title: Still shimming or already measuring?--Quantitative reaction monitoring for small molecules on the sub minute timescale by NMR.
abstract: In order to enable monitoring of rapidly occurring reactions Wagner et al. recently presented a simple scheme for 1D NMR experiments with continuous data acquisition, without inter-scan delays, using a spatially-selective and frequency-shifted excitation approach (Wagner et al., 2013). This scheme allows acquisition of proton spectra with temporal resolutions on the millisecond timescale. Such high temporal resolutions are desired in the case of reaction monitoring using stopped flow setups. In regular (1)H NMR-spectra without spatial selection the line width increases for a given shim setting with changes in sample volume, susceptibility, convection and temperature or concentration gradients due to the disturbance of magnetic field homogeneity. Concerning reaction monitoring this is unfortunate as shimming prior to acquisition becomes necessary to obtain narrow signals after injection of a reactant into an NMR sample. Even automatic shim routines may last up to minutes. Thus fast reactions can hardly be monitored online without large hardware dead times in a single stopped flow experiment. This problem is reduced in the spatially-selective and frequency-shifted continuous NMR experiment as magnetic field inhomogeneties are less pronounced and negative effects on the obtained line shapes are reduced as pointed out by Bax and Freeman (1980) [2] and demonstrated by Wagner et al. (2013). Here we present the utilization of this technique for observation of reactions in small molecule systems in which chemical conversion and longitudinal relaxation occur on the same timescale. By means of the alkaline ethyl acetate hydrolysis, a stoichiometric reaction, we show advantages of spatially-selective excitation on both temporal resolution and line shapes in stopped flow experiments. Results are compared to data obtained by non-selective small angle excitation experiments.
authors.affiliation: Clemens-Schöpf-Institute for Organic Chemistry and Biochemistry, Technische Universität Darmstadt, Alarich-Weiss-Str. 16, D-64287 Darmstadt, Germany.
authors.forename: J
authors.initials: J
authors.lastname: Kind
authors.affiliation: Clemens-Schöpf-Institute for Organic Chemistry and Biochemistry, Technische Universität Darmstadt, Alarich-Weiss-Str. 16, D-64287 Darmstadt, Germany. Electronic address: cthiele@thielelab.de.
authors.forename: C M
authors.initials: CM
authors.lastname: Thiele
keywords: (1)H NMR; Reaction monitoring; Shimming; Slice selection; Stoichiometric reaction