C(NH2)3(I3O8)(HI3O8)(H2I2O6)(HIO3)4·3H2O: An Unprecedented Asymmetric Guanidinium Polyiodate with a Strong Second-Harmonic-Generation Response and a Wide Band Gap.

Herein, we report an unprecedented asymmetric guanidinium polyiodate, namely, C(NH2)3(I3O8)(HI3O8)(H2I2O6)(HIO3)4·3H2O (1). The title compound was obtained via the hybridization of polyiodate anions and planar π-conjugated C(NH2)3+; meanwhile, its strong second-harmonic-generation (SHG) response (2.1 × KDP, where KDP = KH2PO4) and wide band gap (3.89 eV) were mainly dominated by the synergy effect of the aforementioned structural units.

[C(NH2)2NHNO2][C(NH2)3](NO3)2: A Mixed Organic Cationic Hybrid Nitrate with an Unprecedented Nonlinear-Optical-Active Unit.

We herein report a mixed organic cationic hybrid nitrate, namely, [C(NH2)2NHNO2][C(NH2)3](NO3)2 (1). It was successfully achieved via combining three different planar groups: [(C(NH2)2NHNO2]+, C(NH2)3+, and NO3-. First-principles calculations confirm that the [(C(NH2)2NHNO2]+ group is an excellent cationic nonlinear-optical (NLO)-active unit. The title compound exhibits a moderate second-harmonic-generation (SHG) response (1.5 × KDP), a wide band gap (3.58 eV), and a suitable birefringence of 0.071 at 550 nm. Theoretical calculations indicate that the synergy effect between the [(C(NH2)2NHNO2]+ and C(NH2)3+ groups dominates the SHG process.

Noncentrosymmetric (C3H7N6)6(H2PO4)4(HPO4)·4H2O and Centrosymmetric (C3H7N6)2SO4·2H2O: Exploration of Acentric Structure by Combining Planar and Tetrahedral Motifs via Hydrogen Bonds.

The combination of organic and inorganic nonlinear active units to obtain organic-inorganic hybrid materials has been proved to be a very effective method to obtain nonlinear optical (NLO) materials with excellent properties. Herein we reported two hybrid melamine-based compounds, namely, acentric (C3H7N6)6(H2PO4)4(HPO4)·4H2O (1) and centrosymmetric (C3H7N6)2SO4·2H2O (2), which were synthesized via facile solvent evaporation method. Compound 1 features a three-dimensional (3D) network structure composed of ∞[(H2PO4)4(HPO4)(H2O)4]6- layers which are further linked with ∞[(C3H7N6)6]6+ layers via hydrogen bonds. Compound 2 displays a 3D structure composed of [(C3H7N6)2(SO4)(H2O)2]∞ layers further linked with each other by hydrogen bonds. Compound 1 presents a second harmonic generation signal of about 0.1 × KDP. Furthermore, UV-vis and infrared spectra, thermal analyses, and theoretical calculation were also adopted to evaluate its NLO performance. The theoretical calculations showed that the SHG response and large birefringence of 1 were primarily caused by the (C3H7N6)+, (H2PO4)-, and (HPO4)2- groups.

KC9H5O6(H2O): A Promising UV Nonlinear-Optical Material with Large Birefringence Based on a π-Conjugated (C9H5O6)- Group.

In order to meet the growing needs for the laser technology and optics industries, the goal is to find suitable fundamental building blocks with large nonlinear-optical (NLO) coefficients and birefringence for an excellent-performance NLO or birefringent system. Via preliminary investigations and calculations, it has been found that the planar π-conjugated group (C9H5O6)- possesses large polarizability anisotropy (δ) and hyperpolarizability (ßmax), comparable to well-known groups such as (B3O6)3-, (C3N3O3)3-, etc. Herein, we report a new alkali-metal 3,5-dicarboxybenzoate, KC9H5O6(H2O) (KH2BTC), which crystallized in the acentric space group Pna21. Second-harmonic-generation (SHG) measurements of KH2BTC under 1064 nm laser radiation show that the SHG response of KH2BTC is 1.2 times that of KDP with type I phase-matching behavior. Birefringence measurements show that KH2BTC owns a large birefringence of about 0.372 at 550 nm. The band gap of KH2BTC obtained by ultraviolet (UV) diffuse-reflectance spectroscopy is 3.91 eV, indicating that KH2BTC has potential applications as UV NLO or birefringent materials. Theoretical calculation further confirmed that the impressive optical properties of KH2BTC are derived from the large polarizability anisotropy of the (C9H5O6)- anions.

