Room-Temperature Ferroelectric Epitaxial Nanowire Arrays with Photoluminescence.

The development of large-scale, high-quality ferroelectric semiconductor nanowire arrays with interesting light-emitting properties can address limitations in traditional wide-bandgap ferroelectrics, thus serving as building blocks for innovative device architectures and next-generation high-density optoelectronics. Here, we investigate the optical properties of ferroelectric CsGeX3 (X = Br, I) halide perovskite nanowires that are epitaxially grown on muscovite mica substrates by vapor phase deposition. Detailed structural characterizations reveal an incommensurate heteroepitaxial relationship with the mica substrate. Furthermore, photoluminescence that can be tuned from yellow-green to red emissions by varying the halide composition demonstrates that these nanowire networks can serve as platforms for future optoelectronic applications. In addition, the room-temperature ferroelectricity and ferroelectric domain structures of these nanowires are characterized using second harmonic generation (SHG) polarimetry. The combination of room-temperature ferroelectricity with photoluminescence in these nanowire arrays unlocks new avenues for the design of novel multifunctional materials.

The surface chemistry of colloidal lead halide perovskite nanowires.

This study explored the interplay between the ligand-surface chemistry of colloidal CsPbBr3 nanowires (NWs) and their optical properties. The ligand equilibrium was probed using nuclear magnetic resonance spectroscopy, and by perturbing the equilibrium via dilution, the gradual removal of ligands from the CsPbBr3 surface was observed. This removal was correlated with an increase in the surface defect density, as suggested by a broadening of the photoluminescence (PL) spectrum, a decrease in the PL quantum yield (PLQY), and quenching of the PL decay. These results highlight similar surface binding between the traditional CsPbBr3 quantum dots and our NWs, thereby expanding the scope of well-established ligand chemistry to a relatively unexplored nanocrystal morphology. By controlling the dilution factor, it was revealed that CsPbBr3 NWs achieve a PLQY of 72% ± 2% and a relatively long average PL lifetime of 400 ± 10 ns, without relying on additional surface passivation techniques, such as ligand exchange.

Complete miscibility of immiscible elements at the nanometre scale.

Understanding the mixing behaviour of elements in a multielement material is important to control its structure and property. When the size of a multielement material is decreased to the nanoscale, the miscibility of elements in the nanomaterial often changes from its bulk counterpart. However, there is a lack of comprehensive and quantitative experimental insight into this process. Here we explored how the miscibility of Au and Rh evolves in nanoparticles of sizes varying from 4 to 1 nm and composition changing from 15% Au to 85% Au. We found that the two immiscible elements exhibit a phase-separation-to-alloy transition in nanoparticles with decreased size and become completely miscible in sub-2 nm particles across the entire compositional range. Quantitative electron microscopy analysis and theoretical calculations were used to show that the observed immiscibility-to-miscibility transition is dictated by particle size, composition and possible surface adsorbates present under the synthesis conditions.

Supramolecular assembly of blue and green halide perovskites with near-unity photoluminescence.

The metal-halide ionic octahedron is the optoelectronic unit for halide perovskites, and a crown ether-assisted supramolecular assembly approach can pack various ionic octahedra into tunable symmetries. In this work, we demonstrate near-unity photoluminescence quantum yield (PLQY) blue and green emission with the supramolecular assembly of hafnium (Hf) and zirconium (Zr) halide octahedral clusters. (18C6@K)2HfBr6 powders showed blue emission with a near-unity PLQY (96.2%), and green emission was also achieved with (18C6@K)2ZrCl4Br2 powders at a PLQY of 82.7%. These highly emissive powders feature facile low-temperature solution-based synthesis conditions and maintain high PLQY in solution-processable semiconductor inks under ambient conditions, and they were used in thin-film displays and emissive three-dimensional-printed architectures that exhibited high spatial resolution.

LncRNA SEMA3B-AS1 suppresses the tumor-initiating characteristics of triple negative breast cancer via engaging in MLL4-mediated H3K4 trimethylation.

