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Controlling CRISPR/Cas9 gene editing at the spatiotemporal resolution level, especially for in vivo applications, remains a great challenge. Here, we developed a near-infrared (NIR) light-activated nanophotonic system (UCPP) for controlled CRISPR-Cas9 gene editing and synergistic photodynamic therapy (PDT). Lanthanide-doped upconversion nanoparticles are not only employed as carriers for intracellular plasmid delivery but also serve as the nanotransducers to convert NIR light (980 nm) into visible light with emission at 460 and 650 nm, which could result in simultaneous activation of gene editing and PDT processes, respectively. Such unique design not only achieves light-controlled precise gene editing of hypoxia-inducible factor 1α with minimal off-target effect, which effectively ameliorates the hypoxic state at tumor sites, but also facilitates the deep-seated PDT process with synergistic antitumor effect. This optogenetically activatable CRISPR-Cas9 nanosystem holds great potential for spatially controlled in vivo gene editing and targeted cancer therapy.

Understanding the dynamics of electrical signals within neuronal assemblies is crucial to unraveling complex brain functions. Despite recent advances in employing optically active nanostructures in transmembrane potential sensing, there remains room for improvement in terms of response time and sensitivity. Here, we report the development of such a nanosensor capable of detecting electric fields with a submillisecond response time at the single-particle level. We achieve this by using ferroelectric nanocrystals doped with rare-earth ions that produce upconversion (UC). When such a nanocrystal experiences a variation of surrounding electric potential, its surface charge density changes, inducing electric polarization modifications that vary, via a converse piezoelectric effect, the crystal field around the ions. The latter variation is finally converted into UC spectral changes, enabling optical detection of the electric potential. To develop such a sensor, we synthesized erbium and ytterbium-doped barium titanate crystals of ≈160 nm in size. We observed distinct changes in the UC spectrum when individual nanocrystals were subjected to an external field via a conductive atomic force microscope tip, with a response time of 100 μs. Furthermore, our sensor exhibits a remarkable sensitivity of 4.8 kV/cm/ Hz , enabling time-resolved detection of a fast-changing electric field of amplitude comparable to that generated during a neuron action potential.

As the landscape of information storage and security continues to evolve, the deployment of sophisticated anticounterfeiting strategies with robust security features and multimodal luminescent capabilities becomes imperative. In this work, Eu 3+ and Er 3+ ions are codoped into CaF 2 phosphors to achieve multimodel optical output. The self-reduction of Eu 3+ within the CaF 2 matrix gives rise to the coexistence of Eu 3+ and Eu 2+ ions, which manifests as a color transition from orange to blue as the excitation wavelength is varied from 300 to 335 nm. Moreover, the distinct temperature-dependent behaviors of Eu 3+ and Eu 2+ ions underscore the material's visible temperature-sensitive luminescence properties, characterized by remarkable thermal sensitivity ( S a = 0.0156 K -1 , S r ions adds an extra dimension, enabling the realization of color-tunable upconversion luminescence through the fine-tuning of Er -1 ). Additionally, the strategic introduction of Er 3+ ions adds an extra dimension, enabling the realization of color-tunable upconversion luminescence through the fine-tuning of Er 3+ concentration. This synergistic integration culminates in the establishment of an efficient three-path authentication model within the CaF 2 host matrix, facilitating a dynamic multicolor response to changes in the excitation wavelength and temperature. By harnessing these diverse luminescent modalities, the study delivers a versatile and potent anticounterfeiting solution, advancing the frontiers of information security.

In recent years, optical temperature probes operating in the second near-infrared (BW-II) and third near-infrared (BW-III) biological windows have garnered significant attention in the scientific community. For biological applications these probes offer distinct advantages, including enhanced tissue penetration depth, minimal autofluorescence, and a remarkable improvement in imaging sensitivity and spatial resolution. Moving toward theranostic applications, there is a growing demand for the development of materials that integrate both BW-II and BW-III thermometry systems with drug delivery functionalities. In this study, we concentrate on the development of GdPO 4 materials, utilizing both hard and sacrificial template routes to synthesize (hollow) GdPO 4 porous sea urchin-like particles. We first investigated the development of a Boltzmann-type thermometer utilizing an Yb-Er upconversion system, designed to operate within the physiological temperature range. Our exploration extends to the potential of GdPO 4 particles in near-infrared (NIR) thermometry, spanning the first, second, and third biological windows with systems like Yb-Ho-Er, Nd-Yb, and Ho-Yb, respectively. We further examined the temperature impact of the Yb-Ho-Er system on the NIR emission within a biologically relevant setting, using a phantom that replicates biological tissue. Furthermore, we illustrate the successful loading of these materials with doxorubicin (DOX·HCl), a model anticancer drug, showing these particles exhibit pH-dependent DOX release. This demonstrates the versatility of these materials as upconversion and NIR thermometers while simultaneously serving as an on-demand drug carrier. The investigation involves assessing their cytotoxicity on specific human cells (Normal Human Dermal Fibroblasts (NHDFs)), to determine their viability for potential use in biological applications. The study also investigates how effectively loading the particles with DOX enables targeted delivery to a cellular model of lymphoma (Jurkat E6-1), resulting in cell death. This comprehensive analysis highlights the promising potential of GdPO 4 particles for medical applications.

In recent years, intensive research has focused on lanthanide-doped nanoparticles (NPs) used as noncontact temperature sensors, particularly in nanomedicine. These NPs must be capable of excitation and emission within biological windows, where biological materials usually show better transparency for radiation. In this article, we propose that NPs sensitized with Er 3+ ions can be applied as temperature sensors in biological materials. We synthesized the NPs through a reaction in high-boiling solvents and confirmed their crystal structure and the formation of core@shell NPs by using X-ray diffraction, high-resolution transmission electron microscopy, and element distribution mapping within the NPs. NaErF 4 @NaYF 4 , NaYF 4 :12.5% Er 3+ , 2.5% Tm 3+ @NaYF 4 , NaYF 4 :7.5% Er 3+ @NaYF 4 , and NaYF 4 :12.5% Er 3+ , 2.5% Ho 3+ @NaYF 4 exhibited intense upconversion (UC) emission under 1532 nm laser excitation detectable also in the whole human blood. We propose that this UC results from energy transfer between Er 3+ ions and from Er 3+ to Tm 3+ or Ho 3+ codopants. To determine the mechanism of UC, we measured the dependence of the emission band intensities on the laser power densities. Importantly, we also analyzed the temperature-dependent emission of the NPs within the 295-360 K range. Based on the collected emission spectra, we calculated the luminescence intensity ratios (LIRs) of the emission bands to assess their potential for optical temperature sensing. The temperature-sensing properties varied with the concentration of Er 3+ ions and the presence of additional Tm 3+ or Ho 3+ codopants. Depending on the NP composition and the emission bands used for luminescence ratio calculations, the maximum relative temperature sensitivity ranged from 4.55%·K -1 to 1.12%·K -1 , with temperature resolution between 0.05 and 2.53 K at room temperature. Finally, as proof of using NPs as temperature sensors in biomedicine, we successfully measured the temperature-dependent emission of NaYF 4 :7.5% Er 3+ @NaYF 4 NPs dispersed in whole blood under 1532 nm excitation. We demonstrated that the ratio of Er 3+ ion emission bands changes with temperature, indicating that these NPs have potential applications in temperature sensing within biological environments. We also confirmed the properties of NPs as temperature sensors by measuring the temperature reading uncertainty and the repeatability of the LIR readings during heating-cooling cycles, thereby confirming the excellent properties of the studied systems as temperature sensors.

