Quantitative and mechanistic studies using the oxygen-18 isotope shift in carbon-13 nuclear magnetic resonance spectroscopy
The {sup 18}O-isotope shift in {sup 13}C NMR spectroscopy was used to study the kinetics of oxygen exchange at the anomeric carbon atoms of several ketoses and aldoses. At 25-26{degree}C and over the pH range from 2 to 10, the relative rates of oxygen exchange for the aldoses studied increased in the following sequence: D-glucose, D-mannose, D-ribose, D-2-deoxyribose. The hydration rates for the open chain forms of the sugars were calculated and the results were analyzed in terms of steric and inductive effects by drawing analogies with the hydration kinetics of simple aldehydes and ketones. Effective molarities associated with ring closure reactions of common monosaccharides are calculated. The position of bond cleavage in the acid-catalyzed hydrolysis of sucrose was elucidated by hydrolyzing the sugar in {sup 18}O-water and assaying the incorporation of {sup 18}O into the several anomeric products using {sup 13}C NMR. Independents supporting experimental evidence was obtained using {sup 1}H NMR. A detailed investigation was made of the complex {sup 13}C NMR spectrum arising from the various {sup 18}O-isotopomers in a solution of {sup 18}O-labeled (1,4-{sup 13}C{sub 2}) succinic acid. The quantitative use of the {sup 18}O isotope shift in {sup 13}C NMR was assessed.
- Research Organization:
- Purdue Univ., Lafayette, IN (USA)
- OSTI ID:
- 6368240
- Resource Relation:
- Other Information: Thesis (Ph. D.)
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
MONOSACCHARIDES
MOLECULAR STRUCTURE
ACID HYDROLYSIS
CARBON 13
CHEMICAL SHIFT
NMR SPECTRA
NUCLEAR MAGNETIC RESONANCE
OXYGEN 18
TRACER TECHNIQUES
CARBOHYDRATES
CARBON ISOTOPES
CHEMICAL REACTIONS
DECOMPOSITION
EVEN-EVEN NUCLEI
EVEN-ODD NUCLEI
HYDROLYSIS
ISOTOPE APPLICATIONS
ISOTOPES
LIGHT NUCLEI
LYSIS
MAGNETIC RESONANCE
NUCLEI
ORGANIC COMPOUNDS
OXYGEN ISOTOPES
RESONANCE
SACCHARIDES
SOLVOLYSIS
SPECTRA
STABLE ISOTOPES
550201* - Biochemistry- Tracer Techniques