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生物拟态法合成硫组化合物纳米复合材料的研究

Bioinspired Route to Hybrid Chalcogenides-Biomaterials Nanocomposites

【作者】 王娜

【导师】 张荻;

【作者基本信息】 上海交通大学 , 材料学, 2007, 硕士

【摘要】 本论文旨在综合生物模板、生物矿化和仿生学等生物拟态过程的思想和方法来探索硫组化合物半导体纳米复合材料的制备,实现了在生物蛋膜基体上原位合成系列硫化物和硒化物纳米结构材料,包括量子点,纳米团簇,纳米方块和多面体结构,并结合对材料的形态结构和形成过程进行分析,对其光学性质进行了较系统的研究。具体归纳如下:1、实现了在酸性体系中利用室温液相浸渍生物活性材料原位合成铅系纳米材料。以蛋壳薄膜作为生物活性载体,醋酸铅/醋酸混合液作为铅源前驱体,硒代硫酸钠作为硒源或硫化钠作为硫源,设计一种在蛋膜参与下室温原位合成硒化铅纳米团簇和纳米方块、硫化铅纳米花形团簇的新方法。通过对浸渍条件如:浸渍时间、硒代硫酸钠溶液的浓度及放置陈化时间等进行调整,可以对硒化铅和硫化铅纳米粒子在蛋膜纤维上的尺寸、形貌、分布和组装状况进行有效控制。2、建立了生物协同湿化学浸渍法,在碱性体系中引入蛋膜活性载体原位成功制备了CdS、ZnS纳米材料。以氯化镉和醋酸锌的稀氨溶液分别作为镉源和锌源,硫化钠作为硫源,通过蛋膜纤维表层活性大分子官能团与无机浸渍液成分之间的复杂物理化学作用,无机粒子在蛋膜上原位成核和生长,并在蛋膜表层氨基酸残基的包覆下组装,得到由硫化镉和硫化锌纳米小晶粒组成的松散团簇体,以及结晶完善的硫化镉多面体结构。3、对用生物拟态法所制备的产物进行光致发光性质分析,表明这些硫组化合物纳米粒子具有明显的量子尺寸效应。而且不同合成条件下如:浸渍前驱液浓度、浸渍反应时间、浸渍次数等的不同,所合成的具有不同尺寸、形貌和结构特点的纳米材料,其相应荧光发射光谱信号也出现变化。这些硫组化合物纳米结构材料将会在生物分子探针,生物标记,激光发射器,红外光谱仪等光电子和生物领域有着广阔的应用前景。

【Abstract】 The aim of this paper is to explore novel routes for fabrication of chalcogenides nanocomposites by bio-inspired strategies integrating biotemplate, biomineralization, biomimetism. A series of chalcogenides nanomaterials including quantum dots, nanoclusters, nanocubes and nanopolyhedrons, were successfully prepared on the eggshell membrane (ESM) through different bio-inspired approaches, further their PL properties were investigated intentively. The details can be summarized as following:1、PbSe, PbS nanomaterials were successfully in-situ synthesized on ESM in acid impregnants at room-temperature. Herein, ESM was introduced as active biosubstrate to be infused into Pb(Ac)2-HAc medium, Na2SeSO3 or Na2S solution to carry out a novel bio-inspired synthesis of PbSe nanoclusters and nanocubes, PbS floriated nanoclusters. The dipping time, the precursor concentration and its preserving time, could affect the size, morphologies, distribution, and assembly of PbSe, PbS nanocrystallites on ESM fibers.2、CdS, ZnS nanostructures were successfully synthesized on active ESM fibers in alkaline media by dipping ESM into CdCl2-NH3·H2O or Zn(Ac)2-NH3·H2O solution, Na2S solution, respectively. CdS and ZnS nanocrystallites could be formed, and grown-up, further assembled into incompact nanoclusters or nanopolyhedrons. The nucleation, growth and assembly were under the direction of functional biomacromolecules of amino acid residues of ESM fibers.3、The samples were characterized by UV-Vis and PL analysis, the results indicate these chalcogenides nanostructures own obvious quantum size effect. Compared with bulk materials, there are clear blue shifts in PL. Moreover, the size, morphology and structure could be affected by precursor concentration, dipping period, and so on, then indirectly influenced the PL properties of as-prepared hybrid chalcogenides-ESM nanocomposites. They have great applications on biomarkers, laser emitter, near infrared spectroscopy, and so on.

  • 【分类号】TB383.1
  • 【被引频次】1
  • 【下载频次】151
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