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Showing papers by "Xiaogang Liu published in 2021"


Journal ArticleDOI
17 Feb 2021-Nature
TL;DR: In this article, the authors demonstrate ultralong-lived X-ray trapping for flat-panel-free, high-resolution, three-dimensional imaging using a series of solution-processable, lanthanide-doped nanoscintillators.
Abstract: Current X-ray imaging technologies involving flat-panel detectors have difficulty in imaging three-dimensional objects because fabrication of large-area, flexible, silicon-based photodetectors on highly curved surfaces remains a challenge1–3. Here we demonstrate ultralong-lived X-ray trapping for flat-panel-free, high-resolution, three-dimensional imaging using a series of solution-processable, lanthanide-doped nanoscintillators. Corroborated by quantum mechanical simulations of defect formation and electronic structures, our experimental characterizations reveal that slow hopping of trapped electrons due to radiation-triggered anionic migration in host lattices can induce more than 30 days of persistent radioluminescence. We further demonstrate X-ray luminescence extension imaging with resolution greater than 20 line pairs per millimetre and optical memory longer than 15 days. These findings provide insight into mechanisms underlying X-ray energy conversion through enduring electron trapping and offer a paradigm to motivate future research in wearable X-ray detectors for patient-centred radiography and mammography, imaging-guided therapeutics, high-energy physics and deep learning in radiology. Using lanthanide-doped nanomaterials and flexible substrates, an approach that enables flat-panel-free, high-resolution, three-dimensional imaging is demonstrated and termed X-ray luminescence extension imaging.

259 citations


Journal ArticleDOI
TL;DR: X-ray activated, lanthanide-based nanoparticles with a tunable emission in the biologically relevant NIR-II spectral region, which allows high-contrast, multimodal in vivo deep-tissue organ imaging.
Abstract: Persistent luminescence is not affected by background autofluorescence, and thus holds the promise of high-contrast bioimaging. However, at present, persistent luminescent materials for in vivo imaging are mainly bulk crystals characterized by a non-uniform size and morphology, inaccessible core-shell structures and short emission wavelengths. Here we report a series of X-ray-activated, lanthanide-doped nanoparticles with an extended emission lifetime in the second near-infrared window (NIR-II, 1,000-1,700 nm). Core-shell engineering enables a tunable NIR-II persistent luminescence, which outperforms NIR-II fluorescence in signal-to-noise ratios and the accuracy of in vivo multiplexed encoding and multilevel encryption, as well as in resolving mouse abdominal vessels, tumours and ureters in deep tissue (~2-4 mm), with up to fourfold higher signal-to-noise ratios and a threefold greater sharpness. These rationally designed nanoparticles also allow the high-contrast multiplexed imaging of viscera and multimodal NIR-II persistent luminescence-magnetic resonance-positron emission tomography imaging of murine tumours.

236 citations


Journal ArticleDOI
TL;DR: In this paper, metal-free organic phosphors based on a molecular design that supports efficient triplet exciton harvesting to enhance radioluminescence have been proposed for X-ray imaging.
Abstract: Materials that exhibit X-ray-excited luminescence have great potential in radiation detection, security inspection, biomedical applications and X-ray astronomy1–5. However, high-performance materials are almost exclusively limited to ceramic scintillators, which are typically prepared under high temperatures6. Herein we report metal-free organic phosphors based on a molecular design that supports efficient triplet exciton harvesting to enhance radioluminescence. These organic scintillators exhibit a detection limit of 33 nGy s–1, which is 167 times lower than the standard dosage for X-ray medical examination and we demonstrate their potential application in X-ray radiography. These findings provide a fundamental design principle and new route for the creation of promising alternatives to incumbent inorganic scintillators. Furthermore, they offer new opportunities for development of flexible, stretchable X-ray detectors and imagers for non-destructive radiography testing and medical imaging. Organic, metal-free materials that act as efficient X-ray scintillators could bring new opportunities for X-ray imaging.

