Reversible Control of Spacing in Charged Lamellar Membrane Hydrogels by Hydrophobically Mediated Tethering with Symmetric and Asymmetric Double-End-Anchored Poly(ethylene glycol)s

Liu, Chenyu; Ewert, Kai K.; Wonder, Emily; Kohl, Phillip; Li, Youli; Qiao, Weihong; Safinya, Cyrus R.

doi:10.1021/acsami.8b16456

Title: Reversible Control of Spacing in Charged Lamellar Membrane Hydrogels by Hydrophobically Mediated Tethering with Symmetric and Asymmetric Double-End-Anchored Poly(ethylene glycol)s

Journal Article · Wed Nov 21 00:00:00 EST 2018 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.8b16456· OSTI ID:1763425

Liu, Chenyu ^[1];

^[2];

^[2]; Kohl, Phillip ^[2];

^[2]; Qiao, Weihong ^[3];

^[2]

Univ. of California, Santa Barbara, CA (United States); Dalian Univ. of Technology (China)
Univ. of California, Santa Barbara, CA (United States)
Dalian Univ. of Technology (China)

Complex materials often achieve their remarkable functional properties by hierarchical assembly of building blocks via competing and/or synergistic interactions. Here, we describe the properties of new double-end-anchored poly(ethylene glycol)s (DEA-PEGs)—macromolecules designed to impart hydrophobically mediated tethering attractions between charged lipid membranes. We synthesized DEA-PEGs (MW 2000 (2K) and 4.6K) with two double-tail (symmetric) or a double-tail and a single-tail (asymmetric) hydrophobic end anchors and characterized their equilibrium and kinetic properties using small-angle X-ray scattering. Control multilayer membranes without and with PEG lipid (i.e., single-end-anchored PEG) swelled continuously, with the interlayer spacing increasing between 30 and 90 wt % water content due to electrostatic as well as, in the case of PEG lipid, steric repulsion. In contrast, interlayer spacings in lamellar membrane hydrogels containing DEA-PEGs expanded over a limited water dilution range and reached a “locked” state, which displayed a near constant membrane wall-to-wall spacing (δ_w) with further increases in water content. Remarkably, the locked state displays a simple relation to the PEG radius of gyration δ_w ≈ 1.6R_G for both 2K and 4.6K PEG. Nevertheless, δ_w being considerably less than the physical size of PEG (2(5/3)^1/2RG) is highly unexpected and implies that, compared to free PEG, anchoring of the PEG tether at both ends leads to a considerable distortion of the PEG conformation confined between layers. Significantly, the lamellar hydrogel may be designed to reversibly transition from a locked to an unlocked (membrane unbinding) state by variations in the DEA-PEG concentration, controlling the strength of the interlayer attractions due to bridging conformations. Lastly, the findings with DEA-PEGs have broad implications for hydrophobic-mediated assembly of lipid- or surfactant-coated building blocks with distinct shape and size, at predictable spacing, in aqueous environments.

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Research Organization:: Univ. of California, Santa Barbara, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division; National Science Foundation Graduate Fellowship

Contributing Organization:: University of California Santa Barbara

Grant/Contract Number:: FG02-06ER46314; DGE 1144085

OSTI ID:: 1763425

Journal Information:: ACS Applied Materials and Interfaces, Vol. 10, Issue 50; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 4 works

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Title: Reversible Control of Spacing in Charged Lamellar Membrane Hydrogels by Hydrophobically Mediated Tethering with Symmetric and Asymmetric Double-End-Anchored Poly(ethylene glycol)s

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