Effect Spectroscopy

H) RAMAN INDUCED KERR EFFECT SPECTROSCOPY (RIKES)... 

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. 

Rikes. See Raman-induced Kerr-effect spectroscopy. 

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.

Some of the transition metal macrocycles adsorbed on electrode surfaces are of special Interest because of their high catalytic activity for dloxygen reduction. The Interaction of the adsorbed macrocycles with the substrate and their orientation are of Importance In understanding the factors controlling their catalytic activity. In situ spectroscopic techniques which have been used to examine these electrocatalytlc layers Include visible reflectance spectroscopy surface enhanced and resonant Raman and Mossbauer effect spectroscopy. This paper Is focused principally on the cobalt and Iron phthalocyanlnes on silver and carbon electrode substrates. 

Mossbauer effect spectroscopy, MES, Is based on the ability of certain nuclei to undergo recoilless emission and absorption ofY rays (16). The energy and multiplicity of the ground and excited states of a given nucleus are modified by the chemical environment. It Is thus most often necessary to compensate for the differences In... 

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. 

Palacios, M.A., Frese, R.N., Gradinaru, C.G., Premvardhan, L., Horton, P., Ruban, A.V., van Grondelle, R., and van Amerongen, H. 2003. Stark effect spectroscopy of the different oligomerisation states of lightharvesting complex II. Biochim. Biophys. Acta 1605 83-95. 

In order to combat this, the rotating frame Overhauser effect spectroscopy (ROESY) techniques can be employed. An in-depth discussion of how this technique works is outside the remit of this book but suffice to say, in the ROESY methods (1- and 2-D), NOE data is acquired as if in a weak r.f. field rather than in a large, static magnetic field and this assures that all NOEs are present and positive, irrespective of tumbling rate and magnet size. It is possible that some TOCSY correlations can break through in ROESY spectra but these will have opposite phase to the genuine ROESY correlations and so should therefore not be a problem - unless they should overlap accidentally with them. A 2-D ROESY spectrum of the naphthalene compound is shown below (Spectrum 8.6). 

GOESY Gradient Overhauser effect spectroscopy. An early version of a 1-D NOESY making use of gradients. 

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

ROESY Rotating-frame Overhauser effect spectroscopy. A variation (one and two dimensional) on the nuclear Overhauser experiment (NOE). The techniques have the advantage of being applicable for all sizes of molecule. See Laboratory frame model. 

Pierce DW, Boxer SG (1995) Stark effect spectroscopy of tryptophan. Biophys J 68 1583-1591... 

The HOESY (Heteronuclear Overhauser Effect Spectroscopy) experiment... 

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>. 

Gas-phase methanol hydrochlorination process, 16 322-323 Gas-phase mirage-effect spectroscopy,... 

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. 

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