A new bismuth-based host material, i.e., Sr 2 BiF 7 , is explored in this work. Undoped and lanthanide ion-doped Sr 2 BiF 7 nanomaterials are prepared using a simple coprecipitation technique at 120 °C. The undoped nanomaterials exhibit a blue color under 365 nm excitation. The downshifting and upconversion photoluminescent properties of Er and Yb codoped Sr 2 BiF 7 nanomaterials are investigated. The optimum up-conversion luminescence is produced by nanomaterials doped with 5% Yb 3+ and 0.2% Er 3+ . These nanomaterials show blue and magenta colors upon excitation at 365 and 395 nm wavelengths, respectively. Sr 2 BiF 7 material doped with Er 3+ shows green emission, while the codoped Er 3+ , Yb 3+ nanomaterials exhibit an orange-red color under 980 nm light. A specific amount of polyvinyl chloride (PVC) is used for producing luminescent ink with these nanoparticles for multimode anticounterfeiting applications. The letters and patterns written with luminescent ink based on Er 3+ , Yb 3+ doped nanomaterials show blue, magenta, and orange-red colors under 365, 395, and 980 nm light, respectively. These results establish that this material can be effectively used as a multimode photoluminescent covert tag to combat counterfeiting.

Heavy-atom-free triplet-triplet annihilation (TTA) upconversion sensitized by a thermally activated delayed fluorescence (TADF) molecule is investigated in a dried gel made of a photo-cross-linked polymer as the solid-state matrix. The upconversion fluorescence quantum yields, Φ UC , of the solid-gel TTA system at different penetration depths are measured accurately based on a developed internal-reference method. It is found that Φ UC is greatest at the surface and then decreases exponentially with increasing depth, influenced by the substrate absorption. The same process is also performed in a TTA solution at different depths, but a completely different result is obtained; there is little difference for Φ UC . To the best of our knowledge, this is the first time the quantum yields at different transmission depths have been mentioned and calculated experimentally. These results illustrate the importance of accurately measuring the quantum yield of solid-phase TTA upconversion and provide a novel way to improve the solid-phase TTA quantum yield by reducing the thickness of the substrate.

Upconverting nanoparticles (UCNPs) doped with Yb 3+ and Tm 3+ are near-infrared (NIR) to ultraviolet (UV) transducers that can be used for NIR-controlled drug delivery. However, due to the low quantum yield of upconversion, high laser powers and long irradiation times are required to trigger this drug release. In this work, we report the one-step synthesis of a nanocomposite consisting of a LiYbF 4 :Tm 3+ @LiYF 4 UCNP coated with mesoporous UV-breakable organosilica shells of various thicknesses. We demonstrate that a thin shell accelerates the breakage of the shell at 1 W/cm 2 NIR light exposure, a laser power up to 9 times lower than that of conventional systems. When the mesopores are loaded with hydrophobic vitamin D 3 precursor 7-dehydrocholesterol (7-DH), shell breakage results in subsequent cargo release. Its minimal toxicity in HeLa cells and successful internalization into the cell cytoplasm demonstrate its biocompatibility and potential application in biological systems. The tunability of this system due to its simple, one-step synthesis process and its ability to operate at low laser powers opens up avenues in UCNP-powered NIR-triggered drug delivery toward a more scalable, flexible, and ultimately translational option.

In response to the ongoing quest for new, highly sensitive upconverting luminescent thermometers, this article introduces, for the first time, upconverting luminescent thermometers based on thermally induced structured phase transitions. As demonstrated, the transition from the low-temperature monoclinic to the high-temperature tetragonal structures of LiYO 2 :Yb 3+ ,Er 3+ induces multifaceted modification in the spectroscopic properties of the examined material, influencing the spectral positions of luminescence bands, energy gap values between thermally coupled energy levels, and the red-to-green emission intensities ratio. Moreover, as illustrated, both the color of the emitted light and the phase transition temperature (from 265 K, for LiYO 2 :Er 3+ , 1%Yb 3+ , to 180 K, for 10%Yb 3+ ), and consequently, the thermometric parameters of the luminescent thermometer can be modulated by the concentration of Yb 3+ sensitizer ions. Establishing a correlation between the phase transition temperature and the mismatch of ion radii between the host material and dopant ions allows for smooth adjustment of the thermometric performance of such a thermometer following specific application requirements. Three different thermometric approaches were investigated using thermally coupled levels ( S R = 1.8%/K at 180 K for 1%Yb 3+ ), green to red emission intensities ratio ( S R = 1.5%/K at 305 K for 2%Yb 3+ ), and single band ratiometric approach ( S R = 2.5%/K at 240 K for 10%Yb 3+ ). The thermally induced structural phase transition in LiYO 2 :Er 3+ ,Yb 3+ has enabled the development of multiple upconverting luminescent thermometers. This innovative approach opens avenues for advancing the field of luminescence thermometry, offering enhanced relative thermal sensitivity and adaptability for various applications.

Single particle tracking (SPT) is a powerful technique for real-time microscopic visualization of the movement of individual biomolecules within or on the surface of living cells. However, SPT often suffers from the suboptimal performance of the photon-emitting labels used to tag the biomolecules of interest. For example, fluorescent dyes have poor photostability, while quantum dots suffer from blinking that hampers track acquisition and interpretation. Upconverting nanoparticles (UCNPs) have recently emerged as a promising anti-Stokes luminescent label for SPT. In this work, we demonstrated targeted SPT using UCNPs. For this, we synthesized 30 nm diameter doped UCNPs and coated them with amphiphilic polymers decorated with polyethylene glycol chains to make them water-dispersible and minimize their nonspecific interactions with cells. Coated UCNPs highly homogeneous in brightness (as confirmed by a single particle investigation) were functionalized by immunoglobulin E (IgE) using a biotin-streptavidin strategy. Using these IgE-UCNP SPT labels, we tracked high-affinity IgE receptors (FcεRI) on the membrane of living RBL-2H3 mast cells at 37 °C in the presence and absence of antigen and obtained good agreement with the literature. Moreover, we used the FcεRI-IgE receptor-antibody system to directly compare the performance of UCNP-based SPT labels to organic dyes (AlexaFluor647) and quantum dots (QD655). Due to their photostability as well as their backgroundless and continuous luminescence, SPT trajectories obtained with UCNP labels are no longer limited by the photophysics of the label but only by the dynamics of the system and, in particular, the movement of the label out of the field of view and/or focal plane.

Harvesting full-spectrum solar energy is a critical issue for developing high-performance photocatalysts. Here, we report a hierarchical heteronanostructure consisting of upconverting, plasmonic, and semiconducting materials as a solar-to-chemical energy conversion platform that can exploit a wide range of sunlight (from ultraviolet (UV) to near-infrared). Lanthanide-doped NaYF 4 nanorod-spherical Au nanocrystals-TiO 2 ternary hybrid nanostructures with a well-controlled configuration and intimate contact between the constituent materials could be synthesized by a wet-chemical method. Notably, the prepared ternary hybrids exhibited high photocatalytic activity for the H 2 evolution reaction under simulated solar and near-infrared light irradiation due to their broadband photoresponsivity and strong optical interaction between the constituents. Through systematic studies on the mechanism of energy transfer during the photocatalysis of the ternary hybrids, we revealed that upconverted photon energy from the upconversion domain transfers to the Au and TiO 2 domains primarily through the Förster resonance energy transfer process, resulting in enhanced photocatalysis.

Designing a novel nanoplatform that integrates multimodal imaging and synergistic therapy for precision tumor nanomedicines is challenging. Herein, we prepared rare-earth ion-doped upconversion hydroxyapatite (FYH) nanoparticles as nanocarriers coated and loaded respectively with polydopamine (PDA) and doxorubicin (DOX), i.e., FYH-PDA-DOX, for tumor theranostics. The developed FYH-PDA-DOX complexes exhibited desirable photothermal conversion, pH/near-infrared-irradiation-responsive DOX release, and multimodal upconversion luminescence/computed tomography/magnetic resonance imaging performance and helped monitor the metabolic distribution process of the complexes and provided feedback to the therapeutic effect. Upon 808 nm laser irradiation, the fast release of DOX facilitated the photothermal-chemotherapy effect, immunogenic cell death, and antitumor immune response. On combining with the anti-programmed cell death 1 ligand 1 antibody, an enhanced tri-mode photothermal-chemo-immunotherapy synergistic treatment against tumors can be realized. Thus, this treatment elicited potent antitumor immunity, producing appreciable T-cell cytotoxicity against tumors, amplifying tumor suppression, and extending the survival of mice. Therefore, the FYH-PDA-DOX complexes are promising as a smart nanoplatform for imaging-guided synergistic cancer treatment.