Coal-based ultrathin N-doped carbon nanosheets synthesized by molten-salt method for high-performance lithium-ion batteries.

Coal is a typical fossil fuel and it is also a natural carbon material, therefore, converting it to functional carbon materials is an effective way to enhance the economic advantages of coal. Here, ultrathin N-doped carbon nanosheets were prepared from low-cost coal via a handy and green molten-salt method, which shown excellent performance for lithium-ion batteries (LIBs). The formation mechanism of ultrathin nanosheets was studied in detail. The eutectic molten salts possess low melting points and become a strong polar solvent at the calcined temperature, making the acidified coal miscible with them in very homogeneously state. Therefore, they can play a gigantic role inin situpore-forming during the carbonization and induce the formation of ultrathin nanosheets due to the salt ions. Simultaneously, the ultrathin N-doped carbon nanosheets with rich defects and controllable surface area was smoothly prepared without any more complex process while revealing brilliant electrochemical performance due to rich ion diffusion pathways. It delivers reversible capacity of 727.0 mAh g-1at 0.2 A g-1after 150 cycles. Thus, the molten-salt method broadens the avenue to construct porous carbon materials with tailor-made morphologies. Equally important, this approach provides a step toward the sustainable materials design and chemical science in the future.

Mechanistic Insights into the Mechanism of Inhibitor Selectivity toward the Dark Kinase STK17B against Its High Homology STK17A.

As a member of the death-associated protein kinase (DAPK) family, STK17B plays an important role in the regulation of cellular apoptosis and has been considered as a promising drug target for hepatocellular carcinoma. However, the highly conserved ATP-binding site of protein kinases represents a challenge to design selective inhibitors for a specific DAPK isoform. In this study, molecular docking, multiple large-scale molecular dynamics (MD) simulations, and binding free energy calculations were performed to decipher the molecular mechanism of the binding selectivity of PKIS43 toward STK17B against its high homology STK17A. MD simulations revealed that STK17A underwent a significant conformational arrangement of the activation loop compared to STK17B. The binding free energy predictions suggested that the driving force to control the binding selectivity of PKIS43 was derived from the difference in the protein-ligand electrostatic interactions. Furthermore, the per-residue free energy decomposition unveiled that the energy contribution from Arg41 at the phosphate-binding loop of STK17B was the determinant factor responsible for the binding specificity of PKIS43. This study may provide useful information for the rational design of novel and potent selective inhibitors toward STK17B.

The Tumor Suppressor Interferon Regulatory Factor 2 Binding Protein 2 Regulates Hippo Pathway in Liver Cancer by a Feedback Loop in Mice.

BACKGROUND AND AIMS: The conserved Hippo pathway regulates organ size, tissue homeostasis, and tumorigenesis. Interferon regulatory factor 2 binding protein 2 (IRF2BP2) was originally identified as a transcriptional corepressor. However, the association between IRF2BP2 and the Hippo pathway remains largely unknown. In addition, the biological function and regulation mechanism of IRF2BP2 in liver cancer are poorly understood. APPROACH AND RESULTS: In this study, we uncovered the clinical significance of IRF2BP2 in suppressing hepatocellular carcinogenesis. We showed that IRF2BP2, a direct target repressed by the Yes-associated protein (YAP)/TEA domain transcription factor 4 (TEAD4) transcriptional complex, inhibited YAP activity through a feedback loop. IRF2BP2 stabilized vestigial-like family member 4 (VGLL4) and further enhanced VGLL4's inhibitory function on YAP. Moreover, liver-specific IRF2BP2 overexpression suppressed tumor formation induced by Hippo pathway inactivation. CONCLUSIONS: These results revealed the important role of IRF2BP2 in repressing liver cancer progression and highlighted a feedback loop underlying the Hippo pathway in organ-size control and tumorigenesis.

