Heterogeneous continuous flow synthetic system using cyclohexane-based multiphase electrolyte solutions

The discovery that supporting electrolytes can be effectively confined in typical organic solvents in a c-Hex-based multiphase electrolyte solution has led to the development of a novel heterogeneous continuous flow synthetic system. PTFE fiber functions as a separation filter that can efficiently isolate the c-Hex phase from multiphase electrolyte solutions. This system has demonstrated both electrochemical solvating and carbon-carbon bond forming reactions. Hydrophobic substrates can be introduced into the reactor as c-Hex solutions, which are then electrochemically transformed into the target hydrophobic products that pass through the PTFE fiber as c-Hex solutions.     

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.     

Metallic conductivity and ferromagnetic interaction of iron(III) d spins in the needle crystals of (ethylenedithiotetrathiafulvalenoquinone-1,3-dithiolemethide)(2).FeBr(4) salt

The 2:1 charge-transfer (CT) salts (1(2).FeBr(4) and 1(2).GaBr(4)) of ethylenedithiotetrathiafulvalenoquinone-1,3-dithiolemethide (1) with FeBr(4)(-) and GaBr(4)(-) counteranions were obtained as needle crystals, whose structures are almost the same as each other. The 1 molecules form a one dimensionally stacked column with alternation of their molecular axis direction, while the counteranions are aligned in parallel with the 1-stacked columns with the direction of their distorted-tetrahedral geometry maintained. The room-temperature electrical conductivities measured on the single crystals of 1(2).FeBr(4) and 1(2).GaBr(4) were 4.6 and 2.1 S cm(-1), respectively. From the temperature dependences of their electrical conductivities in both cases the electrical conducting properties were metallic between ca. 170 and 300 K, but below ca. 170 K converted to be semiconducting and continued till 5 K, although the activation energies are very small (4-10 meV). For 1(2).FeBr(4) very weak and antiferromagnetic interaction occurred between the d spins of FeBr(4)(-) ions in the temperature range of ca. 1-300 K. However, below ca. 15 K the ferromagnetic interaction was reversely preferential possibly by participation of the pi spin of 1.     

Beta-replacement reaction of serine-O-carbonate derivatives with thiols catalyzed by a pyridoxal model having an ionophore side-chain

Serine-O-carbonate derivatives, including peptides having a serine-O-carbonate residue at the N-terminal position, are catalytically transformed into S-substituted cysteine derivatives employing the pyridoxal model having an ionophore function in the presence of Li+; this is the first artificial model mimicking cystathionine Beta-synthase.     

Formation of the first monoanion and dianion of stannole

The first syntheses of mono- and dianions of stannole were accomplished by transmetallation or reduction of the novel bi(1,1-stannole).     

Self-written waveguides in photopolymerizable resins

We study the optically induced growth and interaction of self-written waveguides in a photopolymerizable resin. We investigate experimentally how the interaction depends on the mutual coherence and the relative power of the input beams and suggest an improved analytical model that describes the growth of single waveguides and the main features of their interaction in photosensitive materials.     

Luminescence and conduction charge in thin-film electroluminescent devices

The luminescence and conduction currents of a doubly-insulated thin-film electroluminescent device were studied under various excitation conditions. The conduction current waveform was calculated numerically from the luminescence waveform. It was composed of two components: a fast transient component j_fc, which rises and decays rapidly when a pulse is applied, and a dc-like component j_dc, which maintains a constant level during the duration of pulse. The ratio of these components varied considerably with applied voltage. Both the slow response of luminescence to voltage change and the change in j_fc when the excitation conditions were changed from repetitive pulses to a single pulse suggest an accumulation of charges inside the electroluminescence layer. This accumulation causes a space charge effect which explains the dominance of j_fc in the high-brightness region. The fact that luminescence intensity in this region is not related to the amplitude of individual pulses, but rather to the average amplitude of the pulse train also indicates that the space-charge-induced internal electric field is the main factor in accelerating the carriers which excite the luminescence centers. It was found that the two conduction current components showed similar characteristics in singly-insulated devices.