Light Upconversion Research Articles

Energy Aggregation for Illuminating Upconversion Multicolor Emission Based on Ho3+ Ions.

Lanthanide-doped upconversion luminescent nanoparticles (UCNPs) have garnered extensive attention due to their notable anti-Stokes shifts and superior photostability. Notably, Ho3+-based UCNPs present a complex energy level configuration, which poses challenges in augmenting their luminescence efficiency. Herein, a rational design strategy was used to enhance the upconversion luminescence intensity of Ho3+ ions by improving the photon absorption ability and energy utilization efficiency. Efficient absorption and transfer of excitation light energy were achieved through carefully selected host materials, precisely controlled sensitizers, and the design of external energy antennas using organic dyes, enhancing upconversion luminescence. Due to the attenuation effect of hydroxyl vibration on upconversion luminescence, the nanomaterials exhibit multicolor luminescent characteristics in different solution environments. Significantly, the composites exhibit intense upconversion of red light in aqueous solution, showing great application potential in biomedicine and colorimetry.

Advances in the photon avalanche luminescence of inorganic lanthanide-doped nanomaterials.

Photon avalanche (PA)-where the absorption of a single photon initiates a 'chain reaction' of additional absorption and energy transfer events within a material-is a highly nonlinear optical process that results in upconverted light emission with an exceptionally steep dependence on the illumination intensity. Over 40 years following the first demonstration of photon avalanche emission in lanthanide-doped bulk crystals, PA emission has been achieved in nanometer-scale colloidal particles. The scaling of PA to nanomaterials has resulted in significant and rapid advances, such as luminescence imaging beyond the diffraction limit of light, optical thermometry and force sensing with (sub)micron spatial resolution, and all-optical data storage and processing. In this review, we discuss the fundamental principles underpinning PA and survey the studies leading to the development of nanoscale PA. Finally, we offer a perspective on how this knowledge can be used for the development of next-generation PA nanomaterials optimized for a broad range of applications, including mid-IR imaging, luminescence thermometry, (bio)sensing, optical data processing and nanophotonics.

Up-Conversion Photoluminescence Reconfiguration in Silicon by Inner Microstructure Control of Hybrid Plasmonic-Semiconductor Nanoparticles.

Hybrid metal-semiconductor nanostructures unifying plasmonic and high-refractive-index materials in a single resonant system demonstrate a wide set of unique optical properties. Such systems are a perspective for a broad palette of applications, but the link between their inner structure and optical properties is a very sensitive issue, which is still not revealed. Here, we describe the influence of internal microstructure of a hybrid gold-silicon nanoparticle (the gold nanoparticle with embedded silicon nanograins) on the up-conversion white-light photoluminescence. The evolution in the internal microstructure of the system during thermal treatment up to 500 °C is tracked in situ through the HAADF and EDS STEM techniques. The studies show the redistribution of the materials inside the hybrid nanoparticle and the reduction of the silicon nanograin numbers under heating without an external modification of the nanoparticle shape. We have established numerically that the dependence of the enhancement factor spectral width on the S/V ratio of the nanoparticle plasmonic component is close to the linear behavior. The shrinkage of the photoluminescence spectrum (up to 42%) of the hybrid nanoparticle reconfigured by laser exposure and thermal treatment is shown experimentally, which supports our numerical conclusions. The results shed light on the connection of optical properties of complex hybrid systems with their complex internal composition, providing a powerful tool to control their optical properties through microstructure rearrangement. They also open the way to the development of reconfigurable silicon-based up-conversion light nanosources for integrated optical devices and biophotonics.

