Intramolecular Cyclization

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Shovan Mondal - One of the best experts on this subject based on the ideXlab platform.

Krishna C. Majumdar - One of the best experts on this subject based on the ideXlab platform.

Steven P. Armes - One of the best experts on this subject based on the ideXlab platform.

  • Extent of Intramolecular Cyclization in RAFT-synthesized methacrylic branched copolymers using 13C NMR spectroscopy
    Polymer Chemistry, 2015
    Co-Authors: Julien Rosselgong, Steven P. Armes
    Abstract:

    Recently, we reported using 1H NMR spectroscopy to assess the degree of Intramolecular Cyclization in a series of soluble methacrylic branched copolymers (see J. Rosselgong and S. P. Armes, Macromolecules, 2012, 45, 2731–2737). The key to success in addressing this long-standing problem in polymer science was the selection of a suitable disulfide-based dimethacrylate as the branching comonomer, which was statistically copolymerized with methyl methacrylate using reversible addition-fragmentation chain transfer (RAFT) polymerization. In this earlier work, estimation of the degree of Intramolecular Cyclization required peak deconvolution of the relevant thiamethylene proton signals. In the present work, we show that quantitative 13C NMR spectroscopy can also be utilized to determine the Intramolecular Cyclization for the same series of methacrylic copolymers via peak deconvolution of the oxymethylene carbon signals. Although this technique requires long spectral accumulation times, it offers superior resolution compared to 1H NMR spectroscopy and hence may ultimately enable this analytical approach to be applied to less esoteric divinyl comonomers.

  • Quantification of Intramolecular Cyclization in Branched Copolymers by 1H NMR Spectroscopy
    Macromolecules, 2012
    Co-Authors: Julien Rosselgong, Steven P. Armes
    Abstract:

    Statistical copolymerization of a monovinyl with a divinyl monomer leads to macroscopic gels, microgels, or soluble branched copolymers, depending on the precise reaction conditions. This approach is widely used for the manufacture of soft contact lenses and also to prepare various biomedical hydrogels for the separation and purification of proteins, DNA, etc. According to Flory–Stockmayer theory, gelation should occur in such copolymerizations if there is more than 0.50 fully reacted divinyl comonomer per primary chain. However, many experimental studies indicate significant deviations from this classical theory, which are generally believed to be due to wastage of the divinyl comonomer via Intramolecular Cyclization. Unfortunately, experimental verification of this side reaction has proven elusive for the past seven decades. In the present study, we use a disulfide-based cleavable bifunctional comonomer to undertake the first experimental quantification of the extent of Intramolecular Cyclization in non...

Dewen Dong - One of the best experts on this subject based on the ideXlab platform.

Caterina Zoni - One of the best experts on this subject based on the ideXlab platform.