Base-catalyzed homo-brook rearrangement of diastereomeric 7,8- epoxy-7(trimethylsilyl)-6-tridecanols

Semi-quantitative rate measurement of base-catalyzed 1,3-migration of a silyl group from carbon to oxygen (homo-Brook rearrangement) using four diastereomerically pure title compounds revealed that the aptitude for the migration depends markedly on the configurational environment around the trimethylsilyl group of the respective substrate.     

The Universal Vassiliev Invariant for the Lie Superalgebra

We compute the universal weight system for Vassiliev coming from the Lie superalgebra applying the construction of [13]. This weight system is a function from the space of chord diagrams to the center Z of the universal enveloping algebra of , and we find a combinatorial expression for it in terms of the standard generators of Z. The resulting knot invariants generalize the Alexander-Conway polynomial. Received: 4 July 1996 / Accepted: 21 August 1996     

IR-Untersuchungen an Polyurethan-Harnstoff-Block-Elastomeren

Ohne Zusammenfassung     

Photoelectron spectroscopic study of simple hydrogen-bonded dimers. I. Supersonic nozzle beam photoelectron spectrometer and the formic-acid dimer

In this paper we describe several characteristics of our supersonic nozzle beam photoelectron spectrometer recently constructed for studying hydrogen-bonded dimers in the gas phase by HeI (58.4 nm) radiation. Using this photoelectron apparatus, we have reinvestigated the HeI photoelectron spectrum of the formic-acid dimer (HCOOH)₂ which is well known as a fairly strong doubly hydrogen-bonded dimer. It was found that the (HCOOH)₂ spectrum deduced here from the spectrum of the monomer—dimer mixture considerably differs from that reported by Carnovale et al. in the region beyond 16.5 eV. New spectral assignments are given for four ionization bands beyond 16.5 eV. It is also indicated that the lower bound of the dissociation energy of (HCOOH)₂⁺ is estimated to be 1.0 ± 0.1 eV from the threshold of the dimer band (11.0 eV) obtained in this experiment. This value is considerably smaller than the value of 1.7 ± 0.2 eV recently reported for the water dimer cation (H₂O)₂⁺.     

Infrared intensities of ion-water interactions in aqueous electrolyte solutions

The i.r. absorption intensities have been measured of the fundamental vibrations of water molecules in metal halide aqueous solutions. Pseudo-isosbestic points were observed in the regions of both the stretching and bending vibrations and interpreted in terms of two states of water molecules in the solutions. The intensities of the stretching vibrations of water molecules coordinated to the dissolved ions have been estimated. The intensities become stronger in the order, Li⁺ > Na⁺ > K⁺ for the cations and F^- > Cl^- > Br^- > I^- for the anions. These orders are consistent with the strengths of the ion-water interactions, which are related to the dynamical behavior of the water molecules in the primary hydration shell.