(1,4,7,10-Tetraazacyclododecane) (diamine or alanine)-Cobalt(III) complexes

(1,4,7,10-Tetraazacyclododecane) [diamine or (S)-alanine]-cobalt(III) complexes [diamine = ethylenediamine, 2-(aminomethyl)pyridine, (R)-1,2-propanediamine, (R,R)-1,2-diaminocyclohexane, trimethylenediamine and 2-methyl-1,3-diaminopropane] are prepared and characterized spectroscopically. The ligand field transitions occur at lower energies than those of the corresponding tetraamine analogues. Severe distortions caused by the too small size of the cyclic ligand are one of the origins. The distortions also exert influence upon circular dichroism spectra.     

白烟灰的物相分析及酸浸脱砷工艺

白烟灰因其含有砷等有毒化合物,其安全堆存是冶金企业面临的难题。 对白烟灰进行物相分析是处理该烟灰,使其达到环保要求堆存的重要依据。 采用X射线光电子能谱(XPS)和X射线粉末衍射(XRD)研究了河南某企业白烟灰的物相组成及化学结合状态,确定其所含化学成分及元素含量。 结果表明,样品中元素As相对含量高达20.99%,其中11%以游离态As₂O₃形式存在,其余以PbAs₂O₆形式存在。 样品中还含有少量的Cu、Pb、Zn等金属及其氧化物。 根据被测样品物相组成,提出了一种氧化酸浸脱砷的方法,并确定了最佳脱砷工艺,在最佳工艺条件下,砷的浸出率高达97.1%,高于文献报道的砷的浸出率。     

Frontispiece: Square-Planar Anionic Pt0 Complexes

A T-shaped Pt⁰ complex with a diphosphine-borane (DPB) ligand was prepared. The Pt→B interaction enhances the electrophilicity of the metal and triggers the addition of Lewis bases to give the corresponding tetracoordinate complexes. For the first time, anionic Pt⁰ complexes are isolated and structurally authenticated. X-ray diffraction analyses show the anionic complexes [(DPB)PtX]⁻ (X=CN, Cl, Br, I) to be square-planar. The d¹⁰ configuration and Pt⁰ oxidation state of the metal were unambiguously established by X-ray photoelectron spectroscopy and DFT calculations. The coordination of Lewis acids as Z-type ligands is a powerful mean to stabilize elusive electron-rich metal complexes and achieve uncommon geometry.     

Wide-Range Color-Tunable Organic Phosphorescence Materials for Printable and Writable Security Inks

Organic materials with long-lived, color-tunable phosphorescence are potentially useful for optical recording, anti-counterfeiting, and bioimaging. Herein, we develop a series of novel host–guest organic phosphors allowing dynamic color tuning from the cyan (502 nm) to orange red (608 nm). Guest materials are employed to tune the phosphorescent color, while the host materials interact with the guest to activate the phosphorescence emission. These organic phosphors have an ultra-long lifetime of 0.7 s and a maximum phosphorescence efficiency of 18.2 %. Although color-tunable inks have already been developed using visible dyes, solution-processed security inks that are temperature dependent and display time-resolved printed images are unprecedented. This strategy can provide a crucial step towards the next-generation of security technologies for information handling.     

Enantio- and diastereoselective hetero-Diels-Alder reactions between 2-aza-3-silyloxy-1,3-butadienes and aldehydes catalyzed by chiral dirhodium(II) carboxamidates

The first catalytic asymmetric hetero-Diels-Alder reaction between 2-aza-3-silyloxy-1,3-butadienes and aldehydes is described. With dirhodium(II) tetrakis[N-benzene-fused-phthaloyl-(S)-piperidinonate], Rh(2)(S-BPTPI)(4), the cycloaddition reaction proceeded exclusively in an endo mode to give all-cis-substituted 1,3-oxazinan-4-ones in high yields with up to 98% ee.     

Combined NMR and quantum chemical studies on the interaction between trehalose and dienes relevant to the antioxidant function of trehalose

