Nuclear magnetic resonance SHAPES technique

The main structural features of yessotoxin (YTX, 1) (Figure 13.1) consist of a ladder-shaped polycyclic ether skeleton, an unsaturated terminal side chain of nine carbons, and two sulfate groups. It was first isolated from scallops, Patinopecten yessoensis, that were implicated in a DSP episode in Japan. The planar structure of YTX was elucidated by means of 2D nuclear magnetic resonance (NMR) techniques, and confirmed by fast atom bombardment mass spectrometry/mass spectrometry (FAB MS/MS) experiments " the stereochemical details were successively determined by assigning the relative and then the absolute stereochemistry. YTX has subsequently been isolated from shellfish collected along the coasts of several different countries such as Norway, Chile, New Zealand, Italy, suggesting the spread of this toxin worldwide. 

While the broad mission of the National Bureau of Standards was concerned with standard reference materials, Dr. Isbell centered the work of his laboratory on his long interest in the carbohydrates and on the use of physical methods in their characterization. Infrared spectroscopy had shown promise in providing structural and conformational information on carbohydrates and their derivatives, and Isbell invited Tipson to conduct detailed infrared studies on the extensive collection of carbohydrate samples maintained by Isbell. The series of publications that rapidly resulted furnished a basis for assigning conformations to pyranoid sugars and their derivatives. Although this work was later to be overshadowed by application of the much more powerful technique of nuclear magnetic resonance spectroscopy, the Isbell— Tipson work helped to define the molecular shapes involved and the terminology required for their description. 

For the investigation of the molecular dynamics in polymers, deuteron solid-state nuclear magnetic resonance (2D-NMR) spectroscopy has been shown to be a powerful method [1]. In the field of viscoelastic polymers, segmental dynamics of poly(urethanes) has been studied intensively by 2D-NMR [78, 79]. In addition to ID NMR spectroscopy, 2D NMR exchange spectroscopy was used to extend the time scale of molecular dynamics up to the order of milliseconds or even seconds. In combination with line-shape simulation, this technique allows one to obtain correlation times and correlation-time distributions of the molecular mobility as well as detailed information about the geometry of the motional process [1]. 

From its very beginning nuclear magnetic resonance (NMR) was used to unravel dynamic processes in amorphous matter, where the high selectivity of this technique was exploited. Recent progress has largely benefited from the development of multidimensional NMR spectroscopy, significantly extending the traditional techniques such as spin-lattice relaxation and line-shape analyses. Modern NMR techniques helped a lot to understand the molecular dynamics in disordered systems such as the a-process. 

A variety of spectroscopic techniques have been applied to DOC isolated from seawater by cross-flow ultrafiltration or adsorption onto XAD resins. The two techniques isolate very different organic fractions from seawater. Hydrophobic fractions (such as marine humic material) are isolated on XAD resins [48], whereas the organic matter extracted by ultrafiltration is retained primarily on the basis of its molecular size and shape [49], resulting in isolates rich in nitrogen and carbohydrates (polysaccharides). Nuclear magnetic resonance (NMR) spectroscopy has proven successful in distinguishing between the specific structures of XAD-bound humics and the carbohydrates concentrated into colloidal size fractions. 

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