DNA‐Grafted Supramolecular Polymers: Helical Ribbon Structures Formed by Self‐Assembly of Pyrene–DNA Chimeric Oligomers

The controlled arraying of DNA strands on adaptive polymeric platforms remains a challenge. Here, the noncovalent synthesis of DNA‐grafted supramolecular polymers from short chimeric oligomers is presented. The oligomers are composed of an oligopyrenotide strand attached to the 5′‐end of an oligodeoxynucleotide. The supramolecular polymerization of these oligomers in an aqueous medium leads to the formation of one‐dimensional (1D) helical ribbon structures. Atomic force and transmission electron microscopy show rod‐like polymers of several hundred nanometers in length. DNA‐grafted polymers of the type described herein will serve as models for the development of structurally and functionally diverse supramolecular platforms with applications in materials science and diagnostics.     

Nucleophile‐electrophile interactions in the reaction of oxiranes with carboxylic acids in the presence of tertiary amines

The nucleophile‐electrophile interactions in the reaction system “N,N‐dimethylaniline – acetic acid – epichlorohydrin” have been investigated using kinetic methods and computer modeling. The observed orders of reactions have been determined for the overall reaction as well as for individual stages. The kinetic equations have been proposed; the activation parameters of the reactions have been evaluated. The behavior of the initial (amine) and intermediate (carboxylate) nucleophiles has been detailed in reaction pathway. Amine reacts with oxirane activated by acidic reagent while carboxylate‐anion—with both activated and nonactivated epichlorohydrin. The mechanism of oxirane ring opening by acid reagent in the presence of tertiary amine has been proposed, which comprise parallel‐consecutive compensation stages of reaction product formation. It has been demonstrated that the observed reaction order with respect to acid reactant depends upon the nature of electrophilic reagent (activated/nonactivated oxirane) and the ratio of the rates of compensation stages.     

Certain congruences on free trioids

Loday and Ronco introduced the notion of a trioid and constructed the free trioid of rank 1. This paper is devoted to the study of congruences on trioids. We characterize the least dimonoid congruences and the least semigroup congruence on the free (commutative, rectangular) trioid.