Studies on the Design, Synthesis and Ion Recognition Properties of Intramolecular Charge Transfer Fluorescent Receptors

对金属阳离子和无机阴离子的荧光识别研究一直是化学领域的研究热点之一。纵观近年来离子荧光识别受体分子的发展，能在水溶液中高灵敏地单一识别外来物种性质的荧光受体分子相对稀少。离子识别受体分子要具有高灵敏度高选择性以及实现在水相中的识别才有可能在环境科学和生命科学领域得到真正应用。现有的离子识别荧光受体分子通常是一些复杂的分子，由多种基团的集成，合成路线长，产率低，实用性不高。因此用简单结构获取优异性能的荧光受体分子对于离子荧光识别受体分子在实际应用领域具有重要的科学和现实意义。本文合成了几个简单结构的荧光受体分子，研究了它们在有机溶剂，含水溶液和纯水溶液中对阴阳离子的识别性质。本文共分四章： 第...Fluorescent recognition of metal cations and inorganic anions are always one of fascinating fields of chemical research. So far, it is rare that florescent receptor molecules can selectively identificate various species in aqueous solution with high sensitivity. Designing and synthesizing of ion recognition fluorescence receptor molecules with high sensitivity, high selectivity, and recognizing ...学位：理学硕士院系专业：化学化工学院化学系_无机化学学号：2052009115134

Copper(Ⅱ) Ion Coordination-Controlled Twisted Intramolecular Charge Transfer Dual Fluorescence Emission

设计合成了2个分子内扭转电荷转移(TICT)荧光体(1和2),铜离子的配位作用可开关其双重荧光发射。2在乙腈/水溶液(1∶1,V/V)中的双重荧光发射随着铜离子的加入以类似电子转移机制“开-关“形式猝灭,而1在铜离子与其计量比为1之内的乙腈/水溶液(1∶1,V/V)中,其双重荧光发射随着铜离子的加入逐渐猝灭;在计量比之后其长波长的TICT荧光发射随着铜离子的加入逐渐增强。即1的TICT荧光发射以“开-关-开“的机制被铜离子诱导。同时还获得了铜离子与1形成的配合物的晶体结构以及配合物的荧光性质。1H nMr波谱滴定实验表明荧光体的电荷转移程度是影响TICT发射的主要因素,1是一个新的且其TICT发射可以被铜离子调制为“开-关-开“的TICT荧光体。Two twisted intramolecular charge transfer(TICT) fluorophores(1 and 2) were designed and synthesized to control the dual fluorescence emission by Cu2 +coordination.The dual fluorescence of 2 is quenched upon the addition of Cu2+ions in an "on-off" process similar to PET inhibition.The dual fluorescence of 1 exhibits emission quenching initially and then long-wavelength band(TICT band) emission enhancement with "on-off-on" signalling behaviour.The crystal structure of the Cu2+complex with 1 was also obtained, and its fluorescence properties were reported.1H NMR spectral titration results indicate that the degree of charge transfer is a crucial factor for the resulting TICT state emission.Fluorophore 1 is a new TICT compound in which TICT emission can be tuned by copper ions with a dramatic change via "on-off-on" signalling behaviour.CCDC: 899958, Cu2+-1.国家自然科学基金(No.21271150); 国家基础科学人才培养基金(No.J1310024)资助项

Progress in fluorescent probes recognition for metal ions in living cell

作者简介:范伟贞(1986-)，女，湖南邵阳人，硕士，主要研究方向为分子识别与荧光成像。 通讯作者:林丽榕，E-mail:linlr@xmu．edu．cn。[中文文摘]金属离子广泛存在于组织细胞和体液中,在人体的生理和病理中发挥着十分重要的作用。金属离子的浓度必须精确控制在一定的范围内,某些离子浓度的微弱变化都将引发人体的疾病。由于细胞是生命活动的基本单位,因此研究各种金属离子对生物体的影响,通过对活体细胞内金属离子的荧光显微成像进行细胞内离子的可视化定量和定性分析引起了人们的极大关注。就近年来人们对识别细胞内金属离子的有机荧光探针与细胞成像研究领域的进展进行了评述。[英文文摘]Metal ions extensively exist in cell and body fluids and play important role in human physiology and pathology.Metal ion concentration must be precisely controlled within a certain range,some slight changes in ion concentration will lead to human diseases.As the cell is the basic unit of life activities,it is important to study various effects of metal ions on the organism.And because the availability of better metal ions-specific probes would provide additional insight into the cell biology of metal ions,interest in the field remains high． Therefore the recognition of metal ions by fluorescence， especially of real-time visualization by fluorescence detection in living cells and tissues was focused in recent years． The latest progresses of fluorescent probes for some metal ions and cell fluorescence imaging in the recent years are reviewed． The developing trends in this field are also discussed．福建省自然科学基金资助项目(2009S0063,2010-J01048);国家基础科学人才培养基金项目(J1030415