Interface-confined intermediate phase in TiO2 enables efficient photocatalysis.

As a prototypical photocatalyst, TiO[Formula: see text] has been extensively studied. An interesting yet puzzling experimental fact was that P25-a mixture of anatase and rutile TiO[Formula: see text]-outperforms the individual phases; the origin of this mysterious fact, however, remains elusive. Employing rigorous first-principles calculations, here we uncover a metastable intermediate structure (MIS), which is formed due to confinement at the anatase/rutile interface. The MIS has a high conduction-band minimum level and thus substantially enhances the overpotential of the hydrogen evolution reaction. Also, the corresponding band alignment at the interface leads to efficient separation of electrons and holes. The interfacial confinement additionally creates a wide distribution of the band gap in the vicinity of the interface, which in turn improves optical absorption. These factors all contribute to the enhanced photocatalytic efficiency in P25. Our insights provide a rationale to the puzzling superior photocatalytic performance of P25 and enable a strategy to achieve highly efficient photocatalysis via interface engineering.

Critical Role of Configurational Disorder in Stabilizing Chemically Unfavorable Coordination in Complex Compounds.

The crystal structure of a material is essentially determined by the nature of its chemical bonding. Consequently, the atomic coordination intimately correlates with the degree of ionicity or covalency of the material. Based on this principle, materials with similar chemical compositions can be successfully categorized into different coordination groups. However, counterexamples have recently emerged in complex ternary compounds. For instance, covalent IB-IIIA-VIA2 compounds, such as AgInS2, prefer a tetrahedrally coordinated structure (TCS), while ionic IA-VA-VIA2 compounds, such as NaBiS2, would favor an octahedrally coordinated structure (OCS). One naturally expects that IB-VA-VIA2 compounds with intermediate ionicity or covalency, such as AgBiS2, should then have a mix-coordinated structure (MCS) consisting of covalent AgS4 tetrahedra and ionic BiS6 octahedra. Surprisingly, only the experimental presence of the OCS was observed for AgBiS2. To resolve this puzzle, we perform first-principles studies of the phase stabilities of ternary compounds at finite temperatures. We find that AgBiS2 indeed prefers MCS at the ground state, in agreement with the typical expectation, but under experimental synthesis conditions, disordered OCS becomes energetically more favorable because of its low mixing energy and high configurational entropy. Our work elucidates the critical role of configurational disorder in stabilizing chemically unfavorable coordination, providing a rigorous rationale for the anomalous coordination preference in IB-VA-VIA2 compounds.

Computational Screening of Promising Deep-Ultraviolet Light Emitters.

Deep-ultraviolet (DUV) light sources are technologically highly important, but DUV light-emitting materials are extremely rare; AlN and its alloys are the only materials known so far, significantly limiting the chemical and structural spaces for materials design. Here, we perform a high-throughput computational search for DUV light emitters based on a set of carefully designed screening criteria relating to the sophisticated electronic structure. In this way, we successfully identify 5 promising material candidates that exhibit comparable or higher radiative recombination coefficients than AlN, including BeGeN2, Mg3NF3, KCaBr3, KHS, and RbHS. Further, we unveil the unique features in the atomic and electronic structures of DUV light emitters and elucidate the fundamental genetic reasons why DUV light emitters are extremely rare. Our study not only guides the design and synthesis of efficient DUV light emitters but also establishes the genetic nature of ultrawide-band-gap semiconductors in general.

Crystal Facet Engineering on SrTiO3 Enhances Photocatalytic Overall Water Splitting.

Single-crystal semiconductor-based photocatalysts exposing unique crystallographic facets show promising applications in energy and environmental technologies; however, crystal facet engineering through solid-state synthesis for photocatalytic overall water splitting is still challenging. Herein, we develop a novel crystal facet engineering strategy through solid-state recrystallization to synthesize uniform SrTiO3 single crystals exposing tailored {111} facets. The presynthesized low-crystalline SrTiO3 precursors enable the formation of well-defined single crystals through kinetically improved crystal structure transformation during solid-state recrystallization process. By employing subtle Al3+ ions as surface morphology modulators, the crystal surface orientation can be precisely tuned to a controlled percentage of {111} facets. The photocatalytic overall water splitting activity increases with the exposure percentage of {111} facets. Owing to the outstanding crystallinity and favorable anisotropic surface structure, the SrTiO3 single crystals with 36.6% of {111} facets lead to a 3-fold enhancement of photocatalytic hydrogen evolution rates up to 1.55 mmol·h-1 in a stoichiometric ratio of 2:1 than thermodynamically stable SrTiO3 enclosed with isotropic {100} facets.

