ABSTRACT
Self-assembly is commonly understood as a process that spontaneously leads to a spatially more ordered arrangement of pre-existent building blocks by virtue of speci˜c interactions. Various de˜nitions can be found in literature,1 but per se selfassembly is neither limited to a certain length scale, a certain type of building block, nor a certain dimensionality of the self-assembled arrangement. Yet, one important common aspect of various de˜nitions is that self-assembly does not dissipate energy, and can thus proceed without external energy supply. The absence of energy dissipation can be viewed as an important difference between self-assembly and selforganization, where the latter also features a more ordered arrangement, but requires
5.1 Self-Assembly: An Attempt of a Brief De˜nition with Focus on Supramolecular Systems ............................................................................ 91
5.2 Supramolecular Monolayers at the Liquid-Solid Interface ............................92 5.3 Thermodynamics of Monolayers at the Liquid-Solid Interface .................. 102 5.4 Limitations of Thermodynamic Descriptions .............................................. 104 5.5 Structural Versatility by Internal and External Parameters ......................... 105 5.6 Self-Healing of Monolayers: Healable Defects and Requirements .............. 106 5.7 Conceivable Applications of Self-Healing Supramolecular Monolayers ..... 109 5.8 Perspective, Outlook, and Future Tasks ....................................................... 111 References .............................................................................................................. 112
continuous energy supply to maintain this state. Oscillating chemical reactions and schools of ˜sh are prominent examples for self-organization in chemistry and biology. In contrast, self-assembly brings a system toward its thermodynamic equilibrium, consequently promotes the minimization of Gibbs energy. Thus, if kinetically allowed, self-assembly yields the thermodynamically most stable state of a system under given external conditions. This is already the very origin of self-healing properties in any type of self-assembled arrangements, because any perturbation of the equilibrium state will generate a thermodynamic driving force directed to the initial state.