Photon upconversion (UC) based on triplet-triplet annihilation is a very promising phenomenon with potential application in several areas, though, due to the intrinsic mechanism, the achievement of diffusion-limited solid materials with air-stable UC is still a challenge. Herein, we report UC coordination polymer nanoparticles (CPNs) combining sensitizer and emitter molecules especially designed with alkyl spacers that promote the amorphous character. Beyond the characteristic constraints of crystalline MOFs, amorphous CPNs facilitate high dye density and flexible ratio tunability. To show the universality of the approach, two types of UC-CPNs are reported, exhibiting highly photostable UC in two different visible spectral regions. Given their nanoscale, narrow size distribution, and good chemical/colloidal stability in water, the CPNs were also successfully printed as anticounterfeiting patterns and used to make highly transparent and photostable films for luminescent solar concentrators, both showing air-stable UC.

As the world is faced with the coronavirus disease 2019 (COVID-19) pandemic, photocatalytic antibacterial ceramics can reduce the consumption of disinfectants and improve the safety of the public health environment. However, these antibacterial ceramics are often limited by poor stability and low light utilization efficiency. Herein, an antibacterial ceramic was developed via the method of facile in situ etching of upconversion glass-ceramics (UGC) (FIEG) with HCl, in which the BiOCl nanosheets were in situ grown on the surface of GC to improve its stability and antibacterial activity. The results suggest that the upconversion antibacterial ceramics can harvest and utilize near-infrared (NIR) photons efficiently, which display notable antibacterial activity for Escherichia coli ( E. coli ) under NIR (≥780 nm) and visible light (420-780 nm) irradiation, with a maximum inactivation rate of 7.5 log in 30 min. Meanwhile, in the cycle experiment, more than 6 log inactivation of E. coli was achieved using an antibacterial ceramic sheet after 2-h NIR light irradiation, and the stability of the antibacterial ceramic was discussed. Furthermore, the reactive species, fluorescence-based live/dead cells, and cell structure of bacteria were analyzed to verify the antibacterial mechanism. This study provides a promising strategy for the construction of efficient and stable antibacterial ceramics.

Whereas lanthanide-based upconverting particles are promising candidates for several micro- and nanothermometry applications, understanding spatially varying effects related to their internal dynamics and interactions with the environment near the surface remains challenging. To separate the bulk from the surface response, this work proposes and performs hyperspectral sample-scanning experiments to obtain spatially resolved thermometric measurements on single microparticles of NaYF 4 : Yb 3+ ,Er 3+ . Our results showed that the particle's thermometric response depends on the excitation laser incidence position, which may directly affect the temperature readout. Furthermore, it was noticed that even minor temperature changes (<1 K) caused by room temperature variations at the spectrometer CCD sensor used to record the luminescence signal may significantly modify the measurements. This work also provides some suggestions for building 2D thermal maps that shall be helpful for understanding surface-related effects in micro- and nanothermometers using hyperspectral techniques. Therefore, the results presented herein may impact applications of lanthanide-based nanothermometers, as in the understanding of energy-transfer processes inside systems such as nanoelectronic devices or living cells.

Lanthanide-ion-doped upconversion materials have been widely used in biological detection, bioimaging, displays, and anticounterfeiting due to their abilities of real-time readings, high spatial resolution, and deep tissue penetration. The typically long fluorescence lifetimes of rare-earth nanoparticles, in the microsecond to millisecond range, make them useful in interference-free lifetime detection imaging. Most detection systems are accompanied by fluorescence resonance energy transfer (FRET), in which the lifetime of the luminescence center can be used as a signal to reveal the degree of FRET. Due to the complex energy level structure and complex energy transfer processes, the apparent lifetimes of upconversion nanoparticles (UCNPs) do not simply equal the decay time of the corresponding energy level, inducing an insignificant lifetime change in the upconversion detection system. In this study, the relationship between the apparent luminescence lifetime of upconversion and the decay rate of each energy level was studied by numerical simulations. It was proved that the apparent lifetime of the emission at 540 nm was mainly affected by the decay rate of Yb 3+ . We then constructed a nanocomposite with Rh1000 fluorophores loaded onto the surface of UCNPs to quench the sensitizer Yb 3+ . We found that the lifetime of the emission at 540 nm from Er 3+ was affected to a large extent by the number of attached Rh1000 molecules, proving the greater influence on the apparent luminescent lifetime of Er 3+ at 540 nm caused by quenching the Yb 3+ excited state. The qualitative detection of hypochlorous acid (HClO) in vivo was also achieved using the luminescent lifetime as the signal.

Luminescent upconversion nanocrystals (UCNCs) have become one of the most promising nanomaterials for biosensing, imaging, and theranostics. However, their ultimate translation into robust luminescent probes for daily use in biological and medical laboratories requires comprehension and control of the many possible deactivation pathways that cause upconversion luminescence (UCL) quenching. Here, we demonstrate that thorough modeling of UCL rise and decay kinetics using a freely accessible software can identify the UCL quenching mechanisms in small (<40 nm) UCNCs with spatial and temporal resolution. Applied to the most relevant β-NaYF 4 :Yb 3+ ,Er 3+ UCNCs, our model showed that only a few distinct nonradiative low-energy transitions were deactivated via specific solvent and ligand vibrations with a strong downstream effect on the population and depopulation dynamics of the emitting states. UCL quenching could penetrate ca. 4 nm inside the UCNC, which resulted in significant size-dependent changes of UCL intensities and spectra. Despite the large surface-to-volume ratios and UCL quenching via the UCNC surface, we found strong contributions of the outer layers to the overall UCL, which will be highly important for the design of UCNPs to investigate biomolecular interactions via distance-dependent energy transfer methods. Our advanced kinetic model is easily scalable to different UCNC architectures, environments, and energy transfer interactions such that relatively simple modeling of UCL kinetics can be used for efficiently optimizing UCNCs for their final application as practical luminescent probes.

Dual-mode luminescent nanomaterials have outstanding performance in biosensing and multistage anticounterfeiting. Herein, we report the tuning of optical attributes of lanthanide-doped nanoparticles (NPs) via simultaneous binary cation exchange. We show that cation exchange of NaYF 4 :Yb/Er (18/2 mol %)@NaLnF 4 (Ln = Y and Gd) NPs with a combination of Ce 3+ and Tb 3+ enables the resultant nanoparticles to exhibit both upconversion and downshifting emissions upon excitation at 980 and 254 nm, respectively. We find that in addition to introducing downshifting emission attributes, the use of Tb 3+ ions allows conservation of the integrity of the parent core@shell NPs by decreasing the dissociation tendency caused by Ce 3+ ions during the cation exchange. The upconversion color output can be tuned from green to red and blue by changing lanthanide combinations in the core NPs. This work not only provides an effective strategy for the optical tuning of lanthanide-doped NPs but also builds a platform for probing the difference in the reactivity nature of lanthanides.