Diversity and community structure of endophytic Bacillus with antagonistic and antioxidant activity in the fruits of Xisha Wild Noni (Morinda citrifolia L.).

Noni (Morinda citrifolia L.) is a tropical crop with strong antibacterial, antioxidant and other abilities, and its fruit has a strong potential for adjuvant treatment of diseases. This study aimed to explore the dynamic change of endophytic bacteria in Noni fruit at different stages and the correlation between the antagonistic and antioxidant activity of the Bacillus which was screened and the change of the host's growth stage. In this study, though the high-throughput sequencing technology (HTS), 106 endophytic bacteria species were found in A, B, C, D, E and F stages of Noni fruit, among which the dominant group were Pantoea (0.3%-20.9%), and Candidatus_Uzinura (2.3%-35.2%) etc. The endophytic bacteria were isolated by culture-dependent method. Through their antagonistic experiments on Staphylococcus aureus and Escherichia coli, the results of 16S polyphasic taxonomic identification showed that the 34 antagonistic strains belonged to Bacillus. Five species of these Bacillus were identified by gyrA polyphase taxonomy, including Bacillus subtilis (76% of all Bacillus), Bacillus licheniformis (9%), Bacillus amyloliquefaciens (6%), Bacillus velezensis (6%) and Bacillus mojavensi (3%), and the RAPD showed these Bacillus are no signs of stable passage. In C, D, E and F stages, the average total antioxidant activity of Bacillus endophytic antagonists against Noni was 7.812 U/mL, 8.144 U/mL, 7.817 U/mL and 7.144 U/mL, which was much higher than that of Noni fruit, and antioxidant activity of Noni juice and Bacillus bacterial liquid vary with host's growth period showed the same trend, both rose slowly at first, and reached the highest in period E, then declined slightly in period F, it showed that the antagonistic Bacillus of Noni had synergistic function with Noni fruit. This study clarified the relationship of function between Noni fruit and endophytic bacteria, and laid a foundation for future study on the dynamic change of endophytic flora succession and efficacy.

Proximity proteomics identifies novel function of Rab14 in trafficking of Ebola virus matrix protein VP40.

Ebola virus is a member of Filoviridae family of viruses that causes fetal hemorrhagic fever in human. Matrix protein VP40 of the Ebola virus is involved in multiple stages of viral maturation processes. In order to fully understand the interacting partners of VP40 in host cells, we applied proximity-dependent biotin-identification (BioID) approach to systematically screen for potential proteins at different time points of VP40 expression. By immunoprecipitation and subsequent proteomics analysis, we found over 100 candidate proteins with various cellular components and molecular functions. Among them, we identified Rab14 GTPase that appears to function at the late stage of VP40 expression. Imaging studies demonstrated that VP40 and Rab14 have substantial colocalization when expressed in HeLa cells. Overexpression of the dominant-negative Rab14(S25N) diminished the plasma membrane (PM) localization of VP40. In addition, we found that secreted VP40 protein can be endocytosed into Rab14 positive compartments. In summary, our study provides evidence that Rab14 is a novel regulator of the intracellular trafficking of Ebola virus matrix protein VP40 in HeLa cells.

Highly Polarizable Hg2+ Induced a Strong Second Harmonic Generation Signal and Large Birefringence in LiHgPO4.

A new ultraviolet nonlinear optical material, namely LiHgPO4, was synthesized using the mild hydrothermal method. The structure of LiHgPO4 features novel double layers constructed by severely distorted HgO6 octahedra and PO4 tetrahedra, which are further interconnected by LiO4 tetrahedra to form a three-dimensional structure. LiHgPO4 exhibits a very strong second harmonic generation (SHG) response of 11.0 times that of KH2PO4 and a relatively large birefringence (0.068 at 1064 nm) among the reported SHG-active phosphates. Theoretical calculations revealed that the introduction of the Hg2+ in a highly distorted HgO6 octahedral geometry is crucial to produce the strong SHG response and large birefringence.

