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.

Genome-wide association studies for the number of piglets born alive and dead in Dongliao black pigs.

Litter size (total number born) trait has a great impact on the economic success of pork production. The total number born consists of the number of piglets born alive and dead. To clarify the genetic background of litter size, genome-wide association studies were undertaken in the present study. Samples of DNA were collected and genotyped using the Porcine 50K BeadChip from 723 Dongliao Black sows. Using three different models (BLINK, FarmCPU, and MLM), a total of 155 significant SNPs were discovered, six of which had been reported in previous pig reproduction association studies. We suggest that rs81318434, located in the GLI3 gene, might be the promising candidate affecting litter size trait. Our findings may provide insights for uncovering the genetic mechanisms for the litter size of pigs.

Design of Organic-Inorganic Hybrid Heterostructured Semiconductors via High-Throughput Materials Screening for Optoelectronic Applications.

Organic-inorganic hybrid semiconductors, of which organometal halide perovskites are representative examples, have drawn significant research interest as promising candidates for next-generation optoelectronic applications. This interest is mainly ascribed to the emergent optoelectronic properties of the hybrid semiconductors that are distinct from those of their purely inorganic and organic counterparts as well as different material fabrication strategies and the other material (e.g., mechanical) properties that combine the advantages of both. Herein, we present a high-throughput first-principles material screening study of the hybrid heterostructured semiconductors (HHSs) that differ entirely from organometal halide perovskite hybrid ion-substituting semiconductors. HHSs crystallize as superlattice structures composed of inorganic tetrahedrally coordinated semiconductor sublayers and organic sublayers made of bidentate chain-like molecules. By changing the composition (e.g., IV, III-V, II-VI, I-III-VI2 semiconductor) and polymorph (e.g., wurtzite and zinc-blende) of the inorganic components, the type of organic molecules (e.g., ethylenediamine, ethylene glycol, and ethanedithiol), and the thickness of the composing layers across 234 candidate HHSs, we investigated their thermodynamic, electronic structure, and optoelectronic properties. Thermodynamic stability analysis indicates the existence of 96 stable HHSs beyond the ZnTe/ZnSe-based ones synthesized experimentally. The electronic structure and optoelectronic properties of HHSs can be modulated over a wide range by manipulating their structural variants. A machine learning approach was further applied to the high-throughput calculated data to identify the critical descriptors determining thermodynamic stability and electronic band gap. Our results indicate promising prospects and provide valuable guidance for the rational design of organic-inorganic hybrid heterostructured semiconductors for potential optoelectronic applications.

LncRNA JPX promotes cervical cancer progression by modulating miR-25-3p/SOX4 axis.

BACKGROUND: The long noncoding RNA (lncRNA) JPX is a molecular switch for X-chromosome inactivation. Accumulating studies have shown that the aberrant expression and function of lncRNAs are involved in the occurrence and development of tumors. However, the functional importance and mechanism of the action of lncRNA JPX in cervical cancer (CC) remain unknown. METHOD: In this study, qRT-PCR and western blotting were used to evaluate the mRNA or protein expression of JPX, miR-25-3p and SOX4 in CC tissues and cell lines. StarBase v2.0 database, luciferase reporter assay and RNA immunoprecipitation assay were used to explore the relationship between JPX and miR-25-3p. EdU assay, CCK-8 assay and transwell assay were utilized to evaluate the proliferation, migration and invasion of CC cells. The tumor xenograft assay in nude mice was performed to demonstrate the role of the JPX/miR-25-3p/SOX4 axis in CC. RESULTS: We found that JPX was markedly upregulated, whereas miR-25-3p was markedly downregulated in CC tissues and cell lines, and the expression of JPX was negatively correlated with miR-25-3p in CC tissues. Moreover, overexpression of JPX increased proliferation, migration and invasion of HeLa cells, whereas knockdown of JPX decreased proliferation, migration and invasion of HeLa cells. In contrast to JPX, overexpression of miR-25-3p decreased proliferation, migration and invasion of HeLa cells. In addition, knockdown of JPX was found to inhibit HeLa cell viability and tumor development via up-regulating the expression of miR-25-3p and inhibiting the expression of SOX4. CONCLUSIONS: Our study demonstrates that JPX promotes cervical cancer progression through modulating the miR-25-3p/SOX4 axis, and may serve as a potential target for CC therapy.

