基于核壳结构的有机荧光分子嵌合型介孔SiO2空心纳米颗粒的制备化学及发光性能

The background of this project is based on the demands for the clinical application of analysis detection and tracer for the multifunctional mesoporous fluorescent nanoparticles system. According to the experiences in controlled synthesis and functionalization of mesoporoues silica, the hollow mesoporous silica nanoparticles with core-shell feature (HMSN) are synthesized and further modified in micro-scale levels; Meanwhile, the metal ion modified aromatic organic fluorescent molecules (MMOFM) are prepared via adjusting component and selecting the organic groups. Moreover, the MMOFM/HMSN assembly matrixes are obtained through covalent coupling, electrostatic adsorption, layer-by-layer grafting or a combination of these. So that, the organic-inorganic hybrid mesoporous fluorescent materials are therefore facilitated with perfectly fluorescent properties such as strong and stable, narrow emission peak and broaden excitation spectrum. In view of the above key sciences and important technologies, the multi-scale dimension and hierarchical HMSN and the MMOFM are systematically studied including their structure morphology, synthesis chemistry, and assembly strategies, in which, the influenced essences of HMSN surface functional groups and chromophore features of MMOFM are demonstrated indetail. The reasonable evaluations for adsorption and diffusion process, charge transfer behavior and energy level transition of MMOFM are suggested using fractal theory with combination of other characterization methods, therefore, the composition-structure-performances relationships could be accurately described, and the related fluorescent mechanism is further proposed. Thus, the new characterization method based on the fractal technology and corresponding new theory about multi-scale dimension and hierarchically mesoporous hollow structure can be further developed, which is very useful to put forward new viewpoints for understanding fluorescence mechanism. In summary, based on the above all experimental and research results, this project could solve key technologies to prepare the organic-inorganic hybrid mesoporous fluorescent materials in application for controlled drug delivery fields, and provide sufficiently theoretical basis and strong technical parameters in the biological chemical and related applications such as petrochemical industry and fine chemicals.

以满足多功能介孔纳米荧光粒子的分析检测和示踪等临床应用为背景，以介孔材料的可控合成与功能化为基础，在微观尺度上制备和修饰具有核壳结构特征的介孔SiO2空心纳米颗粒（HMSN），通过功能筛选获得金属离子改性的有机荧光分子(MMOFM)，采用共价偶联、静电吸附、层层包裹等策略制备MMOFM/HMSN组装体，藉此得到具有发光强且稳定、发射峰窄、激发光谱宽等效果的有机-无机杂化介孔荧光材料。系统研究具有多尺度多维化核壳结构的HMSN和MMOFM 结构信息，调控措施和组装条件对荧光性能的影响，阐明HMSN壳层表面官能团和MMOFM发色团的作用本质；应用分形理论并结合其他表征方法，描述MMOFM吸附和扩散过程以及能级跃迁方式和电荷传递行为，揭示构效关系，明晰发光机制；丰富和发展分形技术，为设计和开发新型杂化介孔荧光材料提供新思路,最终为解决关键技术以及在相关领域中的应用提供重要的理论依据和技术指导。

本项目以满足多功能介孔纳米荧光粒子的分析检测和示踪等临床应用为背景，以介孔材料的可控合成与功能化为基础，采用共价偶联、静电吸附、层层包裹等策略成功制备出核壳型介孔空心纳米球，从而获得有机荧光分子与空心纳米球的组装体。. 研究内容包括：（1）介孔空心球的可控制备；（2）以聚N-异丙基丙烯酰胺共聚丙烯酸为壳，以双模型介孔SiO2（BMMs）为核，制备出可控壳层厚度的pH/温度双敏型P@BMMs，并作为载体研究了对布洛芬的pH/温度响应释放性能；（3）钴，镍，铜，锌，铁等离子改性1,8-萘二酸酐/BMMs杂化材料的制备及其荧光性能；（4）pH/温度双敏型介孔杂化材料在药物传输中的分形特征和荧光性能；（5）BMMs固载联吡啶脯氨酸衍生物及其在Aldol反应中的应用和荧光性能；（6）采用结构促进剂法和疏水改性合成了斜发沸石，NaY和β分子筛，及其对CH4/N2分离和异丙苯催化裂化的影响。. 结果表明：（1）聚苯类或酚醛树脂类乳胶粒子表面性能对调控空腔“核”大小和介孔“ 壳”厚度具有重要影响，明晰了介孔壳结构的制备规律和径向分布以及空腔“核”的控制措施。（2）应用分形理论阐述了发光体溶胶粒子的结构变化和分形特征，从而揭示出表面氨基、羧基、磺酸基以及巯基等与发光体的作用机制。（3）归纳与优化了调控措施和组装条件等合成工艺和过程参数对P@BMMs激发光谱和荧光性能的影响。（4）分别从热力学和动力学角度阐明了发色团的能级跃迁规律和能量传递方式及其所诱发的荧光蓝移（或红移）行为。这些研究结果为设计和开发新型杂化介孔荧光材料在药物传输及其相关领域中的应用提供了重要的理论依据和技术指导。. 在本项目资助下，发表学术论文30篇，申请发明专利6项；培养14名博士或硕士生顺利毕业；23人次参加国内外10个学术会议；1人出国学术合作；1人获全国优秀留学生奖；1人被评聘为副教授；1人获得校级教学名师称号。

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