Laser control of reactions of photoswitching functional molecules

Laser control schemes of reactions of photoswitching functional molecules are proposed based on the quantum mechanical wave-packet dynamics and the design of laser parameters. The appropriately designed quadratically chirped laser pulses can achieve nearly complete transitions of wave packet among electronic states. The laser parameters can be optimized by using the Zhu-Nakamura theory of nonadiabatic transition. This method is effective not only for the initial photoexcitation process but also for the pump and dump scheme in the middle of the overall photoswitching process. The effects of momentum of the wave packet crossing a conical intersection on the branching ratio of products have also been clarified. These control schemes mentioned above are successfully applied to the cyclohexadiene/hexatriene photoisomerization (ring-opening) process which is the reaction center of practical photoswitching molecules such as diarylethenes. The overall efficiency of the ring opening can be appreciably increased by using the appropriately designed laser pulses compared to that of the natural photoisomerization without any control schemes.     

Aminohydroxyphosphine ligand for the copper-catalyzed enantioselective conjugate addition of organozinc reagents

An alanine-derived aminohydroxyphosphine ligand was developed for copper-catalyzed asymmetric conjugate addition of organozinc reagents to alpha,beta-unsaturated carbonyl compounds. This new tridentate ligand induces consistently high enantioselectivity in reactions of a variety of acyclic substrates. Theoretical mechanistic analysis suggests that the C-C bond formation takes place through a highly ordered transition state by the coordination of the phosphorus and nitrogen atoms to the copper(III) and zinc(II) atoms, respectively, and of the oxygen anion to both the metal centers.     

An efficient in silico screening method based on the protein-compound affinity matrix and its application to the design of a focused library for cytochrome P450 (CYP) ligands

A new method has been developed to design a focused library based on available active compounds using protein-compound docking simulations. This method was applied to the design of a focused library for cytochrome P450 (CYP) ligands, not only to distinguish CYP ligands from other compounds but also to identify the putative ligands for a particular CYP. Principal component analysis (PCA) was applied to the protein-compound affinity matrix, which was obtained by thorough docking calculations between a large set of protein pockets and chemical compounds. Each compound was depicted as a point in the PCA space. Compounds that were close to the known active compounds were selected as candidate hit compounds. A machine-learning technique optimized the docking scores of the protein-compound affinity matrix to maximize the database enrichment of the known active compounds, providing an optimized focused library.     

Observation of strong low-lying E1 strength in the two-neutron halo nucleus 11Li

An exclusive measurement has been made of the Coulomb dissociation of the two-neutron halo nucleus 11Li at 70 MeV/nucleon at RIKEN. Strong low-energy (soft) E1 excitation is observed, peaked at about Ex = 0.6 MeV with B(E1) = 1.42(18) e2fm2 for Erel < or = 3 MeV, which was largely missed in previous measurements. This excitation represents the strongest E1 transition ever observed at such low excitation energies. The spectrum is reproduced well by a three-body model with a strong two-neutron correlation, which is further supported by the E1 non-energy-weighted cluster sum rule.     

Surface acceleration of fast electrons with relativistic self-focusing in preformed plasma

We report an observation of surface acceleration of fast electrons in intense laser-plasma interactions. When a preformed plasma is presented in front of a solid target with a higher laser intensity, the emission direction of fast electrons is changed to the target surface direction from the laser and specular directions. This feature could be caused by the formation of a strong static magnetic field along the target surface which traps and holds fast electrons on the surface. In our experiment, the increase in the laser intensity due to relativistic self-focusing in plasma plays an important role for the formation. The strength of the magnetic field is calculated from the bent angle of the electrons, resulting in tens of percent of laser magnetic field, which agrees well with a two-dimensional particle-in-cell calculation. The strong surface current explains the high conversion efficiency on the cone-guided fast ignitor experiments.     

A class of integral equations and approximation of p-Laplace equations

Let ${\Omega\subset\mathbb{R}^n}$ be a bounded domain, and let 1 < p < ∞ and σ < p. We study the nonlinear singular integral equation $$ M[u](x) = f_0(x)\quad {\rm in}\,\Omega$$ with the boundary condition u = g ₀ on ?Ω, where ${f_0\in C(\overline\Omega)}$ and ${g_0\in C(\partial\Omega)}$ are given functions and M is the singular integral operator given by $$M[u](x)={\rm p.v.} \int\limits_{B(0,\rho(x))} \frac{p-\sigma}{|z|^{n+\sigma}}|u(x+z)-u(x)|^{p-2} (u(x+z)-u(x))\,{\rm dz},$$ with some choice of ${\rho\in C(\overline\Omega)}$ having the property, 0 < ρ(x) ≤ dist (x, ?Ω). We establish the solvability (well-posedness) of this Dirichlet problem and the convergence uniform on ${\overline\Omega}$ , as σ → p, of the solution u _σ of the Dirichlet problem to the solution u of the Dirichlet problem for the p-Laplace equation νΔ _p u = f ₀ in Ω with the Dirichlet condition u = g ₀ on ?Ω, where the factor ν is a positive constant (see (7.2)).     

Iron‐Catalyzed Chemoselective ortho Arylation of Aryl Imines by Directed C?H Bond Activation

Naheliegende Alternative : Eine eisenkatalysierte Imin‐gesteuerte C‐H‐Aktivierung mit einem Diarylzinkreagens führt eine Arylgruppe in ortho‐Stellung an einem von Acetophenon abgeleiteten Imin ein (siehe Schema); mit einem Palladiumkatalysator tritt dagegen eine gewöhnliche Substitution auf. Die Titelreaktion ist eine milde C‐H‐Aktivierung, die in Gegenwart von 1,2‐Dichlorisobutan mit Arylbromiden, ‐chloriden oder ‐sulfonaten selektiv verläuft.

     

Investigation of degradation mechanisms in mechanical properties of polyimide films exposed to a low earth orbit environment

The degradation of the mechanical properties of polyimide films was evaluated by means of tensile tests after exposure to a low earth orbit (LEO) environment. Polyimide films irradiated with atomic oxygen (AO), ultraviolet (UV) light, and electron beam (EB) rays using ground simulation facilities were also evaluated similarly and compared. In these experiments tensile stress (7.0 MPa or less) was applied to the samples in order to assess its effects on mechanical properties. The mechanical properties of the flight samples decreased concomitantly with increased exposure duration. The fracture surfaces exhibited characteristic radiated patterns initiating from the exposed surfaces which showed a rough texture. In the AO-irradiated samples the mechanical properties degraded and the surface texture developed as the AO fluence increased; similar fracture surfaces appeared in the flight samples. In contrast, UV and EB irradiation had little impact on mechanical properties. Based on these results, the eroded surfaces by AO irradiation served as the starting points of the rupture, resulting in degradation of mechanical properties of polyimide films exposed to a LEO environment. The tensile stress states induced no difference in evaluations.     

Total synthesis of brevenal

The convergent total synthesis of brevenal, a non-toxic brevetoxin antagonist, has been achieved. The ABC ring segment and the E ring precursor were connected by the intramolecular allylation followed by ring-closing metathesis to furnish the pentacyclic ether compound. An alternative route to the key synthetic intermediate, a pentacyclic ether core, was also examined. The right- and left-hand side chains were introduced by Wittig and Horner-Wadsworth-Emmons reactions, respectively, to furnish brevenal (1).