Large-Area Near-Infrared Emission Enhancement on Single Upconversion Nanoparticles by Metal Nanohole Array.

Single lanthanide (Ln) ion doped upconversion nanoparticles (UCNPs) exhibit great potential for biomolecule sensing and counting. Plasmonic structures can improve the emission efficiency of single UCNPs by modulating the energy transferring process. Yet, achieving robust and large-area single UCNP emission modulation remains a challenge, which obstructs investigation and application of single UCNPs. Here, we present a strategy using metal nanohole arrays (NHAs) to achieve energy-transfer modulation on single UCNPs simultaneously within large-area plasmonic structures. By coupling surface plasmon polaritons (SPPs) with higher-intermediate state (1D2 → 3F3, 1D2 → 3H4) transitions, we achieved a remarkable up to 10-fold enhancement in 800 nm emission, surpassing the conventional approach of coupling SPPs with an intermediate ground state (3H4 → 3H6). We numerically simulate the electrical field distribution and reveal that luminescent enhancement is robust and insensitive to the exact location of particles. It is anticipated that the strategy provides a platform for widely exploring applications in single-particle quantitative biosensing.

Local Structure Engineering in Lanthanide-Doped Nanocrystals for Tunable Upconversion Emissions.

Upconversion emissions from lanthanide-doped nanocrystals have sparked extensive research interests in nanophotonics, biomedicine, photovoltaics, photocatalysis, etc. Rational modulation of upconversion emissions is highly desirable to meet the requirements of specific applications. Among the diverse developed methods, local structure engineering is fundamentally feasible, through which the upconversion emission intensity, selectivity, wavelength shift, and lifetime can be tuned effectively. The underlying mechanism of the local-structure-dependent upconversion emissions lies in the degree of parity hybridization and energy level splitting of lanthanide ions as well as the interionic energy transfer efficiency. Over the past few years, there has been significant progress in local-structure-engineered upconversion emissions. In this Perspective, we first introduce the principles of upconversion emissions and typical characterization methods for local structure. Subsequently, we summarize recent achievements in tuning of upconversion emissions through local structure engineering, including host composition adjustment, external field regulation, and interfacial strain management. Finally, we propose a few perspectives that should tackle the current bottlenecks. This Perspective is expected to deepen the understanding of local-structure-dependent upconversion emissions and arouse adequate attention to the engineering of local structure for desired properties of inorganic nanocrystals.

Desilylation Induced by Metal Fluoride Nanocrystals Enables Cleavage Chemistry In Vivo.

Metal fluoride nanocrystals are widely used in biomedical studies owing to their unique physicochemical properties. The release of metal ions and fluorides from nanocrystals is intrinsic due to the solubility equilibrium. It used to be considered as a drawback because it is related to the decomposition and defunction of metal fluoride nanocrystals. Many strategies have been developed to stabilize the nanocrystals, and the equilibrium concentrations of fluoride are often <1 mM. Here we make good use of this minimum amount of fluoride and unveil that metal fluoride nanocrystals could effectively induce desilylation cleavage chemistry, enabling controlled release of fluorophores and drug molecules in test tubes, living cells, and tumor-bearing mice. Biocompatible PEG (polyethylene glycol)-coated CaF2 nanocrystals have been prepared to assay the efficiency of desilylation-induced controlled release of functional molecules. We apply the strategy to a prodrug activation of monomethyl auristatin E (MMAE), showing a remarkable anticancer effect, while side effects are almost negligible. In conclusion, this desilylation-induced cleavage chemistry avails the drawback on empowering metal fluoride nanocrystals with a new function of perturbing or activating for further biological applications.

Lanthanide Upconverted Microlasing: Microlasing Spanning Full Visible Spectrum to Near-Infrared under Low Power, CW Pumping.