A theoretical study on the mechanism of photocatalytic oxygen evolution on BiVO4 in aqueous solution.

The oxygen evolution reaction (OER) is regarded as one of the key issues in achieving efficient photocatalytic water splitting. Monoclinic scheelite BiVO(4) is a visible-light-responsive semiconductor which has proved to be effective for oxygen evolution. Recently, the synthesis of a series of monoclinic BiVO(4) single crystals was reported, and it was found that the (010), (110), and (011) facets are highly exposed and that the photocatalytic O(2) evolution activity depends on the degree of exposure of the (010) facets. To explore the properties of and photocatalytic water oxidation reaction on different facets, DFT calculations were performed to investigate the geometric structure, optical properties, electronic structure, water adsorption, and the whole OER free-energy profiles on BiVO(4) (010) and (011) facets. The calculated results suggest both favorable and unfavorable factors for OER on the (010) and the (011) facets. Due to the combined effects of the above-mentioned factors, different facets exhibit quite different photocatalytic activities.

Effects of Zn2+ and Pb2+ dopants on the activity of Ga2O3-based photocatalysts for water splitting.

Zn-doped and Pb-doped ß-Ga2O3-based photocatalysts were prepared by an impregnation method. The photocatalyst based on the Zn-doped ß-Ga2O3 shows a greatly enhanced activity in water splitting while the Pb-doped ß-Ga2O3 one shows a dramatic decrease in activity. The effects of Zn(2+) and Pb(2+) dopants on the activity of Ga2O3-based photocatalysts for water splitting were investigated by HRTEM, XPS and time-resolved IR spectroscopy. A ZnGa2O4-ß-Ga2O3 heterojunction is formed in the surface region of the Zn-doped ß-Ga2O3 and a slower decay of photogenerated electrons is observed. The ZnGa2O4-ß-Ga2O3 heterojunction exhibits type-II band alignment and facilitates charge separation, thus leading to an enhanced photocatalytic activity for water splitting. Unlike Zn(2+) ions, Pb(2+) ions are coordinated by oxygen atoms to form polyhedra as dopants, resulting in distorted surface structure and fast decay of photogenerated electrons of ß-Ga2O3. These results suggest that the Pb dopants act as charge recombination centers expediting the recombination of photogenerated electrons and holes, thus decreasing the photocatalytic activity.

Theoretical study of structure, stability, and the hydrolysis reactions of small iridium oxide nanoclusters.

The geometric structures and relative stabilities of small iridium oxide nanoclusters, Ir(m)O(n) (m = 1-5 and n = 1-2m), have been systematically investigated using density functional theory (DFT) calculations at the B3LYP level. Our results show that the lowest-energy structures of these clusters can be obtained by the sequential oxidation of small "core" iridium clusters. The iridium-monoxide-like clusters have relatively higher stability because of their relatively high binding energy and second difference in energies. On the basis of the optimized lowest-energy structures of neutral and cationic (IrO(2))(n) (n = 1-5), DFT has been used to study the hydrolysis reaction of these clusters with water molecules. The calculated results show that the addition of water molecules to the cationic species is much easier than the neutral ones. The overall hydrolysis reaction energies are more exothermic for the cationic clusters than for the neutral clusters. Our calculations indicate that H(2)O can be more easily split on the cationic iridium oxide clusters than on the neutral clusters.

One-pot room-temperature synthesis of a BiOCl hierarchical microsphere assembled from nanosheets with exposed {001} facets for enhanced photosensitized degradation.

