Lipid scrambling is a general feature of protein insertases.

Glycerophospholipids are synthesized primarily in the cytosolic leaflet of the endoplasmic reticulum (ER) membrane and must be equilibrated between bilayer leaflets to allow the ER and membranes derived from it to grow. Lipid equilibration is facilitated by integral membrane proteins called "scramblases." These proteins feature a hydrophilic groove allowing the polar heads of lipids to traverse the hydrophobic membrane interior, similar to a credit card moving through a reader. Nevertheless, despite their fundamental role in membrane expansion and dynamics, the identity of most scramblases has remained elusive. Here, combining biochemical reconstitution and molecular dynamics simulations, we show that lipid scrambling is a general feature of protein insertases, integral membrane proteins which insert polypeptide chains into membranes of the ER and organelles disconnected from vesicle trafficking. Our data indicate that lipid scrambling occurs in the same hydrophilic channel through which protein insertion takes place and that scrambling is abolished in the presence of nascent polypeptide chains. We propose that protein insertases could have a so-far-overlooked role in membrane dynamics as scramblases.

In Situ Hybridization Strategy Constructs Heterogeneous Interfaces to Form Electronically Modulated MoS2/FeS2 as the Anode for High-Performance Lithium-Ion Storage.

The interfacial effect is important for anodes of transition metal dichalcogenides (TMDs) to achieve superior lithium-ion storage performance. In this paper, a MoS2/FeS2 heterojunction is synthesized by a simple hydrothermal reaction to construct the interface effect, and the heterostructure introduces an inherent electric field that accelerates the de-embedding process of lithium ions, improves the electron transfer capability, and effectively mitigates volume expansion. XPS analysis confirms evident chemical interaction between MoS2 and FeS2 via an interfacial covalent bond (Mo-S-Fe). This MoS2/FeS2 anode shows a distinct interfacial effect for efficient interatomic electron migration. The electrochemical performance demonstrated that the discharge capacity can reach up to 1217.8 mA h g-1 at 0.1 A g-1 after 200 cycles, with a capacity retention rate of 72.9%. After 2000 cycles, the capacity retention is about 61.6% at 1.0 A g-1, and the discharge capacity can still reach 638.9 mA h g-1. Electrochemical kinetic analysis indicated an enhanced pseudocapacitance contribution and that the MoS2/FeS2 had sufficient adsorption of lithium ions. This paper therefore argues that this interfacial engineering is an effective solution for designing sulfide-based anodes with good electrochemical properties.

Weighted gene coexpression correlation network analysis reveals the potential molecular regulatory mechanism of citrate and anthocyanin accumulation between postharvest 'Bingtangcheng' and 'Tarocco' blood orange fruit.

BACKGROUND: Organic acids and anthocyanins are the most important compounds for the flavor and nutritional quality of citrus fruit. However, there are few reports on the involvement of co-regulation of citrate and anthocyanin metabolism. Here, we performed a comparative transcriptome analysis to elucidate the genes and pathways involved in both citrate and anthocyanin accumulation in postharvest citrus fruit with 'Tarocco' blood orange (TBO; high accumulation) and 'Bingtangcheng' sweet orange (BTSO; low accumulation). RESULTS: A robust core set of 825 DEGs were found to be temporally associated with citrate and anthocyanin accumulation throughout the storage period through transcriptome analysis. Further according to the results of weighted gene coexpression correlation network analysis (WGCNA), the turquoise and brown module was highly positively correlated with both of the content of citrate and anthocyanin, and p-type ATPase (PH8), phosphoenolpyruvate carboxylase kinase (PEPCK), chalcone isomerase (CHI), flavanone 3-hydroxylase (F3H), flavonoid 3'-hydroxylase (F3'H) and glutathione S transferase (GST) were considered key structural genes. Moreover, MYB family transcription factor (PH4), Zinc finger PHD-type transcription factor (CHR4, HAC12), Zinc finger SWIM-type transcription factor (FAR1) and Zinc finger C3H1-type transcription factor (ATC3H64) were considered hub genes related to these structural genes. Further qRT-PCR analysis verified that these transcription factors were highly expressed in TBO fruit and their expression profiles were significantly positively correlated with the structural genes of citrate and anthocyanin metabolism as well as the content of citrate and anthocyanin content. CONCLUSIONS: The findings suggest that the CHR4, FAR1, ATC3H64 and HAC12 may be the new transcription regulators participate in controlling the level of citrate and anthocyanin in postharvest TBO fruit in addition to PH4. These results may providing new insight into the regulation mechanism of citrate and anthocyanin accumulation in citrus fruit.

