Kinetically Controlled Synthesis of Quasi-Square CsPbI3 Nanoplatelets with Excellent Stability.

Nanoplatelets (NPLs) share excellent luminescent properties with their symmetric quantum dots counterparts and entail special characters benefiting from the shape, like the thickness-dependent bandgap and anisotropic luminescence. However, perovskite NPLs, especially those based on iodide, suffer from poor spectral and phase stability. Here, stable CsPbI3 NPLs obtained by accelerating the crystallization process in ambient-condition synthesis are reported. By this kinetic control, the rectangular NPLs into quasi-square NPLs are tuned, where enlarged width endows the NPLs with a lower surface-area-to-volume ratio (S/V ratio), leading to lower surficial energy and thus improved endurance against NPL fusion (cause for spectral shift or phase transformation). The accelerated crystallization, denoting the fast nucleation and short period of growth in this report, is enabled by preparing a precursor with complete transformation of PbI2 into intermediates (PbI3 -), through an additional iodide supplier (e.g., zinc iodide). The excellent color stability of the materials remains in the light-emitting diodes under various bias stresses.

Construction of Fe-doped NiS-NiS2 Heterostructured Microspheres Via Etching Prussian Blue Analogues for Efficient Water-Urea Splitting.

Developing efficient and robust non-precious-metal-based catalysts to accelerate electrocatalytic reaction kinetics is crucial for electrochemical water-urea splitting. Herein, Fe-doped NiS-NiS2 heterostructured microspheres, an electrocatalyst, are synthesized via etching Prussian blue analogues following a controlled annealing treatment. The resulting microspheres are constructed by mesoporous nanoplates, granting the virtues of large surface areas, high structural void porosity, and accessible inner surface. These advantages not only provide more redox reaction centers but also strengthen structural robustness and effectively facilitate the mass diffusion and charge transport. Density functional theory simulations validate that the Fe-doping improves the conductivity of nickel sulfides, whereas the NiS-NiS2 heterojunctions induce interface charge rearrangement for optimizing the adsorption free energy of intermediates, resulting in a low overpotential and high electrocatalytic activity. Specifically, an ultralow overpotential of 270 mV at 50 mA cm-2 for the oxygen evolution reaction (OER) is achieved. After adding 0.33 M urea into 1 M KOH, Fe-doped NiS-NiS2 obtains a strikingly reduced urea oxidation reaction potential of 1.36 V to reach 50 mA cm-2 , around 140 mV less than OER. This work provides insights into the synergistic modulation of electrocatalytic activity of non-noble catalysts for applications in energy conversion systems.

Encapsulating Fe2 O3 Nanotubes into Carbon-Coated Co9 S8 Nanocages Derived from a MOFs-Directed Strategy for Efficient Oxygen Evolution Reactions and Li-Ions Storage.

The development of high-efficiency, robust, and available electrode materials for oxygen evolution reaction (OER) and lithium-ion batteries (LIBs) is critical for clean and sustainable energy system but remains challenging. Herein, a unique yolk-shell structure of Fe2 O3 nanotube@hollow Co9 S8 nanocage@C is rationally prepared. In a prearranged sequence, the fabrication of Fe2 O3 nanotubes is followed by coating of zeolitic imidazolate framework (ZIF-67) layer, chemical etching of ZIF-67 by thioacetamide, and eventual annealing treatment. Benefiting from the hollow structures of Fe2 O3 nanotubes and Co9 S8 nanocages, the conductivity of carbon coating and the synergy effects between different components, the titled sample possesses abundant accessible active sites, favorable electron transfer rate, and exceptional reaction kinetics in the electrocatalysis. As a result, excellent electrocatalytic activity for alkaline OER is achieved, which delivers a low overpotential of 205 mV at the current density of 10 mA cm-2 along with the Tafel slope of 55 mV dec-1 . Moreover, this material exhibits excellent high-rate capability and excellent cycle life when employed as anode material of LIBs. This work provides a novel approach for the design and the construction of multifunctional electrode materials for energy conversion and storage.

Tailorable Membrane-Penetrating Nanoplatform for Highly Efficient Organelle-Specific Localization.

