A community-built calibration system: The case study of quantification of metabolites in grape juice by qNMR spectroscopy.

Nuclear Magnetic Resonance (NMR) is an analytical technique extensively used in almost every chemical laboratory for structural identification. This technique provides statistically equivalent signals in spite of using spectrometer with different hardware features and is successfully used for the traceability and quantification of analytes in food samples. Nevertheless, to date only a few internationally agreed guidelines have been reported on the use of NMR for quantitative analysis. The main goal of the present study is to provide a methodological pipeline to assess the reproducibility of NMR data produced for a given matrix by spectrometers from different manufacturers, with different magnetic field strengths, age and hardware configurations. The results have been analyzed through a sequence of chemometric tests to generate a community-built calibration system which was used to verify the performance of the spectrometers and the reproducibility of the predicted sample concentrations.

Monitoring organic reactions by UF-NMR spectroscopy.

Standard 2D NMR experiments suffer from the many t1 increments needed for spectra with sufficient digital resolution in the indirect dimension. Despite the different methodological approaches to overcome this problem, these increments have prevented studies of fast reactions. The development of ultrafast NMR (UF-NMR) has decisively speeded up the time scale of standard NMR to allow the study of organic reactions as they happen in real time to reveal mechanistic details. This mini-review summarizes the results achieved in monitoring organic reactions through this exciting technique.

2D ultrafast HMBC 1H,31P: obtaining mechanistic details on the Michaelis­Arbuzov reaction.

Ultrafast NMR spectroscopy (UF-NMR) can be used to monitor chemical reactions in real time and to provide insights into their mechanisms and the nature of the intermediates formed. Here, we have developed a 2D 1H,31P UF-HMBC method and the corresponding NMR experimental setup to enable the study of a Michaelis­Arbuzov reaction at two different temperatures, 25 and 70 °C. The specific reaction studied was between triethyl phosphite and benzyl bromide to produce diethylbenzyl phosphonate. Our results show that at 70 °C the reaction takes place directly, without the detection of an intermediate by 1H,31P UF-HMBC. In contrast, at 25 °C, using zinc bromide as a catalyst, our results show the formation of benzyltriethoxy phosphonium bromide as an intermediate. The experiments again show the power of UF-NMR in mechanistic studies of reactions involving various phosphorus chemical species.

Discovering mechanistic insights by application of tandem ultrafast multidimensional NMR techniques.

Ultrafast multidimensional NMR acquisition techniques have shown promising capabilities in studies of dynamic systems in real time. The method's characteristics have permitted the focus to be on the mechanistic details of organic reactions. The tandem UF-TOCSY/HMBC sequence applied here combines both homonuclear and heteronuclear details and therefore provides complete information about the evolution of a dynamic reaction in real time. The methodology will be applied to find an explanation of the low reactivity of alicyclic ketones such as cyclohexanone in reactions with triflic anhydride and aliphatic nitriles, which leads to bicyclic pyrimidines.