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Mechanoluminescent materials have broad application prospects in advanced displays, stress imaging, and anti-counterfeiting owing to their ability to convert mechanical stimuli into light. However, most previous studies have focused on the visible and near-infrared regions. Although natural ultraviolet C (UVC) light is nearly absent on the Earth's surface, it plays an important role in many fields. Therefore, the development of smart materials capable of emitting UVC mechanoluminescence (ML) and expanding the application scenarios of UVC ML are significant but challenging. Here the ML property of Sr2P2O7:Pr3+ is examined, which stems from the 5dâ4f transition of Pr3+ and is located over the UVC region. The peak wavelength of the UVC ML of Sr2P2O7:Pr3+ is ≈230 nm, which is, to the best of this knowledge, the shortest ML wavelength reported to date. It is further demonstrated that the UVC ML of Sr2P2O7:Pr3+ is associated with trapped charge carriers and can be conveniently regulated by adjusting the X-ray excitation time. Relying on this unique characteristic, the potential of the UVC ML of Sr2P2O7:Pr3+ as an indicator of the X-ray radiation dose is demonstrated. This study enriches the family of mechanoluminescent materials and expands the available wavelength of ML to the UVC region.
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Distinct types of luminescence that are activated by various stimuli in a single material offer exciting developmental opportunities for functional materials. A versatile sensing platform that exhibits photoluminescence (PL), persistent luminescence (PersL), and mechanoluminescence (ML) is introduced, which enables the sensitive detection of temperature, pressure, and force/stress. The developed Sr2MgSi2O7:Eu2+/Dy3+ material exhibits a linear relationship between ML intensity and force and can be used as an ML stress sensor. Additionally, the bandwidth of the PL emission band and the PL lifetime of this material are remarkably sensitive to temperature, with values of ≈0.05 nm K-1 and 1.29%/K, respectively. This study demonstrates PersL pressure sensing for the first time, using long-lasting (seconds) lifetime as a manometric parameter. The developed material functions as an exceptionally sensitive triple-mode visual pressure sensor; specifically, it exhibits: i) a sensitivity of ≈-297.4 cm GPa-1 (8.11 nm GPa-1) in bandshift mode, ii) a sensitivity of ≈272.7 cm-1/GPa (14.8 nm GPa-1) in bandwidth mode, and iii) a sensitivity of 42%GPa-1 in PL-lifetime mode, which is the highest value reported to date. Notably, anti-counterfeiting, night-vision safety-sign, 8-bit optical-coding, and QR-code applications that exhibit intense PersL are demonstrated by 3D-printing the studied material in combination with a polymer.
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Mechanoluminescence (ML)-based sensors are emerging as promising wearable devices, attracting attention for their self-powered visualization of mechanical stimuli. However, challenges such as weak brightness, high activation threshold, and intermittent signal output have hindered their development. Here, a mechanoluminescent/electric dual-mode strain sensor is presented that offers enhanced ML sensing and reliable electrical sensing simultaneously. The strain sensor is fabricated via an optimized dip-coating method, featuring a sandwich structure with a single-walled carbon nanotube (SWNT) interlayer and two polydimethylsiloxane (PDMS)/ZnS:Cu luminescence layers. The integral mechanical reinforcement framework provided by the SWNT interlayer improves the ML intensity of the SWNT/PDMS/ZnS:Cu composite film. Compared to conventional nanoparticle fillers, the ML intensity is enhanced nearly tenfold with a trace amount of SWNT (only 0.01 wt.%). In addition, the excellent electrical conductivity of SWNT forms a conductive network, ensuring continuous and stable electrical sensing. These strain sensors enable comprehensive and precise monitoring of human behavior through both electrical (relative resistance change) and optical (ML intensity) methods, paving the way for the development of advanced visual sensing and smart wearable electronics in the future.
