Room-Temperature Anisotropic Actuation Driven by a Synergistic Order-Disorder and Displacive Phase Transition in a Ferroelectric Crystal.

Actuating materials convert different forms of energy into mechanical responses. To satisfy various application scenarios, they are desired to have rich categories, novel functionalities, clear structure-property relationships, fast responses, and, in particular, giant and reversible shape changes. Herein, we report a phase transition-driven ferroelectric crystal, (rac-3-HOPD)PbI3 (3-HOPD = 3-hydroxypiperidine cation), showing intriguingly large and anisotropic room-temperature actuating behaviors. The crystal consists of rigid one-dimensional [PbI3] anionic chains running along the a-axis and discrete disk-like cations loosely wrapping around the chains, leaving room for anisotropic shape changes in both the b- and c-axes. The shape change is switched by a ferroelectric phase transition occurring at around room temperature (294 K), driven by the exceptionally synergistic order-disorder and displacive phase transition. The rotation of the cations exerts internal pressure on the stacking structure to trigger an exceptionally large displacement of the inorganic chains, corresponding to a crystal lattice transformation with length changes of +24.6% and -17.5% along the b- and c-axis, respectively. Single crystal-based prototype devices of circuit switches and elevators have been fabricated by exploiting the unconventional negative temperature-dependent actuating behaviors. This work provides a new model for the development of multifunctional mechanically responsive materials.

Rational Design of 2D Metal Halide Perovskites with Low Congruent Melting Temperature and Large Melt-Processable Window.

Metal halide perovskites (MHPs) have garnered significant attention due to their distinctive optical and electronic properties, coupled with excellent processability. However, the thermal characteristics of these materials are often overlooked, which can be harnessed to cater to diverse application scenarios. We showcase the efficacy of lowering the congruent melting temperature (Tm) of layered 2D MHPs by employing a strategy that involves the modification of flexible alkylammonium through N-methylation and I-substitution. Structural-property analysis reveals that the N-methylation and I-substitution play pivotal roles in reducing hydrogen bond interactions between the organic components and inorganic parts, lowering the rotational symmetry number of the cation and restricting the residual motion of the cations. Additional I···I interactions enhance intermolecular interactions and lead to improved molten stability, as evidenced by a higher viscosity. The 2D MHPs discussed in this study exhibit low Tm and wide melt-processable windows, e.g., (DMIPA)2PbI4 showcasing a low Tm of 98 °C and large melt-processable window of 145 °C. The efficacy of the strategy was further validated when applied to bromine-substituted 2D MHPs. Lowering the Tm and enhancing the molten stability of the MHPs hold great promise for various applications, including glass formation, preparation of high-quality films for photodetection, and fabrication of flexible devices.

From Oxygen Redox to Sulfur Redox: A Paradigm for Li-Rich Layered Cathodes.

The utilization of anionic redox chemistry provides an opportunity to further improve the energy density of Li-ion batteries, particularly for Li-rich layered oxides. However, oxygen-based hosts still suffer from unfavorable structural rearrangement, including the oxygen release and transition metal (TM)-ion migration, in association with the tenuous framework rooted in the ionicity of the TM-O bonding. An intrinsic solution, by using a sulfur-based host with strong TM-S covalency, is proposed here to buffer the lattice distortion upon the highly activating sulfur redox process, and it achieves howling success in stabilizing the host frameworks. Experimental results demonstrate the prolonged preservation of the layered sulfur lattice, especially the honeycomb superlattice, during the Li+ extraction/insertion process in contrast to the large structural degeneration in Li-rich oxides. Moreover, the Li-rich sulfide cathodes exhibited a negligible overpotential of 0.08 V and a voltage drop of 0.13 mV/cycle, while maintaining a substantial reversible capacity upon cycling. These superior electrochemical performances can be unambiguously ascribed to the much shorter trajectories of sulfur in comparison to those of oxygen revealed by molecular dynamics simulations at a large scale (∼30 nm) and a long time scale (∼300 ps) via high-dimensional neural network potentials during the delithiation process. Our findings highlight the importance of stabilizing host frameworks and establish general guidance for designing Li-rich cathodes with durable anionic redox chemistry.

Synthetic lethal targeting of TET2-mutant haematopoietic stem and progenitor cells by XPO1 inhibitors.

