Pr3+ doped NaYF4 and LiYF4 nanocrystals combining visible-to-UVC upconversion and NIR-to-NIR-II downconversion luminescence emissions for biomedical applications.

Lanthanide-doped fluoride nanocrystals (NCs) are known to exhibit unique optical properties, such as upconversion and downconversion luminescence (UCL and DCL), which can be employed for various applications. In this work, we demonstrate that by doping praseodymium(III) and ytterbium(III) ions (Pr3+ and Yb3+) into a nanosized fluoride matrix (i.e. NaYF4 and LiYF4), it is possible to combine their UCL and DCL properties that can be concurrently used for biomedical applications. In particular, the emissive modes combined in a single nanoparticle co-doped with Pr3+ and Yb3+ include DCL emission (excited at 980 nm and peaked at 1320 nm), which can be used for near infrared (NIR) DCL bioimaging in the NIR-II window of biological tissue transparency (∼1000-1350 nm) and UCL emission (excited at 447 nm and peaked at 275 nm) that can be employed for germicide action (via irradiation by light in the UVC range). A possibility of the latter was demonstrated by the denaturation of double-stranded DNA (dsDNA) into single-stranded ones that was caused by the UVC UCL emission from the NCs under 447 nm irradiation; it was evidenced by the hyperchromicity observed in the irradiated dsDNA solution and also by a fluorometric analysis of DNA unwinding (FADU) assay. Concurrently, the possibility of NIR-II luminescence bioimaging through biological tissues (bovine tooth and chicken flesh) was demonstrated. The proposed concept paves a way for NIR-II imaging guided antimicrobial phototherapy using lanthanide-doped fluoride nanocrystals.

Halogen-doped phosphorescent carbon dots for grayscale patterning.

Flexible organic materials that exhibit dynamic ultralong room temperature phosphorescence (DURTP) via photoactivation have attracted increasing research interest for their fascinating functions of reversibly writing-reading-erasing graphic information in the form of a long afterglow. However, due to the existence of a nonnegligible activation threshold for the initial exposure dose, the display mode of these materials has thus far been limited to binary patterns. By resorting to halogen element doping of carbon dots (CDs) to enhance intersystem crossing and reduce the activation threshold, we were able to produce, for the first time, a transparent, flexible, and fully programmable DURTP composite film with a reliable grayscale display capacity. Examples of promising applications in UV photography and highly confidential steganography were constructed, partially demonstrating the broad future applications of this material as a programmable platform with a high optical information density.

Tumor-Microenvironment-Activated NIR-II Nanotheranostic Platform for Precise Diagnosis and Treatment of Colon Cancer.

Rational design of tumor-microenvironment (TME)-activated nanoformulation for precisely targeted cancer treatment has recently attracted an enormous attention. However, the all-in-one TME-activated theranostic nanosystems with a simple preparation and high biocompatibility are still rarely reported. Herein, catalase nanocrystals (CatCry) are first introduced as a tumor microenvironment activatable nanoplatform for selective theranostics of colon cancer. They are engaged as (i) a "nanoreactor" for silver nanoparticles (AgNP) synthesis, (ii) a nanovehicle for tumor delivery of anticancer drug doxorubicin (DOX), and (iii) an in situ O2 generator to relief tumor hypoxia. When CatCry-AgNP-DOX nanoformulation is within a tumor, the intratumoral H2S turns AgNP into Ag2S nanoparticles, inducing a photothermal effect and NIR-II emission under 808 nm laser irradiation and also triggering DOX release. Simultaneously, CatCry catalyzes intratumoral H2O2 into O2, relieving hypoxia and enhancing chemotherapy. In contrast, when delivered to healthy tissue without increased concentration of H2S, the developed nanoformulation remains in the "off" state and no theranostic action takes place. Studies with colon cancer cells in vitro and a murine colon cancer model in vivo demonstrated that CatCry-AgNP-DOX delivered a synergistic combination of PTT and enhanced chemotherapy, enabling complete eradication of tumor with minimal side effects. This work not only introduces nanoplatform for theranostics of H2S-rich tumors but also suggests a general strategy for protein-crystal-based nanomedicine.

Catalase Nanocrystals Loaded with Methylene Blue as Oxygen Self-Supplied, Imaging-Guided Platform for Photodynamic Therapy of Hypoxic Tumors.

Photodynamic therapy (PDT) is a well-known method for cancer therapy in the clinic. However, the inherent hypoxia microenvironment of solid tumors enormously restricts the PDT efficiency. Herein, catalase nanocrystals (CatCry) are introduced as in situ oxygen (O2 )-generating system to relieve tumor hypoxia and enhance PDT efficiency for solid tumors. After loading with photosensitizer methylene blue (MB), a PDT drug platform (CatCry-MB) emerges, allowing for significant increasing PDT efficiency instigated by three factors. First, the high stability and recyclable catalytic activity of CatCry enable a long-term endogenous H2 O2 decomposition for continuous O2 supply for sustained relief of tumor hypoxia. Second, both the produced O2 and loaded MB are confined within CatCry nanoporous structure, shortening the diffusion distance between O2 and MB to maximize the production of singlet oxygen (1 O2 ). Third, the MB molecules are uniformly dispersed within CatCry lattice, avoiding MB aggregation and causing more MB molecules be activated to produce more 1 O2 . With the three complementary mechanisms, tumor hypoxia is eradicated and the resulted enhancement in PDT efficiency is demonstrated in vitro and in vivo. The proposed approach opens up a new venue for the development of other O2 -dependent tumor treatments, such as chemotherapy, radiotherapy, and immunotherapy.

