The exciting applications of molecular motion are still limited and are in urgent pursuit, although some fascinating concepts such as molecular motors and molecular machines have been proposed for years. Utilizing molecular motion in a nanoplatform for practical application has been scarcely explored due to some unconquered challenges such as how to achieve effective molecular motion in the aggregate state within nanoparticles. Here, we introduce a class of near infrared-absorbing organic molecules with intramolecular motion-induced photothermy inside nanoparticles, which enables most absorbed light energy to dissipate as heat. Such a property makes the nanoparticles a superior photoacoustic imaging agent compared to widely used methylene blue and semiconducting polymer nanoparticles and allow them for high-contrast photoacoustic imaging of tumours in live mice. This study not only provides a strategy for developing advanced photothermal/photoacoustic imaging nanoagents, but also enables molecular motion in a nanoplatform to find a way for practical application.
Purely organic room temperature phosphorescence (RTP) has attracted wide attention recently due to its various application potentials. However, ultralong RTP (URTP) with high efficiency is still rarely achieved. Herein, by dissolving 1,8-naphthalic anhydride in certain organic solid hosts, URTP with a lifetime of over 600 ms and overall quantum yield of over 20% is realized. Meanwhile, the URTP can also be achieved by mechanical excitation when the host is mechanoluminescent. Femtosecond transient absorption studies reveal that intersystem crossing of the host is accelerated substantially in the presence of a trace amount of 1,8-naphthalic anhydride. Accordingly, we propose that a cluster exciton spanning the host and guest forms as a transient state before the guest acts as an energy trap for the RTP state. The cluster exciton model proposed here is expected to help expand the varieties of purely organic URTP materials based on an advanced understanding of guest/host combinations.
Pure organic materials with ultralong room-temperature phosphorescence (RTP) are attractive alternatives to inorganic phosphors. However, they generally show inefficient intersystem crossing (ISC) owing to weak spin-orbit coupling (SOC). A design principle based on the realization of small energy gap between the lowest singlet and triplet states (ΔE ) and pure ππ* configuration of the lowest triplet state (T ) via structural isomerism was used to obtain efficient and ultralong RTP materials. The meta isomer of carbazole-substituted methyl benzoate exhibits an ultralong lifetime of 795.0 ms with a quantum yield of 2.1 %. Study of the structure-property relationship shows that the varied steric and conjugation effects imposed by ester substituent at different positions are responsible for the small ΔE and pure ππ* configuration of T .
Multimodality imaging is highly desirable for accurate diagnosis by achieving high sensitivity, spatial-temporal resolution, and penetration depth with a single structural unit. However, it is still challenging to integrate fluorescent and plasmonic modalities into a single structure, as they are naturally incompatible because of significant fluorescence quenching by plasmonic noble-metal nanoparticles. Herein, we report a new type of silver@AIEgen (aggregation-induced emission luminogen) core-shell nanoparticle (AACSN) with both strong aggregated-state fluorescence of the AIEgen and distinctive plasmonic scattering of silver nanoparticles for multimodality imaging in living cells and small animals. The AACSNs were prepared through a redox reaction between silver ions and a redox-active AIEgen, which promoted synergistic formation of the silver core and self-assembly of the AIEgen around the core. The resulting AACSNs exhibited good biocompatibility and high resistance to environmental damage. As a result, excellent performance in fluorescence imaging, dark-field microscopy, and X-ray computed tomography-based multimodality imaging was achieved.
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