Stereochemical assignments of rubiaquinones A–C,naphthoquinone derivatives from Rubia yunnanensis

Three new naphthoquinone derivatives, rubiaquinones A–C (1–3), were isolated from the roots of Rubia yunnanensis. Rubiaquinone A (1) was a racemic naphthoquinone dimer consisting of a 1,4-dihydroxynaphthalene and a 4-hydroxy-1,2-naphthoquinone moieties with a 2-oxo-propyl group. Rubiaquinones B (2) and C (3) were structurally unique trimeric naphthoquinones with a racemic nature possessing one chiral axis and one chiral carbon in common. The planar structures of 1–3 were assigned by detailed spectroscopic analyses, and enantiomers of 1–3 were obtained by optical resolutions. The absolute configurations of (+)-1 and (?)-1 were elucidated by interpretation of the ECD spectra with the aid of TDDFT ECD calculation, while those of enantiomers obtained from 2 and 3 were assigned by analyses of the composite ECD spectra generated by summing appropriate ECD spectra of enantiomers. Rubiaquinone A (1) exhibited antimicrobial activity against Bacillus subtilis.     

Palladium-Catalyzed Asymmetric Synthesis of Silicon-Stereogenic 5,10-Dihydrophenazasilines via Enantioselective 1,5-Palladium Migration

A palladium-catalyzed asymmetric synthesis of silicon-stereogenic 5,10-dihydrophenazasilines was developed that proceeds via an unprecedented enantioselective 1,5-palladium migration. High enantioselectivity was achieved by employing 4,4′-bis(trimethylsilyl) (R)-Binap as the chiral ligand, and a series of mechanistic investigations were carried out to probe the catalytic cycle of this process.     

Numerical simulation of expansion/compression effect on shock induced turbulent flow

The interaction of homogeneous and isotropic turbulence with a shock wave is observed by solving the Reynolds-averaged Navier–Stokes equations with the k–? turbulence model. All turbulent fluctuations are measured at the period of expansion in the turbulent field and during compression by the reflected shock on turbulent field, and it is observed that the longitudinal turbulent velocity fluctuation is enhanced more at the period of expansion due to incident shock wave movement far from the turbulent field. The amplification of the turbulent kinetic energy (TKE) level in the shock/turbulence interaction depends on the shock wave strength and the longitudinal velocity difference across the shock wave. On decreasing the longitudinal velocity difference across the shock, the turbulent kinetic energy (TKE) level is less amplified. The TKE level is amplified by the factor of 1.5–1.8 in the shock/turbulence interaction where the dissipation rate of TKE decreases in all cases of shock/turbulence interaction. After the shock/turbulence interaction, the turbulent dissipative-length scale is amplified slightly and the amplification of the length scales decreases when increasing the shock strength. To cite this article: M.A. Jinnah, K. Takayama, C. R. Mecanique 333 (2005).     

Near-wall hindered Brownian diffusion of nanoparticles examined by three-dimensional ratiometric total internal reflection fluorescence microscopy (3-D R-TIRFM)

A three-dimensional nanoparticle tracking technique using ratiometric total internal reflection fluorescence microscopy (R-TIRFM) is presented to experimentally examine the classic theory on the near-wall hindered Brownian diffusive motion. An evanescent wave field from the total internal reflection of a 488-nm bandwidth argon-ion laser is used to provide a thin illumination field on the order of a few hundred nanometers from the wall. Fluorescence-coated polystyrene spheres of 200±20 nm diameter (specific gravity=1.05) are used as tracers and a novel ratiometric analysis of their images allows the determination of fully three-dimensional particle locations and velocities. The experimental results show good agreement with the lateral hindrance theory, but show discrepancies from the normal hindrance theory. It is conjectured that the discrepancies can be attributed to the additional hindering effects, including electrostatic and electro-osmotic interactions between the negatively charged tracer particles and the glass surface.

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Discovery of the Last Remaining Binary Platinum‐Group Pernitride RuN2

The last remaining marcasite‐type RuN₂ was successfully synthesized by direct chemical reaction between ruthenium and molecular nitrogen above the pressure of 32 GPa. For the first time, we found that Ru 4d is weakly hybridized with N 2p in the structure by using transmission electron microscopy equipped with electron‐energy‐loss spectroscopy. Our finding give important knowledge about the platinum‐group pernitride with respect to the chemical bonding between platinum‐group element and nitrogen.     

True Boundary for the Formation of Homoleptic Transition‐Metal Hydride Complexes

Despite many exploratory studies over the past several decades, the presently known transition metals that form homoleptic transition‐metal hydride complexes are limited to the Groups 7–12. Here we present evidence for the formation of Mg₃CrH₈, containing the first Group 6 hydride complex [CrH₇]^5?. Our theoretical calculations reveal that pentagonal‐bipyramidal H coordination allows the formation of σ‐bonds between H and Cr. The results are strongly supported by neutron diffraction and IR spectroscopic measurements. Given that the Group 3–5 elements favor ionic/metallic bonding with H, along with the current results, the true boundary for the formation of homoleptic transition‐metal hydride complexes should be between Group 5 and 6. As the H coordination number generally tends to increase with decreasing atomic number of transition metals, the revised boundary suggests high potential for further discovery of hydrogen‐rich materials that are of both technological and fundamental interest.     

