Solid state self-assembly

Lin, J., Zhou, W., Kumbhar, A., Wiemann, J., Fang, J., Carpenter, E.E. and O Connor, C.J. (2001) Gold-coated iron (Fe-Au) nanoparticles Synthesis, characterization, and magnetic field-induced self-assembly./. Solid State Chem., 159, 26-31. 

It is well known that block copolymers and graft copolymers composed of incompatible sequences form the self-assemblies (the microphase separations). These morphologies of the microphase separation are governed by Molau s law [1] in the solid state. Nowadays, not only the three basic morphologies but also novel morphologies, such as ordered bicontinuous double diamond structure, are reported [2-6]. The applications of the microphase separation are also investigated [7-12]. As one of the applications of the microphase separation of AB diblock copolymers, it is possible to synthesize coreshell type polymer microspheres upon crosslinking the spherical microdomains [13-16]. 

AB diblock copolymers in the presence of a selective surface can form an adsorbed layer, which is a planar form of aggregation or self-assembly. This is very useful in the manipulation of the surface properties of solid surfaces, especially those that are employed in liquid media. Several situations have been studied both theoretically and experimentally, among them the case of a selective surface but a nonselective solvent [75] which results in swelling of both the anchor and the buoy layers. However, we concentrate on the situation most closely related to the micelle conditions just discussed, namely, adsorption from a selective solvent. Our theoretical discussion is adapted and abbreviated from that of Marques et al. [76], who considered many features not discussed here. They began their analysis from the grand canonical free energy of a block copolymer layer in equilibrium with a reservoir containing soluble block copolymer at chemical potential peK. They also considered the possible effects of micellization in solution on the adsorption process [61]. We assume in this presentation that the anchor layer is in a solvent-free, melt state above Tg. The anchor layer is assumed to be thin and smooth, with a sharp interface between it and the solvent swollen buoy layer. 

The diaminopyridodipyrimidinedione 73 has been synthesised as a cytosine-like Tecton designed for self assembly into a helical superstructure. Self recognition occurs in the solid state <96MI02 96CA(125)221771 >. 

The phase transition boundaries (phase envelope) of adamantane need to be investigated and constmcted. Predictable and diverse geometries are important features for molecular self-assembly and pharmacophore-based dmg design. Incorporation of higher diamondoids in solid-state systems and polymers should provide high-temperature stability, a property already found in polymers synthesized from lower diamondoids. 

The chiral l,3,5-triazepane-2,6-dione 149 and its ring fused analogue 150 have been shown to form H-bonded helical molecular tapes with P chirality on self assembly in the solid state. With 149, this self assembly proceeds through aromatic-aromatic ring interactions resulting in hollow tubular structures <06CC4069>. 

W.J. Macknight, E.A. Ponomarenko, and D.A. Tirrell, Self-assembled poly electrolyte-surfactant complexes in nonaqueous solvents and in the solid state. Acc. Chem. Res. 31, 781-788 (1998). 

George M. Whitesides is Mallinckrodt Professor of Chemistry at Harvard University. He received his A.B. from Harvard College in 1960 and his Ph.D. from the California Institute of Technology in 1964. His research areas are Materials Science and Organic Chemistry, with specific focus in surface chemistry, materials science, self-assembly, capillary electrophoresis, organic solid state, molecular virology, directed ligand discovery, and protein chemistry. He is a member of the National Academy of Sciences, and he received the U.S. National Medal of Science in 1998. 

Afonin S, Durr UHN, Wadhwani P, Salgado J, Ulrich AS (2008) Solid state NMR structure analysis of the antimicrobial peptide gramicidin S in lipid membranes concentration-depen-dent re-alignment and self-assembly as a beta-barrel. Top Curr Chem 273 139-154... 

Confinement effects may also be employed to characterize the nucleation and growth of porous materials [211]. The underlying mechanisms of self-assembly and crystallization of these complex heterogeneous systems may be traced by solid state NMR methods well before their detection by diffraction methods. 

The indium compounds In[Se2P(OR)2]3, R = Et, Pr display distorted octahedral geometries and are self-assembled in solid state through intermolecular Se- Se secondary bonds.445... 

The indium complexes In(Se2PPh2)3 L (where L = THF, MePh) are self-assembled dimers in solid state through Se- Se secondary interactions.450... 

