Designing a Hypoxia-Activated Sensing Platform Using an Azo Group-Triggered Reaction with the Formation of Silicon Nanoparticles.

Hypoxia is known as a specific signal of various diseases, such as liver fibrosis. We designed a hypoxia-sensitive fluorometric approach that cleaved the azo bond (N═N) in the presence of hypoxia-controlled agents (sodium dithionite and azoreductase). 4-(2-Pyridylazo) resorcinol (Py-N═N-RC) bears a desirable hypoxia-responsive linker (N═N), and its azo bond breakup can only occur in the presence of sodium dithionite and azoreductase and leads to the release of 2,4-dihydroxyaniline, which can react with 3-[2-(2-aminoethylamino)ethylamino]propyltrimethoxysilane to generate yellow fluorescent silicon nanoparticles. This approach exhibited high selectivity and sensitivity toward both sodium dithionite and azoreductase over other potential interferences. The mouse liver microsome, which is known to contain azoreductase, was applied and confirmed the feasibility of the designed platform. Py-N═N-RC is expected to be a practical substrate for hypoxia-related biological analyses. Furthermore, silicon nanoparticles were successfully applied for Hela cell imaging owing to their negligible cytotoxicity and superb biocompatibility.

Organic-Inorganic Hybrid Cuprous-Based Metal Halides with Unique Two-Dimensional Crystal Structure for White Light-Emitting Diodes.

Ternary cuprous (Cu+)-based metal halides, represented by cesium copper iodide (e.g., CsCu2I3 and Cs3Cu2I5), are garnering increasing interest for light-emitting applications owing to their intrinsically high photoluminescence quantum yield and direct bandgap. Toward electrically driven light-emitting diodes (LEDs), it is highly desirable for the light emitters to have a high structural dimensionality as it may favor efficient electrical injection. However, unlike lead-based halide perovskites whose light-emitting units can be facilely arranged in three-dimensional (3D) ways, to date, nearly all ternary Cu+-based metal halides crystallize into 0D or 1D networks of Cu-X (X = Cl, Br, I) polyhedra, whereas 3D and even 2D structures remain mostly uncharted. Here, by employing a fluorinated organic cation, we report a new kind of ternary Cu+-based metal halides, (DFPD)CuX2 (DFPD+ = 4,4-difluoropiperidinium), which exhibits unique 2D layered crystal structure. Theoretical calculations reveal a highly dispersive conduction band of (DFPD)CuBr2, which is beneficial for charge carrier injection. It is also of particular significance to find that the 2D (DFPD)CuBr2 crystals show appealing properties, including improved ambient stability and an efficient warm white-light emission, making it a promising candidate for single-component lighting and display applications.

Continuous Solar Energy Conversion Windows Integrating Zinc Anode-Based Electrochromic Device and IoT System.

Integration of solar cells and electrochromic windows offers crucial contributions to green buildings. Solar-charging zinc anode-based electrochromic devices (ZECDs) present opportunities for addressing the solar intermittency issue. However, the limited energy storage capacity of ZECDs results in wasted harnessing of solar energy as well as overcharging. Herein, spectral-selective dual-band ZECDs that continuously transport solar energy to indoor appliances by remotely controlling the repeated bleached-tinted cycles during the daytime, are reported. Hexagonal phase cesium-doped tungsten bronze (h-Cs0.32WO3, CWO) nanocrystals are adopted for dual-band ZECDs due to their independent control ability of near-infrared (NIR) and visible (VIS) light transmittance (∆T = 73.0%, 700 nm; ∆T = 83.7%, 1200 nm) and excellent cycling stability (0.8% optical contrast decay at 1200 nm after 10 000 cycles). The prototype device (i.e., CWO//Zn//CWO) delivers extraordinary thermal insulation capability, displaying a 10 °C difference between "bright" and "dark" modes. Furthermore, an Internet of Things (IoT) controller to control the NIR and VIS lights of the CWO//Zn//CWO window wirelessly with a smartphone, empowering the continuous discharging of the solar-charged window during the daytime remotely, is developed. Such windows represent an intriguing potential technology whose future impact on green buildings may be substantial.

