Supramolecular Assembly of Polymers

Viney, C. (1997). Natural silks Archetypal supramolecular assembly of polymer fibres. Supramol. Sci. 4, 75—81. 

In this chapter, we present a brief overview of supramolecular polymers and polymerization and supramolecular interactions of polymer side chains. We provide examples of the control over the solution state polymer strucmre that can be achieved at the molecular level and then extended to micro- and macroscale assemblies. 

Despite their solid appearance, within the gel the liquid component is mobile and is only held by capillary forces. The solid network can be either a covalent polymer or a supramolecular assembly of small molecules. The latter class of compound, termed low molecular weight gelators (LMWG) of which 14.11 14.15 are examples, is perhaps of most interest to supramolecular chemists. Perhaps the most well known gels are metal oxide based polymeric materials produced by the sol-gel process. The sol-gel process involves the hydrolysis and polycondensation of monomeric metal salts such as early transition... 

Nie, Z. H., Fava, D., Rubinstein, M., Kumacheva, E., Supramolecular assembly of gold nanorods end-terminated with polymer Pom-Poms Effect of pom-pom structure on the association modes. J. Am. Chem. Soc. 2008, 130, 3683-3689. 

With the exception of the last example we have mainly dealt with supramolecular assemblies and structures of polymers which are formed by dispersion interaction forces so far. Self-assembly of polymers by more specific interactions, which justifies the denotation as supramolecular complexes is still limited in number and mostly poorly defined. 

Polymer micelles are supramolecular assemblies of amphiphilic block copolymers that have a characteristic... 

The employment of diphenylphosphinopropanoic acid as a building block in the supramolecular assembly of a cyclometalated platinum(II) polymer 49 directed by -stacking and hydrogen-bonding interactions has been described [ 16g]. 

Pyridine moieties can also have H-bonding interactions with other H-bond donors to create nanostmctured materials, as shown by Stamm et al. [44]. Well-ordered nanostmctured thin polymer films from the supramolecular assemblies of PS-P4VP and 2-(4 -hydroxybenzeneazo)benzoic acid (HABA) have been fabricated (Fig. 2.6) [44]. This assembly formed cylindrical P4VP-HABA nanodomains surrounded by the PS matrix. 

Sidorenko et al. succeeded in fabrication of well-ordered nanostructures in thin polymer films by supramolecular assembly of PS-Zi-P4VP and 2-(4-hydro-xybenzeneazo) benzoic acid (HABA), consisting of cylindrical nanodomains formed by P4VP-HABA associates in a matrix of PS (Sidorenko et al., 2003). As shown in Scheme 12.7, extraction of HABA with a selective solvent results in nanochannel membranes with a hexagonal lattice of hollow channels in the diameter crossing the membrane from top to bottom. 

Early work on the mechanically induced deformation of supramolecular assemblies of chromophores in polymer matrices was inspired by the surprising discovery that solid-state tensile deformation of blends of minute amounts of the highly... 

Osada K, Kataoka K (2006) Drug and gene delivery based on supramolecular assembly of PEG-polypeptide hybrid block copolymers. Adv Polym Sci 202 113-153... 

Abstract Nature utilizes hydrogen bonding to guide the supramolecular assembly of lipids, proteins, and DNA, thereby imparting remarkable stimuli-responsiveness, structure-forming ability, and elasticity. Supramolecular polymers and networks... 

Fig. 31 Supramolecular assembly of 2,4-bls(2-ethylhexylureido)toluene (EHUT) to form rigid structures and poly(isobutene) PIBUT) to form dynamic comb-shaped polymers. Reprinted with permission from [167]. Copyright 2010 American Chemical Society...

Noro A, Ishihara K, Matsushita Y (2011) Nanophase-separated supramolecular assemblies of two functionalized polymers via acid-base complexation. Macromolecules 44 (16) 6241-6244... 

Figure 29 Schematic illustration of the approach combining (1) peptide-directed self-assembly of polymer-peptide conjugates and (2) polymerization of positioned diacetylene moieties. Peptide-polymer conjugates (top, a) first organize into supramolecular assemblies (top, b), which exhibit a distinct superhelical structure (bottom) this can be converted into conjugated polymers (red) under retention of their previously assembled structure (top, c). Reprinted with permission from Frauenrath, H. Jahnke, E. Chem. Eur. J. 2008, 14, 2942. Copyright 2007, Wiley-VCH.

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