Temperature-Independent Cuprate Pseudogap from Planar Oxygen NMR

Planar oxygen nuclear magnetic resonance (NMR) relaxation and shift data from all cuprate superconductors available in the literature are analyzed. They reveal a temperature-independent pseudogap at the Fermi surface, which increases with decreasing doping in family-specific ways, i.e., for some materials, the pseudogap is substantial at optimal doping while for others it is nearly closed at optimal doping. The states above the pseudogap, or in its absence are similar for all cuprates and doping levels, and Fermi liquid-like. If the pseudogap is assumed exponential it can be as large as about 1500 K for the most underdoped systems, relating it to the exchange coupling. The pseudogap can vary substantially throughout a material, being the cause of cuprate inhomogeneity in terms of charge and spin, so consequences for the NMR analyses are discussed. This pseudogap appears to be in agreement with the specific heat data measured for the YBaCuO family of materials, long ago. Nuclear relaxation and shift show deviations from this scenario near Tc, possibly due to other in-gap states.

Measuring transverse relaxation in highly paramagnetic systems

The enhancement of nuclear relaxation rates due to the interaction with a paramagnetic center (known as Paramagnetic Relaxation Enhancement) is a powerful source of structural and dynamics information, widely used in structural biology. However, many signals affected by the hyperfine interaction relax faster than the evolution periods of common NMR experiments and therefore they are broadened beyond detection. This gives rise to a so-called blind sphere around the paramagnetic center, which is a major limitation in the use of PREs. Reducing the blind sphere is extremely important in paramagnetic metalloproteins. The identification, characterization, and proper structural restraining of the first coordination sphere of the metal ion(s) and its immediate neighboring regions is key to understand their biological function. The novel HSQC scheme we propose here, that we termed R2-weighted, HSQC-AP, achieves this aim by detecting signals that escaped detection in a conventional HSQC experiment and provides fully reliable R2 values in the range of 1H R2 rates ca. 50–400 s−1. Independently on the type of paramagnetic center and on the size of the molecule, this experiment decreases the radius of the blind sphere and increases the number of detectable PREs. Here, we report the validation of this approach for the case of PioC, a small protein containing a high potential 4Fe-4S cluster in the reduced [Fe4S4]2+ form. The blind sphere was contracted to a minimal extent, enabling the measurement of R2 rates for the cluster coordinating residues.