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Mechanoluminescence (ML) and digital image correlation (DIC) have emerged as promising optical methods to visualize and measure deformation fields. In this study, a dual-modal sensing skin, called the ML-DIC skin is introduced, that is capable of emitting ML and facilitating DIC measurements under various lighting conditions, including daylight, night or darkness, and UV irradiation. Four ML-DIC skins are fabricated with or without carbon nanotubes (CNTs) using a composite powder consisting of SrAl2O4: Eu,Dy (SAO), and acrylic resin, with CNT milling times of 48, 72, and 96 h for three of four skins, respectively. DIC measurements are performed under multiple lighting conditions for measuring photoluminescence, persistence luminescence, and reflection. Uniaxial tension tests demonstrate the superior performance of ML-DIC skins with CNTs compared with pristine SAO skins, with the skin subjected to 48 h of CNT dispersion exhibiting optimal performance. Further investigations focus on ML emission and DIC measurements near the crack-tip vicinity of static and propagating cracks as well as on surfaces above subsurface cracks. The integration of ML and DIC techniques offers a versatile approach for comprehensive deformation analysis applicable to diverse environments, with implications for materials science, engineering, and structural health monitoring.
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Rare earth and transition metal ion-doped CaZnOS has garnered significant attention for its exceptional mechanoluminescence (ML) performance under mild mechanical stimuli and its capability for multicolor emissions. Since powdered phosphors are not directly usable, they require encapsulation within with polymers to create stable structures. This study investigates Mn2+-doped CaZnOS (CaZnOS:Mn2+) as the ML phosphor, optimizing its performance by varying the Mn2+ content, resulting in bright orange-red emissions from the d-d transitions of the Mn2+ activator. A quantum efficiency of 59.08% was achieved through the self-sensitization of the matrix lattice and energy transfer to the Mn2+ luminescent centers. The enhancement in ML due to Mn2+ doping is attributed to the reduced trap depth and increased trap concentration. Encapsulation with four polymers-PDMS, PU, SIL, and RTV-2-was explored to further optimize ML performance. Among these, PDMS provides the best ML output and sensitivity, owing to its slightly cross-linked structure and good triboelectric properties. The optimized CaZnOS:0.03Mn2+/PDMS composite, featuring excellent flexibility and recoverability, shows great potential for applications in anti-counterfeiting encryption, stress sensors, and wearable devices.
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Organic-inorganic hybrid manganese(II) halides (OIMnHs) have garnered tremendous interest across a wide array of research fields owing to their outstanding optical properties, abundant structural diversity, low-cost solution processibility, and low toxicity, which make them extremely suitable for use as a new class of luminescent materials for various optoelectronic applications. Over the past years, a plethora of OIMnHs with different structural dimensionalities and multifunctionalities such as efficient photoluminescence (PL), radioluminescence, circularly polarized luminescence, and mechanoluminescence have been newly created by judicious screening of the organic cations and inorganic Mn(II) polyhedra. Specifically, through precise molecular and structural engineering, a series of OIMnHs with near-unity PL quantum yields, high anti-thermal quenching properties, and excellent stability in harsh conditions have been devised and explored for applications in light-emitting diodes (LEDs), X-ray scintillators, multimodal anti-counterfeiting, and fluorescent sensing. In this review, the latest advancements in the development of OIMnHs as efficient light-emitting materials are summarized, which covers from their fundamental physicochemical properties to advanced optoelectronic applications, with an emphasis on the structural and functionality design especially for LEDs and X-ray detection and imaging. Current challenges and future efforts to unlock the potentials of these promising materials are also envisioned.
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Macrophage engineering has emerged as a promising approach for modulating the anti-tumor immune response in cancer therapy. However, the spatiotemporal control and real-time feedback of macrophage regulatory process is still challenging, leading to off-targeting effect and delayed efficacy monitoring therefore raising risk of immune overactivation and serious side effects. Herein, a focused ultrasound responsive immunomodulator-loaded optical nanoplatform (FUSION) is designed to achieve spatiotemporal control and status reporting of macrophage engineering in vivo. Under the stimulation of focused ultrasound (FUS), the immune agonist encapsulated in FUSION can be released to induce selective macrophage M1 phenotype differentiation at tumor site and the near-infrared mechanoluminescence of FUSION is generated simultaneously to indicate the initiation of immune activation. Meanwhile, the persistent luminescence of FUSION is enhanced due to hydroxyl radical generation in the pro-inflammatory M1 macrophages, which can report the effectiveness of macrophage regulation. Then, macrophages labeled with FUSION as a living immunotherapeutic agent (FUSION-M) are utilized for tumor targeting and focused ultrasound activated, immune cell-based cancer therapy. By combining the on-demand activation and feedback to form a closed loop, the nanoplatform in this work holds promise in advancing the controllability of macrophage engineering and cancer immunotherapy for precision medicine.
