Multiscale Self-Assembly

The simultaneous combination of the all three aforementioned techniques allows for a precise control over the structure of materials at several scales [52]. One of the most useful characteristics of molecular self-assembly is that it can take place simultaneously at multiple scales, producing highly hierarchical structures. This allows for the programmed organization of molecules, biological structures, and nanoparticles in the final architecture of the material in a bottom-up fashion [5], 

The key to controlling multiscale self-assembly is based on (i) the existence of previous individual components (ii) the weak-noncovalent-interactions between them and (iii) the dynamic formation of multiple suprastructures of which the most favored is that which minimizes its energy by a maximum number of interactions between individual components [48]. For this reason, the ultimate structure is predefined by various parameters of the initial components such as functionality, surface chemistry, shape, and size. 

Hierarchical self-assembly starts with the integration of individual components into complex structures, which in turn organize themselves to form higher-level architectures. This spontaneous assembly continues in a hierarchical way until the solid is completely built. This phenomenon-common to supramolecular chemistry and many biological systems- [53] produces solids with new properties that are not present in its original components. 

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Impressive, highly ordered centimetre-sized fibres are obtained whose synergistic growth mechanism based on the kinetic cross-coupling of a dynamical supramolecular self-assembly and a stabilizing silica mineralization may well be the basis of the synthetic paths used by Nature to obtain its materials with well-defined multiscale architectures in biological systems. 

Lepeie M, Chevallard C, Hernandez J-F, Mitraki A, Guenoun P. Multiscale surface self-assembly of an amyloid-like peptide. Langmuir 2007 23 8150-8155. 

Not mentioned in this review but certainly important to multiscale modeling related to solid mechanics are topics, such as self-assemblies, thin films, thermal barrier coatings, patterning, phase transformations, nanomaterials design, and semiconductors, all of which have an economic motivation for study. Studies related to these types of materials and structures require multiphysics formulations to understand the appropriate thermodynamics, kinetics, and kinematics. 

Multiscale ordering of functional colloidal nanoparticles is a powerful technique for the creation of macroscopic devices. This can be performed via selective polymerization, self-assembly processes, or through controlled molecular recognition processes (Fig. 4). Further assembly between NBB is addressed following three main strategies, namely, electrostatic coupling, covalent, or self-assembly-based noncovalent binding. 

As with the development of new catalysts, effective new materials benefit from a thorough understanding of structure/property relationships. This involves multiscale modeling and experimental efforts in surface science, including morphology. Enabling the use of new materials will also require extensive development of new nano- and microfabrication techniques, including biodirected or self-assembly syntheses. 

M. Brun, R. Demadrille, P. Rannou, A. Pron, J.P. Travers, and B. Grevin, Multiscale scanning tunneling microscopy study of self-assembly phenomena in two-dimensional polycrystals of pi-conjugated polymers the case of regioregular poly (dioctylbithiophene-alt-fluore-none). Adv. Mater., 16, 2087 (2004). 

Liu J, Liao CY, Zhou J Multiscale simulations of protein G B1 adsorbed on charged self-assembled monolayers, Lati mm r 29 11366—11374, 2013. 

LiuJ, Yu GB, ZhouJ Ribonuclease A adsorption onto charged self-assembled monolayers a multiscale simulation study, Chem Eng Sci 121 331—339, 2015. 

Emergent behavior The multiscale model must be able to predict self-assembly of cells in structures that lead to tissues with desired function. 

Clearly, this multiscale model can predict self-assembly of heterogeneous cell populations into structures that mimic the stratified structure of several tissues. It is also important to note that self-assembly is not a result of some programmed behavior of the two cell phenotypes. The two cell subpopulations self-assemble in structures like those of Figures 26.4b and 26.4c as a result of the interplay between mass transport dynamics (nutrient depletion) and differential effects of essential cellular functions (different nutrient uptake rates and resistance to necrosis). 

The mixing of nanoparticles and polymers (e.g., homopolymer and copolymer) provides an efficient self-assembly route to create highly ordered nanophase structures. However, the final structures are very complex and usually consist of a multiscale structure and different phases (Figure 3.2). It is thus very important to identify the different possible phases and the phase diagram. Theoretically, it is a great challenge to properly predict the morphology of such systems because the... 

Design and Applications of Multiscale Organic-Inorganic Hybrid Materials Derived from Block Copolymer Self-Assembly... 

Pierleoni C, Addison C, Hansen JP, Krakoviack V. Multiscale coarse graining of diblock copolymer self-assembly From monomers to ordered micelles. Phys Rev Lett 2006 96 128302. 

Finally, the synthesis of PMOs involving surfactant-directed self-assembly and self-directed assembly allows reaching a multiscale structuration of the material with controlled optoelectronic properties. 

Solvation behavior can be effectively predicted using electronic structure methods coupled with solvation methods, for example, the combination of continuum solvation methods such as COSMO with DFT as implemented in DMoF of Accelrys Materials Studio. An attractive alternative is statistical-mechanical 3D-RISM-KH molecular theory of solvation that predicts, from the first principles, the solvation structure and thermodynamics of solvated macromolecules with full molecular detail at the level of molecular simulation. In particular, this is illustrated here on the adsorption of bitumen fragments on zeolite nanoparticles. Furthermore, we have shown that the self-consistent field combinations of the KS-DFT and the OFE method with 3D-RISM-KH can predict electronic and solvation structure, and properties of various macromolecules in solution in a wide range of solvent composition and thermodynamic conditions. This includes the electronic structure, geometry optimization, reaction modeling with transition states, spectroscopic properties, adsorption strength and arrangement, supramolecular self-assembly,"and other effects for macromolecular systems in pure solvents, solvent mixtures, electrolyte solutions, " ionic liquids, and simple and complex solvents confined in nanoporous materials. Currently, the self-consistent field KS-DFT/3D-RISM-KH multiscale method is available only in the ADF software. 

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