SELF-ASSEMBLY AND FOLDING: FROM AMINO ACID AMPHIPHILES TO AZOBENZENE PHOSPHORAMIDITES
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The Ohio State University / OhioLINK
2012
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| Online Access: | http://rave.ohiolink.edu/etdc/view?acc_num=osu1331093060 |
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ndltd-OhioLink-oai-etd.ohiolink.edu-osu13310930602021-08-03T06:04:48Z SELF-ASSEMBLY AND FOLDING: FROM AMINO ACID AMPHIPHILES TO AZOBENZENE PHOSPHORAMIDITES Dumbleton, Jacob P. Chemistry Reported are the studies of the self-assembly and polymerization of nanotubes derived from L-lysine based amphiphiles and the synthesis of an azobenzene phosphoramidite catalyst. One dimensional (1D) assembled nanoscale molecules are of particular interest due to the development of optoelectronic nanodevices. While there are many examples of molecular self-assembly of defined nanostructures, there are few that exploit the functionalization with polymeric motifs. Polymerization of defined nanostructures has been shown to improve structural elements as well as allow for the versatility of polymer chemistry to design hybrid materials. Our design focuses on a series of naphthalene diimide (NDI) substituted L-lysine derivatives functionalized at the terminus with strained groups capable of undergoing polymerization. Self-assembly of these systems are induced from the amphiphilicity derived from the hydrophobic and hydrophilic interactions of the molecule, as well as stabilization of the NDI core through long range π-π interactions. Aqueous ring opening metathesis polymerization (ROMP) was performed on these self assembled systems using Grubb’s 1st and 2nd generation catalysts. The studies reveal that a stable polymer nanotube is achieved after aqueous polymerization. This polymer becomes disturbed upon the addition of an organic solvent and is no longer capable of adopting a helical structure when re introduced into water. Co-self-assembly studies were performed with a bolaamphiphile known to assemble into discrete tubular structures and an achiral C3 symmetric discotic observed to assemble in aqueous media. Samples were mixed at various concentrations in attempts to elucidate successful chirality transfer from the nanotube to the discotic. UV and CD spectroscopy were used to investigate if self-assembly had occurred. Lastly, a phosphoramidite catalyst was proposed exploiting the folding nature of an azobenzene oligomer. Since it is known that axial chirality in phosphoramidites can be derived from diols such as BINOL and TADDOL, an achiral azobenzene oligomer was designed to investigate if the dynamic chirality of the oligomer can control asymmetric catalysis. The oligomer design is derived from the meta- connectivity of the aromatic groups that forces the molecule to adopt a folded state stabilized through hydrogen bonding and π-π stacking. Incorporation of the azobenzene moieties allows for the potential to control catalysis photochemically. 2012-06-19 English text The Ohio State University / OhioLINK http://rave.ohiolink.edu/etdc/view?acc_num=osu1331093060 http://rave.ohiolink.edu/etdc/view?acc_num=osu1331093060 unrestricted This thesis or dissertation is protected by copyright: all rights reserved. It may not be copied or redistributed beyond the terms of applicable copyright laws. |
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NDLTD |
| language |
English |
| sources |
NDLTD |
| topic |
Chemistry |
| spellingShingle |
Chemistry Dumbleton, Jacob P. SELF-ASSEMBLY AND FOLDING: FROM AMINO ACID AMPHIPHILES TO AZOBENZENE PHOSPHORAMIDITES |
| author |
Dumbleton, Jacob P. |
| author_facet |
Dumbleton, Jacob P. |
| author_sort |
Dumbleton, Jacob P. |
| title |
SELF-ASSEMBLY AND FOLDING: FROM AMINO ACID AMPHIPHILES TO AZOBENZENE PHOSPHORAMIDITES |
| title_short |
SELF-ASSEMBLY AND FOLDING: FROM AMINO ACID AMPHIPHILES TO AZOBENZENE PHOSPHORAMIDITES |
| title_full |
SELF-ASSEMBLY AND FOLDING: FROM AMINO ACID AMPHIPHILES TO AZOBENZENE PHOSPHORAMIDITES |
| title_fullStr |
SELF-ASSEMBLY AND FOLDING: FROM AMINO ACID AMPHIPHILES TO AZOBENZENE PHOSPHORAMIDITES |
| title_full_unstemmed |
SELF-ASSEMBLY AND FOLDING: FROM AMINO ACID AMPHIPHILES TO AZOBENZENE PHOSPHORAMIDITES |
| title_sort |
self-assembly and folding: from amino acid amphiphiles to azobenzene phosphoramidites |
| publisher |
The Ohio State University / OhioLINK |
| publishDate |
2012 |
| url |
http://rave.ohiolink.edu/etdc/view?acc_num=osu1331093060 |
| work_keys_str_mv |
AT dumbletonjacobp selfassemblyandfoldingfromaminoacidamphiphilestoazobenzenephosphoramidites |
| _version_ |
1719430518006611968 |