S U P R A M O L E C U L A R    C H E M I S T R Y
 
Self-assembly, self-organization and self-reproduction of surfactant aggregates
 
This work started in the early nineties. Thanks mostly to the work of a very capable graduate student, Pascale Vonmont-Bachmann,  we were able to find conditions under which reverse micelles could increase their population number by an autocatalytic growth process (Bachmann et al,1990; Bachmann et al, 1991a; Bachmann et al 1991b; Luisi et al, 1993). In these studies, mostly fatty acids were used as surfactants. 
A  couple of years later this was extended to the case of aqueous micelles formed by fatty acids like caprylate. The results were published in Nature (Bachmann et al,1992). Also in this case, the process was based on the binding of a water-insoluble precursor by the hydrophobic micelles, followed by hydrolysis that yield more surfactant molecules. The principle is illustrated in the following figure: 
 
The molecules formed make more micelles, and the more micelles, the more is the surfactant bound and hydrolysed (autocatalysis). Since the process of growth is induced by the internal chemistry of the closed structure (micelles and later on vesicles), the process can be considered an autopoietic one, following the nomenclature and concepts developed by Francisco Varela and Humberto Maturana.

An actual experiment with aqueous micelles is shown below: 
 

Since the process of self-assembly and self-reproduction take place spontaneously, we made the suggestion (Bachmann et al,1992) that Nature may have utilised this facile mechanism for the early prebiotic processes of self-reproduction. The case of self-reproducing nucleotides in reverse micelles was also analysed (Bohler et al,1993). 
Later on we applied the same principle to the self-reproduction of caprylate and oleate vesicles (Walde et al,1994; Luisi et al,1994; Walde et al,1994). The study was extended in the Ph.D. work of Kenichi Morigaki to surfactants containing chiral centres (Morigaki et al,1997). 

The study on vesicle self-reproduction is still in progress. Silvia Rasi as part of her graduate program for a Ph.D. is presently studying the mechanism of the self-reproduction of oleate vesicles, and the mechanism of addition of oleate to liposomes formed from phosphatidylcholine liposomes such as POPC. The binding and uptake mechanism is also being studied from a theoretical and modellistic point of view by Dr. Fabio Mavelli. He has already produced, in collaboration with Prof. Marco Maestro of the University of Bari, a theoretical framework for self-reproduction processes of reverse micelles (Mavelli & Luisi,1996; Fresta et al,1994). Also collaborating with us in the study of the aggregation phenomena of fatty acids is Prof. Brian H. Robinson of the University of East Anglia at Norwich, UK; as well as Prof. Jack Szostak at the Harvard Medical School. Both are also interested in the “matrix effect” as outlined in one of the projects below. 
A constant interest in the group, that also belongs to this general field of self-assembly, concerns the behaviour of lipid surfactants. In the past we have devoted considerable interest to reverse micelles formed by lecithins and similar derivatives (Peng & Luisi,1990; Walde et al,1990; Colombo et al,1991) as well as liposomes (Walde & Bloechliger,1997; Walde et al,1997). Furthermore, conditions have been described, under which phosphatidylcholine vesicles can be formed by irradiation of a precursor (Veronese et al,1998). Self-assembly studies with phospholipids, in order to form new type of reverse micelles or new liposomes, are presently in progress in our group.