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The upconversion luminescence (UCL) in the second near-infrared window (NIR-II) is highly attractive due to its excellent performance in high-resolution bioimaging, anticounterfeiting, and temperature sensing. However, upconvertion nanoparticles (UCNPs) are normally emitted in visible light, potentially impacting the imaging quality. Here, a monochromatic Er3+-rich (NaErF4:x%Yb@NaYF4) nanoparticles with excitation at 1532 nm and emission at 978 nm is proposed, both situated in the NIR-II region. The proper proportion of Yb3+ ions doping has a positive effect on the NIR-II emission, by enhancing the cross relaxation efficiency and accelerating the energy transfer rate. Owing to the interaction between the Er3+ and Yb3+ is inhibited at low temperatures, the UCL emission intensities at visible and NIR-II regions show opposite trend with temperature changing, which establishes a fitting formula to derive temperature from the luminous intensity ratio, promoting the potential application of UCL in NIR-II regions for the temperature sensing.
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Upconversion nanoparticles (UCNPs) represent a group of NPs that can convert near-infrared (NIR) light into ultraviolet and visible light, thus possess deep tissue penetration power with less background fluorescence noise interference, and do not induce damage to biological tissues. Due to their unique optical properties and possibility for surface modification, UCNPs can be exploited for concomitant antigen delivery into dendritic cells (DCs) and monitoring by molecular imaging. In this study, we focus on the development of a nano-delivery platform targeting DCs for immunotherapy and simultaneous imaging. OVA 254-267 (OVA24) peptide antigen, harboring a CD8 T cell epitope, and Pam3CysSerLys4 (Pam3CSK4) adjuvant were chemically linked to the surface of UCNPs by amide condensation to stimulate DC maturation and antigen presentation. The OVA24-Pam3CSK4-UCNPs were thoroughly characterized and showed a homogeneous morphology and surface electronegativity, which promoted a good dispersion of the NPs. In vitro experiments demonstrated that OVA24-Pam3CSK4-UCNPs induced a strong immune response, including DC maturation, T cell activation, and proliferation, as well as interferon gamma (IFN-γ) production. In vivo, highly sensitive upconversion luminescence (UCL) imaging of OVA24-Pam3CSK4-UCNPs allowed tracking of UCNPs from the periphery to lymph nodes. In summary, OVA24-Pam3CSK4-UCNPs represent an effective tool for DC-based immunotherapy.
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Nanopartículas , Células Dendríticas , Luz , Luminescência , Imagem Molecular , Nanopartículas/químicaRESUMO
Organic lanthanide complexes have garnered significant attention in various fields due to their intriguing energy transfer mechanism, enabling the upconversion (UC) of two or more low-energy photons into high-energy photons. In comparison to lanthanide-doped inorganic nanoparticles, organic UC complexes hold great promise for biological delivery applications due to their advantageous properties of controllable size and composition. This review aims to provide a summary of the fundamental concept and recent developments of organic lanthanide-based UC materials based on different mechanisms. Furthermore, we also detail recent applications in the fields of bioimaging and solar cells. The developments and forthcoming challenges in organic lanthanide-based UC offer readers valuable insights and opportunities to engage in further research endeavors.
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Triplet-triplet annihilation upconversion (TTA-UC) nanoparticles (NPs) have emerged as imaging probes and therapeutic probes in recent years due to their excellent optical properties. In contrast to lanthanide ion-doped inorganic materials, highly efficient TTA-UC can be generated by low excitation power density, which makes it suitable for clinical applications. In the present study, we used biodegradable poly(lactic-co-glycolic acid) (PLGA)-NPs as a delivery vehicle for TTA-UC based on the heavy metal porphyrin Platinum(II) octaethylporphyrin (PtOEP) and the polycyclic aromatic hydrocarbon 9,10-diphenylanthracene (DPA) as a photosensitizer/emitter pair. TTA-UC-PLGA-NPs were successfully synthesized according to an oil-in-water emulsion and solvent evaporation method. After physicochemical characterization, UC-efficacy of TTA-UC-PLGA-NPs was assessed in vitro and ex vivo. TTA-UC could be detected in the tumour area 96 h after in vivo administration of TTA-UC-PLGA-NPs, confirming the integrity and suitability of PLGA-NPs as a TTA-UC in vivo delivery system. Thus, this study provides proof-of-concept that the advantageous properties of PLGA can be combined with the unique optical properties of TTA-UC for the development of advanced nanocarriers for simultaneous in vivo molecular imaging and drug delivery.