The prediction of influenza-like illness using national influenza surveillance data and Baidu query data.

BACKGROUND: Seasonal influenza and other respiratory tract infections are serious public health problems that need to be further addressed and investigated. Internet search data are recognized as a valuable source for forecasting influenza or other respiratory tract infection epidemics. However, the selection of internet search data and the application of forecasting methods are important for improving forecasting accuracy. The aim of the present study was to forecast influenza epidemics based on the long short-term memory neural network (LSTM) method, Baidu search index data, and the influenza-like-illness (ILI) rate. METHODS: The official weekly ILI% data for northern and southern mainland China were obtained from the Chinese Influenza Center from 2018 to 2021. Based on the Baidu Index, search indices related to influenza infection over the corresponding time period were obtained. Pearson correlation analysis was performed to explore the association between influenza-related search queries and the ILI% of southern and northern mainland China. The LSTM model was used to forecast the influenza epidemic within the same week and at lags of 1-4 weeks. The model performance was assessed by evaluation metrics, including the mean square error (MSE), root mean square error (RMSE) and mean absolute error (MAE). RESULTS: In total, 24 search queries in northern mainland China and 7 search queries in southern mainland China were found to be correlated and were used to construct the LSTM model, which included the same week and a lag of 1-4 weeks. The LSTM model showed that ILI% + mask with one lag week and ILI% + influenza name were good prediction modules, with reduced RMSE predictions of 16.75% and 4.20%, respectively, compared with the estimated ILI% for northern and southern mainland China. CONCLUSIONS: The results illuminate the feasibility of using an internet search index as a complementary data source for influenza forecasting and the efficiency of using the LSTM model to forecast influenza epidemics.

Dual-Level Enhanced Nonradiative Carrier Recombination in Wide-Gap Semiconductors: The Case of Oxygen Vacancy in SiO2.

The conventional single-defect-mediated Shockley-Read-Hall model suggests that the nonradiative carrier recombination rate in wide-band gap (WBG) semiconductors would be negligible because the single-defect level is expected to be either far from valence-band-maximum (VBM) or conduction-band-minimum (CBM), or both. However, this model falls short of elucidating the substantial nonradiative recombination phenomena often observed experimentally across various WBG semiconductors. Owing to more localized nature of defect states inherent to WBG semiconductors, when the defect charge state changes, there is a pronounced structural relaxation around the local defect site. This suggests that a defect at each charge state may exhibit a few distinct local configurations, namely, a stable configuration and a few metastable/transit state configurations. Consequently, a dual-level nonradiative recombination model should more realistically exist in WBG semiconductors. In this model, through the dual-level mechanism, electron and hole trap levels are different from each other and could be closer to the CBM for the electron trap and closer to the VBM for the hole trap, respectively; therefore, this significantly increases the corresponding electron and hole capture rates, enhancing the overall process of nonradiative recombination, and explains the experimental observations. In this work, taking technically important SiO2 as an illustrative example, we introduce the dual-level mechanism to elucidate the mechanism of nonradiative carrier recombination in WBG semiconductors. Our findings demonstrated strong alignment with available experimental data, reinforcing the robustness of our proposed dual-level model. Our fundamental understanding, therefore, provides a clear physical picture of the issue and can also be applied to predict the defect-related nonradiative carrier recombination characteristics in other WBG materials.

Direct Observation of Group-V Dopant Substitutional Defects in CdTe Single Crystals.

Point defect chemistry strongly affects the fundamental properties of materials and has a decisive impact on device performance. The Group-V dopant is prominent acceptor species with high hole concentration in CdTe; however, its local atomic structure is still not clear owing to difficulties in definitive measurements and discrepancies between experimental observations and theoretical models. Herein, we report on direct observation of the local structure for the As dopant in CdTe single crystals by the X-ray fluorescence holography (XFH) technique, which is a powerful tool to visualize three-dimensional atomic configurations around a specific element. The XFH result shows the As substituting on both Cd (AsCd) and Te (AsTe) sites. Although AsTe has been well known as a shallow acceptor, AsCd has not attracted much attention and been discussed so far. Our results provide new insights into point defects by expanding the experimental XFH study in combination with theoretical first-principles studies in II-VI semiconductors.