TET2 inactivating mutations serve as initiating genetic lesions in the transformation of haematopoietic stem and progenitor cells (HSPCs). In this study, we analysed known drugs in zebrafish embryos for their ability to selectively kill tet2-mutant HSPCs in vivo. We found that the exportin 1 (XPO1) inhibitors, selinexor and eltanexor, selectively kill tet2-mutant HSPCs. In serial replating colony assays, these small molecules were selectively active in killing murine Tet2-deficient Lineage-, Sca1+, Kit+ (LSK) cells, and also TET2-inactivated human acute myeloid leukaemia (AML) cells. Selective killing of TET2-mutant HSPCs and human AML cells by these inhibitors was due to increased levels of apoptosis, without evidence of DNA damage based on increased γH2AX expression. The finding that TET2 loss renders HSPCs and AML cells selectively susceptible to cell death induced by XPO1 inhibitors provides preclinical evidence of the selective activity of these drugs, justifying further clinical studies of these small molecules for the treatment of TET2-mutant haematopoietic malignancies, and to suppress clonal expansion in age-related TET2-mutant clonal haematopoiesis.

Unveiling Chiral Perovskite CD Signal Scaling: Discerning Authentic and Counterfeit Signals through Sample-State Analysis.

Circular dichroism (CD) spectroscopy is a well-known and powerful technique widely used for distinguishing chiral enantiomers based on their differential absorbance of the right and left circularly polarized light. With the increasing demand for solid-state chiral optics, CD spectroscopy has been extended to elucidate the chirality of solid-state samples beyond the traditional solution state. However, due to the sample preparation differential, the CD spectra of the same compound measured by different researchers may not be mutually consistent. In this study, we employ solution, powder, thin-film, and single-crystal samples to explore the challenges associated with CD measurements and distinguish between genuine and fake signals. Rational fabrication of the solid-state samples can effectively minimize the macroscopic anisotropic nature of the samples and thereby mitigate the influence of linear dichroism (LD) and linear birefringence (LB) effects, which arise from anisotropy-induced differences in the absorbances and refractive indices. The local anisotropic and overall isotropic features of the high-quality thin-film sample achieve an optically isotropic state, which exhibits superior CD signal repeatability at the front and back sides at different angles by rotating the sample along the light path. In addition, sample thickness-induced CD signal overload and absorption saturation pose more severe challenges than the LBLD-induced amplified CD signal but are rarely focused on. The CD signal overload in the deep UV region leads to the presence of fake signals, while absorption saturation results in a complete loss of the CD signal. These findings help obtain accurate CD signals by a well-fabricated optically isotropic sample to avoid LDLB and optimize the sample thickness to avoid fake signals and no signals.

Heterostructure Interface Engineering in CoP/FeP/CeOx with a Tailored d-Band Center for Promising Overall Water Splitting Electrocatalysis.

Accomplishing a green hydrogen economy in reality through water spitting ultimately relies upon earth-abundant efficient electrocatalysts that can simultaneously accelerate the oxygen and hydrogen evolution reactions (OER and HER). The perspective of electronic structure modulation via interface engineering is of great significance to optimize electrocatalytic output but remains a tremendous challenge. Herein, an efficient tactic has been explored to prepare nanosheet-assembly tumbleweed-like CoFeCe-containing precursors with time-/energy-saving and easy-operating features. Subsequently, the final metal phosphide materials containing multiple interfaces, denoted CoP/FeP/CeOx, have been synthesized via the phosphorization process. Through the optimization of the Co/Fe ratio and the content of the rare-earth Ce element, the electrocatalytic activity has been regulated. As a result, bifunctional Co3Fe/Ce0.025 reaches the top of the volcano for both OER and HER simultaneously, with the smallest overpotentials of 285 mV (OER) and 178 mV (HER) at 10 mA cm-2 current density in an alkaline environment. Multicomponent heterostructure interface engineering would lead to more exposed active sites, feasible charge transport, and strong interfacial electronic interaction. More importantly, the appropriate Co/Fe ratio and Ce content can synergistically tailor the d-band center with a downshift to enhance the per-site intrinsic activity. This work would provide valuable insights to regulate the electronic structure of superior electrocatalysts toward water splitting by constructing rare-earth compounds containing multiple heterointerfaces.