A Unique Etching-Doping Route to Fe/Mo Co-Doped Ni Oxyhydroxide Catalyst for Enhanced Oxygen Evolution Reaction.

Fe-doped Ni (oxy)hydroxide shows intriguing activity toward oxygen evolution reaction (OER) in alkaline solution, yet it remains challenging to further boost its performance. In this work, a ferric/molybdate (Fe3+ /MoO4 2- ) co-doping strategy is reported to promote the OER activity of Ni oxyhydroxide. The reinforced Fe/Mo-doped Ni oxyhydroxide catalyst supported by nickel foam (p-NiFeMo/NF) is synthesized via a unique oxygen plasma etching-electrochemical doping route, in which precursor Ni(OH)2 nanosheets are first etched by oxygen plasma to form defect-rich amorphous nanosheets, followed by electrochemical cycling to trigger simultaneously Fe3+ /MoO4 2- co-doping and phase transition. This p-NiFeMo/NF catalyst requires an overpotential of only 274 mV to reach 100 mA cm-2 in alkaline media, exhibiting significantly enhanced OER activity compared to NiFe layered double hydroxide (LDH) catalyst and other analogs. Its activity does not fade even after 72 h uninterrupted operation. In situ Raman analysis reveals that the intercalation of MoO4 2- is able to prevent the over-oxidation of NiOOH matrix from ß to γ phase, thus keeping the Fe-doped NiOOH at the most active state.

Structural Evolution and Electronic Properties of V2Sin-/0 (n = 7-14) Clusters: Anion Photoelectron Spectroscopy and Theoretical Calculations.

A systematic study of the structures and electronic properties of V2-doped silicon clusters, V2Sin-/0 (n = 7-14), was carried out by anion photoelectron spectroscopic experiments combined with theoretical calculations. According to the experimental spectra of V2Sin- (n = 7-14) clusters, the V2Si12- cluster has the highest vertical detachment energy (VDE) of 3.66 eV, while V2Si7- and V2Si14- clusters have lower VDEs of 2.81 and 2.84 eV, respectively. The most stable structure searches find that two V atoms in the V2Sin- clusters with size n = 7 and 8 are located at the surface, while V2Sin- clusters with n ≥ 9 prefer cage-like structures. Based on the analysis of the structural evolution of V2Sin- (n = 9-14) clusters, it can be clearly seen how the antihexagonal prism with one V encapsulated in the cage is gradually built from n = 9 to 12 and further developed from n = 12 to 14 with the extra silicon atoms located at the surface of the Si12 cage. The molecular orbital and the atoms in molecule analysis of the V2Sin- (n = 7-14) anions demonstrate that the strong V-V bond and the delocalized interaction between the V2 moiety and the Sin ligand play a significant role in stabilizing the cluster structures. A strong linear correlation has been found between the Wiberg bond order of the V-V bond and the electron density at the V-V bond critical points.

Unleashing the Potential of EIL Transcription Factors in Enhancing Sweet Orange Resistance to Bacterial Pathologies: Genome-Wide Identification and Expression Profiling.