HBa2.5(IO3)6(I2O5) and HBa(IO3)(I4O11): Explorations of Second-Order Nonlinear Optical Materials in the Alkali-Earth Polyiodate System.

Two new barium polyiodate compounds in the alkali-earth system, namely, HBa2.5(IO3)6(I2O5) ( Fdd2) and HBa(IO3)(I4O11) ( P1̅) have been obtained through hydrothermal reaction. Interestingly, the structures of both compounds feature different polyiodate groups, i.e., I2O5 and I4O11 groups. HBa2.5(IO3)6(I2O5) can be depicted as an alternative stacking of two-dimensional (2D) [Ba4(IO3)8(I2O5)2] and [Ba(IO3)4(I2O5)2]2- layers with the I2O5 and IO3 group serving as linkers. HBa(IO3)(I4O11) can be depicted as a 3D network with 2D [Ba(I4O11)] layers being interconnected by IO3 groups. The 0D I4O11 polyiodate group can be seen also viewed as formed by an I3O8 group further corner-sharing with an IO3 group or an I2O5 group further corner-sharing with two IO3 groups. Powder second harmonic generation (SHG) measurements show that HBa2.5(IO3)6(I2O5) crystals display a moderate SHG efficiency of ∼1.6 times that of KH2PO4 (KDP) and are phase-matchable. Optical properties measurements, thermal analyses, and laser damage threshold (LDT) measurements have been performed. Results of theoretical calculation show that the formation of I4O112- is thermodynamically much easier than I3O8- and I2O5, because of the lower reaction energy. Our studies shed light on exploring alkali-earth polyiodates as potential NLO materials.

Three Cadmium Tartratoborates with Good Second Harmonic Generation (SHG) or Luminescence Performances.

Three new cadmium(II) tartratoborates, namely, Cd5[(C4H2O6)2B]2(H2O)8·3H2O (1), K2Cd4[(C4H2O6)2B]2(H2O)2 (2), and Li0.92K1.08Cd1.5[(C4H2O6)2B](H2O)2 (3), have been successfully synthesized by the hydrothermal method. Compounds 1-3 belong to centric C2/ c, acentric Pc, and the polar C2, respectively. Through based on the same hybrid borate-tartrate [(C4H2O6)2B]5- anions, they exhibit different structures. The [(C4H2O6)2B]5- anion is composed of two tartrate anions and a B(OH)4- unit. Compound 1 features a novel 3D network formed by 2D {Cd3[(C4H2O6)2B]2(H2O)2}4- anionic layers and [Cd2O10] dimers, forming tunnels of large 14-MRs which are filled by the non-coordination water molecules. Compound 2 has a characteristic 3D network based on {Cd2[(C4H2O6)2B]}- units interlinked via carboxylate groups, forming tunnels of 11-MRs, half of which stuffed with the K+ ions. Compound 3 features 2D {Cd4[(C4H2O6)4B]}3+ layers which are separated by K/Li ions. Luminescent studies suggest that they emit blue light. Compounds 2 and 3 display phase-matchable second harmonic generation signs of about 3.2× and 1.5× KH2PO4, respectively.

Thrombocytopenia: A prognostic factor for hepatocellular carcinoma patients with portal vein tumor thrombus after hepatectomy.

