Structure prediction and aromaticity of acenes and phenylenes series. A combination method between asymmetric Kekulé structures

The combination method between asymmetric Kekulé structures (CMAK) was expanded to the structure prediction of a series of acenes and phenylenes. The structures predicted by the CMAK correspond to those calculated by the ab initio molecular orbital (MO) and B3LYP density functional methods. The CMAK can characterize the structures. The aromaticity for the whole ring and each ring in the treated compounds was estimated by the index of deviation from aromaticity (IDA). The estimated aromaticity corresponds fairly well to the characterization of the structure predicted by the CMAK. The predicted structures of linear acenes reveal the aromaticity of the central ring and also explain its reactivity. The side ring in [n]phenacene shows high aromaticity. The critical difference in the structure and aromaticity for the central six‐membered ring of the isomers benzo[1,2:4,5]dicyclobutene and benzo[1,2:5,6]dicyclobutene was explained. Copyright © 2012 John Wiley & Sons, Ltd.     

A reversible near-infrared fluorescence probe for reactive oxygen species based on Te-rhodamine

We have designed and synthesized a reversible near-infrared (NIR) fluorescence probe, 2-Me TeR, for reactive oxygen species (ROS), utilizing the redox properties of the tellurium (Te) atom. 2-Me TeR is oxidized to fluorescent 2-Me TeOR by various ROS, while the generated 2-Me TeOR is quickly reduced in the presence of glutathione to regenerate 2-Me TeR. This redox-induced reversible NIR-fluorescence response of 2-Me TeR allowed us to detect the endogenous production of ROS and subsequent homeostatic recovery of the intracellular reductive environment in hydrogen peroxide-stimulated HL-60 cells. This probe is expected to be useful for monitoring the dynamics of ROS production continuously in vivo.     

Laser patterning and preferential orientation of two-dimensional planar β-BaB2O4 crystals on the glass surface

The laser-induced crystallization method is applied to pattern two-dimensional planar β-BaB₂O₄ crystals on the surface of Sm₂O₃–BaO–B₂O₃ glass. By scanning Yb:YVO₄ fiber lasers (wavelength: 1080 nm) continuously with a small step (0.5 μm) between laser irradiated areas, homogeneous planar β-BaB₂O₄ crystals are patterned successfully, and a preferential growth orientation of β-BaB₂O₄ crystals is confirmed from linearly polarized micro-Raman scattering spectrum and second harmonic intensity measurements. It is found that the crystal growth direction is perpendicular to the laser scanning direction. This relation, i.e., the perpendicular relation, is different from the behavior in discrete crystal line patterning, where the crystal growth direction is consistent with the laser scanning direction. The present study proposes the possibility of the control of crystal growth direction in laser-induced crystallization in glasses.     

Dynamic Deformation Behavior of a Golf Ball during Normal Impact

The normal impact between a golf ball and a rigid steel target was studied to examine ball deformation and the contact force during the impact. Using high-speed video images, the normal and tangential compression ratios of the ball were measured to analyze the ball deformation quantitatively. In addition, the inbound and rebound ball velocities, contact time, and coefficient of restitution were determined as basic parameters of the impact. As the inbound ball velocity increased, the maximum normal compression ratio increased while the maximum tangential compression ratio, contact time and coefficient of restitution decreased. The ball center displacements during the impact were measured to determine the ball center velocity and acceleration, and the contact force was calculated by the product of the mass and acceleration. The contact force increased almost linearly with the inbound ball velocity, and its relationship agreed well quantitatively with the results from a load-cell, and also agreed well qualitatively with Hertz contact theory.     

