Two Dimensional Correlation Spectroscopy

COSY Correlated spectroscopy, two-dimensional shift correlations via spin-spin coupling, homonuclear (e.g. HH) or heteronuclear (e.g. CH)... 

NOESY Nuclear Overhauser effect spectroscopy. Two-dimensional technique that correlates nuclei to each other if there is any NOE between them. 

In the case of the 7-hydroxy-substituted compounds 44 (Scheme 2), 54 different derivatives were investigated by 13C NMR spectroscopy and, in some cases, also by 1SN NMR spectroscopy <1995JST(335)273>. With the help of proton-coupled 13C NMR spectra, semi-selective INEPT (insensitive nuclei enhanced by polarization transfer) experiments, and heteronuclear multiple bond correlation (HMBC) two-dimensional 2D-NMR spectra, all shifts could be unequivocally assigned. While the C-7 shifts did not allow the existing tautomeric situation to be determined, a clear decision could be made by H NMR spectroscopy in this respect. The 1SN NMR spectra revealed an equilibrium between the N(4)H and N(3)H tautomeric forms, which is fast on the NMR timescale. 

In order to assign the chemical shifts of the carbon atoms of the conjugated diene system of each CLA isomer, it was necessary to conduct INADEQUATE, HMBC (heteronuclear multiple bond correlation) and two-dimensional 1H-13C correlation spectroscopy (COSY) techniques on the carbon signals of the diene system of the ,Z-isomers. The results of these experiments for the CLA isomers are summarized in Table 13. 

Thus far, we have reviewed basic theories and experimental techniques of Raman spectroscopy. In this chapter we shall discuss the principles, experimental design and typical applications of Raman spectroscopy that require special treatments. These include high pressure Raman spectroscopy, Raman microscopy, surface-enhanced Raman spectroscopy, Raman spectroelectro-chemistry, time-resolved Raman spectroscopy, matrix-isolation Raman spectroscopy, two-dimensional correlation Raman spectroscopy, Raman imaging spectrometry and non-linear Raman spectroscopy. The applications of Raman spectroscopy discussed in this chapter are brief in nature and are shown to illustrate the various techniques. Later chapters are devoted to a more extensive discussion of Raman applications to indicate the breadth and usefulness of the Raman technique. 

X-ray absorption near-edge structure X-ray photoelectron spectroscopy two dimensional correlation analysis of IR dynamic spectra... 

Other two-dimensional techniques, such as COSY (122), DEPT (123), HOHAHA, soHd state (124) etc. give varying degrees of success when apphed to the stmcture-property relationship of cellulose triesters. The recent appHcation of multiple-bond correlation (HMBC) spectroscopy for... 

Figure 3.1 The various time periods in a two-dimensional NMR experiment. Nuclei are allowed to approach a state of thermal equilibrium during the preparation period before the first pulse is applied. This pulse disturbs the equilibrium ptolariza-tion state established during the preparation period, and during the subsequent evolution period the nuclei may be subjected to the influence of other, neighboring spins. If the amplitudes of the nuclei are modulated by the chemical shifts of the nuclei to which they are coupled, 2D-shift-correlated spectra are obtained. On the other hand, if their amplitudes are modulated by the coupling frequencies, then 2D /-resolved spectra result. The evolution period may be followed by a mixing period A, as in Nuclear Overhauser Enhancement Spectroscopy (NOESY) or 2D exchange spectra. The mixing period is followed by the second evolution (detection) period) ij.

Two-dimensional spectroscopy is a rather novel concept, and a powerful tool in analysing spectra. The advantages of generalised 2D correlation spectroscopy are ... 

I. Noda and Y. Ozaki, Two-Dimensional Correlation Spectroscopy, Wiley-Interscience, New York, NY (2004). 

As noted by Liu et al. [42], there is a resurgence of interest in measuring diffusion coefficients using NMR spectroscopy, particularly in complex biological fluids which contain a number of molecules having a broad range of molecular weights and concentrations. These authors demonstrated the use of two-dimensional diffusion-edited total correlation NRM spectroscopy to measure diffusion coefficients in human blood samples. 

M Lui, JK Nicholson, JA Parkinson, JC Lindon. Measurement of bimolecular diffusion coefficients in blood plasma using two-dimensional 1II-1 II diffusion-edited total-correlation NMR spectroscopy. Anal Chem 69 1504-1509, 1997. 

Advanced EPR techniques such as CW and pulsed ENDOR, electron spin-echo envelope modulation (ESEEM), and two-dimensional (2D)-hyperfine sublevel correlation spectroscopy (HYSCORE) have been successfully used to examine complexation and electron transfer between carotenoids and the surrounding media in which the carotenoid is located. 

TOCSY Total correlation spectroscopy. One and two-dimensional techniques that are analogous to COSY but which differ in that it shows couplings within specific spin systems. 

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