Given the breadth of currently arising opportunities and concerns associated with nanoparticles for biomedical imaging, various types of nanoparticles have been widely exploited, especially for cellular/subcellular level probing. However, most currently reported nanoparticles either have inefficient delivery into cells or lack specificity for intracellular destinations. The absence of well-defined nanoplatforms remains a critical challenge hindering practical nano-based bio-imaging. Herein, the authors elaborate on a tailorable membrane-penetrating nanoplatform as a carrier with encapsulated actives and decorated surfaces to tackle the above-mentioned issues. The tunable contents in such a versatile nanoplatform offer huge flexibility to reach the expected properties and functions. Aggregation-induced emission luminogen (AIEgen) is applied to achieve sought-after photophysical properties, specific targeting moieties are installed to give high affinity towards different desired organelles, and critical grafting of cell-penetrating cyclic disulfides (CPCDs) to promote cellular uptake efficiency without sacrificing the specificity. Hereafter, to validate its practicability, the tailored nano products are successfully applied to track the dynamic correlation between mitochondria and lysosomes during autophagy. The authors believe that the strategy and described materials can facilitate the development of functional nanomaterials for various life science applications.

Hierarchical CoFe LDH/MOF nanorods array with strong coupling effect grown on carbon cloth enables efficient oxidation of water and urea.

Oxygen evolution reaction (OER) and urea oxidation reaction (UOR) play important roles in the fields of hydrogen energy production and pollution treatment. Herein, a facile one-step chemical etching strategy is provided for fabricating one-dimensional hierarchical nanorods array composed of CoFe layered double hydroxide (LDH)/metal-organic frameworks (MOFs) supported on carbon cloth as efficient and stable OER and UOR catalysts. By precisely controlling the etching rate, the ligands from Co-MOFs are partially removed, the corresponding metal centers then coordinate with hydroxyl ions to generate ultrathin amorphous CoFe LDH nanosheets. The resultant CoFe LDH/MOFs catalyst possesses large active surface area, enhanced conductivity and extended electron/mass transfer channels, which are beneficial for catalytic reactions. Additionally, the intimate contact between CoFe LDH and MOFs modulates the local electronic structure of the catalytic active site, leading to enhanced adsorption of oxygen-containing intermediates to facilitate fast electrocatalytic reaction. As a result, the optimized CoFe LDH/MOF-0.06 exhibits superior OER activity with a low overpotential of 276 at a current density of 10 mA cm-2with long-term durability. Additionally, it merely requires a voltage of 1.45 V to obtain 10 mA cm-2in 1 M KOH solution with 0.33 urea and is 56 mV lower than the one in pure KOH. The work presented here may hew out a brand-new route to construct multi-functional electrocatalysts for water splitting, CO2reduction, nitrogen reduction reactions and so on.

Activatable MRI probes for the specific detection of bacteria.

Activatable fluorescent probes have been successfully used as molecular tools for biomedical research in the last decades. Fluorescent probes allow the detection of molecular events, providing an extraordinary platform for protein and cellular research. Nevertheless, most of the fluorescent probes reported are susceptible to interferences from endogenous fluorescence (background signal) and limited tissue penetration is expected. These drawbacks prevent the use of fluorescent tracers in the clinical setting. To overcome the limitation of fluorescent probes, we and others have developed activatable magnetic resonance probes. Herein, we report for the first time, an oligonucleotide-based probe with the capability to detect bacteria using magnetic resonance imaging (MRI). The activatable MRI probe consists of a specific oligonucleotide that targets micrococcal nuclease (MN), a nuclease derived from Staphylococcus aureus. The oligonucleotide is flanked by a superparamagnetic iron oxide nanoparticle (SPION) at one end, and by a dendron functionalized with several gadolinium complexes as enhancers, at the other end. Therefore, only upon recognition of the MRI probe by the specific bacteria is the probe activated and the MRI signal can be detected. This approach may be widely applied to detect bacterial infections or other human conditions with the potential to be translated into the clinic as an activatable contrast agent.

Light-Up Lipid Droplets Dynamic Behaviors Using a Red-Emitting Fluorogenic Probe.