Robust links in photoactive covalent organic frameworks enable effective photocatalytic reactions under harsh conditions.

Developing heterogeneous photocatalysts for the applications in harsh conditions is of high importance but challenging. Herein, by converting the imine linkages into quinoline groups of triphenylamine incorporated covalent organic frameworks (COFs), two photosensitive COFs, namely TFPA-TAPT-COF-Q and TFPA-TPB-COF-Q, are successfully constructed. The obtained quinoline-linked COFs display improved stability and photocatalytic activity, making them suitable photocatalysts for photocatalytic reactions under harsh conditions, as verified by the recyclable photocatalytic reactions of organic acid involving oxidative decarboxylation and organic base involving benzylamine coupling. Under strong oxidative condition, the quinoline-linked COFs show a high efficiency up to 11831.6 µmol·g-1·h-1 and a long-term recyclable usability for photocatalytic production of H2O2, while the pristine imine-linked COFs are less catalytically active and easily decomposed in these harsh conditions. The results demonstrate that enhancing the linkage robustness of photoactive COFs is a promising strategy to construct heterogeneous catalysts for photocatalytic reactions under harsh conditions.

Optimizing Energy Levels and Improving Film Compactness in PbS Quantum Dot Solar Cells by Silver Doping.

PbS quantum dot (QD) solar cells harvest near-infrared solar radiation. Their conventional hole transport layer has limited hole collection efficiency due to energy level mismatch and poor film quality. Here, how to resolve these two issues by using Ag-doped PbS QDs are demonstrated. On the one hand, Ag doping relieves the compressive stress during layer deposition and thus improves film compactness and homogeneity to suppress leakage currents. On the other hand, Ag doping increases hole concentration, which aligns energy levels and increases hole mobility to boost hole collection. Increased hole concentration also broadens the depletion region of the active layer, decreasing interface charge accumulation and promoting carrier extraction efficiency. A champion power conversion efficiency of 12.42% is achieved by optimizing the hole transport layer in PbS QD solar cells, compared to 9.38% for control devices. Doping can be combined with compressive strain relief to optimize carrier concentration and energy levels in QDs, and even introduce other novel phenomena such as improved film quality.

Fast and Stable Zinc Anode-Based Electrochromic Displays Enabled by Bimetallically Doped Vanadate and Aqueous Zn2+/Na+ Hybrid Electrolytes.

Vanadates are a class of the most promising electrochromic materials for displays as their multicolor characteristics. However, the slow switching times and vanadate dissolution issues of recently reported vanadates significantly hinder their diverse practical applications. Herein, novel strategies are developed to design electrochemically stable vanadates having rapid switching times. We show that the interlayer spacing is greatly broadened by introducing sodium and lanthanum ions into V3O8 interlayers, which facilitates the transportation of cations and enhances the electrochemical kinetics. In addition, a hybrid Zn2+/Na+ electrolyte is designed to inhibit vanadate dissolution while significantly accelerating electrochemical kinetics. As a result, our electrochromic displays yield the most rapid switching times in comparison with any reported Zn-vanadate electrochromic displays. It is envisioned that stable vanadate-based electrochromic displays having video speed switching are appearing on the near horizon.

Highly Enhancing CO2 Photoreduction by Metallization of an Imidazole-linked Robust Covalent Organic Framework.

Converting CO2 into value-added chemicals to solve the issues caused by carbon emission is promising but challenging. Herein, by embedding metal ions (Co2+ , Ni2+ , Cu2+ , and Zn2+ ) into an imidazole-linked robust photosensitive covalent organic framework (PyPor-COF), effective photocatalysts for CO2 conversion are rationally designed and constructed. Characterizations display that all of the metallized PyPor-COFs (M-PyPor-COFs) display remarkably high enhancement in their photochemical properties. Photocatalysis reactions reveal that the Co-metallized PyPor-COF (Co-PyPor-COF) achieves a CO production rate as high as up to 9645 µmol g-1 h-1 with a selectivity of 96.7% under light irradiation, which is more than 45 times higher than that of the metal-free PyPor-COF, while Ni-metallized PyPor-COF (Ni-PyPor-COF) can further tandem catalyze the generated CO to CH4 with a production rate of 463.2 µmol g-1 h-1 . Experimental analyses and theory calculations reveal that their remarkable performance enhancement on CO2 photoreduction should be attributed to the incorporated metal sites in the COF skeleton, which promotes the adsorption and activation of CO2 and the desorption of generated CO and even reduces the reaction energy barrier for the formation of different intermediates. This work demonstrates that by metallizing photoactive COFs, effective photocatalysts for CO2 conversion can be achieved.

