High-Pressure Effects on Hofmann-Type Clathrates: Promoted Release and Restricted Insertion of Guest Molecules.

The search for effective methods to accurately control host-guest relationship is the central theme of host-guest chemistry. In this work, high pressure successfully promotes guest release in the Hofmann-type clathrate of [Ni(NH3)2Ni(CN)4]·2C6H6 (Ni-Bz) and restricts guest insertion into Ni(NH3)2Ni(CN)4 (Ni-Ni). Because of the weak host-guest interactions of Ni-Bz, external force gradually removes guest benzene from the host framework, leading to puckered layers. Further theoretical calculations reveal the positive pressure contribution to breaking the energy barrier between Ni-Bz and Ni-Ni, explaining guest release from an energy standpoint. Inversely, guest insertion is restricted in the synthesized host of Ni-Ni because of the steric hindrance effect at high pressure. This study not only reveals structural effects on host-guest behaviors but also proves the role of pressure in controlling host-guest interactions. This unique observation is also crucial for the further application of host-guest materials in sustained and intelligent drug release, molecular separation, and transportation.

Ab initio structure determination of n-diamond.

A systematic computational study on the crystal structure of n-diamond has been performed using first-principle methods. A novel carbon allotrope with hexagonal symmetry R32 space group has been predicted. We name it as HR-carbon. HR-carbon composed of lonsdaleite layers and unique C3 isosceles triangle rings, is stable over graphite phase above 14.2 GPa. The simulated x-ray diffraction pattern, Raman, and energy-loss near-edge spectrum can match the experimental results very well, indicating that HR-carbon is a likely candidate structure for n-diamond. HR-carbon has an incompressible atomic arrangement because of unique C3 isosceles triangle rings. The hardness and bulk modulus of HR-carbon are calculated to be 80 GPa and 427 GPa, respectively, which are comparable to those of diamond. C3 isosceles triangle rings are very important for the stability and hardness of HR-carbon.

Structural, mechanical, and electronic properties of Rh2B and RhB2: first-principles calculations.

The crystal structures of Rh2B and RhB2 at ambient pressure were explored by using the evolutionary methodology. A monoclinic P21/m structure of Rh2B was predicted and donated as Rh2B-I, which is energetically much superior to the previously experimentally proposed Pnma structure. At the pressure of about 39 GPa, the P21/m phase of Rh2B transforms to the C2/m phases. For RhB2, a new monoclinic P21/m phase was predicted, named as RhB2-II, it has the same structure type with Rh2B. Rh2B-I and RhB2-II are both mechanically and dynamically stable. They are potential low compressible materials. The analysis of electronic density of states and chemical bonding indicates that the formation of strong and directional covalent B-B and Rh-B bonds in these compounds contribute greatly to their stabilities and high incompressibility.

Ab initio investigation of CaO-ZnO alloys under high pressure.

Ca(x)Zn(1-x)O alloys are potential candidates to achieve wide band-gap, which might significantly promote the band gap engineering and heterojunction design. We performed a crystal structure search for CaO-ZnO system under pressure, using an ab initio evolutionary algorithm implemented in the USPEX code. Four stable ordered Ca(x)Zn(1-x)O structures are found in the pressure range of 8.7-60 GPa. We further constructed the pressure vs. composition phase diagram of CaO-ZnO alloys based on the detailed enthalpy calculations. With the increase in Ca concentration, the CaO-ZnO alloy first undergoes a hexagonal to monoclinic transition, and then transforms back to a hexagonal phase. At Above 9 GPa, there is no cubic structure in the alloys, in contrast to the insostructural components (B1-B1). The band gap of the Ca(x)Zn(1-x)O alloy shows an almost linear increase as a function of the Ca concentration. We also investigated the variation regularity of the band gap under pressure.

First-principles study on the structural and electronic properties of metallic HfH2 under pressure.

The crystal structures and properties of hafnium hydride under pressure are explored using the first-principles calculations based on density function theory. The material undergoes pressure-induced structural phase transition I4/mmm → Cmma → P21/m at 180 and 250 GPa, respectively, and all of these structures are metallic. The superconducting critical temperature Tc values of I4/mmm, Cmma, and P21/m are 47-193 mK, 5.99-8.16 K and 10.62-12.8 K at 1 atm, 180 and 260 GPa, respectively. Furthermore, the bonding nature of HfH2 is investigated with the help of the electron localization function, the difference charge density and Bader charge analyses, which show that HfH2 is classified as a ionic crystal with the charges transferring from Hf atom to H.

Miscibility and ordered structures of MgO-ZnO alloys under high pressure.

The MgxZn(1-x)O alloy system may provide an optically tunable family of wide band gap materials that can be used in various UV luminescences, absorption, lighting, and display applications. A systematic investigation of the MgO-ZnO system using ab initio evolutionary simulations shows that MgxZn(1-x)O alloys exist in ordered ground-state structures at pressures above about 6.5 GPa. Detailed enthalpy calculations for the most stable structures allowed us to construct the pressure-composition phase diagram. In the entire composition, no phase transition from wurzite to rock-salt takes place with increasing Mg content. We also found two different slops occur at near x = 0.75 of Eg-x curves for different pressures, and the band gaps of high pressure ground-state MgxZn(1-x)O alloys at the Mg concentration of x > 0.75 increase more rapidly than x < 0.75.

The CCAAT enhancer-binding protein alpha (C/EBPalpha) requires a SWI/SNF complex for proliferation arrest.

The transcription factor CCAAT enhancer-binding protein alpha (C/EBPalpha) is a tumor suppressor in myeloid cells and inhibits proliferation in all cell types examined. C/EBPalpha interacts with the SWI/SNF chromatin-remodeling complex during the regulation of differentiation-specific genes. Here we show that C/EBPalpha fails to suppress proliferation in SWI/SNF defective cell lines after knock-down of SWI/SNF core components or after deletion of the SWI/SNF interaction domain in C/EBPalpha, respectively. Reconstitution of SWI/SNF function restores C/EBPalpha-dependent proliferation arrest. Our results show that the anti-proliferation activity of C/EBPalpha critically depends on components of the SWI/SNF core complex and suggest that the functional interaction between SWI/SNF and C/EBPalpha is a prerequisite for proliferation arrest.