Stereochemistry of protected ornithine side chains of gramicidin S derivatives: X-ray crystal structure of the bis-Boc-tetra-N-methyl derivative of gramicidin S

An X-ray crystallographic analysis of the bis-Ndelta-Boc-tetra-Nalpha-methyl derivative of gramicidin S, cyclo(-Val-MeOrn(Boc)-Leu-d-MePhe-Pro-)2, was undertaken successfully (R-factor = 0.088). As expected, the main chain adopts an antiparallel pleated beta-sheet conformation, but the pleated sheet is slightly twisted, and the sense of twisting is opposite to that found in the reported crystal structures of the gramicidin S-urea complex and the bis-Ndelta-(trichloroacetyl) and bis-Ndelta-(m-bromobenzoyl) derivatives of gramicidin S. In agreement with the observed resistance toward N-methylation, the urethane NH groups of the protected Orn side chains are hydrogen bonded to the carbonyl groups of the d-Phe residues. However, the side-chain-main-chain hydrogen bonding is in the i --> i - 3 mode, although hydrogen bonding in the i --> i + 2 mode was deduced from a 1H NMR study of protected gramicidin S derivatives and was actually found in the crystal structures of the diacylated gramicidin S.     

Equivariant surgery with middle dimensional singular sets. II: Equivariant framed cobordism invariance

Let be a finite group and let be a degree 1, -framed map such that and are simply connected, closed, oriented, smooth manifolds of dimension and such that the dimension of the singular set of the -space is at most . In the previous article, assuming is -connected, we defined the -equivariant surgery obstruction in a certain abelian group. There it was shown that if then is -framed cobordant to a homotopy equivalence . In the present article, we prove that the obstruction is a -framed cobordism invariant. Consequently, the -surgery obstruction is uniquely associated to above even if it is not -connected.

     

Synthesis and electrolytic polymerization of the ethylenedioxy-substituted terthiophene-fullerene dyad

[reaction: see text] Two derivatives of ethylenedioxy-substituted terthiophene-fullerene dyads were newly synthesized as the precursors for polythiophene having fullerene side chains. By electrolytic oxidation of dyad 1, the charm-bracelet type polythiophene, poly-1, was obtained as a purple film, which showed electrochemical activity, electrochromism, and photoelectronic response.     

Excimer emission of crystalline naphthalene

Excimer emission of naphthalene has been observed in microcrystals obtained by grinding single crystals mechanically and in evaporated films. The emission spectrum of the excimer in the microcrystal was equal to that in the evaporated film. The decay times of both excimer emissions were about 140 ns at 77 K. The temperature dependence of these decay times has been interpreted by the distribution of the excimers in thermal equilibrium between two vibrational states.     

A constitutive equation derived from the model of doi and edwards for concentrated polymer solutions and polymer melts

In deriving a constitutive equation from a molecular model of polymers in concentrated solutions and melts, Doi and Edwards used a mathematical approximation, the “independent alignment approximation,” which has recently been shown to produce significant error in the particular case of stress relaxation following a double-step strain in opposite direction. In the present paper, in order to examine the approximation in general cases, we derive a new constitutive equation without using the independent alignment approximation. The new equation is a nonlinear integro-differential equation and is solved numerically for several cases, i.e., steady shear and elongational flows, and the transient flows after the start of shear and elongation. It is found that, in the cases examined here, the new constitutive equation gives nearly the same results as the old one: the rheological functions calculated from the two theories differ no more than 30%. This substantiates the expectation that the independent alignment approximation does not produce drastic error as long as the flow direction is not reversed.     

A model for structural safety using the extreme value approach

A new method of evaluating the safety of a structure using the maximum mean largest value concept is introduced. The paper is characterized by the following points: The maximum probability of failure is defined by employing the upper bound of load and the lower bound of resistance, that is, the structural safety is evaluated under the worst-state both for load and resistance. This is a distribution-free approach to the concept of structural safety, and the probability of failure is calculated without assuming the probability density distributions of load and resistance. Three new characteristics are introduced so that the character of the data is strongly reflected on the estimation of the maximum probability of failure. A numerical example is given using the test data.