170 citations


Journal ArticleDOI
TL;DR: In this article, a simple chemical strategy for achieving high-performance blue phosphors, based on confining isolated chromophores in ionic crystals, is presented, which can suppress non-radiative recombination channels and increase the phosphorescence efficiency of blue-emitting heavy-atom-free emitters.
Abstract: High-efficiency blue phosphorescence emission is essential for organic optoelectronic applications. However, synthesizing heavy-atom-free organic systems having high triplet energy levels and suppressed non-radiative transitions—key requirements for efficient blue phosphorescence—has proved difficult. Here we demonstrate a simple chemical strategy for achieving high-performance blue phosphors, based on confining isolated chromophores in ionic crystals. Formation of high-density ionic bonds between the cations of ionic crystals and the carboxylic acid groups of the chromophores leads to a segregated molecular arrangement with negligible inter-chromophore interactions. We show that tunable phosphorescence from blue to deep blue with a maximum phosphorescence efficiency of 96.5% can be achieved by varying the charged chromophores and their counterions. Moreover, these phosphorescent materials enable rapid, high-throughput data encryption, fingerprint identification and afterglow display. This work will facilitate the design of high-efficiency blue organic phosphors and extend the domain of organic phosphorescence to new applications. A strategy to confine phosphorescent organic chromophores within ionic crystals proves effective in suppressing non-radiative recombination channels and increasing the phosphorescence efficiency of blue-emitting heavy-atom-free emitters.

156 citations


Journal ArticleDOI
TL;DR: The twisted intramolecular charge transfer (TICT) mechanism has guided the development of numerous bright and sensitive fluorophores as mentioned in this paper, with emphasis on understanding the structure-property relationships between the twisted geometries and how they can directly affect the fluorescence of the molecules.
Abstract: The twisted intramolecular charge transfer (TICT) mechanism has guided the development of numerous bright and sensitive fluorophores. This review briefly overviews the history of establishing the TICT mechanism, and systematically summarizes the molecular design strategies in modulating the TICT tendency of various organic fluorophores towards different applications, along with key milestone studies and representative examples. Additionally, we also succinctly review the twisted intramolecular charge shuttle (TICS) and twists during photoinduced electron transfer (PET), and compare their similarities and differences with TICT, with emphasis on understanding the structure–property relationships between the twisted geometries and how they can directly affect the fluorescence of the molecules. Such structure–property relationships presented herein will greatly aid the rational development of fluorophores that involve molecular twisting in the excited state.

128 citations



Journal ArticleDOI
TL;DR: It is demonstrated that DNA-bridged chiral assemblies of gold nanoparticles exert a circularly-polarized-light-dependent force on the cytoskeleton, and that the light-induced periodic mechanical deformation of actin nanofibres with a frequency of 50 Hz stimulates the differentiation of neural stem cells into the neuronal phenotype.
Abstract: The biological effects of circularly polarized light on living cells are considered to be negligibly weak. Here, we show that the differentiation of neural stem cells into neurons can be accelerated by circularly polarized photons when DNA-bridged chiral assemblies of gold nanoparticles are entangled with the cells’ cytoskeletal fibres. By using cell-culture experiments and plasmonic-force calculations, we demonstrate that the nanoparticle assemblies exert a circularly-polarized-light-dependent force on the cytoskeleton, and that the light-induced periodic mechanical deformation of actin nanofibres with a frequency of 50 Hz stimulates the differentiation of neural stem cells into the neuronal phenotype. When implanted in the hippocampus of a mouse model of Alzheimer’s disease, neural stem cells illuminated following a polarity-optimized protocol reduced the formation of amyloid plaques by more than 70%. Our findings suggest that circularly polarized light can guide cellular development for biomedical use. Chiral photons can accelerate the differentiation of neural stem cells into neurons in vitro and in vivo when DNA-bridged chiral assemblies of gold nanoparticles are tightly entangled with the cells’ cytoskeletal fibres.

