Dipolar recoupling in solid-state NMR is an essential method for establishing correlations between nuclei that are close in space. In applications on protein samples, the traditional experiments like ramped and adiabatic DCP suffer from the fact that dipolar recoupling occurs only within a limited volume of the sample. This selection is dictated by the radiofrequency (rf) field inhomogeneity profile of the excitation solenoidal coil. We employ optimal control strategies to design dipolar recoupling sequences with substantially larger responsive volume and increased sensitivity. We show that it is essential to compensate for additional temporal modulations induced by sample rotation in a spatially inhomogeneous rf field. Such modulations interfere with the pulse sequence and decrease its performance. Using large-scale optimizations we developed pulse schemes for magnetization transfer from amide nitrogen to carbonyl (NCO) as well as aliphatic carbons (NCA). Our experiments yield a signal intensity increased by a factor of 1.5 and 2.0 for NCA and NCO transfers, respectively, compared to conventional ramped DCP sequences. Consistent results were obtained using several biological samples and NMR instruments.

Bruker Biospin Silberstreifen 4 76278 Rheinstetten Germany

Department Chemie Technische Universität München Lichtenbergstr 4 85747 Garching Germany

Dept of Chemistry Faculty of Science Charles University Hlavova 8 CZ 12842 Prague 2 Czech Republic

Helmholtz Zentrum München Deutsches Forschungszentrum für Gesundheit und Umwelt Ingolstädter Landstr 1 85764 Neuherberg Germany

Institute for Biophysical Chemistry and Center for Biomolecular Magnetic Resonance Goethe University Frankfurt Frankfurt 60438 Germany

Munich Center for Integrated Protein Science Lichtenbergstr 4 85747 Garching Germany

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