A multiband NIR upconversion core-shell design for enhanced light harvesting of silicon solar cells

Exploring lanthanide light upconversion (UC) has emerged as a promising strategy to enhance the near-infrared (NIR) responsive region of silicon solar cells (SSCs). However, its practical application under normal sunlight conditions has been hindered by the narrow NIR excitation bandwidth and the low UC efficiency of conventional materials. Here, we report the design of an efficient multiband UC system based on Ln3+/Yb3+-doped core-shell upconversion nanoparticles (Ln/Yb-UCNPs, Ln3+ = Ho3+, Er3+, Tm3+). In our design, Ln3+ ions are incorporated into distinct layers of Ln/Yb-UCNPs to function as near-infrared (NIR) absorbers across different spectral ranges. This design achieves broad multiband absorption withtin the 1100 to 2200 nm range, with an aggregated bandwidth of ~500 nm. We have identified a synthetic electron pumping (SEP) effect involving Yb3+ ions, facilitated by the synergistic interplay of energy transfer and cross-relaxation between Yb3+ and other ions Ln3+ (Ho3+, Er3+, Tm3+). This SEP effect enhances the UC efficiency of the nanomaterials by effectively transferring electrons from the low-excited states of Ln3+ to the excited state of Yb3+, resulting in intense Yb3+ luminescence at ~980 nm within the optimal response region for SSCs, thus markedly improving their overall performance. The SSCs integrated with Ln/Yb-UCNPs with multiband excitation demonstrate the largest reported NIR response range up to 2200 nm, while enabling the highest improvement in absolute photovoltaic efficiency reported, with an increase of 0.87% (resulting in a total efficiency of 19.37%) under standard AM 1.5 G irradiation. Our work tackles the bottlenecks in UCNP-coupled SSCs and introduces a viable approach to extend the NIR response of SSCs.

(Invited) Exploiting Near-Infrared Light for Theranostics

Since first reported, luminescent rare earth doped nanoparticles have attracted a great deal of interest. In the last decade, however, the field has rapidly taken off, progressing from the basic understanding of the photophysical properties governing their nanoscale luminescence, particularly upconversion, to their use in a plethora of applications, with considerable focus in biology and medicine. This interest stems primarily from the ability to stimulate these luminescent nanoparticles with near-infrared (NIR) light as well as their diverse emission wavelengths spanning the UV to the NIR. Therefore, with a single NIR excitation wavelength, it is possible to observe higher energy luminescence, known as upconversion, or single photon NIR emission (known as down-shifted luminescence). The former upconversion process proceeds through the sequential absorption of multiple NIR photons through the long-lived 4f electronic energy states of the tri-positive rare earth ions. As a result, upconversion is several of orders more efficient than conventional multiphoton absorption processes. This is especially interesting for applications in theranostics (therapy + diagnostics on the same platform) where the upconverted light can be used to trigger another light activated modality (therapy) while the NIR luminescence can be used for bioimaging and nanothermometry (diagnostics). Here, we present our work on the synthesis and development of various NIR excited (and emitting) core/shell rare earth doped nanostructures/nanoplatforms and demonstrate how their various emissions could be harnessed for applications in biology and nanomedicine.

Evidence of the Quantum Optical Nature of High-Harmonic Generation

High-harmonic generation is a light up-conversion process occurring in a strong laser field, leading to coherent bursts of extreme ultrashort broadband radiation [Lewenstein , Phys. Rev. A , 2117 (1994)]. As a new perspective, we propose that ultrafast strong-field electronic or photonic processes such as high-harmonic generation can potentially generate nonclassical states of light well before the decoherence of the system occurs [Gorlach , Nat. Commun. , 4598 (2020); Stammer ., Phys. Rev. Lett. , 123603 (2022)]. This could address fundamental challenges in quantum technology such as scalability, decoherence, or the generation of massively entangled states [Lewenstein , Luca Argenti Michael Chini, 27 (2024)]. Here, we report experimental evidence of the nonclassical nature of the harmonic emission in several semiconductors excited by a femtosecond infrared laser. By investigating single- and double-beam intensity cross-correlation [Loudon, Rep. Prog. Phys. , 913 (1980)], we measure characteristic nonclassical features in the single-photon statistics. We observe two-mode squeezing in the generated harmonic radiation, which depends on the laser intensity that governs the transition from super-Poissonian to Poissonian photon statistics. The measured violation of the Cauchy-Schwarz inequality realizes a direct test of multipartite entanglement in high-harmonic generation [Wasak, Phys. Rev. A , 033616 (2014)]. This result is supported by the theory of multimodal detection and the Hamiltonian from which the effective squeezing modes of the harmonics can be derived [Gonoskov , Phys. Rev. B , 125110 (2024); Christ New J. Phys. , 033027 (2011)]. With this work, we show experimentally that high-harmonic generation is a new quantum bosonic platform that intrinsically produces nonclassical states of light with unique features such as multipartite broadband entanglement or multimode squeezing. The source operates at room temperature, using standard semiconductors and a standard commercial fiber laser, opening up new routes for the quantum industry, such as optical quantum computing, communication, and imaging. Published by the American Physical Society 2024