Hollow Starlike Ag/CoMo-LDH Heterojunction with a Tunable d-Band Center for Boosting Oxygen Evolution Reaction Electrocatalysis.

It is a challenging task to utilize efficient electrocatalytic metal hydroxide-based materials for the oxygen evolution reaction (OER) in order to produce clean hydrogen energy through water splitting, primarily due to the restricted availability of active sites and the undesirably high adsorption energies of oxygenated species. To address these challenges simultaneously, we intentionally engineer a hollow star-shaped Ag/CoMo-LDH heterostructure as a highly efficient electrocatalytic system. This design incorporates a considerable number of heterointerfaces between evenly dispersed Ag nanoparticles and CoMo-LDH nanosheets. The heterojunction materials have been prepared using self-assembly, in situ transformation, and spontaneous redox processes. The nanosheet-integrated hollow architecture can prevent active entities from agglomeration and facilitate mass transportation, enabling the constant exposure of active sites. Specifically, the powerful electronic interaction within the heterojunction can successfully regulate the Co3+/Co2+ ratio and the d-band center, resulting in rational optimization of the adsorption and desorption of the intermediates on the site. Benefiting from its well-defined multifunctional structures, the Ag0.4/CoMo-LDH with optimal Ag loading exhibits impressive OER activity, the overpotential being 290 mV to reach a 10 mA cm-2 current density. The present study sheds some new insights into the electron structure modulation of hollow heterostructures toward rationally designing electrocatalytic materials for the OER.

Structural Descriptors to Correlate Pb Ion Displacement and Broadband Emission in 2D Halide Perovskites.

2D hybrid lead halide perovskites exhibit versatile photoluminescent behaviors for narrowband to broadband emissions (BBEs) and have become attractive candidates for potential applications such as solid-state lighting. Establishing the relationship between the perovskite structural distortion and BBE is key but challenging in designing and optimizing the perovskite luminophores. Conventional attention is given to analyzing the intra-octahedron distortion of the [PbX6]4- (X = halide) unit that has not yet provided a clear structure-luminescence relationship. Herein, we introduce a descriptor, Pb displacement, to describe the inter-octahedron distortion to clarify the structure-emission relationship. The displacement of adjacent Pb centers represents the lattice distortion, which determines the broadband/narrowband emission instead of the octahedron distortion itself. We find a kite-type quadrilateral rule in (001) type 2D perovskites, that is, the degree to which the four octahedral central ions deviate from a square relates to the BBE. The kite-type arrangement of the Pb ions usually corresponds to the BBEs due to the large structure distortions. In contrast, the square-type arrangement of the Pb ions corresponds to the narrowband emissions because of the small distortions. The distortion descriptor magnifies the distortion scale, making it larger than the conventional one for the intra-octahedron distortion, which matches the general concept of excitons based on the scale of the crystal lattice. Therefore, the set of structural descriptors is better to correlate the perovskite structures and emission properties.

Bulk Mn2+ Doped 1D Hybrid Lead Halide Perovskite with Highly Efficient, Tunable and Stable Broadband Light Emissions.

Mn2+ doped colloidal three-dimensional (3D) lead halide perovskite nanocrystal (PNC) has attracted intensive research attention; however, the low exciton binding energy and fatal optical instability of 3D PNC seriously hinder the optoelectronic application. Therefore, it remains significant to explore new stable host perovskite with strongly bound exciton to realize more desirable luminescent property. In this work, we utilized bulk one-dimensional (1D) hybrid perovskite of [AEP]PbBr5 ⋅ H2 O (AEP=N-aminoethylpiperazine) as structural platform to rationally optimize the luminescent property by a controllable Mn2+ doping strategy. Significantly, the series of Mn2+ -doped 1D [AEP]PbBr5 ⋅ H2 O show enhanced energy transfer efficiency from the strongly bound excitons of host material to 3d electrons of Mn2+ ions, resulting in tunable broadband light emissions from weak yellow to strong red spectral range with highest photoluminescence quantum yield up to 28.41 %. More importantly, these Mn2+ -doped 1D perovskites display ultrahigh structural and optical stabilities in humid atmosphere, water and high temperature exceeding the conventional 3D PNC. Combined highly efficient, tunable and stable broadband light emissions enable Mn2+ -doped 1D perovskite as excellent down-converting phosphor showcasing the potential application in white light emitting diode. This work not only provides a profound understanding of low-dimensional perovskites but also opens a new way to rationally design high-performance broadband light emitting perovskites for solid-state lighting and displaying devices.

