Quaternary Supramolecular Nanoparticles as a Photoerasable Luminescent Ink and Photocontrolled Cell‐Imaging Agent

Abstract

Photoswitchable luminescent supramolecular assemblies based on cyclodextrins have attracted considerable attention owing to their potential applications as smart materials, but most of the assemblies reported to date emit green or blue light with low contrast and high interference. In this study, novel photoluminescent red‐luminescent quaternary supramolecular nanoparticles (2) are constructed from a dithienylethene derivative (1), a β‐cyclodextrin‐functionalized ruthenium complex (Ru‐HOP‐CD), Pluronic F‐127, and cetrimonium bromide. Compared with the binary assembly 1@Ru‐HOP‐CD, the quaternary nanoparticles exhibit high fluorescence resonance energy transfer efficiency, with Ru‐HOP‐CD acting as the donor and 1 as the acceptor. Owing to the reversible photoswitched interconversion of the two forms of the dithienylethene component, the fluorescence of the nanoparticles could be switched on/off by irradiation with UV or visible light, both in solution and in the solid state. As a result, the nanoparticles could be used as a photoerasable red‐luminescent ink and as a photocontrolled cell‐imaging agent. These functional nanoparticles can be expected to be useful in the fields of information security and biology.

Organic photoresponsive materials for information storage: a review

“…S2 in the Supplemental Materials). 55 These supramolecular nanoparticles were watersoluble and exhibited the same photoswitching behavior as the above system. Therefore, information coding and anticounterfeiting applications were realized using the aqueous solution of supramolecular nanoparticles as ink.…”

“…The remarkable properties allow their successful application in information storage, including rapid light response, good reversibility, outstanding fatigue resistance, excellent thermal stability, and high photoisomerization quantum yield. [50][51][52][53][54][55] SP also undergoes reversible ring opening-closure photoisomerization. It becomes the purple merocyanine (MC) form under UV light irradiation, while it reverts into the colorless SP form by heating or irradiating with visible light [ Fig.…”

“…61 Among them, DAE and its derivatives have gained great attention owing to their rapid light response, good thermal stability, outstanding fatigue resistance, and high photoisomerization quantum yield. [50][51][52][53][54][55] In addition, SP and its derivatives, photoresponsive tetraphenylethylene (TPE) derivatives, redox dyes, and dianthryl sulfoxides were also successfully applied to information storage.…”

Future‐Oriented Advanced Diarylethene Photoswitches: From Molecular Design to Spontaneous Assembly Systems

“…Recently, Liu et al also attached an adamantane group to a DAE core combined with a β-CD-functionalized ruthenium complex, Pluronic F-127, and cetrimonium bromide to construct quaternary supramolecular nanoparticles. [99] Hydrophobic interactions and noncovalent host-guest interactions were key factors in the assembly process. TEM and a DLS analysis showed that the average diameter of the obtained discrete spherical nanoparticles was 175 nm, and switching the DAE units between their open and closed forms did not significantly affect their microscopic morphology.…”

“…[207] The bioimaging potential of stimulus-responsive supramolecular assemblies has also received attention in recent years, [208] and it requires biocompatible assemblies. [209] Based on their previous research, [210] Liu et al [99] reported quaternary supramolecular nanoparticles based on a β-CD modified ruthenium complex (Ru-HOP-CD), DAE derivatives, Pluronic F-127, and cetrimonium bromide. Ru-HOP-CD emitted red fluorescence under excitation at 450 nm.…”