By Claudio Luchinat, Mario Piccioli (auth.), Gerd N. La Mar (eds.)
Since A. Kowalsky's first document of the spectrum of cytochrome c in 1965, curiosity within the detection, task and interpretation of paramagnetic molecules has surged, particularly within the final decade.
periods of structures have performed a key position within the improvement of the sector: heme proteins and iron-sulfur proteins. those structures are distinct in lots of respects, one in every of that's that they include well-defined chromophores, each one of that are studied intimately outdoors the protein matrix. they're the main effectively studied macromolecules, and the 1st 8 and final six of the seventeen contributions to this e-book care for heme and/or iron-sulfur proteins. the center 3 chapters survey the development on, and demanding promise of, tougher platforms which don't own a chromophore, yet that have however yielded awesome insights into their constitution.
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Extra info for Nuclear Magnetic Resonance of Paramagnetic Macromolecules
62], with permission) 42 The active site of cobalt-substituted superoxide dismutase is shown in Fig. 7[67-69]. In this case we have a copper(II) (S=l/2) and a high spin (S=3/2) cobalt(II) coupled. antiferromagnetically susceptibility Magnetic measurements have shown that J= 33 cm-1 . The coupling energy is therefore small compared to kT, so that at room temperature all the magnetically almost coupled equally levels populated. are The Figure 7. Schematic drawing of the metal sites in superoxide dismutase.
An NMR investigation of the thiocyanate adduct of the cobalt(II)-substituted human carbonic anhydrase II, J. Magn. Reson. in press 26 45. S. W. G.. 291. 46. , Monnanni, R. and Scozzafava, A (1985) Investigation of Cu2Co2SOD and its anion derivatives. 1H NMR and electronic spectra, J. Am. Chem. Soc. 107, 4391-4396. 47. , Luchinat, C. and Piccioli, M. (1994) Copper zinc superoxide dismutase a paramagnetic protein that provides a unique frame for the NMR investigations, Progr. Nucl. Magn. Reson. Spectrosc.
For protons in paramagnetic molecules Curie spin relaxation is the only sizable form of chemical shift anisotropy. 15 CDC A t 2 • 0 c 21 2H 200 400_ t ... 0 11 eoo 11 11 800 ppm ppm 60 40 20 ppm 40 60 20 ppm 60 40 20 6 1'HI Figure 10. 15N_lH HMQC experiments performed on (A) anion-free Cu 2co2 SOD, (B) Cu 2 co2 SOD+N 3 -, (C) Cu 2 co 2SOD+CW. 15 N enriclunent was about 98%. The experiments were performed in magnitude mode, using the four pulse sequence described by Bax et al. [53). The delay between the first two pulses was set to match the T2 values of the proton signals (I.
Nuclear Magnetic Resonance of Paramagnetic Macromolecules by Claudio Luchinat, Mario Piccioli (auth.), Gerd N. La Mar (eds.)