One‐Step Versus Multistep Equilibrium of Carbazole‐Bridged Dinuclear Zinc(II) Complex Formation: Metal‐Assisted π‐Association and ‐Dissociation Processes

This work demonstrates a selection criteria that determines whether molecular assembly occurs through a one‐step or stepwise manner in ligand‐bridged dinuclear zinc(II) (Zn²⁺) complex formation, which is associated with the π stacking of building blocks. The building blocks of carbazole ligands ( L¹ and L⁴ ) that contain two imidazole moieties at the 3,6‐positions form 4:2 complexes (i.e., [ L ]₄?(Zn²⁺)₂) at a molar ratio of 0.50 ([Zn²⁺]/[ L ]₀=0.50), thereby providing π stacking between the carbazole ligands. At the molar ratio of 0.67 ([Zn²⁺]/[ L ]₀=0.67), the 4:2 complexes change to 3:2 complexes (i.e., [ L ]₃?(Zn²⁺)₂) with no π‐stacked carbazole unit. In contrast, when the imidazole groups in L¹ are replaced with benzoimidazole groups ( L³ ), L³ also yields the 4:2 complex [( L³ )₄?(Zn²⁺)₂] at a molar ratio of 0.50. However, there is no structural transition from ( L³ )₄?(Zn²⁺)₂ to other complex species above a molar ratio of 0.50. Similarly, when two imidazole groups are introduced into the carbazole ring at 2,7‐positions ( L⁵ ), L⁵ also gives the 4:2 complex [( L⁵ )₄?(Zn²⁺)₂] that shows no structural transition to other complex species at a higher molar ratio.     

Observation of two-hole states at high excitation energy in (p,t) reactions

Bumps of two-hole states at high excitation energies were observed systematically in the triton spectra from (p, t) reactions with 52 MeV protons on nuclei in a broad range of masses. The cross sections of the bumps are almost equal for various targets with the same deep major shells. These cross sections vary discontinuously with variation of the corresponding deep major shell. About 20 to 50 % of the total expected strength is observed experimentally, if the bumps are assumed to arise from two-neutron pickup from the deep major shells. The centres of gravity of the bumps are located at excitation energies of about 7 to 9 MeV in all cases. On the other hand, the widths of the bumps change from about 3 MeV for ⁶⁶Zn to about 9 MeV for ²³⁰Th.     

In Vivo Laser Tomographic Imaging of Mouse Leg by Coherent Detection Imaging Method

The coherent detection imaging (CDI) technique based on the optical heterodyne detection method enables selective filtering of the directional coherent retaining emergent photons from biological tissues with a highly scattering nature. Therefore, the CDI can acquire on-axis information in the transillumination mode and use the same data-acquisition protocol and reconstruction algorithm as those in X-ray computed tomography (CT). Although the CDI-based laser CT cannot image thick subjects such as the head and chest, it can delineate subjects with a thickness up to several cm at a spatial resolution of sub-millimeters. We are planning to apply the technique to early diagnosis of rheumatoid arthritis (RA). Here, we performed an experiment using mice to confirm the feasibility. We compared in vivo CT images at the level of ankle joints of two mice, one normal and the other with collagen induced arthritis (CIA) as an RA model, and demonstrated that there occur significant discrepancies between the two distributions of image intensities, i.e., reconstructed scattering coefficients in each region of interest (ROI) prepared. We suggest that combining the morphological information with the quantitative information can be effective for early diagnosis of bone diseases and disorders such as rheumatoid arthritis.     

Surface pattern formation on soft polymer substrate through photo‐initiated graft polymerization

Techniques for large‐area pattern formation on polymeric substrates are important for fabricating a large variety of functional devices, such as flexible electronics, tunable optical devices, adhesives, and so on. The present study demonstrates a method for pattern formation on poly(dimethylsiloxane) that involves grafting methacrylate polymers through photo‐initiated polymerization. The influence of substrate stiffness and monomers type on pattern formation was investigated. Firstly, the stiffness of the substrate was found to affect the topology of the patterns produced. The gap width of convex regions of the pattern was enlarged with decreasing stiffness. It was found that the gap width trended in a manner that was consistent with previous reports, but in this study, relatively large gap widths were observed compared with those from previous studies. Secondly, it was revealed that the solubility of the monomer in the poly(dimethylsiloxane) precursor was the dominant factor in determining whether or not pattern formation occurred. When using insoluble monomers (glycidyl methacrylate and benzyl methacrylate), characteristic patterns were observed. It is speculated that intermolecular attractive forces between the grafted polymers induce lateral aggregation on the substrate, resulting in buckling instability of the grafted polymer layer caused by a mismatch in the equilibrium between the grafted polymer layer and the substrate. Copyright © 2017 John Wiley & Sons, Ltd.     

Self‐Discriminating Termination of Chiral Supramolecular Polymerization: Tuning the Length of Nanofibers

Directing the supramolecular polymerization towards a preferred type of organization is extremely important in the design of functional soft materials. Proposed herein is a simple methodology to tune the length and optical chirality of supramolecular polymers formed from a chiral bichromophoric binaphthalene by the control of enantiomeric excess (ee). The enantiopure compound gave thin fibers longer than a few microns, while the racemic mixture favored the formation of nanoparticles. The thermodynamic study unveils that the heterochiral assembly gets preference over the homochiral assembly. The stronger heterochiral binding over homochiral one terminated the elongation of fibrous assembly, thus leading to a control over the length of fibers in the nonracemic mixtures. The supramolecular polymerization driven by π–π interactions highlights the effect of the geometry of a twisted π‐core on this self‐sorting assembly.