The miniaturization of lasers holds promise in ultradense data storage and biosensing, but greater pump power is required to reach the lasing thresholds to overcome increased optical losses with reduced resonant cavity sizes. Here, the whispering galley mode (WGM) of Yb3+ /Tm3+ doped upconversion nanoparticles (UCNPs) coupled with microcavities (≈5 µm) is used to achieve ultralow threshold upconverted lasing at 800 nm with excitation fluences as low as 4 W cm-2 . The continuous-wave (CW) upconverted lasing, with a Q factor on the order of 103 , can remain stable for more than 6 h. In addition, ultralow threshold upconverted microlasers spanning the full visible spectrum from Yb3+ /Er3+ , Yb3+ /Ho3+ , and Yb3+ /Tm3+ doped UCNPs are obtained with the same WGM cavity design. These upconverted microlasers working under low power CW 980 nm laser will enable promising applications in biosensing and imaging.

Design, Identification, and Evolution of a Surface Ruthenium(II/III) Single Site for CO Activation.

RuII compounds are widely used in catalysis, photocatalysis, and medical applications. They are usually obtained in a reductive environment as molecular O2 can oxidize RuII to RuIII and RuIV . Here we report the design, identification and evolution of an air-stable surface [bipy-RuII (CO)2 Cl2 ] site that is covalently mounted onto a polyphenylene framework. Such a RuII site was obtained by reduction of [bipy-RuIII Cl4 ]- with simultaneous ligand exchange from Cl- to CO. This structural evolution was witnessed by a combination of in situ X-ray and infrared spectroscopy studies. The [bipy-RuII (CO)2 Cl2 ] site enables oxidation of CO with a turnover frequency of 0.73×10-2  s-1 at 462 K, while the RuIII site is completely inert. This work contributes to the study of structure-activity relationship by demonstrating a practical control over both geometric and electronic structures of single-site catalysts at molecular level.

Engineering of Upconverted Metal-Organic Frameworks for Near-Infrared Light-Triggered Combinational Photodynamic/Chemo-/Immunotherapy against Hypoxic Tumors.

Metal-organic frameworks (MOFs) have shown great potential as nanophotosensitizers (nPSs) for photodynamic therapy (PDT). The use of such MOFs in PDT, however, is limited by the shallow depth of tissue penetration of short-wavelength light and the oxygen-dependent mechanism that renders it inadequate for hypoxic tumors. Here, to combat such limitations, we rationally designed core-shell upconversion nanoparticle@porphyrinic MOFs (UCSs) for combinational therapy against hypoxic tumors. The UCSs were synthesized in high yield through the conditional surface engineering of UCNPs and subsequent seed-mediated growth strategy. The heterostructure allows efficient energy transfer from the UCNP core to the MOF shell, which enables the near-infrared (NIR) light-triggered production of cytotoxic reactive oxygen species. A hypoxia-activated prodrug tirapazamine (TPZ) was encapsulated in nanopores of the MOF shell of the heterostructures to yield the final construct TPZ/UCSs. We demonstrated that TPZ/UCSs represent a promising system for achieving improved cancer treatment in vitro and in vivo via the combination of NIR light-induced PDT and hypoxia-activated chemotherapy. Furthermore, the integration of the nanoplatform with antiprogrammed death-ligand 1 (α-PD-L1) treatment promotes the abscopal effect to completely inhibit the growth of untreated distant tumors by generating specific tumor infiltration of cytotoxic T cells. Collectively, this work highlights a robust nanoplatform for combining NIR light-triggered PDT and hypoxia-activated chemotherapy with immunotherapy to combat the current limitations of tumor treatment.

Intrinsically Active Surface in a Pt/γ-Mo2N Catalyst for the Water-Gas Shift Reaction: Molybdenum Nitride or Molybdenum Oxide?

Apart from active metals, supports also contribute significantly to the catalytic performance of supported metal catalysts. On account of the formed strain and defects, the heterostructured surface of the support may play a crucial role to activate the reactant molecules, while it is usually neglected. In this work, the Pt/γ-Mo2N catalyst was prepared via a facile solution method. This Pt/γ-Mo2N catalyst showed excellent activity and stability for catalyzing the water-gas shift (WGS) reaction. The reaction rates at 240 °C were 16.5 molCO molPt-1s-1 in product-free gas and 5.36 molCO molPt-1 s-1 in full reformate gas, which were almost 20 times that of the catalysts reported. It is found that the molybdenum species in the surface of the Pt/γ-Mo2N catalyst is molybdenum oxide as MoO3. This surface MoO3 is very easily reduced even at room temperature, and it transformed into highly distorted MoOx (2 < x < 3) in the WGS reaction. The MoOx on the catalyst surface greatly enhanced the capability of generating active oxygen vacancies to dissociate H2O molecules, which induced unexpectedly superior catalytic performance. Therefore, the intrinsically active surface in the Pt/γ-Mo2N catalyst for the WGS reaction was molybdenum oxide as MoOx (2 < x < 3).

