Deciphering Oxygen-Independent Augmented Photodynamic Oncotherapy by Facilitating the Separation of Electron-Hole Pairs.

Developing Type-I photosensitizers provides an attractive approach to solve the dilemma of inadequate efficacy of photodynamic therapy (PDT) caused by the inherent oxygen consumption of traditional Type-II PDT and anoxic tumor microenvironment. The challenge for the exploration of Type-I PSs is to facilitate the electron transfer ability of photosensitization molecules for transforming oxygen or H2O to reactive oxygen species (ROS). Herein, we propose an electronic acceptor-triggered photoinduced electron transfer (a-PET) strategy promoting the separation of electron-hole pairs by marriage of two organic semiconducting molecules of a non-fullerene scaffold-based photosensitizer and a perylene diimide that significantly boost the Type-I PDT pathway to produce plentiful ROS, especially, inducing 3.5-fold and 2.5-fold amplification of hydroxyl (OH⋅) and superoxide (O2 -⋅) generation. Systematic mechanism exploration reveals that intermolecular electron transfer and intramolecular charge separation after photoirradiation generate a competent production of radical ion pairs that promote the Type-I PDT process by theoretical calculation and ultrafast femtosecond transient absorption (fs-TA) spectroscopy. By complementary tumor diagnosis with photoacoustic imaging and second near-infrared fluorescence imaging, this as-prepared nanoplatform exhibits fabulous photocytotoxicity in harsh hypoxic conditions and terrific cancer revoked abilities in living mice. We envision that this work will broaden the insight into high-efficiency Type-I PDT for cancer phototheranostics.

A miniature CuO nanoarray sensor for noninvasive detection of trace salivary glucose.

An ultrasensitive mini-sensor has been developed for nonenzymatic and noninvasive determination of trace glucose in saliva. The miniature detector exhibits ultra-high sensitivity and resolution at very low glucose concentration owing to the excellent electrocatalytic activity and electron transfer rate of the prepared 3D ordered CuO nanoflake array in-situ grown on a copper foil. The structure and morphology of the cupric oxide nanoarray were characterized by X-ray powder diffraction and scanning electron microscopy. The electrocatalysis of the CuO nanoarray modified electrode to glucose was demonstrated by cyclic voltammetry and chronoamperometry. The modified electrode presents a high sensitivity of 4954 µA mM-1 cm-2 to glucose at + 0.55 V with a wide linear range of 1.0 µmol/L to 6000 µmol/L and a low detection limit of 0.1 µmol/L and long-term stability. Furthermore, the mini-sensor can clearly distinguish diabetics from healthy people because of its excellent sensing performance. The developed miniaturized sensor holds the prospect for noninvasive determination of trace glucose in saliva for diabetic patients.

J-Aggregation Strategy toward Potentiated NIR-II Fluorescence Bioimaging of Molecular Fluorophores.

Molecular fluorophores emitting in the second near-infrared (NIR-II, 1000-1700 nm) window with strong optical harvesting and high quantum yields hold great potential for in vivo deep-tissue bioimaging and high-resolution biosensing. Recently, J-aggregates are harnessed to engineer long-wavelength NIR-II emitters and show unique superiority in tumor detection, vessel mapping, surgical navigation, and phototheranostics due to their bathochromic-shifted optical bands in the required slip-stacked arrangement aggregation state. However, despite the preliminary progress of NIR-II J-aggregates and theoretical study of structure-property relationships, further paradigms of NIR-II J-aggregates remain scarce due to the lack of study on aggregated fluorophores with slip-stacked fashion. In this effort, how to utilize the specific molecular structure to form slip-stacked packing motifs with J-type aggregated exciton coupling is emphatically elucidated. First, several molecular regulating strategies to achieve NIR-II J-aggregates containing intermolecular interactions and external conditions are positively summarized and deeply analyzed. Then, the recent reports on J-aggregates for NIR-II bioimaging and theranostics are systematically summarized to provide a clear reference and direction for promoting the development of NIR-II organic fluorophores. Eventually, the prospective efforts on ameliorating and promoting NIR-II J-aggregates to further clinical practices are outlined.

Response of organic aerosol characteristics to emission reduction in Yangtze River Delta region.

Organic aerosol (OA) is a major component of atmospheric particulate matter (PM) with complex composition and formation processes influenced by various factors. Emission reduction can alter both precursors and oxidants which further affects secondary OA formation. Here we provide an observational analysis of secondary OA (SOA) variation properties in Yangtze River Delta (YRD) of eastern China in response to large scale of emission reduction during Chinese New Year (CNY) holidays from 2015 to 2020, and the COVID-19 pandemic period from January to March, 2020. We found a 17% increase of SOA proportion during the COVID lockdown. The relative enrichment of SOA is also found during multi-year CNY holidays with dramatic reduction of anthropogenic emissions. Two types of oxygenated OA (OOA) influenced by mixed emissions and SOA formation were found to be the dominant components during the lockdown in YRD region. Our results highlight that these emission-reduction-induced changes in organic aerosol need to be considered in the future to optimize air pollution control measures. Electronic Supplementary Material: Supplementary material is available in the online version of this article at 10.1007/s11783-023-1714-0 and is accessible for authorized users.