A fast NMR method for resonance assignments: application to metabolomics.

We present a new method for rapid NMR data acquisition and assignments applicable to unlabeled ((12)C) or (13)C-labeled biomolecules/organic molecules in general and metabolomics in particular. The method involves the acquisition of three two dimensional (2D) NMR spectra simultaneously using a dual receiver system. The three spectra, namely: (1) G-matrix Fourier transform (GFT) (3,2)D [(13)C, (1)H] HSQC-TOCSY, (2) 2D (1)H-(1)H TOCSY and (3) 2D (13)C-(1)H HETCOR are acquired in a single experiment and provide mutually complementary information to completely assign individual metabolites in a mixture.

Site-specific 13C content by quantitative isotopic 13C nuclear magnetic resonance spectrometry: a pilot inter-laboratory study.

Isotopic (13)C NMR spectrometry, which is able to measure intra-molecular (13)C composition, is of emerging demand because of the new information provided by the (13)C site-specific content of a given molecule. A systematic evaluation of instrumental behaviour is of importance to envisage isotopic (13)C NMR as a routine tool. This paper describes the first collaborative study of intra-molecular (13)C composition by NMR.

Long-range 1H-15N heteronuclear shift correlation across wide F1 spectral windows.

Long-range (1)H-(15)N heteronuclear shift correlation experiments at natural abundance are becoming more routinely utilized in the characterization of unknown chemical structures from a diverse range of sources including natural products and pharmaceuticals. Apart from the inherent challenges of the low gyromagnetic ratio and natural abundance of (15)N, investigators are also occasionally hampered by having to deal with the wide spectral range inherent to various nitrogen functional groups, which can exceed 500 ppm. Earlier triple resonance cryoprobe designs typically provided 90° (15)N pulses in the range of 35-40 µs, which did not allow the uniform excitation of wide F(1) spectral ranges for (1)H-(15)N GHMBC spectra.

Single or triple gradients?

Pulsed Field Gradients (PFGs) have become ubiquitous tools not only for Magnetic Resonance Imaging (MRI), but also for NMR experiments designed to study translational diffusion, for spatial encoding in ultra-fast spectroscopy, for the selection of desirable coherence transfer pathways, for the suppression of solvent signals, and for the elimination of zero-quantum coherences. Some of these experiments can only be carried out if three orthogonal gradients are available, while others can also be implemented using a single gradient, albeit at some expense of performance. This paper discusses some of the advantages of triple- with respect to single-gradient probes.

Extending the scope of singlet-state spectroscopy.

Different decoupling sequences are tested-using various shaped radio-frequency (RF) pulses-to achieve the longest possible lifetimes of singlet-state populations over the widest possible bandwidths, that is, ranges of offsets and relative chemical shifts of the nuclei involved in the singlet states. The use of sinc or refocusing broadband universal rotation pulses (RE-BURP) for decoupling during the intervals where singlet-state populations are preserved allows one to extend the useful bandwidth with respect to prior state-of-the-art methods based on composite-pulse WALTZ decoupling. The improved sinc decoupling sequences afford a more reliable and sensitive measure of the lifetimes of singlet states in pairs of spins that have widely different chemical shifts, such as the two aromatic protons H(5) and H(6) in uracil.