71 citations


Journal ArticleDOI
TL;DR: In this paper, surface coordination of bidentate picolinic acid molecules to NaGdF4:Yb/Tm nanoparticles enhances four-photon upconversion by 11,000-fold.
Abstract: Upconversion nanocrystals have been extensively investigated for optical imaging and biomedical applications1,2. However, their photoluminescence is strongly attenuated by surface quenching as the nanocrystal size diminishes3. Despite considerable efforts4,5, the quenching mechanism remains poorly understood. Here we report that surface coordination of bidentate picolinic acid molecules to NaGdF4:Yb/Tm nanoparticles enhances four-photon upconversion by 11,000-fold. Mechanistic studies indicate that surface ligand coordination reconstructs orbital hybridization and crystal-field splitting, minimizing the energy difference between the 4f orbitals of surface and inner lanthanide sensitizers. The 4f-orbital energy resonance facilitates energy migration within the ytterbium sublattice, impeding energy diffusion to surface defects and ultimately enhancing energy transfer to the emitters. Moreover, ligand coordination can exert energy-level reconstruction with a ligand–sensitizer separation of over 2 nm. These findings offer insights into the development of highly emissive nanohybrids and provide a platform for constructing optical interrogation systems at single-particle levels. Strong lanthanide-doped upconversion luminescence enhancement is achieved by the use of surface molecules which enhance four-photon upconversion emission. The results may lead to new, highly emissive, nanohybrid systems.

52 citations


Journal ArticleDOI
TL;DR: Based on the change in electron distribution of the benzopyrylium unit before and after sulfite addition, a 2-(2'-hydroxyphenyl)benzothiazole (HBT)-based fluorophore generated the ESIPT process with a near-infrared enhanced emission at 836 nm and a large Stokes shift (286 nm).

51 citations


Journal ArticleDOI
TL;DR: In this paper, the working principles and characteristics of biological neurons and synapses, which can be mimicked by memristive devices, are presented, and a perspective on challenges in developing memriserive materials for device engineering and computing science is given.
Abstract: Neuromorphic computing holds promise for building next-generation intelligent systems in a more energy-efficient way than the conventional von Neumann computing architecture. Memristive hardware, which mimics biological neurons and synapses, offers high-speed operation and low power consumption, enabling energy- and area-efficient, brain-inspired computing. Here, recent advances in memristive materials and strategies that emulate synaptic functions for neuromorphic computing are highlighted. The working principles and characteristics of biological neurons and synapses, which can be mimicked by memristive devices, are presented. Besides device structures and operation with different external stimuli such as electric, magnetic, and optical fields, how memristive materials with a rich variety of underlying physical mechanisms can allow fast, reliable, and low-power neuromorphic applications is also discussed. Finally, device requirements are examined and a perspective on challenges in developing memristive materials for device engineering and computing science is given.

51 citations


Journal ArticleDOI
TL;DR: In this paper, tetraphenylethene (TPE) and naphthalimide (NI) were connected through non-conjugated linkages and conjugate linkages.

Journal ArticleDOI
TL;DR: This review presents an overview of interparticle interactions governing their assembly in a liquid phase and discusses future research directions and challenges in controlling self-assembly at a level of precision that is most crucial to technology development.
Abstract: The self-assembly of colloidal nanoparticles has made it possible to bridge the nanoscopic and macroscopic worlds and to make complex nanostructures. The nanoparticle-mediated assembly enables many potential applications, from biodetection and nanomedicine to optoelectronic devices. Properties of assembled materials are determined not only by the nature of nanoparticle building blocks, but also by spatial positions of nanoparticles within the assemblies. A deep understanding of nanoscale interactions between nanoparticles is a prerequisite to controlling nanoparticle arrangement during assembly. In this review, we present an overview of interparticle interactions governing their assembly in a liquid phase. Considerable attention is devoted to examples that illustrate nanoparticle assembly into ordered superstructures using different types of building blocks, including plasmonic nanoparticles, magnetic nanoparticles, lanthanide-doped nanophosphors, and quantum dots. We also cover the physicochemical properties of nanoparticle ensembles, especially those arising from particle coupling effects. We further discuss future research directions and challenges in controlling self-assembly at a level of precision that is most crucial to technology development.

