Synthesis of Substituted Tricyclo[5.3.1.04,9]undecan‐2,6‐dione from 4,4‐Disubstituted Cyclohexanone Enamines and Methacryloyl Chloride

Morpholine enamines 4‐acetyl‐4‐methyl‐1‐morpholinocyclohexene 4a, 4‐acetyl‐4‐phenyl‐1‐morpholinocyclohexene 4b, and 4‐acetyl‐4‐isopropenyl‐1‐morpholinocyclohexene 4c react with methacryloyl chloride to give 1,7‐dimethyl‐4(N‐morpholino) tricyclo[5.3.1.0^4,9]undecan‐2,6‐dione 9a , 1‐phenyl‐7‐methyl‐4(N‐morpholino) tricyclo[5.3.1.0^4,9]undecan‐2,6‐dione 9b , and 1‐ispropenyl‐7‐methyl‐4(N‐morpholino) tricyclo[5.3.1.0^4,9]undecan‐2,6‐dione 9c respectively, along with the corresponding substituted adamandane‐2,4‐diones.     

Spectroscopic and theoretical studies of optically active porphyrin dimers: a system uninterpretable by exciton coupling theory.

The electronic excited states of a meso-meso beta-beta doubly linked bis-porphyrin are comprehensively investigated by measuring its circular dichroism (CD) and magnetic circular dichroism (MCD) spectra. The observed spectroscopic properties are rationalized by DFT calculations. The frontier molecular orbitals (MOs) are constructed by the linear combinations of the constituent monomers' four MOs. Comparison of a theoretical CD spectrum based on time-dependent DFT (TDDFT) with the experimental spectra resulted in the assignment of the helical conformation of the dimer. This assignment is contrary to the previous assignment based on the point-dipole approximation (exciton coupling theory).     

Characterization of amorphous hydrogenated carbon formed by low-pressure inductively coupled plasma enhanced chemical vapor deposition using multiple low-inductance antenna units

Three-dimensional plasma enhanced chemical vapor deposition (CVD) of hydrogenated amorphous carbon (a-C:H) has been demonstrated using a new type high-density volumetric plasma source with multiple low-inductance antenna system. The plasma density in the volume of phi 200 mm x 100 mm is 5.1 x 10(10) cm(-3) within +/-5% in the lateral directions and 5.2 x 10(10)cm(-3) within +/-10% in the axial direction for argon plasma under the pressure of 0.1 Pa and the total power as low as 400 W. The uniformity of the thickness and refractive index is within +/-3.5% and +/-1%, respectively, for the a-C:H films deposited on the substrates placed on the six side walls, the top of the phi 60 mm x 80 mm hexagonal substrate holder in the pure toluene plasma under the pressure is as low as 0.04 Pa, and the total power is as low as 300 W. It is also found that precisely controlled ion bombardment by pulse biasing led to the explicit observation in Raman and IR spectra of the transition from polymer-like structure to diamond-like structure accompanied by dehydrogenation due to ion bombardment. Moreover, it is also concluded that the pulse biasing technique is effective for stress reduction without a significant degradation of hardness. The stress of 0.6 GPa and the hardness of 15 GPa have been obtained for 2.0 microm thick films deposited with the optimized deposition conditions. The films are durable for the tribology test with a high load of 20 N up to more than 20,000 cycles, showing the specific wear rate and the friction coefficient were 1.2 x 10(-7) mm3/Nm and 0.04, respectively.     

On the Nature of Functional Differentiation: The Role of Self-Organization with Constraints

The focus of this article is the self-organization of neural systems under constraints. In 2016, we proposed a theory for self-organization with constraints to clarify the neural mechanism of functional differentiation. As a typical application of the theory, we developed evolutionary reservoir computers that exhibit functional differentiation of neurons. Regarding the self-organized structure of neural systems, Warren McCulloch described the neural networks of the brain as being “heterarchical”, rather than hierarchical, in structure. Unlike the fixed boundary conditions in conventional self-organization theory, where stationary phenomena are the target for study, the neural networks of the brain change their functional structure via synaptic learning and neural differentiation to exhibit specific functions, thereby adapting to nonstationary environmental changes. Thus, the neural network structure is altered dynamically among possible network structures. We refer to such changes as a dynamic heterarchy. Through the dynamic changes of the network structure under constraints, such as physical, chemical, and informational factors, which act on the whole system, neural systems realize functional differentiation or functional parcellation. Based on the computation results of our model for functional differentiation, we propose hypotheses on the neuronal mechanism of functional differentiation. Finally, using the Kolmogorov–Arnold–Sprecher superposition theorem, which can be realized by a layered deep neural network, we propose a possible scenario of functional (including cell) differentiation.     