Crystal-liquid duality enhanced dynamical stability of hybrid perovskites.

The organic molecules in hybrid perovskites can easily rotate within the inorganic lattice at room temperature, leading to a crystal-liquid duality. The liquid-like behavior of the organic molecules is commonly believed to play a critical role in the dynamical stability, but the microscopic mechanism remains unclear. Furthermore, the presence of dynamically rotating molecules raises concerns regarding the reliability of assessing the stability of hybrid perovskites based on simple yet commonly used descriptors such as the Goldschmidt tolerance factor. Here we assess the finite-temperature phonons of hybrid perovskites by mapping ab initio molecular dynamics configurations onto an equivalent dynamical pseudo-inorganic lattice and extracting the effective force constants. We find that as compared to the formamidinium or cesium cations, stronger anisotropy and wider range of the thermal motion of the methylammonium molecule are essential for enhancing the dynamical stability of hybrid perovskites. The cation radius that determines the tolerance factor is, in fact, less important. This work not only enables a pathway to further improve the stability of hybrid perovskites, but also provides a general scheme to assess the stability of hybrid materials with dynamical disorder.

Socioeconomic factors, perceived stress, and social support effect on neonatal nurse burnout in China: a cross-sectional study.

BACKGROUND: Neonatal nurses' working environments are highly stressful, and burnout is common. This study examines the effect of socioeconomic factors, perceived stress, and social support on neonatal nurse burnout. METHODS: A total of 311 neonatal nurses participated in this study. They were administered a validated Maslach Burnout Inventory. The study employed a 14-item perceived stress scale (PSS-14) and a social support rate scale (SSRS) to examine stress, socioeconomic factors, and lifestyles. RESULTS: Of the neonatal nurses, 40.19% had burnout, 89.60% had mild burnout, and 10.40% had moderate burnout; no neonatal nurse experienced severe burnout. Young nurses and those with low technical skills, poor interpersonal relationships, irregular diet, and insufficient rest were exposed to burnout (all p < 0.05).Most burnout nurses experienced moderate-severe perceived stress, and their PSS-14 scores were higher (all p < 0.05).The scores for objective social support, subjective social support, utilization of social support, total SSRS scores, and the level of social support were all lower in burnout nurses (all p < 0.05). Perceived stress was correlated positively and significantly with emotional exhaustion and personal accomplishment (all p < 0.05). Social support correlated significantly with and reduced personal accomplishments (p < 0.05). Age, poor interpersonal relationships, perceived stress, and social support were all independent factors associated with neonatal nurse burnout (all p < 0.05). CONCLUSION: The prevalence of burnout in neonatal nurses was higher than average. Socioeconomic factors, higher perceived stress, and lower social support contribute to neonatal nurse burnout. Nursing managers should pay attention to socioeconomic factors, perceived stress, and social support among neonatal nurses and employ strategies to reduce neonatal nurse burnout.

Designing Ultra-flat Bands in Twisted Bilayer Materials at Large Twist Angles: Theory and Application to Two-Dimensional Indium Selenide.

Intertwisted bilayers of two-dimensional (2D) materials can host low-energy flat bands, which offer opportunity to investigate many intriguing physics associated with strong electron correlations. In the existing systems, ultra-flat bands only emerge at very small twist angles less than a few degrees, which poses a challenge for experimental studies and practical applications. Here, we propose a new design principle to achieve low-energy ultra-flat bands with increased twist angles. The key condition is to have a 2D semiconducting material with a large energy difference of band edges controlled by stacking. We show that the interlayer interaction leads to defect-like states under twisting, which forms a flat band in the semiconducting band gap with dispersion strongly suppressed by the large energy barriers in the moiré superlattice even for large twist angles. We explicitly demonstrate our idea in bilayer α-In2Se3 and bilayer InSe. For bilayer α-In2Se3, we show that a twist angle of ∼13.2° is sufficient to achieve the band flatness comparable to that of twist bilayer graphene at the magic angle ∼1.1°. In addition, the appearance of ultra-flat bands here is not sensitive to the twist angle as in bilayer graphene, and it can be further controlled by external gate fields. Our finding provides a new route to achieve ultra-flat bands other than reducing the twist angles and paves the way toward engineering such flat bands in a large family of 2D materials.