Long noncoding RNAs (lncRNAs) are crucial regulators of tumor-initiating cells (TICs) and hold particular importance in triple negative breast cancer (TNBC). Yet, the precise mechanisms by which TIC-associated lncRNAs influence TNBC remain unclear. Our research utilized The Cancer Genome Atlas Breast Cancer (BC) data set to identify prognostic lncRNAs. We then conducted extensive assays to explore their impact on the tumor-initiating phenotype of TNBC cells and the underlying mechanisms. Notably, we found that low expression of lncRNA SEMA3B-AS1 correlated with unfavorable survival in BC patients. SEMA3B-AS1 was also downregulated in TNBC and linked to advanced tumor stage. Functional experiments confirmed its role as a TIC-suppressing lncRNA, curtailing mammosphere formation, ALDH + TIC cell proportion, and impairing clonogenicity, migration, and invasion. Mechanistic insights unveiled SEMA3B-AS1's nuclear localization and interaction with MLL4 (mixed-lineage leukemia 4), triggering H3K4 methylation-associated transcript activation and thus elevating the expression of SEMA3B, a recognized tumor suppressor gene. Our findings emphasize SEMA3B-AS1's significance as a TNBC-suppressing lncRNA that modulates TIC behavior. This study advances our comprehension of lncRNA's role in TNBC progression, advocating for their potential as therapeutic targets in this aggressive BC subtype.

Energy Funneling in a Noninteger Two-Dimensional Perovskite.

Energy funneling is a phenomenon that has been exploited in optoelectronic devices based on low-dimensional materials to improve their performance. Here, we introduce a new class of two-dimensional semiconductor, characterized by multiple regions of varying thickness in a single confined nanostructure with homogeneous composition. This "noninteger 2D semiconductor" was prepared via the structural transformation of two-octahedron-layer-thick (n = 2) 2D cesium lead bromide perovskite nanosheets; it consisted of a central n = 2 region surrounded by edge-lying n = 3 regions, as imaged by electron microscopy. Thicker noninteger 2D CsPbBr3 nanostructures were obtained as well. These noninteger 2D perovskites formed a laterally coupled quantum well band alignment with virtually no strain at the interface and no dielectric barrier, across which unprecedented intramaterial funneling of the photoexcitation energy was observed from the thin to the thick regions using time-resolved absorption and photoluminescence spectroscopy.

Intranasal mask for protecting the respiratory tract against viral aerosols.

The spread of many infectious diseases relies on aerosol transmission to the respiratory tract. Here we design an intranasal mask comprising a positively-charged thermosensitive hydrogel and cell-derived micro-sized vesicles with a specific viral receptor. We show that the positively charged hydrogel intercepts negatively charged viral aerosols, while the viral receptor on vesicles mediates the entrapment of viruses for inactivation. We demonstrate that when displaying matched viral receptors, the intranasal masks protect the nasal cavity and lung of mice from either severe acute respiratory syndrome coronavirus 2 or influenza A virus. With computerized tomography images of human nasal cavity, we further conduct computational fluid dynamics simulation and three-dimensional printing of an anatomically accurate human nasal cavity, which is connected to human lung organoids to generate a human respiratory tract model. Both simulative and experimental results support the suitability of intranasal masks in humans, as the likelihood of viral respiratory infections induced by different variant strains is dramatically reduced.

Operando High-Energy-Resolution X-ray Spectroscopy of Evolving Cu Nanoparticle Electrocatalysts for CO2 Reduction.

Advances in electrocatalysis research rely heavily on building a thorough mechanistic understanding of catalyst active sites under realistic operating conditions. Only recently have techniques emerged that enable sensitive spectroscopic data collection to distinguish catalytically relevant surface sites from the underlying bulk material under applied potential in the presence of an electrolyte layer. Here, we demonstrate that operando high-energy-resolution fluorescence detected X-ray absorption spectroscopy (HERFD-XAS) is a powerful spectroscopic method which offers critical surface chemistry insights in CO2 electroreduction with sub-electronvolt energy resolution using hard X-rays. Combined with the high surface area-to-volume ratio of 5 nm copper nanoparticles, operando HERFD-XAS allows us to observe with clear evidence the breaking of chemical bonds between the ligands and the Cu surface as part of the ligand desorption process occurring under electrochemical potentials relevant for the CO2 reduction reaction (CO2RR). In addition, the dynamic evolution of oxidation state and coordination number throughout the operation of the nanocatalyst was continuously tracked. With these results in hand, undercoordinated metallic copper nanograins are proposed to be the real active sites in the CO2RR. This work emphasizes the importance of HERFD-XAS compared to routine XAS in catalyst characterization and mechanism exploration, especially in the complicated electrochemical CO2RR.

High-entropy halide perovskite single crystals stabilized by mild chemistry.