Direct Identification of Active Surface Species for the Water-Gas Shift Reaction on a Gold-Ceria Catalyst.

The crucial role of the metal-oxide interface in the catalysts of the water-gas shift (WGS) reaction has been recognized, while the precise illustration of the intrinsic reaction at the interfacial site has scarcely been presented. Here, two kinds of gold-ceria catalysts with totally distinct gold species, <2 nm clusters and 3 to 4 nm particles, were synthesized as catalysts for the WGS reaction. We found that the gold cluster catalyst exhibited a superiority in reactivity compared to gold nanoparticles. With the aid of comprehensive in situ characterization techniques, the bridged -OH groups that formed on the surface oxygen vacancies of the ceria support are directly determined to be the sole active configuration among various surface hydroxyls in the gold-ceria catalysts. The isotopic tracing results further proved that the reaction between bridged surface -OH groups and CO molecules adsorbed on interfacial Au atoms contributes dominantly to the WGS reactivity. Thus, the abundant interfacial sites in gold clusters on the ceria surface induced superior reactivity compared to that of supported gold nanoparticles in catalyzing the WGS reaction. On the basis of direct and solid experimental evidence, we have obtained a very clear image of the surface reaction for the WGS reaction catalyzed by the gold-ceria catalyst.

Scalable Direct Writing of Lanthanide-Doped KMnF3 Perovskite Nanowires into Aligned Arrays with Polarized Up-Conversion Emission.

The use of one-dimensional nano- and microstructured semiconductor and lanthanide materials is attractive for polarized-light-emission studies. Up-conversion emission from single-nanorod or anisotropic nanoparticles with a degree of polarization has also been discussed. However, microscale arrays of nanoparticles, especially well-aligned one-dimensional nanostructures as well as their up-conversion polarization characterization, have not been investigated yet. Herein, we present a novel and facile paradigm for preparing highly aligned arrays of lanthanide-doped KMnF3 (KMnF3:Ln) perovskite nanowires, which are good candidates for polarized up-conversion emission studies. These perovskite nanowires, with a width of 10 nm and length of a few micrometers, are formed through the oriented attachment of KMnF3:Ln nanocubes along the [001] direction. By the employment of KMnF3:Ln nanowire gel as nanoink, a direct-writing method is developed to obtain diverse types of aligned patterns from the nanoscale to the wafer scale. Up-conversion emissions from the highly aligned nanowire arrays are polarized along the array direction with a polarization degree up to 60%. Taking advantage of microscopic nanowire arrays, these polarized up-conversion emissions should offer potential applications in light or information transportation.

Selective Cation Exchange Enabled Growth of Lanthanide Core/Shell Nanoparticles with Dissimilar Structure.

Core/shell nanostructure is versatile for improving or integrating diverse functions, yet it is still limited to homeomorphism with isomorphic core and shell structure. Here, we delineate a selective cation exchange strategy to construct lanthanide core/shell nanoparticles with dissimilar structure. Hexagonal NaLnF4, a typical photon conversion material, was selected to grow cubic CaF2 shell to protect surface exposed Ln3+. Preferential cation exchange between Ca2+ and Na+ triggered the surface hexagonal-to-cubic structure evolution, which remediated the large barrier for heteroepitaxy of monocrystalline CaF2 shell. The heterostructured CaF2 shell leads to greatly enhanced upconversion emission with increased absolute quantum yield from 0.2% to 3.7%. Moreover, it is advantageous in suppressing the interfacial diffusion of Ln3+, as well as the leakage of Ln3+ from nanoparticle to aqueous system. These findings open up a new avenue for fabricating heterostructured core/shell nanoparticles, and are instructive for modulating various properties.

Heterodimers Made of Upconversion Nanoparticles and Metal-Organic Frameworks.