General Model for Defect Dynamics in Ionizing-Irradiated SiO2 -Si Structures.

Irradiation damage is a key issue for the reliability of semiconductor devices under extreme environments. For decades, the ionizing-irradiation-induced damage in transistors with silica-silicon (SiO2 -Si) structures at room temperature has been modeled by a uniform generation of E'γ centers in the bulk silica region through the capture of irradiation-induced holes, and an irreversible conversion from E'γ to Pb centers at the SiO2 /Si interface through reactions with hydrogen molecules (H2 ). However, the traditional model fails to explain experimentally-observed dose dependence of the defect concentrations, especially at low dose rate. Here, it is proposed that the generation of E'γ centers is decelerated because the holes migrate dispersively in disordered silica and the diffusion coefficient decays as the irradiation goes on. It is also proposed that the conversion between E'γ and Pb centers is reversible because the huge activation energy of the reverse reaction can be reduced by a "phonon-kick" effect of the vibrational energy of H2 and Pb centers transferred from nearby nonradiative recombination centers. Experimental studies are carried out to demonstrate that the derived analytic model based on these two new concepts can consistently explain the fundamental but puzzling dose dependence of the defect concentrations for an extremely wide dose rate range.

Origin of Efficiency Enhancement by Lattice Expansion in Hybrid-Perovskite Solar Cells.

It has been experimentally observed that light-induced lattice expansion could enhance the solar conversion efficiency in hybrid perovskites, but the origin remains elusive. By performing rigorous first-principles calculations for a prototypical hybrid-perovskite FAPbI_{3} (FA: formamidinium), we show that 1% lattice expansion could already reduce the nonradiative capture coefficient by one order of magnitude. Unexpectedly, the suppressed nonradiative capture is not caused by changes in the band gap or defect transition level due to lattice expansion, but originates from enhanced defect relaxations associated with charge-state transitions in the expanded lattice. These insights not only provide a rationale for the efficiency enhancement by lattice expansion in hybrid perovskites, but also offer a general approach to the manipulation of nonradiative capture via strain engineering in a wide spectrum of optoelectronic materials.

Novel mutation signatures in the prognosis of EGFR-TKIs targeted therapy for non-small cell lung cancer patients based on the 1000-gene panel sequencing.

The application of epidermal growth factor receptor (EGFR) tyrosine kinase inhibitors (EGFR-TKIs) in non-small cell lung cancer (NSCLC) may be affected by somatic mutations. The purpose of this study was to explore the effect of mutations on the prognosis and tumor markers of NSCLC patients treated with EGFR-TKIs. 21 NSCLC patients treated with EGFR-TKIs were selected, and the targeted sequencing of the tumor tissues or whole blood samples with the 1000-gene panel was conducted to screen mutations. Afterward, functional enrichment analysis was performed based on mutant genes. Subsequently, the correlation between mutations and clinical indicators, prognosis, and tumor markers were analyzed. Finally, the prognosis after taking osimertinib was compared between NSCLC patients with EGFR p.T790M positive and negative mutations, and the EGFR p.T790M concomitant and uncommon mutations were screened. A total of 485 mutations in 251 genes were identified, in which MTOR, AXIN2, AR, EGFR, NOTCH1, and HRAS mutations were significantly correlated with PFS and/or tumor markers. There was no significant difference in PFS, therapeutic effect, and prognosis between EGFR p.T790M positive and negative patients who received osimertinib treatment. Besides, we also found 80 concomitant mutations and 54 uncommon mutations of EGFR p.T790M. AR, HRAS, EGFR, AXIN2, NOTCH1, and MTOR might be key genes to the prognosis of NSCLC treated with EGFR-TKIs. Osimertinib has certain efficacy in EGFR p.T790M negative NSCLC patients.

Phytochemical library screening reveals betulinic acid as a novel Skp2-SCF E3 ligase inhibitor in non-small cell lung cancer.

