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基于溴代异喹啉级联组装的高效磷光/荧光超分子开关在水溶液中。

A Highly Efficient Phosphorescence/Fluorescence Supramolecular Switch Based on a Bromoisoquinoline Cascaded Assembly in Aqueous Solution.

机构信息

College of Chemistry, State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin, 300071, P. R. China.

出版信息

Adv Sci (Weinh). 2022 May;9(14):e2200524. doi: 10.1002/advs.202200524. Epub 2022 Mar 13.

Abstract

Despite ongoing research into photocontrolled supramolecular switches, reversible photoswitching between room-temperature phosphorescence (RTP) and delayed fluorescence is rare in the aqueous phase. Herein, an efficient RTP-fluorescence switch based on a cascaded supramolecular assembly is reported, which is constructed using a 6-bromoisoquinoline derivative (G ), cucurbit[7]uril (CB[7]), sulfonatocalix[4]arene (SC4A4), and a photochromic spiropyran (SP) derivative. Benefiting from the confinement effect of CB[7], initial complexation with CB[7] arouses an emerging RTP signal at 540 nm for G . This structure subsequently coassembles with amphiphilic SC4A4 to form tight spherical nanoparticles, thereby further facilitating RTP emission (≈12 times) in addition to a prolonged lifetime (i.e., 1.80 ms c.f., 50.1 µs). Interestingly, following cascaded assembly with a photocontrolled energy acceptor (i.e., SP), the efficient light-driven RTP energy transfer occurs when SP is transformed to its fluorescent merocyanine (MC) state. Ultimately, this endows the final system with an excellent RTP-fluorescence photoswitching property accompanied by multicolor tunable long-lived emission. Moreover, this switching process can be reversibly modulated over multiple cycles under alternating UV and visible photoirradiation. Finally, the prepared switch is successfully applied to photocontrolled multicolor cell labeling to offer a new approach for the design and fabrication of novel advanced light-responsive RTP materials in aqueous environments.

摘要

尽管人们一直在研究光控超分子开关,但在水相体系中,室温磷光(RTP)和延迟荧光之间的可逆光开关仍然很少见。在此,报道了一种基于级联超分子组装的高效 RTP-荧光开关,该开关由 6-溴异喹啉衍生物(G)、葫芦[7]脲(CB[7])、磺化杯[4]芳烃(SC4A4)和光致变色螺吡喃(SP)衍生物构建。受益于 CB[7]的限制作用,与 CB[7]的初始络合引起 G 的新出现的 RTP 信号在 540nm 处。该结构随后与两亲性 SC4A4 共聚形成紧密的球形纳米粒子,从而除了延长寿命(即 1.80ms,相比之下,50.1µs)之外,还进一步促进 RTP 发射(≈12 倍)。有趣的是,在与光控能量受体(即 SP)级联组装后,当 SP 转化为荧光变色体(MC)状态时,会发生高效的光驱动 RTP 能量转移。最终,这使最终系统具有出色的 RTP-荧光光开关性能,并伴有可调的多色长寿命发射。此外,该开关过程可以在交替的 UV 和可见光光照射下,通过多个循环可逆地进行调节。最后,成功地将制备的开关应用于光控多色细胞标记,为在水相环境中设计和制造新型先进的光响应 RTP 材料提供了一种新方法。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/48ce/9108601/7d1cd2ff8280/ADVS-9-2200524-g002.jpg

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