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Collaborative therapy is regarded as an effective approach in increasing the therapeutic efficacy of cancer. In this work, we have proposed and validated the concept of upconversion lumienscence image guided synergy of photodynamic therapy (PDT) and radiotherapy (RT) for deep cancer, via a specially designed nanoplatform integrating near infrared (NIR) light activated luminescence upconversion and X-ray induced scintillation. Upon NIR light irradiation, the nanoplatform emits highly monochromatic red light solely for imaging the targeted cancer cells without triggering therapy; however, when the irradiation turns to a low dose of X-rays, scintillation will occur which induces effectively the PDT destroying the cancer cells together with X-ray induced RT. The novel theranostic nanoplatform is constructed in such a way that the interactions between the upconversion core and the outmost scintillating shell are blocked effectively by an inert layer between them. This structural design not only enables a nearly perfect excitation energy delivery (â¼100% at a spectral overlapping wavelength of â¼540 nm) from the outermost scintellating layer to the surface-anchored photosensitizers and so a maximum yield of radical oxygen species, but also achieves a strong NIR induced upconversion luminescence for imaging. Since PDT and RT attack different parts of a cancer cell, this synergy is more effective in destroying cancer than a single therapy, resulting in the reduction of the X-ray irradiation dosage. As a proof of principle, the theranostic effect is validated by in vitro and in vivo experiments, exhibiting the great potential of this sort of nanoplatform in deep cancer treatment.
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Internal hydroxyl impurity is known as one of the main detrimental factors affecting the upconversion (UC) efficiency of upconversion luminescence (UCL) nanomaterials. Different from surface/ligand-related emission quenching which can be effectively diminished by, e.g., core/shell structure, internal hydroxyl is easy to be introduced in synthesis but difficult to be quantified and controlled. Therefore, it becomes an obstacle to fully understand the relevant UC mechanism and improve UC efficiency of nanomaterials. Here we report a progress in quantifying and large-range adjustment of the internal hydroxyl impurity in NaYF4 nanocrystals. By combining the spectroscopy study and model simulation, we have quantitatively unraveled the microscopic interactions underlying UCL quenching between internal hydroxyl and the sensitizers and activators, respectively. Furthermore, the internal hydroxyl-involved UC dynamical process is interpreted with a vivid concept of "Survivor effect," i.e., the shorter the migration path of an excited state, the larger the possibility of its surviving from hydroxyl-induced quenching. Apart from the consistent experimental results, this concept can be further evidenced by Monte Carlo simulation, which monitors the variation of energy migration step distribution before and after the hydroxyl introduction. The new quantitative insights shall promote the construction of highly efficient UC materials.
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Side effect is one of the main factors affecting the success of cancer therapies in clinic. Patients treated with photodynamic therapy (PDT) suffer mainly from the phototoxicity due to the relatively long time blood circulation of the tumor enrichment and they have also to be protected from background light for days after the treatment. Here we introduce a new design of nanophotosensitizers in which the luminescence upconversion nanoparticles loaded with photosensitizers are self-assembled into a nanoball with the aid of a specific pH-sensitive polymer layer containing overloaded photosensitizers and quenching molecules. This design makes the therapy function "off/on" possible, i.e. only imaging during the circulation of the nanoballs ascribing to the near-infrared (NIR) photon upconversion of the nanoballs and the pH-sensitive shell. Activation of PDT solely occurs once the nanoballs are taken up by the cancer cells due to the acidic microenvironment. This design prevents effectively the photodamage of the photosensitizers during enrichment and targeting process of tumor, as validated in vitro and in vivo, which enables imaging-guided PDT treatment of deep-seated tumor in a much more relax and comfortable way for patients. This patient-friendly nanomaterial construction strategy can also be extended to other therapies.
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Nanopartículas , Neoplasias , Fotoquimioterapia , Humanos , Concentração de Íons de Hidrogênio , Neoplasias/diagnóstico por imagem , Neoplasias/tratamento farmacológico , Imagem Óptica , Fármacos Fotossensibilizantes/uso terapêutico , Microambiente TumoralRESUMO
A perfect "off" to "on" switch of the therapeutic function is very important to minimize the phototoxicity of nanoplatforms assisted imaging-guided photodynamic therapy (PDT) of cancer. Current approaches rely on preloaded photosensitizers, where the off/on state of PDT is regulated by the sensitizing light of photosensitizers. However, the photoactivities inevitably occur when imaging/diagnosis or exposure to sunlight, etc. These preloading approaches will cause the damage to normal cells and the photosensitivity to the skin. Taking upconversion photodynamic therapy as an example we report here a biorthogonal chemistry solution to circumvent this problem. The luminescence upconversion nanoparticles (UCNPs) are anchored with one handle of click reaction and targeting entity, these nanoplatforms enable the imaging/labelling/tracking, especially for imaging-guided surgery. Once they are targeted, the photosensitizers armed with the other match handle will be injected in situ and click reaction will occur between the two handles to link the photosensitizers closely with the targeted nanoplatforms in a very short time, enabling the PDT function of the nanoplatforms. Proof of principle has been demonstrated in vitro and in vivo. This approach can be readily extended to chemotherapy, radiotherapy, etc. to overcome the side effect of these therapies of cancers.
