Exchange and nmr

Ichikawa, K. and Matsumoto, T., An aluminium-27 NMR study of chemical exchange and NMR line broadening in molten butylpyridinium chloride + AlClg ll,/. Magn. Reson., 63,445,1985. 

Jacobs, M. D. Fox, R. O. (1994). Staphylococcal nuclease folding intermediate charaterized by hydrogen exchange and NMR spectroscopy. Proc. Natl. Acad. Sci. USA 91,449-453. 

Does the considerable secondary structure retained by the molten globule represent part of the native structure, as it should if the molten globules were actually identical to the thermodynamically stable kinetic intermediates observed upon protein folding before organization of the specific tertiary structure [107,111,112,119,120] Hydrogen exchange and NMR studies of the structure of the supposedly... 

Jen J (1978) Chemical exchange and NMR T2 relaxation - multisite case. J Magn Reson 30 ... 

Zhang, Y.-Z. (1995) Protein and peptide structure and interactions studied by hydrogen exchange and NMR. Ph.D. dissertation. University of Pennsylvania. 

These exchanges often occur while the system is in macroscopic equilibrium—the sample itself remains the same and the dynamics may be invisible to other teclmiques. It is merely the enviromnent of a given nucleus that changes. Since NMR follows an individual nucleus, it can easily follow these dynamic processes. This is just one of several reasons that the study of chemical exchange by NMR is important. 

The NMR experimental methods for studying chemical exchange are all fairly routine experiments, used in many other NMR contexts. To interpret these results, a numerical model of the exchange, as a frmction of rate, is fitted to the experimental data. It is therefore necessary to look at the theory behind the effects of chemical exchange. Much of the theory is developed for intennediate exchange, and this is the most complex case. However, with this theory, all of the rest of chemical exchange can be understood. 

The method for studying intennediate exchange in NMR is to obtain an excellent equilibrium spectmm of tlie system as a fiinction of temperature. Then the theoretical apparatus developed above can be used to simulate and to fit the experimental data, in order to obtain the rate data. 

Kleier D A and Binsch G 1970 General theory of exchange-broadened NMR line shapes. II. Exploitation of invariance properties J. Magn. Reson. 3 146-60... 

In 1971 the Protein Data Bank - PDB [146] (see Section 5.8 for a complete story and description) - was established at Brookhaven National Laboratories - BNL -as an archive for biological macromolccular cr7stal structures. This database moved in 1998 to the Research Collaboratory for Structural Bioinformatics -RCSB. A key component in the creation of such a public archive of information was the development of a method for effreient and uniform capture and curation of the data [147], The result of the effort was the PDB file format [53], which evolved over time through several different and non-uniform versions. Nevertheless, the PDB file format has become the standard representation for exchanging inacromolecular information derived from X-ray diffraction and NMR studies, primarily for proteins and nucleic acids. In 1998 the database was moved to the Research Collaboratory for Structural Bioinformatics - RCSB. 

Cyanuric acid is a titrable weak acid (pffai — 6.88, pifa2 — H-40, pffas — 13.5) (10). The pH of a saturated aqueous solution of pure CA at room temperature is - 4.8. Thermodynamic properties of CA are given ia Table 1. Spectroscopic data are available (1 3). Proton nmr is of limited usefulness because of proton exchange and CA s symmetry and low solubiUty. Nuclear quadmpole resonance measurements ( " N) have been reported (12). 

It is also possible to measme the rate of enolization by isotopic exchange. NMR spectroscopy provides a very convenient method for following hydrogen-deuterium exchange, and this is now the preferred method. Data for several ketones are given in... 

AHC(S1), pp. 384,385]. For some derivatives of 119 and 120, the relative stability of oxo isomers may be enhanced. Thus, the predominance of the 5,5-diphenyldihydro-4//-l,2,3-triazol-4-one structure 121 in solution has been confirmed by UV and and NMR studies (93CB103). Also, 1-methyl-5-hydroxy-l,2,3-triazole exists mainly in the tautomeric form 120 (R = Me, R = H) [76AHC(S1), p. 385], although the existence of a minor amount of oxo form 122 was postulated to explain the exchange of the 4-position proton in D2O. 

Tile tautomeric equilibrium of pyrimido[4,5-h][4, 5 -e]thiazine 157 was studied in DMSO-dg by NMR spectroscopy (92CHE1219). Based on and NMR chemical shifts, fast proton exchange was concluded to occur between 157b and 157c. Monoprotonation of 157 has been assumed to form... 

The structures of these ylide polymers were determined and confirmed by IR and NMR spectra. These were the first stable sulfonium ylide polymers reported in the literature. They are very important for such industrial uses as ion-exchange resins, polymer supports, peptide synthesis, polymeric reagent, and polyelectrolytes. Also in 1977, Hass and Moreau [60] found that when poly(4-vinylpyridine) was quaternized with bromomalonamide, two polymeric quaternary salts resulted. These polyelectrolyte products were subjected to thermal decyana-tion at 7200°C to give isocyanic acid or its isomer, cyanic acid. The addition of base to the solution of polyelectro-lyte in water gave a yellow polymeric ylide. 

Shaw, C.F. Ill, Eldridge, J. and Cancro, M.O. (1981) Carbon-13 NMR studies of aurothioglucose ligand exchange and redox disproportionation reactions. Journal of Inorganic Biochemistry, 14, 267-274. 

Beryllium(II) is the smallest metal ion, r = 27 pm (2), and as a consequence forms predominantly tetrahedral complexes. Solution NMR (nuclear magnetic resonance) (59-61) and x-ray diffraction studies (62) show [Be(H20)4]2+ to be the solvated species in water. In the solid state, x-ray diffraction studies show [Be(H20)4]2+ to be tetrahedral (63), as do neutron diffraction (64), infrared, and Raman scattering spectroscopic studies (65). Beryllium(II) is the only tetrahedral metal ion for which a significant quantity of both solvent-exchange and ligand-substitution data are available, and accordingly it occupies a... 

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