Skp2 is overexpressed in multiple cancers and plays a critical role in tumor development through ubiquitin/proteasome-dependent degradation of its substrate proteins. Drugs targeting Skp2 have exhibited promising anticancer activity. Here, we identified a plant-derived Skp2 inhibitor, betulinic acid (BA), via high-throughput structure-based virtual screening of a phytochemical library. BA significantly inhibited the proliferation and migration of non-small cell lung cancer (NSCLC) through targeting Skp2-SCF E3 ligase both in vitro and in vivo. Mechanistically, BA binding to Skp2, especially forming H-bonds with residue Lys145, decreases its stability by disrupting Skp1-Skp2 interactions, thereby inhibiting the Skp2-SCF E3 ligase and promoting the accumulation of its substrates; that is, E-cadherin and p27. In both subcutaneous and orthotopic xenografts, BA significantly inhibited the proliferation and metastasis of NSCLC through targeting Skp2-SCF E3 ligase and upregulating p27 and E-cadherin protein levels. Taken together, BA can be considered a valuable therapeutic candidate to inhibit metastasis of NSCLC.

More Se Vacancies in Sb2 Se3 under Se-Rich Conditions: An Abnormal Behavior Induced by Defect-Correlation in Compensated Compound Semiconductors.

It was believed that the Se-rich synthesis condition can suppress the formation of deep-level donor defect VSe (selenium vacancy) in Sb2 Se3 and is thus critical for fabricating high-efficiency Sb2 Se3 solar cells. However, here it is shown that by first-principles calculations the density of VSe increases unexpectedly to 1016 cm-3 when the Se chemical potential increases, so Se-rich condition promotes rather than suppresses the formation of VSe . Therefore, high density of VSe is thermodynamically inevitable, no matter under Se-poor or Se-rich conditions. This abnormal behavior can be explained by a physical concept "defect-correlation", i.e., when donor and acceptor defects compensate each other, all defects become correlated with each other due to the formation energy dependence on Fermi level which is determined by densities of all ionized defects. In quasi-1D Sb2 Se3 , there are many defects and the complicated defect-correlation can give rise to abnormal behaviors, e.g., lowering Fermi level and thus decreasing the formation energy of ionized donor VSe 2+ in Se-rich Sb2 Se3 . Such behavior exists also in Sb2 S3 . It explains the recent experiments that the extremely Se-rich condition causes the efficiency drop of Sb2 Se3 solar cells, and demonstrates that the common chemical intuition and defect engineering strategies may be invalid in compensated semiconductors.

A Comparison of Tumor-Associated and Non-Tumor-Associated Gastric Microbiota in Gastric Cancer Patients.

BACKGROUND: How gastric cancer (GC) incidence is associated with changes in the gastric microbiome has not been firmly established. The present study therefore aims to investigate the microbial communities present within the gastric mucosa of patients with superficial gastritis (SG) or GC. METHODS: Paired tumor and paracancerous samples of the gastric mucosa were collected from 18 patients being surgically treated for GC and from 32 patients with SG being treated via gastroscopy. The gastric microbiome in these samples was then profiled via 16S rRNA sequencing, with a linear discriminant analysis effect size (LEfSe) approach used to identify and compare different bacteria, and with PICRUSt used for predictive functional analyses. RESULTS: GC patients exhibited a distinct gastric microbiota profile from that observed in SG patients. These changes were evident in both tumor and paracancerous tissues from GC patients. Specifically, we found that 6 bacterial genera were specifically enriched in GC tissue samples relative to SG samples, while 18 genera were depleted in these same samples. Based on the differential abundance of these bacteria, we were able to calculate microbial dysbiosis index (MDI) values, which were significantly higher in GC patients than in SG patients. In addition, MDI values were negatively correlated with gastric Shannon index and were positively correlated with relative Helicobacter spp. abundance. Importantly, these MDI values were readily able to discriminate between GC and SG patient samples. Functional analysis suggested that GC patients were more likely to harbor a nitrosating microbial community. CONCLUSIONS: GC patients exhibited a gastric microbiome profile distinct from that observed in SG patients, with these differences being evident in both tumor and paracancerous tissues. Differences in the relative abundance of Helicobacter spp. may be the primary driver of gastric dysbiosis in GC patients.