BiOCl hierarchical microspheres assembled from nanosheets with exposed {001} facets were successfully synthesized using PEG-2000 as template by a one-pot room-temperature hydrolysis method. The PEG-modified BiOCl photocatalyst exhibits a significantly enhanced RhB photosensitized degradation activity under visible light. After 10 min white LED irradiation, the degradation efficiency of RhB by the PEG-modified BiOCl sample S 0.07 reaches 99.5%. The degradation rate constant of the PEG-modified sample S 0.07 over RhB is 0.4568 min-1, which is 6.76 times that of the unmodified sample S 0 (0.0676 min-1). After 4 min of xenon lamp (λ ≥ 420 nm) irradiation, the degradation rate of RhB by S 0.07 is almost 100%. The exposed {001} facets with surface defects contribute to the superior adsorption capacity of BiOCl towards RhB, which immensely accelerates the electron transfer efficiency from the excited RhB into the conduction band of BiOCl, forming superoxide radical (˙O2 -) active species to degrade the pollutants. Moreover, the superior RhB-sensitized BiOCl system provides high photocatalytic degradation activity over MO. This work provides a facile and efficient BiOCl synthesis method that is conducive to large-scale production and simultaneously opens up new ideas for the synthesis of other photocatalysts.

Entropy-Driven Stabilization of Multielement Halide Double-Perovskite Alloys.

Currently, a major obstacle restricting the commercial application of halide perovskites is their low thermodynamic stability. Herein, inspired by the high-stability high-entropy alloys, we theoretically investigated a variety of multielement double-perovskite alloys. First-principles calculations show that the entropy contribution to Gibbs free energy, which offsets the positive enthalpy contribution by up to 35 meV/f.u., can significantly enhance the material stability of double-perovskite alloys. We found that the electronic properties of bandgaps (1.04-2.21 eV) and carrier effective masses (0.34 to greater than 2 m0) of the multielement double-perovskite alloys can be tuned over a wide range. Meanwhile, the parity-forbidden condition of optical transitions in the Cs2AgInCl6 perovskite can be broken because of the lower symmetry of the configurational disorder, leading to enhanced transition intensity. This work demonstrates a promising strategy by utilizing the alloy entropic effect to further improve the material stability and optoelectronic performance of halide perovskites.

Interface Engineering of Cu(In,Ga)Se2 Solar Cells by Optimizing Cd- and Zn-Chalcogenide Alloys as the Buffer Layer.

The optimization of band alignment at the buffer/absorber interface is realized by tuning compositions of Cd and Zn chalcogenides as the buffer layer toward high-efficiency Cu(In,Ga)Se2 (CIGS) solar cells. Using the special quasi-random structure (SQS) approach, we construct randomly disordered ZnxCd1-xSySe1-y alloys and ZnSxO1-x alloys as alternatives to the traditional CdS buffer layer. The compositional dependence of formation energies, lattice parameters, band-gap energies, and band alignments of ZnxCd1-xSySe1-y and ZnSxO1-x alloys is investigated by first-principles density functional theory calculations. For quaternary ZnxCd1-xSySe1-y alloys, we find that the miscibility temperatures and the bandgap bowing coefficients are proportional to the lattice mismatch between the mixing elements. The linear dependence of lattice parameters, trinomial dependence of band-gap energies and band-edge positions on the alloy-composition of ZnxCd1-xSySe1-y alloys are established. For ZnSxO1-x alloys, we find the lattice parameters also exhibit a linear dependence on its composition. Because of the large lattice mismatch and the chemical disparity between ZnO and ZnS, the bowing coefficient for the bandgap energies of ZnSxO1-x alloys is composition dependent, and is larger for dilute ZnSxO1-x alloys. With the optimization criteria of moderate spike-like conduction band offset, large valance band offset, sufficiently wide bandgap, and lattice match with respect to the CIGS absorber, we illustrate the optimal composition range of both ZnxCd1-xSySe1-y alloys and ZnSxO1-x alloys as the buffer layer of the CIGS solar cells. Our work demonstrates that ZnxCd1-xSySe1-y alloys and ZnSxO1-x alloys are promising buffer layers for high-efficiency CIGS solar cells.

Electron donation of non-oxide supports boosts O2 activation on nano-platinum catalysts.