Multi-model generalised predictive control for intravenous anaesthesia under inter-individual variability.

Inter-individual variability possesses a major challenge in the regulation of hypnosis in anesthesia. Understanding the variability towards anesthesia effect is expected to assist the design of controller for anesthesia regulation. However, such studies are still very scarce in the literature. This study aims to analyze the inter-individual variability in propofol pharmacokinetics/pharmacodynamics (PK/PD) model and proposed a suitable controller to tackle the variability. This study employed Sobol' sensitivity analysis to identify significance parameters in propofol PK/PD model that affects the model output Bispectral Index (BIS). Parameters' range is obtained from reported clinical data. Based on the finding, a multi-model generalized predictive controller was proposed to regulate propofol in tackling patient variability. [Formula: see text] (concentration that produces 50% of the maximum effect) was found to have a highly-determining role on the uncertainty of BIS. In addition, the Hill coefficient, [Formula: see text], was found to be significant when there is a drastic input, especially during the induction phase. Both of these parameters only affect the process gain upon model linearization. Therefore, a predictive controller based on switching of model with different process gain is proposed. Simulation result shows that it is able to give a satisfactory performance across a wide population. Both the parameters [Formula: see text] and [Formula: see text], which are unknown before anesthesia procedure, were found to be highly significant in contributing the uncertainty of BIS. Their range of variability must be considered during the design and evaluation of controller. A linear controller may be sufficient to tackle most of the variability since both [Formula: see text] and [Formula: see text] would be translated into process gain upon linearization.

A g-Type Lysozyme from Deep-Sea Hydrothermal Vent Shrimp Kills Selectively Gram-Negative Bacteria.

Lysozyme is a key effector molecule of the innate immune system in both vertebrate and invertebrate. It is classified into six types, one of which is the goose-type (g-type). To date, no study on g-type lysozyme in crustacean has been documented. Here, we report the identification and characterization of a g-type lysozyme (named LysG1) from the shrimp inhabiting a deep-sea hydrothermal vent in Manus Basin. LysG1 possesses conserved structural features of g-type lysozymes. The recombinant LysG1 (rLysG1) exhibited no muramidase activity and killed selectively Gram-negative bacteria in a manner that depended on temperature, pH, and metal ions. rLysG1 bound target bacteria via interaction with bacterial cell wall components, notably lipopolysaccharide (LPS), and induced cellular membrane permeabilization, which eventually caused cell lysis. The endotoxin-binding capacity enabled rLysG1 to alleviate the inflammatory response induced by LPS. Mutation analysis showed that the bacterial binding and killing activities of rLysG1 required the integrity of the conserved α3 and 4 helixes of the protein. Together, these results provide the first insight into the activity and working mechanism of g-type lysozyme in crustacean and deep-sea organisms.

Fibroblast growth factor receptor-like-1: a new therapeutic target and unfavorable prognostic indicator for rectal adenocarcinoma.

Fibroblast growth factor receptor-like-1 (FGFRL1) is important to cell motility and links with tumorigenic potential in various types of cancers. To investigate the biological function and underlying mechanism of FGFRL1 in rectal adenocarcinoma, we conducted this study. TCGA and Oncomine databases were used to analyze FGFRL1 expression and its association with clinical characteristics or overall survival (OS) in rectal adenocarcinoma patients. siRNA strategy was implemented to knockdown FGFRL1 expression in rectal adenocarcinoma cells. CCK8, colony formation, wound healing, and transwell assays were implemented to measure cell behaviors. qRT-PCR and western blot were utilized to identify mRNA and protein expression levels. FGFRL1 was significantly increased in rectal adenocarcinoma tissue samples, either colon or rectum. High-regulation of FGFRL1 expression induced poorer outcome of rectal adenocarcinoma patients. Downregulation of FGFRL1 inhibited the proliferation, colony formation, migration, and invasion of SW837 cells. The MAPK pathway-related proteins, phosphorylation of MEK and ERK, were also decreased after si-FGFRL1 transfection. These findings demonstrated that FGFRL1, acting as a potential inducator, may promote the progression of rectal adenocarcinoma via activating the MAPK signaling pathway.