Techniques for realizing practical application of sulfur cathodes in future Li-ion batteries

The development of lithium-sulfur batteries is associated with many problems. These problems include polysulfide dissolution, the shuttle phenomenon, the low electric and ionic conductivity of S, and the volume change that occurs during charge and discharge. In this review, various elemental techniques for overcoming these problems are summarized from the standpoints of the supporting materials. These techniques include preventing polysulfide dissolution from the cathodes through physical and chemical adsorption on the supporting materials, the use of electrolytes that do not dissolve polysulfides via the coordination of Li⁺ and solvents, and the use of ion-exchange polymers to permeate Li⁺ selectively. The following approaches to enable practical applications of S cathodes in future Li-ion batteries are introduced: the utilization of Li-free anode materials, such as C and Si; the use of Li₂S cathodes, which are prepared via a pre-lithiation process; and increasing the areal capacity of the S cathode by using a suitable current collector such as Al foam, thus providing a large amount of space for Li⁺ to migrate and the electron-conductive path. The utilization of an Al foam current collector is one of the promising approaches to creating a cost-effective Li-ion battery owing to the established mass production of Al foam for use in NiMH batteries; such Li-ion battery can achieve an unprecedentedly high areal capacity of 21.9 mAh cm^?2. Owing to the resulting areal capacity, the possibility of developing a lithium-sulfur battery with an energy density greater than 200 Wh kg^?1 has been demonstrated. Consequently, the combination of these approaches, as introduced in this review, would help create a bright, sustainable society.     

A survey of metabolic changes in potato leaves by NMR‐based metabolic profiling in relation to resistance to late blight disease under field conditions

Non‐targeted nuclear magnetic resonance (NMR)‐based metabolic profiling was applied to potato leaves to survey metabolic changes associated with late blight resistance under field conditions. Potato plants were grown in an experimental field, and the compound leaves with no visible symptoms were collected from 20 cultivars/lines at two sampling time points: (i) the time of initial presentation of symptoms in susceptible cultivars and (ii) 12 days before this initiation. ¹H NMR spectra of the foliar metabolites soluble in deuterium oxide‐ or methanol‐d₄‐based buffers were measured and used for multivariate analysis. Principal component analysis for six cultivars at symptom initiation showed a class separation corresponding to their levels of late blight resistance. This separation was primarily explained by higher levels of malic acid, methanol, and rutin and a lower level of sucrose in the resistant cultivars than in the susceptible ones. Partial least squares regression revealed that the levels of these metabolites were strongly associated with the disease severity measured in this study under field conditions. These associations were observed only for the leaves harvested at the symptom initiation stage, but not for those collected 12 days beforehand. Subsequently, a simple, alternative enzymatic assay for l ‐malic acid was used to estimate late blight resistance, as a model for applying the potential metabolic marker obtained. This study demonstrated the potential of metabolomics for field‐grown plants in combination with targeted methods for quantifying marker levels, moving towards marker‐assisted screening of new cultivars with durable late blight resistance. Copyright © 2016 John Wiley & Sons, Ltd.     

First total synthesis of artepillin C established by o,o'-diprenylation of p-halophenols in water

We have demonstrated that prenylation of p-halophenols was dependent on the solvent effect and succeeded in o,o'-diprenylation of p-halophenols in water. Following the Mizoroki-Heck coupling of the diprenyl-p-iodophenol 3c with methyl acrylate and then hydrolysis, we first synthesized artepillin C [3-(4-hydroxy-3,5-di(3-methyl-2-butenyl)phenyl)-2(E)-propenoic acid] (1), which is a biologically active constituent of propolis. These reactions may be applicable to the synthesis of various useful natural products such as 2,4,6-trisubstituted phenol derivatives.     

Identification of a Single Phosphorylation Site Within Octopus Rhodopsin

Abstract— Light-dependent phosphorylation of rhodopsin (Rho) is a first step in the desensitization of the signaling state of the receptor during vertebrate and invertebrate visual transduction. We found that only ³⁵⁸Ser of the photoac-tivated octopus Rho (oRho*) was phosphorylated by octopus rhodopsin kinase (oRK). Tryptic truncation of the C-terminal PPQGY repeats of oRho that follow the phosphorylation region did not influence spectral or G-protein activation properties of oRho but abolished phos phorylation. Despite significant structural differences between oRK and mammalian RK, these results provide i further evidence of the importance of singly phosphorylated species of Rho* in the generation of arrestin binding sites.     

Electrochemistry in ultrahigh vacuum: underpotential deposition of Al on polycrystalline W and Au from room temperature AlCl(3)/1-ethyl-3-methylimidazolium chloride melts

The voltammetric characteristics of polycrystalline Au and W electrodes cleaned (thermal annealing at 1100 K) and characterized (Auger electron spectroscopy) in ultrahigh vacuum (UHV) have been examined in ultrapure AlCl(3)/1-ethyl-3-methylimidazolium chloride (EtMeImCl) melts in UHV. These experiments were performed using a custom-designed transfer system that allows for the all-Al electrochemical cell to be filled with EtMeImCl in an auxiliary UHV chamber and later transferred under UHV to the main UHV chamber that houses the Auger electron spectrometer. The results obtained for the underpotential (UPD) and bulk deposition of Al on Au were found to be very similar to those reported in the literature for measurements carried out under 1 atm of an inert gas in a glovebox. For the far more reactive W surfaces, voltammetric features ascribed to the stripping of underpotential-deposited Al could be observed following a single scan from 1.0 V vs Al(3+)/Al to a potential negative enough for bulk deposition of Al to ensue. This behavior is unlike that reported in the literature for experiments performed in a glovebox, which required either extensive potential cycling in the Al bulk deposition and stripping region or excursions to potentials positive enough for chlorine evolution to ensue for Al UPD features to be clearly discerned. These observations open new prospects for fundamental electrochemical studies of well-characterized, highly reactive metals, including single crystals, in a variety of low vapor pressure ionic liquids.