Activation of O2 is a critical step in heterogeneous catalytic oxidation. Here, the concept of increased electron donors induced by nitrogen vacancy is adopted to propose an efficient strategy to develop highly active and stable catalysts for molecular O2 activation. Carbon nitride with nitrogen vacancies is prepared to serve as a support as well as electron sink to construct a synergistic catalyst with Pt nanoparticles. Extensive characterizations combined with the first-principles calculations reveal that nitrogen vacancies with excess electrons could effectively stabilize metallic Pt nanoparticles by strong p-d coupling. The Pt atoms and the dangling carbon atoms surround the vacancy can synergistically donate electrons to the antibonding orbital of the adsorbed O2. This synergistic catalyst shows great enhancement of catalytic performance and durability in toluene oxidation. The introduction of electron-rich non-oxide substrate is an innovative strategy to develop active Pt-based oxidation catalysts, which could be conceivably extended to a variety of metal-based catalysts for catalytic oxidation.

[Raman spectroscopy study on the interaction of ginsenoside Rb1 with DPPC bilayers].

In the present work, the authors studied the interaction of ginsenoside Rh1 with lipid bilayers composed of DPPC using Raman spectroscopy. The conformational changes of DPPC molecule were further revealed by analyzing its vibrational modes such as the C--N stretching mode in the polar head-group region (650-850 cm(-1)), C--C stretching (1000-1200 cm(-1)), and C--H stretching (2750-3000 cm(-1)). The results indicated that there was little influence of Rb1 on the conformation of O--C--C--N+ backbone in the choline group of DPPC bilayers. The polar head group is still extending parallel to the bilayer sur face. The intensity ratios I1096/I1126 and I1096/I1062 represent the gauche/trans ratio. Both of them increased with adding the concentration of Rb1 to DPPC bilayers. The increment of gauche/trans ratio indicates that the disorder/order proportion of the alkyl chains arises. The ordering conformations in lipid chains decreased while the interchain disorder increased. The intensity ratio I2848/I2880 in the region of hydrocarbon chain C--H stretching mode reflects phase transition and has been demonstrated as a sensitive parameter of both inter-chain and intra-chain disorder/order intensity ratio in bilayer alkyl chains. The higher the ratio, the more disordered the hydrocarbon chains. Therefore, the increasing ratio I2848/I2880 with increasing amount of Rb1 indicates that this drug decreases the intermolecular ordering of the lipid lattice, and simultaneously increases the membrane lipid fluidity. In addition, previous study showed that an electrostatic interaction exists between sphingomyelin bilayers and drugs like scopolamine and anisodamine. Compared with those results, the action mode of ginsenoside Rb1 on DPPC bilayers may be because of hydrogen bonds that can be easily formed for the sugar moieties and the hydroxyls in Rb1 molecule. Therefore, the mechanism of drug action on DPPC bilayers may be resulting from the intra or inter hydrogen bonds and the head-group hydrophilic region of the DPPC membrane.

Band Structure Engineering of Cs2AgBiBr6 Perovskite through Order-Disordered Transition: A First-Principle Study.

Cs2AgBiBr6 was proposed as one of the inorganic, stable, and nontoxic replacements of the methylammonium lead halides (CH3NH3PbI3, which is currently considered as one of the most promising light-harvesting material for solar cells). However, the wide indirect band gap of Cs2AgBiBr6 suggests that its application in photovoltaics is limited. Using the first-principle calculation, we show that by controlling the ordering parameter at the mixed sublattice, the band gap of Cs2AgBiBr6 can vary continuously from a wide indirect band gap of 1.93 eV for the fully ordered double-perovskite structure to a small pseudodirect band gap of 0.44 eV for the fully random alloy. Therefore, one can achieve better light absorption simply by controlling the growth temperature and thus the ordering parameters and band gaps. We also show that controlled doping in Cs2AgBiBr6 can change the energy difference between ordered and disordered Cs2AgBiBr6, thus providing further control of the ordering parameters and the band gaps. Our study, therefore, provides a novel approach to carry out band structure engineering in the mixed perovskites for optoelectronic applications.