Efficient and long-term stable triplet-triplet annihilation upconversion (TTA-UC) can be achieved by effectively protecting the excited organic triplet ensembles from photoinduced oxygen quenching, and discovery of a new material platform that promotes TTA-UC in ambient conditions is of paramount importance for practical applications. In this study, we present the first demonstration of an organic nonparaffin phase-change material (PCM) as an air-tolerant medium for TTA-UC with a unique solid-liquid phase transition in response to temperature variation. For the proposed concept, 2,4-hexadien-1-ol is used and extensively characterized with several key features, including good solvation capacity, mild melting point (30.5 °C), and exclusive antioxidant property, enabling a high-efficiency, low-threshold, and photostable TTA-UC system without energy-intensive degassing processes. In-depth characterization reveals that the triplet diffusion among the transient species, i.e., 3 sensitizer* and 3 acceptor*, is efficient and well protected from oxygen quenching in both aerated liquid- and solid-phase 2,4-hexadien-1-ol. We also propose a new strategy for the nanoencapsulation of PCM by employing hollow mesoporous silica nanoparticles as vehicles. This scheme is applicable to both aqueous- and solid-phase TTA-UC systems as well as suitable for various applications, such as thermal energy storage and smart drug delivery.

Integrating chemodynamic therapy (CDT) and photodynamic therapy (PDT) into one nanoplatform can produce much more reactive oxygen species (ROS) for tumor therapy. Nevertheless, it is still a great challenge to selectively generate sufficient ROS in tumor regions. Meanwhile, CDT and PDT are restricted by insufficient H 2 O 2 content in the tumor as well as by the limited tumor tissue penetration of the light source. In this study, a smart pH/ROS-responsive nanoplatform, Fe 2+ @UCM-BBD, is rationally designed for tumor combination therapy. The acidic microenvironment can induce the pH-responsive release of doxorubicin (DOX), which can induce tumor apoptosis through DNA damage. Beyond that, DOX can promote the production of H 2 O 2 , providing sufficient materials for CDT. Of note, upconversion nanoparticles at the core can convert the 980 nm light to red and green light, which are used to activate Ce6 to produce singlet oxygen ( 1 O 2 ) and achieve upconversion luminescence imaging, respectively. Then, the ROS-responsive linker bis-(alkylthio)alkene is cleaved by 1 O 2 , resulting in the release of Fenton reagent (Fe 2+ ) to realize CDT. Taken together, Fe 2+ @UCM-BBD exhibits on-demand therapeutic reagent release capability, excellent biocompatibility, and remarkable tumor inhibition ability via synergistic chemo/photodynamic/chemodynamic combination therapy.

Despite the unique ability of lanthanide-doped upconversion nanoparticles (UCNPs) to convert near-infrared (NIR) light to high-energy UV-vis radiation, low quantum efficiency has rendered their application unpractical in biomedical fields. Here, we report anatase titania-coated plasmonic gold nanorods decorated with UCNPs (Au NR@aTiO 2 @UCNPs) for combinational photothermal and photodynamic therapy to treat cancer. Our novel architecture employs the incorporation of an anatase titanium dioxide (aTiO 2 ) photosensitizer as a spacer and exploits the localized surface plasmon resonance (LSPR) properties of the Au core. The LSPR-derived near-field enhancement induces a threefold boost of upconversion emissions, which are re-absorbed by neighboring aTiO 2 and Au nanocomponents. Photocatalytic experiments strongly infer that LSPR-induced hot electrons are injected into the conduction band of aTiO 2 , generating reactive oxygen species. As phototherapeutic agents, our hybrid nanostructures show remarkable in vitro anticancer effect under NIR light [28.0% cancer cell viability against Au NR@aTiO 2 (77.3%) and UCNP@aTiO 2 (98.8%)] ascribed to the efficient radical formation and LSPR-induced heat generation, with cancer cell death primarily following an apoptotic pathway. In vivo animal studies further confirm the tumor suppression ability of Au NR@aTiO 2 @UCNPs through combinatorial photothermal and photodynamic effect. Our hybrid nanomaterials emerge as excellent multifunctional phototherapy agents, providing a valuable addition to light-triggered cancer treatments in deep tissue.

Photochemical upconversion (UC) via triplet-triplet annihilation (TTA) has attracted considerable attention for its potential applications in solar energy conversion, photocatalysis, and bioimaging. Achieving a large anti-Stokes shift in photochemical UC is appealing but still a great challenge, especially for purely organic sensitizers. Here, we develop solid-state TTA UC systems with metal- and heavy atom-free dyes as the sensitizers, which sensitize the 9,10-diphenylanthracene acceptor through thermally activated triplet-triplet energy transfer. Solid-state UC emission with remarkable anti-Stokes shifts up to 1.10 eV is achieved owing to an evident enthalpy gain by the endothermic sensitization. The solid upconverter shows air-stable UC emission and potentials in dual-mode anti-counterfeiting and encryption applications. The present UC approach involving thermally activated sensitization enabled by purely organic dyes provides a versatile strategy to develop TTA UC materials with large anti-Stokes shift, air-tolerant emission, and environmental compatibility, which would have promising applications in information encryption, photochemical conversion, and bioimaging.

Lanthanide-based upconversion (UC) allows harvesting sub-bandgap near-infrared photons in photovoltaics. In this work, we investigate UC in perovskite solar cells by implementing UC single crystal BaF 2 :Yb 3+ , Er 3+ at the rear of the solar cell. Upon illumination with high-intensity sub-bandgap photons at 980 nm, the BaF 2 :Yb 3+ , Er 3+ crystal emits upconverted photons in the spectral range between 520 and 700 nm. When tested under terrestrial sunlight representing one sun above the perovskite's bandgap and sub-bandgap illumination at 980 nm, upconverted photons contribute a 0.38 mA/cm 2 enhancement in the short-circuit current density at lower intensity. The current enhancement scales non-linearly with the incident intensity of sub-bandgap illumination, and at higher intensity, 2.09 mA/cm 2 enhancement in current was observed. Hence, our study shows that using a fluoride single crystal like BaF 2 :Yb 3+ , Er 3+ for UC is a suitable method to extend the response of perovskite solar cells to near-infrared illumination at 980 nm with a subsequent enhancement in current for very high incident intensity.

Lead halide perovskite quantum dots (PQDs) exhibit excellent photoelectric and optical properties, but their poor stability and low multiphoton absorption efficiency greatly limit their biological applications. Efforts have been made to combine upconversion nanoparticles (UCNPs) with PQDs to produce a composite material that is NIR-excitable, upconverting, and emission-tunable due to the unique optical properties of UCNPs, which converts tissue-penetrating near-infrared light into visible light based on an upconversion multiphoton excitation process. However, it is challenging to make such a nanocrystal heterostructure and maintain good optical properties and stability of both UCNPs and PQDs because they have different crystal structures. Here, we report the synthesis of heterostructured UCNP-PQD nanocrystals to bring hexagonal-phase NaYF 4 UCNPs and cubic-phase CsPbBr 1 X 2 PQDs in close proximity in a single nanocrystal, leading to efficient Förster resonance energy transfer (FRET) from the UCNP to the PQD under NIR excitation, as compared to their counterparts in solution. Moreover, by further improving the lattice matching between the UCNP and PQD using Gd to replace Y, heterostructured CsPbBr 3 -NaGdF 4 :Yb,Tm nanocrystals are successfully synthesized, with much enhanced luminescence and stability at high temperatures or in polar solvents or under continuous ultraviolet light excitation as compared to those of the CsPbBr 3 -NaYF 4 :Yb,Tm nanocrystals and pure PQDs.

Fluorophores with multifunctional properties known as rare-earth-doped nanoparticles (RENPs) are promising candidates for bioimaging, therapy, and drug delivery. When applied in vivo , these nanoparticles (NPs) have to retain long blood-circulation time, bypass elimination by phagocytic cells, and successfully arrive at the target area. Usually, NPs in a biological medium are exposed to proteins, which form the so-called "protein corona" (PC) around the NPs and influence their targeted delivery and accumulation in cells and tissues. Different surface coatings change the PC size and composition, subsequently deciding the fate of the NPs. Thus, detailed studies on the PC are of utmost importance to determine the most suitable NP surface modification for biomedical use. When it comes to RENPs, these studies are particularly scarce. Here, we investigate the PC composition and its impact on the cellular uptake of citrate-, SiO 2 -, and phospholipid micelle-coated RENPs (LiYF 4 :Yb 3+ ,Tm 3+ ). We observed that the PC of citrate- and phospholipid-coated RENPs is relatively stable and similar in the adsorbed protein composition, while the PC of SiO 2 -coated RENPs is larger and highly dynamic. Moreover, biocompatibility, accumulation, and cytotoxicity of various RENPs in cancer cells have been evaluated. On the basis of the cellular imaging, supported by the inhibition studies, it was revealed that RENPs are internalized by endocytosis and that specific endocytic routes are PC composition dependent. Overall, these results are essential to fill the gaps in the fundamental understanding of the nano-biointeractions of RENPs, pertinent for their envisioned application in biomedicine.