Magnetic Field-Assisted Interface Embedding Strategy to Construct 2D/3D Composite Structure for Stable Perovskite Solar Cells with Efficiency Over 24.

Perovskite solar cells (PSCs) based on 2D/3D composite structure have shown enormous potential to combine high efficiency of 3D perovskite with high stability of 2D perovskite. However, there are still substantial non-radiative losses produced from trap states at grain boundaries or on the surface of conventional 2D/3D composite structure perovskite film, which limits device performance and stability. In this work, a multifunctional magnetic field-assisted interfacial embedding strategy is developed to construct 2D/3D composite structure. The composite structure not only improves crystallinity and passivates defects of perovskite layer, but also can efficiently promote vertical hole transport and provide lateral barrier effect. Meanwhile, the composite structure also forms a good surface and internal encapsulation of 3D perovskite to inhibit water diffusion. As a result, the multifunctional effect effectively improves open-circuit voltage and fill factor, reaching maximum values of 1.246 V and 81.36%, respectively, and finally achieves power conversion efficiency (PCE) of 24.21%. The unencapsulated devices also demonstrate highly improved long-term stability and humidity stability. Furthermore, an augmented performance of 21.23% is achieved, which is the highest PCE of flexible device based on 2D/3D composite perovskite films coupled with the best mechanical stability due to the 2D/3D alternating structure.

Intelligent interior atmosphere lamp system based on quantum dot LEDs for safe driving assistance.

A driver safety assisting system is essential to reduce the probability of traffic accidents. But most of the existing driver safety assisting systems are simple reminders that cannot improve the driver's driving status. This paper proposes a driver safety assisting system to reduce the driver's fatigue degree by the light with different wavelengths that affect people's moods. The system consists of a camera, an image processing chip, an algorithm processing chip, and an adjustment module based on quantum dot LEDs (QLEDs). Through this intelligent atmosphere lamp system, the experimental results show that blue light reduced the driver's fatigue degree when just turned on; but as time went on, the driver's fatigue degree rebounded rapidly. Meanwhile, red light prolonged the driver's awake time. Different from blue light alone, this effect can remain stable for a long time. Based on these observations, an algorith was designed to quantify the degree of fatigue and detect its rising trend. In the early stage, the red light is used to prolong the awake time and the blue light to suppress when the fatigue value increases, so as to maximize the awake driving time. The result showed that our device prolonged the awake driving time of the drivers by 1.95 times and reduced fatigue during driving: the quantitative value of fatigue degree generally decreased by about 0.2 times. In most experiments, the subjects were able to complete four hours of safe driving, which reached the maximum length of continuous driving at night allowed by China laws. In conclusion, our system changes the assisting system from a reminder to a helper, thus effectively reducing the driving risk.

Boosting charge separation in graphdiyne quantum dots/hollow tubular carbon nitride heterojunction for water pollutant degradation.

Non-desirable solar energy absorption and poor charge transfer efficiency are two problems that limit the peroxymonosulfate (PMS) photocatalytic techniques. Herein, a metal-free boron-doped graphdiyne quantum dot (BGDs) modified hollow tubular g-C3N4 photocatalyst (BGD/TCN) was synthesized to activate PMS and achieved effective space separation of carriers for degradation of bisphenol A. With 0.5 mM PMS, the degradation rate of bisphenol A (20 ppm) was 0.0634 min-1, 3.7-fold higher than that of TCN itself. The roles of BGDs in the distribution of electrons and photocatalytic property were well identified by experiments and density functional theory (DFT) calculations. The possible degradation intermediate products of bisphenol A were monitored by mass spectrometer and demonstrated to be nontoxic using ecological structure activity relationship modeling (ECOSAR). Finally, this newly-designed material was successfully applied in actual water bodies, which further renders its promising prospect for actual water remediation.

