Lateral diffusion processes in biomimetic polymer membranes

Molecular self-assembly offers an important bottom-up approach to generate new materials with great potential for applications in nano-, life- and medical- sciences and engineering. The interest in “soft” materials suitable for the generation of artificial, biomimetic membranes has increased rapidly over the last years. These membranes combine the advantages of specificity and efficiency found in nature and the robustness and stability of synthetic materials from polymer science. There are currently two approaches to design biomimetic membranes. One uses natural phospholipids, while the other ones uses synthetic lipid mimics as the advanced alternative, which have shown great mechanical and chemical stability compared to their natural counterparts. This is important for technological application where durable devices are required. Biological membrane proteins, which provide selective and very efficient membrane transport, can be inserted into these synthetic block copolymer membranes. This combination of a synthetic membrane with biological membrane proteins is an intriguing phenomenon because the fundamental requirements for successful insertion are still matter of debate. One important issue is that polymeric membranes have thicknesses that exceed the height of the membrane proteins by several factors and the two lengths actually do not match. However, this significant height mismatch can be overcome by choosing a polymer with high flexibility, which has been shown to allow membrane proteins insertion in their active conformation. Flexibility and fluidity are essential membrane properties allowing successful generation of biomimetic membranes.
In this thesis, the fluid properties of synthetic membranes composed of synthetic amphiphiles are studied based on a large library of block copolymers. These consist of poly(2-methyloxazoline) (PMOXA) and poly(dimethylsiloxane) (PDMS) and are used as diblock (PMOXA-b-PDMS, AB) and triblock (PMOXA-b-PDMS-b-PMOXA, ABA) copolymers. Variation of the molecular weight induces changes in the membrane thickness and thus the fluidity of the membrane. The diffusion of membrane proteins within synthetic triblock copolymer membranes was investigated. The study revealed that the membrane proteins are mobile even at hydrophobic mismatches of up to 7 nm, which is a factor of seven compared to mismatches existing in biological membranes. The advantage of PDMS-containing block copolymers is their enormous flexibility even at high molecular weights, which provides a similar membrane environment compared to biological phospholipid membranes. This explains and displays the ability of PDMS to compress in contact to membrane proteins. Their diffusion decreases steadily with increasing thickness mismatch.
The importance of a very flexible polymer for the generation of biomimetic membranes was elucidated for membrane protein insertion, such as PDMS, which offers high fluidity and high membrane stability within membranes with even large thicknesses. The properties of these synthetic membranes investigated here, i.e. fluidity, lateral diffusion and membrane thickness, are important for the generation of biomimetic membranes for technological applications.