BACKGROUND AND AIM: Portal vein tumor thrombus (PVTT) predicts a poor prognosis in hepatocellular carcinoma (HCC) patients. Platelets (PLTs) play an important role in HCC progression and metastasis. However, the relationship between PLTs and PVTT remains unclear. This study aimed to evaluate the value of PLT counts in the prognosis of HCC patients with PVTT after hepatectomy. METHODS: From January 2002 to December 2012, 694 HCC patients with PVTT after hepatectomy were evaluated. The patients were divided into the thrombocytopenia group (PLT < 100 × 109 /L), the normal group, and the thrombocytosis group (PLT > 300 × 109 /L) based on the preoperative PLT level. A propensity score matching (PSM) analysis was used. RESULTS: Before the PSM, PVTT patients with thrombocytopenia exhibited longer recurrence-free survival (RFS) and overall survival (OS) compared with those with normal PLT counts (both P < 0.001) or thrombocytosis (P = 0.008 and P = 0.046). For the thrombocytopenia group and the normal group, the 1-, 2-, and 3-year RFS values were 30.0%, 17.6%, and 15.7% and were 10.8%, 6.6%, and 5.8% (P < 0.001), respectively; the 1-, 2-, and 3-year OS values were 61.9%, 37.9%, and 31.2% and were 38.3%, 23.3%, and 16.0% (P < 0.001), respectively. After the PSM, the median survival time was 16.6 versus 8.6 months (P < 0.002) in the two groups. A subgroup analysis revealed that thrombocytopenia is associated with improved OS in those with type I PVTT (P = 0.021) or type II PVTT (P = 0.029). CONCLUSION: According to the PSM, preoperative thrombocytopenia predicts an increased RFS and OS in HCC patients with PVTT after hepatectomy.

A Facile Route to Nonlinear Optical Materials: Three-Site Aliovalent Substitution Involving One Cation and Two Anions.

Two mixed-metal gallium iodate fluorides, namely, α- and ß-Ba2 [GaF4 (IO3 )2 ](IO3 ) (1 and 2), have been designed by the aliovalent substitutions of α- and ß-Ba2 [VO2 F2 (IO3 )2 ](IO3 ) (3 and 4) involving one cationic and two anionic sites. Both 1 and 2 display large second-harmonic generation responses (≈6×KH2 PO4 (KDP)), large energy band gaps (4.61 and 4.35 eV), wide transmittance ranges (≈0.27-12.5 µm), and high relevant laser-induced damage thresholds (29.7× and 28.3×AgGaS2 , respectively), which indicates that 1 and 2 are potential second-order nonlinear optical materials in the ultraviolet to mid-infrared. Our studies propose that three-site aliovalent substitution is a facile route for the discovery of good NLO materials.

REI5 O14 (RE=Y and Gd): Promising SHG Materials Featuring the Semicircle-Shaped I5 O14 3- Polyiodate Anion.

The first examples of rare-earth polyiodates, namely, REI5 O14 (RE=Y and Gd), have been prepared by hydrothermal reactions of RE2 O3 and H5 IO6 in H3 PO4 (≥85 wt % in H2 O), with extremely high yields (>95 %). They crystalize in the polar space group Cm and feature a brand-new semicircle-shaped [I5 O14 ]3- pentameric polyiodate anion composed of two IO3 and three IO4 polyhedra. Remarkably, both compounds exhibit very large second-harmonic generation (SHG) signals (14× and 15×KH2 PO4 (KDP) upon 1064 nm laser radiation for Y and Gd compounds, respectively). Our work shows that the hydrothermal reaction in a phosphoric acid medium facilitates the formation of rare-earth polyiodates.

Acentric La3(IO3)8(OH) and La(IO3)2(NO3): Partial Substitution of Iodate Anions in La(IO3)3 by Hydroxide or Nitrate Anion.

Partial substitution of iodate anions in La(IO3)3 by OH- or NO3- anion led to acentric La3(IO3)8(OH) and chiral La(IO3)2(NO3). The structure of La3(IO3)8(OH) can be seen as a complex three-dimensional (3D) network composed of two-dimensional [La3(IO3)2(OH)]6+ cationic layers that are further bridged by remaining iodate anions, or alternatively as a 3D network composed of one-dimensional [La3(IO3)6(OH)]2+ cationic columns being further interconnected by additional iodate anions, while the structure of La(IO3)2(NO3) can be seen as a novel 3D structure with planar NO3 groups serving as linkage between the [La3(IO3)6]3+ triple layers. Compared to La(IO3)3, both compounds show considerably wide band gaps and enhanced thermal stability. La(IO3)2(NO3) shows a moderate second harmonic generation (SHG) response of ∼0.6 times that of KDP (KH2PO4), a wide band gap of 4.23 eV, and a high LDT value (22 × AgGaS2). Optical property measurements, thermal analysis, as well as theoretical calculations on SHG origin, were performed. It can be deduced that partial substitution of iodate anions can be a facile route to design new noncentrosymmetric metal iodates with novel structure and potential application.

