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Aqueous Self-Assembly of Hydrophobic Macromolecules with Adjustable Rigidity of the Backbone

Abstract

P(FpC3P) (Fp: CpFe(CO)2; C3P: propyl diphenyl phosphine) has a helical backbone, resulting from the piano stool metal coordination geometry, which is rigid with intramolecular aromatic interaction of the phenyl groups. The macromolecule is hydrophobic, but the polarized CO groups can interact with water for aqueous self-assembly. The stiffness of P(FpC3P), which is adjustable by temperature, is an important factor influencing the morphologies of kinetic trapped assemblies. P(FpC3P)7 self-assembles in DMSO/water (10/90 by volume) into lamellae at 25 oC, vesicles at 40 oC and irregular aggregates at higher temperatures (60 and 70 oC). The colloidal stability decreases in the order of lamellae, vesicles and irregular agregates. Dissipative particle dynamic (DPD) simulation reveals the same temperature-dependent self-assembled morphologies with an interior of hydrophobic aromatic groups covered by the metal coordination units. The rigid backbone at 25 oC accounts for the formation of the layered morphology. While the less rigidity of the same P(FpC3P)7 at 40 oC curves up the lamellae into vesicles. At a higher temperature (60 or 70 oC), P(FpC3P)7 behaves as a random coil without obvious amphiphilic segregation resulting in irregular aggregates. The stiffness is, therefore, a crucial factor for the aqueous assembly of macromolecules without obvious amphiphilic segregation, which is reminiscent of the solution behavior observed for many hydrophobic biological macromolecules such as protein.

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Publication details

The article was accepted on 09 Jun 2017 and first published on 09 Jun 2017


Article type: Paper
DOI: 10.1039/C7SM01101F
Citation: Soft Matter, 2017, Accepted Manuscript
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    Aqueous Self-Assembly of Hydrophobic Macromolecules with Adjustable Rigidity of the Backbone

    Z. Guan, D. Liu, J. Lin and X. Wang, Soft Matter, 2017, Accepted Manuscript , DOI: 10.1039/C7SM01101F

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