Naphthofluorescein-based organic nanoparticles with superior stability for near-infrared photothermal therapy.

Photothermal agents (PTAs) based on organic small molecules with near-infrared (NIR) absorption (700-900 nm) have attracted increasing attention in cancer photothermal therapy (PTT). However, NIR organic PTAs often suffer from poor stability. Fluorescein and its derivatives have been widely used in biological imaging and sensing due to their minimal cytotoxicity. But fluorescein and its derivatives have not been used in PTT because most of them don't have NIR absorption. In this work, two NIR naphthofluorescein derivatives, namely NFOM-1 and NFOM-2, were synthesized. In contrast to NFOM-1, NFOM-2 possesses an intramolecular hydrogen bonding network, which extends the absorption to the NIR region and significantly improves the photostability. NFOM-2 was encapsulated into an amphiphilic polymer (DSPE-mPEG2000) to obtain NFOMNPs as PTAs. Compared to the organic molecule NFOM-2, the absorption of NFOMNPs is broadened and further red-shifted to fit an 808 nm light source. Moreover, NFOMNPs exhibit good photothermal conversion efficiency (PCE, 40.4%, 808 nm, 1.0 W cm-2), remarkable photostability and physiological stability, and significant PTT efficacy in vitro and in vivo was achieved. In other words, this study provides an intramolecular hydrogen bond network strategy and a fluorescein-based molecular platform to construct ultra-stable PTAs for efficient NIR PTT.

An unexpected strategy to alleviate hypoxia limitation of photodynamic therapy by biotinylation of photosensitizers.

The most common working mechanism of photodynamic therapy is based on high-toxicity singlet oxygen, which is called Type II photodynamic therapy. But it is highly dependent on oxygen consumption. Recently, Type I photodynamic therapy has been found to have better hypoxia tolerance to ease this restriction. However, few strategies are available on the design of Type I photosensitizers. We herein report an unexpected strategy to alleviate the limitation of traditional photodynamic therapy by biotinylation of three photosensitizers (two fluorescein-based photosensitizers and the commercially available Protoporphyrin). The three biotiylated photosensitizers named as compound 1, 2 and 3, exhibit impressive ability in generating both superoxide anion radicals and singlet oxygen. Moreover, compound 1 can be activated upon low-power white light irradiation with stronger ability of anion radicals generation than the other two. The excellent combinational Type I / Type II photodynamic therapy performance has been demonstrated with the photosensitizers 1. This work presents a universal protocol to provide tumor-targeting ability and enhance or trigger the generation of anion radicals by biotinylation of Type II photosensitizers against tumor hypoxia.

Extending the Legible Time of Light-Responsive Rewritable Papers with a Tunable Photochromic Diarylethene Molecule.

Inkless printing based on rewritable papers has recently made great progress because it can improve the utilization rate of papers, which is of great significance for saving resources and protecting the environment. Among them, light-responsive rewritable papers (LRPs) are a hot research topic because light is clean, easily available, wavelength and intensity adjustable, and noncontacting. However, the photochromic material, as the imaging substance of LRPs, is easily affected by environmental conditions, resulting in insufficient time to read the information. In view of this, we designed and constructed an acid/base tunable diarylethene molecular system that can effectively adjust the photochromic properties by reversibly changing the electron density of the diarylethene photoreaction center through protonation and demonstrated its potential as an imaging material with a longer legible time. What makes us more satisfied is that the acidification can not only extend the legible time of carrying information but also bring a clear and stable absorption/fluorescence imaging dual mode, which can better reflect details and improve contrast. Therefore, we believe that this tunable photochromic diarylethene molecule is a potential imaging material for the development of new LRPs.

Enhancing Intersystem Crossing to Achieve Thermally Activated Delayed Fluorescence in a Water-Soluble Fluorescein Derivative with a Flexible Propenyl Group.

It is a challenge to rationally design an organic molecule with thermally activated delayed fluorescence (TADF) due to the intrinsically spin-forbidden transition. Meanwhile, those reported TADF organic molecules have difficulty to be directly applied in the field of biological and medical imaging because they usually have no water solubility. Here, a water-soluble TADF organic molecule DCF-BXJ was developed by introducing a flexible propenyl group into the commercial traditional fluorophore DCF (2,7-dichlorofluorescein). The flexible group provides nonradiative rotational motion, which causes an efficient energy level cross between the S1 state and the T2 state of DCF-BXJ. Results of transient absorption spectra and theoretical calculations supported that nonradiative rotational motion of the flexible group can enhance intersystem crossing (ISC) and bring out TADF. This work provides a new mechanism explanation for TADF existing in organic molecules.

Red-to-blue photon up-conversion with high efficiency based on a TADF fluorescein derivative.

A new photon up-conversion system with a TADF fluorescein derivative as a photosensitizer was developed to achieve a quite large anti-Stokes shift from red to blue with a fairly high up-conversion emission quantum yield. This TADF photosensitizer has a very small ΔEST to provide a 207 nm anti-Stokes shift photon up-conversion. Meanwhile, it has a quite long triplet state lifetime (22.11 µs) and a large molar extinction coefficient to assure a high up-conversion efficiency of 11.2%. These results fully demonstrated the potential of the TADF fluorescein derivative as the photosensitizer used in photon up-conversion for the first time.