Creating nanoparticle dimers has attracted extensive interest. However, it still remains a great challenge to synthesize heterodimers with asymmetric compositions and synergistically enhanced functions. In this work, we report the synthesis of high quality heterodimers composed of porphyrinic nanoscale metal-organic frameworks (nMOF) and lanthanide-doped upconversion nanoparticles (UCNPs). Due to the dual optical properties inherited from individual nanoparticles and their interactions, absorption of low energy photons by the UCNPs is followed by energy transfer to the nMOFs, which then undergo activation of porphyrins to generate singlet oxygen. Furthermore, the strategy enables the synthesis of heterodimers with tunable UCNP size and dual NIR light harvesting functionality. We demonstrated that the hybrid architectures represent a promising platform to combine NIR-induced photodynamic therapy and chemotherapy for efficient cancer treatment. We believe that such heterodimers are capable of expanding their potential for applications in solar cells, photocatalysis, and nanomedicine.

NIR Ratiometric Luminescence Detection of pH Fluctuation in Living Cells with Hemicyanine Derivative-Assembled Upconversion Nanophosphors.

It is crucial for cell physiology to keep the homeostasis of pH, and it is highly demanded yet challenging to develop luminescence resonance energy transfer (LRET)-based near-infrared (NIR) ratiometric luminescent sensor for the detection of pH fluctuation with NIR excitation. As promising energy donors for LRET, upconversion nanoparticles (UCNPs) have been widely used to fabricate nanosensors, but the relatively low LRET efficiency limits their application in bioassay. To improve the LRET efficiency, core/shell/shell structured ß-NaGdF4@NaYF4:Yb,Tm@NaYF4 UCNPs were prepared and decorated with hemicyanine dyes as an LRET-based NIR ratiometric luminescent pH fluctuation-nanosensor for the first time. The as-developed nanosensor not only exhibits good antidisturbance ability, but it also can reversibly sense pH and linearly sense pH in a range of 6.0-9.0 and 6.8-9.0 from absorption and upconversion emission spectra, respectively. In addition, the nanosensor displays low dark toxicity under physiological temperature, indicating good biocompatibility. Furthermore, live cell imaging results revealed that the sensor can selectively monitor pH fluctuation via ratiometric upconversion luminescence behavior.

Minimizing the Heat Effect of Photodynamic Therapy Based on Inorganic Nanocomposites Mediated by 808 nm Near-Infrared Light.

Photodynamic therapy (PDT) based on photosensitizers (PSs) constructed with nanomaterials has become popular in cancer treatment, especially oral carcinoma cell. This therapy is characterized by improved PS accumulation in tumor regions and generation of reactive oxygen species (ROS) for PDT under specific excitation. In the selection of near-infrared (NIR) window, 808 nm NIR light because it can avoid the absorption of water is particularly suitable for the application in PDT. Hence, multiband emissions under a single 808 nm near-infrared excitation of Nd3+ -sensitized upconversion nanoparticles (808 nm UCNPs) have been applied for the PDT effect. 808 nm UCNPs serve as light converter to emit UV light to excite inorganic PS, graphitic carbon nitride quantum dots (CNQDs), thereby generating ROS. In this study, a nanocomposite consisting UCNPs conjugated with poly-l-lysine (PLL) to improve binding with CNQDs is fabricated. According to the research results, NIR-triggered nanocomposites of 808 nm UCNP-PLL@CNs have been verified by significant improvement in ROS generation. Consequently, 808 nm UCNP-PLL@CNs exhibit high capability for ROS production and efficient PDT in vitro and in vivo. Moreover, the mechanism of PDT treatment by 808 nm UCNP-PLL@CNs is evaluated using the cell apoptosis pathway.

Upconversion of rare Earth nanomaterials.

Rare earth nanomaterials, which feature long-lived intermediate energy levels and intraconfigurational 4f-4f transitions, are promising supporters for photon upconversion. Owing to their unique optical properties, rare earth upconversion nanomaterials have found applications in bioimaging, theranostics, photovoltaic devices, and photochemical reactions. Here, we review recent advances in the photon upconversion processes of these nanomaterials. We start by considering energy transfer models involved in the study of upconversion emissions, as well as well-established synthesis strategies to control the size and shape of rare earth upconversion nanomaterials. Progress in engineering energy transfer pathways, which play a dominant role in determining upconversion emission outputs, is then discussed. Lastly, representative optical applications of these materials are considered. The aim of this review is to provide inspiration for researchers to explore novel upconversion nanomaterials and extended optical applications.