Although high-entropy materials are excellent candidates for a range of functional materials, their formation traditionally requires high-temperature synthetic procedures of over 1,000 °C and complex processing techniques such as hot rolling1-5. One route to address the extreme synthetic requirements for high-entropy materials should involve the design of crystal structures with ionic bonding networks and low cohesive energies. Here we develop room-temperature-solution (20 °C) and low-temperature-solution (80 °C) synthesis procedures for a new class of metal halide perovskite high-entropy semiconductor (HES) single crystals. Due to the soft, ionic lattice nature of metal halide perovskites, these HES single crystals are designed on the cubic Cs2MCl6 (M=Zr4+, Sn4+, Te4+, Hf4+, Re4+, Os4+, Ir4+ or Pt4+) vacancy-ordered double-perovskite structure from the self-assembly of stabilized complexes in multi-element inks, namely free Cs+ cations and five or six different isolated [MCl6]2- anionic octahedral molecules well-mixed in strong hydrochloric acid. The resulting single-phase single crystals span two HES families of five and six elements occupying the M-site as a random alloy in near-equimolar ratios, with the overall Cs2MCl6 crystal structure and stoichiometry maintained. The incorporation of various [MCl6]2- octahedral molecular orbitals disordered across high-entropy five- and six-element Cs2MCl6 single crystals produces complex vibrational and electronic structures with energy transfer interactions between the confined exciton states of the five or six different isolated octahedral molecules.

High-Photovoltage Silicon Nanowire for Biological Cofactor Production.

Photocathodic conversion of NAD+ to NADH cofactor is a promising platform for activating redox biological catalysts and enzymatic synthesis using renewable solar energy. However, many photocathodes suffer from low photovoltage, consequently requiring a high cathodic bias for NADH production. Here, we report an n+p-type silicon nanowire (n+p-SiNW) photocathode having a photovoltage of 435 mV to drive energy-efficient NADH production. The enhanced band bending at the n+/p interface accounts for the high photovoltage, which conduces to a benchmark onset potential [0.393 V vs the reversible hydrogen electrode (VRHE)] for SiNW-based photocathodic NADH generation. In addition, the n+p-SiNW nanomaterial exhibits a Faradaic efficiency of 84.7% and a conversion rate of 1.63 µmol h-1 cm-1 at 0.2 VRHE, which is the lowest cathodic potential to achieve the maximum productivity among SiNW-sensitized cofactor production.

Understanding the Structural Evolution of IrFeCoNiCu High-Entropy Alloy Nanoparticles under the Acidic Oxygen Evolution Reaction.

High-entropy alloy (HEA) nanoparticles are promising catalyst candidates for the acidic oxygen evolution reaction (OER). Herein, we report the synthesis of IrFeCoNiCu-HEA nanoparticles on a carbon paper substrate via a microwave-assisted shock synthesis method. Under OER conditions in 0.1 M HClO4, the HEA nanoparticles exhibit excellent activity with an overpotential of ∼302 mV measured at 10 mA cm-2 and improved stability over 12 h of operation compared to the monometallic Ir counterpart. Importantly, an active Ir-rich shell layer with nanodomain features was observed to form on the surface of IrFeCoNiCu-HEA nanoparticles immediately after undergoing electrochemical activation, mainly due to the dissolution of the constituent 3d metals. The core of the particles was able to preserve the characteristic homogeneous single-phase HEA structure without significant phase separation or elemental segregation. This work illustrates that under acidic operating conditions, the near-surface structure of HEA nanoparticles is susceptible to a certain degree of structural dynamics.

Photochemical Diodes for Simultaneous Bias-Free Glycerol Valorization and Hydrogen Evolution.

Artificial photosynthesis offers a route to producing clean fuel energy. However, the large thermodynamic requirement for water splitting along with the corresponding sluggish kinetics for the oxygen evolution reaction (OER) limits its current practical application. Here, we offer an alternative approach by replacing the OER with the glycerol oxidation reaction (GOR) for value-added chemicals. By using a Si photoanode, a low GOR onset potential of -0.05 V vs RHE and a photocurrent density of 10 mA/cm2 at 0.5 V vs RHE can be reached. Coupled with a Si nanowire photocathode for the hydrogen evolution reaction (HER), the integrated system yields a high photocurrent density of 6 mA/cm2 with no applied bias under 1 sun illumination and can run for over 4 days under diurnal illumination. The demonstration of the GOR-HER integrated system provides a framework for designing bias-free photoelectrochemical devices at appreciable currents and establishes a facile approach to artificial photosynthesis.

A ceRNA network-mediated over-expression of cuproptosis-related gene SLC31A1 correlates with poor prognosis and positive immune infiltration in breast cancer.