Intracellular lipid metabolism occurs in lipid droplets (LDs), which is critical to the survival of cells. Imaging LDs is an intuitive way to understand their physiology in live cells. However, this is limited by the availability of specific probes that can properly visualize LDs in vivo. Here, an LDs-specific red-emitting probe is proposed to address this need, which is not merely with an ultrahigh signal-to-noise (S/N) ratio and a large Stokes shift (up to 214 nm) but also with superior resistance to photobleaching. The probe has been successfully applied to real-time tracking of intracellular LDs behaviors, including fusion, migration, and lipophagy processes. We deem that the proposed probe here offers a new possibility for deeper understanding of LDs-associated behaviors, elucidation of their roles and mechanisms in cellular metabolism, and determination of the transition between adaptive lipid storage and lipotoxicity as well.

Efficient and High-Luminance Perovskite Light-Emitting Diodes Based on CsPbBr3 Nanocrystals Synthesized from a Dual-Purpose Organic Lead Source.

Rational engineering of the surface properties of perovskite nanocrystals (PeNCs) is critical to obtain light emitters with simultaneous high photoluminescence efficiency and excellent charge transport properties for light-emitting diodes (LEDs). However, the commonly used lead halide sources make it hard to rationally optimize the surface compositions of the PeNCs. In addition, previously developed ligand engineering strategies for conventional inorganic nanocrystals easily deteriorate surface properties of the PeNCs, bringing additional difficulties in optimizing their optoelectronic properties. In this work, a novel strategy of employing a dual-purpose organic lead source for the synthesis of highly luminescent PeNCs with enhanced charge transport property is developed. Lead naphthenate (Pb(NA)2 ), of which the metal ions work as lead sources while the naphthenate can function as the surface ligands afterward, is explored and the obtained products under different synthesis conditions are comprehensively investigated. Monodispersed cesium lead bromide (CsPbBr3 ) with controllable size and excellent optical properties, showing superior photoluminescence quantum yields up to 80%, is obtained. Based on the simultaneously enhanced electrical properties of the Pb(NA)2 -derived PeNCs, the resultant LEDs demonstrate a high peak external quantum efficiency of 8.44% and a superior maximum luminance of 31 759 cd cm-2 .

A Multi-responsive Fluorescent Probe Reveals Mitochondrial Nucleoprotein Dynamics with Reactive Oxygen Species Regulation through Super-resolution Imaging.

Understanding the biomolecular interactions in a specific organelle has been a long-standing challenge because it requires super-resolution imaging to resolve the spatial locations and dynamic interactions of multiple biomacromolecules. Two key difficulties are the scarcity of suitable probes for super-resolution nanoscopy and the complications that arise from the use of multiple probes. Herein, we report a quinolinium derivative probe that is selectively enriched in mitochondria and switches on in three different fluorescence modes in response to hydrogen peroxide (H2 O2 ), proteins, and nucleic acids, enabling the visualization of mitochondrial nucleoprotein dynamics. STED nanoscopy reveals that the proteins localize at mitochondrial cristae and largely fuse with nucleic acids to form nucleoproteins, whereas increasing H2 O2 level leads to disassociation of nucleic acid-protein complexes.

Hybrid Rhodamine Fluorophores in the Visible/NIR Region for Biological Imaging.

Fluorophores and probes are invaluable for the visualization of the location and dynamics of gene expression, protein expression, and molecular interactions in complex living systems. Rhodamine dyes are often used as scaffolds in biological labeling and turn-on fluorescence imaging. To date, their absorption and emission spectra have been expanded to cover the entire near-infrared region (650-950 nm), which provides a more suitable optical window for monitoring biomolecular production, trafficking, and localization in real time. This review summarizes the development of rhodamine fluorophores since their discovery and provides strategies for modulating their absorption and emission spectra to generate specific bathochromic-shifts. We also explain how larger Stokes shifts and dual-emissions can be obtained from hybrid rhodamine dyes. These hybrid fluorophores can be classified into various categories based on structural features including the alkylation of amidogens, the substitution of the O atom of xanthene, and hybridization with other fluorophores.

Gasotransmitter Regulation of Phosphatase Activity in Live Cells Studied by Three-Channel Imaging Correlation.

