The Synthesis, Characterization, and Properties of Stiff, Hydrophilic, Dendritic, Phenylacetylene Macromolecules
Pesak, Douglas Jay
This item is only available for download by members of the University of Illinois community. Students, faculty, and staff at the U of I may log in with your NetID and password to view the item. If you are trying to access an Illinois-restricted dissertation or thesis, you can request a copy through your library's Inter-Library Loan office or purchase a copy directly from ProQuest.
Permalink
https://hdl.handle.net/2142/84368
Description
Title
The Synthesis, Characterization, and Properties of Stiff, Hydrophilic, Dendritic, Phenylacetylene Macromolecules
Author(s)
Pesak, Douglas Jay
Issue Date
1997
Doctoral Committee Chair(s)
Moore, Jeffrey S.
Department of Study
Chemistry
Discipline
Chemistry
Degree Granting Institution
University of Illinois at Urbana-Champaign
Degree Name
Ph.D.
Degree Level
Dissertation
Keyword(s)
Chemistry, Polymer
Language
eng
Abstract
A series of phenylacetylene dendrimers bearing t-butyl ester groups on their periphery were prepared by a modified convergent growth scheme. The structures of these organic soluble compounds were confirmed by a variety characterization techniques including NMR, mass spectrometry, elemental analysis, GPC, and HPLC. Careful analysis of an apparently pure dendrimer revealed the presence structures incorporating small quantities of isopropyl esters derived from a trace impurity in the monomer. Conversion of the t-butyl esters to carboxylic acids was accomplished by an efficient solid-state thermolytic process which required no solvents, reagents or catalysts. The resulting dendrimers were soluble in aqueous base, but much more difficult to characterize owing to their solubility in a limited number of solvents. Electrospray ionization mass spectrometry and capillary electrophoresis were useful methods to probe structure and sample homogeneity, respectively. The higher generation carboxylic acid terminated dendrimers appeared to be lightly crosslinked as a result of the thermolysis reaction. Carboxylate terminated tridendrons were shown to solubilize perylene and toluene in aqueous solution. A second series of dendrimers were prepared with 2- (2-(2-methoxy-ethoxy)-ethoxy) ethyl ester groups on their periphery. Solution phase hydrolysis under basic conditions was employed to convert the esters to carboxylates. A high generation dendrimer prepared by this process was observed to be homogeneous by capillary electrophoresis. The 2- (2-(2-methoxy-ethoxy)-ethoxy) ethyl ester terminated tridendrons exhibited hexagonal columnar discotic mesophases. Finally, a series of asymmetric tridendrons containing a large lipophilic domains and hydrophilic domains of varying size were prepared. Aggregation of these macromolecular amphililes in lipophilic solvents was studied.
Use this login method if you
don't
have an
@illinois.edu
email address.
(Oops, I do have one)
IDEALS migrated to a new platform on June 23, 2022. If you created
your account prior to this date, you will have to reset your password
using the forgot-password link below.
