多光子吸收生物显影功能配合物的设计合成

Multi-photon absorption materials possess advantages of strong penetration ability, high resolved localization and low phototoxicity to obtain the detailed information within cells and deep tissues, which have bright application prospect in life science. In the present item, with the guidance of applications in biological body for the multi-photon absorption materials, relying on the characters of the ions, cells and tissues in life body, multi-photon absorption organic ligands with bio-activities were designed and synthesized. Bio-active complexes were prepared from the designed ligands and selected inorganic component. Novel multi-photon absorption materials were constructed from the functional organic salt or complex ions with coordination polymer. The key scientific problems, such as structure-property relationships, directional assembly, functional modification were investigated for the multi-photon absorption materials in the biological environment, with aid of crystal information, theoretical calculation and photophysical properties. The interaction mechanisms between the multi-photon absorption complexes and biological cells and tissue were investigated with aid of high resolved microscopy and cell TEM technologies. Design and synthesis of the multi-photon absorption complexes were directed over theoretical calculation and molecular linking. The potential applications of the coordination compounds in ion sensor, biological imaging, and photodynamic therapy were searched for. The results of the investigations will grow out of a new concept for design and synthesis of novel multi-photon absorption materials with bio-imaging.

多光子吸收材料在生命体中具有穿透力强、定位准确、光毒性低等优点，可获得细胞和组织深层次结构信息，在生命科学领域有光明的应用前景。本项目以多光子吸收配合物在生物体中的应用为导向，针对生命体系中离子、细胞和组织结构特点，设计合成兼具有多光子吸收效应和生物显影功能的有机配体，选择不同的金属离子，合成多光子吸收生物显影功能配合物和配位聚合物。将晶体结构信息与理论计算、光物理性质研究相结合，研究多光子吸收配合物的构效关系、导向组装、功能修饰等关键科学问题。利用多光子吸收配合物的优势，实现近红外光激发，用超分辨共聚焦显影和细胞TEM技术探明生物活性多光子吸收配合物分子（离子）与活体细胞或组织的作用机理。通过理论计算和分子对接，指导新型多光子吸收配合物的设计合成，探索配合物在离子识别、生物显影和光动力学治疗等方面的应用。本项目研究将为设计制备多光子吸收生物显影配合物及其在生命科学领域中的应用提供新思路。

设计合成了一批具有多光子吸收性能的配位化合物，完善了多光子吸收性能的配位化合物的设计理论，研究了具有预期结构的多光子吸收性能的配位化合物的可控组装方法；研究了该类配位化合物中有机配体分子的取代基团、桥联基团等对多光子吸收性能的配位化合物性能的影响规律及其机理。围绕多光子吸收性能的配位化合物的结构设计与可控制备和性能调控等关键问题，系统研究多光子吸收性能的配位化合物中有机配体分子的取代基团、桥联基团、同核和多核金属的变化，引起材料光物理性质的变化规律，以及超快速激光作用下红外波段非线性光学效应、多光子吸收的特点；结合理论计算，探明金属配合物的构效关系及规律；解决多光子吸收性能的配位化合物非线性光学效应增强和红外光波段可控等关键问题，为制备此类新型材料提供理论指导，获得超快响应、高损伤阈值多光子吸收性能的配位化合物。对含金属 Fe、Mn、Zn、Ir 和 Pt 配合物杂化红外非线性光学材料的制备、功能有机分子与金属杂化轨道的匹配、能量传递机理及其发光规律开展了系统研究，研究了提高杂化材料在近红外波段非线性光学的微观机理和构效关系；探索了多光子吸收性能的配位化合物在生物成像、离子识别、生物特异性与诊疗方面给的应用，取得了一系列原创性研究成果，本项目研究成果将为设计制备多光子吸收生物显影配合物及其在生命科学领域中的应用提供新思路。研究成果已在Adv. Mater.、Angew. Chem. Inter. Ed.、Chem. Sci.、Adv. Healthcare Mater.、Inorg. Chem.、Chem. Commun.、Anal. Chem. 等刊物发表 SCI 论文 39 篇，获得国家发明专利授权 8 项。参加国际学术会议 3 人次，国内学术会议与交流 19人次。培养研究生中6人获博士学位，19人获硕士学位。