Light and heat control over secondary structure and amyloid-like fiber formation in an overcrowded-alkene-modified Trp zipper

The external photocontrol over peptide folding, by the incorporation of molecular photoswitches into their structure, provides a powerful tool to study biological processes. However, it is limited so far to switches that exhibit only a rather limited geometrical change upon photoisomerization and that show thermal instability of the photoisomer. Here we describe the use of an overcrowded alkene photoswitch to control a model β-hairpin peptide. This photoresponsive unit undergoes a large conformational change and has two thermally stable isomers which has major influence on the secondary structure and the aggregation of the peptide, permitting the phototriggered formation of amyloid-like fibrils.     

Invariant Dissipative Mechanisms for the Spatial Motion of Rods Suggested by Artificial Viscosity

The introduction of artificial viscosity into the partial differential equations of mechanics is often useful for both analytic and numerical studies. The traditional forms of artificial viscosity, originally designed to treat problems for fluids, when applied to problems for solids often lead to equations describing material properties that are not invariant under rigid motions. Consequently, for rapidly rotating bodies, artificial viscosity could produce serious errors. In this paper it is shown how to introduce artificial viscosity in a properly invariant way, and that the resulting systems have a rich and attractive structure, which beckons analysis.     

Generalizations of the Nikodym boundedness and Vitali–Hahn–Saks theorems

Generalizations of the Nikodym boundedness and Vitali–Hahn–Saks theorems for scalar-valued measures on rings of sets that are in general not σ-rings are presented. As a consequence, the rings of subsets of N with density zero and uniform density zero are shown to have the Nikodym property. In addition, vector measure generalizations of the Vitali–Hahn–Saks theorem are given.     

Investigation into the absolute stereochemistry of the marine sponge alkaloid pyrinodemin A

The absolute configuration of the marine sponge alkaloid pyrinodemin A is established by organic synthesis.     

Ambient connections realising conformal Tractor holonomy

For a conformal manifold we introduce the notion of an ambient connection, an affine connection on an ambient manifold of the conformal manifold, possibly with torsion, and with conditions relating it to the conformal structure. The purpose of this construction is to realise the normal conformal Tractor holonomy as affine holonomy of such a connection. We give an example of an ambient connection for which this is the case, and which is torsion free if we start the construction with a C-space, and in addition Ricci-flat if we start with an Einstein manifold. Thus, for a C-space this example leads to an ambient metric in the weaker sense of Čap and Gover, and for an Einstein space to a Ricci-flat ambient metric in the sense of Fefferman and Graham. Current address for first author: Erwin Schr?dinger International Institute for Mathematical Physics (ESI), Boltzmanngasse 9, 1090 Vienna, Austria Current address for second author: Department of Mathematics, University of Hamburg, Bundesstra?e 55, 20146 Hamburg, Germany     

Synthesis and photophysical properties of fluorescent 2-aryl-1,3-dialkylbenzimidazolium ions and a l-alkyl-2-arylbenzimidazole with excited state intramolecular proton-transfer

To improve the solubility, photostability and fluorescence quantum yield (Φ) of 2-arylbenzimidazolium ions the N-1 hydrogen was replaced by an alkyl group before N-3 was quatemized; this substitution did not reduce Φ, proving the absence of steric inhibition to attainment of coplanarity in the excited state. A related symmetrical 2,2′-arylenebis(1,3-dimethyldibenzimidazolium ion) had Φ = 0.86. The related 2,5-bis(1-methyl-2-benzimidazolyl)phenol had Φ = 0.38 at 22° as well as a very large Stokes' shift due to proton-transfer. These findings supported a new insight into the electron distribution of the first excited singlet state of oligophenylenes. The compounds are of interest as laser dyes and scintillation fluors.