Quantitative measurement of small through-hydrogen-bond and ‘through-space’1H-113Cd and1H-199Hg J couplings in metal-substituted rubredoxin fromPyrococcus furiosus

  title={Quantitative measurement of small through-hydrogen-bond and ‘through-space’1H-113Cd and1H-199Hg J couplings in metal-substituted rubredoxin fromPyrococcus furiosus},
  author={Paul R. Blake and B X B Lee and Michael F. Summers and M. W. W. Adams and J B Park and Z. H. Zhou and Adriaan Bax},
  journal={Journal of Biomolecular NMR},
SummaryA method is described for measurement of small unresolvable heteronuclear J couplings. The method is based on quantitative analysis of a phase-purged heteronuclear spin-echo difference spectrum, and is demonstrated for measuring1H-113Cd and1H-199Hg J couplings in metal-substituted rubredoxin (Mr ∼ 5.4 kDa) fromPyrococcus furiosus. Couplings from cadmium to backbone amide protons that are hydrogen bonded to the Cys-S atoms directly bonded to Cd vary from smaller than 0.3 to 1.8 Hz; a… Expand
Measurement of two- and three-bond 13C−1H J couplings to the Cδ carbons of leucine residues in staphylococcal nuclease
A new 1H-detected 3D NMR experiment is described that permits quantitative measurement of two- and three-bond 13C−1H couplings in proteins with selectively 13C-enriched methyl sites, and the χ2- and the stereospecific assignments of the Cδ methyl group with respect to the prochiral β-protons were determined. Expand
Observation of through-hydrogen-bond 2hJHC' in a perdeuterated protein.
It is demonstrated that J connectivity between amide protons and hydrogen-bond-accepting carbonyl carbons can be observed in perdeuterated human ubiquitin. A selective pulse scheme is used to detectExpand
NMR determination of the global structure of the 113Cd derivative of desulforedoxin: Investigation of the hydrogen bonding pattern at the metal center
The presence of “H‐bond mediated” coupling in Dx indicates that the NH‐S H‐bonds at the metal center have significant covalent character, and the similarity between the H‐ bonding pattern seen at theMetal center in DX, Rd, and many zinc‐finger proteins suggests that these H‐Bonds are structurally vital for stabilization of the metal centers in these proteins. Expand
Cofactor‐Apoprotein Hydrogen Bonding in Oxidized and Fully Reduced Flavodoxin Monitored by Trans‐Hydrogen‐Bond Scalar Couplings
Good correlations between hJ coupling constants and donor‐group 1H chemical shifts and also crystallographic donor–acceptor distances are observed and the magnitudes of both hJ and regular J couplings are found to be dependent on the redox state. Expand
The use of 113Cd NMR chemical shifts as a structural probe in tetrathiolate metalloproteins
Abstract A wide range of 113Cd chemical shifts has been observed for 113Cd-substituted metalloproteins ranging from −100 ppm, for Cd with octahedral oxygen ligands, to +760 ppm for tetrahedral sulfurExpand
Estimates of ϕ and ψ torsion angles in proteins from one-, two- and three-bond nuclear spin-spin couplings: Application to staphylococcal nuclease
Calculated coupling constants (3JHNHα, 1JCαHα, 2JC′H α, 1 JCαN and 2JCαN) have been used to generate error surfaces that can provide estimates of the ϕ and ψ angles in proteins. Expand
Quantum-mechanical study of lead coordination in sulfur-rich proteins: mode and structure recognition in UV resonance Raman spectra.
  • A. Jarzecki
  • Chemistry, Medicine
  • The journal of physical chemistry. A
  • 2012
The characteristic Pb-S symmetric stretching bands, predicted without additional refinements such as scaling of a force field or frequencies, are found and present an experimental challenge for clear detection of lead coordination via solely UVRR spectroscopy. Expand
NMR scalar couplings across Watson-Crick base pair hydrogen bonds in DNA observed by transverse relaxation-optimized spectroscopy.
NMR observation of 15N---15N and 1H--- 15N scalar couplings across the hydrogen bonds in Watson-Crick base pairs in a DNA duplex, hJNN and hJHN represents new parameters of interest for both structural studies of DNA and theoretical investigations into the nature of the hydrogen Bonds. Expand
Direct NMR Detection of Bifurcated Hydrogen Bonding in the α-Helix N-Caps of Ankyrin Repeat Proteins
New insights into the H-bonding properties of histidine are provided, a refined structural rationalization for the folding cooperativity of AR proteins, and a challenging benchmark for the calculation of HBCs are provided. Expand
Nonbonded Indirect Nuclear Spin–Spin Couplings (J Couplings “Through-Space”) for Structural Determination in Small Organic and Organometallic Species
Abstract Spin–spin coupling constant J provides decisive data for organic compound characterization. This electron-mediated coupling is usually taught as transmitted between covalently bondedExpand


NH---S hydrogen bonds in Peptococcus aerogenes ferredoxin, Clostridium pasteurianum rubredoxin, and Chromatium high potential iron protein.
Results from refinement of the crystal structures of P. aerogenes ferredoxin and C. pasteurianum rubredoxin determined by x-ray diffraction show that there are 15-18 NH---S bonds in the former and six in the latter, which suggests why the -2 form of the Fe4S4 cluster is preferred in ferred toxin over the -1 form found in high potential iron protein. Expand
Correlation of connected transitions by two‐dimensional NMR spectroscopy
A novel and general concept of restricting coherence transfer in nuclear spin systems is described. It opens new possibilities for editing one‐ and two‐dimensional NMR spectra. For example, theExpand
Relaxation-allowed cross-peaks in two-dimensional N.M.R. correlation spectroscopy
An analysis is made of the effects of non-exponential transverse relaxation during the free precession periods of two-dimensional N.M.R. experiments. It is shown, both theoretically and experimenta...