Improving Broadband White-Light Emission Performances of 2D Perovskites by Subtly Regulating Organic Cations.

Recently, 2D organic-inorganic hybrid lead halide perovskites have attracted intensive attention in solid-state luminescence fields such as single-component white-light emitters, and rational optimization of the photoluminescence (PL) performance through accurate structural-design strategies is still significant. Herein, by carefully choosing homologous aliphatic amines as templates, isotypical perovskites [DMEDA]PbCl4 (1, DMEDA=N,N-dimethylethylenediamine) and [DMPDA]PbCl4 (2, DMPDA=N,N-dimethyl-1,3-diaminopropane) having tunable and stable broadband bluish white emission properties were rationally designed. The subtle regulation of organic cations leads to a higher degree of distortion of the 2D [PbCl4 ]2- layers and enhanced photoluminescence quantum efficiencies (<1 % for 1 and 4.9 % for 2). The broadband light emissions could be ascribed to self-trapped excitons on the basis of structural characterization, time-resolved PL, temperature-dependent PL emission, and theoretical calculations. This work gives a new guidance to rationally optimize the PL properties of low-dimensional halide perovskites and affords a platform to probe the structure-property relationship.

CYP3A4 and microRNA-122 are involved in the apoptosis of HepG2 cells induced by ILs 1-decyl-3-methylimidazolium bromide.

Ionic liquids (ILs) as green alternatives for volatile organic solvents are increasingly used in commercial applications. It is necessary to explore the cytotoxic mechanism of ILs to reduce the risk to human health. For this purpose, cell viability, apoptosis, cytochrome P450 3A4 (CYP3A4), glucose transporter type 2 (GLUT2), and microRNA-122 (miR-122) gene expression in HepG2 cells was evaluated after IL exposure. The results showed that ILs reduced the viability of HepG2 cells through apoptotic cell death. Moreover, ILs markedly upregulated the transcription and protein levels of CYP3A4, but did not affect the expression of GLUT2 in either messenger RNA level or protein level. Finally, ILs increased the expression of miR-122 and inhibition of miR-122 with miR-122 inhibitor blocked ILs-induced apoptosis in HepG2 cells. This finding may contribute to an increased understanding of the in vitro molecular toxicity mechanism of ILs to further understand IL-related human health risks.

Oxidation of salicylic acid in water by the O3 and UV/O3 processes: removal and reaction byproducts.

In this study, the removal of salicylic acid (SA) in water by ozone (O3) and ultraviolet/ozone (UV/O3) processes was investigated. Results showed that more than 50% of SA (10 mg/L) could be effectively removed after 1 min during these two processes. However, the UV/O3 process was much more effective than the O3 process for SA mineralization, and the total organic carbon reduction after 30 min was 69.5% and 28.1%, respectively. In the two processes, the optimum pH value for SA removal was 4.3, while that for SA mineralization was 10.0. Both bicarbonate and dissolved organic carbon significantly inhibited SA removal during the two processes. Eleven oxidation byproducts were detected in O3 process, but only four byproducts were observed in UV/O3 process. Three hydroxylation aromatic products were identified as the initial byproducts during SA degradation. Glyoxylic acid monohydrate, glycolic acid, and oxalic acid were accumulated in O3 process but not observed in UV/O3 process. Oxalic acid was the only detected small molecular byproduct in UV/O3 process, and it could be further mineralized, thereby indicating that UV/O3 had a greater potential for degrading both SA and its reaction byproducts.

[The Automatic Recognition and Detection of Sky-Subtraction Residual Componentin the Stellar Spectra].