Enzyme activity in live cells is dynamically regulated by small-molecule transmitters for maintaining normal physiological functions. A few probes have been devised to measure intracellular enzyme activities by fluorescent imaging, but the study of the regulation of enzyme activity via gasotransmitters in situ remains a long-standing challenge. Herein, we report a three-channel imaging correlation by a single dual-reactive fluorescent probe to measure the dependence of phosphatase activity on the H2 S level in cells. The two sites of the probe reactive to H2 S and phosphatase individually produce blue and green fluorescent responses, respectively, and resonance energy transfer can be triggered by their coexistence. Fluorescent analysis based on the three-channel imaging correlation shows that cells have an ideal level of H2 S to promote phosphatase activity up to its maximum. Significantly, a slight deviation from this H2 S level leads to a sharp decrease of phosphatase activity. The discovery further strengthens our understanding of the importance of H2 S in cellular signaling and in various human diseases.

A reversible and highly selective two-photon fluorescent "on-off-on" probe for biological Cu2+ detection.

A two-photon active probe for physiological copper (Cu2+) detection is expected to play an important role in monitoring biological metabolism. Herein, a novel Schiff base derivative (E)-2,2'-((4-((4-(diethylamino)-2-hydroxybenzylidene)amino)phenyl)azanediyl)bis(ethan-1-ol) (L) with remarkable two-photon activity was developed and synthetically investigated. L presents high selectivity and sensitivity for Cu2+ sensing in ethanol/HEPES buffer (v/v, 1 : 1), which is accompanied by the fluorescence switching "off" and subsequently "on" with the addition of EDTA. The mechanism for the detection of Cu2+ is further analyzed using 1H NMR titration, mass spectra and theoretical calculations. Furthermore, since the probe L possesses good photophysical properties, excellent biocompatibility and low cytotoxicity, it is successfully applied to track Cu2+ in the cellular endoplasmic reticulum by two-photon fluorescence imaging, showing its potential value for practical applications in biological systems.

Construction of unique NiCoP/FeNiCoP hollow heterostructured ellipsoids with modulated electronic structure for enhanced overall water splitting.

Transition metal phosphides have been demonstrated to be promising non-noble catalysts for water splitting, yet their electrocatalytic performance is impeded by unfavorable free energies of adsorbed intermediates. The achievement of nanoscale modulation in morphology and electronic states is imperative for enhancing their intrinsic electrocatalytic activity. Herein, we propose a strategy to expedite the water splitting process over NiCoP/FeNiCoP hollow ellipsoids by modulating the electronic structure and d-band center. These unique phosphorus (P) vacancies-rich ellipsoids are synthesized through an ion-exchange reaction between uniform NiCo-nanoprisms and K3[Fe(CN)6], followed by NaH2PO2-assisted phosphorization under N2 atmosphere. Various characterizations reveals that the titled catalyst possesses high specific surface area, abundant porosity, and accessible inner surfaces, all of which are beneficial for efficient mass transfer and gas diffusion. Moreover, density functional theory (DFT) calculations further confirms that the NiCoP/FeNiCoP heterojunction associated with P vacancies regulate the electronic structures of d-electrons and p-electrons of Co and P atoms, respectively, resulting in a higher desorption efficiency of adsorbed H* intermediates with a lower energy barrier for water splitting. Due to the aforementioned advantages, the resultant NiCoP/FeNiCoP hollow ellipsoids exhibit remarkably low overpotentials of 45 and 266 mV for hydrogen and oxygen evolution reaction to achieve the current densities of 10 and 50 mA cm-2, respectively. This work not only reports the synthesis of a hollow double-shell structure of NiCoP/FeNiCoP but also introduces a novel strategy for constructing a multifunctional electrocatalyst for water splitting.

Response strategies and biological applications of organic fluorescent thermometry: cell- and mitochondrion-level detection.

Temperature homeostasis is critical for cells to perform their physiological functions. Among the diverse methods for temperature detection, fluorescent temperature probes stand out as a proven and effective tool, especially for monitoring temperature in cells and suborganelles, with a specific emphasis on mitochondria. The utilization of these probes provides a new opportunity to enhance our understanding of the mechanisms and interconnections underlying various physiological activities related to temperature homeostasis. However, the complexity and variability of cells and suborganelles necessitate fluorescent temperature probes with high resolution and sensitivity. To meet the demanding requirements for intracellular/subcellular temperature detection, several strategies have been developed, offering a range of options to address this challenge. This review examines four fundamental temperature-response strategies employed by small molecule and polymer probes, including intramolecular rotation, polarity sensitivity, Förster resonance energy transfer, and structural changes. The primary emphasis was placed on elucidating molecular design and biological applications specific to each type of probe. Furthermore, this review provides an insightful discussion on factors that may affect fluorescent thermometry, providing valuable perspectives for future development in the field. Finally, the review concludes by presenting cutting-edge response strategies and research insights for mitigating biases in temperature sensing.

