Sensitivity considerations in polarization transfer and filtering using dipole–dipole couplings: Implications for biomineral systems

• Published in: Solid state nuclear magnetic resonance Vol. 29; no. 1; pp. 170 - 182
• Main Authors: Christiansen, Sean C., Hedin, Niklas, Epping, Jan D., Janicke, Michael T., del Amo, Yolanda, Demarest, Mark, Brzezinski, Mark, Chmelka, Bradley F.
• Format: Journal Article
• Language: English
• Published: Netherlands Elsevier Inc 01.02.2006
• Subjects: 13C CP MAS; 15N CP MAS; 29Si CP MAS; Biopolymers - analysis; Biopolymers - chemistry; Carbon Isotopes; Cross-polarization; Diatoms; Filtration - methods; Glycine; Heteronuclear dipole–dipole couplings; Minerals - analysis; Minerals - chemistry; Nuclear Magnetic Resonance, Biomolecular - methods; Polarization transfer efficiency; Protons; Reproducibility of Results; Sensitivity and Specificity; Signal sensitivity; TEDOR; Polarization transfer efficiency; TEDOR; 13C CP MAS; Cross-polarization; 15N CP MAS; Glycine; Diatoms; 29Si CP MAS; Heteronuclear dipole–dipole couplings; Signal sensitivity
• ISSN: 0926-2040; 1527-3326
• DOI: 10.1016/j.ssnmr.2005.10.010

The robustness and sensitivities of different polarization-transfer methods that exploit heteronuclear dipole–dipole couplings are compared for a series of heterogeneous solid systems, including polycrystalline tetrakis(trimethylsilyl)silane (TKS), adamantane, a physical mixture of doubly 13C, 15N-enriched and singly 13C-enriched polycrystalline glycine, and a powder sample of siliceous marine diatoms, Thalossiosira pseudonana. The methods were analyzed according to their respective frequency-matching spectra or resultant signal intensities. For a series of 13C{ 1H} cross-polarization experiments, adiabatic passage Hartmann–Hahn cross-polarization (APHH-CP) was shown to have several advantages over other methods, including Hartmann–Hahn cross-polarization (HHCP), variable-amplitude cross-polarization (VACP), and ramped-amplitude cross-polarization (RACP). For X–Y systems, such as 13C{ 15N}, high and comparable sensitivities were obtained by using APHH-CP with Lee–Goldburg decoupling or by using the transferred-echo double resonance (TEDOR) experiment. The findings were applied to multinuclear 1H, 13C, 15N, and 29Si CP MAS characterization of a powder diatom sample, a challenging inorganic–organic hybrid solid that places high demands on NMR signal sensitivity.