Chemically directed self-assembly

In chemistry, self-assembly is defined as a phenomenon by which molecules order themselves into a particular arrangement without external intervention. The process occurs under the guidance of numerous weak non-covalent bonding interactions that represent the core of supramolecular chemistry. It is not surprising that chemists engaged in the synthesis of topologically non-trivial structures are interested in utilizing self-assembly to direct the templation of chemical components into intermediates prone to cyclization, followed by the formation of covalent bonds. 

Messina MT, Metrangolo P, Resnati G (2000) Resolution of racemic perfluorocar-bons through self-assembly driven by donor-acceptor intermolecular recognition. In Ramachandran PV (ed) Asymmetric fluoro-organic chemistry synthesis, applications, and future directions. ACS symposium series 746. American Chemical Society, Washington DC, p 239... 

Y.D. Jin, Y. Shao, and S.J. Dong, Direct electrochemistry and surface plasmon resonance characterization of alternate layer-by-layer self-assembled DNA-myoglobin thin films on chemically modified gold surfaces. Langmuir 19, 4771—4777 (2003). 

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-...

In contrast to the use of self-assembly reactions and metal ion coordination preferences to direct the construction of mixed cofactor systems, the use of SPPS or selective chemical ligation allows for the direct covalent attachment of cofactors for the construction of mixed cofactor systems within de novo design. Figure 11 shows the flavocy-tochrome maquette constructed by Dutton and co-workers (149) using a flavin moiety covalently attached to a unique cysteine residue inside a four helix bundle with bis-histidine binding sites for heme... 

The nse of self-assembled monolayers of proteins by direct chemical attachment of the peptide to a modified snrface obviates some of the protein orientation difficnlties observed in the construction of LB mono-layers. An initial report of the construction of peptide SAMs on silanized qnartz was pnblished in early 1998 (185). Pilloud et al. have utilized the covalent ligation of protein cysteine thiols to thiol-terminated silanized... 

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