Editorial

On behalf of the board of editors of the journal Shock Waves, I am pleased to give a brief overview of recent shock wave research activities. Shock waves are comprehensive representations of phenomena that appear in non-linear wave dynamics. Historically, shock wave phenomena started to be intensively investigated with the advent of high-speed gas-dynamics and these investigations are nowadays supported by the development of both super-computation and advanced experimental technology. Meanwhile, shock wave research has been expanding its scope to various interdisciplinary applications. A particular case is shock wave research in condensed matter which has a history as long as that of corresponding research in the field of gas-dynamics. However, although there are many dynamic similarities between shock wave motion in gases and condensed matter, the difference with respect to physical properties of both media was so dominating that for a long time research activities in these two fields have been regrettably rather isolated with only little communication between both scientific communities. Realizing that many methodologies are increasingly overlapping, it is now a good time for all of us - in the spirit of the advancement of science and technology - to try to look at shock wave phenomena in various media in order to understand their common features. The sheer variety of multi-faceted applications in shock wave research are reflected by an impressive number of international meetings such as the International Symposium on Shock Waves, the International Colloquium on the Dynamics of Explosions and Reactive Systems and the Conference on Shock Compression of Condensed Matter. In addition to these major international activities, many countries regularly organize national shock wave symposia. As a result of such activities the Asia-Pacific Shock Wave Research Society was established in 2003, whose wide membership includes researchers from the Asia-Pacific region and beyond. On the occasion of assuming the position as new Editor-in-Chief of the journal Shock Waves, I would like to thank my predecessor, Prof. Hans Grönig, for the many years of effort devoted to this task. I will continue to promote this journal as a major publishing platform that supports all international and interdisciplinary shock wave research activities and provides readers with an invaluable source of information.     

Delayed contrast enhancement of MRI in hypertrophic cardiomyopathy

Fibrotic lesions in the myocardium exhibit delayed contrast enhancement (DCE) on MR images. On the other hand, plexiform fibrosis is observed in hypertrophic cardiomyopathy (HCM), indicating an association of this condition with the pathogenesis of heart failure and arrhythmia. To examine the occurrence and extent of DCE and its relation to cardiac function and arrhythmia in HCM, we studied 59 patients with HCM who had undergone MRI. The relationship of DCE to cardiac function and arrhythmia was further investigated. DCE occurred in 45 (76.3%) of the 59 patients with HCM, with a high frequency of localization in regions, where the right ventricle is attached. As for the relationship of DCE to cardiac function, a significant decrease (P=0.007) in cardiac function was observed in the group in which 4 or more segments exhibited DCE, compared with the group in which DCE was observed in 3 or less segments. Regarding the relationship of DCE to arrhythmia, both the occurrence of DCE and the extent of DCE were significantly larger (p<0.05, p=0.026, respectively) in the group with VT. These results indicate that DCE may save to identify severe cases of HCM on the basis of cardiac function, arrhythmia, and pathophysiological aspects.     

Universality of the Mott–Ioffe–Regel limit in metals

The absence of resistivity saturation in many strongly correlated metals, including the high-temperature superconductors, is critically examined from the viewpoint of optical conductivity measurements. Coherent quasiparticle conductivity, in the form of a Drude peak centred at zero frequency, is found to disappear as the mean free path (at ω?=?0) becomes comparable with the interatomic spacing. This basic loss of coherence at the so-called Mott–Ioffe–Regel (MIR) limit suggests that the universality of the MIR criterion is preserved even in the presence of strong electron correlations. We argue that the shedding of spectral weight at low frequencies, induced by strong correlation effects, is the primary origin of the extended positive slope of the resistivity to high temperatures observed in all so-called ‘bad metals’. Moreover, in common with those metals which exhibit resistivity saturation at high temperatures, the scattering rate itself, as extracted from optical spectra, saturates at a value consistent with the MIR limit. We consider possible implications that this ceiling in the scattering rate may have for our understanding of transport within a wide variety of bad metals and suggest a better method for analysing their optical response.     

Multi-response analysis in the material characterisation of electrospun poly (lactic acid)/halloysite nanotube composite fibres based on Taguchi design of experiments: fibre diameter, non-intercalation and nucleation effects

Poly (lactic acid) (PLA)/halloysite nanotube (HNT) composite fibres were prepared by using a simple and versatile electrospinning technique. The systematic approach via Taguchi design of experiments (DoE) was implemented to investigate factorial effects of applied voltage, feed rate of solution, collector distance and HNT concentration on the fibre diameter, HNT non-intercalation and nucleation effects. The HNT intercalation level, composite fibre morphology, their associated fibre diameter and thermal properties were evaluated by means of X-ray diffraction (XRD) analysis, scanning electron microscopy (SEM), imaging analysis and differential scanning calorimetry (DSC), respectively. HNT non-intercalation phenomenon appears to be manifested as reflected by the minimal shift of XRD peaks for all electrospun PLA/HNT composite fibres. The smaller-fibre-diameter characteristic was found to be sequentially associated with the feed rate of solution, collector distance and applied voltage. The glass transition temperature (T _g) and melting temperature (T _m) are not highly affected by varying the material and electrospinning parameters. However, as the indicator of the nucleation effect, the crystallisation temperature (T _c) of PLA/HNT composite fibres is predominantly impacted by HNT concentration and applied voltage. It is evident that HNT’s nucleating agent role is confirmed when embedded with HNTs to accelerate the cold crystallisation of composite fibres. Taguchi DoE method has been found to be an effective approach to statistically optimise critical parameters used in electrospinning in order to effectively tailor the resulting physical features and thermal properties of PLA/HNT composite fibres.