Synthesis and luminescent properties of multi-mode core-shell-shell LaPO4:RE (RE³⁺ = Er³⁺, Eu³⁺) microspheres for anti-counterfeiting ink applications

To meet the demands for product and consumer protection, we developed biocompatible multi-mode emitting core-shell-shell rare earth phosphates for anti-counterfeiting inks. These core-shell-shell structures feature SiO2 microspheres as the core, with LaPO4 nanocrystals doped with erbium (Er) and europium (Eu) as the interlayer, and an outer SiO2 shell. The SiO2@LaPO4:Er0.1,Eux@SiO2 (x = 0.01, 0.02, 0.03, 0.04, 0.05) microspheres display dual emissions when excited by 254 nm and 365 nm UV light, offering a novel anti-counterfeiting approach. Another core-shell-shell structure was created with LaPO4:Er3+ and LaPO4:Eu3+ separately coated on SiO2 cores, mixed, and then covered with a SiO2 shell. Under 980 nm near-infrared laser excitation, these structures emit bright upconverted green light, while 254/365 nm UV light induces red/yellow down-conversion luminescence. This design minimizes up-conversion luminescence quenching of Er3+ ions from cross-relaxation with Eu3+ ions. The SiO2 core minimizes energy loss, regulates particle size, and enhances luminescence. A certain thickness of the silicon shell layer also protects against luminescence quenching. The inks exhibit high dispersibility, non-reproducibility, and excellent luminescence, making them effective for anti-counterfeiting.

Long-wavelength infrared upconversion time-stretch spectroscopy

High-speed spectroscopy in the molecular fingerprint spectral region (≈6–12 μm) is essential for the detection of ultrafast molecular dynamic processes, rapid combustion analysis, and biological diagnostics. However, ultrafast spectroscopy in the long-wavelength infrared (LWIR) region remains a challenge due to the limitations of laser sources and the lack of ultrafast and sensitive detectors in this wavelength region. Here, we demonstrate broadband LWIR time-stretch spectroscopy, which can realize a single-shot high-speed spectral measurement in a 8–10 μm region, by combining the LWIR femtosecond (fs) light generation and upconversion time-stretching detection with specific dispersive fiber. Broadband tunable fs light generated in the 8–10 μm region is upconverted to the 1.1–1.2 μm near-infrared wavelength via difference-frequency generation with the 1 μm chirped pump pulse. Time-stretch detection of the upconverted light can then be realized by adopting dispersion shifted fiber, which has a superior dispersion-to-loss ratio in the 1.1–1.2 μm wavelength region, as the dispersive medium. As a result, we experimentally demonstrate LWIR time-stretch spectroscopy in the 8–10 μm region with a spectral resolution of 1.07 cm−1, at a rate of 200 kSpectra s−1, which is only limited by the repetition rate of the 1 μm pump source. The demonstration of high-speed time-stretch spectroscopy in the LWIR region would open the possibility in exploring the transient dynamics of molecular fingerprint spectroscopy.

