Investigation into the GC separation of enantiomers on a trifluoroacetylated cyclodextrin. Part II: Effect of derivatization on stereoselectivity towards alcohols

Two acyl and three fluoroacyl derivatives of 32 chiral alcohols have been chromatographed on a GC column coated with octakis(2,6-di-O-n-pentyl-3-O-trifluoroacetyl)- γ-cyclodextrin. Significant differences were observed between the stereoselectivity obtained for the derivatives and that for the underivatized alcohols. Of the derivatives, only the fluoroacylated compounds were separated into enantiomers. Derivatization with fluoroacyl groups reversed the elution order for at least some of the analytes. Stereoselectivity towards simple 2- and 3-hydroxy alkanes and their fluoroacyl derivatives was highest for those alcohols with a four-carbon chain attached to the stereogenic center. For longer-chain fluoroacyl derivative groups stereoselectivity was higher for the 2- and 3-hydroxy alkanes. Differences in stereoselectivity towards alcohols with a methyl-branched alkane chain and their fluoroacyl derivatives was related to the distance between the methyl group and the hydroxyl or fluoroacyl groups. Different degrees of saturation in the carbon chain resulted in differences in stereoselectivity. Thermodynamic data calculated for a number of analytes suggest that the alcohols and trifluoroacetate derivatives are interacting with the stationary phase by similar mechanisms. The stereospecific interaction appears to have a hydrogen bonding or dipole–dipole contribution and some form of steric component, depending upon the shape and/or size of the solute.     

Ein in der reinen Zahlentheorie unbeweisbarer Satz über endliche Folgen von natürlichen Zahlen

Ohne Zusammenfassung     

Applications of electron spin resonance in the analytical chemistry of transition metal ions: Part I. Factors affecting the signal amplitude

An evaluation of the effect of modulation amplitude (M) and microwave power (P) on the peak-to-peak amplitude (A) of the first derivative e.s.r. signal of each of Mn²⁺, VO²⁺ and Cu²⁺ is described. It is shown that A is not directly proportional to M over all values of M and therefore for optimal precision of measurement, M should be kept constant. A varies with P^k, where k is a constant for a particular metal ion-solvent system. Limits of detection and concentration ranges of analytical utility are also reported.     

High-K quasiparticle structures in 159Er and 160Er

A series of new strongly coupled high-K, multi-quasiparticle structures have been observed in the light erbium transitional nuclei, ¹⁵⁹Er and ¹⁶⁰Er. The interpretation of these bands is discussed within the framework of the cranked shell model. These sequences, when taken together with the existing quasiparticle excitations, form a near complete set of low-lying, multi-quasiparticle structures on which a coherent series of aligned angular momentum, band crossing and blocking arguments can be based. The measured B(M1)/B(E2) ratios are compared with geometrical calculations to test the proposed configuration assignments. Received: 19 November 1997     

Limits on massive Majorana neutrinos from neutrinoless double β-decay

It is pointed out that present lower bounds on the lifetime for neutrinoless double β-decay put stringent upper limits on the mixing of a heavy Majorana neutrino (< a few MeV) with the dominantly coupled light neutrino of β-decay.     

The effect of stoichiometry on chain segment and ion mobility in partially polymerized epoxy systems

The temperature dependence of steady-shear viscosity and ionic conductivity were measured for a series of unreacted mixtures and partially cured, ungelled samples of diglycidyl ether of bisphenol-A (DGEBA) and an amine cross-linking agent, diamino diphenyl sulfone (DDS). Six stoichiometric ratios of epoxide groups to amine hydrogens were examined. Free volume expressions were used to model the temperature dependence of the conductivity and viscosity for the unreacted DGEBA-DDS mixtures. In addition, these expressions were combined to successfully correlate changes in viscosity and conductivity during the DGEBA-DDS polymerization prior to gelation. It also was demonstrated that the change in weight average molecular weight during polymerization could be interpreted from the dielectric data. Through studying variations in the stoichiometry, it was possible to examine the effects of changes in chemical structure and ion concentration on the fitted parameters in the free volume models. The inherent ion transport factor (ζ₀) was found to be inversely proportional to the concentration of ions in the test samples. The fractional free volume for segmental motion (B) was found to increase with an increase in the glass transition temperature and to be a function of the rigidity of the polymer. ©1995 John Wiley & Sons, Inc.     

A note on a boundary-layer collision on a rotating sphere

A recent study of the unsteady boundary layer near the equator of a spinning sphere provided strong numerical evidence that the solution develops a singularity a finite time after the motion is initiated. In this paper we reformulate and complete the asymptotic structure proposed to describe this singularity. It is then self-consistent and provides convincing evidence of the accuracy of the computations and of the existence of the singularity.

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Zusammenfassung Eine neuere Untersuchung über die nicht-stationäre Grenzschicht nahe am Äquator einer rotierenden Kugel ergab starke numerische Evidenz für das Auftreten einer Singularität in der Lösung nach einer endlichen Zeit, vom Beginn der Bewegung gerechnet. In dieser Arbeit wird die asymptotische Struktur zur Beschreibung der Singularität neu formuliert und ergänzt. Sie wird selbstkonsistent und gibt ein wichtiges Zeugnis für die Genauigkeit der Berechnungen und für die Existenz der Singularität.

     

New photoluminescence features of cinnabar (α-HgS) crystals grown by chemical vapor transport

We report new broad bands and narrow lines in the photoluminescence of cinnabar (α-HgS) crystals grown by chemical vapor transport. For exciting light, ?ω > Eg, our spectra resemble those due to other workers, however, for ?ω < Eg we observe a new broad luminescence band and two sharp features separated by ～ 18 meV.