Halide Double Perovskite Nanocrystals Doped with Rare-Earth Ions for Multifunctional Applications.

Most lead-free halide double perovskite materials display low photoluminescence quantum yield (PLQY) due to the indirect bandgap or forbidden transition. Doping is an effective strategy to tailor the optical properties of materials. Herein, efficient blue-emitting Sb3+ -doped Cs2 NaInCl6 nanocrystals (NCs) are selected as host, rare-earth (RE) ions (Sm3+ , Eu3+ , Tb3+ , and Dy3+ ) are incorporated into the host, and excellent PLQY of 80.1% is obtained. Femtosecond transient absorption measurement found that RE ions not only served as the activator ions but also filled the deep vacancy defects. Anti-counterfeiting, optical thermometry, and white-light-emitting diodes (WLEDs) are exhibited using these RE ions-doped halide double perovskite NCs. For the optical thermometry based on Sm3+ -doped Cs2 NaInCl6 :Sb3+ NCs, the maximum relative sensitivity is 0.753% K-1 , which is higher than those of most temperature-sensing materials. Moreover, the WLED fabricated by Sm3+ -doped Cs2 NaInCl6 :Sb3+ NCs@PMMA displays CIE color coordinates of (0.30, 0.28), a luminous efficiency of 37.5 lm W-1 , a CCT of 8035 K, and a CRI over 80, which indicate that Sm3+ -doped Cs2 NaInCl6 :Sb3+ NCs are promising single-component white-light-emitting phosphors for next-generation lighting and display technologies.

Wide-coverage and Efficient NIR Emission from Single-component Nanophosphors through Shaping Multiple Metal-halide Packages.

Wide-coverage near infrared (NIR) phosphor-converted LEDs possess promising potential for practical applications, but little is developed towards the efficient and wide-coverage NIR phosphors. Here, we report the single-component lanthanide (Ln3+ ) ions doped Cs2 M(In0.95 Sb0.05 )Cl6 (M=alkali metal) nanocrystals (NCs), exhibiting emission from 850 to 1650 nm with high photoluminescence quantum yield of 20.3 %, which is accomplished by shaping the multiple metal halide octahedra of double perovskite via the simple alkali metal substitution. From Judd-Ofelt theoretical calculation and spectroscopic investigations, the shaping of metal halide octahedra in Cs2 M(In1-x Sbx )Cl6 NCs can break the forbidden of f-f transition of Ln3+ , thus increasing their radiative transition rates and simultaneously boosting the energy transfer efficiency from host to Ln3+ . Finally, the wide-coverage NIR LEDs based on Sm3+ , Nd3+ , Er3+ -tridoped Cs2 K0.5 Rb0.5 (In0.95 Sb0.05 )Cl6 NCs are fabricated and employed in the multiplex gas sensing and night-vision application.

Near-Infrared LEDs Based on Quantum Cutting-Activated Electroluminescence of Ytterbium Ions.

Cesium lead halide perovskite nanocrystals (PNCs) exhibit promising prospects for application in optoelectronic devices. However, electroactivated near-infrared (NIR) PNC light-emitting diodes (LEDs) with emission peaks over 800 nm have not been achieved. Herein, we demonstrate the electroactivated NIR PNC LEDs based on Yb3+-doped CsPb(Cl1-xBrx)3 PNCs with extraordinary high NIR photoluminescence quantum yields over 170%. The fabricated NIR LEDs possess an irradiance of 584.7 µW cm-2, an EQE of 1.2%, and a turn-on voltage of 3.1 V. The ultrafast quantum cutting process from the PNC host to Yb3+ has been revealed as the main mechanism of electroluminescence (EL)-activated Yb3+ for the first time via exploring how the trend between the EL intensity of PNC and Yb3+ varies with different voltages along with the tendency of temperature- and doping-concentration-dependent PL and EL spectra. This work will extend the application of PNCs to optical communication, night-vision devices, and biomedical imaging.

Machine Learning Guided Discovery of Superoxide Dismutase Nanozymes for Androgenetic Alopecia.