Two Barium Gold Iodates: Syntheses, Structures, and Properties of Polar BaAu(IO3)5 and Nonpolar HBa4Au(IO3)12 Materials.

Two new barium gold iodates, namely, BaAu(IO3)5 and HBa4Au(IO3)12, have been prepared. BaAu(IO3)5 crystallizes in the polar space group Pca21, whereas HBa4Au(IO3)12 crystallizes in the centrosymmetric space group P21/c. BaAu(IO3)5 consists of unique polar [Au(IO3)4]- anions whose four iodate groups are located at both sides of the AuO4 plane and the polarity points in the [001̅] direction. BaAu(IO3)5 displays strong second-harmonic-generation (SHG) effects about 0.6KTiOPO4 (KTP) and is phase-matchable. Thermal properties, optical spectra analyses, and theoretical calculations are also reported.

Bi(IO3 )F2 : The First Metal Iodate Fluoride with a Very Strong Second Harmonic Generation Effect.

The first metal iodate fluoride, Bi(IO3 )F2 , with a strong second harmonic generation (SHG) effect has been prepared. Bi(IO3 )F2 crystallizes in the polar space group C2 and features a three-dimensional [BiF2 ]+ cationic framework with IO3 groups capping the inner walls of the one-dimensional tunnels. This [BiF2 ]+ cationic framework acts as a template for the assembly of the polar IO3 units in a favorable superposed fashion, which leads to the polar structure of the material. Bi(IO3 )F2 displays a rather wide transmittance window (0.3-11 µm) and exhibits a very strong SHG response that is about 11.5 times larger than that of KH2 PO4 (KDP) under 1064 nm laser radiation and the same as that of KTiOPO4 (KTP) under 2.05 µm laser radiation. Preliminary investigations indicate that Bi(IO3 )F2 is a promising nonlinear optical material in the visible and mid-IR region.

LnBSb2O8 (Ln = Sm, Eu, Gd, Tb): A Series of Lanthanide Boroantimonates with Unusual 3D Anionic Structures.

A series of lanthanide boroantimonates, namely, LnBSb2O8 (Ln = Sm 1, Eu 2, Gd 3, and Tb 4) have been successfully synthesized by high temperature solid-state reactions for the first time. They are isostructural and feature novel three-dimensional (3D) frameworks composed of 2D [Sb3O12]9- layers interconnected by 1D [SbBO7]6- chains with remaining BO3 groups hanging on the walls of the 1D 6-membered-ring (MR) tunnels along the a-axis, and the lanthanide ions filled in the voids of the anionic structure. They exhibit high thermal stability (up to 900 °C). Luminescent studies suggest that compounds 1, 2, and 4 have potential application as orange, red, and green light luminescent materials, respectively. Magnetic measurements reveal ferromagnetic coupling interactions in compound 3 and antiferromagnetic coupling interactions between magnetic centers in compounds 1, 2, and 4.

The Kto-Skd complex can regulate ptc expression by interacting with Cubitus interruptus (Ci) in the Hedgehog signaling pathway.

The hedgehog (Hh) signaling pathway plays a very important role in metazoan development by controlling pattern formation. Drosophila imaginal discs are subdivided into anterior and posterior compartments that derive from adjacent cell populations. The anterior/posterior (A/P) boundaries, which are critical to maintaining the position of organizers, are established by a complex mechanism involving Hh signaling. Here, we uncover the regulation of ptc in the Hh signaling pathway by two subunits of mediator complex, Kto and Skd, which can also regulate boundary location. Collectively, we provide further evidence that Kto-Skd affects the A/P-axial development of the whole wing disc. Kto can interact with Cubitus interruptus (Ci), bind to the Ci-binding region on ptc promoter, which are both regulated by Hh signals to down-regulate ptc expression.