Sustainable Heterogeneous Platinum Catalyst for Direct Methylation of Secondary Amines by Carbon Dioxide and Hydrogen

Pt and MoO_x co‐loaded TiO₂ is found to be highly effective for direct methylation of aliphatic and aromatic secondary amines by CO₂ and H₂ under solvent‐free conditions. This is the first additive‐free and reusable heterogeneous catalytic system with acceptable turnover number.     

A one-dimensional coordination polymer, BBDTA.InCl4: possible spin-Peierls transition with high critical temperature of 108 K

We have studied the crystal structure and magnetic properties of the organic radical cation salt, BBDTA.InCl4. This material formed a one-dimensional coordination polymer. Magnetic measurements indicated the spin-Peierls transition-like behavior at 108 K, which was higher than those typically observed for the other organic spin-Peierls materials. The structural aspects of the lattice distortion from X-ray diffraction measurements at 50 K have been discussed.     

Molecular dynamics simulations of self-organized polyicosahedral Si nanowire

A novel polyicosahedral nanowire is spontaneously formed in a series of annealing molecular dynamics simulations of liquid Si inside a nanopore of 1.36 nm in diameter. The polyicosahedral Si nanowire is stable even in a vacuum up to about 77% of the melting temperature of bulk Si. Our structural energy calculations reveal that the polyicosahedral nanowire is energetically advantageous over the pentagonal one for a wire whose diameter is less than 6.02 nm, though the latter has been recently proposed as the lowest energy wire. These results suggest the possibility of the formation of a new stable polyicosahedral Si nanowire.     

Proton-conducting ionic liquids based upon multivalent anions and alkylimidazolium cations

Alkylimidazolium type ionic liquids have been prepared with acidic anions derived from multivalent anions with the expectation of excellent thermal properties and ionic conductivity, including proton conduction.     

Dependence of electron spin g-factor on magnetic field in quantum wells

The dependence of electron spin g-factor on magnetic field has been investigated in GaAs/AlGaAs quantum wells. We have estimated the electron g-factor from spin precession frequency in time-resolved photoluminescence measurements under a magnetic field in different configurations; the magnetic field perpendicular (g_⊥) and parallel (g_∥) to the quantum confinement direction. When the angle between the magnetic field and the confinement direction is 45°, we have found that g-factor varies depending on the direction of magnetic field and the circular polarization type of excitation light (σ⁺ or σ^?). These dependences of g-factor exhibit main features of Overhauser effect that nuclear spins react back on electron spin precession. The value of g_⊥ and g_∥ corrected for the nuclear effects agree well with the results of four-band k·p perturbation calculations.     

Design and concise synthesis of novel vitamin D analogues bearing a functionalized aromatic ring on the side chain

Five novel vitamin D analogues (2a, 2b, 3a, 3b and 4) bearing an aromatic side chain have been designed and synthesized in a convergent manner. The requisite CD-ring synthons (10a–c) were prepared from C22 aldehyde (5) using four- or five-step procedures. Using turbo-Grignard reagents allowed aromatic side chains with a polar functional moiety to be installed in a single step with excellent yields. A preliminary biological evaluation using bovine thymus vitamin D receptor (VDR) suggested that incorporating a carboxylic acid instead of the C25-hydroxy group had a positive effect on the VDR affinity compared with the corresponding esters.     

Development of dissociative force field for all-atomistic molecular dynamics calculation of fracture of polymers

A dissociative force field for all-atomistic molecular dynamics calculations has been developed to investigate impact fracture of polymers accompanying dissociation of chemical bonds of polymer main chain. Energy of dimer molecules was evaluated as a function of both bond-length b and bond-angle θ by CASPT2 calculations, whose quality is enough to describe dissociation of chemical bonds. Because we found that the bond dissociation energy D decreases with increasing bond-angle, we employed the Morse-type function V_Bond(b, θ) = {D − V_Angle(θ)}[1 − exp{−α(b − b₀) − β(b − b₀)²}] where a quartic function V_Angle(θ) = k₁(θ − θ₀) + k₂(θ − θ₀)² + k₃(θ − θ₀)³ + k₄(θ − θ₀)⁴ . This function reproduced well the CASPT2 potential energy surface in a wide range of b and θ. The parameters have been obtained for four popular glassy polymers, polyethylene, poly(methyl methacrylate), poly(styrene), and polycarbonate. © 2019 Wiley Periodicals, Inc.     

Scaling molecular dynamics beyond 100,000 processor cores for large-scale biophysical simulations

The growing interest in the complexity of biological interactions is continuously driving the need to increase system size in biophysical simulations, requiring not only powerful and advanced hardware but adaptable software that can accommodate a large number of atoms interacting through complex forcefields. To address this, we developed and implemented strategies in the GENESIS molecular dynamics package designed for large numbers of processors. Long-range electrostatic interactions were parallelized by minimizing the number of processes involved in communication. A novel algorithm was implemented for nonbonded interactions to increase single instruction multiple data (SIMD) performance, reducing memory usage for ultra large systems. Memory usage for neighbor searches in real-space nonbonded interactions was reduced by approximately 80%, leading to significant speedup. Using experimental data describing physical 3D chromatin interactions, we constructed the first atomistic model of an entire gene locus (GATA4). Taken together, these developments enabled the first billion-atom simulation of an intact biomolecular complex, achieving scaling to 65,000 processes (130,000 processor cores) with 1 ns/day performance. Published 2019. This article is a U.S. Government work and is in the public domain in the USA.     

The asymptotic behavior of nonlinear semigroups and invariant means

Various first-order sufficient optimality criteria for continuous-time nonlinear programming problems with nonlinear equality and inequality constraints are established under generalized convexity assumptions, and applications of these criteria to optimal control and continuous-time fractional programming problems are briefly discussed.