Highly water-dispersible surface-modified Gd(2)O(3) nanoparticles for potential dual-modal bioimaging.

Water-dispersible and luminescent gadolinium oxide (GO) nanoparticles (NPs) were designed and synthesized for potential dual-modal biological imaging. They were obtained by capping gadolinium oxide nanoparticles with a fluorescent glycol-based conjugated carboxylate (HL). The obtained nanoparticles (GO-L) show long-term colloidal stability and intense blue fluorescence. In addition, L can sensitize the luminescence of europium(III) through the so-called antenna effect. Thus, to extend the spectral ranges of emission, europium was introduced into L-modified gadolinium oxide nanoparticles. The obtained EuIII-doped particles (Eu:GO-L) can provide visible red emission, which is more intensive than that without L capping. The average diameter of the monodisperse modified oxide cores is about 4 nm. The average hydrodynamic diameter of the L-modified nanoparticles was estimated to be about 13 nm. The nanoparticles show effective longitudinal water proton relaxivity. The relaxivity values obtained for GO-L and Eu:GO-L were r1=6.4 and 6.3 s−1 mM−1 with r2/r1 ratios close to unity at 1.4 T. Longitudinal proton relaxivities of these nanoparticles are higher than those of positive contrast agents based on gadolinium complexes such as Gd-DOTA, which are commonly used for clinical magnetic resonance imaging. Moreover, these particles are suitable for cellular imaging and show good biocompatibility.

P-doped Co3S4/NiS2 heterostructures embedded in N-doped carbon nanoboxes: Synergistical electronic structure regulation for overall water splitting.

Water splitting using transition metal sulfides as electrocatalysts has gained considerable attention in the field of renewable energy. However, their electrocatalytic activity is often hindered by unfavorable free energies of adsorbed hydrogen and oxygen-containing intermediates. Herein, phosphorus (P)-doped Co3S4/NiS2 heterostructures embedded in N-doped carbon nanoboxes were rationally synthesized via a pyrolysis-sulfidation-phosphorization strategy. The hollow structure of the carbon matrix and the nanoparticles contained within it not only result in a high specific surface area, but also protects them from corrosion and acts as a conductive pathway for efficient electron transfer. Density functional theory (DFT) calculations indicate that the introduction of P dopants improves the conductivity of NiS2 and Co3S4, promotes the charge transfer process, and creates new electrocatalytic sites. Additionally, the NiS2-Co3S4 heterojunctions can enhance the adsorption efficiency of hydrogen intermediates (H*) and lower the energy barrier of water splitting via a synergistic effect with P-doping. These characteristics collectively enable the titled catalyst to exhibit excellent electrocatalytic activity for water splitting in alkaline medium, requiring only small overpotentials of 150 and 257 mV to achieve a current density of 10 mA cm-2 for hydrogen and oxygen evolution reactions, respectively. This work sheds light on the design and optimization of efficient electrocatalysts for water splitting, with potential implications for renewable energy production.

Amorphous and defective Co-P-O@NC ball-in-ball hollow structure for highly efficient electrocatalytic overall water splitting.

Electrochemical water splitting using hollow and defect-rich catalysts has emerged as a promising strategy for efficient hydrogen production. However, the rational design and controllable synthesis of such catalysts with intricate morphology and composition present significant challenges. Herein, we propose a template-engaged approach to fabricate a novel ball-in-ball hollow structure of Co-P-O@N-doped carbon with abundant oxygen vacancies. The synthesis process involves the preparation of uniform cobalt-glycerate (Co-gly) polymer microspheres as precursors, followed by surface coating with ZIF-67 layer, adjustable chemical etching by phytic acid, and controllable pyrolysis at high temperature. The resulting ball-in-ball structure offers a large number of accessible active sites and high redox reaction centers, facilitating efficient charge transport, mass transfer, and gas evolution, which are beneficial for the acceleration of electrocatalytic reaction. Additionally, density functional theory (DFT) calculations indicate that the incorporation of oxygen and the presence of Co-P dangling bonds in CoP significantly enhance the adsorption of oxygenated species, leading to improved intrinsic electroactivity at the single-site level. As a sequence, the titled catalyst exhibits remarkable electrocatalytic activity and stability for water splitting in alkaline media. Notably, it only requires a low overpotential of 283 mV to achieve a current density of 10 mA cm-2 for the oxygen evolution reaction. This work may provide some new insights into the design of complex hollow structures of phosphides with abundant defects for energy conversion.

