Category Archives: pulse sequence

Boosting sensitivity and suppressing artifacts via multi-acquisition in direct polarization NMR experiments with small flip-angle pulses

This is not directly related to DNP spectroscopy but an interesting method to increase the sensitivity specifically in solid-state NMR experiments. This method is compatible with DNP and in combination can lead to even larger sensitivity gains than just DNP.

Fu, Riqiang, and Arturo J. Hernández-Maldonado. “Boosting Sensitivity and Suppressing Artifacts via Multi-Acquisition in Direct Polarization NMR Experiments with Small Flip-Angle Pulses.” Journal of Magnetic Resonance 293 (August 1, 2018): 34–40.

https://doi.org/10.1016/j.jmr.2018.05.015

A small flip-angle pulse direct polarization is the simplest method commonly used to quantify various compositions in many materials applications. This method sacrifices the sensitivity per scan in exchange for rapid repeating of data acquisition for signal accumulation. In addition, the resulting spectrum often encounters artifacts from background signals from probe components and/or from acoustic rings leading to a distorted baseline, especially in low-γ nuclei and wideline NMR. In this work, a multi-acquisition scheme is proposed to boost the sensitivity per scan and at the same time effectively suppress these artifacts. Here, an adiabatic inversion pulse is first applied in order to bring the magnetization from the +z to −z axis and then a small flip-angle pulse excitation is used before the data acquisition. Right after the first acquisition, the adiabatic inversion pulse is applied again to flip the magnetization back to the +z axis. The second data acquisition takes place after another small flip-angle pulse excitation. The difference between the two consecutive acquisitions cancels out any artifacts, while the wanted signals are accumulated. This acquisition process can be repeated many times before going into next scan. Therefore, by acquiring the signals multiple times in a single scan the sensitivity is improved. A mixture sample of flufenamic acid and 3,5-difluorobenzoic acid and a titanium silicate sample have been used to demonstrate the advantages of this newly proposed method.

DNP enhanced NMR with flip-back recovery #DNPNMR

Bjorgvinsdottir, S., et al., DNP enhanced NMR with flip-back recovery. J Magn Reson, 2018. 288: p. 69-75.

https://www.ncbi.nlm.nih.gov/pubmed/29414065

DNP methods can provide significant sensitivity enhancements in magic angle spinning solid-state NMR, but in systems with long polarization build up times long recycling periods are required to optimize sensitivity. We show how the sensitivity of such experiments can be improved by the classic flip-back method to recover bulk proton magnetization following continuous wave proton heteronuclear decoupling. Experiments were performed on formulations with characteristic build-up times spanning two orders of magnitude: a bulk BDPA radical doped o-terphenyl glass and microcrystalline samples of theophylline, l-histidine monohydrochloride monohydrate, and salicylic acid impregnated by incipient wetness. For these systems, addition of flip-back is simple, improves the sensitivity beyond that provided by modern heteronuclear decoupling methods such as SPINAL-64, and provides optimal sensitivity at shorter recycle delays. We show how to acquire DNP enhanced 2D refocused CP-INADEQUATE spectra with flip-back recovery, and demonstrate that the flip-back recovery method is particularly useful in rapid recycling regimes. We also report Overhauser effect DNP enhancements of over 70 at 592.6GHz/900MHz.

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