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Nanopartículas/química , Fotoquimioterapia/métodos , Fármacos Fotossensibilizantes/química , Animais , Carbonatos/química , Química Click/métodos , Citometria de Fluxo , Humanos , Células MCF-7 , Camundongos , Camundongos Nus , Polietilenoglicóis/química , Oxigênio Singlete/química , Succinimidas/químicaRESUMO
Classical Chinese poetry is a jewel in the treasure house of Chinese culture. Previous poem generation models only allow users to employ keywords to interfere the meaning of generated poems, leaving the dominion of generation to the model. In this paper, we propose a novel task of generating classical Chinese poems from vernacular, which allows users to have more control over the semantic of generated poems. We adapt the approach of unsupervised machine translation (UMT) to our task. We use segmentation-based padding and reinforcement learning to address under-translation and over-translation respectively. According to experiments, our approach significantly improve the perplexity and BLEU compared with typical UMT models. Furthermore, we explored guidelines on how to write the input vernacular to generate better poems. Human evaluation showed our approach can generate high-quality poems which are comparable to amateur poems.
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Photoswitchable materials are important in broad applications. Recently appeared inorganic photoswitchable upconversion nanoparticles (PUCNPs) become a competitive candidate to surmount the widespread issue of the organic counterparts -photobleaching. However, current PUCNPs follow solely Yb3+/Nd3+ cosensitizing mode, which results in complex multilayer doping patterns and imperfectness of switching in UV-blue region. In this work, we have adopted a new strategy to construct Nd3+ free PUCNPs-NaErF4@NaYF4@NaYbF4:0.5%Tm@NaYF4. These PUCNPs demonstrate the superior property of photoswitching. A prominent UV-blue emission from Tm3+ is turned on upon 980 nm excitation, which can be completely turned off by 800 nm light. The quasi-monochromatic red upconversion emission upon 800 nm excitation-a distinct feature of undoping NaErF4 upconversion system-endows the PUCNPs with promising image-guided photoinduced "off-on" therapy in biomedicine. As a proof-of-concept we have demonstrated the imaging-guided photodynamic therapy (PDT) of cancer, where 800 nm excitation turns off the UV-blue emission and leaves the emission at 660 nm for imaging. Once the tumor site is targeted, excitation switching to 980 nm results in UV-blue emission and the red emission. The former is used to induce PDT, whereas the latter is to monitor the therapeutic process. Our study implies that this upconversion photoswitching material is suitable for real-time imaging and image-guided therapy under temporal and spatial control.
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Nanopartículas/química , Fármacos Fotossensibilizantes/química , Raios Infravermelhos , Fotoquimioterapia , Raios UltravioletaRESUMO
A three-color warm-white organic light-emitting diode employing an efficient phosphor-phosphor type host-guest emitting system achieves efficiencies of 27.3% for external quantum efficiency and 74.5 lm W(-1) for power efficiency at a luminance of 1000 cd m(-2) , which maintained the high levels of 24.3% and 45.8 lm W(-1) at 10 000 cd m(-2) , with a stable color-rendering index of 86-87.
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A novel phosphorescent host FPYPCA possessing the bipolar charge transporting ability realizes the most efficient deep-red PhOLED, which maintains very high-level EQEs of >23% at rather a high and wide luminance range of 1000-10 000 cd m(-2).
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This paper is concerned with the task of automatically generating captions for images, which is important for many image-related applications. Examples include video and image retrieval as well as the development of tools that aid visually impaired individuals to access pictorial information. Our approach leverages the vast resource of pictures available on the web and the fact that many of them are captioned and colocated with thematically related documents. Our model learns to create captions from a database of news articles, the pictures embedded in them, and their captions, and consists of two stages. Content selection identifies what the image and accompanying article are about, whereas surface realization determines how to verbalize the chosen content. We approximate content selection with a probabilistic image annotation model that suggests keywords for an image. The model postulates that images and their textual descriptions are generated by a shared set of latent variables (topics) and is trained on a weakly labeled dataset (which treats the captions and associated news articles as image labels). Inspired by recent work in summarization, we propose extractive and abstractive surface realization models. Experimental results show that it is viable to generate captions that are pertinent to the specific content of an image and its associated article, while permitting creativity in the description. Indeed, the output of our abstractive model compares favorably to handwritten captions and is often superior to extractive methods.