Chiral discrimination of β‐3‐homo‐amino acids using the kinetic method

Chiral discrimination of seven enantiomeric pairs of β‐3‐homo‐amino acids was studied by using the kinetic method and trimeric metal‐bound complexes, with natural and unnatural α‐amino acids as chiral reference compounds and divalent metal ions (Cu²⁺ and Ni²⁺) as the center ions. The β‐3‐homo‐amino acids were selected for this study because, first of all, chiral discrimination of β‐amino acids has not been extensively studied by mass spectrometry. Moreover, these β‐3‐homo‐amino acids studied have different aromatic side chains. Thus, the emphasis was to study the effect of the side chain (electron density of the phenyl ring, as well as the difference between phenyl and benzyl side chains) for the chiral discrimination. The results showed that by the proper choice of a metal ion and a chiral reference compound, all seven enantiomeric pairs of β‐3‐homo‐amino acids could be differentiated. Moreover, it was noted that the β‐3‐homo‐amino acids with benzyl side chains provided higher enantioselectivity than the corresponding phenyl ones. However, increasing or decreasing the electron density of the aromatic ring by different substituents in both the phenyl and benzyl side chains had practically no role for chiral discrimination of β‐3‐homo‐amino acids studied. When copper was used as the central metal, the phenyl side chain containing reference molecules (S)‐2‐amino‐2‐phenylacetic acid (L ‐Phg) and (S)‐2‐amino‐2‐(4‐hydroxyphenyl)‐acetic acid (L ‐4′‐OHPhg) gave rise to an additional copper‐reduced dimeric fragment ion, [Cu^I(ref)(A)]⁺. The inclusion of this ion improved noticeably the enantioselectivity values obtained. Copyright © 2010 John Wiley & Sons, Ltd.     

Thermo‐ and Acid‐Responsive Photochromic Spironaphthoxazine‐Containing Organogelators

A series of photochromic spironaphthoxazine derivatives has been designed, synthesized, and characterized by using ¹H NMR spectroscopy, FAB mass spectrometry, and elemental analysis. Their photophysical and photochromic behavior have been investigated. Two of the compounds (G¹²‐en‐SA‐SO and G¹⁶‐en‐SA‐SO) have been shown to be capable of forming stable thermoreversible organogels in organic solvents, tested by the “stable‐to‐inversion of a test tube” method. Addition of p‐toluenesulfonic acid was found to induce the formation of stable organogels at concentrations below that of the critical gelation concentration (c.g.c.), with a concomitant change in color from colorless to purple. Transmission electron microscopy and scanning electron microscopy of the xerogels showed typical fibrous structures in the micrometer scale. The activation parameters for the bleaching reaction of G⁸‐en‐SA‐SO in the solution state and G¹⁶‐en‐SA‐SO in the gel state have been determined in ethanol through kinetic studies at various temperatures. The results showed that the rate of the bleaching reaction in the gel state was much slower than that in the solution state.     

Ultra-short distributed feedback fiber laser with sub-kilohertz linewidth for sensing applications

A low-noise, ultra-short linear-cavity distributed feedback fiber laser (DFB-FL) with extremely narrow linewidth is presented. The FL has a total length of 17 mm, which is, to our knowledge, the shortest DFB-FL being reported. It has a measured linewidth of merely 250 Hz without active stabilization. It has a polarization beat frequency of 101 MHz, which is several times lower than that of most FLs. The relaxation oscillation frequency and relative peak are 110 kHz and −76.5 dB/Hz, respectively. The FL exhibited low-noise characteristics, with an intensity noise of −107 dB/Hz at 1 MHz. Due to low dopant concentration of the EDF and low splice loss with ordinary single-mode fibers, the net insertion loss amounts to only 0.45 dB. Such low pump power loss greatly enhances the capability of multiplexing a large number of FL sensors. Thus, these ultra-short DFB-FLs open up new opportunities for the development of compact-sized point sensor array systems for large-scale high sensitivity sensing applications.     

Towards a superstatistical SU(2) Yang-Mills EoS

We study an SU(2) lattice gauge field system on a 10⁴ symmetric and on a 10³ × 2 asymmetric lattice in order to learn about the equation of state.     

On the invariant faces associated with a cone-preserving map

For an nonnegative matrix , an isomorphism is obtained between the lattice of initial subsets (of ) for and the lattice of -invariant faces of the nonnegative orthant . Motivated by this isomorphism, we generalize some of the known combinatorial spectral results on a nonnegative matrix that are given in terms of its classes to results for a cone-preserving map on a polyhedral cone, formulated in terms of its invariant faces. In particular, we obtain the following extension of the famous Rothblum index theorem for a nonnegative matrix: If leaves invariant a polyhedral cone , then for each distinguished eigenvalue of for , there is a chain of distinct -invariant join-irreducible faces of , each containing in its relative interior a generalized eigenvector of corresponding to (referred to as semi-distinguished -invariant faces associated with ), where is the maximal order of distinguished generalized eigenvectors of corresponding to , but there is no such chain with more than members. We introduce the important new concepts of semi-distinguished -invariant faces, and of spectral pairs of faces associated with a cone-preserving map, and obtain several properties of a cone-preserving map that mostly involve these two concepts, when the underlying cone is polyhedral, perfect, or strictly convex and/or smooth, or is the cone of all real polynomials of degree not exceeding that are nonnegative on a closed interval. Plentiful illustrative examples are provided. Some open problems are posed at the end.

     

On families of quadratic surfaces having fixed intersections with two hyperplanes

We investigate families of quadrics all of which have the same intersection with two given hyperplanes. The cases when the two hyperplanes are parallel and when they are nonparallel are discussed. We show that these families can be described with only one parameter and describe how the quadrics are transformed as the parameter changes. This research was motivated by an application in mixed integer conic optimization. In that application, we aimed to characterize the convex hull of the union of the intersections of an ellipsoid with two half-spaces arising from the imposition of a linear disjunction.     

Effect of atmospheric pressure variations on the <Superscript>222</Superscript>Rn activity concentration in the air of a wine cellar

We have measured the variation of atmospheric pressure and of ²²²Rn activity concentration in the air of a wine cellar with an AlphaGAURD type ionization chamber radon monitor. We have found that the ²²²Rn activity concentration varies inversely with pressure. To explain this behavior we have done model calculations. We have compared the results of model calculations with the results of experimental measurements, and we have found that the model is capable to reproduce some part of the variation of ²²²Rn activity concentration.