In a previous study (Oku, K.; Watanabe, H.; Kubota, M.; Fukuda, S.; Kurimoto, M.; Tujisaka, Y.; Komori, M.; Inoue, Y.; Sakurai, M. J. Am. Chem. Soc. 2003, 125, 12739), we investigated the mechanism of the antioxidant function of trehalose against unsaturated fatty acids (UFAs) and revealed that the key factor relevant to the function is the formation of OH...pi and CH...O hydrogen bonds between trehalose and the cis double bonds of the UFA. Here, we investigate whether such intriguing interactions also occur between this sugar and cis double bonds in other unsaturated compounds. For this purpose, we selected various diene compounds (1,3-butadiene, 1,3-pentadiene, 1,4-pentadiene, and 2,5-heptadiene) as interaction partners. All NMR experiments performed, including 1H-1H NOESY measurements, indicated that trehalose selectively interacts with the cis-olefin proton pair in the above diene with a 1:1 stoichiometry, and the C-3 (C-3') and C-6' (C-6) sites of the sugar are responsible for the interaction. Similar interactions were not observed for the mixtures of the diene and other saccharides (neotrehalose, kojibiose, nigerose, maltose, isomaltose, sucrose, maltitol, and sorbitol). Quantum chemical calculations revealed that the OH-3 and OH-6 groups bind to the olefin double bonds of the diene through OH...pi and CH...O types of hydrogen bonds, respectively, and the stabilization energy of the resulting complex is 5-6 kcal mol(-1). These results strongly support the above NMR results. Finally, the activation energies were calculated for the hydrogen abstraction reactions from the activated methylene group of heptadiene. In particular, when the reaction was initiated by a methyl radical, the activation energy was only 10 kcal mol(-1) for the free heptadiene, but on complexation with trehalose it drastically increased to ca. 40 kcal mol(-1). This indicates that trehalose has a significant depression effect on the oxidation of the diene compounds. These results strongly support the antioxidant mechanism deduced in the previous study and indicate that the formation of unique multiple hydrogen bonds between trehalose and cis-olefin bonds is rather a general event not confined to the case of UFA.     

Three-dimensional acoustic sound field reproduction based on hybrid combination of multiple parametric loudspeakers and electrodynamic subwoofer

Auditory Mixed Reality (MR) systems that reproduce Three-Dimensional (3-D) acoustic sound fields have recently become a research focus because the combination of visual and auditory MR systems can achieve a greater sense of presence than conventional visual MR systems. General auditory MR systems usually use a headphone-based system with a Head-Related Transfer Function (HRTF), which is a major system for reproducing 3-D acoustic sound fields. However, the localization accuracy of sound images with a HRTF depends on the individual. On the other hand, we have already proposed a system for reproducing a 3-D acoustic sound field with parametric loudspeakers instead of headphones. The 3-D acoustic sound field reproduced by this system has achieved a highly accurate localization of sound images. However, one problem is that it is difficult to reproduce lower frequency sounds using parametric loudspeakers, which causes a poorer sound quality. We tried to accomplish a greater sense of presence for 3-D acoustic sound fields based on a hybrid combination of an electrodynamic subwoofer and the parametric loudspeakers by improving the sound quality. Sound images were formed at the target location using the parametric loudspeakers, and a lower frequency sound was compensated for by using the electrodynamic subwoofer. Subjective evaluation experiments were conducted to verify the effectiveness of the proposed system. We confirmed the improved sound quality while maintaining a higher accuracy of sound image localization by using the proposed system. We also confirmed the optimum parameters of the proposed system to achieve a greater sense of presence.     

Active control of coaxial jet mixing with manipulation of primary vortical structures by arrayed micro flap actuators

Active mixing control of a methane/air isothermal coaxial jet was achieved using micro magnetic flap actuators arranged on the inner surface of the outer annular nozzle. The spatio-temporal evolution of vortical structures and the scalar mixing were studied through the particle image velocimetry and planar laser-induced fluorescence methods. In contrast to studies on jet control using acoustic forcing, the mechanical movement of the flap directly generated large-scale intense vortices. The mixing was enhanced significantly by the vortices formed in the inner shear layer, although the control input was given to the outer shear layer. It was found that the primary vortex rings dominated the near-field mixing, while streamwise vortices were responsible for the downstream mixing. It was also demonstrated that the radial range of the inner fuel transportation could be manipulated flexibly by adjusting the shedding interval of the vortices. Especially, the mixing was enhanced most significantly when the primary vortices were most densely populated near the nozzle exit at the control Strouhal number of unity.     

Accommodation mechanisms for grain boundary sliding as inferred from texture evolution during superplastic deformation

To gain insight into accommodation mechanisms for local stress concentrations produced by grain boundary sliding (GBS), we systematically examined texture evolution within a superplastic magnesium alloy undergoing deformation at a relatively low deformation temperature (at which basal slip is known to be the preferred slip system in magnesium). Although we did observe an overall weakening of the initial basal texture during superplastic deformation, we also observed within the interior of the specimen a convergent evolution that depends on loading direction. We attribute this texture evolution within the bulk to the competing effects of (a) orientation divergence due to grain rotation accompanied by GBS and (b) convergent evolution due to slip, which acts primarily as an accommodation mechanism for GBS. In contrast, at the near-surface, we found the initial orientation to be preserved, indicating that slip accommodation is less important near the surface than within the bulk.     

Stable triplex formation using the strong stacking effect of consecutive thionucleoside moieties

In this study, it was found that the arrangement of consecutive thiocarbonyl groups of s(2)T and m(5)s(2)C remarkably stabilized the pre-protonated form of the triplex, and that the stabilization of the pre-protonated form increased the pKa value of a cytosine derivative in the triplex.