The ETHYLENE INSENSITIVE3-LIKE (EIL) family is one of the most important transcription factor (TF) families in plants and is involved in diverse plant physiological and biochemical processes. In this study, ten EIL transcription factors (CsEILs) in sweet orange were systematically characterized via whole-genome analysis. The CsEIL genes were unevenly distributed across the four sweet orange chromosomes. Putative cis-acting regulatory elements (CREs) associated with CsEIL were found to be involved in plant development, as well as responses to biotic and abiotic stress. Notably, quantitative reverse transcription polymerase chain reaction (qRT-PCR) revealed that CsEIL genes were widely expressed in different organs of sweet orange and responded to both high and low temperature, NaCl treatment, and to ethylene-dependent induction of transcription, while eight additionally responded to Xanthomonas citri pv. Citri (Xcc) infection, which causes citrus canker. Among these, CsEIL2, CsEIL5 and CsEIL10 showed pronounced upregulation. Moreover, nine genes exhibited differential expression in response to Candidatus Liberibacter asiaticus (CLas) infection, which causes Citrus Huanglongbing (HLB). The genome-wide characterization and expression profile analysis of CsEIL genes provide insights into the potential functions of the CsEIL family in disease resistance.

Heterointerface Engineered Core-Shell Fe2O3@TiO2 for High-Performance Lithium-Ion Storage.

The rational design of the heterogeneous interfaces enables precise adjustment of the electronic structure and optimization of the kinetics for electron/ion migration in energy storage materials. In this work, the built-in electric field is introduced to the iron-based anode material (Fe2O3@TiO2) through the well-designed heterostructure. This model serves as an ideal platform for comprehending the atomic-level optimization of electron transfer in advanced lithium-ion batteries (LIBs). As a result, the core-shell Fe2O3@TiO2 delivers a remarkable discharge capacity of 1342 mAh g-1 and an extraordinary capacity retention of 82.7% at 0.1 A g-1 after 300 cycles. Fe2O3@TiO2 shows an excellent rate performance from 0.1 A g-1 to 4.0 A g-1. Further, the discharge capacity of Fe2O3@TiO2 reached 736 mAh g-1 at 1.0 A g-1 after 2000 cycles, and the corresponding capacity retention is 83.62%. The heterostructure forms a conventional p-n junction, successfully constructing the built-in electric field and lithium-ion reservoir. The kinetic analysis demonstrates that Fe2O3@TiO2 displays high pseudocapacitance behavior (77.8%) and fast lithium-ion reaction kinetics. The capability of heterointerface engineering to optimize electrochemical reaction kinetics offers novel insights for constructing high-performance iron-based anodes for LIBs.

Theoretical study on exohedral complexes C6H6TMB40 (TM = Sc-Ni).

Exohedral borospherene complexes comprised of 3d transition metal (TM) atoms with borospherene B40 and benzene (C6H6) molecules, C6H6TMB40, were systematically studied by using density functional theory (DFT). Results show that in the ground states, the bonding type between TM and B40 changes from η7 (TM = Sc-V) to η6 (TM = Cr-Fe) and then to η7 (TM = Co, Ni) with the increasing number of d electrons. Except for C6H6TiB40 and C6H6FeB40 being triplets, all C6H6TMB40 clusters have the lowest spin. Namely, the ground spin state with an even number of electrons is a singlet state, and the ground spin state with an odd number of electrons is a doublet state. The investigated C6H6TMB40 clusters (TM = Sc-Ni) possess higher stabilities through the ionic-covalent interactions between transition metals, benzene and the B40 cage.

SNHG16 promotes hepatocellular carcinoma development via activating ECM receptor interaction pathway.

