THIS PROJECT IS DIRECTED AT NEW METHODS FOR THE SYNTHESIS OF """"""""CHIRALLY DEUTERATED AMINO ACIDS AND IS DESCRIBED IN DETAIL IN THE HIGHLIGHTS SECTION OF THIS REPORT. THE """"""""CHIRALLY DEUTERATED"""""""" AMINO ACIDS ARE REQUIRED NMR ANALYSIS OF PROTEIN STRUCTURE. THE B-METHYLENE PROTONS FOUND IN FIFTEEN OF THE TWENTY COMMON AMINO ACIDS ARE DIASTEREOTOPIC. THEREFORE, THEY ARE CHEMICALLY INEQUIVALENT GIVING RISE TO A TIGHTLY COUPLED AB MULTIPLET IN THEIR PROTON NMR SPECTRUM. THUS SCALAR COUPLED RESONANCES ARE OBSERVED FOR EACH OF THE B-METHYLENE PROTONS EXACERBATING SPECTRAL CROWDING IN THIS REGION. THIS SPECTRAL CROWDING PROBLEM CAN BE SOLVED BY STEREOSELECTIVELY REPLACING THE PROS (OR PROR) PROTON WITH A DEUTERON EFFECTIVELY ELIMINATING HALF OF THE B-METHYLENE PROTON RESONANCES AND INCREASING THE INTER PROTON DISTANCE. IN ADDITION, CHIRAL SUBSTITUTION OF THE PRO-CHIRAL METHYLENE PROTONS WOULD PROVIDE AN UNEQUIVOCAL METHOD FOR MAKING STEREOCHEMICAL ASSIGNMENTS TO THESE PROTON RESONANCES. SIMILAR TO THE DIASTEREOTOPIC HYDROGENS AT THE B-CARBON, VALINE AND LEUCINE HAVE DIASTEREOTOPIC METHYL GROUPS. DIFFERENTIAL 2H LABELING OF THESE METHYL GROUPS WILL REDUCEIN HALF THE NUMBER OF RESONANCES IN A CROWDED METHYL REGION OF THE SPECTRUM AND PROVIDE UNEQUIVOCAL STEREOCHEMICAL ASSIGNMENTS OF T HE METHYL RESONANCES. THIS PROJECT HAS DEVELOPED METHODS FOR DEUTERATING DIASTEREOTOPIC B-METHYLENE PROTONS AND DIASTEREOTOPIC METHYL GROUPS IN AMINO ACIDS. OPPOLZER'S CAMPHOR SULTAM CHIRAL AUXILIARY WAS USED TO INDUCE THE STEREOCHEMISTRY AT THE B-CARBON.
| Martinez, Rodolfo A; Glass, David R; Ortiz, Erick G et al. (2014) Synthesis of isotopically labeled 1,3-dithiane. J Labelled Comp Radiopharm 57:338-41 |
| Martinez, Rodolfo A; Glass, David R; Ortiz, Erick G et al. (2013) Large-scale preparation of (13) C-labeled 2-(phenylthio)acetic acid and the corresponding labeled sulfoxides and sulfones. J Labelled Comp Radiopharm 56:31-5 |
| Creager, Melinda S; Jenkins, Janelle E; Thagard-Yeaman, Leigh A et al. (2010) Solid-state NMR comparison of various spiders' dragline silk fiber. Biomacromolecules 11:2039-43 |
| Jenkins, Janelle E; Creager, Melinda S; Lewis, Randolph V et al. (2010) Quantitative Correlation between the protein primary sequences and secondary structures in spider dragline silks. Biomacromolecules 11:192-200 |
| Kim, Sun Hee; Aznar, Constantino; Brynda, Marcin et al. (2004) An EPR, ESEEM, structural NMR, and DFT study of a synthetic model for the covalently ring-linked tyrosine-histidine structure in the heme-copper oxidases. J Am Chem Soc 126:2328-38 |
| Ollivault-Shiflett, Morgane; Kimball, David B; Silks, L A Pete (2004) Synthesis of chiral 13C,77Se-labeled selones. J Org Chem 69:5150-2 |
| Schmidt, Bryan; Hillier, Warwick; McCracken, John et al. (2004) The use of stable isotopes and spectroscopy to investigate the energy transducing function of cytochrome c oxidase. Biochim Biophys Acta 1655:248-55 |
| Schmidt, Bryan; McCracken, John; Ferguson-Miller, Shelagh (2003) A discrete water exit pathway in the membrane protein cytochrome c oxidase. Proc Natl Acad Sci U S A 100:15539-42 |
| Gray, Chandele R; Sanz-Cervera, Juan F; Silks, Louis A et al. (2003) Studies on the biosynthesis of asperparaline A: origin of the spirosuccinimde ring system. J Am Chem Soc 125:14692-3 |
| Van Dien, Stephen J; Strovas, Tim; Lidstrom, Mary E (2003) Quantification of central metabolic fluxes in the facultative methylotroph methylobacterium extorquens AM1 using 13C-label tracing and mass spectrometry. Biotechnol Bioeng 84:45-55 |
Showing the most recent 10 out of 72 publications
