A cluster anion of vinyl compounds in the gaseous phase has served as one of the simplest microscopic models of the initial stages of anionic polymerization. Herein, we describe our investigations into the initial stage mechanisms of anionic polymerization of acrylonitrile (AN; CH2═CHCN) trimer anions. While the cyclic oligomer is found in mass and photoelectron spectroscopic studies of (AN)3(-...

A transition-metal-free controlled polymerization for the attainment of poly(p-aryleneethynylene)s is developed. The polymerization of 1-pentafluorophenyl-4-[(trimethylsilyl)ethynyl]benzene with a catalytic amount of fluoride anions proceeds in a chain-growth-like manner to afford polymers with controlled molecular weights and low polydispersity indexes. The mechanism involves a pentacoordinate...

A new polymer with an alternating germanium-carbon backbone has been synthesized from 1,1-dimesitylneopentylgermene via addition polymerization using an anionic initiator.

A strained 1-phenyl-2,3-dimethylphosphirene undergoes anionic ring-opening polymerization upon initiation with n-butyl lithium at ambient temperature to yield polyvinylenephosphine, an unsaturated organophosphorus polymer.

A p-biquinodimethane species formed during the Gilch polymerization of an extremely twisted biphenyl monomer has been identified by in situ(1)H-NMR spectroscopy for the first time. From the identification of chain ends, we conclude that the chain growth during Gilch polymerization of biphenyl type monomers is both radical and anionic in nature.

A series of block copolymers bearing a single amino in-chain functionality was synthesized via anionic polymerization of styrene and ethylene oxide. By means of both a conventional and a continuous setup, living polystyrene was quantitatively end functionalized with an oxirane (DBAG) prior to the polymerization of the poly(ethylene oxide) segment. The in-chain amine was conjugated with a fluore...

An alternative method to synthesize well-defined cyclic polymers via combination of anionic polymerization high vacuum techniques and Williamson etherification reaction in moderate dilution up 1 g scale.

Oligoanions such as sodium triphosphate or GTP prevent and/or reverse vinblastine-induced polymerization of tubulin. We now show that the anions of glutamate-rich extreme C termini of tubulin are similarly involved in the regulation of the vinblastine effect. Cleavage of the C termini by limited proteolysis with subtilisin enhances vinblastine-induced tubulin polymerization and abolishes the an...