Abstract

The incorporation of polymers or smaller complex molecules into lipid membranes allows for property modifications or the introduction of new functional elements. The corresponding molecular-scale details, such as changes in dynamics or features of potential supramolecular structures, can be studied by a variety of solid-state NMR techniques. Here, we review various approaches to characterizing the structure and dynamics of the guest molecules as well as the lipid phase structure and dynamics by different high-resolution magic-angle spinning proton and 13C NMR experiments as well as static 31P NMR experiments. Special emphasis is placed upon the incorporation of novel synthetic polyphilic molecules such as shape-persistent T- and X-shaped molecules as well as di- and tri-block copolymers. Most of the systems studied feature dynamic heterogeneities, for instance those arising from the coexistence of different phases; possibilities for a quantitative assessment are of particular concern.

Highlights

  • Biological membranes play an important role in living matter

  • This review presents an overview of a variety of NMR techniques that are relevant for the study of guestmolecules in interaction with lipid membranes, and illustrates these with results obtained within the Research Unit FOR1145 funded by the German Research Foundation

  • The variety of 1 H–13 C separated local-field (SLF) NMR methods published so far may be separated into two main groups, namely carbon-detected local field (CDLF) and proton-detected local field (PDLF), and are described in the two sections

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Summary

Introduction

Biological membranes play an important role in living matter. They form boundaries of cells and organelles within the cell and they are the site of many biochemical events. These molecules consist of a stiff hydrophobic π-conjugated phenylene–ethinylene backbone of about 3 nm length, which roughly matches the hydrophobic thickness of a DPPC bilayer. In interaction with lipid bilayers, these X-shaped bolapolyphiles form supramolecular structures that can be tuned by structural variations of the molecules, such as different hydrophilic head groups or different lengths of the side chains [22]. We illustrate the use of static 31 P NMR, which provides a probe of slow (μs to ms) headgroup motions reflecting either lipid diffusion along a curved membrane or motions of the membrane itself, such as undulations

Interactions in SSNMR
High-Resolution SSNMR
Overview of SSNMR Applications to Lipid Membranes
Experimental Aspects
High-Resolution SSNMR Applications to Lipid Membranes
Nuclear Overhauser Enhancement Spectroscopy
C–H Order Parameters
SLF NMR Spectroscopy
Carbon-Detected Local Field NMR
Proton-Detected Local Field NMR
Intermediate Motional Regime
H–H Order Parameters
Experimental Considerations
DQ Build-Up Curve Analysis
DQ Sideband-Pattern Analysis
Static 31 P NMR as a Probe of Headgroup Mobility
Findings
Conclusions
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