文献类型：期刊文献

中文题名：近红外染料抗对称性破缺的构效关系研究

英文题名：Study on the structure-property relationship of near-infrared dyes with resistance to symmetry breaking

作者：朱晨[1];朱志远[1];罗潇[1];杨有军[1];钱旭红[1,2]

机构：[1]生物反应器工程国家重点实验室,上海市化学生物学重点实验室,华东理工大学药学院,上海200237;[2]上海市分子治疗与新药开发工程研究中心,华东师范大学化学与分子工程学院,上海200241

年份：2025

卷号：55

期号：8

起止页码：2549

中文期刊名：中国科学:化学

外文期刊名：SCIENTIA SINICA Chimica

收录：;北大核心:【北大核心2023】；

基金：国家自然科学基金(编号:22278138)资助项目。

语种：中文

中文关键词：近红外染料;对称性破缺;呫吨染料;摩尔消光系数;刚性化

外文关键词：near-infrared dyes;symmetry breaking;xanthene;molar extinction coefficient;rigidification

摘要：面向大深度活体荧光成像的高性能近红外染料的理性设计是染料化学领域的研究前沿.近红外染料由于跃迁偶极矩大,在极性溶剂中,易发生溶剂诱导的对称性破缺(Peierls transition),大幅降低摩尔消光系数.如何抑制对称性破缺,是染料化学领域亟待回答的问题.我们在前期研究中发现,相较于花菁类近红外染料,EC5染料表现出优异的抗对称性破缺的能力,在各类极性和非极性溶剂中,都表现出了优异的摩尔消光系数.我们推测,EC5染料共轭链上方的两个双键(锁骨双键)是EC5染料抗对称性破缺的关键.为回答该科学假设,我们构建了具有饱和碳链的ES5分子进行平行比对研究.对其光物理性质、光谱反卷积数据以及晶体结构进行了分析,确认双键有利于染料抵抗对称性破缺,使其即使在极性溶液中也能保持高亮度.这为染料抗对称性破缺能力的构效关系提供了新的见解,为设计高性能近红外染料提供了指导.
Rational design of high-performance near-infrared(NIR)dyes for deep-tissue in vivo fluorescence imaging represents a frontier in dye chemistry.Due to large transition dipole moments,NIR dyes are prone to solvent-induced symmetry breaking(Peierls transition)in polar solvents,leading to a significant reduction in molar extinction coefficients.Inhibiting symmetry breaking remains a critical challenge in this field.Our previous studies revealed that EC5 dyes exhibit superior resistance to symmetry breaking compared to cyanine,maintaining excellent molar extinction coefficients in both polar and non-polar solvents.We hypothesize that the two double bonds above the conjugated chain(clavicular double bonds)in EC5 dyes are key to this resistance.To test this hypothesis,we synthesized ES5 molecules with saturated carbon chains for parallel comparison.Analysis of photophysical properties,spectral deconvolution data,and crystal structures confirmed that these double bonds enhance the dye’s resistance to symmetry breaking,enabling high brightness even in polar solutions.This work provides novel insights into the structure-property relationship governing symmetry-breaking resistance,offering guidance for designing next-generation high-performance NIR dyes.