Journal ArticleDOI
TL;DR: In this paper, the authors developed a novel NIR heavy-atom-free photosensitizer design strategy by introducing sterically bulky and electron-rich moieties at the meso position of the pentamethine cyanine (Cy5) skeleton, which simultaneously enhanced intersystem crossing and prolonged excited-state lifetime.
Abstract: Heavy-atom-based photosensitizers usually exhibit shortened triplet-state lifetimes, which is not ideal for hypoxic tumor photodynamic therapy. Although several heavy-atom-free photosensitizers possess long triplet-state lifetimes, the clinical applicability is limited by their short excitation wavelengths, poor photon capture abilities, and intrinsically hydrophobic structures. Herein we developed a novel NIR heavy-atom-free photosensitizer design strategy by introducing sterically bulky and electron-rich moieties at the meso position of the pentamethine cyanine (Cy5) skeleton, which simultaneously enhanced intersystem crossing (ISC) and prolonged excited-state lifetime. We found that the 1O2 generation ability is directly correlated to the electron-donating ability of the meso substituent in cyanine, and the excited-state lifetime was simultaneously much elongated when the substituents were anthracene derivatives substituted at the 9-position. Our star compound, ANOMe-Cy5, exhibits intense NIR absorption, the highest 1O2 quantum yield (4.48-fold higher than Cy5), the longest triplet-state lifetime (9.80-fold longer than Cy5), and lossless emission intensity (nearly no change compared with Cy5). Such excellent photophysical properties coupled with its inherently cationic and hydrophilic nature enable the photosensitizer to realize photoablation of solid tumor and antitumor lung metastasis. This study highlights the design of a new generation of NIR photosensitizers for imaging-guided photodynamic cancer treatment.

Journal ArticleDOI
TL;DR: In this paper, the authors highlight recent advances in upconversion emission modulation enabled by coupling up-conversion nanoparticles with well-defined plasmonic nanostructures and emphasize fundamental understanding of luminescence enhancement, monochromatic emission amplification, lifetime tuning, and polarization control at nanoscale.
Abstract: Lanthanide-doped nanoparticles have great potential for energy conversion applications, as their optical properties can be precisely controlled by varying the doping composition, concentration, and surface structures, as well as through plasmonic coupling In this Perspective we highlight recent advances in upconversion emission modulation enabled by coupling upconversion nanoparticles with well-defined plasmonic nanostructures We emphasize fundamental understanding of luminescence enhancement, monochromatic emission amplification, lifetime tuning, and polarization control at nanoscale The interplay between localized surface plasmons and absorbed photons at the plasmonic metal-lanthanide interface substantially enriches the interpretation of plasmon-coupled nonlinear photophysical processes These studies will enable novel functional nanomaterials or nanostructures to be designed for a multitude of technological applications, including biomedicine, lasing, optogenetics, super-resolution imaging, photovoltaics, and photocatalysis

Journal ArticleDOI
TL;DR: FePS3 nanosheets (NSs) are explored for the first time as novel microenvironment-selective therapeutic nanoagents for bacterial biofilm infections with both self-enhanced Fenton activity for an anti-biofilm effect and reactive oxygen species (ROS) scavenging properties for anAnti-inflammatory effect.
Abstract: Bacterial biofilm infections are intractable to traditional antibiotic treatment and usually cause persistent inflammation. Chemodynamic therapy (CDT) based on the Fenton reaction has recently emerged as a promising anti-biofilm strategy. However, the therapeutic efficacy of current Fenton agents often suffers from inefficient Fenton activity and lacks anti-inflammatory capability. Herein, FePS3 nanosheets (NSs) are explored for the first time as novel microenvironment-selective therapeutic nanoagents for bacterial biofilm infections with both self-enhanced Fenton activity for an anti-biofilm effect and reactive oxygen species (ROS) scavenging properties for an anti-inflammatory effect. In biofilms with acidic microenvironments, FePS3 NSs release Fe2+ to generate toxic ROS by Fenton reaction and reductive [P2S6]4- to enhance the Fenton activity by reducing Fe3+ to Fe2+. In the surrounding normal tissues with neutral pH, FePS3 NSs scavenge ROS by reductive [P2S6]4- with an anti-inflammatory effect. This work demonstrates multifunctional Fenton nanoagents with microenvironment-selective ROS generation and elimination properties for effective treatment of bacterial biofilm infections with both anti-biofilm and anti-inflammatory effects.