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Unlike traditional photoluminescence (PL), mechanoluminescence (ML) achieved under mechanical excitation demonstrates unique characteristics such as high penetrability, spatial resolution, and signal-to-background ratio (SBR) for bioimaging applications. However, bioimaging with organic mechanoluminescent materials remains challenging because of the shallow penetration depth of ML with short emission wavelengths and the absence of a suitable mechanical force to generate ML in vivo. To resolve these issues, the present paper reports the achievement of ultrasound (US)-excited fluorescence and phosphorescence from purely organic luminogens for the first time with emission wavelengths extending to the red/NIR region, with the penetrability of the US-excited emission being considerably higher than that of PL. Consequently, US-excited subcutaneous phosphorescence imaging can be achieved using a mechanoluminescent-luminogen-based capsule device with a quantified intensity of 9.15 ± 1.32 × 104 p s-1 cm-2 sr-1 and an SBR of 24. Moreover, the US-excited emission can be adequately tuned using the packing modes of the conjugated skeletons, dipole orientation of mechanoluminescent luminogens, and strength and direction of intermolecular interactions. Overall, this study innovatively expands the kind of excitation sources and the emission wavelengths of organic mechanoluminescent materials, paving the way for practical biological applications based on US-excited emission.
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Ultrasonic guided waves, which are often generated and detected by piezoelectric transducers, are well established to monitor engineering structures. Wireless solutions are sought to eliminate cumbersome wire installation. This work proposes a method for remote ultrasonic-based structural health monitoring (SHM) using mechanoluminescence (ML). Propagating guided waves transmitted by a piezoelectric transducer attached to a structure induce elastic deformation that can be captured by elastico-ML. An ML coating composed of copper-doped zinc sulfide (ZnS:Cu) particles embedded in PVDF on a thin aluminium plate can be used to achieve the elastico-ML for the remote sensing of propagating guided waves. The simulation and experimental results indicated that a very high voltage would be required to reach the threshold pressure applied to the ML particles, which is about 1.5 MPa for ZnS particles. The high voltage was estimated to be 214 Vpp for surface waves and 750 Vpp for Lamb waves for the studied configuration. Several possible technical solutions are suggested for achieving ultrasonic-induced ML for future remote SHM systems.
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Multimodal luminescent materials hold great promise in a diversity of frontier applications. However, achieving the multimodal responsive luminescence at the single nanoparticle level, especially besides light stimuli, has remained a challenge. Here, we report a conceptual model to realize multimodal luminescence by constructing both mechanoluminescence and photoluminescence in a single nanoparticle. We show that the lanthanide-doped fluoride nanoparticles are able to produce excellent mechanoluminescence through X-ray irradiation, and color-tunable mechanoluminescence becomes available by selecting suitable lanthanide emitters in a core-shell-shell structure. Furthermore, the design of a multilayer core-shell nanostructure enables multimodal emissions including radioluminescence, persistent luminescence, mechanoluminescence, upconversion, downshifting, and thermal-stimulated luminescence simultaneously in a single nanoparticle under multichannel excitation and stimuli. These results provide new insights into the mechanism of X-ray induced mechanoluminescence in nanocrystals and contribute to the development of smart luminescent materials toward X-ray imaging encryption, stress sensing, and anticounterfeiting.