Theoretical study on the role of Ca(2+) at the S2 state in photosystem II.

In photosynthesis, calcium is crucial for oxygen evolution. In the absence of Ca(2+), the Kok cycle has been proven to stop at S2 with Yz•. To explore the reason, photosystem II (PSII) S2 models (in total 32452 atoms) with different metal ions (Ca(2+), Sr(2+), and K(+)) or without Ca(2+) involved in the oxygen evolution complex (OEC) have been theoretically studied based on the previous dynamic study of PSII. It is found that the portion of the Mn1 d-orbital decreases in the highest occupied molecular orbitals for Ca(2+)-depleted PSII. This feature is unfavorable for the electron transfer from the OEC to the Yz•. Furthermore, the proton donor-acceptor distance was found elongated by the alternation of the binding water in the absence of Ca(2+). The isolated vibrational modes of the key water molecules along the path and their high frequency of the OH stretching modes also suggested the difficulty of the proton transfer from the OEC toward the proton exit channel. This work provides one mechanistic explanation for the inactivity of Ca(2+)-depleted PSII.

A wide visible-light-responsive tunneled MgTa2O(6-x)N(x) photocatalyst for water oxidation and reduction.

We demonstrate for the first time that a nitrogen-doped tunneled oxide MgTa2O(6-x)N(x) with an absorption edge of ca. 570 nm can drive both water oxidation and reduction half reactions in the presence of scavengers under visible light irradiation, showing great potential in solar water splitting.

Selective photocatalytic conversion of glycerol to hydroxyacetaldehyde in aqueous solution on facet tuned TiO2-based catalysts.

Glycerol is selectively converted to hydroxyacetaldehyde (HAA) and H2 in aqueous solution on TiO2-based photocatalysts. The product selectivity was verified to be strongly dependent on the facets of TiO2. Rutile with high percentage of {110} facets results in over 90% superior selectivity of HAA, while anatase with {001} or {101} facets gives only 16% and 49% selectivity for HAA, respectively.

Spatial separation of photogenerated electrons and holes among {010} and {110} crystal facets of BiVO4.

Charge separation is crucial for increasing the activity of semiconductor-based photocatalysts, especially in water splitting reactions. Here we show, using monoclinic bismuth vanadate crystal as a model photocatalyst, that efficient charge separation can be achieved on different crystal facets, as evidenced by the reduction reaction with photogenerated electrons and oxidation reaction with photogenerated holes, which take place separately on the {010} and {110} facets under photo-irradiation. Based on this finding, the reduction and oxidation cocatalysts are selectively deposited on the {010} and {110} facets respectively, resulting in much higher activity in both photocatalytic and photoelectrocatalytic water oxidation reactions, compared with the photocatalyst with randomly distributed cocatalysts. These results show that the photogenrated electrons and holes can be separated between the different facets of semiconductor crystals. This finding may be useful in semiconductor physics and chemistry to construct highly efficient solar energy conversion systems.

Detection of proteins on silica-silver core-shell substrates by surface-enhanced Raman spectroscopy.

We have employed the proposed Silica-Silver Core-Shell (SSCS) SERS-active substrates to detect four model proteins: lysozyme (a protein without chromophore), cytochrome c (a protein with chromophore of heme), fluorescein isothiocyanate (FITC)-anti human IgG (labeled with FITC) and atto610-biotin/avidin (recognition with labeled small molecules). SERS spectra of these proteins and Raman labels on the SSCS substrates show both high sensitivity and reproducibility, which are due to electromagnetic SERS enhancement with additional localization field within closely packed Ag nanoparticles decorated on the SiO(2) nanoparticles and the aggregation of SiO(2)@Ag particles. We have found that the SERS intensities of atto610-biotin/avidin adsorbed on the SSCS substrates are about 20 times stronger than those from Ag plating on Au-decorated substrate. Moreover, the broad surface plasmon resonance (SPR) of the proposed substrates will extend SERS applications to more biological molecules with different laser excitations.