物,并采用核磁共振氢谱(1H NMR)、傅里叶红外光谱(FT-IR)等对其进行了表征。通过直接溶解法制备了胶束,加入三乙胺促进APTS上的乙氧基水解缩合,得到有机硅杂化纳米颗粒,通过动态光散射(DLS)研究表明,其z均半径为76.26nm,且单分散性好。利用透射电镜(TEM)观察发现,其为带有支臂的球状结构。通过DLS研究发现有机硅杂化纳米颗粒具有p H响应性。2、以PEO-DE、聚丙二醇二缩水甘油醚(PPO-DE)和APTS为原料成功合成出了中间产物,采用了1H NMR、FT-IR、凝胶渗透色谱(GPC)等对其进行了表征。采用直接溶解法制备胶束,然后通过加入三乙胺促进APTS上的乙氧基水解缩合,制备出有机硅杂化纳米颗粒。以芘为探针通过荧光光谱仪测定了其在水中的临界胶束浓度(CMC),为4.3×10-6mol/L。用扫描电镜(SEM)和TEM观察发现,其为具有核壳结构的规整球状结构。通过DLS和浊点(CP)研究发现,其具有明显的温度和p H响应性能。利用可见分光光度计研究发现,有机硅杂化纳米颗粒对石墨具有一定的分散性。通过紫外-可见光谱研究发现,有机硅杂化纳米颗粒对水溶性染料甲基橙、酸性红18和罗丹明B具有选择性吸附性能。
[Abstract]:When exposed to external stimuli such as temperature, light, and so on, the properties, size, structure or interaction of responsive nanoparticles will change, resulting in the change of particle rearrangement or aggregation phase. This enables responsive nanoparticles to have unique physical and chemical properties, so that they are recovered in oil. It has potential applications in sensor and drug transport. The ether bond in PEO structure of polyether has hydrogen bond with water, which makes it temperature-responsive. In addition, PEO has the advantages of low toxicity, good biocompatibility and so on. Therefore, PEO is used to prepare responsive nanoparticles. However, the mechanical stability of the single PEO structure is poor. The addition of inorganic components containing siloxane can improve this situation. In this study, organosilicon hybrid nanoparticles were prepared by nucleophilic addition / ring opening condensation reaction between amino and epoxy groups. Compared with atom transfer radical polymerization (ATRP) and reversible addition-break chain transfer polymerization (RAFT), this method is simple and green. In this paper, organosilicon hybrid nanoparticles were successfully prepared by using this synthetic method. The results of transmission electron microscopy (TEM), dynamic light scattering (DLS) and cloud point (CPP) show that the organic silicon hybrid nanoparticles have been successfully prepared. The nanoparticles are spherical structure with core-shell structure, and have the properties of temperature and pH stimulation response. The specific research contents and results are as follows: 1. The intermediate product was prepared by using PEO-DEG and APTSs as raw materials, and 1H NMR was used. The micelles were prepared by direct dissolution method and triethylamine was added to promote the hydrolysis and condensation of ethoxy on APTS to obtain organosilicon hybrid nanoparticles. The results of dynamic light scattering (DLS) show that the z mean radius is 76.26 nm, and its monodispersity is good. The organosilicon hybrid nanoparticles were found to be p-H responsive to PEO-DE by DLS. Polypropanediol diglycidyl ether (PPO-DE) and APTS were used as raw materials to synthesize the intermediate product, and 1H-NMR-FT-IR was used. Gel permeation chromatography (GPC) was used to characterize the micelles. The micelles were prepared by direct dissolution method. Triethylamine was added to promote the hydrolysis and condensation of ethoxy on APTS. Organosilicon hybrid nanoparticles were prepared and the critical micelle concentration (CMC) in water was determined by fluorescence spectrometer using pyrene as a probe. It was found to be a regular spherical structure with core-shell structure by scanning electron microscopy (SEM) and TEM. It was found by DLS and cloud point analysis. The organosilicon hybrid nanoparticles were found to be dispersed to graphite by visible spectrophotometer. Organosilicon hybrid nanoparticles have selective adsorption properties for water-soluble dyes methyl orange, acid red 18 and rhodamine B.
【学位授予单位】：郑州大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TB383.1

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