(Invited) Near-Infrared Triggered Theranostics

In the last decade, the field of luminescent lanthanide doped nanoparticles has had a meteoric rise, progressing from the basic understanding of the photophysical properties governing their nanoscale luminescence, in particular upconversion, to their use in a plethora of applications, with considerable focus in biology and medicine. This interest stems primarily from the ability to stimulate these luminescent nanoparticles with near-infrared (NIR) light as well as their diverse emission wavelengths spanning the UV to the NIR. Therefore, with a single NIR excitation wavelength, it is possible to observe higher energy multiphoton luminescence, known as upconversion, or single photon NIR emission (known as down-shifted luminescence). The former upconversion process proceeds through the sequential absorption of multiple NIR photons through the long-lived 4f electronic energy states of the tri-positive lanthanide ions. As a result, upconversion is several of orders more efficient than conventional multiphoton absorption processes. This is especially interesting for applications in theranostics (therapy + diagnostics on the same platform) where the upconverted light can be used to trigger another light activated modality (therapy) while the NIR luminescence can be used for bioimaging and nanothermometry (diagnostics). Here, we present our work on the synthesis and development of various NIR excited (and emitting) core/shell lanthanide-doped nanostructures/nanoplatforms and demonstrate how their various emissions could be harnessed for applications in biology and nanomedicine.

NIR Light and GSH Dual-Responsive Upconversion Nanoparticles Loaded with Multifunctional Platinum(IV) Prodrug and RGD Peptide for Precise Cancer Therapy.

Platinum(II) drugs as a first-line anticancer reagent are limited by side effects and drug resistance. Stimuli-responsive nanosystems hold promise for precise spatiotemporal manipulation of drug delivery, with the aim to promote bioavailability and minimize side effects. Herein, a multitargeting octahedral platinum(IV) prodrug with octadecyl aliphatic chain and histone deacetylase inhibitor (phenylbutyric acid, PHB) at axial positions to improve the therapeutic effect of cisplatin was loaded on the upconversion nanoparticles (UCNPs) through hydrophobic interaction. Followed attachment of DSPE-PEG2000 and arginine-glycine-aspartic (RGD) peptide endowed the nanovehicles with high biocompatibility and tumor specificity. The fabricated nanoparticles (UCNP/Pt(IV)-RGD) can be triggered by upconversion luminescence (UCL) irradiation and glutathione (GSH) reduction to controllably release Pt(II) species and PHB, inducing profound cytotoxicity. Both in vitro and in vivo experiments demonstrated that UCNP/Pt(IV)-RGD exhibited remarkable antitumor efficiency, high tumor-targeting specificity, and real-time UCL imaging capacity, presenting an intelligent platinum(IV) prodrug-loaded nanovehicle for UCL-guided dual-stimuli-responsive combination therapy.

Tunable Intracavity Coherent Up-Conversion with Giant Nonlinearity in a Polar Fluidic Medium.

The study has demonstrated a novel microcavity-based flexible photon up-conversion system using second harmonic generation (SHG) from a polar nematic fluidic medium doped with a laser dye. The idea is based on coherent light generation via stimulated emission (lasing) and simultaneous frequency doubling inside a microcavity. The polar nematic fluid equips very high even-order optical nonlinearity due to its polar symmetry and large dipole moment along the molecular long axis. At the same time, its inherent fluidic nature allows to easily functionalize the media just by doping, in the present case, with an emissive laser dye. The demonstrated system exhibits a giant nonlinear optical response to input light, while enabling spectral narrowing and multiple-signal output of up-converted light, which is not attainable through the simple SH-conversion of input light. Furthermore, the susceptibility of the liquid crystal offers dynamic modulation capabilities by an external stimulus, such as signal switching by the application of electric field or wavelength tuning through temperature variation. Such a brand-new type of simple coherent flexible up-conversion system must be promising as a new principle for easily accessible and down-scalable wavelength conversion devices.

Interface Allocation Precisely Customized Janus Upconversion Nanomotor for Atherosclerosis Amelioration

AbstractSpatial and temporal precisely control of direction and speed is crucial for nanomotors to enable complex operations and applications in microsurgery, drug delivery, isolation of biological targets, and so on. Judicious material design involving Janus nanoparticles has been popular over the past decades, however, precise and customizable modulation of Janus structure with a specific asymmetric ratio for motion control is still challenging. In this study, a universal “interface allocation” strategy is developed for efficient and controllable preparation of Janus mesoporous silica‐coated upconversion nanoparticles (Janus UCNP@mSiO2) with precisely tuned asymmetric ratio to achieve near‐infrared (NIR)‐controlled active mobility for relieving vessel plaque. Mesoporous silica with a thickness of 50 nm is precisely coated onto the nanoparticles’ surface with an optimal coverage ratio of 50% to encapsulate gas propellant. Upon exposure to upconverted blue light, the nanomotors release nitric oxide, facilitating their motion and pathologically improving atherosclerosis through endothelium‐dependent vasodilation. Experimental and theoretical simulation results demonstrate the advantages of NIR‐controlled Janus upconversion nanomotors in atherosclerosis treatment, including enhanced nanoparticle‐transmittance rate (34.83% to 85.57%) and excellent in vivo therapeutic efficacy.