Journal ArticleDOI
TL;DR: In this article, the authors presented a lanthanide nanoprobe whose electronic configuration enables long-term STED imaging with reduced background noise, achieving near-unity (98.8%) luminescence suppression under 19'kW'cm−2 saturation intensity.
Abstract: Stimulated-emission depletion (STED) microscopy has profoundly extended our horizons to the subcellular level1–3. However, it remains challenging to perform hours-long, autofluorescence-free super-resolution imaging in near-infrared (NIR) optical windows under facile continuous-wave laser depletion at low power4,5. Here we report downshifting lanthanide nanoparticles that enable background-suppressed STED imaging in all-NIR spectral bands (λexcitation = 808 nm, λdepletion = 1,064 nm and λemission = 850–900 nm), with a lateral resolution of below 20 nm and zero photobleaching. With a quasi-four-level configuration and long-lived (τ > 100 μs) metastable states, these nanoparticles support near-unity (98.8%) luminescence suppression under 19 kW cm−2 saturation intensity. The all-NIR regime enables high-contrast deep-tissue (~50 μm) imaging with approximately 70 nm spatial resolution. These lanthanide nanoprobes promise to expand the application realm of STED microscopy and pave the way towards high-resolution time-lapse investigations of cellular processes at superior spatial and temporal dimensions. The application of stimulated-emission depletion (STED) microscopy for deep-tissue imaging in the near-infrared optical window is challenged by high cellular autofluorescence. Here the authors present a lanthanide nanoprobe whose electronic configuration enables long-term STED imaging with reduced background noise.

Journal ArticleDOI
TL;DR: In this paper, the insertion of an indazole unit into ICT scaffold can fully amplify the intramolecular rotation in donor-indazoleπ-acceptor fluorophores, whereas efficiently suppressing the rotation in their EWT-substituted system (fluorescence ON).
Abstract: Intramolecular charge transfer (ICT) is a fundamental mechanism that enables the development of numerous fluorophores and probes for bioimaging and sensing. However, the electron-withdrawing targets (EWTs)-induced fluorescence quenching is a long-standing and unsolved issue in ICT fluorophores, and significantly limits the widespread applicability. Here we report a simple and generalizable structural-modification for completely overturning the intramolecular rotation driving energy, and thus fully reversing the ICT fluorophores' quenching mode into light-up mode. Specifically, the insertion of an indazole unit into ICT scaffold can fully amplify the intramolecular rotation in donor-indazole-π-acceptor fluorophores (fluorescence OFF), whereas efficiently suppressing the rotation in their EWT-substituted system (fluorescence ON). This molecular strategy is generalizable, yielding a palette of chromophores with fluorescence umpolung that spans visible and near-infrared range. This strategy expands the bio-analytical toolboxes and allows exploiting ICT fluorophores for light-up sensing of EWTs including N-acetyltransferases and nerve agents.

Journal ArticleDOI
TL;DR: In this article, the anti-Stokes emission within nanometric volumes enables the design of ultracompact, miniaturized photonic devices for a host of applications, such as photonic sensors.
Abstract: Efficient generation of anti-Stokes emission within nanometric volumes enables the design of ultracompact, miniaturized photonic devices for a host of applications. Many subwavelength crystals, suc...

Journal ArticleDOI
TL;DR: In this article, a bio-orthogonal nanoprobes with high tumor-targeting specificity for in vivo NIR-IIb luminescence imaging and magnetic resonance imaging (MRI) is reported.
Abstract: Lanthanide-based NIR-IIb nanoprobes are ideal for in vivo imaging. However, existing NIR-IIb nanoprobes often suffer from low tumor-targeting specificity, limiting their widespread use. Here the application of bioorthogonal nanoprobes with high tumor-targeting specificity for in vivo NIR-IIb luminescence imaging and magnetic resonance imaging (MRI) is reported. These dual-modality nanoprobes can enhance NIR-IIb emission by 20-fold and MRI signal by twofold, compared with non-bioorthogonal nanoprobes in murine subcutaneous tumors. Moreover, these bioorthogonal probes enable orthotopic brain tumor imaging. Implementation of bio-orthogonal chemistry significantly reduces the nanoprobe dose and hence cytotoxicity, providing a paradigm for real-time in vivo visualization of tumors.

