Zhou Yunyun, Zhuang Yaping, Li Xin, Ågren Hans, Yu Lin, Ding Jiandong, Zhu Liangliang
State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, Shanghai, 200433, China.
Division of Theoretical Chemistry and Biology, School of Biotechnology, KTH Royal Institute of Technology, 10691, Stockholm, Sweden.
Chemistry. 2017 Jun 7;23(32):7642-7647. doi: 10.1002/chem.201700947. Epub 2017 May 11.
Although organic light-emitting molecules have received a growing attention and applicability in modern bioimaging science, the design and control of complex photoluminescent properties in unimolecularly selective imaging remains a challenging topic. Considering that tunable multipathway imaging can be advantagedly connected with treatment processes in therapy, the integration of an azulene and a cyanostyryl moiety into one skeleton is carried out for the generation of in situ stimuli-responsive luminescent materials, with the aim to achieve tunable and effective emissions in distinct channels through smart molecular design on a single-molecular platform. This strategy takes advantage of 1) the Z/E isomerization of the cyanostyryl unit that can vary the push-pull effect of the substitution on azulene, accompanied by altering absorption and emission of individual excited states, and 2) an optimized excited-state regulation for opening a near infrared emissive channel and making up for a controllable dual-pathway luminescent system together with the utilization of visible emission. As exemplified by a demonstration of manipulating the luminescence at the cell level, the materials exhibit a superior application potential for unimolecularly selective imaging, labeling and probing events.
尽管有机发光分子在现代生物成像科学中受到越来越多的关注并具有广泛的适用性，但在单分子选择性成像中设计和控制复杂的光致发光特性仍然是一个具有挑战性的课题。考虑到可调谐多途径成像可以有利地与治疗过程中的治疗相联系，将一个薁和一个氰基苯乙烯基部分整合到一个骨架中，以生成原位刺激响应发光材料，目的是通过在单分子平台上进行智能分子设计，在不同通道中实现可调谐和有效的发射。该策略利用了以下两点：1）氰基苯乙烯单元的Z/E异构化，它可以改变薁上取代基的推-拉效应，同时改变各个激发态的吸收和发射；2）优化的激发态调控，用于打开近红外发射通道，并与可见发射的利用一起构成一个可控的双途径发光系统。通过在细胞水平上对发光进行操控的实例表明，这些材料在单分子选择性成像、标记和探测事件方面具有优异的应用潜力。
