New side chain liquid crystalline polymers: synthesis and thermal properties of side chain polyacrylates having segmented spacers

In order to acquire high mobility of a mesogenic group, we propose a new type of side chain liquid crystal polymer having segmented spacers, consisting of binary moieties of an oligo(ethylene oxide) segment and analkylene segment. Six kinds of polyacrylates having segmented spacers consisting of different lengths of an oligo(ethylene oxide) and an alkylene, and having 4'-cyanobiphenyl as a mesogenic group have been synthesized, and their thermal properties investigated. Some of these polyacrylates exhibit a mesophase and show an extremely low glass transition temperature compared with LC polyacrylates having ordinary alkylene spacers.     

Half‐Sandwich Iridium Complexes Bearing a Diprotic Glyoxime Ligand: Structural Diversity Induced by Reversible Deprotonation

Synthesis and deprotonation reactions of half‐sandwich iridium complexes bearing a vicinal dioxime ligand were studied. Treatment of [{Cp*IrCl(μ‐Cl)}₂] (Cp*=η⁵‐C₅Me₅) with dimethylglyoxime (LH₂) at an Ir:LH₂ ratio of 1:1 afforded the cationic dioxime iridium complex [Cp*IrCl(LH₂)]Cl ( 1 ). The chlorido complex 1 undergoes stepwise and reversible deprotonation with potassium carbonate to give the oxime–oximato complex [Cp*IrCl(LH)] ( 2 ) and the anionic dioximato(2?) complex K[Cp*IrCl(L)] ( 3 ) sequentially. Meanwhile, twofold deprotonation of the sulfato complex [Cp*Ir(SO₄)(LH₂)] ( 4 ) resulted in the formation of the oximato‐bridged dinuclear complex [{Cp*Ir(μ‐L)}₂] ( 5 ). X‐ray analyses disclosed their supramolecular structures with one‐dimensional infinite chain ( 1 and 2 ), hexagonal open channels ( 3 ), and a tetrameric rhomboid ( 4 ) featuring multiple intermolecular hydrogen bonds and electrostatic interactions.     

Effect of halogen atom on electron spin polarization studied by CIDEP,using halogen substituted aromatic acyl compounds

The reaction and spin dynamics of the photocleavage reaction of 2-chloro-2′-acetylnaphthalene were studied by time-resolved FT-EPR and transient absorption (TA) spectroscopy. The photocleavage reaction from both singlet and triplet states was observed by TA and EPR experiments, although the radical cleavage reaction in the excited triplet state is energetically unfavourable. This feature has been explained by the ionic cleavage reaction due to the electro-negativity of the chlorine atoms. The time-resolved FT-EPR spectra were similar to those observed in the bromine substituted compound, 2-BAN, reported in a previous paper. The origin of the electron spin polarization was assigned to the radical triplet pair mechanism (RTPM) and free radical pair mechanism (F-pair RPM) from analysis of the time profiles of the spin polarization.     

Mechanism of BPh3-Catalyzed N-Methylation of Amines with CO2 and Phenylsilane: Cooperative Activation of Hydrosilane

BPh₃ catalyzes the N-methylation of secondary amines and the C-methylenation (methylene-bridge formation between aromatic rings) of N,N-dimethylanilines or 1-methylindoles in the presence of CO₂ and PhSiH₃; these reactions proceed at 30–40 °C under solvent-free conditions. In contrast, B(C₆F₅)₃ shows little or no activity. ¹¹B NMR spectra suggested the generation of [HBPh₃]⁻. The detailed mechanism of the BPh₃-catalyzed N-methylation of N-methylaniline ( 1 ) with CO₂ and PhSiH₃ was studied by using DFT calculations. BPh₃ promotes the conversion of two substrates (N-methylaniline and CO₂) into a zwitterionic carbamate to give three-component species [Ph(Me)(H)N⁺CO₂⁻⋅⋅⋅BPh₃]. The carbamate and BPh₃ act as the nucleophile and Lewis acid, respectively, for the activation of PhSiH₃ to generate [HBPh₃]⁻, which is used to produce key CO₂-derived species, such as silyl formate and bis(silyl)acetal, essential for the N-methylation of 1 . DFT calculations also suggested other mechanisms involving water for the generation of [HBPh₃]⁻ species.     

The reductive repair of 1, 3-dhnethylthymine bromohydrin into 1, 3-dimethylthymine by 1, 5-dihydro-5-deazaflavin or 1, 4-dihydroquinoline

The reductive conversion of 1, 3-dimethylthymine bromohydrin into 1, 3-dimethylthymine by 10-ethyl-3-methyl-1, 5-dihydro-5-deazaflavin or 1-benzyl-3-carbamoyl-1, 4-dihydroquinoline has been achieved in the presence of trifluoroacetic acid.     