Journal ArticleDOI
TL;DR: In this paper, a probe, LD-FG, was proposed for imaging lipid droplet dynamics using structured illumination microscopy (SIM) for long-term super-resolution imaging of live cells.
Abstract: Although super-resolution imaging offers an opportunity to visualize cellular structures and organelles at the nanoscale level, cellular heterogeneity and unpredictability still pose a significant challenge in the dynamic imaging of live cells. It is thus vital to develop better-performing and more photostable probes for long-term super-resolution imaging. Herein, we report a probe, LD-FG, for imaging lipid droplet (LD) dynamics using structured illumination microscopy (SIM). LD-FG allows wash-free imaging of LDs, owing to a hydrogen-bond sensitive fluorogenic response. The replacement of photobleached LD-FG by intact probe molecules outside the LDs ensures the long-time stability of the fluorescence imaging. With this buffering fluorogenic probe, fast and unpredictable dynamic processes of LDs can be visualized. Using this probe, two LD coalescence modes were discovered. The dynamic imaging also allowed us to propose a new model of LD maturation during adipocyte differentiation, i.e., a fast LD coalescence followed by a slow ripening step. The excellent performance of LD-FG makes the buffer strategy an effective method for designing fluorescent probes for cell dynamic imaging.

Journal ArticleDOI
TL;DR: In this paper, a donor-acceptor energy-relaying exciplex and its utility in fabricating single-emissive-layer, thermally activated delayed fluorescence-based white organic light-emitting diodes was reported.
Abstract: Development of white organic light-emitting diodes based on purely thermally activated delayed fluorescence with a single-emissive-layer configuration has been a formidable challenge. Here, we report the rational design of a donor-acceptor energy-relaying exciplex and its utility in fabricating single-emissive-layer, thermally activated delayed fluorescence-based white organic light-emitting diodes that exhibit 100% internal quantum efficiency, 108.2 lm W−1 power efficiency, and 32.7% external quantum efficiency. This strategy enables thin-film fabrication of an 8 cm × 8 cm thermally activated delayed fluorescence white organic light-emitting diodes (10 inch2) prototype with 82.7 lm W−1 power efficiency and 25.0% external quantum efficiency. Introduction of a phosphine oxide-based acceptor with a steric group to the exciplex limits donor-acceptor triplet coupling, providing dual levels of high-lying and low-lying triplet energy. Transient spectroscopic characterizations confirm that a ladder-like energy relaying occurs from the high-lying triplet level of the exciplex to a blue emitter, then to the low-lying triplet level of the phosphine oxide acceptor, and ultimately to the yellow emitter. Our results demonstrate the broad applicability of energy relaying in multicomponent systems for exciton harvesting, providing opportunities for the development of third-generation white organic light-emitting diode light sources. Realizing efficient white organic light-emitting diodes (WOLEDs) with a single thermally-activated delayed fluorescence (TADF) emissive layer remains a challenge. Here, the authors design energy-relaying exciplex hosts with multi-triplet excited states for efficient single-emissive-layer TADF WOLEDs.

Journal ArticleDOI
TL;DR: Nanomaterials have presented promising strategies for tumor treatment in recent years as discussed by the authors, and they combine therapeutic and bio-imaging functionalities at the single nanoparticle level.


Journal ArticleDOI
TL;DR: In this paper, the 9,10-diphenylanthracene (9, 10-DPA) single crystals are used as a representative model, which are grown via low-temperature solution processes, exhibiting intense X-ray radioluminescence with ultrahigh photon-conversion efficiency, ultrafast response and high sensitivity.
Abstract: Low-dose, high-resolution X-ray imaging is vital for medical diagnostics and material/device analyses. Current X-ray imagers are dominated by expensive inorganic materials via high-temperature solid processes (up to 1700 °C, e.g., CsI:Tl) with heavy metal elements. It is essential to search for new materials as X-ray imagers with low growth temperature, low cost, high sensitivity, along with high chemical and environmental stability. Here, 9,10-diphenylanthracene (9,10-DPA) single crystals are used as a representative model, which are grown via low-temperature solution processes, exhibiting intense X-ray radioluminescence with ultrahigh photon-conversion efficiency, ultrafast response and high sensitivity. The resolution of devices based on organic crystals exceeds 20.00 lp mm-1 . Meanwhile the crystals exhibit high cycle performance under X-ray irradiation and environmental stability. This study demonstrates that organic semiconductors have potential use in low-cost, high-sensitivity and low-dose X-ray imaging systems.

