Photo-CIDNP experiments with an optimized presaturation pulse train, gated continuous illumination, and a background-nulling pulse grid.
Methods to record chemically induced dynamic nuclear polarization (CIDNP) spectra that are virtually free from background magnetization and avoid the sensitivity loss and subtraction artifacts of difference spectroscopy have been developed. Presaturation by a string of composite pi/2 pulses, each followed by a defocussing field gradient, is analyzed, and guidelines for the optimization of pulse phases and gradient strengths are derived. Subsequent gated illumination during a grid of pi pulses with a prescribed timing causes the background magnetization to vanish at those moments of a pulse sequence when CIDNP magnetization is to be sampled or transferred. By shifting the illumination intervals within such a grid, the sign of the polarizations can be inverted without influencing the development of the background magnetization, allowing a further strong suppression of residual background by a phase cycle. Experimental examples for the application of these methods to more complex CIDNP experiments (1D-CIDNP-COSY, 1D-CIDNP-TOCSY, CIDNP-induced heteronuclear Overhauser effects, water suppression in protein CIDNP) are given.
Goez
Martin
M
Fachbereich Chemie, Martin-Luther-Universität Halle-Wittenberg, Kurt-Mothes-Strasse 2, D-06120 Halle/Saale, Germany. goez@chemie.uni-halle.de
Mok
K Hun
KH
Hore
P J
PJ
D000818:Animals; D016477:Artifacts; D002417:Cattle; D005415:Flavins / Q000737:chemistry; D007768:Lactalbumin / Q000737:chemistry*; D019906:Nuclear Magnetic Resonance, Biomolecular / Q000379:methods*; D012680:Sensitivity and Specificity; D014364:Tryptophan / Q000737:chemistry
D005415:Flavins; D014364:Tryptophan; D007768:Lactalbumin