Less is More: Asymmetric D-A Type Agent to Achieve Dynamic Self-Assembled Nanoaggregates for Long-Acting Photodynamic Therapy.

To enhance the phototheranostic performance, agents with high reactive oxygen species (ROS) generation, good tumor-targeting ability, and prolonged retention are urgently needed. However, symmetric donor-acceptor (D-A) type agents usually produce spherical nanoaggregates, leading to good tumor targeting but inferior retention. Rod-like nanoaggregates are desired to extend their retention in tumors; however, this remains a challenge. In particular, agents with dynamically changeable shapes that integrate merits of different morphologies are seldomly reported. Therefore, self-assembled organic nanoaggregates with smart shape tunability are designed here using an asymmetric D-A type TIBT. The photoluminescence quantum yield in solids is up to 52.24% for TIBT. TIBT also exhibits high ROS generation in corresponding nanoaggregates (TIBT-NCs). Moreover, dynamic self-assembly in shape changing from nanospheres to nanorods occurrs in TIBT-NCs, contributing to the enhancement of ROS quantum yield from 0.55 to 0.72. In addition, dynamic self-assembly can be observed for both in vitro and in vivo, conferring TIBT-NCs with strong tumor targeting and prolonged retention. Finally, efficient photodynamic therapy to inhibit tumor growth is achieved in TIBT-NCs, with an inhibition rate of 90%. This work demonstrates that asymmetric D-A type agents can play significant roles in forming self-assembled organic nanoaggregates, thus showing great potential in long-acting cancer therapy.

One Stone, Two Birds: High-Brightness Aggregation-Induced Emission Photosensitizers for Super-Resolution Imaging and Photodynamic Therapy.

Most aggregation-induced emission (AIE) luminogens exhibit high brightness, excellent photostability, and good biocompatibility, but these AIE-active agents, which kill two birds with one stone to result in applications in both stimulated emission depletion (STED) super-resolution imaging and photodynamic therapy (PDT), have not been reported yet but are urgently needed. To meet the requirements of STED nanoscopy and PDT, D-A-π-A-D type DTPABT-HP is designed by tuning conjugated π spacers. It exhibits red-shifted emission, high PLQY of 32.04%, and impressive 1O2 generation (9.24 fold compared to RB) in nanoparticles (NPs). Then, DTPABT-HP NPs are applied in cell imaging via STED nanoscopy, especially visualizing the dynamic changes of lysosomes in the PDT process at ultrahigh resolution. After that, in vivo PDT was also conducted by DTPABT-HP NPs, resulting in significantly inhibited tumor growth, with an inhibition rate of 86%. The work here is beneficial to the design of multifunctional agents and the deep understanding of their phototheranostic mechanism in biological research.

Aggregation-induced emission (AIE)-active metallacycles with near-infrared emission for photodynamic therapy.

Multifunctional metallacycles with solid-state emission are highly important in cancer therapy. Here, an aggregation-induced emission (AIE)-active metallacycle of DTPABT-MC-R is developed with efficient emission in the NIR region in the solid state (PLQYs = 4.92%). DTPABT-MC-R-based nanoparticles also display excellent photo-stability, and impressive photosensitive characteristics (ROS efficiency = 10.74%), finally leading to applications in cellular imaging and photodynamic therapy (PDT).

All-in-One Theranostic Platforms: Deep-Red AIE Nanocrystals to Target Dual-Organelles for Efficient Photodynamic Therapy.

Aggregation-induced emission (AIE) nanoparticles have been widely applied in photodynamic therapy (PDT) over the past few years. However, amorphous nanoaggregates usually occur in their preparation, resulting in loose packing with disordered molecular structures. This still allows free intramolecular motions, thus leading to limited brightness and PDT efficiency. Herein, we report deep-red AIE nanocrystals (NCs) of DTPA-BS-F by following the facile method of nanoprecipitation. It is observed that DTPA-BS-F NCs possess not only a high photoluminescence quantum yield value of 8% in the deep-red region (600-850 nm) but also an impressive reactive oxygen species (ROS) generation efficiency of up to 69%. Moreover, DTPA-BS-F NCs targeting dual-organelles of lysosomes and nucleus to generate ROS are also achieved, thus boosting the PDT effect in cancer therapy both in vitro and in vivo. This work provides high-performance AIE NCs to simultaneously target two organelles for efficient photodynamic therapy, indicating their promising application in all-in-one theranostic platforms.

Recent advances in luminescent materials for super-resolution imaging via stimulated emission depletion nanoscopy.

Stimulated emission depletion (STED) nanoscopy is a promising fluorescence microscopy to detect unresolvable structures at the nanoscale level and then achieve a superior imaging resolution in materials science and biological research. However, in addition to the optimization of the microscope, luminescent materials in STED nanoscopy are also of great significance to obtain imaging, visualization and even long-term tracking at an ultra-high resolution (less than 100 nm), but this is seldom summarized. Based on this consideration, recent progress on STED fluorophores for super-resolution imaging is outlined here, including inorganic fluorophores, fluorescent proteins, organic luminescent materials, aggregation-induced emission (AIE) luminogens, and fluorescent nanoparticles. Characteristics of these aforementioned STED fluorophores are also included and compared to provide a deep understanding of the relationship between the properties in luminescent materials and their performance in STED imaging. According to the results on such luminescent materials, it is anticipated that guidelines to select proper probes and even develop new materials for super-resolution imaging via STED nanoscopy will be provided here, finally promoting the development of super-resolution imaging in both materials science and biological research.

A Facilely Synthesized Dual-State Emission Platform for Picric Acid Detection and Latent Fingerprint Visualization.

To achieve a highly efficient, dual-state emission platform for picric acid (PA) detection and latent fingerprint (LFP) visualization, flexible alkyl chains have been facilely attached to the commercial organic dye 3,4,9,10-perylenetetracarboxylic dianhydride to provide the target perylenetetracarboxylate molecules PTCA-C4, PTCA-C6, and PTCA-C12. Interestingly, all these molecules exhibited impressive fluorescence characteristics with high photoluminescence quantum yields (PLQYs) of around 93.0 % in dilute solution. Also, emissive features were observed in the solid state because close molecular packing is prevented by the alkyl chains, especially for PTCA-C6, which has a high PLQY value of 49.0 %. Benefiting from its impressive fluorescence performance in both solution and as aggregates, PTCA-C6 was used as a dual-state emission platform for PA detection and also LFP visualization. For example, double-responsive fluorescence quenching in solution was observed in PA detection studies, resulting in high quenching constants (KSV ) and also low limit-of-detection values. Furthermore, the fingerprint powder based on PTCA-C6 also presented an impressive performance on various substrates in terms of fluorescence intensity and resolution, clearly providing the specific fine details of latent fingerprints. These results demonstrate that the facilely synthesized PTCA-C6 with efficient dual-state emission exhibits great potential in the real-world applications of PA detection and LFP visualization.