Versatile supramolecular gelators that can harden water, organic solvents and ionic liquids

We developed novel supramolecular gelators with simple molecular structures that could harden a broad range of solvents: aqueous solutions of a wide pH range, organic solvents, edible oil, biodiesel, and ionic liquids at gelation concentrations of 0.1-2 wt %. The supramolecular gelators were composed of a long hydrophobic tail, amino acids and gluconic acid, which were prepared by liquid-phase synthesis. Among seven types of the gelators synthesized, the gelators containing L-Val, L-Leu, and L-Ile exhibited high gelation ability to various solvents. These gelators were soluble in aqueous and organic solvents, and also in ionic liquids at high temperature. The gelation of these solvents was thermally reversible. The microscopic observations (TEM, SEM, and CLSM) and small-angle X-ray scattering (SAXS) measurements suggested that the gelator molecules self-assembled to form entangled nanofibers in a large variety of solvents, resulting in the gelation of these solvents. Molecular mechanics and density functional theory (DFT) calculations indicated the possible molecular packing of the gelator in the nanofibers. Interestingly, the gelation of an ionic liquid by our gelator did not affect the ionic conductivity of the ionic liquid, which would provide an advantage to electrochemical applications.     

Measurement of all Deuteron Analyzing Powers for {\overrightarrow{d} + p} Elastic Scattering at 294 MeV/Nucleon

We have measured all deuteron analyzing powers ${(A_{y}^{d}, A_{yy}, A_{xx}, A_{xz})}$ for deuteron-proton elastic scattering at 294 MeV/nucleon in order to study the properties of three nucleon forces (3 NFs). Measurement was made at in an angular range of ${\theta_{{\rm c.m.}} = 35.6^{\circ} - 163.0^{\circ}}$ . Obtained data were compared with Faddeev calculations with and without the 3 NFs. At ${\theta_{{\rm c.m.}}\lesssim 120^{\circ}}$ all the data have general agreement with the calculations, while the measured data at ${\theta_{{\rm c.m.}} \gtrsim 120^{\circ}}$ are not explained by any theoretical calculations. These results were consistent with those at 250 MeV/nucleon.     

Measurements of the Cross Sections and A y for D(p, n) Inclusive Breakup Reaction at 170 MeV

The effects of three-nucleon force (3NF) has been actively studied by using the nucleon–deuteron (Nd) scattering states. The differential cross sections of the elastic Nd scattering at the energy below 150 MeV can be well reproduced by incorporating 3NF in the Faddeev calculation based on modern nucleon–nucleon (NN) interactions. On the other hand, the differential cross sections of Nd elastic and inelastic scatterings at 250 MeV show large discrepancies between the data and the Faddeev calculations with 3NF. It indicates the presence of the missing features of the three nucleon system at this energy region. For the systematic study about the energy dependence of this large discrepancies, we measured the differential cross sections and the vector analyzing power A _y for the ²H(p, n) inclusive breakup reaction at 170 MeV. The experiment was carried out at RCNP by detecting scattered neutrons by using the neutron detector NPOL3. The data was compared with the results of the Faddeev calculations with and without the 3NF.     

Thickness dependence of photoluminescence-decay profiles of exciton-exciton scattering in ZnO thin films

We have investigated the photoluminescence (PL) dynamics of ZnO thin films under intense excitation conditions using an optical-Kerr-gating method. The PL bands originating from exciton-exciton scattering (P emission) and biexciton (M emission) have been observed at 10 K. The ultrashort gating time of 0.6 ps has enabled us to obtain precise information of the temporal profiles of the peak energies and the intensities of the P- and M-PL bands. We have found that the decay time of the P emission becomes longer with increasing film thickness, while that of the M emission is independent of the film thickness. Although the decay time of the P emission is an increasing function of the film thickness, the relation is not in proportion, which is contrary to the predicted proportionality based on a simple model of photon-like polariton propagation.     

Numerical (error) issues on compressible multicomponent flows using a high-order differencing scheme: Weighted compact nonlinear scheme

A weighted compact nonlinear scheme (WCNS) is applied to numerical simulations of compressible multicomponent flows, and four different implementations (fully or quasi-conservative forms and conservative or primitive variables interpolations) are examined in order to investigate numerical oscillation generated in each implementation. The results show that the different types of numerical oscillation in pressure field are generated when fully conservative form or interpolation of conservative variables is selected, while quasi-conservative form generally has poor mass conservation property. The WCNS implementation with quasi-conservative form and interpolation of primitive variables can suppress these oscillations similar to previous finite volume WENO scheme, despite the present scheme is finite difference formulation and computationally cheaper for multi-dimensional problems. Series of analysis conducted in this study show that the numerical oscillation due to fully conservative form is generated only in initial flow fields, while the numerical oscillation due to interpolation of conservative variables exists during the computations, which leads to significant spurious numerical oscillations near interfaces of different component of fluids. The error due to fully conservative form can be greatly reduced by smoothing interface, while the numerical oscillation due to interpolation of conservative variables cannot be significantly reduced. The primitive variable interpolation is, therefore, considered to be better choice for compressible multicomponent flows in the framework of WCNS. Meanwhile better choice of fully or quasi-conservative form depends on a situation because the error due to fully conservative form can be suppressed by smoothed interface and because quasi-conservative form eliminates all the numerical oscillation but has poor mass conservation.     

