Probing the Structural Degradation of CsPbBr3 Perovskite Nanocrystals in the Presence of H2O and H2S: How Weak Interactions and HSAB Matter.

Structural degradation of all inorganic CsPbBr3 in the presence of moisture is considered as one of its major limitations to use as an active component in various light-harvesting and light-emitting devices. Herein, we used two similar molecules, H2O and H2S, with similar structures, to follow the decomposition mechanism of CsPbBr3 perovskite nanocrystals. Interestingly, H2O acts as a catalyst for the decomposition of CsPbBr3, which is in contrast to H2S. Our experimental observations followed by density functional theory (DFT) calculations showed that the water molecule is intercalated in the CsPbBr3 perovskite whereas H2S is adsorbed in the (100) planes of CsPbBr3 by a weak electrostatic interaction. According to Pearson's hard-soft acid-base theory, both cations present in CsPbBr3 prefer soft/intermediate bases. In the case of the water molecule, it lacks a soft base and thus it is not directly involved in the reaction whereas H2S can provide a soft base and thus it gets involved in the reaction. Understanding the mechanistic aspects of decomposition can give different methodologies for preventing such unwanted reactions.

Biomolecular interactions between the antibacterial ceftolozane and the human inflammatory disease target ADAM17: a drug repurposing study.

Inhibition of a disintegrin and metalloproteinase-17 (ADAM17), a metzincin, is proposed as a novel therapeutic strategy to suppress overproduction of the proinflammatory cytokine TNF-α in rheumatoid arthritis and inflammatory bowel disease. Existing ADAM17 inhibitors generate toxic metabolites in-vivo or haven't progressed in clinical trials. Previous studies suggest that ligands which bind to ADAM17 active site by interacting with the Zn ion and L-shaped hydrophobic S1'- and S3'-pockets and forming favorable hydrogen bonds could act as potential ADAM17 inhibitors. Here, we investigated whether the FDA-approved anti-bacterial drug ceftolozane, a cephalosporin containing aromatic groups and carboxyl groups as probable zinc binding groups (ZBGs), forms non-covalent interactions resulting in its binding in the active site of ADAM17. In this study, the density functional theory (DFT), molecular docking and molecular dynamics calculations with the catalytic chain of ADAM17 show that carboxyl group of ceftolozane acts as moderate ZBG, and its extended geometry forms hydrogen bonds and hydrophobic interactions resulting in a binding affinity comparable to the co-crystallized known ADAM17 inhibitor. The favorable binding interactions identified here suggest the potential of ceftolozane to modulate ADAM17 activity in inflammatory diseases. ADAM17 cleaves and releases epidermal growth factor (EGF) ligands from the cell surface. The shed EGF ligands then bind to the EGF receptors to drive embryonic development. Therefore, our findings also suggest that use of ceftolozane during pregnancy may inhibit ADAM17-mediated shedding of EGF and thus increase the risk of birth defects in humans.Communicated by Ramaswamy H. Sarma.

Structures and chemical properties of silicene: unlike graphene.

The discovery of graphene and its remarkable and exotic properties have aroused interest in other elements and molecules that form 2D atomic layers, such as metal chalcogenides, transition metal oxides, boron nitride, silicon, and germanium. Silicene and germanene, the Si and Ge counterparts of graphene, have interesting fundamental physical properties with potential applications in technology. For example, researchers expect that silicene will be relatively easy to incorporate within existing silicon-based electronics. In this Account, we summarize the challenges and progress in the field of silicene research. Theoretical calculations have predicted that silicene possesses graphene-like properties such as massless Dirac fermions that carry charge and the quantum spin Hall effect. Researchers are actively exploring the physical and chemical properties of silicene and tailoring it for wide variety of applications. The symmetric buckling in each of the six-membered rings of silicene differentiates it from graphene and imparts a variety of interesting properties with potential technological applications. The pseudo-Jahn-Teller (PJT) distortion breaks the symmetry and leads to the buckling in silicenes. In graphene, the two sublattice structures are equivalent, which does not allow for the opening of the band gap by an external electric field. However, in silicene where the neighboring Si atoms are displaced alternatively perpendicular to the plane, the intrinsic buckling permits a band gap opening in silicene in the presence of external electric field. Silicene's stronger spin orbit coupling than graphene has far reaching applications in spintronic devices. Because silicon prefers sp(3) hybridization over sp(2), hydrogenation is much easier in silicene. The hydrogenation of silicene to form silicane opens the band gap and increases the puckering angle. Lithiation can suppress the pseudo-Jahn-Teller distortion in silicene and hence can flatten silicene's structure while opening the band gap. So far, chemists have not successfully synthesized and characterized a free-standing silicene. But recently chemists have successfully produced silicene sheets and nanoribbons over various substrates such as silver, diboride thin films, and iridium. The supporting substrate critically controls the electronic properties of silicene, and the match of the appropriate support and its use is critical in applications of silicene.

Tip enhanced Raman spectroscopy (TERS) as a probe for the buckling distortion in silicene.

Silicene, the all-Si analogue of graphene, is symmetrically buckled in each of the six-membered units and this buckling is periodically translated across the surface. Raman spectra of silicene clusters were calculated using first principles DFT methods to explore the intrinsic buckling in silicene. The presence of metal clusters as a tip over the silicene units affects the intensity of the buckling modes which can be enhanced by increasing the number of atoms in the clusters. The favourable sites of chemisorption of metal clusters over the silicene surface are studied along with the resulting red shift in buckling frequency and chemical enhancement in the Raman intensity.

Molecular Balances Based on Aliphatic CH-π and Lone-Pair-π Interactions.

CH···π and lone-pair···π interactions are estimated for a series of conformationally dynamic bicyclic N-aryliimides. On the basis of their strengths and mutual synergy/competition, the molecules prefer a folded/unfolded conformation. Calculations suggest strategies to selectively isolate the folded form by increasing the strength of the attractive CH···π interaction or removing the lone-pair···π repulsion. While the barrier for the folded ⇄ unfolded transformation is too large to conformationally lock the molecules in either of the conformers, the dynamics for hopping of the alkyl group across rings and tumbling over the rings are found to be facile in the folded conformation.

Structures and electronic properties of silicene clusters: a promising material for FET and hydrogen storage.

Structures and electronic properties of clusters of an all-Si analogue of graphene, silicene, have been studied through quantum chemical calculations. The structures of the six-membered rings show interesting chair like puckering, which for large sheet-like clusters form ordered ripples. Binding energies, HOMO-LUMO gaps and polarizabilities for the silicene clusters show interesting monotonic trends analogous to polyacenes. Stacking of two silicene layers leads to the formation of closed 3D clusters with high symmetry and strong Si-Si bonds. The heat of hydrogenation of silicene to form silicanes is overwhelmingly exothermic and leads to the opening up of the HOMO-LUMO gaps. Thus, analogous to graphanes, silicanes are predicted to be interesting materials for hydrogen storage and for their band engineering properties.