新型双功能富勒烯基核素促排剂的制备与性能调控

The main research objective of this project is to synthesize a bifunctional water-soluble fullerene-based chelate for metal nuclides through Radionuclide chelating is the key technology to various nuclear emergencies. Therefore, development of efficient, low toxicity, wide-adaptability multi-functional novel radionuclide chelating agents is hot and difficult research field in nuclear science and technology. Based on our preliminary work, this project aims to synthesize water-soluble fullerene (known as “radical sponge”) derivatives via covalent bonding of fullerene with catechol, hydroxy pyridone, and other water-soluble chelating groups, respectively. The purpose of this project is to obtain novel water-soluble fullerene derivatives which have both anti-free radicals restoration and radionuclide chelating properties. Moreover, the relationship between these two properties and molecular structures will be investigated by studying their dissociation energy, electrostatic potential, and resonance energy via first principle. The corresponding mathematical model will be established to reveal their inherent laws, achieving anti-free radical and radionuclide chelating performance regulation and laying the foundation for design and preparation of high efficient bifunctional wide-adaptability radionuclide chelating agents. This study has important scientific significance and practical value for expanding applications of fullerene and enriching fullerene science and chelating theory.

核素促排是核应急处理的关键核心技术，开发高效低毒广谱性多功能新型核素促排剂是核科学与技术领域的研究热点和难点。本项目旨在前期工作基础上，设计将邻苯二酚（CAMS），羟基吡啶酮（HOPO）等水溶性促排基团在分子层面上键联到具有“自由基海绵”之称的富勒烯上，制备得到系列兼具促排和抗自由基修复双重功能的新型水溶性富勒烯衍生物。研究目标物清除自由基及对核素体外促排性能，结合密度泛函理论（DFT）计算所得目标物有关键离解能、静电势和共振能等分子结构参数，利用遗传函数近似方法模拟目标物清除自由基及对核素体外促排性能与分子结构之间的关系，建立相关数学模型，揭示其内在规律，用以指导并实现抗自由基与核素促排性能的耦合与调控，最终设计制备出最优自由基猝灭和最佳核素促排效果的双功能核素促排剂，为研制新型高效多功能广谱性核素促排剂奠定基础。本研究对于拓展富勒烯应用领域、丰富富勒烯科学和促排理论具有重要科学意义。

核素促排是核应急处理的关键核心技术，开发高效低毒广谱性多功能新型核素促排剂是核科学与技术领域的研究热点和难点。本项目针对该问题提出将邻苯二酚，羟基吡啶酮等水溶性促排基团在分子层面上键联到具有“自由基海绵”之称的富勒烯上，制备得到系列兼具促排和抗自由基修复双重功能的新型水溶性富勒烯衍生物。以富勒烯、邻苯二酚、羟基吡啶酮、丙二酰氯等为原料，设计合成10种邻苯二酚类/羟基吡啶酮类配体和22种富勒烯基核素促排剂，并采用紫外可见光谱、红外光谱、质谱、X-射线光电子能谱、核磁共振谱等表征手段对产物结构进行了表征；采用ESR法、DPPH自由基法对邻苯二酚类配体和富勒烯基核素促排剂的抗氧性能进行研究，采用基于密度泛函理论的量子化学计算等方法研究富勒烯基核素促排剂的分子结构参数与清除自由基能力之间的定量关系，建立促排剂分子清除自由基能力与其分子结构参数关系的数学模型；采用电位滴定、光谱滴定、分光光度法对邻苯二酚类配体和富勒烯基核素促排剂的螯合性能进行研究，采用基于密度泛函理论的量子化学计算研究富勒烯基核素促排剂的分子结构参数与螯合促排性能之间的关系，初步建立促排剂分子螯合促排能力与分子结构参数关系的数学模型。该项目研究工作拓展了富勒烯的研究领域，促进富勒烯科学和核素促排学科的发展，为开发和利用新型核素促排剂开辟了新的技术途径。