Exploring the Underlying Correlation between the Structure and Ionic Conductivity in Halide Spinel Solid-State Electrolytes with Neutron Diffraction.

The development of cutting-edge solid-state electrolytes (SSEs) entails a deep understanding of the underlying correlation between the structure and ionic conductivity. Generally, the structure of SSEs encompasses several interconnected crystal parameters, and their collective influence on Li+ transport can be challenging to discern. Here, we systematically investigate the structure-function relationship of halide spinel LixMgCl2+x (2 ≥ x ≥ 1) SSEs. A nonmonotonic trend in the ionic conductivity of LixMgCl2+x SSEs has been observed, with the maximum value of 8.69 × 10-6 S cm-1 achieved at x = 1.4. The Rietveld refinement analysis, based on neutron diffraction data, has revealed that the crystal parameters including cell parameters, Li+ vacancies, Debye-Waller factor, and Li-Cl bond length assume diverse roles in influencing ionic conductivity of LixMgCl2+x at different stages within the range of x values. Besides, mechanistic analysis demonstrates Li+ transport along three-dimensional pathways, which primarily governs the contribution to ionic conductivity of LixMgCl2+x SSEs. This study has shed light on the collective influence of crystal parameters on Li+ transport behaviors, providing valuable insights into the intricate relationship between the structure and ionic conductivity of SSEs.

Nanoparticles Displaying Allergen and Siglec-8 Ligands Suppress IgE-FcεRI-Mediated Anaphylaxis and Desensitize Mast Cells to Subsequent Antigen Challenge.

Siglec-8 is an inhibitory receptor expressed on eosinophils and mast cells. In this study, we took advantage of a novel Siglec-8 transgenic mouse model to assess the impact of modulating IgE-dependent mast cell degranulation and anaphylaxis using a liposomal platform to display an allergen with or without a synthetic glycan ligand for Siglec-8 (Sig8L). The hypothesis is that recruitment of Siglec-8 to the IgE-FcεRI receptor complex will inhibit allergen-induced mast cell degranulation. Codisplay of both allergen and Sig8L on liposomes profoundly suppresses IgE-mediated degranulation of mouse bone marrow-derived mast cells or rat basophilic leukemia cells expressing Siglec-8. In contrast, liposomes displaying only Sig8L have no significant suppression of antigenic liposome-induced degranulation, demonstrating that the inhibitory activity by Siglec-8 occurs only when Ag and Sig8L are on the same particle. In mouse models of anaphylaxis, display of Sig8L on antigenic liposomes completely suppresses IgE-mediated anaphylaxis in transgenic mice with mast cells expressing Siglec-8 but has no protection in mice that do not express Siglec-8. Furthermore, mice protected from anaphylaxis remain desensitized to subsequent allergen challenge because of loss of Ag-specific IgE from the cell surface and accelerated clearance of IgE from the blood. Thus, although expression of human Siglec-8 on murine mast cells does not by itself modulate IgE-FcεRI-mediated cell activation, the enforced recruitment of Siglec-8 to the FcεRI receptor by Sig8L-decorated antigenic liposomes results in inhibition of degranulation and desensitization to subsequent Ag exposure.

Substitution engineering of lead-free halide perovskites for photocatalytic applications assisted by machine learning.

Lead-free perovskites (A3B2X9) have drawn much attention in recent years. However, a thorough understanding of these materials is still in its early stages. This is because A3B2X9 perovskites have large-scale component tunability, in which the A+, B3+, and X- ions can be replaced or partially substituted with other elements. Here, based on density functional theory and machine learning techniques we propose a data-driven method to find suitable configurations for photocatalytic water splitting. By replacing atoms in A3B2X9, 3.4 million configurations are constructed and studied. Our results show that the substitutional position plays an important role in determining the photocatalytic performance. Specifically, the co-existence of Br and I elements is favorable for X-sites, while for B-site atoms, it is better to choose atoms from groups IIIB and IIIA with a period greater than 3. Considering their rarity and toxicity, we believe that In is a good choice for B-sites and propose CsRb2BiInBr5I4 as a promising candidate. These results may provide guidance for the discovery of novel lead-free perovskites for photocatalytic applications.

A Collision Relationship-Based Driving Behavior Decision-Making Method for an Intelligent Land Vehicle at a Disorderly Intersection via DRQN.