Fluoride-based compounds doped with rare-earth cations are the preferred choice of materials to achieve efficient upconversion, of interest for a plethora of applications ranging from bioimaging to energy harvesting. Herein, we demonstrate a simple route to fabricate bright upconverting films that are transparent, self-standing, flexible, and emit different colors. Starting from the solvothermal synthesis of uniform and colloidally stable yttrium fluoride nanoparticles doped with Yb 3+ and Er 3+ , Ho 3+ , or Tm 3+ , we find the experimental conditions to process the nanophosphors as optical quality films of controlled thickness between few hundreds of nanometers and several micrometers. A thorough analysis of both structural and photophysical properties of films annealed at different temperatures reveals a tradeoff between the oxidation of the matrix, which transitions through an oxyfluoride crystal phase, and the efficiency of the upconversion photoluminescence process. It represents a significant step forward in the understanding of the fundamental properties of upconverting materials and can be leveraged for the optimization of upconversion systems in general. We prove bright multicolor upconversion photoluminescence in oxyfluoride-based phosphor transparent films upon excitation with a 980 nm laser for both rigid and flexible versions of the layers, being possible to use the latter to coat surfaces of arbitrary shape. Our results pave the way toward the development of upconverting coatings that can be conveniently integrated in applications that demand a large degree of versatility.

Fluorescence intensity ratio-based temperature sensing with a self-referencing characteristic is highly demanded for reliable and accurate sensing. Although enormous efforts have been devoted to explore high-performance luminescent temperature probes, it remains a daunting challenge to achieve highly relative sensitivity which determines temperature resolution. Herein, we employ a novel strategy to achieve temperature probes with ultrahigh relative sensitivity through integrating both positive and negative thermal quenching effect into a hydrogel. Specifically, Er 3+ ions show evidently a positive thermal quenching effect in Yb/Er:NaYF 4 @NaYF 4 nanocrystals while Nd 3+ and Tm 3+ ions in a Yb 2 W 3 O 12 bulk exhibit prominently a negative thermal quenching effect. With elevating temperature from 313 to 553 K, the fluorescence intensity ratio of Er (540 nm) to Nd (799 nm) and Tm (796 nm) to Er (540 nm) is significantly decreased about 1654 times and increased about 14,422 times, respectively. The maximum relative sensitivity of 15.3% K -1 at 553 K and 23.84% K -1 at 380 K are achieved. The strategy developed in this work sheds light on highly sensitive probes using lanthanide ion-doped materials.

Crosstalk-free reconstruction of multiple images within a single element can greatly boost the image capacity and information security. We herein demonstrate a viable approach by integrating upconversion and holographic images into a single holographic polymer nanocomposite. The holographic image is reconstructed through photopolymerization-induced phase separation under a 460 nm laser and identifiable under room light, while the upconversion image recognizable under a 980 nm laser is photopatterned via spatially photobleaching of the dye embedded in the upconversion nanoparticle (UCNP) shell under 365 nm light. To this end, the lanthanide-doped UCNP in the core/shell/shell nanostructure of NaYF 4 :20%Yb 3+ ,0.5%Tm 3+ @NaYF 4 @SiO 2 is designed, and the dye, fluorescein isothiocyanate (FITC), is fixed in the outermost SiO 2 shell via the amine-isothiocyanate reaction and the subsequent sol-gel reaction. Energy transfer from the core of the UCNP to FITC embedded in the shell is critical to boosting the contrast of the upconversion image, which dials the emission color from blue to yellow-green. It is also found that the upconversion image can be brightened by increasing the UCNP content while the holographic image is weakened when the UCNP content is over 15 wt %. This study paves a new way toward advanced anticounterfeiting.

Biomarker-activatable theranostic formulations offer the potential for removing specific tumors with a high diagnostic accuracy and a significant pharmacological effect. Herein, we developed a novel activatable theranostic nanoformulation UAS-PD [upconversion nanophosphor (UCNP)-aptamer/ssDNA-pyropheophorbide-a (PPA)-doxyrubicin (DOX)], which can recognize specific cancer cells with sensitivity and trigger the localized photodynamic destruction and enhanced chemotherapy. UAS-PD was constructed by the conjugation of UCNPs and aptamer probes containing the photosensitizer PPA and the chemotherapeutic drug DOX. When cancer cells are present, the UAS-PD specifically binds to PTK7, an overexpressed protein present on the surface of cancer cells, through conformational recombination of the aptamer structure and switches its upconversion luminescence from 655 to 540 nm. This long-lived ratiometric optical signal provides an ultrasensitive detection limit as low as 3.9 nM for PTK7. Changes in the conformation of UAS-PD can also induce PPA to approach UCNPs, which can produce cytotoxic singlet oxygens under near-infrared excitation to destroy the cell membrane and enhance its permeability for the simultaneously released DOX that targets cellular DNA degradation, which results in a highly effective tumor-killing effect by synergistic extra-intracellular sequential damage.

DNA methylation is a kind of a crucial epigenetic marker orchestrating gene expression, molecular function, and cellular phenotype. However, manipulating the methylation status of specific genes remains challenging. Here, a clustered regularly interspaced palindromic repeats-Cas9-based near-infrared upconversion-activated DNA methylation editing system (CNAMS) was designed for the optogenetic editing of DNA methylation. The fusion proteins of photosensitive CRY2PHR, the catalytic domain of DNMT3A or TET1, and the fusion proteins for CIBN and catalytically inactive Cas9 (dCas9) were engineered. The CNAMS could control DNA methylation editing in response to blue light, thus allowing methylation editing in a spatiotemporal manner. Furthermore, after combination with upconversion nanoparticles, the spectral sensitivity of DNA methylation editing was extended from the blue light to near-infrared (NIR) light, providing the possibility for remote DNA methylation editing. These results demonstrated a meaningful step forward toward realizing the specific editing of DNA methylation, suggesting the wide utility of our CNAMS for functional studies on epigenetic regulation and potential therapeutic strategies for related diseases.

This study presents a controlled synthesis of NaYbF 4 @NaYF 4 core-shell upconversion nanoparticles using the hot-injection technique. NaYF 4 shells with tunable morphologies including long-rod, short-rod, and quasi-sphere are grown on identical NaYbF 4 core nanoparticles by controlled injection of acetate or trifluoroacetate precursors. Mechanistic investigations reveal that anisotropic interfacial strain accounts for the preferential growth of shell layers along the c -axis. However, the strain effect can be offset by the fast injection of shell precursors, leading to nearly isotropic growth of NaYF 4 shells over the NaYbF 4 core nanoparticles. The core-shell nanoparticles are further modified with DNA molecules and incubated with adenocarcinomic human alveolar basal epithelial cells. Based on a combination of characterizations by flow cytometry and confocal microscopy, favorable cellular uptake and DNA delivery are observed for the quasi-sphere nanoparticles, owing to the high dispersibility and easy membrane wrapping. The method described here could be extended to synthesize other types of functional nanostructures for the study of morphology-dependent properties.