Whole-body counter surveys of over 2700 babies and small children in and around Fukushima Prefecture 33 to 49 months after the Fukushima Daiichi NPP accident

BABYSCAN, a whole-body counter (WBC) for small children was developed in 2013, and units have been installed at three hospitals in Fukushima Prefecture. Between December, 2013 and March, 2015, 2707 children between the ages of 0 and 11 have been scanned, and none had detectable levels of radioactive cesium. The minimum detectable activities (MDAs) for ¹³⁷Cs were ≤3.5 Bq kg⁻¹ for ages 0–1, decreasing to ≤2 Bq kg⁻¹ for ages 10–11. Including the ¹³⁴Cs contribution, these translate to a maximum committed effective dose of ∼16 µSv y⁻¹ even for newborn babies, and therefore the internal exposure risks can be considered negligibly small.Analysis of the questionnaire filled out by the parents of the scanned children regarding their families’ food and water consumption revealed that the majority of children residing in the town of Miharu regularly consume local or home-grown rice and vegetables, while in Minamisoma, a majority avoid tap water and produce from Fukushima. The data show, however, no correlation between consumption of locally produced food and water and the children’s body burdens.     

Time series-based bifurcation diagram reconstruction

We consider the problem of reconstructing bifurcation diagrams (BDs) of maps using time series. This study goes along the same line of ideas presented by Tokunaga et al. [Physica D 79 (1994) 348] and Tokuda et al. [Physica D 95 (1996) 380]. The aim is to reconstruct the BD of a dynamical system without the knowledge of its functional form and its dependence on the parameters. Instead, time series at different parameter values, assumed to be available, are used. A three-layer fully-connected neural network is employed in the approximation of the map. The task of the network is to learn the dynamics of the system as function of the parameters from the available time series. We determine a class of maps for which one can always find a linear subspace in the weight space of the network where the network’s bifurcation structure is qualitatively the same as the bifurcation structure of the map. We discuss a scheme in locating this subspace using the time series. We further discuss how to recognize time series generated by this class of maps. Finally, we propose an algorithm in reconstructing the BDs of this class of maps using predictor functions obtained by neural network. This algorithm is flexible so that other classes of predictors, apart from neural networks, can be used in the reconstruction.     

Reentrant excitation in an analog-digital hybrid circuit model of cardiac tissue

We propose an analog-digital hybrid circuit model of one-dimensional cardiac tissue with hardware implementation that allows us to perform real-time simulations of spatially conducting cardiac action potentials. Each active nodal compartment of the tissue model is designed using analog circuits and a dsPIC microcontroller, by which the time-dependent and time-independent nonlinear current-voltage relationships of six types of ion channel currents employed in the Luo-Rudy phase I (LR-I) model for a single mammalian cardiac ventricular cell can be reproduced quantitatively. Here, we perform real-time simulations of reentrant excitation conduction in a ring-shaped tissue model that includes eighty nodal compartments. In particular, we show that the hybrid tissue model can exhibit real-time dynamics for initiation of reentries induced by uni-directional block, as well as those for phase resetting that leads to annihilation of the reentry in response to impulsive current stimulations at appropriate nodes and timings. The dynamics of the hybrid model are comparable to those of a spatially distributed tissue model with LR-I compartments. Thus, it is conceivable that the hybrid model might be a useful tool for large scale simulations of cardiac tissue dynamics, as an alternative to numerical simulations, leading toward further understanding of the reentrant mechanisms.     

Photocleavage reaction of bromine substituted aromatic acyl compounds studied by CIDEP and transient absorption spectroscopy

The photocleavage of the CBr bond in bromoacetylnaphthalene is investigated by transient absorption and time resolved EPR spectroscopy. In the transient absorption of 2-bromo-2′-acetylnaphthalene, the absorption band observed at λ_max ~440 nm is assigned to the triplet state of the parent molecule. After decay of the triplet absorption, a long lived absorption band is observed at λ_max ~380 nm, which is assigned to naphthoylmethyl radical. The yield of this radical is not dependent on the concentration of oxygen even though the absorption band of the triplet state was quenched by addition of oxygen. Thus we conclude that the spin multiplicity of the precursor molecule is singlet. The CW time resolved EPR spectrum shows a typical E?/A CIDEP pattern of three hyperfine lines of the naphthoylmethyl radical. This result suggests some contribution from triplet precursor molecules. However, a careful analysis of the time profile of the CIDEP intensity observed by FT-EPR revealed that the polarization is generated from the radical pair mechanism (RPM) from the encountered pair of two free naphthoylmethyl radicals and the radical-triplet pair mechanism. RPM polarization by the geminate radical pair, formed by the Br atom and the naphthoylmethyl radical, is not observed. This fact indicates that large spin-orbit coupling (Δg and/or fast spin relaxation by g anisotropy) spoils the RPM polarization. The finding is in contrast to the recent observation of RPM polarization in the Cl cleavage reaction of 1-(chloromethyl)naphthalene.