Multi-NMR spectroscopy

The 15N enriched XeN(H)S02F+ cation was prepared from H2NS02F and XeF+AsFg in HF and from [H3NS02F+AsFg and XeF2 in BrF5 and has been characterized by multi-NMR spectroscopy [109]. 

Typical characterization of the thermal conversion process for a given molecular precursor involves the use of thermogravimetric analysis (TGA) to obtain ceramic yields, and solution NMR spectroscopy to identify soluble decomposition products. Analyses of the volatile species given off during solid phase decompositions have also been employed. The thermal conversions of complexes containing M - 0Si(0 Bu)3 and M - 02P(0 Bu)2 moieties invariably proceed via ehmination of isobutylene and the formation of M - O - Si - OH and M - O - P - OH linkages that immediately imdergo condensation processes (via ehmination of H2O), with subsequent formation of insoluble multi-component oxide materials. For example, thermolysis of Zr[OSi(O Bu)3]4 in toluene at 413 K results in ehmination of 12 equiv of isobutylene and formation of a transparent gel [67,68]. 

NMR spectroscopy is one of the most widely used analytical tools for the study of molecular structure and dynamics. Spin relaxation and diffusion have been used to characterize protein dynamics [1, 2], polymer systems[3, 4], porous media [5-8], and heterogeneous fluids such as crude oils [9-12]. There has been a growing body of work to extend NMR to other areas of applications, such as material science [13] and the petroleum industry [11, 14—16]. NMR and MRI have been used extensively for research in food science and in production quality control [17-20]. For example, NMR is used to determine moisture content and solid fat fraction [20]. Multi-component analysis techniques, such as chemometrics as used by Brown et al. [21], are often employed to distinguish the components, e.g., oil and water. 

Although the condensation of phenol with formaldehyde has been known for more than 100 years, it is only recently that the reaction could be studied in detail. Recent developments in analytical instrumentation like GC, GPC, HPLC, IR spectroscopy and NMR spectroscopy have made it possible for the intermediates involved in such reactions to be characterized and determined (1.-6). In addition, high speed computers can now be used to simulate the complicated multi-component, multi-path kinetic schemes involved in phenol-formaldehyde reactions (6-27) and optimization routines can be used in conjunction with computer-based models for phenol-formaldehyde reactions to estimate, from experimental data, reaction rates for the various processes involved. The combined use of precise analytical data and of computer-based techniques to analyze such data has been very fruitful. 

The [l,3]oxazino[4,3- ][l,3]oxazine 387 was obtained as the main product of a combined Asinger and Ugi multi-component reaction from MeOH, NH3, 2,2-dimethyl-3-hydroxypropanal, allyl isocyanate, and C02 in 40% yield. As shown by NMR spectroscopy and X-ray crystallography, 387 is formed as a single diastereomer <1998ACS107>. 

Inomata K, Ohno A, Tochio H, Isogai S, Tenno T, Nakase I, Takeuchi T, Futaki S, Ito Y, Hiroaki H, Shirakawa M (2009) High-resolution multi-dimensional NMR spectroscopy of proteins in human cells. Nature 458 106-109... 

Characterization is the foundahon for the development and commercialization of new zeolites and zeolite-containing catalysts and adsorbents. Chapter 4 provides an overview of the most commonly employed characterization techniques and emphasizes the uhlity and limitations of each of these methods. An example is provided as to how a multi-technique characterization approach is necessary in order to determine the structure of a newly invented zeolite. Techniques covered in this chapter include X-ray powder diffraction, electron microscopy, infrared (IR) spectroscopy, nuclear magnetic resonance (NMR) spectroscopy and physical/ chemical methods. 

Since the advent of pulsed NMR spectroscopy, a number of advanced two-dimensional techniques have been devised. These methods afford valuable information for the solution of complex structural problems. The technical detail behind multi-dimensional NMR is beyond the scope of this book. 

Lesage et al. have shown that the resolution of the proton NMR spectroscopy of powdered solids can be improved significantly when multi-pulse sequences are employed [44a]. In the approach based on combined rotation and multipulse spectroscopy (CRAMPS) (Figure 7.9) the problem of dipolar line broadening is usually overcome. 

Notwithstanding all its advantages, the principle of solid-phase synthesis cannot be applied to all kinds of chemical reactions. Although reactants are used in excess, reaction is not always quantitative. The resulting impurities cannot be separated on the solid phase, giving rise to separation problems particularly in multi-step systems. Moreover, only limited use can often be made of conventional analytical methods (NMR, MS). Recent methods of 13C-NMR spectroscopy on solid phases [21] or in gel phases [22] are ideally suited for solid-phase synthesis, but are not universally available owing to the expensive instrumentation. 

The opposite, the reversal of drug-membrane interaction by addition of Ca2+ ions, has been also studied by NMR spectroscopy using the example of multi drug resistance modifiers [14]. 

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