Introduction: Solute carrier family 31 member 1(SLC31A1) has been reported as the copper importer, and was identified to be involved in the process of "cuproptosis". However, the mechanism of SLC31A1 in breast cancer remains unclear. Methods: We examined the expression of SLC31A1 mRNA in breast cancer tissues and cell lines using Real-time PCR. The data for this study were obtained from The Cancer Genome Atlas (TCGA) database and analyzed via R 3.6.3. TIMER, UALCAN, GEPIA2, STRING, Metascape, Kaplan-Meier Plotter, starBase and miRNet websites were used for a comprehensive analysis of SLC31A1. Results: Our study suggested that SLC31A1 mRNA was over-expressed in breast tumor tissue and breast cancer cell lines, and which was closely related to poor relapse-free survival (RFS) and distant metastasis-free survival (DMFS). In addition, we constructed a co-expression network of SLC31A1. Functional enrichment analysis indicated that they were mainly involved in copper ion transport. Interestingly, SLC31A1 expression was positively associated with all m6A-related genes, especially with YTHDF3 (r = 0.479). Importantly, the LINC00511/miR-29c-3p/SLC31A1 axis was identified as the most potential pathway promoting breast cancer progress by affecting copper transport. Furthermore, the expression level of SLC31A1 in breast cancer was positively correlated with tumor immune cell infiltration, immune cell biomarkers and cancer-associated fibroblast (CAF). Conclusion: Up-regulation of SLC31A1 expression and regulation of copper ion transport mediated by LINC00511-miR-29-3p axis is related to poor prognosis and positively correlated with tumor immune infiltration in breast cancer.

Thermally driven phase transition of halide perovskites revealed by big data-powered in situ electron microscopy.

Halide perovskites are promising light-absorbing materials for high-efficiency solar cells, while the crystalline phase of halide perovskites may influence the device's efficiency and stability. In this work, we investigated the thermally driven phase transition of perovskite (CsPbIxBr3-x), which was confirmed by electron diffraction and high-resolution transmission electron microscopy results. CsPbIxBr3-x transitioned from δ phase to α phase when heated, and the γ phase was obtained when the sample was cooled down. The γ phase was stable as long as it was isolated from humidity and air. A template matching-based data analysis method enabled visualization of the thermally driven phase evolution of perovskite during heating. We also proposed a possible atomic movement in the process of phase transition based on our in situ heating experimental data. The results presented here may improve our understanding of the thermally driven phase transition of perovskite as well as provide a protocol for big-data analysis of in situ experiments.

Chemical and Structural Evolution of AgCu Catalysts in Electrochemical CO2 Reduction.

Silver-copper (AgCu) bimetallic catalysts hold great potential for electrochemical carbon dioxide reduction reaction (CO2RR), which is a promising way to realize the goal of carbon neutrality. Although a wide variety of AgCu catalysts have been developed so far, it is relatively less explored how these AgCu catalysts evolve during CO2RR. The absence of insights into their stability makes the dynamic catalytic sites elusive and hampers the design of AgCu catalysts in a rational manner. Here, we synthesized intermixed and phase-separated AgCu nanoparticles on carbon paper electrodes and investigated their evolution behavior in CO2RR. Our time-sequential electron microscopy and elemental mapping studies show that Cu possesses high mobility in AgCu under CO2RR conditions, which can leach out from the catalysts by migrating to the bimetallic catalyst surface, detaching from the catalysts, and agglomerating as new particles. Besides, Ag and Cu manifest a trend to phase-separate into Cu-rich and Ag-rich grains, regardless of the starting catalyst structure. The composition of the Cu-rich and Ag-rich grains diverges during the reaction and eventually approaches thermodynamic values, i.e., Ag0.88Cu0.12 and Ag0.05Cu0.95. The separation between Ag and Cu has been observed in the bulk and on the surface of the catalysts, highlighting the importance of AgCu phase boundaries for CO2RR. In addition, an operando high-energy-resolution X-ray absorption spectroscopy study confirms the metallic state of Cu in AgCu as the catalytically active sites during CO2RR. Taken together, this work provides a comprehensive understanding of the chemical and structural evolution behavior of AgCu catalysts in CO2RR.

Transcriptomic Establishment of Pig Macrophage Polarization Signatures.