An intelligent land vehicle utilizes onboard sensors to acquire observed states at a disorderly intersection. However, partial observation of the environment occurs due to sensor noise. This causes decision failure easily. A collision relationship-based driving behavior decision-making method via deep recurrent Q network (CR-DRQN) is proposed for intelligent land vehicles. First, the collision relationship between the intelligent land vehicle and surrounding vehicles is designed as the input. The collision relationship is extracted from the observed states with the sensor noise. This avoids a CR-DRQN dimension explosion and speeds up the network training. Then, DRQN is utilized to attenuate the impact of the input noise and achieve driving behavior decision-making. Finally, some comparative experiments are conducted to verify the effectiveness of the proposed method. CR-DRQN maintains a high decision success rate at a disorderly intersection with partially observable states. In addition, the proposed method is outstanding in the aspects of safety, the ability of collision risk prediction, and comfort.

Au-nanorod-clusters patterned optical fiber SERS probes fabricated by laser-induced evaporation self-assembly method.

Optical fiber surface-enhanced Raman scattering (SERS) probes provide a novel platform for liquid-phase in situ and remote SERS detections. However, it is still a challenge to fabricate noble metal nanostructures with large SERS enhancement factor (EF) onto optical fiber surfaces. In this article, we successfully prepare Au-nanorod cluster structures on optical fiber facets by a laboratory-developed laser-induced evaporation self-assembly method. It is demonstrated that the optimized optical fiber SERS probes show high detection sensitivity (10-10 M for rhodamine 6G solution, and 10-8 M for malachite green or crystal violet solution) and excellent reproducibility (relative standard deviation less than 6%). As the laser-induced evaporation self-assembly method is a simple and low-cost method capable of achieving automatic and reproducible preparations of cluster patterned optical fiber SERS probes, this work may find important application prospects in various liquid-phase SERS detection areas.

Two-dimensional few-layered PC3 as a promising photocatalyst for overall water splitting.

Recently, 2D carbon phosphides (PCs) have attracted much attention due to their superior electronic and photovoltaic properties suitable for potential applications in field effect transistors and photodetectors. In this work, we systematically investigate the stability, electronic properties, optical absorption and photocatalytic water splitting performance of few-layered PC3 by using the first principles calculation method. Numerical results indicate that both monolayered and bilayered PC3 can serve as efficient photocatalysts for overall water splitting due to their high stability, moderate band gaps, suitable band edge positions, anisotropic high carrier mobilities and strong capacity of solar absorption. Compared with monolayered PC3, bilayered PC3 displays higher carrier mobilities (2500-23 000 cm2 V-1 s-1) and a wider optical absorption spectrum. Moreover, by applying an in-plane biaxial strain, the utilization of solar energy and the pH range suitable for overall water splitting can be improved effectively for both monolayered and bilayered PC3. Our work reliably expands the potential application of 2D few-layered PC3 in the field of nano-electronics and nano-optoelectronics.

Modulation of the electronic band structure of silicene by polar two-dimensional substrates.

Using the density functional theory (DFT) calculations, we find that  Janus group-III chalcogenide monolayers can serve as a suitable substrate for silicene, and the Dirac electron band properties of silicene are also fully preserved. The maximum opened band gap can reach 179 meV at the Dirac point due to the interaction of silicene and the polar two-dimensional (2D) substrate. In addition, the electronic band structure of the heterostructure can be modulated by applying an electric field where its predicted band gap increases or decreases according to the direction of the applied external electric field. Furthermore, an insight into the electron structures can be understood by analyzing the electron energy-loss (EEL) spectra. From these results, we also predict that heterostructures with polar 2D substrates have broad application prospects in multi-functional devices. Besides, Janus group-III chalcogenide monolayers can be used as good substrates for growing silicene and the modulation of the electronic structure can also be applied to nanodevices and optoelectronic devices.

A Sulfonamide Sialoside Analogue for Targeting Siglec-8 and -F on Immune Cells.

The Siglec family of cell surface receptors have emerged as attractive targets for cell-directed therapies due to their restricted expression on immune cells, endocytic properties, and ability to modulate receptor signaling. Human Siglec-8, for instance, has been identified as a therapeutic target for the treatment of eosinophil and mast cell disorders. A promising strategy to target Siglecs involves the use of liposomal nanoparticles with a multivalent display of Siglec ligands. A key challenge for this approach is the identification of a high affinity ligand for the target Siglec. Here, we report the development of a ligand of Siglec-8 and its closest murine functional orthologue Siglec-F that is capable of targeting liposomes to cells expressing Siglec-8 or -F. A glycan microarray library of synthetic 9-N-sulfonyl sialoside analogues was screened to identify potential lead compounds. The best ligand, 9-N-(2-naphthyl-sulfonyl)-Neu5Acα2-3-[6-O-sulfo]-Galß1-4GlcNAc (6'-O-sulfo NSANeu5Ac) combined the lead 2-naphthyl sulfonyl C-9 substituent with the preferred sulfated scaffold. The ligand 6'-O-sulfo NSANeu5Ac was conjugated to lipids for display on liposomes to evaluate targeted delivery to cells. Targeted liposomes showed strong in vitro binding/uptake and selectivity to cells expressing Siglec-8 or -F and, when administered to mice, exhibit in vivo targeting to Siglec-F+ eosinophils.