Spectroscopic and Interferometric Sum-Frequency Imaging of Strongly Coupled Phonon Polaritons in SiC Metasurfaces.

Phonon polaritons enable waveguiding and localization of infrared light with extreme confinement and low losses. The spatial propagation and spectral resonances of such polaritons are usually probed with complementary techniques such as near-field optical microscopy and far-field reflection spectroscopy. Here, infrared-visible sum-frequency spectro-microscopy is introduced as a tool for spectroscopic imaging of phonon polaritons. The technique simultaneously provides sub-wavelength spatial resolution and highly-resolved spectral resonance information. This is implemented by resonantly exciting polaritons using a tunable infrared laser and wide-field microscopic detection of the upconverted light. The technique is employed to image hybridization and strong coupling of localized and propagating surface phonon polaritons in a metasurface of SiC micropillars. Spectro-microscopy allows to measure the polariton dispersion simultaneously in momentum space by angle-dependent resonance imaging, and in real space by polariton interferometry. Notably, it is possible to directly image how strong coupling affects the spatial localization of polaritons, inaccessible with conventional spectroscopic techniques. The formation of edge states is observed at excitation frequencies where strong coupling prevents polariton propagation into the metasurface. The technique is applicable to the wide range of polaritonic materials with broken inversion symmetry and can be used as a fast and non-perturbative tool to image polariton hybridization andpropagation.

Upconversion of Infrared Light by Graphitic Microparticles Due to Photoinduced Structural Modification

Recent reports of upconversion and white light emission from graphitic particles warrant an explanation of the physics behind the process. A model is offered, wherein the upconversion is facilitated by photoinduced electronic structure modification allowing for multiphoton processes. As per the prediction of the model, it is experimentally shown that graphite upconverts infrared light centered around 1.31 μm (0.95 eV) to broadband white light centered around 0.85 μm (1.46 eV). The results suggest that upconversion from shortwave infrared (≈3 μm, 0.45 eV) to visible region may be possible. The experiments show that the population dynamics of the electronic states involved in this upconversion process occur in the timescale of milliseconds.

"Three Musketeers" Enhances Photodynamic Effects by Reducing Tumor Reactive Oxygen Species Resistance.

Photodynamic therapy (PDT) based on upconversion nanoparticles (UCNPs) has been widely used in the treatment of a variety of tumors. Compared with other therapeutic methods, this treatment has the advantages of high efficiency, strong penetration, and controllable treatment range. PDT kills tumors by generating a large amount of reactive oxygen species (ROS), which causes oxidative stress in the tumor. However, this killing effect is significantly inhibited by the tumor's own resistance to ROS. This is because tumors can either deplete ROS by high concentration of glutathione (GSH) or stimulate autophagy to eliminate ROS-generated damage. Furthermore, the tumor can also consume ROS through the lactic acid metabolic pathway, ultimately hindering therapeutic progress. To address this conundrum, we developed a UCNP-based nanocomposite for enhanced PDT by reducing tumor ROS resistance. First, Ce6-doped SiO2 encapsulated UCNPs to ensure the efficient energy transfer between UCNPs and Ce6. Then, the biodegradable tetrasulfide bond-bridged mesoporous organosilicon (MON) was coated on the outer layer to load chloroquine (CQ) and α-cyano4-hydroxycinnamic acid (CHCA). Finally, hyaluronic acid was utilized to modify the nanomaterials to realize an active-targeting ability. The obtained final product was abbreviated as UCNPs@MON@CQ/CHCA@HA. Under 980 nm laser irradiation, upconverted red light from UCNPs excited Ce6 to produce a large amount of singlet oxygen (1O2), thus achieving efficient PDT. The loaded CQ and CHCA in MON achieved multichannel enhancement of PDT. Specifically, CQ blocked the autophagy process of tumor cells, and CHCA inhibited the uptake of lactic acid by tumor cells. In addition, the coated MON consumed a high level of intracellular GSH. In this way, these three functions complemented each other, just as the "three musketeers" punctured ROS resistance in tumors from multiple angles, and both in vitro and in vivo experiments had demonstrated the elevated PDT efficacy of nanomaterials.

