Abstract
Attempts were made to obtain model compounds for once-broken rod molecules by two different methods. In one of them, N-carboxy anhydride of γ-benzylglutamate (BG–NCA) was polymerized in dimethylformamide (DMF) containing trimethylenediamine (TMDA) as an initiator. In the other, BLG–NCA was polymerized in DMF with the preformed polymer of BDG–NCA as an initiator. It is expected that the molecule obtained by the first method yields a polymer chain which contains the TMDA residue somewhere in its central portion, whereas the second method gives a block copolymer of the DL type. The initiator residue in the former and the boundary between the L and D chains in the latter are intolerant of helix formation even in helicogenic solvents, and they should act as flexible joints of two helical rods. As an additional attempt, BLG–NCA was polymerized in DMF containing the polymer preformed by TMDA-initiated polymerization of BDG–NCA, in the hope of synthesizing a block copolymer of the LDL type. This polymer is expected to assume the form of a thrice-broken rod when dissolved in a helicogenic solvent. The postulated structures of the polypeptides thus obtained were confirmed by measurements of polymerization rate and optical rotation. It was difficult to prepare high-molecular-weight samples of the desired broken-rod structure by the procedures employed.
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Nakagawa, K., Nishioka, N., Teramoto, A. et al. Solution Properties of Synthetic Polypeptides. XIV. Synthesis and Characterization of Broken-rod Polypeptides. Polym J 4, 332–340 (1973). https://doi.org/10.1295/polymj.4.332
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DOI: https://doi.org/10.1295/polymj.4.332