Macrophages are the foremost controllers of innate and acquired immunity, playing important roles in tissue homeostasis, vasculogenesis, and congenital metabolism. In vitro macrophages are crucial models for understanding the regulatory mechanism of immune responses and the diagnosis or treatment of a variety of diseases. Pigs are the most important agricultural animals and valuable animal models for preclinical studies, but there is no unified method for porcine macrophage isolation and differentiation at present; no systematic study has compared porcine macrophages obtained by different methods. In the current study, we obtained two M1 macrophages (M1_IFNγ + LPS, and M1_GM-CSF) and two M2 macrophages (M2_IL4 + IL10, and M2_M-CSF), and compared the transcriptomic profiles between and within macrophage phenotypes. We observed the transcriptional differences either between or within phenotypes. Porcine M1 and M2 macrophages have consistent gene signatures with human and mouse macrophage phenotypes, respectively. Moreover, we performed GSEA analysis to attribute the prognostic value of our macrophage signatures in discriminating various pathogen infections. Our study provided a framework to guide the interrogation of macrophage phenotypes in the context of health and disease. The approach described here could be used to propose new biomarkers for diagnosis in diverse clinical settings including porcine reproductive and respiratory syndrome virus (PRRSV), African swine fever virus (ASFV), Toxoplasma gondii (T. gondii), porcine circovirus type 2 (PCV2), Haemophilus parasuis serovar 4 (HPS4), Mycoplasma hyopneumoniae (Mhp), Streptococcus suis serotype 2 (SS2), and LPS from Salmonella enterica serotype minnesota Re 595.

Nanowire photochemical diodes for artificial photosynthesis.

Artificial photosynthesis can provide a solution to our current energy needs by converting small molecules such as water or carbon dioxide into useful fuels. This can be accomplished using photochemical diodes, which interface two complementary light absorbers with suitable electrocatalysts. Nanowire semiconductors provide unique advantages in terms of light absorption and catalytic activity, yet great control is required to integrate them for overall fuel production. In this review, we journey across the progress in nanowire photoelectrochemistry (PEC) over the past two decades, revealing design principles to build these nanowire photochemical diodes. To this end, we discuss the latest progress in terms of nanowire photoelectrodes, focusing on the interplay between performance, photovoltage, electronic band structure, and catalysis. Emphasis is placed on the overall system integration and semiconductor-catalyst interface, which applies to inorganic, organic, or biologic catalysts. Last, we highlight further directions that may improve the scope of nanowire PEC systems.

Direct Observation of Transient Structural Dynamics of Atomically Thin Halide Perovskite Nanowires.

Halide perovskite is a unique dynamical system, whose structural and chemical processes happening across different timescales have significant impact on its physical properties and device-level performance. However, due to its intrinsic instability, real-time investigation of the structure dynamics of halide perovskite is challenging, which hinders the systematic understanding of the chemical processes in the synthesis, phase transition, and degradation of halide perovskite. Here, we show that atomically thin carbon materials can stabilize ultrathin halide perovskite nanostructures against otherwise detrimental conditions. Moreover, the protective carbon shells enable atomic-level visualization of the vibrational, rotational, and translational movement of halide perovskite unit cells. Albeit atomically thin, protected halide perovskite nanostructures can maintain their structural integrity up to an electron dose rate of 10,000 e-/Å2·s while exhibiting unusual dynamical behaviors pertaining to the lattice anharmonicity and nanoscale confinement. Our work demonstrates an effective method to protect beam-sensitive materials during in situ observation, unlocking new solutions to study new modes of structure dynamics of nanomaterials.

Operando studies reveal active Cu nanograins for CO2 electroreduction.

Carbon dioxide electroreduction facilitates the sustainable synthesis of fuels and chemicals1. Although Cu enables CO2-to-multicarbon product (C2+) conversion, the nature of the active sites under operating conditions remains elusive2. Importantly, identifying active sites of high-performance Cu nanocatalysts necessitates nanoscale, time-resolved operando techniques3-5. Here, we present a comprehensive investigation of the structural dynamics during the life cycle of Cu nanocatalysts. A 7 nm Cu nanoparticle ensemble evolves into metallic Cu nanograins during electrolysis before complete oxidation to single-crystal Cu2O nanocubes following post-electrolysis air exposure. Operando analytical and four-dimensional electrochemical liquid-cell scanning transmission electron microscopy shows the presence of metallic Cu nanograins under CO2 reduction conditions. Correlated high-energy-resolution time-resolved X-ray spectroscopy suggests that metallic Cu, rich in nanograin boundaries, supports undercoordinated active sites for C-C coupling. Quantitative structure-activity correlation shows that a higher fraction of metallic Cu nanograins leads to higher C2+ selectivity. A 7 nm Cu nanoparticle ensemble, with a unity fraction of active Cu nanograins, exhibits sixfold higher C2+ selectivity than the 18 nm counterpart with one-third of active Cu nanograins. The correlation of multimodal operando techniques serves as a powerful platform to advance our fundamental understanding of the complex structural evolution of nanocatalysts under electrochemical conditions.