Near-infrared light-induced homogeneous photoelectrochemical biosensor based on 3D walking nanomotor-assisted CRISPR/Cas12a for ultrasensitive microRNA-155 detection

The dysregulation of microRNA (miRNA) expression levels is intricately linked to a myriad of human diseases, and the precise and delicate detection thereof holds paramount significance in the realm of clinical diagnosis and therapy. Herein, a near-infrared (NIR) light-mediated homogeneous photoelectrochemical (PEC) biosensor was constructed for miRNA-155 detection based on NaYF4: Yb, Tm@ZnIn2S4 (NYF@ ZIS) coupled with a three-dimensional (3D) walking nanomotor-assisted CRISPR/Cas12a strategy. The upconverted light emitted by the NYF in the visible and UV region upon NIR light excitation could be utilized to excite ZIS to produce a photocurrent response. The presence of target miRNA-155 initiated an amplification reaction within the 3D walking nanomotor, resulting in the production of multiple nucleic acid fragments. These fragments could activate the collateral cleavage capability of CRISPR/Cas12a, leading to the indiscriminate cleavage of single-stranded DNA (ssDNA) on ALP-ssDNA-modified magnetic beads and the subsequent liberation of alkaline phosphatase (ALP). The released ALP facilitated the catalysis of ascorbic acid 2-phosphate to generate ascorbic acid as the electron donor to capture the photogenerated holes on the NYF@ZIS surface, resulting in a positively correlated alteration in the photocurrent response. Under optimal conditions, the NIR light-initiated homogeneous PEC biosensor had the merits of good linear range (0.1 fM to 100 pM), an acceptable limit of detection (65.77 aM) for miRNA-155 detection. Considering the pronounced sensitivity, light stability, and low photodamage, this strategy presents a promising platform for detecting various other miRNA biomarkers in molecular diagnostic practice.

Upconversion dual-photosensitizer-expressing bacteria for near-infrared monochromatically excitable synergistic phototherapy.

Synergistic phototherapy stands for superior treatment prospects than a single phototherapeutic modality. However, the combined photosensitizers often suffer from incompatible excitation mode, limited irradiation penetration depth, and lack of specificity. We describe the development of upconversion dual-photosensitizer-expressing bacteria (UDPB) for near-infrared monochromatically excitable combination phototherapy. UDPB are prepared by integrating genetic engineering and surface modification, in which bacteria are encoded to simultaneously express photothermal melanin and phototoxic KillerRed protein and the surface primary amino groups are derived to free thiols for biorthogonal conjugation of upconversion nanoparticles. UDPB exhibit a near-infrared monochromatic irradiation-mediated dual-activation characteristic as the photothermal conversion of melanin can be initiated directly, while the photodynamic effect of KillerRed can be stimulated indirectly by upconverted visible light emission. UDPB also show living features to colonize hypoxic lesion sites and inhibit pathogens via bacterial community competition. In two murine models of solid tumor and skin wound infection, UDPB separately induce robust antitumor response and a rapid wound healing effect.