Androgenetic alopecia (AGA) is a common form of hair loss, which is mainly caused by oxidative stress induced dysregulation of hair follicles (HF). Herein, a highly efficient manganese thiophosphite (MnPS3) based superoxide dismutase (SOD) mimic was discovered using machine learning (ML) tools. Remarkably, the IC50 of MnPS3 is 3.61 µg·mL-1, up to 12-fold lower than most reported SOD-like nanozymes. Moreover, a MnPS3 microneedle patch (MnMNP) was constructed to treat AGA that could diffuse into the deep skin where HFs exist and remove excess reactive oxygen species. Compared with the widely used minoxidil, MnMNP exhibits higher ability on hair regeneration, even at a reduced frequency of application. This study not only provides a general guideline for the accelerated discovery of SOD-like nanozymes by ML techniques, but also shows a great potential as a next generation approach for rational design of nanozymes.

High-Performance Perovskite Light-Emitting Diodes Enabled by Passivating Defect and Constructing Dual Energy-Transfer Pathway through Functional Perovskite Nanocrystals.

Quasi-2D perovskites have emerged as a promising luminescent material for perovskite light-emitting diodes (Pe-LEDs). However, efficiency and stability are still obstacles to practical application due to numerous defects and inefficient energy transfer of perovskite films. Herein, functional phenethylammonium bromine-modified CsPbBr3 nanocrystals (PEA-CsPbBr3 NCs) are first introduced as multifunctional additive to simultaneously improve abovementioned problems. PEA-CsPbBr3 NCs not only serve as heteronuclear seeds and trigger growth, thus greatly reducing leakage current, but also deliver Cs+ and Br- to passivate the intrinsic defects inside film. More importantly, the PEA-CsPbBr3 construct a new carrier-transfer pathway from the small-n phase of the quasi-2D perovskite to the PEA-CsPbBr3 , which not only accelerates the energy-transfer process but also promotes radiation recombination of carriers due to stronger quantum confinement effect. Afterward, the poly(3,4-ethylenedioxythiophene):polystyrene sulfonate/poly[9,9-dioctylfluoreneco-N-[4-(3-methylpropyl)]diphenylamine]:black phosphorus quantum dot double hole-transport layer is successfully constructed to enhance its carrier-injection and charge-transport abilities. Consequently, a champion external quantum efficiency of 25.32% and maximal brightness of 128 842 cd m-2 are achieved, which is the record efficiency of the quasi-2D Pe-LED with pure green emission at 530 nm. Moreover, an impressive 174 min lifetime is obtained at T50 , which is about five times longer than the control device.

Significant boost of the stability and PLQYof CsPbBr3 NCs by Cu-BTC MOF.

Developing stable perovskite nanocrystals (NCs) with enhancing luminescent properties holds great importance for future potential applications in optoelectronics. Here, we engaged perovskite NCs in Cu2+ ion-based metal-organic framework (MOF) Cu-BTC (BTC = 1,3,5-benzene tricarboxylate) by physical mixing of MOF with CsPbBr3 NCs in toluene solution. MOF-protected perovskite NCs achieved high photoluminescence quantum yield 96.51% than pristine state CsPbBr3 NCs (51.66%). Along with the improvement in optical properties, the long-term stability of CsPbBr3 NCs in the solution phase also increases considerably upon loading in Cu-BTC MOF. Moreover, the changes in the luminescent intensity of the samples have been observed for 3 months in the solution. After 1 month, pristine CsPbBr3 NCs lose their emission intensity 68% from the initial, while the MOF-protected CsPbBr3 NCs show only a 10% reduction from the initial. These results indicate that the effective passivation of Cu-BTC MOF inhibits the aggregation of NCs, protecting them from the defective atmosphere. The excellent photoluminescence findings provide a new pathway for future optoelectronic applications.

Efficient and Stable CF3PEAI-Passivated CsPbI3 QDs toward Red LEDs.

