Improvement of TiO2/Dye/Electrolyte Interface Conditions by Positional Change of Alkyl Chains in Modified Panchromatic Ru Complex Dyes

A series of panchromatic ruthenium sensitizers ( MJ sensitizers) with attached thiophene and phenyl units bearing alkyl chains was synthesized. A new synthetic route was used to examine all possible positions for the alkyl chains. The absorption spectra showed the sum of a ruthenium complex and peripheral organic chromophore units. The hypochromic effect and blueshift of the metal‐to‐ligand charge‐transfer band observed in the modified ruthenium sensitizers were suppressed by changing the positions of the alkyl chains on the attached thiophene ring. Changing only one alkyl chain also influenced the performance of dye‐sensitized solar cells. Ruthenium sensitizer MJ‐10 with bulky substituent harvests visible and near‐infrared light, and solar cells sensitized by MJ‐10 exhibit an efficiency of 9.1 % under 1 sun irradiation.     

Humidity-responsive thermal conduction properties of bacterial cellulose films

Cellulose - High hygroscopicity is an unavoidable feature of cellulose materials, and it is important for clarifying the humidity dependence of the target function toward precise utilization....     

Tailoring D‐Amino Acid Oxidase from the Pig Kidney to R‐Stereoselective Amine Oxidase and its Use in the Deracemization of α‐Methylbenzylamine

The deracemization of racemic amines to yield enantioenriched amines using S‐stereoselective amine oxidases (AOx) has recently been attracting attention. However, R‐stereoselective AOx that are suitable for deracemization have not yet been identified. An R‐stereoselective AOx was now evolved from porcine kidney D ‐amino acid oxidase (pkDAO) and subsequently use for the deracemization of racemic amines. The engineered pkDAO, which was obtained by directed evolution, displayed a markedly changed substrate specificity towards R amines. The mutant enzyme exhibited a high preference towards the substrate α‐methylbenzylamine and was used to synthesize the S amine through deracemization. The findings of this study indicate that further investigations on the structure–activity relationship of AOx are warranted and also provide a new method for biotransformations in organic synthesis.     

Distribution patterns of gamma radiation dose rate in the high background radiation area of Odisha,India

Journal of Radioanalytical and Nuclear Chemistry - Absorbed dose rates in air for 20 residential areas in Odisha were measured using a vehicle-mounted NaI(Tl) scintillation spectrometer. The...     

Organic electroluminescent and nonlinear optical materials

The multilayer electroluminescent(EL) devices composed of vacuum-sublimed organic films are discussed with the aims of achieving high luminance and proposing an optical micro-cavity. For the former purpose, requirements for confinements of carriers and excitons within the thin emissive layer are shown by taking accounts of ionization potentials, electron affinities and excitation energies in organic thin films. Concerning the interference effect of emitted light, we show the variation in the intensity of emission and a strongly directional light from the micro-cavity. Second-order nonlinear optical(NLO) films are designed by preparing noncentrosymmetric LB multilayers composed of an pyrazine derivative with large hyperpolarizability and arachidic acid. Third-order nonlinear optical(NLO) films are proposed by using polyarylenevinylene films. In order to fabricate excellent third-order nonlinear optical(NLO) films, highly oriented polyarylenevinylene films are prepared by using a LB technique.     

Electroreduction of tetra-coordinate phosphonium derivatives; one-pot transformation of triphenylphosphine oxide into triphenylphosphine

Electroreduction of triphenylphosphine dichloride in acetonitrile was performed successfully in an undivided cell fitted with an aluminium sacrificial anode and a platinum cathode, wherein Al³⁺, which was electrogenerated at the anode would react as a Lewis acid with triphenylphosphine dichloride to afford tetra-coordinate chlorotriphenylphosphonium species and subsequent two-electron reduction at the cathode would give triphenylphosphine. One-pot transformation of triphenylphosphine oxide to triphenylphosphine was achieved successfully by the treatment of triphenylphosphine oxide with oxalyl chloride and subsequent electroreduction. In a similar manner, some tetra-coordinate triphenylphosphonium species derived from triphenylphosphine oxide were reduced electrochemically to triphenylphosphine in moderate yields.     

Determination of kynurenic acid levels in rat brain microdialysis samples and changes in kynurenic acid levels induced by N‐acetylaspartic acid

The levels of kynurenic acid, an endogenous antagonist of α₇ nicotinic acetylcholine and N‐methyl‐D ‐aspartate receptors, were measured in microdialysis samples obtained from the prefrontal cortices of rats using column‐switching high‐performance liquid chromatography with fluorescence detection. When the perfusate was constantly infused at a rate of 1.0 μ/min, the in vitro recovery of kynurenic acid through the dialysis membrane was approximately 20.4%, and the precision was within 1.31%. Endogenous kynurenic acid in the microdialysis sample was clearly detected using column‐switching high‐performance liquid chromatography. As an application study, N‐acetyl‐L ‐aspartic acid, an endogenous metabolite and precursor of N‐acetyl‐L ‐aspartyl‐L ‐glutamic acid, which is an agonist of metabotropic glutamate receptors, was infused for 120 min through the microdialysis probe. The kynurenic acid level significantly increased during the infusion of N‐acetyl‐L ‐aspartic acid, suggesting that kynurenic acid might have some association with N‐acetyl‐L ‐aspartic acid in vivo. Copyright © 2009 John Wiley & Sons, Ltd.     

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.     

ToF atom-probe fim study of LaB6 single crystals

The field evaporation mass spectra of LaB₆ are obtained with time-of-flight atom-probe field ion microscope in vacuum and in the presence of hydrogen, nitrogen and oxygen. The spectra are consistent with a preferential chemisorption of these gases on boron sites.