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Smectic ordering in solutions and films of a rod-like polymer owing to monodispersity of chain length

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Abstract

Solutions and melts of stiff (‘rod-like’) macromolecules often exhibit nematic liquid crystalline phases characterized by orientational, but not positional, molecular order1,2. Smectic phases, in which macromolecular rods are organized into layers roughly perpendicular to the direction of molecular orientation, are rare, owing at least in part to the polydisperse nature (distribution of chain lengths) of polymers prepared by conventional polymerization processes. Bacterial methods for polypeptide synthesis3, in which artificial genes encoding the polymer are expressed in bacterial vectors, offer the opportunity to make macromolecules with very well defined chain lengths. Here we show that a monodisperse derivative of poly(γ-benzyl α,L-glutamate) prepared in this way shows smectic ordering in solution and in films. This result suggests that methods for preparing monodisperse polymers might provide access to new smectic phases with layer spacings that are susceptible to precise control on the scale of tens of nanometres.

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Figure 1: Comparative gel electrophoresis of PLGAs.
Figure 2: 500 MHz NMR spectra of PBLG-1 (top trace) and conventional PBLG (Mr 20,100, polydispersity index PDI = 1.2, Sigma Chemical Co.; bottom trace) in CDCl3/TFA.
Figure 3: a, Polarizing optical micrograph of an ∼35% solution of PBLG-1 in CHCl3/TFA 3 d after dissolution.
Figure 4: a, Polarizing optical micrograph of a dioxane swollen film of PBLG-1 (∼35% polymer) orientated at 50 °C in a 1.98 T magnetic field.

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Acknowledgements

This work was supported by the National Science Foundation Materials Research Science and Engineering Center at the University of Massachusetts.

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Author notes

  1. Maurille J. Fournier & Thomas L. Mason

    Present address: Biochemistry and Molecular Biology Department, University of Massachusetts, Massachusetts, 01003, Amherst, USA

  2. Vincent P. Conticello

    Present address: Chemistry Department, Emory University, Atlanta, Georgia, 30322, USA

  3. Guanghui Zhang

    Present address: United States Surgical Corporation, North Haven, Connecticut, 06473, USA

  4. Christoph Kayser

    Present address: Max-Planck-Institut for Polymer Research, Mainz, D-55116, Germany

Authors and Affiliations

  1. Polymer Science and Engineering Department, Massachusetts, 01003, Amherst, USA

    Seungju M. Yu, Vincent P. Conticello, Guanghui Zhang, Christoph Kayser & David A. Tirrell

  2. Biochemistry and Molecular Biology Department, University of Massachusetts, Massachusetts, 01003, Amherst, USA

    Vincent P. Conticello, Guanghui Zhang & Christoph Kayser

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  1. Seungju M. Yu
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  2. Vincent P. Conticello
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  5. Maurille J. Fournier
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  6. Thomas L. Mason
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  7. David A. Tirrell
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Correspondence to David A. Tirrell.

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Yu, S., Conticello, V., Zhang, G. et al. Smectic ordering in solutions and films of a rod-like polymer owing to monodispersity of chain length. Nature 389, 167–170 (1997). https://doi.org/10.1038/38254

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