QM/MM calculation of protein magnetic shielding tensors with generalized hybrid-orbital method: a GIAO approach

A method to compute magnetic shielding tensors with generalized hybrid-orbital (GHO) QM/MM scheme is developed at the levels of Hartree-Fock and second-order M?ller-Plesset perturbation theory using gauge-including atomic orbitals. A feature of the GHO method is utilized to ensure gauge-origin independency of GHO shielding tensors in a simple way. The benchmark calculations indicate that the GHO method reproduced full-QM shielding constants nearly quantitatively for atoms not directly coupled to the GHO linking atoms. As an application to a realistic protein, carbon chemical shifts are calculated for the retinal chromophore in visual rhodopsin.     

New synthesis of 3-trifluoromethylpyrroles by condensation of mesoionic 4-trifluoroacetyl-1,3-oxazolium-5-olates with phosphorus ylides

Mesoionic 4-trifluoroacetyl-1,3-oxazolium-5-olates (1), obtained from the reaction of N-acyl-N-alkylglycines with trifluoroacetic anhydride, react with phosphorus ylides to give β-trifluoromethylpyrroles (2) in good yields. The novel ring transformations of 1 into 2 occur via an initial attack of the ylide anions on the C-2 position of the ring.     

Structures and spin states of mono- and dinuclear iron(II) complexes of imidazole-4-carbaldehyde azine and its derivatives

Mononuclear [Fe(H₂L^R)₂]X₂ (R = H, 2-Me, 5-Me, 2-Et-5-Me; X = ClO₄, BF₄) and dinuclear [Fe₂(H₂L^R)₃]X₄ complexes containing imidazole-4-carbaldehyde azine (H₂L^H) and its derivatives prepared by condensation of 4-formylimidazole, 2-methyl- or 5-methyl-4-formylimidazole, or 2-ethyl-4-methyl-5-formylimidazole, with hydrazine in a 2:1 mole ratio in methanol, were prepared and their magnetostructural relationships were studied. In the mononuclear complexes, H₂L^R acts as an unsymmetrical tridentate ligand with two imidazole nitrogen atoms and one azine nitrogen atom, while in the dinuclear complexes, H₂L^R acts as a dinucleating ligand employing four nitrogen atoms to form a triple helicate structure. At room temperature, [Fe₂(H₂L^H)₃](ClO₄)₄ and [Fe₂(H₂L^2-Me)₃](ClO₄)₄ were in the high-spin (HS) and low-spin (LS) states, respectively. The results are in accordance with the ligand field strength of H₂L^2-Me with electron-donating methyl groups being stronger than H₂L^H, with the order of the ligand field strengths being H₂L^2-Me > H₂L^H. However, in the mononuclear [Fe(H₂L^H)₂](ClO₄)₂ and [Fe(H₂L^2-Me)₂](ClO₄)₂ complexes, a different order of ligand field strengths, H₂L^H > H₂L^2-Me, was observed because [Fe(H₂L^H)₂](ClO₄)₂ was in the LS state while [Fe(H₂L^2-Me)₂](ClO₄)₂ was in the HS state at room temperature. X-ray structural studies revealed that the interligand steric repulsion between a methyl group of an H₂L^2-Me ligand and the other ligand in [Fe(H₂L^2-Me)₂](ClO₄)₂ is responsible for the observed change in the spin state. The same is true for [Fe(H₂L^2-Et-5-Me)₂](ClO₄)₂, while [Fe(H₂L^5-Me)₂](ClO₄)₂ does not involve such a steric congestion and stays in the LS state over the temperature range 5–300 K. Two kinds of crystals (polymorphs) were isolated for [Fe₂(H₂L^H)₃](BF₄)₄ and [Fe₂(H₂L^2-Et-5-Me)₃](ClO₄)₄, and they exhibited different magnetic behaviors.     

Nucleosome Assembly Alters the Accessibility of the Antitumor Agent Duocarmycin B2 to Duplex DNA

To evaluate the reactivity of antitumor agents in a nucleosome architecture, we conducted in vitro studies to assess the alkylation level of duocarmycin B₂ on nucleosomes with core and linker DNA using sequencing gel electrophoresis. Our results suggested that the alkylating efficiencies of duocarmycin B₂ were significantly decreased in core DNA and increased at the histone‐free linker DNA sites when compared with naked DNA conditions. Our finding that nucleosome assembly alters the accessibility of duocarmycin B₂ to duplex DNA could advance its design as an antitumor agent.