Heat and mass transfer characteristics of organic sorbent coated on heat transfer surface of a heat exchanger

This paper describes heat and mass transfer characteristics of organic sorbent coated on heat transfer surface of a fin-tube heat exchanger. The experiments in which the moist air was passed into the heat exchanger coated with sorption material were conducted under various conditions of air flow rate (0.5–1.0 m/s) and the temperature of brine (14–20°C) that was the heat transfer fluid to cool the air flow in the dehumidifying process. It is found that the sorption rate of vapor is affected by the air flow rate and the brine temperature. Meanwhile, the attempt of clarifying the sorption mechanism is also conducted. Finally the average mass transfer coefficient of the organic sorbent coated on heat transfer surface of a fin-tube heat exchanger is non-dimensionalzed as a function of Reynolds number and non-dimensional temperature, and it is found that the effect of non-dimensional temperature on them is larger than Reynolds number .     

Three dimensional freezing around a coolant-carrying tube

The 3-D freezing of water around a coolant carrying horizontal tube placed in an adiabatic rectangular cavity is investigated mainly by means of a numerical analysis. The results are not sensitive to the coolant flow velocity and the tube length, but are very responsive to the coolant inlet temperature and the initial water temperature. The numerical analysis predicts fairly experimental results without introducing a heat transfer coefficient.     

The reaction of fullerene C(60) with phthalazine: the mechanochemical solid-state reaction yielding a new C(60) dimer versus the liquid-phase reaction affording an open-cage fullerene.

The reaction of fullerene C(60) with phthalazine was studied both in solution and in the solid state using the high-speed vibration-milling technique. The reaction in solution gave open-cage fullerene derivative 1 in 44% yield by a one-pot reaction. In contrast, the solid-state reaction afforded dimeric derivative 2 as the sole product. Dimeric derivative 2 was found to undergo intramolecular [2 + 2] cycloaddtion between the two C(60) cages located in close proximity to give a new C(60) dimer 6 in quantitative yield. The structures of these new derivatives of C(60) were determined by spectroscopic methods, and the electrochemical behavior of 2 and 6 was also studied.     

The reaction of fullerene C(60) with 4,6-dimethyl-1,2,3-triazine: formation of an open-cage fullerene derivative.

A thermal reaction of fullerene C(60) with 4,6-dimethyl-1,2,3-triazine (4) in o-dichlorobenzene gave azacyclohexadiene-fused fullerene derivative 5, by the reaction with intermediate azete 11, and then, after flash chromatography over SiO(2), open-cage fullerene derivative 6 having an eight-membered ring orifice on the C(60) cage. Compound 6 is assumed to be formed via addition of diradical intermediate 13 to C(60). Compound 6 underwent a further photochemical reaction with singlet oxygen with the cleavage of one of the double bonds at the rim of the orifice to afford triketone derivative 8 having a 12-membered ring orifice.     

Formation of 1,2,4-trioxolanes via 9,10-dicyanoanthracene(DCA)-sensitized photo-oxygenation of 2,2-diaryl-3-(2,2-diarylvinyl)oxiranes

9,10-Dicyanoanthracene-sensitized photo-oxygenation of 2,2-diaryl-3-(2,2-diarylvinyl)oxiranes 3 in acetonitrile did not afford the corresponding 1,2,4-trioxepines 4, but 1,2,4-trioxolanes 7. The structural assignment of 7 was reported, and the mechanism of the formation of 7 was proposed.     

Phase diagram of the SrS–Ga2S3 system and its application to the single-crystal growth of SrGa2S4

Ce-doped SrGa₂S₄ compound is expected as a new host material of blue EL devices. However, the basic properties of bulk single crystals have not been fully clarified, since this compound has been mostly synthesized in the form of polycrystals or thin films. Here, we firstly present the pseudo-binary phase diagram of the SrS–Ga₂S₃ system constructed in accordance with our DTA data for single-crystal growth of SrGa₂S₄. It is shown that SrGa₂S₄ compound has a congruent melting point and a eutectic reaction in the side of excess of Ga₂S₃ concentration. On the basis of the phase diagram, single crystals of SrGa₂S₄ are grown using Ga₂S₃ as a self-flux in a horizontal Bridgman furnace. Colorless and transparent crystals having a typical size 2×2×2 mm³ are obtained.