Nanocrystals having single-band red emission under near-infrared (NIR) excitation through the upconversion process offer great advantages in terms of enhanced cellular imaging in in vitro and in vivo experiments in the biological window (600-900 nm), as a security ink, in photothermal therapy (PTT), in photodynamic therapy (PDT), and so forth but are challenging for materials scientists. In this work, we report for the first time the preparation of a super bright red emitter at 655 nm from monodispersed NaErF 4 :0.5%Tm@NaYF 4 :20%Yb nanocrystals (core@active shell). This phosphor exhibits 35 times stronger photoluminescence as compared to NaErF 4 :0.5%Tm@NaYF 4 (core@inactive shell). Here, an Er 3+ -enriched host matrix works simultaneously as an activator and a sensitizer under NIR excitation. Upconversion red emission at 655 nm arises due to the electronic transition of Er 3+ via the involvement of a three-photon absorption (expected to be a two-photon absorption), which has been confirmed via a power-dependent luminescence study. Tm 3+ ions incorporated into the core with the active shell act as trapping centers, which promote the red band emission via the back-energy transfer process. Moreover, the active shell containing Yb 3+ ions efficiently transfers the energy to the Er 3+ -enriched core, which suppresses the nonradiative channel rate, and Tm 3+ ions act as trapping centers, which reduce the luminescence quenching via reduction of energy migration to the surface of the host lattice. Also, we have shown the potential applications of these nanocrystals: cellular imaging through downconversion and upconversion processes and security ink.

Organic-inorganic hybrid perovskite solar cells (PSCs) have achieved rapid progress in this decade. However, the limited solar spectral utilization has restricted the further improvement of performance of the PSCs. One promising approach to solving this problem is utilizing IR to visible upconversion nanoparticles (UCNPs) in the PSC devices. Despite being confined by the lower quantum yield (QY) and smaller absorption cross section of the traditional UCNPs, their application is still a great challenge. In this work, the IR-783 dye-sensitized core/shell NaYF 4 :Yb 3+ , Er 3+ @NaYF 4 :Yb 3+ , and Nd 3+ UCNPs were synthesized and coupled with plasmonic Au nanorods films. Thereby, the upconversion luminescence (UCL) intensity was enhanced by about 120-fold, whereas the luminescent QY was improved from 0.2 to 1.2%. Then, the composite UCNPs were assembled on the SnO 2 layer of the PSCs, which resulted in the power conversion efficiency (PCE) increasing from 19.4 to 20.5% under simulated 100 mw/cm 2 AM 1.5G irradiation. Up to now, it is the highest PCE for the PSCs based on various upconversion devices. Under the irradiation of a sun concentrator (1 W/cm 2 ), the PCE of the device can be further improved to 21.1%. In-depth studies indicate that under standard sunlight irradiation, the improvement of PCE is due to both the IR to visible UCL and the scattering effect of the UCNPs. Under irradiation of a sun concentrator, the UCL contributes dominantly to the further improvement of PCE. This work provides an effective method for increasing the luminescent QY utilized in the PSCs and is of great significance for future PSCs that use sunlight concentrator.

Inorganic photochromic material is an available medium to obtain optical information storage. The photochromic property of the inorganic material is mainly from the defects of the host. However, the formation of defects in the host is uncontrollable, in particular, the revisable formation and removement of defects are difficult. Thus, there are few inorganic materials with the revisable photochromism upon the entire light stimulation. Therefore, it is an urgent need to find a suitable approach to design inorganic photochromic materials. Here, the photochromic PbWO 4 :Yb 3+ , Er 3+ ceramic was designed with the help of valence state change of W 6+ → W 5+ and Pb 2+ → Pb 4+ . Upon the 532 nm laser stimulation, the photochromism of the PbWO 4 :Yb 3+ , Er 3+ ceramic was obtained based on the Pb 2+ + h ν (532 nm) → Pb 4+ + 2e - and W 6+ + e - + h ν (532 nm) → W 5+ reaction, resulting in the optical information writing. Under the stimulation of an 808 nm laser, the written optical information was erased based on the W 5+ + h ν (808 nm) → W 6+ + e - and Pb 4+ + 2e - + h ν (808 nm) → Pb 2+ reaction. In addition, the photochromism-induced upconversion emission modification was obtained in the PbWO 4 :Yb 3+ , Er 3+ ceramic, realizing the effective and nondestructive reading out of optical information. The cyclic experiment demonstrated a good reproducibility of both photochromism and upconversion emission modification, exhibiting the potential application of the PbWO 4 :Yb 3+ , Er 3+ ceramic as the optical data storage medium.

Upconversion nanoparticles (UCNPs) have been used effectively as light transducers to convert near-infrared irradiation to short-wavelength emissions for photoactivation in deep tissues. UCNPs with single/multiple emissions under excitation at a single wavelength can be used for simultaneous activation of single or multiple photosensitive molecules only; an ideal multifunctional UCNP nanoplatform should not only have the ability to load multiple molecules but also should activate them at the right time with the right dose when necessary, depending upon the application for which it is used. The control of many biological processes requires complex (simultaneous or subsequent) photoactivation at different time points. Subsequent photoactivation requires UCNPs with orthogonal fluorescence emissions, which can be controlled independently. So far, there are only a few reports about UCNPs with orthogonal emissions. Synthesis of these orthogonal emission nanoparticles is complicated and tedious because nanoparticles with multiple shells need to be synthesized, and different lanthanide ions need to be doped into different shells. Also, there is no flexibility for changing the doped ions and emission profile after the nanoparticles are produced. Here, we have demonstrated a versatile method to modularly assemble individual UCNPs into UCNP clusters (UCNPs-C) with adjustable emissions. The synthesis is much easier, and there is a lot of flexibility in changing the particle size, shape, doped ions, and emission profile. We have demonstrated the use of such UCNPs-C for color encoding at the nanoscale. We further designed orthogonal photoactivatable UCNPs-C (OP-UCNPs-C), which can be independently activated under 980 nm excitation for red emission and 808 nm excitation for UV/blue emission. These OP-UCNPs-C were used for independent activation of processes for cell imaging (980 nm) and drug delivery (808 nm). In comparison to the traditional nonprogrammed activation, a programmed controlled imaging and drug delivery process could guarantee highly targeted and enhanced cell death of cancerous cells.

Greatly enhanced upconversion luminescence was demonstrated by integrating the core-shell upconversion nanorods with the Ag nanogratings. Both the Ag nanogratings and upconversion nanorods were fabricated/synthesized in a facile, cost-effective, high-throughput way. Experimental results showed that the upconversion luminescence intensity of Er 3+ in the core-shell upconversion nanorods can be well tuned and enhanced by changing the shell thickness and the period of the Ag nanograting. The underlying physical mechanism for the upconversion luminescence enhancement was attributed to the plasmonically enhanced near infrared broadband absorption of the periodic Ag nanograting and the localized surface plasmon resonance of Ag nanocrystals. The maximum enhanced factors of 523 nm, 544 nm (green emission), and 658 nm (red emission) of Er 3+ ions excited at 980 nm are 3.8-, 5.5-, and 4.6-folds, respectively. Our fabrication approach and results suggest that such a simple integration is potentially useful for biosensing/imaging and anti-counterfeiting applications.

The development of a stimulus-responsive nanosystem provides an effective method for improving the accuracy and efficiency of chemotherapy. Meanwhile, traditional photodynamic therapy (PDT) has been substantially restricted by the low dosage of photosensitizer and limited penetration depth of the ultraviolet (UV) or visible light used for excitation. Here, we designed a smart multifunctional nanoplatform by coating core-shell composite mesoporous silica-encapsulated upconversion nanoparticles and chlorin e6 (Ce6) with degradable calcium phosphate, followed by the loading of doxorubicin (DOX). In our structure, the as-synthesized nanoplatform exhibits high responsiveness to a low pH value and degrades rapidly in the weakly acidic tumor microenvironment, allowing the quick release of loaded DOX in tumor sites. Interestingly, the loaded DOX, whose release depends on the pH value and positively correlates with the calcium-ion concentration, enables drug release to be monitored in real time. Combined with photosensitizer Ce6-induced PDT triggered by an 808 nm near-infrared light, synergistic chemo-photodynamic therapy is achieved, thus leading to a highly efficient anticancer treatment in vitro and in vivo. Importantly, the inherent properties of rare earth ions (Gd 3+ , Yb 3+ , and Nd 3+ ) make the nanoplatform possess UCL, MRI, and CT trimode imaging capabilities, thus achieving a multiple imaging modality-guided synergistic therapy.