Real-Time Imaging of Short-Wave Infrared Luminescence Lifetimes for Anti-counterfeiting Applications.

Rare-earth doped nanoparticles (RENPs) have been widely used for anti-counterfeiting and security applications due to their light frequency conversion features: they are excited at one wavelength, and they display spectrally narrow and distinguished luminescence peaks either at shorter wavelengths (i.e., frequency/energy upconversion) or at longer wavelengths (frequency/energy downconversion). RENPs with a downconversion (DC) photoluminescence (PL) in short-wave infrared (SWIR) spectral range (~1,000-1,700 nm) have recently been introduced to anti-counterfeiting applications, allowing for multilevel protection based on PL imaging through opaque layers, due to a lesser scattering of SWIR PL emission. However, as the number and spectral positions of the discrete PL bands exhibited by rare-earth ions are well-known, it is feasible to replicate luminescence spectra from RENPs, which results in a limited anti-counterfeiting security. Alternatively, lifetime of PL from RENPs can be used for encoding, as it can be finely tuned in broad temporal range (i.e., from microseconds to milliseconds) by varying type of dopants and their content in RENPs, along with the nanoparticle morphology and size. Nevertheless, the current approach to decoding and imaging the RENP luminescence lifetimes requires multiple steps and is highly time-consuming, precluding practical applications of PL lifetime encoding for anti-counterfeiting. Herein, we report the use of a rapid lifetime determination (RLD) technique to overcome this issue and introduce real-time imaging of SWIR PL lifetime for anti-counterfeiting applications. NaYF4:20% Yb, x% Er (x = 0, 2, 20, 80)@NaYF4 core@shell RENPs were synthesized and characterized, revealing DC PL in SWIR region, with maximum at ~1,530 nm and PL lifetimes ranging from 3.2 to 6 ms. Imaging of the nanoparticles with different lifetimes was performed by the developed time-gated imaging system engaging RLD method and the precise manipulation of the delay between the excitation pulses and camera gating windows. Moreover, it is shown that imaging and decrypting can be performed at a high rate (3-4 fps) in a cyclic manner, thus allowing for real-time temporal decoding. We believe that the demonstrated RLD-based fast PL lifetime imaging approach can be employed in other applications of photoluminescent RENPs.

Co-encapsulating indocyanine green and CT contrast agent within nanoliposomes for trimodal imaging and near infrared phototherapy of cancer.

X-ray CT imaging can be complementary to fluorescence and photoacoustic imaging (FLI and PAI), allowing for high spatial resolution and high-sensitivity multimodal imaging for imaging guided treatment. In this study, the CT contrast agent iohexol was co-encapsulated with indocyanine green (ICG) within nanoliposomes (NLs) to explore their interaction and possible application of this liposomal formulation (LGI) in cancer theranostics. The photophysical properties of LGI were studied to assess the effect of iohexol on ICG that can enhance the efficiency of ICG-based near infrared photodynamic therapy (PDT). The CT, FLI and PA imaging abilities of LGI were also investigated. Furthermore, the near infrared phototherapy of cancer cells in vitro was performed, exhibiting higher phototherapy efficacy of LGI in comparison with other ICG formulations. We conclude that LGI can serve as a highly efficient theranostic nanoplatform for multimodal (fluorescence, CT and PA) imaging and near infrared phototherapy.

Inhibiting tumor oxygen metabolism and simultaneously generating oxygen by intelligent upconversion nanotherapeutics for enhanced photodynamic therapy.

Hypoxia is one of the hallmarks of solid tumor, which heavily restricts the clinical cancer therapy treatments, especially for the oxygen (O2) -dependent photodynamic therapy (PDT). Herein, an intelligent multi-layer nanostructure was developed for decreasing the O2-consumption and elevating the O2-supply simultaneously. The cell respiration inhibitor -atovaquone (ATO) molecules were reserved in the middle mesoporous silicon layer, and thus were intelligently released at the tumor site after the degradation of gatekeeper of MnO2 layer, which effectively inhibit tumor respiration metabolism to elevate oxygen content. Meanwhile, the degradation of MnO2 layer can generate O2, further boosting oxygen content. Moreover, the inner upconversion nanostructures as the near infrared (NIR) light-transducers enable to activate photosensitizers for deep-tissue PDT. Systematic experiments demonstrate that this suppressing O2-consumption and O2-generation strategy improved oxygen supply to boost the singlet oxygen generation to eradicate cancer cells under NIR light excitation. Better still, superior trimodality imaging capabilities (computed tomography (CT), NIR-II window fluorescence, and tumor microenvironment-responsive T1-weighted magnetic resonance (MR) imaging) of the nanoplatform were evaluated. Our findings offer a promising aproach to conquer the serious hypoxia problem in cancer therapy by turning down the O2 metabolism aveneue and simultaneously generating O2.

Antireflection Enhancement by Composite Nanoporous Zeolite 3A-Carbon Thin Film.

A straightforward and effective spin-coating technique at 120 °C was investigated for the deposition of a thin nanoporous layer with antireflection properties onto glass and indium tin oxide (ITO) coated glass. A mixture of zeolite 3A powder and high iodine value vegetable oil was deposited, creating a carbonic paste with embedded nanoporous grains. Experimental results evidenced excellent broadband antireflection over the visible-near-infrared wavelength range (450-850 nm), with a diffuse reflectance value of 1.67% and 1.79%. Structural and optical characteristics stabilized over time. The results are promising for the accessible and cost-effective fabrication of an antireflective surface for optoelectronic devices.