BACKGROUND: Accumulating data have suggested that long non-coding RNAs (lncRNAs) play important roles in regulating tumor cell growth. This study was designed to investigate the role of SNHG16 in hepatocellular carcinoma (HCC). METHODS: SNHG16 expression was detected with real-time polymerase chain reaction (PCR). The cutoff value of SNHG16 for tumor-free survival (TFS) was determined with receiver operating characteristic curve analysis. Small interfering RNA was used to inhibit the expression of SNHG16 in HCC cell lines. The biologic behavior of HCC cell was determined with cell viability assay and Transwell assay in vitro. The potential predictive value of SNHG16 on prognosis was analyzed by Kaplan-Meier curves and Cox proportional hazards regression model. RESULTS: SNHG16 expression was upregulated in tumor tissues and HCC cell lines. High expression of SNHG16 was associated with tumor recurrence and poor prognosis after surgery. Multivariate analysis revealed that SNHG16 was an independent prognostic factor for poor recurrence-free survival. Moreover, inhibition of SNHG16 in HepG2, Hep3B, and BEL-7402 cells significantly reduced cell invasiveness and proliferation. Mechanistic analyses indicated that the ECM-receptor interaction pathway was remarkably activated by SNHG16. CONCLUSIONS: SNHG16 might be a promising biomarker for predicting tumor recurrence in HCC patients after surgery and a potential therapeutic target for HCC.

On the nature of bonding in a new boronyl species Zn2(BO)2: a linear four-center two-electron σ bond.

The Zn-Zn bond as one of the metal-to-metal bonds in clusters and molecules is of fundamental interest in many areas of natural science. Neutral boronyl can be viewed as a σ radical and is found in boronyl metal complexes. However, a complex with the Zn-Zn bond stabilized by boronyl ligands has not been found so far. Herein, we report on the computational design of the simplest case of such a system: linear D∞h OBZnZnBO. The structural and electronic properties and chemical bonding on a series of zinc complexes Znx(BO)y (x = 1,2; y = 1,2) with boronyl as ligands have been studied using quantum chemical calculations at the B3LYP and PBE0 levels, respectively. For the Zn2(BO)2 cluster, the linear D∞h OBZnZnBO is the global minimum, in which the calculated Zn-Zn bond length of rZn-Zn = 2.400 Å at the B3LYP level, which appears to be close to the latest recommended covalent radii (2.40 Å) of the proposed single bond covalent radii of the Zn-Zn bond. Chemical bonding analyses show that D∞h OBZnZnBO possesses a linear four-center two-electron (4c-2e) σ bond. The σ bond framework has a contribution of Zn orbitals 54% and B orbitals 44%, which involve Zn 4s 20% and 4p 34%, and B 2s 28% and 2p 16%, respectively. Furthermore, the D∞h HZnZnH and NCZnZnCN clusters also exhibit one linear 4c-2e σ bond due to the secondary contribution from the H s and C sp components, respectively. The linear 4c-2e σ bond greatly stabilizes the dizinc complexes. D∞h OBZnZnBO is thermochemically stable with respect to the possible formation channel at room temperature, whereas the formation energy of the exergonic channel, 2ZnBO (C∞v, 2Σg) → OBZnZnBO (D∞h, 1Σg), is evaluated to be -58.75 kcal mol-1 at the B3LYP level. Thus, D∞h OBZnZnBO as the first observation of the Zn-Zn covalent bond in zinc complexes with boronyl as ligands may be synthesized in laboratories in the near future.

Visible-Light-Promoted C2 Selective Arylation of Quinoline and Pyridine N-Oxides with Diaryliodonium Tetrafluoroborate.

A protocol of visible-light-promoted C2 selective arylation of quinoline and pyridine N-oxides, with diaryliodonium tetrafluoroborate as an arylation reagent, using eosin Y as a photocatalyst for the construction of N-heterobiaryls was presented. This methodology provided an efficient way for the synthesis of 2-aryl-substituted quinoline and pyridine N-oxides. This strategy has the following advantages: specific regioselectivity, simple operation, good functional group tolerance, and high to moderate yields under mild conditions.

Appearance of V-encapsulated tetragonal prism motifs in VSi10- and VSi11- clusters.

