Spectroscopy nuclear Overhauser effect

For large molecules, such as proteins, the main method in use is a 2D technique, called NOESY (nuclear Overhauser effect spectroscopy). The basic experiment [33, 34] consists of tluee 90° pulses. The first pulse converts die longitudinal magnetizations for all protons, present at equilibrium, into transverse magnetizations which evolve diirhig the subsequent evolution time In this way, the transverse magnetization components for different protons become labelled by their resonance frequencies. The second 90° pulse rotates the magnetizations to the -z-direction. 

The 2-D nuclear Overhauser effect spectroscopy (2-D-NOESY) experiment resembles the COSY however, the cross-peaks arise from... 

NOESY Nuclear Overhauser effect spectroscopy, detection of NOE in the HH COSY square format, traces out closely spaced protons in larger molecules... 

Figure 1. Pulse sequences of some typical 2D-NMR experiments. COSY = correlation SpectroscopY, DQFCOSY = Double Quantum Filtered COSY, RELAY = RELAYed Magnetization Spectroscopy, and NOESY = Nuclear Overhauser Effect SpectroscopY.

Rao, B. D. N. Two-dimensional transferred nuclear Overhauser effect spectroscopy (TRNOESY) smdies of nucleotide conformations in creatine kinase complexes effects due to weak nonspedftc binding. Biochemistry 1993,... 

Guichard, G., Briand, J. P., Muller, S., Cung, M. T. Structure of antibody-bound peptides and retro-inverso analogues. A transferred nuclear Overhauser effect spectroscopy and molecular dynamics approach. Biochemistry 2001, 40, 5720-5727. 

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

Conformations of mycothiol bimane (MSmB) were studied by H and 13C NMR using rotational nuclear Overhauser effect spectroscopy (ROESY) and heteronuclear single quantum correlation (HSQC) methods with expansions of the anomeric region <2003JOC3380>. NMR characterization of iV-acetyl-L-(Y)-cysteinyl monobimane and peracetylated MSmB was also published (Section 12.10.15.4) <2002JA3492>. 

Benzoylation of D-g/ycero-D-gw/o-heptono-1,4-lactone with an excess of benzoyl chloride and pyridine afforded the hept-2-enono-1,4-lactone as the main product (198). The di- and triunsaturated compounds were isolated in very low yield from the mother liquors (199). Higher yields of the di- and triunsaturated derivatives 153 and 154 were obtained when the /5-elimination reaction was performed with triethylamine on the previously synthesized per-O-benzoyl D-g/ycero-D-gw/o-heptono-1,4-lactone. Employing 10% triethylamine in chloroform, the lactone 153 was obtained as an E, Z dias-tereomeric mixture in 9 11 ratio as determined by H n.m.r. When 20% triethylamine was used, the furanone 154 was obtained in 59% yield (200). Its structure was assigned, on the basis of H and 13C n.m.r. spectra, as 3 -benzoyloxy - (5Z)-[(Z)-3 - benzoyloxy - 2 - propenyliden] -2(5 H)- furanone. The stereochemistry of the exocyclic double bonds was established (201) by nuclear Overhauser effect spectroscopy (NOESY). 

Sowinski and coworkers40 reported a structure of vacidin A (63), an aromatic hep-taene macrolide antibiotic. The constitution of vacidin A, a representative of the aromatic heptaene macrolide antibiotics, was established on the basis of 13C and H- H double quantum filtered correlated spectroscopy, rotating frame nuclear Overhauser effect spectroscopy, 7-resolved 11 as well as H-13C correlation NMR spectra. The geometry of the polyene chromophore was determined as 22E, 24E, 26E, 28Z, 30Z, 32E, 34E. 

The data from H NMR studies of 63, which included double quantum filtered phase sensitive correlated spectroscopy (DQF-COSY) and rotating frame nuclear Overhauser effect spectroscopy (ROESY) experiments (Figure 12), are collected in Table 17. 

Another, yet completely different access to macroscopic binding strengths of selectands on CSPs has been described by Hellriegel et al. [65] employing suspended-state NMR spectroscopy. Thus, HR-MAS 2D transfer-nuclear Overhauser effect spectroscopy (NOESY) was utilized to distinguish solutes strongly binding to the... 

TTie TOCSY 2D NMR experiment correlates all protons of a spin system, not just those directly connected via three chemical bonds. For the protein example, the alpha proton, Ft , and all the other protons are able to transfer magnetization to the beta, gamma, delta, and epsilon protons if they are connected by a continuous chain—that is, the continuous chain of protons in the side chains of the individual amino acids making up the protein. The COSY and TOCSY experiments are used to build so-called spin systems—that is, a list of resonances of the chemical shift of the peptide main chain proton, the alpha proton(s), and all other protons from each aa side chain. Which chemical shifts correspond to which nuclei in the spin system is determined by the conventional correlation spectroscopy connectivities and the fact that different types of protons have characteristic chemical shifts. To connect the different spin systems in a sequential order, the nuclear Overhauser effect spectroscopy... 

Two-dimensional (2D) Nuclear Overhauser Effect Spectroscopy (NOESY) has been proven to be a valuable technique which provides both structural and... 

Two-Dimensional NMR—Basically, the two-dimensional NMR techniques of nuclear Overhauser effect spectroscopy (NOESY) and correlation spectroscopy (COSY) depend on the observation that spins on different protons interact with one another. Protons that are attached to adjacent atoms can be directly spin-coupled and thus can be studied using the COSY method. This technique allows assignment of certain NMR frequencies by tracking from one atom to another. The NOESY approach is based on the observation that two protons closer than about 0.5 nm perturb one another s spins even if they are not closely coupled in the primary structure. This allows spacial geometry to be determined for certain molecules. 

ROESY rotahonal frame nuclear overhauser effect spectroscopy... 

The most conclusive evidence for the presence of duplexes la la and 2 2 came from 2-D H-NMR [nuclear Overhauser effect spectroscopy (NOESY)] and X-ray crystallography. The NOESY spectrum of lb in CDCI3 contains interstrand NOEs (Fig. 9.2a) between protons c and e, c and i, and c and j, which are consistent with an H bonded dimer. The crystal structures of la and 2 both revealed the expected dimeric stmctures held together by intermolecular H bonds (Fig. 9.2b). 

Figure 9.18 Partial 2-D H-NMR spectra of disulfide cross-linked 26-27 in (a) CDCI3 (rotational nuclear Overhauser effect spectroscopy, 278 000, 0.3-s mixing time) and (b) H20/THF-(7g (80/20, v/v NOESY, 278 000, 0.3-s mixing time). The same interstrand NOEs were detected in both CDCI3 and H20/THF-ii8.

Lin, Y Nageswara Rao, B.D. Structural characterization of adenine nucleotides bound to Escherichia coli adenylate kinase. 1. adenosine conformations by proton two-dimensional transferred nuclear overhauser effect spectroscopy. Biochemistry, 39, 3636-3646 (2000)... 

Nuclear Overhauser effect spectroscopy NOESY Interactions through space/chemical exchange... 

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