Formation of Bloch Flat Bands in Polar Twisted Bilayers without Magic Angles.

The existence of Bloch flat bands of electrons provides a facile pathway to obtain exotic quantum phases owing to strong correlation. Despite the established magic angle mechanism for twisted bilayer graphene, understanding of the emergence of flat bands in twisted bilayers of two-dimensional polar crystals remains elusive. Here, we show that due to the polarity between constituent elements in the monolayer, the formation of complete flat bands in twisted bilayers is triggered as long as the twist angle is less than a certain critical value. Using the twisted bilayer of hexagonal boron nitride (hBN) as an example, our simulations using the density-functional tight-binding method reveal that the flat band originates from the stacking-induced decoupling of the highest occupied (lowest unoccupied) states, which predominantly reside in the regions of the moiré superlattice where the anion (cation) atoms in both layers are overlaid. Our findings have important implications for the future search for and study of flat bands in polar materials.

Self-Catalyzed Sensitization of CuO Nanowires via a Solvent-free Click Reaction.

Recent advances in organic surface sensitization of metal oxide nanomaterials focused on two-step approaches with the first step providing a convenient functionalized chemical "hook", such as an alkyne functionality connected to a carboxylic group in prop-2-ynoic acid. The second step then took advantage of copper-catalyzed click chemistry to deliver the desired structure (such as benzyl or perylene) attached to an azide to react with the surface-bound alkyne. The use of this approach on CuO not only resulted in a successful morphology preserving chemical modification but also has demonstrated that surface Cu(I) can be obtained during the process and promote a surface-catalyzed click reaction without additional copper catalyst. Here, it is demonstrated that this surface-catalyzed chemistry can be performed on a surface of the CuO nanomaterial without a solvent, as a "dry click" reaction, as confirmed with spectroscopic and microscopic investigations with X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, X-ray diffraction, solid-state nuclear magnetic resonance, and scanning electron microscopy. Computational studies provided instructive information on the interaction between the surface prop-2-yonate and azide functional group to better understand the mechanism of this surface-catalyzed click reaction.

Unconventional deformation potential and half-metallicity in zigzag nanoribbons of 2D-Xenes.

Realization of half-metallicity (HM) in low dimensional materials is a fundamental challenge for nano spintronics and a critical component for developing alternative generations of information technology. Using first-principles calculations, we reveal an unconventional deformation potential for zigzag nanoribbons (NRs) of 2D-Xenes. Both the conduction band minimum (CBM) and valence band maximum (VBM) of the edge states have negative deformation potentials. This unique property, combined with the localization and spin-polarization of the edge states, enables us to induce spin-splitting and HM using an inhomogeneous strain pattern, such as simple in-plane bending. Indeed, our calculation using the generalized Bloch theorem reveals the predicted HM in bent zigzag silicene NRs. Furthermore, the magnetic stability of the long range magnetic order for the spin-polarized edge states is maintained well against the bending deformation. These aspects indicate that it is a promising approach to realize HM in low dimensions with the zigzag 2D-Xene NRs.

Strain induced spin-splitting and half-metallicity in antiferromagnetic bilayer silicene under bending.

Searching for half-metals in low dimensional materials is not only of scientific importance, but also has important implications for the realization of spintronic devices on a small scale. In this work, we show theoretically that simple bending can induce spin-splitting in bilayer silicene. For bilayer silicene with Bernal stacking, the monolayer has a long range ferromagnetic spin order and between the two monolayers, the spin orders are opposite, giving rise to an antiferromagnetic configuration for the ground state of the bilayer silicene. Under bending, the antiferromagnetic spin order is retained but the energetic degeneracy of opposite spin states is lifted. Due to the unusual deformation potentials of the conduction band minimum (CBM) and valence band maximum (VBM) as revealed by density-functional theory calculations and density-functional tight-binding calculations, this spin-splitting is nearly proportional to the degree of bending deformation. Consequently, the spin-splitting can be significant and the desired half-metallic state may emerge when the bending increases, which has been verified by direct simulation of the bent bilayer silicene using the generalized Bloch theorem. Our results hint that bilayer silicene may be an excellent candidate for half-metallicity.