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Mechanoluminescence (ML) is the nonthermal luminescence generated in the process of force-to-light conversion, which has broad prospects in stress sensing, wearable devices, biomechanics, and multiple information anticounterfeiting. Multivalence emitter ions utilize their own self-reduction process to realize multiband ML without introducing another dopant, such as Eu3+/Eu2+, Sm3+/Sm2+, and Mn4+/Mn2+. However, self-reduction-induced ML in bismuth-activated materials has rarely been reported so far. In this work, a novel visible-to-near-infrared (vis-NIR) ML induced by the self-reduction of Bi3+ to Bi2+ in the spinel-type compound (MgGa2O4) is reported. The photoluminescence (PL) spectra, PL excitation (PLE) spectra, and PL lifetime curves demonstrate that Bi3+/Bi2+ ions are the main luminescence centers. Notably, the possible self-reduction model is proposed, where a magnesium vacancy (VMgâ³) is considered as the driving force for the self-reduction of Bi3+ to Bi2+. Furthermore, an oxygen vacancy (VOâ¢â¢) is confirmed by electron paramagnetic resonance (EPR) spectroscopy. Combined with thermoluminescence (TL) glow curves and ML spectra, a plausible trap-controlled ML mechanism is illustrated, where electron-hole (VOâ¢â¢/VMgâ³) pairs play a significant role in capturing electrons and holes. It is worth noting that the proof-of-concept dual-mode electronic signature application is implemented based on the flexible ML film, which improves the capabilities of signature anticounterfeiting for high-level security applications. Besides, multistimulus-responsive luminescence behaviors of the ML film are realized under the excitation of a 254 nm UV lamp, thermal disturbance, 980 nm laser, and mechanical stimuli. In general, this study provides new insights into designing vis-NIR ML materials toward wider application possibilities.
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The concept of simulating external mechanical stimuli to generate luminescence has been a long-standing aspiration in real-time dynamic visualization. However, creating self-power and self-restoring mechanoluminescent electronic skins for artificial sensors poses significant challenges. In this study, we introduce a cutting-edge triboelectric-mechanoluminescent electronic skin (TMES) that exhibits a remarkable response to multiple external stimuli. This advancement is achieved by integrating a mechanoluminescent intermediate layer within a triboelectric nanogenerator (TENG). When pressure is applied to TMES, the maximum detection voltage can reach hundreds of volts and the maximum correlation sensitivity is 11.76 V/N. Moreover, we incorporate luminescence materials into mechanoluminescence layer, and the maximum absolute sensitivity SR can reach 1.41%. The device can not only distinguish between external stimuli such as pressing and bending but also continuously track external mechanical stimuli. A 4 × 4 matrix and motion prediction of 8 different postures were established to further demonstrate the significant advantages of the developed device in spatial detection. The versatility and performance of the TMES hint at its vast potential in areas such as human-computer interaction and wearable electronics, paving the way for more intuitive and dynamic technological interfaces.
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Dispositivos Electrónicos Vestibles , Humanos , Luminiscencia , Suministros de Energía Eléctrica , Mediciones Luminiscentes/métodosRESUMEN
Elastico-mechanoluminescence technology has shown significant application prospects in stress sensing, artificial skin, remote interaction, and other research areas. Its progress mainly lies in realizing stress visualization and 2D or even 3D stress-sensing effects using a passive sensing mode. However, the widespread promotion of mechanoluminescence (ML) technology is hindered by issues such as high stress or strain thresholds and a single sensing mode based on luminous intensity. In this study, a highly efficient green-emitting ML with dual-mode stress-sensing characteristics driven by microscale strain is developed using LiTaO3:Tb3+. In addition to single-mode sensing based on the luminous intensity, the self-defined parameter (Q) is also introduced as a dual-mode factor for sensing the stress velocity. Impressively, the fabricated LiTaO3:Tb3+ film is capable of generating discernible ML signals even when supplied with strains as low as 500 µst. This is the current minimum strain value that can drive green-emitting ML. This study offers an ideal photonic platform for exploring the potential applications of rare-earth-doped elastico-ML materials in remote interaction devices, high-precision stress sensors, and single-molecule biological imaging.