The skylines, superimposing on the target spectrum as a main noise, will reduce the signal-to-noise ratio of the spectrum. If the spectrum still contains a large number of high strength skylight residuals after sky-subtraction processing, it will not be conducive to the follow-up analysis of the target spectrum. At present, the study on the automatic recognition of the abnormal sky-subtraction stellar spectra is limited in number. We can only find the abnormal sky-subtraction spectra by manual inspection, and this will reduce the speed of detection. This paper analyzes the influence factors of sky-subtraction results and finds the characteristics of the abnormal sky-subtraction spectra. A simple and effective method is proposed to automatic recognize the abnormal sky-subtraction stellar spectra which have been processed with the LAMOST Pipeline processing procedure and find the positions of the abnormal skylines. In this method, all the spectra are normalized first; the abnormal skyline is determined by detecting whether there exits any high strength skyline residuals which are similar to the emission line or absorption line. Finally, all the abnormal skyline positions in the spectra are obtained in this method. The experimental results with the LAMOST spectroscopic dataset show that this method can recognize the abnormal sky-subtraction spectra and find the abnormal skyline positions of different residual strength effectively. In addition, the method is simple and has high recognition efficiency, and can be applied to the automatic detection of abnormal sky-subtraction of large number of spectra.

[Stellar Alpha Element Abundance Estimation Using LASSO Algorithm].

In this paper, a new method based on LASSO algorithm is studied for the estimation of stellar alpha element abundance. The information of alpha elements (O, Mg, Ca, Si, and Ti) of massive stars will help us to better understand the evolution of the galaxy. Presently the main method of determining the alpha element abundances from the low resolution spectra is the template matching method. However, it is difficult for us to optimize the algorithm parameters and the algorithm is sensitive to the noise. Thus, it is necessary to study the new method to determine the abundance. The experimental results show that the accuracy of LASSO algorithm on ELODIE spectra is 0.003 (0.078) dex. To explore the impact of the spectral resolution variation, we use ELODIE spectra to generate the spectral data sets with following resolutions: 42 000, 21 000, 10 500, 4 200 and 2 100 by using the Gaussian convolution. The results of the LASSO algorithm on these data sets are 0.003 3 (0.078) dex, -0.05 (0.059) dex, -0.007 (0.069) dex and -0.004 5 (0.067) dex, respectively. These results show that the LASSO algorithm is not sensitive to the change of the resolution. In order to verify the robustness of LASSO algorithm against the change of SNRs, we use ELODIE to generate the spectral data sets with following SNRs: 30, 25, 20, 15 and 5. The results of LASSO algorithm on the above data sets are: -0.002 (0.076) dex, -0.090 (0.073) dex, 0.003 6 (0.075) dex, 0.007 6 (0.078) dex and -0.009 (0.080) dex, respectively. Thus, LASSO algorithm is not sensitive to the change of SNR. Therefore, the LASSO algorithm is suitable for low resolution and low SNR spectra such as LAMOST and SDSS spectra. The accuracy of Lasso algorithm on the SDSS spectra is 0.003 7 (0.097) dex, and the results of LASSO on globular and open clusters show good agreement with literature values (within 1σ). Therefore, the LASSO algorithm can be used to estimate the alpha element abundances of stars.

[Research on M Dwarf Sub-Classification Based on the Measurement of Residual Distribution].

The classification of stellar spectra is an important job in data processing of astronomy, which is mainly used for searching celestial spectra with known types in massive data survey. This paper focuses on LAMOST M dwarfs fine classification based on measurement of residual distribution. Residual distribution measurement is a measurement method used to measure the distance between two spectra. In the process of calculating the distance between two spectra, normalized processing should come first. Then the residuals of the sampling points of corresponding wavelength are calculated. Eventually the standard deviation of the residual distribution as the distance between the spectra is calculated. In this paper, the M star of LAMOST DR2 is used as the experimental data of classification. The experimental results show that the spectra data can be classified more accurately with the measurement method of residual distribution than the use of other traditional classification methods. The effect of spectral classification is affected by signal to noise ratio, outliers, residual standardized coefficient and other factors.

[Research on the Clustering of Massive Stellar Spectra Based on Line Index].

Clustering algorithm is an important algorithm used to find the data distribution and implicit scheme in data mining. It can study spectra of large amount, multi-parameter and categories unknown simply and effectively. Using lick index as the eigenvalues of spectra can effectively improve the speed to calculate the high-dimensional spectra which can also retain more astrophysical characteristics of spectra. This paper finishes clustering of the survey data with k-means algorithm, using lick index as the eigenvalues of data with finished analysis results. The results show that the new method can gather data with similar physical characteristics together quicker and efficiently, with very good results in discovering rare stars. This method can be applied to the study of Survey data.