Energy transfer in lanthanide upconversion studies for extended optical applications.

Lanthanide pairs, which can upconvert low energy photons into higher energy photons, are promising for efficient upconversion emission. A typical system with Yb(3+) as a sensitizer can convert short NIR into visible/ultraviolet light via energy transfer between lanthanide ions. Such upconverting nanocrystals doped with lanthanide ions have found significant potential in bioimaging, photochemical reactions and energy conversion. This review presents a fundamental understanding of energy transfer in lanthanide-supported photon upconversion. We introduce the emerging progress in excitation selection based on the energy transfer within lanthanide ions or activation from antennae, with an outlook in the development and applications of the lanthanide upconversion emissions.

Efficient Tailoring of Upconversion Selectivity by Engineering Local Structure of Lanthanides in Na(x)REF(3+x) Nanocrystals.

Efficient tailoring of upconversion emissions in lanthanide-doped nanocrystals is of great significance for extended optical applications. Here, we present a facile and highly effective method to tailor the upconversion selectivity by engineering the local structure of lanthanides in Na(x)REF(3+x) nanocrystals. The local structure engineering was achieved through precisely tuning the composition of nanocrystals, with different [Na]/[RE] ([F]/[RE]) ratio. It was found that the lattice parameter as well as the coordination number and local symmetry of lanthanides changed with the composition. A significant difference in the red to green emission ratio, which varied from 1.9 to 71 and 1.6 to 116, was observed for Na(x)YF(3+x):Yb,Er and Na(x)GdF(3+x):Yb,Er nanocrystals, respectively. Moreover, the local structure-dependent upconversion selectivity has been verified for Na(x)YF(3+x):Yb,Tm nanocrystals. In addition, the local structure induced upconversion emission from Er(3+) enhanced 9 times, and the CaF2 shell grown epitaxially over the nanocrystals further promoted the red emission by 450 times, which makes it superior as biomarkers for in vivo bioimaging. These exciting findings in the local structure-dependent upconversion selectivity not only offer a general approach to tailoring lanthanide related upconversion emissions but also benefit multicolor displays and imaging.

Paradigms and challenges for bioapplication of rare earth upconversion luminescent nanoparticles: small size and tunable emission/excitation spectra.

Rare earth (RE) materials, which are excited in the ultraviolet and emit in the visible light spectrum, are widely used as phosphors for lamps and displays. In the 1960's, researchers reported an abnormal emission phenomenon where photons emitted from a RE element carried more energy than those absorbed, owing to the sequential energy transfer between two RE ions--Yb(3+)-sensitized Er(3+) or Tm(3+)--in the solid state. After further study, researchers named this abnormal emission phenomenon upconversion (UC) emission. More recent approaches take advantage of solution-based synthesis, which allows creation of homogenous RE nanoparticles (NPs) with controlled size and structure that are capable of UC emission. Such nanoparticles are useful for many applications, especially in biology. For these applications, researchers seek small NPs with high upconversion emission intensity. These UCNPs have the potential to have multicolor and tunable emissions via various activators. A vast potential for future development remains by developing molecular antennas and energy transfer within RE ions. We expect UCNPs with optimized spectra behavior to meet the increasing demand of potential applications in bioimaging, biological detection, and light conversion. This Account focuses on efforts to control the size and modulate the spectra of UCNPs. We first review efforts in size control. One method is careful control of the synthesis conditions to manipulate particle nucleation and growth, but more recently researchers have learned that the doping conditions can affect the size of UCNPs. In addition, constructing homogeneous core/shell structures can control nanoparticle size by adjusting the shell thickness. After reviewing size control, we consider how diverse applications impose different requirements on excitation and/or emission photons and review recent developments on tuning of UC spectral profiles, especially the extension of excitation/emission wavelengths and the adjustment and purification of emission colors. We describe strategies that employ various dopants and others that build rationally designed nanostructures and nanocomposites to meet these goals. As the understanding of the energy transfer in the UC process has improved, core/shell structures have been proved useful for simultaneous tuning of excitation and emission wavelengths. Finally, we present a number of typical examples to highlight the upconverted emission in various applications, including imaging, detection, and sensing. We believe that with deeper understanding of emission phenomena and the ability to tune spectral profiles, UCNPs could play an important role in light conversion studies and applications.