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Near-infrared mechanoluminescence is a phenomenon that produces high penetrating near-infrared light under external stimulation. Near-infrared light coincides with the biological window, lower optical loss, and the fact that the mechanoluminescence material is a medium that converts mechanical energy into light energy. The near-infrared mechanoluminescence material has potential application prospects in the fields of biological imaging, medical diagnosis, and monitoring of building materials. In this article, we report on a perovskite-type Sr3Sn2O7:Nd3+ near-infrared mechanoluminescence material, and its peaks locate in the first near-infrared window (800-1000 nm) and the second near-infrared window (1080, 1350 nm), respectively. Under the condition of pre-sintering with Li2CO3 as flux, the best sintering conditions are obtained, and the luminescence of material is in perfect agreement with the applied mechanical stress. In addition, a near-infrared mechanoluminescence sensor is proposed to solve the problem of building damage and timely maintenance.
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Rayos Infrarrojos , Mediciones Luminiscentes , Titanio , Luminiscencia , Óxidos/química , Estroncio/química , Neodimio/química , Compuestos de Calcio/químicaRESUMEN
Multi-dimensional force sensing that combines intensity, location, area and the like could gather a wealth of information from mechanical stimuli. Developing materials with force-induced optical and electrical dual responses would provide unique opportunities to multi-dimensional force sensing, with electrical signals quantifying the force amplitude and the luminescence output providing spatial distribution of force. However, the reliance on external power supply and high-energy excitation source brings significant challenges to the applicability of multi-dimensional force sensors. Here we reported the mechanical energy-driven and sunlight-activated materials with force-induced dual responses, and investigated the underlying mechanisms of self-sustainable force sensing. Theoretical analysis and experimental data unraveled that trap-controlled luminescence and interfacial electron transfer play a major role in force-induced optical and electrical output. These materials were manufactured into pressure sensor with renewable dual-mode output for quantifying and visualization of pressures by electrical and optical output, respectively, without power supply and high-energy irradiation. The quantification of tactile sensation and stimuli localization of mice highlighted the multi-dimensional sensing ability of the sensor. Overall, this self-powered pressure sensor with multimodal output provides more modalities of force sensing, poised to change the way that intelligent devices sense with the world.
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Knee replacement surgery confronts challenges including patient dissatisfaction and the necessity for secondary procedures. A key requirement lies in dual-modal measurement of force and temperature of artificial joints during postoperative monitoring. Here, a novel non-toxic near-infrared (NIR) phosphor Sr3Sn2O7:Nd, Yb, is designed to realize the dual-modal measurement. The strategy is to entail phonon-assisted upconversion luminescence (UCL) and trap-controlled mechanoluminescence (ML) in a single phosphor well within the NIR biological transmission window. The phosphor is embedded in medical bone cement forming a smart joint in total knee replacements illustrated as a proof-of-concept. The sensing device can be charged in vitro by a commercial X-ray source with a safe dose rate for ML, and excited by a low power 980 nm laser for UCL. It attains impressive force and temperature sensing capabilities, exhibiting a force resolution of 0.5% per 10 N, force detection threshold of 15 N, and a relative temperature sensitive of up to 1.3% K-1 at 309 K. The stability against humidity and thermal shock together with the robustness of the device are attested. This work introduces a novel methodological paradigm, paving the way for innovative research to enhance the functionality of artificial tissues and joints in living organisms.
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Artroplastia de Reemplazo de Rodilla , Temperatura , Humanos , Estroncio/química , Iterbio/química , Luminiscencia , Neodimio/química , Mediciones Luminiscentes/métodos , Rayos InfrarrojosRESUMEN
Hybrid metal halides (HMHs) with efficient circularly polarized luminescence (CPL) have application prospects in many fields, due to their abundant host-guest structures and high photoluminescence quantum yield (PLQY). However, CPLs in HMHs are predominantly excited by light or electricity, limiting their use in multivariate environments. It is necessary to explore a novel excitation method to extend the application of chiral HMHs as smart stimuli-responsive optical materials. In this work, an enantiomeric pair of 0D hybrid manganese bromides, [H2(2R,4R)-(+)/(2S,4S)-(-)-2,4-bis(diphenylphosphino)pentane]MnBr4 [(R/S)-1] is presented, which exhibits efficient CPL emissions with near-unity PLQYs and high dissymmetry factors of ± 2.0 × 10-3. Notably, (R/S)-1 compounds exhibit unprecedented and bright circularly polarized mechanoluminescence (CPML) emissions under mechanical stimulation. Moreover, (R/S)-1 possess high mechanical force sensitivities with mechanoluminescence (ML) emissions detectable under 0.1 N force stimulation. Furthermore, this ML emission exhibits an extraordinary antithermal quenching effect in the temperature range of 300-380 K, which is revealed to originate from a thermal activation energy compensation mechanism from trap levels to Mn(II) 4T1 level. Based on their intriguing optical properties, these compounds as chiral force-responsive materials are demonstrated in multilevel confidential information encryption.