Toward barrier free contact to MoSe2/WSe2 heterojunctions using two-dimensional metal electrodes.

In the design of electronic devices based on two-dimensional heterojunctions, the contact between electrodes and different surfaces of two-dimensional heterojunctions may produce different effects. Furthermore, metal-semiconductor contact plays an important role in modern devices. However, due to the Fermi level pinning effect (FLPE), it is difficult to tune the Schottky barrier height between common metals (e.g. Au, Ag, and Cu) and semiconductors. Fortunately, the FLPE becomes weak at the contact between the 2D metal and 2D semiconductor, due to the suppression of metal-induced gap states. Here, we choose monolayer NbS2 as the electrode to be in contact with the MoSe2/WSe2 bilayer. The interfacial properties as well as the stacking dependence are discussed based on the density functional theory, combined with the nonequilibrium Green's functions. Two configurations are considered, i.e. the WSe2/MoSe2/NbS2 and MoSe2/WSe2/NbS2 stacking sequences. Our results show that barrier free contact can be formed in these 2D metal-semiconductor junctions (MSJs). In addition, the transport properties of the proposed devices are sensitive to the stacking sequence. The drain-source current versus bias voltage (I-V) curve exhibits a linear relationship for the WSe2/MoSe2/NbS2 system and its resistance is much lower than the MoSe2/WSe2/NbS2 MSJ. Detailed analysis reveals that the transport properties are governed by the electronic coupling between specific interlayer states. In WSe2/MoSe2/NbS2 configuration, large overlapping states are observed, which facilitate charge transfer and result in good ohmic contact. Our work may provide a theoretical guidance for the designing of next-generation ultrathin and flexible devices.

Second harmonic generation in Janus MoSSe a monolayer and stacked bulk with vertical asymmetry.

A recently synchronized Janus TMD material with broken out-of-plane symmetry offers a vertical dipole to enhance nonlinear optical behavior. Here, by comparing the second harmonic generation properties of MoS2 and MoSSe monolayers, we investigated the nonzero out-of-plane SHG susceptibilities of a Janus MoSSe 2D material. A three-fold enhancement of out-of-plane SHG susceptibilities exists in three stacked bulks of Janus MoSSe compared to that in the monolayer. A sensitivity to their stack pattern is also found. The broken out-of-plane symmetry, vertical dipole, and intrinsic tunable electronic properties of Janus two-dimensional materials make MoSSe a promising nanomaterial for nonlinear optical devices.

Dissipative dynamics in a tunable Rabi dimer with periodic harmonic driving.

Recent progress on qubit manipulation allows application of periodic driving signals on qubits. In this study, a harmonic driving field is added to a Rabi dimer to engineer photon and qubit dynamics in a circuit quantum electrodynamics device. To model environmental effects, qubits in the Rabi dimer are coupled to a phonon bath with a sub-Ohmic spectral density. A nonperturbative treatment, the Dirac-Frenkel time-dependent variational principle together with the multiple Davydov D2 ansatz, is employed to explore the dynamical behavior of the tunable Rabi dimer. In the absence of the phonon bath, the amplitude damping of the photon number oscillation is greatly suppressed by the driving field, and photons can be created, thanks to the resonance between the periodic driving field and the photon frequency. In the presence of the phonon bath, one can still change the photon numbers in two resonators and indirectly alter the photon imbalance in the Rabi dimer by directly varying the driving signal in one qubit. It is shown that qubit states can be manipulated directly by the harmonic driving. The environment is found to strengthen the interqubit asymmetry induced by the external driving, opening up a new venue to engineer the qubit states.

Flavone of Hippophae (H-flavone) lowers atherosclerotic risk factors via upregulation of the adipokine C1q/tumor necrosis factor-related protein 6 (CTRP6) in macrophages.

