The sphere-rod transition of micelles of dodecyldimethylammonium bromide in aqueous NaBr solutions,and the effects of counterion binding on the micelle size,shape and structure

Micelle size and shape of dodecyldimethylammonium bromide have been determined by measurement of light scattering from its aqueous NaBr solutions. In water and in the presence of NaBr up to 0.07 M, the Debye plots give straight lines with positive slopes, and spherical micelles having molecular weight less than 30 000 are formed. At higher NaBr concentrations, the Debye plots decrease with increasing micelle concentration, indicating the aggregation of the primary spherical micelles into larger secondary micelles. The molecular weight and the radius of gyration of the secondary micelles increase with increasing NaBr concentration, and the relation between molecular weight and radius of gyration suggests that they are rodlike and flexible. Linear logarithmic relations between micelle molecular weight and ionic strength hold for spherical and rodlike micelles, respectively, and the threshold concentration of NaBr for the sphere-rod transition is located at 0.07 M. The spherical micelle of dodecyldimethylammonium ions has a size more than 20 surfactant ions larger in NaBr solutions than in NaCl solutions, and their rodlike micelle has a shorter length in NaBr solutions than in NaCl solutions, when compared at an identical aggregation number, indicating 2 more surfactant ions in its cross-section.     

Changes of electrochemical responses of the bulk solution species by thermotropic permeability of liquid crystalline membranes coated on electrodes

Liquid crystalline/polymer composite membrane-coated electrodes were prepared by casting a 1,2-dichloroethane solution of N-(4-ethoxybenzylidene)-4′-n-butylaniline (EBBA) and polycarbonate (PC) on an electrode surface. The temperature-dependence of the permeability of the EBBA/PC composite membrane on electrodes to Fe(CN)^3?₆ ion as a solution-phase redox ion was investigated by means of hydrodynamic voltammetry at a rotating disk electrode. The permeability changed with temperature over the range of the crystalline-nematic-phase transition temperature of EBBA. It is demonstrated that the observed temperature-dependence of the permeability reflects the thermotropic properties of EBBA in the EBBA/PC composite membrane. Furthermore, the dependence of the limiting current of the steady-state current-potential curves for the reduction of Fe(CN)^—₆ at the EBBA/PC composite membrane-coated electrode upon the membrane thickness, the blend ratio of EBBA and PC and the concentration of Fe(CN)^3?₆ in a bulk solution was examined in order to understand the transport process of Fe(CN)^?3₆ through the EBBA/PC composite membrane from the membrane/solution interface to the electrode/membrane interface. The transport process of Fe(CN)^3?₆ within the membrane was found to obey Fick's Law.     

Analysis of labor productivity using large-scale data of firm’s financial statements

We investigated labor productivity distribution by analyzing large-scale financial statement data consisting of listed and unlisted Japanese firms to clarify the characteristics of the Japanese labor market. Both high and low productivity sides of the labor productivity distribution follows the power-law distribution. Large inequality in the low productivity side was observed only for the manufacturing sectors in Japan fiscal year (JFY) 1999 and observed for both the manufacturing and non-manufacturing sectors in JFY 2002. The decline in the Japanese GDP in JFY 1999 and JFY 2002 were coincided with the large inequality in the low productivity side of the distribution. A lower peak was found for all non-manufacturing sectors. This might be the origin of the low productivity of the non-manufacturing sectors reported in recent economic studies.     

InBr3-catalyzed reduction of ketones with a hydrosilane: deoxygenation of aromatic ketones and selective synthesis of secondary alcohols and symmetrical ethers from aliphatic ketones

An InBr₃-Et₃SiH reducing system was developed to selectively convert aliphatic ketones to a variety of secondary alcohols in moderate to good yields. An initial mixing of InBr₃ and PhSiH₃ was followed by the addition of aliphatic ketones and a solvent to afford the symmetrical ether derivatives.     

Proton magnetic resonance studies of quantum mechanical tunnelling of ammonium ions in several ammonium salts

Proton magnetic resonance spectra were measured at 1·8 K for the compounds NH₄Br, NH₄I, NH₄SCN, (NH₄)₂CrO₄, and NH₄NO₃. The observed derivative curves cannot be explained on the basis only of the dipolar interactions between protons in the NH₄ ⁺ ion held rigidly in the crystal lattices. We considered the effect of quantum mechanical tunnelling on the rotation of an NH₄ ⁺ ion about its C₃-axis and calculated the theoretical lineshapes for various assumed values of the tunnelling splitting constants. Comparison between experiment and theory is quite satisfactory, and the tunnelling splitting constants, Δ, in the librational ground state of the ammonium ion in these salts are determined. It is found that there is a linear relation between the Δ values and the potential barrier to reorientation.     

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.     

Synthesis of a Pentacene‐Type Silaborin via Double Dehydrogenative Cyclization of 1,4‐Diboryl‐2,5‐disilylbenzene

A new pentacene‐type silaborin, in which three benzene rings are bridged by silicon and boron atoms, has been synthesized and characterized by using NMR spectroscopy and X‐ray crystallographic analysis. The precursor, 1,4‐bis(dimesitylboryl)‐2,5‐bis(phenylsilyl)benzene ( 4 ), was prepared by stepwise introduction of a silyl group and a boryl group to a benzene ring starting from 1,4‐dibromobenzene. Double cyclization of 4 proceeds by a H‐Mes exchange and a B‐H/C‐H dehydrogenative condensation to afford pentacene‐type silaborin 5 . X‐ray crystal structure analysis reveals that 5 adopts a bent structure rather than a planar one. UV/Vis spectra and DFT calculations for 5 reveal a lowering of the LUMO energy level compared with corresponding anthracene‐type 3 .