STM studies on the reconstruction of the Ni2P (101̅0) surface

The surface structure of Ni₂P (101?0), a model for highly active hydrodesulfurization catalysts, was studied using scanning tunneling microscopy (STM) and low energy electron diffraction (LEED) in order to understand the reconstruction of the surface layers. Annealing at 573 K revealed a (1 × 1) LEED pattern which changed to a c(2 × 4) arrangement by further heating to 723 K. Atomic scale STM images were obtained for both the (1 × 1) and c(2 × 4) structures. Bright spots observed in the STM images were interpreted to be due to surface phosphorus atoms and this was supported by a density functional theory (DFT) simulation. Several possible models for the c(2 × 4) reconstructed structures were proposed including a P-dimer defect model, a missing-row model and a missing-row + added-row model. The last model gave the best explanation for the c(2 × 4)structure. The mechanism for the c(2 × 4) reconstruction on the Ni₂P (101?0) surface is discussed.     

High speed parallel synthesis of banana-shaped molecules and phase transition behaviour of 4-bromo-substituted derivatives

Novel derivative series of the well known bent-shaped P-n-O-PIMB liquid crystal mesogens, referred to as '4Br-P-n-O-PIMB', '4Cl-P-n-O-PIMB' and '5Cl-P-n-O-PIMB', having halogen atoms substituted on the phenyl ring in the central core, were synthesized by solution phase parallel synthesis based on a combinatorial approach. The mesomorphic behaviour and physical properties of all the new compounds were studied by means of optical microscopy, differential scanning calorimetry, X-ray and circular dichroism spectroscopy. We found interesting transitional behaviour for the 4Br-P-n-O-PIMB homologous series. The homologues with alkyl tails having carbon numbers of n=3-10, 12, 14 exhibit rather complicated mesomorphic behaviour, which is strongly sensitive to n. The chiral fluid smectic B2 phase with SmC_AP_A structure and unidentified smectic Bx phase were observed in the homologues with n=9, 10, 12, 14 and n=3-5, respectively. Interestingly, every member exhibits frustrated and/or helical ordered phases at low temperatures, designated as X1, X2, and X3 phases, which result from a spontaneous escape from a macroscopic polarization. The mesomorphic behaviour and mesophase structures differ remarkably from those of the parent P-n-O-PIMB homologues, suggesting that substitution of the halogen atoms at the central core essentially creates a particular interaction between molecules.     

Synthesis,Structures and Reactions of Polychalcogenadisilabicyclo[l.m.n]alkanes and Their Germanium Analogues

1,3-Bis[tris(trimethylsilyl)methyl]-2,4,5-trichalcogena-1,3-disilabicyclo[1.1.1]pentanes display unusual short bridgehead Si---Si distances despite the absence of formal Si—Si bonds, and chalcogen---chalcogen interactions are observed by nmr, X-ray analysis and electronic spectroscopy.     

High speed parallel synthesis of banana-shaped molecules and phase transition behaviour of 4-bromo-substituted derivatives

Novel derivative series of the well known bent-shaped P-n-O-PIMB liquid crystal mesogens, referred to as ‘4Br-P-n-O-PIMB’, ‘4Cl-P-n-O-PIMB’ and ‘5Cl-P-n-O-PIMB’, having halogen atoms substituted on the phenyl ring in the central core, were synthesized by solution phase parallel synthesis based on a combinatorial approach. The mesomorphic behaviour and physical properties of all the new compounds were studied by means of optical microscopy, differential scanning calorimetry, X-ray and circular dichroism spectroscopy. We found interesting transitional behaviour for the 4Br-P-n-O-PIMB homologous series. The homologues with alkyl tails having carbon numbers of n=3–10, 12, 14 exhibit rather complicated mesomorphic behaviour, which is strongly sensitive to n. The chiral fluid smectic B2 phase with SmC_AP_A structure and unidentified smectic Bx phase were observed in the homologues with n=9, 10, 12, 14 and n=3–5, respectively. Interestingly, every member exhibits frustrated and/or helical ordered phases at low temperatures, designated as X1, X2, and X3 phases, which result from a spontaneous escape from a macroscopic polarization. The mesomorphic behaviour and mesophase structures differ remarkably from those of the parent P-n-O-PIMB homologues, suggesting that substitution of the halogen atoms at the central core essentially creates a particular interaction between molecules.     