In this study, we examined the mechanism of Flavone of Hippophae (H-flavone) in regulating macrophage foaming and atherosclerosis (AS) plaque formation. H-flavone treatment increased the secretion of C1q/tumor necrosis factor-related proteins 6 (CTRP6) in Ox-LDL-treated mouse peripheral blood macrophage cells (PBMC) and significantly reduced the percentage of cholesteryl ester (CE) in PBMC. Additionally, H-flavone suppressed Ox-LDL-induced cell foaming and the production of inflammatory cytokines through upregulating CTPR6 expression. Next, we further validated the inhibitory effect of H-flavone on plaque formation and inflammation in a mouse AS model. A substantial reduction in the secretion of inflammatory cytokines was observed in apoE-/- mice by H-flavone. Immunohistochemistry and Oil Red O staining results showed that H-flavone suppressed macrophage infiltration and the development of AS plaque. These effects were more pronounced in early administration. Our results suggest that H-flavone effectively inhibits macrophage foaming, inflammation and vascular plaque formation by upregulating CTRP6 and may be used to reduce AS risk.

Sialylated keratan sulfate proteoglycans are Siglec-8 ligands in human airways.

Human siglecs are a family of 14 sialic acid-binding proteins, most of which are expressed on subsets of immune cells where they regulate immune responses. Siglec-8 is expressed selectively on human allergic inflammatory cells-primarily eosinophils and mast cells-where engagement causes eosinophil apoptosis and inhibits mast cell mediator release. Evidence supports a model in which human eosinophils and mast cells bind to Siglec-8 sialoglycan ligands on inflammatory target tissues to resolve allergic inflammation and limit tissue damage. To identify Siglec-8-binding sialoglycans from human airways, proteins extracted from postmortem human trachea were resolved by size-exclusion chromatography and composite agarose-acrylamide gel electrophoresis, blotted and probed by Siglec-8-Fc blot overlay. Three size classes of Siglec-8 ligands were identified: 250 kDa, 600 kDa and 1 MDa, each of which was purified by affinity chromatography using a recombinant pentameric form of Siglec-8. Proteomic mass spectrometry identified all size classes as the proteoglycan aggrecan, a finding validated by immunoblotting. Glycan array studies demonstrated Siglec-8 binding to synthetic glycans with a terminal Neu5Acα2-3(6-sulfo)-Gal determinant, a quantitatively minor terminus on keratan sulfate (KS) chains of aggrecan. Treating human tracheal extracts with sialidase or keratanase eliminated Siglec-8 binding, indicating sialylated KS chains as Siglec-8-binding determinants. Treating human tracheal histological sections with keratanase also completely eliminated the binding of Siglec-8-Fc. Finally, Siglec-8 ligand purified from human trachea extracts induced increased apoptosis of freshly isolated human eosinophils in vitro. We conclude that sialylated KS proteoglycans are endogenous human airway ligands that bind Siglec-8 and may regulate allergic inflammation.

Tuning the electronic and magnetic properties of InSe nanosheets by transition metal doping.

Magnetic two-dimensional materials have attracted considerable attention for their significant potential application in spintronics. Here, we systematically study the electronic structures and magnetic properties of a 3d transition metal doped InSe monolayer based on density functional theory (DFT). Our results show that InSe monolayer can be turned into a half-metal when the Ti, Cr, or Ni atom is doped. Further calculations indicate that the Cr-InSe monolayer possesses a robust ferromagnetic ground state due to the effective p-d exchange. The predicted Curie temperature of Cr-InSe is above the room temperature, showing a powerful potential in spintronics. Application in the spin valve is also explored using quantum transport simulations. Our results indicate that the magnetoresistance of a Cr-InSe spin valve attains 100% due to the half-metallic characteristics. These findings may pave the way for designing 2D nano-devices for future spin transport applications.

Intelligent Land-Vehicle Model Transfer Trajectory Planning Method Based on Deep Reinforcement Learning.

To address the problem of model error and tracking dependence in the process of intelligent vehicle motion planning, an intelligent vehicle model transfer trajectory planning method based on deep reinforcement learning is proposed, which is able to obtain an effective control action sequence directly. Firstly, an abstract model of the real environment is extracted. On this basis, a deep deterministic policy gradient (DDPG) and a vehicle dynamic model are adopted to jointly train a reinforcement learning model, and to decide the optimal intelligent driving maneuver. Secondly, the actual scene is transferred to an equivalent virtual abstract scene using a transfer model. Furthermore, the control action and trajectory sequences are calculated according to the trained deep reinforcement learning model. Thirdly, the optimal trajectory sequence is selected according to an evaluation function in the real environment. Finally, the results demonstrate that the proposed method can deal with the problem of intelligent vehicle trajectory planning for continuous input and continuous output. The model transfer method improves the model's generalization performance. Compared with traditional trajectory planning, the proposed method outputs continuous rotation-angle control sequences. Moreover, the lateral control errors are also reduced.

