A deuterium NMR investigation of polymorphism in benzene pizzanes

The polymorphism of three members of the homologous series hexa(p-alkoxyphenoxymethyl) benzene (benzene pizzanes) with 5, 6 and 7 carbons in the alkoxy chains and several of their deuteriated isotopomers have been investigated by differential scanning calorimetry, polarizing optical microscopy, X-ray diffraction and deuterium NMR spectroscopy. These homologues exhibit several solid phases and a high temperature M phase, which is isomorphic in the three homologues and whose nature is discussed. In the solid phases, the benzene cores of the molecules remain rigid, but the side chains are mobile, as reflected by rapid pi-flips of the benzene rings in the side chains. It is found that there are two types of such benzene rings, differing in the rates of flips. In the M phase the molecules undergo fast overall reorientation and the side chains are even more disordered than in the solid phases. However the X-ray measurements do not provide a clear cut determination as to whether this phase is crystalline or mesomorphic. Mixing of the benzene pizzanes with p-xylene yields lyomesophases, which appear to belong to the Dho class.     

Liquid chromatographic/mass spectrometric determination of biologically active alkaloids in extracts of Peschiera fuschiaefolia

Four alkaloids were isolated from an alcoholic extract of the bark from the stem of Peschiera fuschiaefolia. Two of these compounds, voacamine and voacamidine, are dimeric alkaloids which are thought to be responsible for the antimalarial activity of these extracts. The mass spectra and the response factors of these four compounds were obtained by liquid chromatography/mass spectrometry in the electrospray positive ionization mode. The concentrations of these alkaloids were measured in two different P. fuschiaefolia extracts. The ion chromatograms of the two extracts were compared on the basis of their [M + H](+) and [M + 2H](+2) ions characteristic of various alkaloids previously isolated from P. fuschiaefolia bark. The two extracts were found to differ mostly in the relative concentrations of the dimeric alkaloids.     

First example of conformational exchange in a natural taxane enolate

A detailed NMR study and full assignments of the (1)H- and (13)C-NMR spectral data for a novel enolate taxane isolated from Taxus canadensis needles is described. The structures of two stable conformers were established using a combination of 1D and 2D NMR techniques including (1)H, (1)H-COSY, gs-HMQC, gs-HMBC, NOESY and T-ROESY. Ab initio quantum mechanical calculations were performed on the B3LYP/6-31G* level of basis set to assist the NMR findings.     

Imperfect Inspection Games Over Time

We consider an inspection game played on a continuous finite time interval. The inspector wishes to detect a violation as soon as possible after it has been made by the operator. The loss to the inspector is assumed to be linear in the duration of the time elapsed between the violation and its detection. This paper is mostly an extension of Diamond's models for a single inspection, which includes the uncertainty aspect, by relaxing the assumption that the inspection is perfect. Here the inspection is imperfect; it has a Type One Error which means that the inspector may call a false alarm (with probability ), and a Type Two Error which means that the inspection may fail to detect (with probability ) a violation which did occur. In addition we will assume that the inspection is silent, i.e., the operator is unaware of the inspection when it takes place, unless the inspector calls a false alarm.     

Zero-sum sequential games with incomplete information

Repeated zero-sum two-person games of incomplete information on one side are considered. If the one-shot game is played sequentially, the informed player moving first, it is proved that the value of then-shot game is constant inn and is equal to the concavification of the game in which the informed player disregards his extra information. This is a strengthening ofAumann andMaschler's results for simultaneous games. Optimal strategies for both players are constructed explicitly.     

On the solid polymorphs of the discotic mesogen hexa-octanoyloxytriphenylene

In an earlier study by van Hecke et al., it was shown that the discotic mesogen hexa-octanoyloxytriphenylene (HAT8) crystallizes in four different solid forms, depending on the thermal history of the sample. The present study is an attempt to characterize three of these solids in more detail using X-ray, carbon-13 and deuterium NMR techniques. It is shown that van Hecke's modification IV is a metastable amorphic solid, while modifications III and II are highly ordered crystalline solids. Both are apparently monoclinic, but with different unit cell dimensions. In all solid phases, the triphenylene core is static on the NMR time-scale, but the side chains are disordered to different degrees in the different modifications. Further NMR studies on the discotic mesophase of HAT8 are also reported.     

On the solid polymorphs of the discotic mesogen hexa-octanoyloxytriphenylene

Abstract

In an earlier study by van Hecke et al., it was shown that the discotic mesogen hexa-octanoyloxytriphenylene (HAT8) crystallizes in four different solid forms, depending on the thermal history of the sample. The present study is an attempt to characterize three of these solids in more detail using X-ray, carbon-13 and deuterium NMR techniques. It is shown that van Hecke's modification IV is a metastable amorphic solid, while modifications III and II are highly ordered crystalline solids. Both are apparently monoclinic, but with different unit cell dimensions. In all solid phases, the triphenylene core is static on the NMR time-scale, but the side chains are disordered to different degrees in the different modifications. Further NMR studies on the discotic mesophase of HAT8 are also reported.     

Investigation of a nanostrip patch antenna in optical frequencies

This is the first report and investigation of a patch antenna in optical frequency range. Variety of plasmonic nanoantenna reported so far is good at enhancing the local field intensity of light by orders of magnitude. However, their far-field radiation efficiency is very poor. The proposed patch antenna emits a directional beam with high efficacy in addition to enhancing the intensity of near field. The nano-patch antenna (NPA) consists of a square patch of gold film of dimension 480 nm², placed on a substrate of dielectric constant \( \varepsilon_{\text{r}} \)  = 3.9 and thickness 150 nm with a ground plane of gold film of dimension 1,080 nm². The NPA resonates at 210 THz and has gain nearly 2 dB and radiation efficiency 45.18 %. The NPA might be useful in variety of applications such as optical communication, nano-photonics, biosensing, and spectroscopy.     

Direct Observation of the Ethyl Radical in the Pyrolysis of Ethane

We report the first direct detection of ethyl radical in the pyrolysis of ethane. Observation of this vital intermediate was made possible in this extremely reactive environment by the use of a microreactor coupled with synchrotron radiation and photoelectron photoion coincidence (PEPICO) spectroscopy, despite its short lifetime and low concentration. Together with ab-initio master equation-calculated rates and fully coupled computational fluid dynamics simulations, our measurements show that even under the low pressures and short residence times in our experiment, ethyl formation can only be explained by bimolecular reactions; the most important is the catalytic attack of ethane by H atoms, which are then regenerated by decomposition of the nascent ethyl radicals. Our results complete the observation of all hypothesized intermediates in this industrially important process and highlight the need for further studies under additional conditions using similar methods to improve existing models and optimize process chemistries.