ABSTRACT
Although the concepts of nonuniform sampling (NUSâââââââ) and non-Fourier spectral reconstruction in multidimensional NMR began to emerge 4 decades ago , it is only relatively recently that NUS has become more commonplace. Advantages of NUS include the ability to tailor experiments to reduce data collection time and to improve spectral quality, whether through detection of closely spaced peaks (i.e., "resolution") or peaks of weak intensity (i.e., "sensitivity"). Wider adoption of these methods is the result of improvements in computational performance, a growing abundance and flexibility of software, support from NMR spectrometer vendors, and the increased data sampling demands imposed by higher magnetic fields. However, the identification of best practices still remains a significant and unmet challenge. Unlike the discrete Fourier transform, non-Fourier methods used to reconstruct spectra from NUS data are nonlinear, depend on the complexity and nature of the signals, and lack quantitative or formal theory describing their performance. Seemingly subtle algorithmic differences may lead to significant variabilities in spectral qualities and artifacts. A community-based critical assessment of NUS challenge problems has been initiated, called the "Nonuniform Sampling Contest" (NUScon), with the objective of determining best practices for processing and analyzing NUS experiments. We address this objective by constructing challenges from NMR experiments that we inject with synthetic signals, and we process these challenges using workflows submitted by the community. In the initial rounds of NUScon our aim is to establish objective criteria for evaluating the quality of spectral reconstructions. We present here a software package for performing the quantitative analyses, and we present the results from the first two rounds of NUScon. We discuss the challenges that remain and present a roadmap for continued community-driven development with the ultimate aim of providing best practices in this rapidly evolving field. The NUScon software package and all data from evaluating the challenge problems are hosted on the NMRbox platform.
ABSTRACT
The grouping of data in bursts, also referred to as clusters, spikes or clumps, is a common phenomenon in stochastic sampling. There have been several reports that suggest that in NMR, the presence of such bursts is beneficial to spectral reconstruction where data are sampled nonuniformly. In this work, we seek to define a mode of sampling that produces bursts of randomly distributed data in a controlled manner. An algorithm is described for achieving this where the burst length and its uniformity is controlled - we refer to this type of sampling mode as clustered sampling. Measures are introduced for assessing the "burstiness" of nonuniformly sampled data in multiple dimensions and properties of the point-spread-function of these schedules are assessed. The clustered sampling method is applied to samples drawn from an exponentially weighted distribution either distributed randomly or pseudo-randomly by use of a jittering algorithm. The results reveal that bursts introduce characteristic sampling artifacts that are shifted to low frequencies (red shifted), with respect to the signal frequency, and that they produce artifact-reduced regions at frequencies related to the burst length. This observation is contrary to that observed for sampling methods that seek to evenly distribute NUS data, such as jittered or Poisson sampling. Extensive evaluation of simulated data with comparable inherent sensitivity, reveals that at high sampling coverage (25% in 1D), the distribution of the data has little impact on common spectral quality measures. Application of the introduced clustered sampling method to an experimental 3D NOESY experiment showed results consistent with that found for the simulated 1D data. However, in the extremes of very sparse sampling, the results suggest that there may be some advantages associated with incorporation of bursts in nonuniform sampling. The tools and theory presented will serve as a starting point to further explore this novel mode of sampling in NMR.