Oleylamine and oleic acid are common organic capping ligands used in the hot injection preparation of perovskite quantum dots (QDs). Their labile nature is responsible for the poor colloidal stability and conductivity that affect the performance of perovskite QD light-emitting diodes (LEDs). We introduced 4-trifluoro phenethylammonium iodide (CF3PEAI) directly in the synthesis and found that CF3PEAI efficiently modified the I- vacancy defects on the QD surface and partially substituted the surface capping ligand oleylamine. The strong electron pulling ability of F in CF3PEAI results in a more positive -NH3+ terminal compared to that of PEAI, which promotes tight bonding of CF3PEAI on the surface of CsPbI3 QDs. As a result, we achieved bright QDs with a photoluminescence quantum yield of 92% and efficient red LEDs. The maximal luminance was improved to 4550 cd m-2 for 685 nm red light, which was nearly 4.6-fold of the LEDs with plain CsPbI3 QDs. Additionally, the peak external quantum efficiency reached 12.5%.

Biomimetic design of graphdiyne supported hemin for enhanced peroxidase-like activity.

Effective electronic interactions between molecular catalysts and supports are critical for heterogeneous enzyme mimics, yet they are frequently neglected in most catalyst designs. Taking the enzyme mimics of hemin immobilized on graphdiyne (Hemin-GDY) as an example, we explicate for the first time the underlying role of GDY as a co-catalyst. Based on the robust conjugation between GDY and hemin, the delocalized π-electrons in GDY act as a ligand for Fe ions so that the orbital interactions including electron transport from GDY â†’ Fe can induce the formation of an electron-rich Fe center and an electron-deficient π-electron conjugated system. This mechanism was validated by electron paramagnetic resonance (EPR), Raman spectroscopy, and DFT calculations. Moreover, both EPR spetra and Lineweaver-Burk plots revealed that Hemin-GDY could efficiently catalyze the decomposition of hydrogen peroxide (H2O2) to produce hydroxyl radical (•OH) and superoxide anion (O2•-) by a ping-pong type catalytic mechanism, and particularly, the catalytic activity was increased by 2.3-fold comparing to that of hemin immobilized on graphene (Hemin-GR). In addition, Hemin-GDY with the exceptional activity and stability was demonstrated for efficient catalytic degradation of organic pollutants under acidic conditions. Collectively, this work provides a theoretical basis for the design of GDY supported catalysts and renders great promises of the GDY based enzyme mimics.

Silver Peroxide Nanoparticles for Combined Antibacterial Sonodynamic and Photothermal Therapy.

Metal peroxide nanoparticles designed to elevate the oxidative stress are considered a promising nanotherapeutics in biomedical applications, including chemotherapy, photodynamic therapy, and bacterial disinfection. However, their lack of specificity towards the therapeutic target can cause toxic side effects to healthy tissues. Here, silver peroxide nanoparticles (Ag2 O2 NPs) capable of controlled reactive oxygen species (ROS) release are synthesized. The release of bactericidal Ag+ ions and ROS is strictly regulated by external stimuli of ultrasound (US) and near-infrared (NIR) light. In vitro and in vivo investigations show that the Ag2 O2 NPs present enhanced antibacterial and antibiofilm capabilities with a killing efficiency >99.9999% in 10 min, significantly accelerate multi-drug resistant Staphylococcus aureus infected skin wound closure with excellent cytocompatibility and hemocompatibility. This work not only provides the first paradigm for fabricating silver peroxide nanoparticle but also introduces a highly efficient noninvasive and safe therapeutic modality for combating bacterial infectious diseases.

Reversible Transformation between Cs3Cu2I5 and CsCu2I3 Perovskite Derivatives and Its Anticounterfeiting Application.

Lead halide perovskites have promising values in photoelectronic and photovoltaic applications, but the toxicity of lead is a hard barrier. Copper halide perovskite derivatives (CHPDs), as a lead-free substitution of lead halide perovskites, also exhibit excellent photoelectric properties. Here, we present a facile one-step route for the synthesis of blue-emissive Cs3Cu2I5 (emission at 440 nm) and yellow-emissive CsCu2I3 (emission at 552 nm) CHPDs in ethanol at room temperature. Triggered by ethanol or CsI, a reversible chemical transformation accompanied by emissive color change between Cs3Cu2I5 and CsCu2I3 CHPDs was achieved. The reversible transformation mechanism was discussed, and this transformation was employed for effective anticounterfeiting.