The structural and electronic properties of V-doped silicon clusters, VSi10-/0 and VSi11-/0, were investigated by using mass-selected anion photoelectron spectroscopy in combination with theoretical calculations. Photoelectron spectroscopy of VSi10- and VSi11- clusters with spectral similarity reveals that the two cluster structures resemble each other. Interestingly, theoretical calculation studies provide definitive evidence of the global minima for the two clusters to be V-encapsulated tetragonal prism motifs with extra Si atoms bicapped and tricapped, respectively. The enhanced stability of the tetragonal prism unit in VSi10- and VSi11- is due to the strong interactions between 3d (V) and 3p (Si) orbitals, and more charge transfers from the Sin framework to the encapsulated V atom. The tetragonal prism unit possessed by both the VSi10- and VSi11- clusters is observed for the first time in the current work, and may offer new ideas in developing components for Si-based nanodevices.

Asymmetrically synchronous reduction and assembly of graphene oxide film on metal foil for moisture responsive actuator.

Graphene has drawn tremendous attention for the fabrication of actuators because of its unique chemical and structural features. Traditional graphene actuators need integration with polymers or other responsive components for shape-changeable behaviour. Searching for a sole material with asymmetric properties is difficult and challenging for actuators that are responsive to external stimulus. Herein, asymmetrically synchronous reduction and assembly of a graphene oxide (GO) film with oxygen-containing group gradients was prepared on various metal foils. Such film possessed asymmetric surface chemical components on both sides, which showed reversible deformation via alternating moisture. Importantly, we can detect the moisture change via recording the voltage pulse during self-deformation on the basis of spontaneous H3O+ ions diffusion across the GO film without the need of power input. Finally, a smart gripper was developed using a moisture responsive GO film. Present work opens a new avenue for developing smart actuator using a sole material and simultaneously realizing the detection of deformation in self-powered mode.

The Association Between Child Abuse and Emotional and Behavioral Problems in Chinese School-Aged Boys With Attention Deficit Hyperactivity Disorder.

The aim of our study was to investigate the relationship between child abuse and emotional and behavioral problems in Chinese school-aged boys with attention deficit hyperactivity disorder (ADHD). Forty-eight school-aged boys with ADHD and 77 male healthy controls completed the final assessments that included the Child Behavior Checklist, the Barratt Impulsiveness Scale Version 11, the Screen for Child Anxiety Related Disorders, the Depression Self-Rating Scale for Children, and the Childhood Trauma Questionnaire, Short Form. Our findings showed that child abuse could associate with the behavioral problems in ADHD. Regression analysis further showed that child abuse (especially emotional abuse and physical abuse), adverse living conditions, and school anxiety significantly could be contributors to behavioral problems in boys with ADHD. Our study indicated that child abuse may be associated with the behavioral problems in Chinese school-aged boys with ADHD.

Planar Tricyclic B8O8 and B8O8- Clusters: Boron Oxide Analogues of s-Indacene C12H8.

Boron clusters and their oxides are electron-deficient species with (π and σ) aromaticity and antiaromaticity, enabling a structural and bonding analogy between them and the aromatic hydrocarbons. s-Indacene C12H8 is normally considered as a border system between the classes of aromatic and antiaromatic hydrocarbons. We show herein, via computer global-minimum searches and B3LYP and single-point CCSD(T) calculations, that boron oxide clusters D2h B8O8 (1, 1Ag) and D2h B8O8- (2, 2B2g) adopt planar tricyclic structures, which feature fused heterocyclic B3O2/B4O2/B3O2 rings and two boronyl (BO) terminals, a structural pattern analogous to the C5/C6/C5 rings in s-indacene. Bonding analyses indicate that B8O8 (1) is a formally antiaromatic 12π system, the molecular orbitals of which are largely similar to those of s-indacene. Infrared and ultraviolet-visible spectra of B8O8 (1) neutral, as well as the photoelectron spectrum of B8O8- (2) anion, are predicted computationally. The latter spectrum shows a sizable energy gap of 3.5 eV for 2, demonstrating the electronic robustness of 1. Our bonding analyses also shed critical light on the nature of bonding in s-indacene.

Photoinduced Intermolecular [4+2] Cycloaddition Reaction for Construction of Benzobicyclo[2.2.2]octane Skeletons.

