Polymorphism of Supramolecular Charge-Transfer Complex Composed of 10,10′-dihydroxy-9,9′-biphenanthryl and p-benzoquinone

Charge-transfer (CT) complexes were prepared using racemic (rac)-10,10′-dihydroxy-9,9′-biphenanthryl, which has a large and highly π-conjugated phenanthrene ring, as the electron donor and p-benzoquinone as the electron acceptor. This CT system showed a polymorphism.     

Phase-transition phenomena of 0.8 microm superfluid 3He slab

We have investigated the transition phenomena of superfluid 3He in thin 0.8 microm slabs with a cw-NMR method. We found that, just below the phase-transition temperature, only the A phase appeared at any pressure. At lower temperatures, the phase transition to the B phase occurred between 0.3 and 2.74 MPa. We obtained a universal critical thickness delta as a function of pressure. When the reduced slab thickness, d/xi(T), is smaller than delta, only the A phase becomes stable.     

A note on the paper by Bugeaud and Laurent “Minoration effective de la distance p-adique entre puissances de nombres algébriques”

We shall make a slight improvement to a result of p-adic logarithms, which gives a nontrivial upper bound for the exponent of p dividing the Fermat quotient xp−1−1.     

Chain‐transfer reaction in the radical polymerization of di‐n‐butyl itaconate at high temperatures

Radical polymerizations of di‐n‐butyl itaconate were investigated. Unexpected resonances (C resonances) were observed in ¹³C NMR spectra of C?O of poly(di‐n‐butyl itaconate)s [poly(DBI)s] obtained at temperatures higher than 60 °C, although two kinds of carbonyl groups showed splittings due to triad tacticities in the spectra of polymers obtained at lower temperatures. The poly(DBI)s formed by the different kinds of initiators or formed in the presence of chain‐transfer agents showed hardly any changes in the intensities of the C resonances; this indicated that the C resonances were not due to the structures formed through initiating and terminating reactions. The poly(DBI)s obtained at different yields showed only a slight increase in the intensities of the C resonances with the yield, which suggested that the C resonances were not attributable to the intermolecular chain‐transfer reaction to the monomer and/or polymer. However, the intensities of the C resonances significantly increased with a decreasing feed monomer concentration; this suggested that intramolecular chain‐transfer reactions took place at high temperatures. Furthermore, a Cu complex‐catalyzed atom transfer radical polymerization mechanism was revealed to be effective for suppressing the intramolecular chain‐transfer reaction at 60 °C. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2415–2426, 2002     

Investigation of shear thinning behavior and microstructures of MWCNT/epoxy and CNF/epoxy suspensions under steady shear conditions

This report investigates the steady-state viscosities of multiwall carbon nanotube (MWCNT)/epoxy and carbon nanofiber (CNF)/epoxy suspensions with varying filler concentrations under different shear rates at various temperatures. In situ observation of filler networks suggests the build-up of shear induced MWCNT and CNF agglomerates at low shear rates, which correlates with the measured shear thinning behavior. The agglomeration process in MWCNT/epoxy suspensions is enhanced at lower shear rates in the case of higher temperatures, whereas, at high shear rates, both nano-fillers show good dispersion. Shear thinning behavior is observed for both types of fillers, and shear thinning exponential parameters are evaluated as a function of filler content. The shear thinning exponent increases in conjunction with increase in filler content, but it is found to saturate at a specific value, independently of filler material. Finally, the micromechanical elasticity-based analogy model is applied to the prediction of steady state shear viscosity of suspensions at higher shear rates with the assumption of complete dispersion and alignment of individual nano-fillers in suspensions. The predicted viscosities and the experimental data at higher shear rates are compared. The results conclude that fairly good agreement can be seen for the cases of CNF/epoxy suspensions at lower temperatures, whereas MWCNT/epoxy suspensions and CNF/epoxy suspensions at higher temperatures show discrepancy between the prediction and the experimental data.     

Modular Design of Domain Assembly in Porous Coordination Polymer Crystals via Reactivity-Directed Crystallization Process

The mesoscale design of domain assembly is crucial for controlling the bulk properties of solids. Herein, we propose a modular design of domain assembly in porous coordination polymer crystals via exquisite control of the kinetics of the crystal formation process. Employing precursors of comparable chemical reactivity affords the preparation of homogeneous solid-solution type crystals. Employing precursors of distinct chemical reactivity affords the preparation of heterogeneous phase separated crystals. We have utilized this reactivity-directed crystallization process for the facile synthesis of mesoscale architecture which are either solid-solution or phase-separated type crystals. This approach can be also adapted to ternary phase-separated type crystals from one-pot reaction. Phase-separated type frameworks possess unique gas adsorption properties that are not observed in single-phasic compounds. The results shed light on the importance of crystal formation kinetics for control of mesoscale domains in order to create porous solids with unique cooperative functionality.     

Resonance structure of dynamic fractional Stark ladders in laser-driven biased superlattices

The resonance structure of an electronic Floquet state in a dynamic fractional Stark ladder (DFSL) is examined based on the scattering theory applied to a dressed potential resulting from renormalization of a laser-electron interaction to an original potential. Here, the DFSL is realized in laser-driven biased superlattices with a fractional matching ratio of a Bloch frequency to a laser frequency. It is revealed that, in contrast to a conventional understanding, the DFSL resonance position and lifetime tend to redshift and shorten, respectively, with an increase in strength of the laser field, and further, these show irregular changes in a limited region of the strength. The underlying physics is discussed in detail.     

Low-temperature STM/STS studies on boron-doped (1 1 1) diamond films

We have performed scanning tunneling microscopy/spectroscopy (STM/STS) experiments on (1 1 1)-oriented epitaxial films of heavily boron-doped diamond (T_c∼5.4 K). We present that tunneling conductance spectra show temperature-dependent spatial variations. In the low-temperature region (T=0.47 K), the tunneling spectra do not show strong spatial dependence and a superconducting energy gap is observed independent of the surface morphology. In the high-temperature region (T=4.2 K), on the other hand, the tunneling conductance spectra show significant spatial dependence, indicating the inhomogeneous distribution of the superconducting property due to the distribution of boron atoms.