The 1,3 dipolar cycloaddition between carbonyl ylids (generated from cyclobutene epoxides flanked by esters) and norbornyl alkenes – the ACE reaction – offers a facile method for the construction of polynorbornyl molecular frameworks. This reaction has, as described in this dissertation, underpinned the construction of molecular frameworks that have peptides and amino acids attached. Such highly rigid peptide-frameworks are of use in the field of peptidomimetics; the template molecule governs the final positioning of any attached groups such that a precise arrangement of amino acids can be achieved without the need to construct entire proteins. In the course of any ACE reaction the ester flanked cyclobutene epoxide is transformed to a 1,3 dipole, the esters serve to stablise this reactive intermediate and are as a consequence incorporated in the reaction product. Modification of these esters provides pseudo-equatorial points for peptide attachment. These methyl esters were replaced with tert-butyl esters to provide pseudo-axial attachment points that could be selectively addressed. The optimal strategy for peptide-framework construction involved direct condensation of carboxyl protected amino acids to bicyclo[2.2.1]hept-5-ene-2-endo-carboxylic acid as well as condensation of amino acids to cyclobutene epoxides derived from this acid. The ACE reaction of (±) bicycloheptene-2-endo-carboxylic acid derivatives with cyclobutene epoxides synthesised from such racemic acid derivatives provided a mixture of enantiomers and meso compounds. In order to control the position of the attachment points – and hence the final location of the attached peptides – the ACE reaction required chiral starting materials. Accordingly, all peptidoframeworks were derived from the chiral (2S)-(-)-bicycloheptene carboxylic acid. The ACE reaction of this (S)-norbornene with the (S)-epoxide provided a peptide framework in which the attached amino acids were positioned pseudo-axially. Deprotection of the amino acid allowed peptide chain building in the pseudo-axial direction. Using this strategy a framework with an alanine residue and a triglycine peptide was synthesised. By combining this strategy with the ter-butyl ester variant a framework with pseudo-axial alanine and pseudo-equatorial glycine residues was manufactured.

Thesis (M.S.) in Earth Sciences--University of Maine, 2009. / Includes vita. Includes bibliographical references (leaves 90-95).

Not available / text

The melting points of rigid, hydrogen bonding, and non-hydrogen bonding organic compounds have been estimated from their chemical structure. The estimation was accomplished through the use of both additive and non-additive non-constitutive properties of the molecule. The melting points of the aforementioned compounds can be estimated by the equation: TM = TMPN + TIHBN + TPACK + 8.9*EXPAN + 73.1*SIGMAL + 196.3 where the dependent variable, TM, is the melting point of the compound in Kelvin, SIGMAL is the logarithm of the symmetry number for the molecule, EXPAN is the eccentricity of the molecule taken to the third power, TMPN is the summation of the melting point number for each functional group in the molecule, TIHBN is the summation of an intramolecular hydrogen bonding index and TPACK is a packing efficiency index. The solubility of naphthalene in binary, ternary, and quinary cosolvent-water mixtures was determined by HPLC analysis. The samples were equilibrated for 48 hours on a test tube rotator, centrifuged, diluted with acetonitrile, and then injected onto a C8 10 micron column. The cosolvent mixtures used were hydro-organic solutions consisting of water with either methanol, ethanol, isopropanol, acetone, acetonitrile, propylene glycol or a combination of these as the cosolvent. The propylene glycol-water mixtures were allowed to equilibrate for 10 days. In all cases, naphthalene solubilities in binary cosolvent mixtures were found to obey log-linear relationships: log X = SIGMA(FRAC) - log X(w) where X is the mole fraction solubility of naphthalene in the mixture, X(w) is the mole fraction solubility in pure water, FRAC is the volume fraction of the cosolvent, and SIGMA is the slope. SIGMA can be estimated by using the UNIFAC method to predict the solubility in 100% cosolvent and by using the generalized solubility equation of Yalkowsky to estimate the water solubility. These binary equations can then be used to generate ternary and higher multicomponent equations.

Diss. (sammanfattning) Umeå : Univ., 2007. / Härtill 5 uppsatser.

Thesis (Ph. D.)--University of Washington, 1990. / Vita. Includes bibliographical references (leaves [163]-175).

Thesis (M.S.)--Rochester Institute of Technology, 1982. / Typescript. Includes bibliographical references (leaves 62-63).

Thesis (Ph.D)--Chemistry and Biochemistry, Georgia Institute of Technology, 2009. / Committee Chair: Dr. Sheldon W. May; Committee Member: Dr. James C. Powers; Committee Member: Dr. Nicholas Hud; Committee Member: Dr. Niren Murthy; Committee Member: Dr. Stanley H. Pollock. Part of the SMARTech Electronic Thesis and Dissertation Collection.

Thesis (Ph.D.)--Victoria University of Wellington, 2008. / Embargoed until 16 March 2011. Includes bibliographical references.

Thesis (Ph. D.)--University of Texas at Austin, 2006. / Vita. Includes bibliographical references.