Nanoscale thermodynamics

To summarize, three conclusions transpire from the nanoscale thermodynamics results (a) The interfacial tension between protein and water is patchy and the result of both nanoscale confinement of interfacial water and local redshifts in dielectric relaxation (b) the poor hydration of polar groups (a curvature-dependent phenomenon) generates interfacial tension, a property previously attributed only to hydrophobic patches and (c) because of its higher occurrence at protein-water interfaces, the poorly hydrated dehydrons become collectively bigger contributors to the interfacial tension than the rarer nonpolar patches on the protein surface. 

Most polymer pairs are thermodynamically incompatible, in the sense that their free energy of mixing is positive. This does not mean that there is absolutely no interdiffusion at all at the interface between them adjacent to the interface limited interdiffusion occurs, which can be seen as an increasing of the low surface entropy implied by a smooth surface [30-33]. This nanoscale roughening of an interface can increase the adhesion between the polymers. 

Micelles the mostly spherical nanoscale aggregates formed by amphiphilic compounds above their critical micelle concentration in aqueous solution have a narrow size distribution and are dynamic, because there is a fast exchange of amphiphiles in solution and those incorporated in micelles. However, micelles are defined as self-assembled structures, since the structure is in thermodynamical equilibrium. 

These two examples show that regular patterns can evolve but, by definition, dissipative structures disappear once the thermodynamic equilibrium has been reached. When one wants to use dissipative structures for patterning of materials, the dissipative structure has to be fixed. Then, even though the thermodynamic instability that led to and supported the pattern has ceased, the structure would remain. Here, polymers play an important role. Since many polymers are amorphous, there is the possibility to freeze temporal patterns. Furthermore, polymer solutions are nonlinear with respect to viscosity and thus strong effects are expected to be seen in evaporating polymer solutions. Since a macromolecule is a nanoscale object, conformational entropy will also play a role in nanoscale ordered structures of polymers. 

Supramolecular systems have the capability of achieving functions not accessible by using molecular components.1,2 Supramolecular chemistry provides the framework to move from the molecular world to the nano- and meso-scale world. In this respect, the development of supramolecular systems provides a bottom-up approach for the construction of nanoscale objects where complexity is paramount to achieve multi-step function. Detailed knowledge of the system s thermodynamics and dynamics is required to rationally design new structures and to modify known ones. 

Gibbs found the solution of the fundamental Equation 9.1 only for the case of moderate surfaces, for which application of the classic capillary laws was not a problem. But, the importance of the world of nanoscale objects was not as pronounced during that period as now. The problem of surface curvature has become very important for the theory of capillary phenomena after Gibbs. R.C. Tolman, F.P. Buff, J.G. Kirkwood, S. Kondo, A.I. Rusanov, RA. Kralchevski, A.W. Neimann, and many other outstanding researchers devoted their work to this field. This problem is directly related to the development of the general theory of condensed state and molecular interactions in the systems of numerous particles. The methods of statistical mechanics, thermodynamics, and other approaches of modem molecular physics were applied [11,22,23],... 

Self-consistent approaches in molecular modeling have to strike a balance of appropriate representation of the primary polymer chemistry, adequate treatment of molecular interactions, sufficient system size, and sufficient statistical sampling of structural configurations or elementary transport processes. They should account for nanoscale confinement and random network morphology and they should allow calculating thermodynamic properties and transport parameters. 

The weak physical forces that hold together self-assembled nanoparticles are, of course, susceptible to disruption under the influence of thermodynamic and/or mechanical stresses. Hence some workers have investigated ways to reinforce nanoscale structures via covalent bonding. For instance, improved stability of protein nanoparticles, in particular, casein micelles, can be achieved by enzymatic cross-linking with the enzyme transglutaminase, which forms bonds between protein-bound glutamine and lysine residues. By this means native casein micelles can be converted from semi-reversible association colloids into permanent nanogel particles (Huppertz and de Kruif, 2008). 

An important nature-mimicking methodology involves the use of covalent synthesis followed by molecular self-assembly of the synthesized molecules. These molecules are generally small mono- or oligomers that interact with each other and with other kinds of mono- or oligomers to form thermodynamically stable, nanoscale structures. See also Molecular Recognition. 

SBM) as a compatibilizer. As a result of the particular thermodynamic interaction between the relevant blocks and the blend components, a discontinuous and nanoscale distribution of the elastomer at the interface, the so-called raspberry morphology, is observed (Fig. 15). Similar morphologies have also been observed when using triblock terpolymers with hydrogenated middle blocks (polystyrene-W<9ck-poly(ethylene-C0-butylene)-Wock-poly(methyl methacrylate), SEBM). It is this discontinuous interfacial coverage by the elastomer as compared to a continuous layer which allows one to minimize the loss in modulus and to ensure toughening of the PPE/SAN blend [69],... 

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