In order to prepare and isolate solid-state, crystalline, oxygenated iron-heme model complexes, chemists learned to synthesize (by self-assembly methods) and oxygenate many types of hindered porphyrins. For instance, capped porphyrins were synthesized by direct condensation of a suitable tetraaldehyde with four pyrrole molecules.37 Picket-fence porphyrins such as I e(TPP)((V-MeIm) (where TPP = meso-tetraphenylporphyrin and /V-Melm = (V-methylimidazole)... 

It was quickly recognized that chirality would play an important role in discotic liquid crystals, not only for the possibility of creating cholesteric and ferroelectric liquid crystals but also as a tool for studying the self-assembly of these molecules as a whole, both in solution and in the solid state. However, initial studies revealed that expression of chirality in discotic liquid crystals was not as straightforward as for liquid crystals derived from calamitic molecules. More recently, with the increase in interest in self-assembly and molecular recognition, considerably more attention has been directed to the study of chiral discotics and their assemblies in solution. The objective of this chapter is... 

Maji, S. K., Haidar, D., Drew, M. G. B., Banerjee, A., Das, A. K., and Banerjee, A. (2004). Self-assembly of /1-turn forming synthetic tripeptides into supramolecular //-sheets and amyloid-like fibrils in the solid state. Tetrahedron 60, 3251-3259. 

Gregory, D. M., Benzinger, T. L., Burkoth, T. S., Miller-Auer, H., Lynn, D. G., Meredith, S. C., and Botto, R. E. (1998). Dipolar recoupling NMR of biomolecular self-assemblies Determining inter- and intrastrand distances in fibrilized Alzheimer s beta-amyloid peptide. Solid State Nucl. Magn. Reson. 13, 149-166. 

Komatsu K (2005) The Mechanochemical Solid-State Reaction of Fullerenes. 254 185-206 Kriegisch V, Lambert C (2005) Self-Assembled Monolayers of Chromophores on Gold Surfaces. 258 257-313... 

The exploitation of the reactivity of molecular crystals lies close to the origins of crystal engineering and is at the heart of the pioneering work of Schmidt [47a]. The idea is that of organizing molecules in the solid state using the principles of molecular recognition and self-assembly. Successful results have been obtained with bimolecular reactions, particularly [2+2] photoreactivity and cyclisation [47b,c]. Another important area is that of host-guest chemistry. 

The examples discussed above illustrate the importance of block copolymer chain segment incompatibilities for the phase separation of bulk materials, combined with the ability to perform chemistry within specific nanoscale domains to impose permanence upon those self-assembled nanostructured morphologies. Each is limited, however, to crosslinking of internal domains within the solid-state assemblies in order to create discrete nanoscale objects. To advance the level of control over regioselective crosslinking and offer methodologies that allow for the production of additional unique nanostructured materials, the pre-assembled structures can be produced in solution (Figure 6.4), as isolated islands with reactivity allowed either internally or on the external... 

The structural state of dendritic macromolecules at air-water (Langmuir mono-layers) and air-solid (adsorbed monolayers, self-assembled films and cast films) interfaces have been reviewed by Tsukruk [17]. Although this work summarizes various characterization techniques for dendritic films by AFM techniques, in this chapter, we will present recent progress on the characterization of the dendritic film surface morphologies. 

Fig. 9.17 Examples of self-assembly of nanoparticles by a) hydrophobic interactions via a shell of unfunctionalized n-alkanes. Depicted is a Schematic 2D Representation of the RS/ Au nanoparticle packing structure in the solid state. Domains or bundles of ordered al-kylthiolate chains on Au particles interdigitate into the chain domains of adjacent particles in order to compensate the free volume of the outer region of the alkyl shell (Reprinted with permission from [146] A. Badia, L. Cuc-cia, L. Demers, et al.,J. Am. Chem. Soc. 1997, 779, 2582-2592. Copyright 1997 American Chemical Society), b) Direct comparison of hydrophobic interactions and chemical bridg-...

Baxter, P. N. W. Lehn, J.-M. Kneisel, B. O. Fenske, D. Self-assembly of a symmetric tetracopper box-grid with guest trapping in the solid state. Chem. Commun. 1997, 22, 2231-2232. 

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