Up to now, the rising edge of the upconversion process does not receive due attention. Herein, a demonstration utilizing the feature of the rising edge to practically detect the linear-velocity of an object is presented. Typically, upconversion processes with different numbers of participant photons would exhibit diversity in the rising edge. On this account, when the emitter is moving, the emission intensity ratio of different multiphoton processes will vary with changing linear-velocity, which enables accurate speed detection through spectral analysis. To illustrate this principle, in this work, the modeling and numerical simulation were first performed, and then experimental demonstration was carried out in which core-shell upconversion nanocrystals were elaborately designed and fabricated as the speed sensing probe to calibrate the speed of a homemade turnplate. It is believed that the present work will exploit a novel speed sensing method and find a new application for lanthanide-doped upconversion materials.

Upconversion nanoparticles (UCNPs) are prospective platforms for bioimaging and phototherapy, but a critical bottleneck is the limited brightness due to the faint absorptivity of lanthanide ions and the low quantum yield. To circumvent this problem, we herein propose our strategy to reconstruct the energy cascade of UCNPs using semiconductor quantum dots (QDs) as light sensitizer of Nd 3+ /Yb 3+ codoped UCNPs. Ag 2 Se QDs with strong absorption at 808 nm acted as efficient antenna and transferred their energy to Yb 3+ via a resonance energy transfer process, significantly enhancing the luminescence of UCNPs. This nanocomposite was then combined with Rose Bengal and applied for photodynamic therapy. Both in vitro and in vivo studies revealed the introduction of QDs improved the therapeutic performance remarkably. Our study suggests Ag 2 Se QDs with excellent photophysical properties can be promising agents to overcome the shortcomings of UCNPs and further strengthen their applications.

The tissue penetration depth of light and the singlet oxygen ( 1 O 2 ) generation efficiency of photosensitizers (PSs) are the two main factors that determine the effectiveness of photodynamic therapy for tumors. Herein, we report a novel strategy to prepare a multifunctional upconversion photosensitizer (UCPS) based on the host/guest nanoarchitecture. By a simple reprecipitation method, host/guest tetracene/pentacene nanorods (Tc/Pc NRs) were synthesized for enhancing triplet-triplet annihilation-upconversion (TTA-UC) or two-photon excited emission and 1 O 2 generation efficiency upon 650 or 808 nm excitation. Tc/Pc NRs had higher 1 O 2 quantum yield (74%) than Tc NRs (28%) upon 650 nm laser irradiation. The proposed mechanism is that doping Pc molecules into Tc NRs induces intermediate states between S 0 and S 1 , shortening the energy gap for 1 O 2 generation and resulting in TTA-UC emission. Equally important, with 808 nm fs laser excitation, Tc/Pc NRs showed an enhanced 1 O 2 generation efficiency and two-photon absorption cross section (σ) compared with Tc NRs. In addition, when the tumors in mice were exposed to Tc/Pc NRs with 650 or 808 nm wavelength irradiation, the tumor inhibition rates achieved 99 and 95%, respectively. This work opens new perspectives for exploring novel nano-UCPSs for biomedical applications.

In situ glass crystallization is an effective strategy to integrate lanthanide-doped upconversion nanocrystals into amorphous glass, leading to new hybrid materials and offering an unexploited way to study light-particle interactions. However, the precipitation of Sc 3+ -based nanocrystals from glass is rarely reported and the incorporation of lanthanide activators into the Sc 3+ -based crystalline lattice is formidably difficult owing to their large radius mismatch. Herein, it is demonstrated that lanthanide dopants with smaller ionic radii can act as nucleating agents to promote the nucleation/growth of KSc 2 F 7 nanocrystals in oxyfluoride aluminosilicate glass. A series of structural and spectroscopic characterizations indicate that Ln-dopant-induced K/Sc/Ln/F amorphous phase separation from glass is an essential prerequisite for the precipitation of KSc 2 F 7 and the partition of Ln dopants into the KSc 2 F 7 lattice by substituting Sc 3+ ions. Importantly, modifying the Ln-to-Sc ratio in glass enables to control competitive crystallization of KSc 2 F 7 and Ln-based (KYb 2 F 7 , KLu 2 F 7 , and KYF 4 ) nanocrystals and produce dual-phase fluoride-embedded nanocomposites with distinct crystal fields. Consequently, tunable multicolor upconversion luminescence can be achieved through diversified regulatory approaches, such as adjustment of the dual-phase ratio, selective separation of Ln 3+ dopants, and alteration of incident pumping laser. As a proof-of-concept experiment, the application of dual-phase glass as a color converter in 980 nm laser-driven upconverting lighting is demonstrated.

Luminescent nanoparticles with dual-mode long-lived luminescence are of great importance for their attractive applications in biosensing, bioimaging, and data encoding. Herein, we report the realization of up- and downconversion emission of Mn 2+ dopants in multilayer nanoparticles of NaGdF 4 :Yb/Tm@NaGdF 4 :Ce/Mn@NaYF 4 upon excitation at 980 and 254 nm, respectively. The dual-mode emission of the Mn 2+ dopants at 531 nm have a long-lived lifetime up to ∼30 ms as a result of the spin-forbidden optical transition of Mn 2+ within the 3d 5 configuration. After ceasing steady excitation at the two wavelengths, the long-lived feature of Mn 2+ luminescence allows a longer persistent time than lanthanide emissions, thereby enabling the ease of data decoding by a cell phone camera under a burst mode. The long-lived green upconversion emission also permits the generation of a long green tail emission upon dynamic excitation at 980 nm. These attributes make the as-prepared Mn 2+ -doped multilayer nanoparticles particularly attractive for multilevel anticounterfeiting.

A recyclable, aqueous phase functioning and biocompatible photon upconverting system is developed. Hollow mesoporous silica microcapsules (HMSMs) with ordered radial mesochannels were employed, for the first time, as vehicles for the post-encapsulation of oil phase triplet-triplet annihilation upconversion (TTA-UC), with the capability of homogeneous suspension in water. In-depth characterization of such upconverting oil-laden HMSMs (UC-HMSMs) showed that the mesoporous silica shells reversibly stabilized the encapsulated UC oil in water to allow efficient upconverted emission, even under aerated conditions. In addition, the UC-HMSMs were found to actively bind to the surface of human mesenchymal stem cells without significant cytotoxicity and displayed upconverted bright blue emission under 640 nm excitation, indicating a potential of our new TTA-UC system in biophotonic applications. These findings reveal the great promise of UC-HMSMs to serve as ideal vehicles not only for ultralow-power in vivo imaging but also for stem cell labeling, to facilitate the tracking of tumor cells in animal models.

Spider silk is a natural material possessing unique properties such as biocompatibility, regenerative and antimicrobial activity, and biodegradability. It is broadly considered an attractive matrix for tissue regeneration applications. Optical monitoring and potential control over tissue regrowth are attractive tools for monitoring of this process. In this work, we show upconversion modification of natural spider silk fibers with inorganic nanoparticles. To achieve upconversion, metal oxide nanoparticles were doped with low concentrations of rare-earth elements, producing potentially biocompatible luminescent nanomaterials. The suggested approach to spider silk modification is efficient and easy to perform, opening up sensing and imaging possibilities of biomaterials in a noninvasive and real-time manner in bio-integration approaches.