Reversible near-infrared light directed reflection in a self-organized helical superstructure loaded with upconversion nanoparticles.

Adding external, dynamic control to self-organized superstructures with desired functionalities is an important leap necessary in leveraging the fascinating molecular systems for applications. Here, the new light-driven chiral molecular switch and upconversion nanoparticles, doped in a liquid crystal media, were able to self-organize into an optically tunable helical superstructure. The resulting nanoparticle impregnated helical superstructure was found to exhibit unprecedented reversible near-infrared (NIR) light-guided tunable behavior only by modulating the excitation power density of a continuous-wave NIR laser (980 nm). Upon irradiation by the NIR laser at the high power density, the reflection wavelength of the photonic superstructure red-shifted, whereas its reverse process occurred upon irradiation by the same laser but with the lower power density. Furthermore, reversible dynamic NIR-light-driven red, green, and blue reflections in a single thin film, achieved only by varying the power density of the NIR light, were for the first time demonstrated.

Plasmonic harvesting of light energy for Suzuki coupling reactions.

The efficient use of solar energy has received wide interest due to increasing energy and environmental concerns. A potential means in chemistry is sunlight-driven catalytic reactions. We report here on the direct harvesting of visible-to-near-infrared light for chemical reactions by use of plasmonic Au-Pd nanostructures. The intimate integration of plasmonic Au nanorods with catalytic Pd nanoparticles through seeded growth enabled efficient light harvesting for catalytic reactions on the nanostructures. Upon plasmon excitation, catalytic reactions were induced and accelerated through both plasmonic photocatalysis and photothermal conversion. Under the illumination of an 809 nm laser at 1.68 W, the yield of the Suzuki coupling reaction was ~2 times that obtained when the reaction was thermally heated to the same temperature. Moreover, the yield was also ~2 times that obtained from Au-TiOx-Pd nanostructures under the same laser illumination, where a 25-nm-thick TiOx shell was introduced to prevent the photocatalysis process. This is a more direct comparison between the effect of joint plasmonic photocatalysis and photothermal conversion with that of sole photothermal conversion. The contribution of plasmonic photocatalysis became larger when the laser illumination was at the plasmon resonance wavelength. It increased when the power of the incident laser at the plasmon resonance was raised. Differently sized Au-Pd nanostructures were further designed and mixed together to make the mixture light-responsive over the visible to near-infrared region. In the presence of the mixture, the reactions were completed within 2 h under sunlight, while almost no reactions occurred in the dark.

Zwitterions Narrow Distribution of Perovskite Quantum Wells for Blue Light-Emitting Diodes with Efficiency Exceeding 15.

While quasi-two-dimensional (quasi-2D) perovskites have emerged as promising semiconductors for light-emitting diodes (LEDs), the broad-width distribution of quantum wells hinders their efficient energy transfer and electroluminescence performance in blue emission. In particular, the underlying mechanism is closely related to the crystallization kinetics and has yet to be understood. Here for the first time, the influence of bifunctional zwitterions with different coordination affinity on the crystallization kinetics of quasi-2D perovskites is systematically investigated. The zwitterions can coordinate with Pb2+ and also act as co-spacer organic species in quasi-2D perovskites, which collectively inhibit the aggregation of colloidal precursors and shorten the distance of quantum wells. Consequently, restricted nucleation of high-n phases and promoted growth of low-n phases are achieved with moderately coordinated zwitterions, leading to the final film with a more concentrated n distribution and improved energy transfer efficiency. It thus enables high-efficiency blue LEDs with a recorded external quantum efficiency of 15.6% at 490 nm, and the operation stability has also been prolonged to 55.3 min. These results provide useful directions for tuning the crystallization kinetics of quasi-2D perovskites, which is expected to lead to high-performance perovskite LEDs.