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.     

Novel route to 5-position vinyl derivatives of thiolactomycin: Olefination vs. deformylation

Vinyl and diene derivatives of thiolactomycin have been prepared via Horner-Wadsworth-Emmons olefination from protected 5-formyl-3,5-dimethylthiotetronic acid. Several 4-position protecting groups and a variety of phosphonates were evaluated, with MOM protection and β-ketophosphonates yielding the highest ratio of the desired product to deformylated product.     

Synthesis and conformational studies of a new host system based on cholic acid

New synthetic hosts have been designed incorporating two molecules of cholic acid linked by a rigid diamine. Proton NMR studies indicate that the compounds exist in a rigid conformation with the steroid hydroxyl groups intramolecularly hydrogen-bonded. Heat or addition of methanol leads to conformational isomerism due to insertion of methanol into the cavity.A preliminary report of this work was presented at the 4th International Symposium on Inclusion Phenomena, July 20–25, 1986, Lancaster, U.K.     

Probing the surface structure of quasicrystals via angle-resolved low-energy ion scattering

Angle-resolved low-energy ion scattering is a valuable technique for examining the topmost surface layers of materials. Using this technique, information about both composition and structure can be obtained. We discuss the physical basis of this technique and present our findings for the fivefold surface of icosahedral (i-) Al–Pd–Mn. Our results clearly show that the exposed surface has a higher Al content than the bulk and can have fivefold periodicity. Information about frequently occurring interatomic distances on the surface can also be obtained by this technique. We discuss the results and compare them to recent scanning tunneling microscopy studies and to bulk structure models.     

Relativistic Dynamics in Basic Chemistry

This paper revisits the historical sequence in which some of the major developments of 20th-century physics occurred, and explores how theories could have turned out differently, if the sequence of developments had been different. It shows how a delay in founding special relativity theory until after (1) at least one puzzling problem in electromagnetic theory could be acknowledged, and (2) sat least some of the experimental observations pertinent to the development of quantum mechanics had become well known, could have resulted in a larger theory that covers both domains in a manner quite different from that of any of the theories we use today. The revised theory dispenses with a separate postulate introducing Planck’s constant h, identifying instead a physical mechanism that implies the constant. Some important aspects of quantum chemistry then follow. Editor, Galilean Electrodynamics, Proceedings of the Natural Philosophy Alliance; Visiting Industry Professor, Tufts University, retired     

SULFOPHTHALOCYANINES FOR PHOTODYNAMIC INACTIVATION OF VIRUSES IN BLOOD PRODUCTS: EFFECT OF STRUCTURAL MODIFICATIONS

Abstract— Transmission of infectious diseases through blood transfusions is well known. Ultraviolet irradiation, solvents and detergents provide a means of sterilizing noncellular blood components. However these harsh methods are not applicable to cellular blood products. Recently, attempts have been made to sterilize biological fluids using photodynamic treatment and phthalocyanine (Pc) dyes have been advanced as photosensitizers for this purpose. We have evaluated a series of water-soluble Pc, chelated with different central metal ions, substituted to different degrees with sulfonato and r-butyl groups, for their effectiveness to reduce virus infectivity in red blood cell suspensions. Vaccinia virus cytopathogenicity was determined by endpoint serial dilutions in the CV-1 cell line. Anti-viral activity increased with the central metal ion in the following order: Ga(III) < Al(III) < Zn(II), and varied inversely with the degree of sulfonation. Furthermore, addition of a t -butyl group onto the trisulfonated dyes (PcS₃[ t -Bul) resulted in a 5–40-fold increase in anti-viral potency, suggesting that amphiphilicity enhances the photodynamic activity of the dye. Strong anti-viral photosensitizing properties cannot be the sole selection criterion. Of equal importance is the preservation of blood component integrity. Accordingly, the photohemolytic activity of the dyes was evaluated using the rate of hemolysis as a parameter and a toxicity index was defined. Among the most active dyes, the AlPcS₃( t -Bu) complex exhibited the most favorable anti-viral properties combined with a low toxicity index. Our results suggest that trisulfophthalocyanines, bearing an additional t -butyl group to enhance amphiphilicity, are particularly promising dyes for photodynamic blood sterilization.