The development of upconversion nanomaterials for many photonic applications requires a detailed understanding of their radiative lifetimes that in turn depend critically on local environmental conditions. In this work, hexagonal (β-phase) sodium-yttrium-fluoride (NaYF 4 ) nanowires (NWs) were synthesized and substitutionally co-doped with a luminescent solid solution of trivalent erbium and ytterbium ions. A single-beam laser trapping instrument was used in tandem with a piezo-controlled, variable-temperature stage to precisely vary the nanowire's distance from the substrate. The spontaneous photoluminescence lifetime of the 4 S 3/2 → 4 I 15/2 transition from Er 3+ ions was observed to change by >60% depending on the ions' separation distance from a planar (water/glass) dielectric interface. The 4 S 3/2 state lifetime is observed to increase by a factor of 1.62 ± 0.01 as the distance from the quartz coverslip increases from ∼0 nm to ∼40 μm. Less significant changes in the luminescence lifetime (≤10%) were observed over a temperature range between 25 and 50 °C. The distance dependence of the lifetime is interpreted quantitatively in the context of classical electromagnetic coupling between Er 3+ ions within the nanowire and the adjacent dielectric interface. We also demonstrate potential applications of the NaYF 4 NWs for both controlling and probing temperatures at nanometer scales by integrating them within a poly(dimethylsiloxane) composite matrix.

Upconversion (UC) of sub-bandgap photons extends the effective light absorption range of photovoltaic and photocatalytic devices, allowing them to reach higher conversion efficiencies. Recent advances in polymer host materials make it possible to translate triplet-triplet annihilation (TTA)-UC, the UC mechanism most suitable for this purpose, to solid films that can be integrated into devices. The promise of these films is currently limited by the narrow light absorption of TTA-UC sensitizer chromophores, but incorporating multiple sensitizers into layered film systems presents a promising strategy for producing UC materials with broadened light absorption. This strategy is herein applied for photocatalytic air purification, demonstrating its use in a real-world application for the first time. We superimpose optimized red-to-blue and green-to-blue UC films within dual-layer systems and develop a new photocatalyst compatible with their fluorescence emission. By integrating the dual-layer UC film systems with films of this photocatalyst, we produce the first devices that use TTA-UC to harness both red and green sub-bandgap photons for hydroxyl radical generation and photocatalytic degradation of gaseous acetaldehyde, a model volatile organic compound (VOC). Under white light-emitting diode excitation, the dual-layer film systems' broadened light absorption enhances their devices' photocatalytic degradation efficiency, enabling them to degrade twice as much acetaldehyde as their single-sensitizer counterparts. We show that as a result of the different absorption profiles of the two sensitizers, the film order significantly impacts UC fluorescence and VOC degradation. By probing the influence of the excitation light source, excitation geometry, and chromophore spectral overlap on the film systems' UC performance, we propose a framework for the design of multilayer TTA-UC film systems suitable for integration with a variety of photovoltaic and photocatalytic devices.

Photodynamic therapy (PDT) is a noninvasive medical technology that has been applied in cancer treatment where it is accessible by direct or endoscope-assisted light irradiation. To lower phototoxicity and increase tissue penetration depth of light, great effort has been focused on developing new sensitizers that can utilize red or near-infrared (NIR) light for the past decades. Lanthanide-doped upconversion nanoparticles (UCNPs) have a unique property to transduce NIR excitation light to UV-vis emission efficiently. This property allows some low-cost, low-toxicity, commercially available visible light sensitizers, which originally are not suitable for deep tissue PDT, to be activated by NIR light and have been reported extensively in the past few years. However, some issues still remain in the UCNP-assisted PDT platform such as colloidal stability, photosensitizer loading efficiency, and accessibility for targeting ligand installation, despite some advances in this direction. In this study, we designed a facile phospholipid-coated UCNP method to generate a highly colloidally stable nanoplatform that can effectively load a series of visible light sensitizers in the lipid layers. The loading stability and singlet oxygen generation efficiency of this sensitizer-loaded lipid-coated UCNP platform were investigated. We also have demonstrated the enhanced cellular uptake efficiency and tumor cell selectivity of this lipid-coated UCNP platform by changing the lipid dopant. On the basis of the evidence of our results, the lipid-complexed UCNP nanoparticles could serve as an effective photosensitizer carrier for NIR light-mediated PDT.

The upconversion luminescence (UCL) of colloidal lanthanide-doped upconversion nanocrystals (UCNCs) can be improved either by precise encapsulation of the surface by optically inert shells around the core, by an alteration of the nearby environment via metal nanoparticles, or by a combination of both. Considering their potential importance in crystalline silicon photovoltaics, the present study investigates both effects for two-dimensional arrangements of UCNCs. Using excitation light of 1500 nm wavelength, we study the variation in the upconversion luminescence from an Er 3+ -doped NaYF 4 core as a function of the thickness of a NaLuF 4 shell in colloidal solutions as well as in spin-cast-assisted self-assembled monolayers of UCNCs. The observed UCL yields and decay times of Er 3+ ions of the UCNCs increase with increasing shell thickness in both cases, and nearly no variation in decay times is observed in the transition of the UCNCs from solution to film configurations. The luminescence efficiency of the UCNC monolayers is further enhanced by electron-beam-lithographic-designed Au nanodiscs deposited either on top of or buried within the monolayer. It is observed that the improvement by the nanocrystal shells is greater than that of the Au nanodiscs.

Self-monitored photothermal therapy (PTT) with minimal collateral damages has emerged as a challenging strategy for antibacterial and cancer treatments, which could be fulfilled via the rational integration of luminescent thermometry and photothermal ablation within a single upconverting (UC) nanoplatform. Herein, 808 nm light-driven dual-functional nanoplatforms LuVO 4 :Nd 3+ /Yb 3+ /Er 3+ @SiO 2 @Cu 2 S were successfully developed using olivelike LuVO 4 :Nd 3+ /Yb 3+ /Er 3+ hollow nanoparticles as the thermal-sensing core and ultrasmall Cu 2 S nanoparticles as the photothermal satellite. Irradiated by 808 nm laser, thermal-sensing behaviors of samples were evaluated based on the high-purity Er 3+ green emissions, while the surface-attached Cu 2 S exhibited superior photothermal effects due to the efficient absorption of incident laser and near-infrared emissions from the luminescent core. The feasibility of bifunctional samples acting as self-monitored photothermal agents in subtissues and antibacterial agents against drug-resistant bacteria was separately assessed. Results provide deeper insights into the desirable design of 808 nm-driven multifunctional nanoplatforms with intense UC emission, sensitive thermometry, and effective photothermal conversion toward self-monitored PTT with high therapeutic accuracy.

The oxygen-deprived environment of a solid tumor is still great restriction in achieving an efficient photodynamic therapy (PDT). In this work, we developed a smart pH-controllable and H 2 O 2 -responsive nanoplatform with degradable property, which was based on honeycomb manganese oxide (hMnO 2 ) nanospheres loaded with Ce6-sensitized core-shell-shell structured up-conversion nanoparticles (NaGdF 4 :Yb/Er,Tm@NaGdF 4 :Yb@NaNdF 4 :Yb) (abbreviated as hMUC). In the system, the speedy breakup of the as-prepared hMnO 2 nanostructures results in release of loaded Ce6-sensitized UCNPs under the condition of H 2 O 2 in acid solution. When exposed to tissue-penetrable 808 nm laser, up-conversion nanoparticles (UCNPs) emit higher-energy visible photons which would be absorbed by Ce6 to yield cytotoxic reactive oxygen species (ROS), thus triggering PDT treatment naturally. Moreover, the in vitro and in vivo experiments demonstrate that hMUC sample with the honeycomb-satellite structure can serve as multimodal bioimaging contrast agent for self-enhanced upconversion luminescence (UCL), magnetic resonance imaging (MRI) and computed tomography (CT) imaging, indicating that the as-prepared hMUC could be used in imaging-guided diagnosis and treatment, which has a potential application in the PDT treatment of tumor.