Artifacts in time-resolved NUS: A case study of NOE build-up curves from 2D NOESY

Rupashree Dass; Paweł Kasprzak; Wiktor Koźmiński; Krzysztof Kazimierczuk

doi:10.1016/j.jmr.2016.01.025

Artifacts in time-resolved NUS: A case study of NOE build-up curves from 2D NOESY

J Magn Reson. 2016 Apr:265:108-16. doi: 10.1016/j.jmr.2016.01.025. Epub 2016 Feb 12.

Authors

Rupashree Dass¹, Paweł Kasprzak², Wiktor Koźmiński¹, Krzysztof Kazimierczuk³

Affiliations

¹ Faculty of Chemistry, Biological and Chemical Research Centre, University of Warsaw, Żwirki i Wigury 101, 02-089 Warsaw, Poland.
² Department of Mathematical Methods in Physics, Faculty of Physics, University of Warsaw, Pasteura 5, Warsaw, Poland.
³ Centre of New Technologies, University of Warsaw, Banacha 2C, 02-097 Warsaw, Poland. Electronic address: k.kazimierczuk@cent.uw.edu.pl.

PMID: 26896866
DOI: 10.1016/j.jmr.2016.01.025

Abstract

Multidimensional NMR spectroscopy requires time-consuming sampling of indirect dimensions and so is usually used to study stable samples. However, dynamically changing compounds or their mixtures commonly occur in problems of natural science. Monitoring them requires the use multidimensional NMR in a time-resolved manner - in other words, a series of quick spectra must be acquired at different points in time. Among the many solutions that have been proposed to achieve this goal, time-resolved non-uniform sampling (TR-NUS) is one of the simplest. In a TR-NUS experiment, the signal is sampled using a shuffled random schedule and then divided into overlapping subsets. These subsets are then processed using one of the NUS reconstruction methods, for example compressed sensing (CS). The resulting stack of spectra forms a temporal "pseudo-dimension" that shows the changes caused by the process occurring in the sample. CS enables the use of small subsets of data, which minimizes the averaging of the effects studied. Yet, even within these limited timeframes, the sample undergoes certain changes. In this paper we discuss the effect of varying signal amplitude in a TR-NUS experiment. Our theoretical calculations show that the variations within the subsets lead to t1-noise, which is dependent on the rate of change of the signal amplitude. We verify these predictions experimentally. As a model case we choose a novel 2D TR-NOESY experiment in which mixing time is varied in parallel with shuffled NUS in the indirect dimension. The experiment, performed on a sample of strychnine, provides a near-continuous NOE build-up curve, whose shape closely reflects the t1-noise level. 2D TR-NOESY reduces the measurement time compared to the conventional approach and makes it possible to verify the theoretical predictions about signal variations during TR-NUS.

Keywords: NOESY; Non-uniform sampling; Signal-to-artifact ratio; Strychnine; Time-resolved spectroscopy; Variable mixing time.

Publication types

Research Support, Non-U.S. Gov't