Overcoming a Tight Coil To Give a Random “Co” Polymer Derived from a Mixed Sandwich Cobaltocene
摘要:
Reversible addition-fragmentation transfer (RAFT) polymerization of a eta(5)-cydopentadienylcobalt-eta(4-)cyclobutadiene (CpCoCb) containing monomer under a wide variety of experimental conditions (e.g., different solvents, temperatures, RAFT agents, concentrations, and [RAFT agent]/[initiator]) was examined. In all cases the results revealed that although the monomer was being consumed over the course of the reaction, there was no significant increase in the molecular weight of the resulting polymer. It was determined that as the polymer chain grows (DP approximate to 10), a tight coil morphology was adopted, which hinders the approach of an additional, sterically demanding CpCoCb-containing monomer. This resulted in premature termination/chain transfer reactions rather than an increase in the polymer chain length. To address this problem, methyl acrylate (MA) with its lower steric demand was copolymerized with the bulky CpCoCb-containing monomer to act as a spacer. This provided the necessary steric relief and an opportunity for the metallopolymer to grow. This copolymerization resulted in dramatic improvements in the polydispersity and molecular weight of the end material. In subsequent experiments, the random copolymer was used as a macro-RAFT agent to prepare diblock copolymers, with good control over the molecular weight, allowing for an examination of the self-assembly behavior of the block copolymer in the solid state.
Cyclotrimerization of phenylacetylene catalyzed by a cobalt half-sandwich complex embedded in an engineered variant of transmembrane protein FhuA
作者:A. Thiel、D. F. Sauer、M. A. S. Mertens、T. Polen、H.-H. Chen、U. Schwaneberg、J. Okuda
DOI:10.1039/c8ob01369a
日期:——
An (η5-cyclopentadienyl)cobalt(I) complex was covalently incorporated into an engineered variant of the transmembrane protein ferric hydroxamate uptake protein component: A, FhuA ΔCVFtev, using a thiol–ene reaction. A CD spectrum shows the structural integrity of the biohybrid catalyst. MALDI-TOF of the segment containing the anchoring site for the cobalt complex Cys545 confirmed successful conjugation