Absolute Minimal Sampling in High‐Dimensional NMR Spectroscopy

Bruschweiler‐Li

et al. 2018

Chemistry A European J

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Many biomolecular NMR applications can benefit from the faster acquisition of multidimensional NMR data with high resolution and their automated analysis and interpretation. In recent years, a number of non-uniform sampling (NUS) approaches have been introduced for the reconstruction of multidimensional NMR spectra, such as compressed sensing, thereby bypassing traditional Fourier-transform processing. Such approaches are applicable to both biomacromolecules and small molecules and their complex mixtures and can be combined with homonuclear decoupling (pure shift) and covariance processing. For homonuclear 2D TOCSY experiments, absolute minimal sampling (AMS) permits the drastic shortening of measurement times necessary for high-throughput applications for identification and quantification of components in complex biological mixtures in the field of metabolomics. Such TOCSY spectra can be comprehensively represented by graphic theoretical maximal cliques for the identification of entire spin systems and their subsequent query against NMR databases. Integration of these methods in webservers permits the rapid and reliable identification of mixture components. Recent progress is reviewed in this Minireview.

true χ^{2} = trueprefixmin ({}, (∥∥, C ((), t_{1}) - C_{exp} ((), t_{1})) + (∥∥, S ((), t_{1}) - S_{exp} ((), t_{1})))

…”

Section: Uniform Versus Non‐uniform Samplingmentioning

confidence: 99%

Section: Uniform Versus Non‐uniform Samplingmentioning

confidence: 99%

See 1 more Smart Citation

Non‐Uniform and Absolute Minimal Sampling for High‐Throughput Multidimensional NMR Applications

Bruschweiler‐Li

et al. 2018

Chemistry A European J

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“…[4] AMS, which is a generalization of SPEED, [5] directly determines spectral parameters, in particular cross-peak positions and their amplitudes, in the time-domain using a non-linear least-squares fitting approach. It differs from CRAFT, [6–7] which uses complete time-domain data.…”

mentioning

confidence: 99%

“…Next, for each frequency ω 2 , the corresponding trace S exp ( t 1 , ω 2 ) along t 1 , sampled at N 1 different time points, is represented by a superposition of M exponentially damped sinoids:

S_{AMS} false(t_{1}, ω_{2} false) = \sum_{k = 1}^{M} A_{k} exp false(i ω_{k} t_{1} - R_{2, k} t_{1} false)

where the coefficients A k correspond to the amplitudes of the complex sinusoids with frequencies ω k and transverse relaxation rates R 2, k . These parameters are determined by a non-linear least squares fit that minimizes [4]

χ^{2} = {true‖ S_{AMS} false(t_{1}, ω_{2} false) - S_{exp} false(t_{1}, ω_{2} false) true‖}^{2}

…”

mentioning

confidence: 99%

Absolute Minimal Sampling of Homonuclear 2D NMR TOCSY Spectra for High‐Throughput Applications of Complex Mixtures

Wang

et al. 2017

Angew Chem Int Ed

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Modern applications of 2D NMR spectroscopy to diagnostic screening, metabolomics, quality control, and other high-throughput applications are often limited by the time-consuming sampling requirements along the indirect time domain t1. 2D Total Correlation Spectroscopy (TOCSY) provides unique spin-connectivity information for the analysis of a large number of compounds in complex mixtures, but standard methods typically require >100 t1-increments for an accurate spectral reconstruction, rendering these experiments ineffective for high-throughput applications. Here, we demonstrate for a complex metabolite mixture how absolute minimal sampling (AMS), based on direct fitting of resonance frequencies and amplitudes in the time domain, yields an accurate spectral reconstruction of TOCSY spectra using as few as 16 t1-points. This permits the rapid collection of homonuclear 2D NMR experiments at high resolution with measurement times that previously were the realm of 1D experiments only.

Absolute Minimal Sampling of Homonuclear 2D NMR TOCSY Spectra for High‐Throughput Applications of Complex Mixtures

Wang

et al. 2017

Angewandte Chemie

Self Cite

Modern applications of 2D NMR spectroscopyt o diagnostic screening,metabolomics,quality control, and other high-throughput applications are often limited by the timeconsuming sampling requirements along the indirect time domain t 1 .2 Dt otal correlation spectroscopy( TOCSY) provides unique spin connectivity information for the analysis of al arge number of compounds in complex mixtures,b ut standardm ethods typically require > 100 t 1 increments for an accurate spectral reconstruction, rendering these experiments ineffective for high-throughput applications.F or ac omplex metabolite mixture it is demonstrated that absolute minimal sampling (AMS), based on direct fitting of resonance frequencies and amplitudes in the time domain, yields an accurate spectral reconstruction of TOCSY spectra using as few as 16 t 1 points.T his permits the rapid collection of homonuclear 2D NMR experiments at high resolution with measurement times that previously were only the realm of 1D experiments.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.