ESR detection of wheat flour before and after irradiation

We revealed free radicals in wheat flour before and after gamma-ray irradiation and their thermal behavior during heat-treatment using electron spin resonance (ESR) spectroscopy. The ESR spectrum of wheat flour before irradiation consists of a sextet centered at g = 2.0 and a singlet signal at the same g-value position. The first one is attributable to a signal with hyperfine (hf) interactions of Mn2+ ion (hf constant: 7.4 mT). The second is originated from carbon-centered radical. Upon gamma-ray irradiation, however, a new signal with two triplet lines at the low and high field ends was detected in wheat flour on top of the Mn2+ sextet lines. We analyzed the triplet ESR lines as powder spectra (rhombic g-tensor symmetry) with nitrogen (14N) hyperfine interactions. This indicates that a new organic radical was induced in the conjugated protein portion of wheat flour by the gamma-ray irradiation. Intensity of the organic free radical at g = 2.0 detected in irradiated wheat flour increased monotonically by the thermal treatment. The analysis of the time-dependent evolution and decay process based on the theory of transient phenomena as well as the nonlinear least-squares numerical method provided a unique time constant for the radical evolution and decay in wheat flour during the heat-treatment.     

An ESR protocol based on relaxation phenomena of irradiated Japanese pepper

We found various free radicals in a commercially available pepper in Japan before and after irradiation using electron spin resonance (ESR) spectroscopy. The typical ESR spectrum of the pepper consists of a sextet centered at g = 2.0, a singlet at the same g-value and a singlet at g = 4.0. Upon gamma ray irradiation, a new pair of signals appeared in the pepper. The progressive saturation behavior (PSB) at various microwave power levels indicated quite different relaxation behaviors of those radicals. Namely, the peak intensity of the organic free radical component decreases in a monotonic fashion, whereas the Mn2+ and Fe3+ ESR signals substantially keep constant. This reflects the evidence of three independent radicals in the pepper before irradiation. The PSB of the pair peaks as induced by irradiation possessed quite different PSB from that of the free radical located at g = 2.0. We proposed a new protocol for the ESR detection of irradiated foods by the PSB method at different microwave power levels. This would call for a major modification of the CEN protocol in European Union.     

Numerical simulation of film coating process in a novel rotating fluidized bed

In this study, numerical simulation of film coating process in a novel rotating fluidized bed (RFB) was conducted by using a Discrete Element Method (DEM)-Computational Fluid Dynamics (CFD) coupling model. Particle movements and fluid motions in a centrifugal force field were simulated at three-dimensional cylindrical coordinate, and this model was applied to film coating process. Film coating process in a RFB was numerically analyzed by using a simplified assumption that a particle was coated only when a particle existed within a spray zone. The experiments were also conducted and uniformity of sprayed material was evaluated by investigating color difference of the coated particles. As a result of the numerical simulation, three-dimensional bubble movements and particle circulation could be well simulated. In addition, mass of the sprayed material on a single particle in a RFB could be visualized by using our proposed model. The relationship between distribution of the sprayed material and the coating time was also analyzed. Calculated mass distributions of the sprayed material could be expressed by a normal distribution function, showing qualitative good agreement with the previous studies. Effect of the operating parameters, such as gas velocity and centrifugal acceleration, on the uniformity of the sprayed material was also investigated by both numerical and experimental approaches. Comparison of the coating process in a RFB with that in a conventional fluidized bed was also conducted by the numerical simulation. The result showed that uniformity of the sprayed material was greatly improved in a RFB due to the much smaller circulation time.     

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.