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Chirality, with its intrinsic symmetry-breaking feature, is frequently utilized in the creation of acentric crystalline functional materials that exhibit intriguing optoelectronic properties. On the other hand, the development of chiral crystals from achiral molecules offers a solution that bypasses the need for enantiopure motifs, presenting a promising alternative and thereby expanding the possibilities of the self-assembly toolkit. Nevertheless, the rational design of achiral molecules that prefer spontaneous symmetry breaking during crystallization has so far been obscure. In this study, we present a series of six achiral molecules, demonstrating that when these conformationally flexible molecules adopt a cis-conformation and engage in multiple non-covalent interactions along a helical path, they collectively self-assemble into chiral superstructures consisting of single-handed supramolecular columns. When these homochiral supramolecular columns align in parallel, they form polar crystals that exhibit intense luminescence upon grinding or scraping. We therefore demonstrate our molecular design strategy could significantly increase the likelihood of symmetry breaking in achiral molecular synthons during self-assembly, offering a facile access to novel chiral crystalline materials with unique optoelectronic properties.
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Composites comprising copper-doped zinc sulfide phosphor microparticles embedded in polydimethylsiloxane (ZnS:Cu-PDMS) have received significant attention over the past decade because of their bright and durable mechanoluminescence (ML); however, the underlying mechanism of this unique ML remains unclear. This study reports empirical and theoretical findings that confirm this ML is an electroluminescence (EL) of the ZnS:Cu phosphor induced by the triboelectricity generated at the ZnS:Cu microparticle-PDMS matrix interface. ZnS:Cu microparticles that exhibit bright ML are coated with alumina, an oxide with strong positive triboelectric properties; the contact separation between this oxide coating and PDMS, a polymer with strong negative triboelectric properties, produces sufficient interfacial triboelectricity to induce EL in ZnS:Cu microparticles. The ML of ZnS:Cu-PDMS composites varies on changing the coating material, exhibiting an intensity that is proportional to the amount of interfacial triboelectricity generated in the system. Finally, based on these findings, a mechanism that explains the ML of phosphor-polymer elastic composites (interfacial triboelectric field-driven alternating-current EL model) is proposed in this study. It is believed that understanding this mechanism will enable the development of new materials (beyond ZnS:Cu-PDMS systems) with bright and durable ML.
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The immune regulation of the lymphatic system, especially the lymph node (LN), is of great significance for the treatment of diseases and the inhibition of pathogenic organisms spreading in the body. However, achieving precise spatiotemporal control of immune cell activation in LN inâ vivo remains a challenge due to tissue depth and off-target effects. Furthermore, minimally invasive and real-time feedback methods to monitor the regulation of the immune system in LN are lacking. Here, focused ultrasound responsive immunomodulator loaded nanoplatform (FURIN) with near-infrared II (NIR-II) luminescence is designed to achieve spatiotemporally controllable immune activation in LN inâ vivo. The NIR-II persistent luminescence of FURIN can track its delivery in LN through bioimaging. Under focused ultrasound (FUS) stimulation, the immunomodulator encapsulated in FURIN can be released locally in the LN to activate immune cells such as dendritic cells and the NIR-II mechanoluminescence of FURIN provides real-time optical feedback signals for immune activation. This work points to a FUS mediated, spatiotemporal selective immune activation strategy inâ vivo with the feedback control of luminescence signals via ultrasound responsive nanocomposite, which is of great significance in improving the efficacy and reducing the side effect of immune regulation for the development of potential immunotherapeutic methods in the future.