Ligand-Induced Cation-π Interactions Enable High-Efficiency, Bright, and Spectrally Stable Rec. 2020 Pure-Red Perovskite Light-Emitting Diodes.

Achieving high-performance perovskite light-emitting diodes (PeLEDs) with pure-red electroluminescence for practical applications remains a critical challenge because of the problematic luminescence property and spectral instability of existing emitters. Herein, high-efficiency Rec. 2020 pure-red PeLEDs, simultaneously exhibiting exceptional brightness and spectral stability, based on CsPb(Br/I)3 perovskite nanocrystals (NCs) capping with aromatic amino acid ligands featuring cation-π interactions, are reported. It is proven that strong cation-π interactions between the PbI6 -octahedra of perovskite units and the electron-rich indole ring of tryptophan (TRP) molecules not only chemically polish the imperfect surface sites, but also markedly increase the binding affinity of the ligand molecules, leading to high photoluminescence quantum yields and greatly enhanced spectral stability of the CsPb(Br/I)3 NCs. Moreover, the incorporation of small-size aromatic TRP ligands ensures superior charge-transport properties of the assembled emissive layers. The resultant devices emitting at around 635 nm demonstrate a champion external quantum efficiency of 22.8%, a max luminance of 12 910 cd m-2 , and outstanding spectral stability, representing one of the best-performing Rec. 2020 pure-red PeLEDs achieved so far.

Cerium Oxide Nanoparticles with Entrapped Gadolinium for High T 1 Relaxivity and ROS-Scavenging Purposes.

Gadolinium chelates are employed worldwide today as clinical contrast agents for magnetic resonance imaging. Until now, the commonly used linear contrast agents based on the rare-earth element gadolinium have been considered safe and well-tolerated. Recently, concerns regarding this type of contrast agent have been reported, which is why there is an urgent need to develop the next generation of stable contrast agents with enhanced spin-lattice relaxation, as measured by improved T 1 relaxivity at lower doses. Here, we show that by the integration of gadolinium ions in cerium oxide nanoparticles, a stable crystalline 5 nm sized nanoparticulate system with a homogeneous gadolinium ion distribution is obtained. These cerium oxide nanoparticles with entrapped gadolinium deliver strong T 1 relaxivity per gadolinium ion (T 1 relaxivity, r 1 = 12.0 mM-1 s-1) with the potential to act as scavengers of reactive oxygen species (ROS). The presence of Ce3+ sites and oxygen vacancies at the surface plays a critical role in providing the antioxidant properties. The characterization of radial distribution of Ce3+ and Ce4+ oxidation states indicated a higher concentration of Ce3+ at the nanoparticle surfaces. Additionally, we investigated the ROS-scavenging capabilities of pure gadolinium-containing cerium oxide nanoparticles by bioluminescent imaging in vivo, where inhibitory effects on ROS activity are shown.

Ion-modulated radical doping of spiro-OMeTAD for more efficient and stable perovskite solar cells.

Record power conversion efficiencies (PCEs) of perovskite solar cells (PSCs) have been obtained with the organic hole transporter 2,2',7,7'-tetrakis(N,N-di-p-methoxyphenyl-amine)9,9'-spirobifluorene (spiro-OMeTAD). Conventional doping of spiro-OMeTAD with hygroscopic lithium salts and volatile 4-tert-butylpyridine is a time-consuming process and also leads to poor device stability. We developed a new doping strategy for spiro-OMeTAD that avoids post-oxidation by using stable organic radicals as the dopant and ionic salts as the doping modulator (referred to as ion-modulated radical doping). We achieved PCEs of >25% and much-improved device stability under harsh conditions. The radicals provide hole polarons that instantly increase the conductivity and work function (WF), and ionic salts further modulate the WF by affecting the energetics of the hole polarons. This organic semiconductor doping strategy, which decouples conductivity and WF tunability, could inspire further optimization in other optoelectronic devices.