Journal ArticleDOI
TL;DR: In this article, the authors demonstrate photon upconversion of diverse lanthanide emitters by harnessing triplet exciton-mediated energy relay, which is less dependent on excitation power and enhances the emission intensity of Tb3+ by 158 times.
Abstract: Exploration of upconversion luminescence from lanthanide emitters through energy migration has profound implications for fundamental research and technology development. However, energy migration-mediated upconversion requires stringent experimental conditions, such as high power excitation and special migratory ions in the host lattice, imposing selection constraints on lanthanide emitters. Here we demonstrate photon upconversion of diverse lanthanide emitters by harnessing triplet exciton-mediated energy relay. Compared with gadolinium-based systems, this energy relay is less dependent on excitation power and enhances the emission intensity of Tb3+ by 158-fold. Mechanistic investigations reveal that emission enhancement is attributable to strong coupling between lanthanides and surface molecules, which enables fast triplet generation (<100 ps) and subsequent near-unity triplet transfer efficiency from surface ligands to lanthanides. Moreover, the energy relay approach supports long-distance energy transfer and allows upconversion modulation in microstructures. These findings enhance fundamental understanding of energy transfer at molecule-nanoparticle interfaces and open exciting avenues for developing hybrid, high-performance optical materials. Photon upconversion in lanthanide-doped nanoparticles enables important technological developments. Here the authors demonstrate a mechanism leading to enhanced upconversion emission in core-shell nanoparticles, and long-distance energy transfer between nanoparticles, through triplet state population of an organic surface ligand.

Journal ArticleDOI
TL;DR: In this paper, the authors report close proximity tetrazine-dye conjugates with minimal distance between tetrazines and the fluorophore, and demonstrate their potential for live cell imaging in combination with unnatural amino acids, wash-free multicolor and super-resolution STED, and SOFI imaging.
Abstract: Small-molecule fluorophores enable the observation of biomolecules in their native context with fluorescence microscopy. Specific labeling via bio-orthogonal tetrazine chemistry combines minimal label size with rapid labeling kinetics. At the same time, fluorogenic tetrazine-dye conjugates exhibit efficient quenching of dyes prior to target binding. However, live-cell compatible long-wavelength fluorophores with strong fluorogenicity have been difficult to realize. Here, we report close proximity tetrazine-dye conjugates with minimal distance between tetrazine and the fluorophore. Two synthetic routes give access to a series of cell-permeable and -impermeable dyes including highly fluorogenic far-red emitting derivatives with electron exchange as the dominant excited-state quenching mechanism. We demonstrate their potential for live-cell imaging in combination with unnatural amino acids, wash-free multicolor and super-resolution STED, and SOFI imaging. These dyes pave the way for advanced fluorescence imaging of biomolecules with minimal label size.

Journal ArticleDOI
Yiming Wu1, Jiahui Xu1, Xian Qin1, Jun Xu1, Xiaogang Liu 
TL;DR: In this article, a programmable logic gate array based on opto-electrochemical modulation can be constructed to convert information-encrypted electrical signals into visible patterns with millisecond photonic readout.
Abstract: Controlling nonlinear optical signals electrically offers many opportunities for technological developments. Lanthanide-activated nanoparticles have recently emerged as leading platforms for nonlinear upconversion of infra-red excitation within nanometric volumes. However, manipulation of upconversion emission is restricted to varying percentages of component materials, nanocrystal structure, and optical pumping conditions. Here, we report temporal modulation of anti-Stokes luminescence by coupling upconversion nanoparticles with an electrochemically responsive molecule. By electrically tailoring orbital energy levels of the molecules anchored on nanoparticle surfaces, we demonstrate reversible control of molecular absorption, resulting in dynamic colour editing of anti-Stokes luminescence at single-particle resolution. Moreover, we show that a programmable logic gate array based on opto-electrochemical modulation can be constructed to convert information-encrypted electrical signals into visible patterns with millisecond photonic readout. These findings offer insights into precise control of anti-Stokes luminescence, while enabling a host of applications from low-threshold infrared logic switches to multichannel, high-fidelity photonic circuits. Though upconversion nanoparticles (UCNPs) are attractive for infrared detecting and modulating photonic devices, devising strategies to electrically manipulate upconversion emission remain a challenge. Here, the authors report molecule-assisted opto-electrochemical modulation of UCNP luminescence.

