Selective ethylene trimerization by titanium complexes bearing phenoxy-imine ligands: NMR and EPR Spectroscopic studies of the reaction intermediates

The catalyst systems (FI)TiCl₃/MAO (FI = phenoxyimine ligand with an additional aryl–O–CH₃ donor) display exceptionally high activity in selective ethylene trimerization. By means of NMR and EPR spectroscopy, the nature of the Ti species formed in the catalyst systems (FI)TiCl₃/MAO, (FI)TiCl₃/MMAO, and (FI)TiCl₃/AlR₃/[Ph₃C]⁺[B(C₆F₅)₄]⁻ (R = Me, Et, ⁱBu) has been studied. It was shown that outer-sphere ion pairs of the type [(FI)TiIVMe₂]⁺[A]⁻ ([A]− = [MeMAO]⁻, [MeMMAO]⁻, [B(C₆F₅)₄]⁻) are formed at the initial stage of the reaction of (FI)TiCl₃ with MAO, MMAO, and AlMe₃/[Ph₃C]⁺[B(C₆F₅)₄]⁻. These ion pairs further partially convert into TiIII and TiII species. In the systems (FI)TiCl₃/MAO and (FI)TiCl₃/AlMe₃/[Ph₃C]⁺[B(C₆F5)₄]⁻, complexes with the proposed structures (FI)TiIIIMe₂, (FI)TiIICl, and [(FI)TiII(S)]⁺[A]⁻ ([A]− = [MeMAO]⁻, [B(C₆F₅)4)]⁻, S = solvent, vacancy) were observed (concentrations of TiIII species was lower than those of the TiII congeners). In contrast, in the system (FI)TiCl₃/MMAO, the concentrations of TiIII species (ion pairs of the type [(FI)TiIII(μ-H)(μ-Cl)AlⁱBu₂]⁺[MeMMAO]⁻) were higher than those of the TiII counterparts (ion pairs [(FI)TiII(S)]⁺[MeMMAO]⁻). The system (FI)TiCl₃/MMAO displays lower activity and selectivity in 1-hexene formation, in comparison to (FI)TiCl₃/MAO, due to undesirable PE generation. Probably, TiII and TiIV ion pairs are those participating in ethylene trimerization

Manipulation of Majorana fermion, Andreev reflection and Josephson current on topological insulators

We study theoretically charge transport properties of normal metal (N) / ferromagnet insulator (FI) / superconductor (S) junction and S/FI/S junction formed on the surface of three-dimensional topological insulator (TI), where chiral Majorana mode (CMM) exists at FI/S interface. We find that CMM generated in N/FI/S and S/FI/S junctions are very sensitively controlled by the direction of the magnetization ${\bm m}$ in FI region. Especially, the current-phase relation of Josephson current in S/FI/S junctions has a phase shift neither 0 nor $\pi$, which can be tuned continuously by the component of ${\bm m}$ perpendicular to the interface

Exploring the Referral and Usage of Science Fiction in HCI Literature

Research on science fiction (sci-fi) in scientific publications has indicated the usage of sci-fi stories, movies or shows to inspire novel Human-Computer Interaction (HCI) research. Yet no studies have analysed sci-fi in a top-ranked computer science conference at present. For that reason, we examine the CHI main track for the presence and nature of sci-fi referrals in relationship to HCI research. We search for six sci-fi terms in a dataset of 5812 CHI main proceedings and code the context of 175 sci-fi referrals in 83 papers indexed in the CHI main track. In our results, we categorize these papers into five contemporary HCI research themes wherein sci-fi and HCI interconnect: 1) Theoretical Design Research; 2) New Interactions; 3) Human-Body Modification or Extension; 4) Human-Robot Interaction and Artificial Intelligence; and 5) Visions of Computing and HCI. In conclusion, we discuss results and implications located in the promising arena of sci-fi and HCI research.Comment: v1: 20 pages, 4 figures, 3 tables, HCI International 2018 accepted submission v2: 20 pages, 4 figures, 3 tables, added link/doi for Springer proceedin

Key mechanistic features of swelling and blistering of helium-ion-irradiated tungsten

Helium-ion-induced swelling and blistering of single-crystal tungsten is investigated using a Helium Ion Microscope for site-specific dose-controlled irradiation (at 25 keV) with analysis by Helium Ion Microscopy, Atomic Force Microscopy and Transmission Electron Microscopy (cross-sectioning by Focused Ion Beam milling). We show that the blister cavity forms at a depth close to the simulated helium peak and that nanobubbles coalesce to form nanocracks within the envelope of the ion stopping range, swelling the blister shell. These results provide the first direct experimental evidence for the interbubble fracture mechanism proposed in the framework of the gas pressure model for blister formation