Multilayer Structure Photovoltaic Cells

The optical and electrical characteristics of heterojunction organic photovoltaic cells consisting of tin–phthalocyanine as a p-type semiconductor and fullerene as an n-type semiconductor were studied using multiple-layer structures incorporating two hetero-junctions. In order to prevent formation of a reverse heterojunction, an ultra-thin layer of Au clusters was set between dual heterojunctions. The power conversion efficiencies of the cells were evaluated and the efficiency of the cell with two incorporated heterojunctions was found to be 4.5 times greater than that of a single hetero-junction. By using surface plasmon polaritons, the power conversion efficiency of an Al/C⋐70/SnPc/Au cell was enhanced and increased by a factor of 3.     

Menzerath’s Law in the Syntax of Languages Compared with Random Sentences

The Menzerath law is considered to show an aspect of the complexity underlying natural language. This law suggests that, for a linguistic unit, the size (y) of a linguistic construct decreases as the number (x) of constructs in the unit increases. This article investigates this property syntactically, with x as the number of constituents modifying the main predicate of a sentence and y as the size of those constituents in terms of the number of words. Following previous articles that demonstrated that the Menzerath property held for dependency corpora, such as in Czech and Ukrainian, this article first examines how well the property applies across languages by using the entire Universal Dependency dataset ver. 2.3, including 76 languages over 129 corpora and the Penn Treebank (PTB). The results show that the law holds reasonably well for x>2. Then, for comparison, the property is investigated with syntactically randomized sentences generated from the PTB. These results show that the property is almost reproducible even from simple random data. Further analysis of the property highlights more detailed characteristics of natural language.     

Size separation and size determination of liposomes

We developed a method for separating liposomes by size and determining their average diameters. Liposomes with different average diameters were separated on a monolithic silica capillary column, and the size of the liposomes corresponding to each peak was determined online with a dynamic light scattering detector coupled to the capillary liquid chromatography system. The calculated diameters for the separated liposomes were similar to the diameter values measured in batch mode. We demonstrate that this combination of a monolithic capillary column and light scattering detection could be used for size separation of liposomes and could provide more details about average diameters than batch-mode analysis.     

Chiral Brønsted acid-catalyzed asymmetric trisubstituted aziridine synthesis using α-diazoacyl oxazolidinones

Despite the remarkable advances in catalytic asymmetric aziridinations over the past decades, establishing a general procedure for the stereoselective synthesis of trisubstituted aziridines has remained an elusive goal. Chiral N-triflyl phosphoramide-catalyzed reactions of N-α-diazoacyl oxazolidinones and N-Boc imines were developed as a solution to this unmet challenge.     

Biosensor for L-phenylalanine based on the optical detection of NADH using a UV light emitting diode

A biosensor was developed for the detection of L-phenylalanine (Phe) and demonstrated for use in the diagnosis of phenylketonuria (PKU). It consists of L-phenylalanine dehydrogenase (L-PheDH) immobilized on a membrane, an ultraviolet light-emitting diode excitation system, and a photomultiplier tube. The L-PheDH was immobilized on a teflon membrane modified with 2-methacryloyloxyethyl phosphorylcholine and placed at the distal and of an optical fiber. The concentration of Phe was determined by immersing the sensor into a sample solution that also contained NAD⁺ and measurement of the fluorescence of the NADH produced by enzymatic reaction. Two L-PheDHs (from Thermoactinomyces intermedius and Sporosarcina sp.) were studied and compared. The fluorescence intensities of the biosensor are linearly related to the L-Phe concentrations in the range from 10 μmol L^?1 to 10 mmol L^?1. The sensor also was operated in the kinetic mode by differential determination of the slope of the signal within 2 min. The analytical range of the sensor is adequate for application in the genotypic diagnosis of PKU (diagnostic value >600 μmol L^?1). High sensitivity, good cost-benefit ratio, and low power consumption are typical features of this biosensing system that can can be applied to routine screening of newborn.

Spectroscopic and electrochemical studies on dinuclear mixed Ni(II)-chelates

Summary Solvatochromic dinuclear mixed Ni(II)-complexes with one 1,2-diacetyl-1,2-dibenzoyl-ethanate (dadb ^2–) and two tetramethylethylenediamine (tmen) ligands have been prepared and characterized. The tetraphenylborate is orange with molecules in bis-square-planar configuration and the nitrate is green with molecules in a bis-octahedral form. They have been investigated by UV, Vis, IR, and Far-IR spectroscopy as well as by electrochemical and magnetochemical methods. In strong donor solvents the nitrate ligands are replaced by solvent molecules. In weak donor solvents the anion-dependent equilibrium between the bis-planar, the bis-octahedral and an intermediate planar-octahedral form was investigated.Dedicated to Professor Dr. Edwin Hengge on occasion of his 60th birthday