Synthesis of polymer-biohybrids: from small to giant surfactants

Amphiphiles or surfactants, more popularly known as soaps, are among the oldest known chemical compounds used by man. Written text on a clay tablet dated to 2200 B.C. indicates that the Babylonians were familiar with soap-like substances. According to the Ebers papyrus (1550 B.C.), the ancient Egyptians bathed regularly in a mixture of animal oils, vegetable extracts, and alkaline salts, and a soap factory with bars of scented soap was found in the ruins of Pompeii (79 A.D.). In modern times, the use of soap has become universal, and we now understand reasonably well what happens when soap molecules are dispersed in aqueous solution and how the cleaning properties of soap work. The latter is related to the surface-active behavior of soap molecules, which is a result of their amphiphilic, also called amphipathic, character. Although the cleaning aspect is still an important issue, scientists are increasingly focusing on other properties of soaps, for example, self-assembling behavior and how this can be used in the design and non-covalent synthesis of new (macro)molecular architectures. These new molecules can be employed in nanotechnology and drug delivery, among other applications. This Account will focus on three different classes of amphiphiles. The first is the low molecular weight amphiphiles, also called classical amphiphiles in this context. A short overview will be given on the research carried out by our group and others on the self-assembly behavior and properties of these compounds; in particular, we focus on the ones that can be stabilized by polymerization (polymerized vesicles). Next, we will introduce the still relatively young field of superamphiphiles, macromolecules consisting of a hydrophobic and a hydrophilic polymeric block. Finally, and this constitutes the main part of this Account, we will provide an overview of a new class of amphiphiles, the so-called giant amphiphiles. These macromolecules have an enzyme or protein as the polar head group and a hydrophobic polymer as a tail. We will finish the Account with conclusions and an outlook to the future.