NMR shielding in helium-3 atoms modified by gaseous nitrogen and oxygen.

Helium-3 nuclear magnetic resonance (3 He NMR) measurements were carried out for the gaseous mixtures of helium-3 with pure nitrogen and synthetic air as the solvents. It was found that 3 He shielding is linearly dependent on solvent density up to approx. 6 mol/L. At higher density of the gaseous solvent, the change of 3 He shielding is nonlinear and especially distinct when helium-3 atoms can interact with two O2 molecules. The interaction with paramagnetic oxygen molecules can induce two kinds of 3 He shielding changes: (1) due to the isotropic Fermi contact interaction and (2) from the dipolar magnetic interaction between unpaired O2 electrons and 3 He nuclear magnetic dipole moment. The two paramagnetic effects in helium-3 shielding cannot be experimentally separated, although for such small molecular objects, they could be presumably modeled by advanced theoretical calculations.

Peptides and peptidoaldehydes as substrates for the Pictet-Spengler reaction.

The Pictet-Spengler (PS) reaction was performed with various types of substrates: H-Trp-OMe and dipeptides with N-terminal Trp as arylethylamine components and Z-protected amino aldehydes and peptidoaldehydes as carbonyl components. We found that the C-terminal part of Trp derivatives did not have any influence on the stereoselectivity of the reaction and the results are the same for simple esters of Trp and dipeptides. On the contrary, the selectivity of the PS reaction with peptidoaldehydes with L configuration of the C-terminus residue is totally different from that obtained with simple L-amino aldehydes. It allows us to obtain cis stereoisomers, which cannot be isolated from the reaction with amino aldehydes. But the utility of the peptidoaldehydes as substrates for the PS reaction is reduced by the side formation of enamides which decrease the yield of cyclization.

Study of near-symmetric cyclodextrins by compressed sensing 2D NMR.

The compressed sensing NMR (CS-NMR) is an approach to processing of nonuniformly sampled NMR data. Its idea is to introduce minimal l(p) -norm (0 < p ≤ 1) constraint to a penalty function used in a reconstruction algorithm. Here, we demonstrate that 2D CS-NMR spectra allow the full spectral assignment of near-symmetric ß-cyclodextrin derivatives (mono-modified at the C6 position). The application of CS-NMR ensures experimental time saving and the resolution improvement, necessary because of very low chemical shift dispersion. In the overnight experimental time, the set of properly resolved 2D NMR spectra required for the unambiguous assignment of mono(6-deoxy-6-(1-1,2,3-triazo-4-yl)-1-propane-3-O-(phenyl)) ß-cyclodextrin was obtained. The highly resolved HSQC spectrum was reconstructed from 5.12% of the data. Moreover, reconstructed 2D HSQC-TOCSY spectrum yielded information about the correlations within one sugar unit, and 2D HSQC-NOESY technique allowed the sequential assignment of the glucosidic units.

Generalized Fourier transform for non-uniform sampled data.

Fourier transform can be effectively used for processing of sparsely sampled multidimensional data sets. It provides the possibility to acquire NMR spectra of ultra-high dimensionality and/or resolution which allow easy resonance assignment and precise determination of spectral parameters, e.g., coupling constants. In this chapter, the development and applications of non-uniform Fourier transform is presented.

Determination of heteronuclear coupling constants from 3D HSQC-TOCSY experiment with optimized random sampling of evolution time space.

An application of 3D version of HSQC-TOCSY experiment for the measurement of heteronuclear coupling constants of organic compounds yielding complex spectra is proposed. The approach presented here is based on the optimized random sampling of the evolution time space followed by Multidimensional Fourier Transform (MFT). In this study, we show that the interpretation of omega(3)-(13)C coupled (1)H-(13)C 3D HSQC-TOCSY spectra with E.COSY-type multiplets allows one to evaluate heteronuclear coupling constants of strychnine with high accuracy, whereas the employment of 2D methods is associated with signal overlap and use of conventionally recorded 3D NMR spectra cannot provide accurate results in an overnight experiment.

Complete (1)H and (13)C signal assignment of prenol-10 with 3D NMR spectroscopy.

The complete assignment of (1)H and (13)C chemical shifts of natural abundance prenol-10 is reported for the first time. It was achieved using 3D NMR experiments, which were based on random sampling of the evolution time space followed by multidimensional Fourier transform. This approach makes it possible to acquire 3D NMR spectra in a reasonable time and preserves high resolution in indirectly detected dimensions. It is shown that the interpretation of 3D COSY-HMBC and 3D TOCSY-HSQC spectra is crucial in the structural analysis of prenol-10.

Structural analysis of 25-hydroxycholesterol stereoisomers differing in configuration in position 17 and 20, by three-dimensional NMR spectra.

The application of 3D NMR experiments and DFT calculations enabled the structure investigation of C-17 epimer of 3-(25-hydroxycholest-5-enyl) acetate is presented. The H-17 and H-20 protons features the same values of 1H chemical shift, what causes that the structure elucidation require additional resolution enabled by 3D NMR experiments. The NMR experiments and theoretical calculations allowed for: the resonance assignment (3D COSY-HMBC and 3D TOCSY-HSQC techniques), the prediction of spatial structure (3D NOESY-HSQC and 3D ROESY-HSQC experiments), and the precise measurement of heteronuclear coupling constants (3D HSQC-TOCSY spectra with E.COSY-type multiplets).

NMR Spectroscopy Protocols for Food Metabolomics Applications.

NMR spectroscopy has become an indispensable tool for the metabolic profiling of foods and food products. In the present protocol, we report an analytical approach based on liquid-state NMR for the determination of polar and nonpolar metabolites in some common liquid (wine, spirits, juice) and solid (cheese, coffee, honey) foods. Although the diversity of foods precludes the use of a single protocol, with small modifications, the proposed methodologies can be adapted to a broader range of foodstuffs.

Three-dimensional NMR Spectroscopy of organic molecules by random sampling of evolution time space and multidimensional Fourier transformation.

In this communication we present the application of a new method, which enables one to acquire 3D NMR spectra in a reasonable time and preserves high resolution in indirectly detected domains. The new method is based on random distribution of time domain data points followed by Quaternion FT with respect to two time variables in one step. The experimental examples include three-dimensional spectra of strychnine in CDCl3, TOCSY-HSQC, COSY-HMBC, and the new technique proposed here: heteronuclear single quantum multiple bond correlation (HSQMBC). The obtained spectra are compared to those recorded at the same time employing the conventional acquisition scheme. We show that high-quality 3D spectra of organic compounds can be obtained in reasonable experimental time and that they are of great interest in cases when direct analysis of 2D spectra is difficult.