Journal ArticleDOI
TL;DR: In this article, a simple bilayer spintronic device for hardware implementation of neuromorphic computing is demonstrated, using the L11 -CuPt/CoPt bilayer as a sigmoidal neuron.
Abstract: Neuromorphic computing has become an increasingly popular approach for artificial intelligence because it can perform cognitive tasks more efficiently than conventional computers. However, it remains challenging to develop dedicated hardware for artificial neural networks. Here, a simple bilayer spintronic device for hardware implementation of neuromorphic computing is demonstrated. In L11 -CuPt/CoPt bilayer, current-inducted field-free magnetization switching by symmetry-dependent spin-orbit torques shows a unique domain nucleation-dominated magnetization reversal, which is not accessible in conventional bilayers. Gradual domain nucleation creates multiple intermediate magnetization states which form the basis of a sigmoidal neuron. Using the L11 -CuPt/CoPt bilayer as a sigmoidal neuron, the training of a deep learning network to recognize written digits, with a high recognition rate (87.5%) comparable to simulation (87.8%) is further demonstrated. This work offers a new scheme of implementing artificial neural networks by magnetic domain nucleation.

Journal ArticleDOI
TL;DR: In this paper, high water-soluble fluorescent polyaromatic-based imidazolium compounds capable of detecting a wide range of nitroaromatics, e.g., nitrophenols and picric acid in aqueous solution with fully quenched fluorescence are reported.
Abstract: Highly water-soluble fluorescent polyaromatic-based imidazolium compounds capable of detecting a wide-range of nitroaromatics, e.g., nitrophenols and picric acid in aqueous solution with fully quenched fluorescence are reported. The two probes contained an anthracene and pyrene group with the increased size and angularity of the pyrene ring in pyrene-based imidazolium (PIM) raising the hydrophobicity or π-π stacking and sensitivity of the probe towards all mono-, di-, and trinitrophenols even under harsh conditions (pH 4-8). The high affinity for nitrophenols was confirmed by single crystal X-ray crystallography. Time-dependent density functional theory (TD-DFT) reveals cation-anion interactions between the imidazolium and picrate ions causing fluorescent quenching through PET and charge transfer involving a dark S1 excited state.

Journal ArticleDOI
TL;DR: A review article is on recent developments while including foundational knowledge for some of the critical concepts in neural prostheses, with emphasis on texture recognition and sensory stimulation strategies that reestablish the lost sensory feedback loop.
Abstract: Current developments being made in upper limb prostheses are focused on replacing lost sensory information to the amputees. Providing sensory stimulation from the prosthesis can directly improve control over the prosthetic and provide a sense of body ownership. The focus of this review article is on recent developments while including foundational knowledge for some of the critical concepts in neural prostheses. Reported concepts follow the flow of information from sensors to signal processing, with emphasis on texture recognition, and then to sensory stimulation strategies that reestablish the lost sensory feedback loop. Prosthetic sensors are used to detect the physical environment, converting pressure, force, and position into electrical signals. The electrical signals can then be processed in an effort to identify the surrounding environment using distinctive characteristics such as stiffness and texture. In order for the amputee to use this information in a natural manner, there must be real-time sensory stimulation, perception, and motor control of the prosthesis. Although truly complete sensory replacement has not yet been realized, some basic percepts can be partially restored, allowing progress towards a more realistic prosthesis with natural sensations.