A novel and efficient method for the synthesis of highly substituted benzobicyclo[2.2.2]octane skeletons has been explored. Under UV-light irradiation, o-divinylbenzenes underwent a pericyclic reaction to form the cyclic o-quinodimethane intermediates which were subsequently reacted with olefins through [4+2] addition to construct the benzobicyclo[2.2.2]octane skeletons in mild conditions. Gram scale reactions demonstrated the synthetic potential application of this protocol.

Synthesis of Oxatricyclooctanes via Photoinduced Intramolecular Oxa-[4+2] Cycloaddition of Substituted o-Divinylbenzenes.

The photolysis of substituted o-divinylbenzenes promotes a one-step and metal-free conversion to oxatricycles at room temperature. Irradiation o-divinylbenzenes results in an pericyclic reaction to form cyclic o-quinodiemthane intermediates, which subsequently undergo intramolecular oxa-[4+2] cycloaddition to form oxacyclic derivatives.

Pentagonal five-center four-electron π bond in ternary B3N2H5 cluster: an extension of the concept of three-center four-electron ω bond.

Boron-based heteroatomic rings can have exotic chemical bonding, in which the p lone-pairs of heteroatoms manage to participate in delocalized π bonding, compensating for boron's electron-deficiency. We explore herein the bonding properties of ternary B-N-H systems with a pentagonal ring, using the B3N2H50/-/2- clusters as examples. Computational structural searches lead to perfectly planar C2v B3N2H5 (1, 1A1) and C2v B3N2H5- (2, 2B1) as global minima for the neutral species and monoanion, which feature a pentagonal B3N2 ring. The corresponding dianion C2v B3N2H52- (3, 1A1) is a local minimum, whose global minimum adopts a chain-like open structure. Bonding analyses reveal a five-center four-electron (5c-4e) π system in 1, dubbed the 5c-4e o-bond. It is a 4π system in the bonding/nonbonding combination, originating from two N 2p lone-pairs, which can be considered as an extension of the concept of 3c-4e ω-bond. The extra electrons in 2 and 3 occupy a markedly destabilized π orbital. Thus, a 4π configuration, rather than a π sextet according to the (4n + 2) Hückel rule, is electronically robust for the B3N2H50/-/2- system. Infrared and photoelectron spectra are predicted for 1 and 2, respectively. Structural evolution of ring-like and chain-like isomers with charge-state in B3N2H50/-/2- is elucidated. B3N2H5- (2) is used as ligand for sandwich-type complexes: C2h [(B3N2H5)2Fe]2- and C2h [(B3N2H5)2Fe]Li2.

MicroRNA-106a-5p facilitates human glioblastoma cell proliferation and invasion by targeting adenomatosis polyposis coli protein.

The invasive behavior of glioblastoma multiforme (GBM) cells is an important reason for its poor prognosis. Tumor cells acquire an ability to digest the extracellular matrix and infiltrate the adjacent normal tissue during invasion. Restraining GBM invasion by changing effector molecules can significantly improve the patient's prognosis. MiRNAs are involved in multiple biological functions via suppressing target genes. In this study, we found that miR-106a-5p expression was high in GBM tissues and cells. The data showed an inverse correlation in GBM tissues between the levels of miR-106a-5p and adenomatosis polyposis coli (APC) mRNAs.Additionally, ectopic expression of miR-106a-5pfacilitated the invasion of GBM cells whereas inhibition of miR-106a-5p expression weakened the invasive ability. Numerous transcription factors are downstream effectors of the Wnt/ß-catenin pathway. Target prediction databases and luciferase data showed that APC is a new direct target of miR-106a-5p. Importantly, westernblot assays demonstrated that miR-106a-5p can reduce APC protein level and enhance target proteins of Wnt/ß-catenin pathway. Thus, we hypothesize that miR-106a-5p directly targets APC, resulting in the activation of Wnt/ß-catenin pathway. Our results suggest that miR-106a-5p is involved in the invasive behavior of GBM cells and by targeting APC and activating Wnt/ß-catenin pathway, it provides a theoretical basis for developing potential clinical strategies.