Silk‐Based Functional Inks with Color‐Tunable Light Upconversion for Printing on Arbitrary Surfaces

AbstractA biocompatible and versatile silk‐based functional ink with hydrophilic upconversion nanoparticles (UCNPs) that can be printed or painted on arbitrary substrates, including biological surfaces is demonstrated. Hydrophilic UCNPs, ready to be dispersed in aqueous silk fibroin solution, are synthesized in large quantities via facile hydrothermal synthesis using citric acid. Based on a systematic study of dopant control to achieve robust red emission from citrate‐capped UCNPs, three primary colors are obtained, which serve as the basis for the expansion of the color palette. The synthesized UCNPs are homogeneously dispersed in regenerated silk fibroin solutions derived from Bombyx mori cocoons to produce water‐based functional inks. Cyan, magenta, and yellow (CMY) inks are created by combining red, green, and blue (RGB) inks. Demonstrator devices, where a variety of colorful patterns and codes are revealed only under near‐infrared irradiation, are realized through stencil printing or brush painting on flexible polymer films, fruit, leaves, silkworm cocoons, and pig skin. The patterns and codes are highly heat resistant (≈230 °C) and can be easily washed off with water after use. The printable/paintable inks and functions proposed here will provide new opportunities for applications where sustainability, biocompatibility, and intentional luminescence are simultaneously required.

Design and synthesis of a UV–vis-NIR response heterostructure system: For efficient solar energy conversion and BPA photocatalytic degradation

Combining upconversion materials with narrow-wide bandgap semiconductors to construct heterostructured composite photocatalysts effectively improves solar energy conversion efficiency. NYF:Ln3+(Ln = Yb,Er,Tm)@BiOX(X = Cl,Br,I) heterostructures were prepared by a two-step hydrothermal method. This work explores the effects of different lanthanide ion doping and narrow-wide bandgap bismuth oxyhalides on the performance of the heterostructures system. Under near-infrared (NIR) light irradiation, NYF:Yb,Er,Tm@BiOI degraded 94 % BPA within 160 min. Significantly, compared with NYF:Yb,Er@BiOCl, NYF:Yb,Er@BiOBr and the NYF:Yb,Er,Tm/BiOI mechanical mixtures, the photocatalytic activity of NYF:Yb,Er,Tm@BiOI was increased by 9.4 times, 3.7 times and 1.8 times, respectively. The enhanced photocatalytic activity is attributed to the doping of Er-Tm double-activated ions, which provides multiple upconversion emissions and forms more overlap in the narrow bandgap BiOI absorption spectrum, making it advantageous to utilize upconversion light fully. Eventually, an underlying mechanism was proposed that the existence of FRET in the NYF:Yb,Er,Tm@BiOI heterostructure leads to enhanced photocatalytic activity. This work provides new insights into the design of advanced structures for NIR-responsive photocatalysts.

NIR-Triggered Release of Nitric Oxide by Upconversion-Based Nanoplatforms to Enhance Osteogenic Differentiation of Mesenchymal Stem Cells for Osteoporosis Therapy.

Stem cell therapy is an attractive approach to bone tissue regeneration in osteoporosis (OP); however, poor cell engraftment and survival within injured tissues limits its success in clinical settings. Nitric oxide (NO) is an important signaling molecule involved in various physiological processes, with emerging evidence supporting its diverse roles in modulating stem cell behavior, including survival, migration, and osteogenic differentiation. To control and enhance osteogenic differentiation of mesenchymal stem cells (MSCs) for OP therapy, we designed a near-infrared (NIR) light-triggered NO-releasing nanoplatform based on upconversion nanoparticles (UCNPs) that converts 808-nm NIR light into visible light, stimulating NO release by light control. We demonstrate that the UCNP nanoplatforms can encapsulate a light-sensitive NO precursor, Roussin's black salt (RBS), through the implementation of a surface mesoporous silica coating. Upon exposure to 808-nm irradiation, NO is triggered by the controlled upconversion of UCNP visible light at the desired time and location. This controlled release mechanism facilitates photoregulated differentiation of MSCs toward osteogenic lineage and avoids thermal effects and phototoxicity on cells, thus offering potential therapeutic applications for treating OP invivo. Following the induction of osteogenic differentiation, the UCNP nanoplatforms exhibit the capability to serve as nanoprobes for the real-time detection of differentiation through enzymatic digestion and fluorescence recovery of UCNPs, enabling assessment of the therapeutic efficacy of OP treatment. Consequently, these UCNP-based nanoplatforms present a novel approach to control and enhance osteogenic differentiation of MSCs for OP therapy, simultaneously detecting osteogenic differentiation for evaluating treatment effectiveness.