Some reactions of diphosphenes and related species

Abstract

Some reactions of diphosphenes and the related species involving oxidation, reduction, alkylation, sulfurization, and ⁶η-coordination are described.     

Structure and bioactivity of a trisnorditerpenoid and a diterpenoid from an Okinawan soft coral, Cespitularia sp.

An Okinawan soft coral Cespitularia sp. has proven to be a good source of cytotoxic metabolites having a carbon skeleton of the seco-type variety of xenicin. This soft coral yielded alcyonolide, the major constituent, and other related compounds, all of which have proven to be cytotoxic. Reinvestigation of the cytotoxic ethyl acetate extracts of the coral yielded two new alcyonolide congeners, trisnorditerpenoid 1 and diterpenoid 2, possessing the same carbon skeleton. Their structures were elucidated by a detailed analysis of spectroscopic data (1D, 2D NMR, and MS). Metabolites 1 and 2 showed cytotoxicity against HCT116 cells (IC₅₀ 6.04 and 47.0 μM, respectively) and a dose dependent, anti-inflammatory effect in LPS/IFN-γ-stimulated inflammatory RAW 264.7 macrophage cells.     

Revisiting the Polymerization of Diphenylacetylenes with Tungsten(VI) Chloride and Tetraphenyltin: An Alternative Mechanism by a Metathesis Catalytic System

An alternative reaction mechanism of the polymerization of diphenylacetylelnes using a catalytic system composed of tungsten(VI) chloride and tetraphenyltin has been proposed through the optimization of reaction conditions and investigation of the effect of the electronic nature of diphenylacetylene monomers on the polymerizability. The detailed structures of the polymers have been suggested by mass spectrometric analysis of the obtained polymers and oligomers, which suggested that a phenyl group of tetraphenyltin has been introduced to an initiating end of the polymer chain. Mass spectrometric analysis also provided information about the termination processes of the polymerization. The experimental results strongly suggested that the polymerization of diphenylacetylenes using tungsten(VI) chloride and tetraphenyltin proceeds through a migratory insertion mechanism rather than the long‐accepted metathesis mechanism.     

Novel gas chromatography-mass spectrometry database for automatic identification and quantification of micropollutants

A novel gas chromatography-mass spectroscopy (GC-MS) database for identification and quantification of micropollutants in environmental and food samples is reported. GC retention times, calibration curves, and mass spectra of nearly 700 chemicals were registered in the database, and the GC retention times of registered chemicals in actual samples were predicted from the retention times of n-alkanes measured before sample analysis. Differences between predicted and actual retention times were less than 3 s, an accuracy that is nearly identical to that obtained by analysis of standard substances. After the retention times were predicted, a calibration file for the GC-MS instrument was created from the predicted retention times, calibration curves, and mass spectra of the registered chemicals. With the resulting calibration file, automated identification of all the chemicals in actual samples was possible without the use of standards, and the identification method was as reliable as conventional methods. When the GC inlet, column, and tuning conditions were adjusted using GC-MS performance check standards, relative standard deviations of 20% or less for determination values could be obtained. More than 90% of the chemicals in the database could be detected at a sensitivity sufficient for all practical purposes (100 pg or less). Because each chemical in the database, to which new substances can easily be added, can be determined in 1 h, micropollutants in samples can be analyzed efficiently and inexpensively.     

Preparation and physical properties of flame retardant acrylic resin containing nano-sized aluminum hydroxide

Poly(methylmethacrylate) (PMMA) shows high strength and transparency but is a flammable material. In this study, the surface of aluminum hydroxide was modified with methacrylate containing phosphoric acid moieties before dispersion in MMA, and organic-inorganic nano-hybrid materials were obtained by bulk polymerization in the presence of the surface-modified aluminum hydroxide. The resulting hybrid materials retained the high transparency of PMMA, with transparency values similar to that of pure PMMA. Moreover, the flame resistance of the hybrid materials was improved in comparison with that of pure PMMA, with depression of the horizontal burning rate becoming a maximum at an inorganic content of 3 wt%. These results suggest that the use of aluminum hydroxide surface-modified with phosphoric acid groups is an efficient method for obtaining good performance fire-resistant polymer materials.     

Surface analysis of environmental samples

The surface chemical compositions of solid samples from environmental sources can differ from bulk or average compositions. The processes of adsorption, desorption, precipitation, dissolution, reaction etc., change the surface composition thereby affecting the surface chemistry. Accordingly, surface analytical information is important for the understanding of environmental chemistry involving solid surfaces. Analysis of environmental solid samples with their complex composition is a challenge to rapidly developing surface analytical techniques.     

Intracellular transport of single-headed molecular motors KIF1A

Motivated by experiments on single-headed kinesin KIF1A, we develop a model of intracellular transport by interacting molecular motors. It captures explicitly not only the effects of adenosine triphosphate hydrolysis, but also the ratchet mechanism which drives individual motors. Our model accounts for the experimentally observed single-molecule properties in the low-density limit and also predicts a phase diagram that shows the influence of hydrolysis and Langmuir kinetics on the collective spatiotemporal organization of the motors. Finally, we provide experimental evidence for the existence of domain walls in our in vitro experiment with fluorescently labeled KIF1A.     

Euler-lagrange correspondence of cellular automaton for traffic-flow models

We propose a Euler-Lagrange transformation for cellular automata (CA) by developing new explicit transformation formulas. This transformation is done in the fully discrete level of variables, and corresponds to the well-known continuous version of it which appears in continuous mechanics such as fluid dynamics and plasma physics. Applying this method to the traffic problem, we have obtained the Lagrange representation of a traffic model, and also succeeded in clarifying the relation between different types of traffic models. It is shown that the Burgers CA, which is a corresponding CA of the continuous Burgers equation, plays a central role in considering this relation.     

Use of radio-gas chromatography and tritium label to optimize derivatization procedures

A sensitive determination of gas chromatographic peak yields by a new radio-gas chromatograph equipped with a synchronized accumulating radioisotope detector is described. Peak yields could be easily determined by the radio-gas chromatograph using [3H]hexadecane or [3H]androstenedione as a standard substance. The usefulness of the determination of peak yields was demonstrated by optimizing the derivatization conditions of 6-keto-prostaglandin F1 alpha.