Highly Tunable Electronic Structures of Phosphorene/Carbon Nanotube Heterostructures through External Electric Field and Atomic Intercalation.

Black phosphorene (BP)/carbon nanotube (CNT) heterostructures can be classified as either type I or II, depending on the size of the CNTs. An external electric field (Eext) can modulate the interfacial electronic structures and separate the electron and hole carriers of the BP/CNT heterostructures. The giant Stark effect is observed, and the band gap of the semiconducting heterostructures can vary several-fold. The intercalation of 3d transition metals can strongly bond BP and CNTs together. Furthermore, strong ferromagnetism with Curie temperature (TC) above room temperature is predicted. It is expected that these BP/CNT heterostructures will provide new opportunities and applications in the fields of optoelectronics and electronics as well as spintronics.

Mast Cell-Specific Expression of Human Siglec-8 in Conditional Knock-in Mice.

Sialic acid-binding Ig-like lectin 8 (Siglec-8) is expressed on the surface of human eosinophils, mast cells, and basophils-cells that participate in allergic and other diseases. Ligation of Siglec-8 by specific glycan ligands or antibodies triggers eosinophil death and inhibits mast cell degranulation; consequences that could be leveraged as treatment. However, Siglec-8 is not expressed in murine and most other species, thus limiting preclinical studies in vivo. Based on a ROSA26 knock-in vector, a construct was generated that contains the CAG promoter, a LoxP-floxed-Neo-STOP fragment, and full-length Siglec-8 cDNA. Through homologous recombination, this Siglec-8 construct was targeted into the mouse genome of C57BL/6 embryonic stem (ES) cells, and chimeric mice carrying the ROSA26-Siglec-8 gene were generated. After cross-breeding to mast cell-selective Cre-recombinase transgenic lines (CPA3-Cre, and Mcpt5-Cre), the expression of Siglec-8 in different cell types was determined by RT-PCR and flow cytometry. Peritoneal mast cells (dual FcεRI⁺ and c-Kit⁺) showed the strongest levels of surface Siglec-8 expression by multicolor flow cytometry compared to expression levels on tissue-derived mast cells. Siglec-8 was seen on a small percentage of peritoneal basophils, but not other leukocytes from CPA3-Siglec-8 mice. Siglec-8 mRNA and surface protein were also detected on bone marrow-derived mast cells. Transgenic expression of Siglec-8 in mice did not affect endogenous numbers of mast cells when quantified from multiple tissues. Thus, we generated two novel mouse strains, in which human Siglec-8 is selectively expressed on mast cells. These mice may enable the study of Siglec-8 biology in mast cells and its therapeutic targeting in vivo.

Siglec-8 and Siglec-9 binding specificities and endogenous airway ligand distributions and properties.

Siglecs are transmembrane sialoglycan binding proteins, most of which are expressed on leukocyte subsets and have inhibitory motifs that translate cell surface ligation into immune suppression. In humans, Siglec-8 on eosinophils, mast cells and basophils and Siglec-9 on neutrophils, monocytes and some T-cells, mediate immune cell death, inhibition of immune mediator release and/or enhancement of anti-inflammatory mediator release. Endogenous sialoglycan ligands in tissues, mostly uncharacterized, engage siglecs on leukocytes to inhibit inflammation. Glycan array analyses demonstrated that Siglec-8, Siglec-9 and their mouse counterparts Siglec-F and Siglec-E (respectively) have distinct glycan binding specificities, with Siglec-8 more structurally restricted. Since siglecs are involved in lung inflammation, we studied Siglec-8 and Siglec-9 ligands in human lungs and airways. Siglec-8 ligands are in tracheal submucosal glands and cartilage but not airway epithelium or connective tissues, whereas Siglec-9 ligands are broadly distributed. Mouse airways do not have Siglec-8 ligands, whereas Siglec-9 ligands are on airways of both species. Extraction of human airways and lung followed by electrophoretic resolution and siglec blotting revealed Siglec-8 ligands in extracts of human trachea and cultured tracheal gland cells, but not parenchyma or cultured airway epithelial cells whereas Siglec-9 ligands were extracted from all airway and lung tissues and cells tested. Siglec-8 and Siglec-9 ligands in airways appear to be high molecular weight O-linked sialoglycoproteins. These data reveal differential glycan specificities of Siglec-8, Siglec-9 and their mouse counterparts Siglec-F and Siglec-E, and the tissue distributions and molecular characteristics of Siglec-8 and Siglec-9 sialoglycan ligands on human airways and lungs.